JP2018199770A - Liquid detergent composition for hard surface - Google Patents

Abstract

To provide a liquid detergent composition for hard surface that is excellent in foaming after storage as well as detergency, and satisfactorily suppresses the deposition of stains onto a hard surface after storage.SOLUTION: A liquid detergent composition for hard surface contains (a) a copolymer that contains a specific constitutional unit having a betaine group (a1) and a specific constitutional unit having a cation group (a2), with a molar ratio between the constitutional unit (a1) and constitutional unit (a2) [constitutional unit (a1)/constitutional unit (a2)] of 30/70 or more and 99.9/0.1 or less, (b) an inorganic salt selected from an alkali metal halide and an alkaline earth metal halide, and (c) a surfactant.SELECTED DRAWING: None

Description

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

  The living environment equipment that surrounds us has various hard surfaces made of tile, plastic, metal, etc., and these hard surfaces are exposed to an environment where various kinds of dirt adhere in daily life. In particular, hard surfaces used as toilets, bathrooms, kitchens, etc. are also surfaces that people come into contact with on a daily basis, so that many stains remain and accumulate, and furthermore, they have properties that are difficult to remove. It has become.

For example, Patent Document 1 discloses a composition for cleaning or rinsing a hard surface in an aqueous medium or an aqueous alcohol medium containing at least one surfactant and at least one polybetaine (B). Wherein the polybetaine (B) has a total constant anion charge and a constant total cation charge within the pH range of 1-14 (each individual betaine unit being the same number of constant anions as the constant cation charge). Hard surface cleaning or rinsing compositions are disclosed that exhibit an absolute weight average molecular weight (Mw) of 5,000 to 3,000,000 g / mole (assuming charge).
Patent Document 2 discloses a copolymer containing a unit A containing a betaine group and a cationic unit B.
In Patent Document 3, (a) the monomer unit (a-1) having a sulfobetaine structure is 50 mol% or more and 95 mol% or less in all monomer units, and the number of carbon atoms other than the monomer unit (a-1) is 1 As mentioned above, 0.01 mass% or more and 10 mass% or less of high molecular compounds which contain the monomer unit (a-2) which has 18 or less alkyl groups in 5 mol% or more and 50 mol% or less in all the monomer units, (b ) 0.1% by mass or more and 5% by mass or less of an inorganic salt selected from alkali metal halides and alkaline earth metal halides, and (c) 0.5% by mass or more and 30% by mass or less of a surfactant. In addition, a liquid treatment composition for hard surfaces containing water is disclosed.

JP 2010-1000086 A US Patent Application Publication No. 2009/0197791 JP-A-2015-105310

Patent Documents 1 to 3 are not sufficient in that they satisfy the foaming after storage, the cleaning power after storage, and the antifouling property after storage.
The present invention is excellent in bubbling after storage (hereinafter also simply referred to as foaming power) and cleaning power after storage (hereinafter also simply referred to as cleaning power), and is capable of suppressing adhesion of dirt to a hard surface after storage (hereinafter referred to as It is related with the liquid detergent composition for hard surfaces which is excellent also in simply antifouling performance.

  The present inventors have found that the above problem can be solved by using a polymer having a specific betaine group and a specific cationic group, a specific inorganic salt, and a surfactant.

  The present invention includes (a) a structural unit (a1) represented by the following formula (1) and a structural unit (a2) represented by the following formula (2), wherein the structural unit (a1) and the structural unit (a2) ) Is a molar ratio of the structural unit (a1) / the structural unit (a2) is 30/70 to 99.9 / 0.1 [hereinafter referred to as component (a)], (b) alkali metal And an inorganic salt selected from halides of alkaline earth metals (hereinafter referred to as component (b)) and (c) a surfactant (hereinafter referred to as component (c)) for hard surfaces The present invention relates to a liquid detergent composition.

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

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

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

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the foaming and cleaning power after a preservation | save, the liquid detergent composition for hard surfaces which is excellent in the adhesion control of the stain | pollution | contamination to the hard surface after a preservation | save, ie, antifouling performance, is provided.

[Liquid detergent composition for hard surface]
<(A) component>
The component (a) is a copolymer containing the structural unit (a1) represented by the formula (1) and the structural unit (a2) represented by the formula (2).
The structural unit (a1) represented by the formula (1) may be a structural unit derived from an unsaturated monomer having a betaine group. The structural unit (a2) represented by the formula (2) may be a structural unit derived from an unsaturated monomer having a cationic group.

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

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

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

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

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

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

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

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

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

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

[Structural units other than structural unit (a1) and structural unit (a2)]
(A) A component may contain structural units other than a structural unit (a1) and a structural unit (a2) in the range which does not impair the effect of this invention. As the structural unit other than the structural unit (a1) and the structural unit (a2), a structural unit derived from an unsaturated monomer other than an unsaturated monomer having a sulfobetaine group is preferable, and hydrophobic unsaturated such as styrene. A structural unit derived from a monomer is more preferable.
The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10 mol% or less, more preferably 5 mol% or less, more preferably from the viewpoint of antifouling properties. Is 1 mol% or less, more preferably 0.5 mol% or less, still more preferably 0.1 mol% or less. The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) may be 0 mol%.
The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably from the viewpoint of antifouling properties. Is 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less. The content of the structural unit other than the structural unit (a1) and the structural unit (a2) in the component (a) may be 0% by mass.

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

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

<(B) component>
The component (b) is an inorganic salt selected from alkali metal halides and alkaline earth metal halides. As the component (b), one or more compounds selected from the group consisting of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and potassium iodide are preferable. The component (b) is more preferably an alkali metal chloride, and even more preferably sodium chloride.

<(C) component>
The component (c) is a surfactant. The component (c) is selected from cationic surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants from the viewpoint of improving sterilizing power, detergency, and foaming power. The surfactant more than a seed | species is mentioned.

Component (c) is preferably one or more surfactants selected from amphoteric surfactants, nonionic surfactants, and anionic surfactants from the viewpoint of improving detergency and foaming power. One or more surfactants selected from surfactants and nonionic surfactants are more preferred.
In addition, the component (c) is selected from a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant from the viewpoint of improving sterilizing power, detergency, and foaming power. It is preferable that it contains at least one surfactant selected from the group consisting of a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. . (C) It is also preferable that a component contains a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

[Cationic surfactant]
As the cationic surfactant, mono- or di-long alkyl quaternary ammonium salts are preferable. As the cationic surfactant, a cationic surfactant selected from a compound represented by the following general formula (c1-1) and a compound represented by the general formula (c1-2) is preferable.

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

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

In the case of a mono long chain alkyl type quaternary ammonium salt, in the general formula (c1-1), R ^1c is preferably an alkyl group, an alkenyl group or a hydroxyalkyl group having 8 to 16 carbon atoms; ^2c , R ^3c and R ^4c are the same or different and are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less.
In the case of the di-long-chain alkyl type quaternary ammonium salt, in the general formula (c1-1), preferably, R ^1c and R ^2c are the same or different and each is an alkyl group having 8 to 16 carbon atoms, An alkenyl group or a hydroxyalkyl group, and R ^3c and R ^4c are the same or different and are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having an average addition mole number of 10 or less. .

In the general formula (c1-2), R ^5c is preferably a linear alkyl group having 12 to 16 carbon atoms, R ^6c and R ^7c are each preferably a methyl group, and R ^8c is preferably a methylene group. ^- is a halogen ion, further chloride ion (Cl ^-) are preferred.

  The cationic surfactant is preferably a cationic surfactant selected from the compounds represented by the general formula (c1-2).

[Amphoteric surfactant]
The amphoteric surfactant preferably contains at least one amphoteric surfactant selected from amine oxide, sulfobetaine and carbobetaine from the viewpoint of detergency and foaming power, and is selected from sulfobetaine and carbobetaine. It is more preferable to include one or more amphoteric surfactants, and it is more preferable to include carbobetaine. Two or more of these may be used.

In the amphoteric surfactant, the content of one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carbobetaine is preferably 50% by mass or more, more preferably from the viewpoint of detergency and foaming power. 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. It is.
In the amphoteric surfactant, the content of one or more amphoteric surfactants selected from sulfobetaine and carbobetaine is preferably 50% by mass or more, more preferably 70%, from the viewpoint of detergency and foaming power. % By mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. is there.

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

  The carbobetaine is preferably an N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine in which the carbon number of the alkyl group is preferably 10 or more, preferably 18 or less, more preferably 14 or less, from the viewpoint of detergency. Or a compound represented by the following general formula (c2-1), and a compound represented by the following general formula (c2-1) is preferred from the viewpoint of detergency.

[Wherein, R ^21c represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, R ^22c represents a propylene group, and R ^23c and R ^24c are each independently an alkyl group having 1 to 3 carbon atoms. Indicates. ]

In the general formula (c2-1), R ^21c is preferably an alkyl group or an alkenyl group of 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, and a nonyl group or a decyl group. , Undecyl group, dodecyl group, and tridecyl group are preferable.
In general formula (c2-1), R ^23c and R ^24c are preferably a methyl group.
Examples of the compound represented by the general formula (c2-1) include almond amidopropyl betaine, apricot amidopropyl betaine, avocado amidopropyl betaine, babasamidopropyl betaine, behenamidopropyl betaine, canola amidopropyl betaine, capryl / capramide Propyl betaine, cocamidopropyl betaine, coco / oleamidopropyl betaine, isostearamidpropyl betaine, lauramidopropylcarbobetaine, milkamidopropyl betaine, mincamidepropyl betaine, myristamidopropyl betaine, oleamidopropyl betaine, oliveamidopropyl Betaine, Palmamamidopropyl Betaine, Palmitamidopropyl Betaine, Ricinolemic Amidopropyl Betaine, Sesamidop Pirubetain, soy amidopropyl betaine, stearamidopropyl betaine, tallow amidopropyl betaine, undecylenic acid amidopropyl betaine, and wheat germ amido propyl betaine and the like.
Among these, at least one selected from lauramidopropyl carbobetaine, myristamidopropyl betaine, oleamidopropyl betaine, and cocamidopropyl betaine is preferable. In these, R ^23c and R ^24c in the general formula (c2-1) are each a compound having a methyl group.

  As an amine oxide, the compound of the following general formula (c2-2) is suitable.

[In the formula, R ^25c represents a hydrocarbon group having 8 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group. R ^26c and R ^27c each independently represents 1 to 3 carbon atoms. The following alkyl groups are shown. D represents a —NHC (═O) — group or a —C (═O) NH— group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p represent m = 0 and p = 0 or m = 1 and p = 1. ]

In the above general formula (c2-2), R ^25c is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, from the viewpoint of detergency, Preferably it is a C12-C14 alkyl group, More preferably, it is a C12 alkyl group. R ^26c and R ^27c are preferably a methyl group having 1 carbon from the viewpoint of detergency.

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

[Nonionic surfactant]
Nonionic surfactants include (c3-1) monoalkyl glyceryl ether (hereinafter referred to as (c3-1) component), (c3-2) polyoxyalkylene monoalkyl or from the viewpoint of detergency and foaming power. Alkenyl ether [hereinafter referred to as (c3-2) component], (c3-3) alkyl polyglycoside (glycoside type nonionic surfactant) [hereinafter referred to as (c3-3) component], (c3-4) sorbitan Nonionic surfactant (hereinafter referred to as (c3-4) component), (c3-5) aliphatic alkanolamide (hereinafter referred to as (c3-5) component), (c3-6) fatty acid monoglyceride (hereinafter referred to as (c3) -6) component], and (c3-7) sucrose fatty acid ester [hereinafter referred to as component (c3-7)] is preferably at least one selected from the group consisting of It may be used or two or more kinds.

The nonionic surfactant preferably contains one or more selected from the component (c3-1), the component (c3-2) and the component (c3-3) from the viewpoints of detergency and foaming power. It is still more preferable that c3-3) component is included.
In the nonionic surfactant, the total content of the component (c3-1), the component (c3-2) and the component (c3-3) is preferably 50% by mass or more from the viewpoint of detergency and foaming power. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, Preferably it is 100 It is below mass%.
In addition, the content of the component (c3-3) in the nonionic surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass from the viewpoints of detergency and foaming power. More preferably, it is 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less.

(C3-1) Component (c3-1) The component is a monoalkyl glyceryl ether.
As the component (c3-1), specifically, a compound represented by the following general formula (c3-1) is preferable.
R ^31c —O— (Gly) _r —H (c3-1)
[Wherein R ^31c represents an alkyl group having 6 to 18 carbon atoms, Gly represents a structural unit derived from glycerin, and preferably represents a residue obtained by removing one hydroxyl group and one hydrogen atom from glycerin; Represents a number from 1 to 4. ]

In General Formula (c3-1), R ^31c is preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 18 or less carbon atoms from the viewpoint of detergency. More preferably, it is an alkyl group having 12 or less carbon atoms, more preferably 10 or less carbon atoms, and straight chain alkyl groups such as hexyl group, heptyl group, octyl group, nonyl group and decyl group can be used. In the invention, an alkyl group having a branched chain is preferable from the viewpoint of detergency, and the specific alkyl group having a branched chain of R ^31c is selected from 2-ethylhexyl group, sec-octyl group, isononyl group and isodecyl group. Group is more preferable, 2-ethylhexyl group or isodecyl group is more preferable, and 2-ethylhexyl group is particularly preferable.

In general formula (c3-1), r is preferably 1 or more and preferably 2 or less. A compound in which r is 1 is more preferable. Particularly preferred compounds are those in which R ^31c is a 2-ethylhexyl group and r is 1.
The structure represented by Gly is a structure represented by —CH ₂ CH (OH) CH ₂ — in which the first and third hydroxyl groups of glycerin are bonded, or the first and second hydroxyl groups of glycerin are bonded. It is a structure represented by —CH (CH ₂ OH) CH ₂ —, which varies depending on the catalyst and reaction conditions.

In order to obtain the compound of the general formula (c3-1), for example, an alkyl alcohol represented by R ^31c —OH is used as an alcohol having 6 to 10 carbon atoms, and an epoxy compound such as epihalohydrin or glycidol is combined with an acid such as BF _3. A method of producing by reacting using a catalyst or an aluminum catalyst can be used. For example, when 2-ethylhexanol is used, the obtained 2-ethylhexyl monoglyceryl ether is a mixture that can contain a plurality of products as described in JP-A No. 2001-49291.

(C3-2) Component (c3-2) The component is a polyoxyalkylene monoalkyl or alkenyl ether.
In the nonionic surfactant of component (c3-2), the number of carbon atoms of the alkyl group or alkenyl group is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and still more preferably, from the viewpoint of detergency. Is 12 or more, and from the same viewpoint, it is preferably 22 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

In the nonionic surfactant as the component (c3-2), the average number of added moles of alkylene oxide is preferably more than 0, more preferably 1 or more, still more preferably 3 or more, and the like, from the viewpoint of detergency. From the viewpoint, it is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and still more preferably 10 or less.
From the viewpoint of detergency, the alkylene oxide is preferably at least one selected from ethylene oxide, propylene oxide, and butylene oxide, more preferably at least one selected from ethylene oxide and propylene oxide.

As a preferred example of the nonionic surfactant as the component (c3-2), a nonionic surfactant represented by the following general formula (c3-2) can be given.
R ^32c O [(C ₂ H ₄ O) ₁ / (C ₃ H ₆ O) _j ] H (c3-2)
[Wherein R ^32c represents a hydrocarbon group having 6 to 22 carbon atoms. l and j represent the average number of moles added, l represents a number from 0 to 30 and j represents a number from 0 to 30. l and j are not 0 at the same time. “/” Indicates that the oxyethylene group and the oxypropylene group may be added either randomly or in a block regardless of the order. ]

The number of carbon atoms of R ^{32c in} the general formula (c3-2) is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, from the viewpoint of detergency, and preferably from the same viewpoint. Is 18 or less, more preferably 16 or less, and still more preferably 14 or less.
R ^32c is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of detergency, and a secondary alkyl group from the viewpoint of detergency. Here, the secondary alkyl group refers to an alkyl group in which the carbon atom of R ^32c bonded to O in R ^32c O in general formula (c3-2) is a secondary carbon atom.
Specifically, as the alkyl group, various octyl groups (including 2-ethylhexyl group), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl group), various tridecyl groups, various tetradecyl groups, Examples include various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups.
Examples of the alkenyl group include various octanyl groups, various nonanyl groups, various decanyl groups, various undecanyl groups, various dodecanyl groups, various tridecanyl groups, various tetradecanyl groups, various pentadecanyl groups, various hexadecanyl groups, various heptadecanyl groups, various octadecanyl groups (for example, Oleyl group, linole group). The “various” means various isomers including n-, sec-, tert-, and iso-.

  In the general formula (c3-2), l and j are each independently preferably 1 or more, more preferably 2 or more, from the viewpoint of storage stability, and from the same viewpoint, preferably 20 or less. More preferably, it is 10 or less, More preferably, it is 5 or less.

The HLB value of the polyoxyalkylene monoalkyl or alkenyl ether as the component (c3-2) and the nonionic surfactant represented by the general formula (c3-2) is preferably 5 or more from the viewpoint of detergency. More preferably, it is 7 or more, and from the same viewpoint, it is preferably 19 or less, more preferably 15 or less, and still more preferably 13 or less.
Here, the HLB value is defined by the following Griffin equation.
HLB value = 20 × Mw / M
(Wherein, M is the molecular weight of the nonionic surfactant, and Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.)
In addition, in general formula (c3-2), a hydrophilic part is a total part of an oxyethylene group and an oxypropylene group.

(C3-3) Component The (c3-3) component is an alkylpolyglycoside (glycoside type nonionic surfactant).
The nonionic surfactant as the component (c3-3) is preferably a nonionic surfactant represented by the following general formula (c3-3).
R ^33c (OR ^34c ) _s G _t (c3-3)
[Wherein, R ^33c represents a linear or branched alkyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, preferably an alkenyl group or an alkylphenyl group, preferably an alkyl group, and R ^34c represents a carbon number. 2 to 4 alkylene groups, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. s shows an average added mole number, and is a number of 0 or more and 5 or less. t represents a number whose average value is 1 or more and 5 or less. ]

In General Formula (c3-3), R ^33c is a linear or branched alkyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 14 or less, from the viewpoint of detergency.
In general formula (c3-3), s is preferably 0 or more and 2 or less, more preferably 0, from the viewpoint of storage stability. From the viewpoint of storage stability, t is preferably 1.1 or more, and preferably 1.5 or less, more preferably 1.4 or less. Here, t is a value measured by proton NMR method.
In general formula (c3-3), G includes a residue derived from one or more monosaccharides selected from glucose and fructose from the viewpoint of availability and cost. Examples of G include a residue derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a monosaccharide of glucose.

(C3-4) component to (c3-7) component (c3-4) sorbitan nonionic surfactant, (c3-5) aliphatic alkanolamide, (c3-6) fatty acid monoglyceride, and (c3-7) The sucrose fatty acid ester preferably has a linear or branched alkyl group having 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 ester group, a phosphate ester group, a phosphonic acid group, a sulfonic acid group or a carboxy group.
From the viewpoint of detergency, the hydrocarbon group possessed by the anionic surfactant preferably has 5 or more carbon atoms, more preferably 6 or more, still more preferably 7 or more, still more preferably 8 or more, and still more preferably. 10 or more, more preferably 12 or more, and preferably 21 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less, a linear or branched alkyl group, alkylene group or aryl group Is preferred.

  The anionic surfactant is (c4-1) a sulfosuccinic acid ester having a hydrocarbon group having 5 to 18 carbon atoms or a salt thereof (hereinafter referred to as (c4-1) component), (c4-2) carbon number. An anionic surfactant having a hydrocarbon group of 8 to 21 and a sulfate ester group or a sulfonic acid group [excluding the component (c4-1)] [hereinafter referred to as the component (c4-2)], ( c4-3) an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a carboxy group (hereinafter referred to as component (c4-3)), and (c4-4) having 8 to 21 carbon atoms. One or more anionic surfactants selected from the group consisting of an anionic surfactant having a hydrocarbon group and a phosphoric acid ester group (hereinafter referred to as component (c4-4)) are preferred. You can use more than seeds .

The anionic surfactant preferably contains at least one selected from the group consisting of the component (c4-1) and the component (c4-2), from the viewpoints of detergency and foaming power, and (c4-2) More preferably, the ingredients are included.
In the anionic surfactant, the total content of the component (c4-2) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass from the viewpoints of detergency and foaming power. More preferably, it is 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less.
In addition, content (mass%) of each component in anionic surfactant is computed based on the quantity of sodium salt conversion.

  The component (c4-2) used in the present invention is an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a sulfate ester group or a sulfonic acid group [provided that the component (c4-1) Except].

  From the viewpoint of detergency, the hydrocarbon group of component (c4-2) has 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 21 or less, preferably 18 or less, more preferably 14 or less. More preferably, it is 12 or less. The hydrocarbon group as the component (c4-2) is preferably an alkyl group or an aryl group.

  The anionic surfactant (c4-2) is preferably at least one selected from alkyl sulfates, polyoxyalkylene alkyl ether sulfates and alkane sulfonates.

The anionic surfactant having a sulfate ester group has a carbon number of 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, and still more preferably 12 from the viewpoint of detergency. The following alkyl sulfate esters having a linear or branched alkyl group are preferred.
The anionic surfactant having a sulfate ester group and a polyoxyalkylene group has a carbon number of 8 or more, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably from the viewpoint of detergency. Has a linear or branched alkyl group of 14 or less, more preferably 12 or less, and the average added mole number of the oxyalkylene group having 2 or more and 3 or less carbon atoms is preferably 0.1 or more, more preferably 0.8. Polyoxyalkylene alkyl ether sulfates having a polyoxyalkylene group of 3 or more, more preferably 0.4 or more, and preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less are suitable.
In addition, as the anionic surfactant having a sulfonic acid group, from the viewpoint of detergency,
(1) an alkylbenzenesulfonate having an alkyl group having 6 to 15 carbon atoms, and (2) 8 or more carbon atoms, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, Preferably, one or more anionic surfactants selected from 12 or less alkane sulfonates are suitable.

  (C4-2) Inorganic surfactant salt selected from sodium salt, ammonium salt, potassium salt, magnesium salt, etc., monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, morpholinium salt An organic ammonium salt selected from among them is preferred.

As the component (c4-2), a compound represented by the following general formula (c4-2) is preferable from the viewpoints of blending stability and foamability.
^{_{R 43c -O- (R 44c O)}} n -SO 3 M 2 (c4-2)
[In the formula, R ^43c is a linear or branched alkyl group having 8 to 21 carbon atoms, R ^44c is an ethylene group and / or propylene group, n is an average added mole number, and is 0 or more. The number is 6 or less. M ² is a hydrogen atom or a cation, preferably an inorganic or organic cation. ]

In general formula (c4-2), R ^43c has 8 or more carbon atoms, preferably 10 or more, and 21 or less, preferably 18 or less, more preferably 14 or less, and still more preferably 12 or less, from the viewpoint of detergency. Or a straight-chain alkyl group, preferably a straight-chain alkyl group. Specifically, R ^43c is preferably an alkyl group selected from an octyl group, a decyl group, a dodecyl group, a tridecyl group, and a tetradecyl group, and more preferably a dodecyl group.

In general formula (c4-2), n is preferably 0 or more, and preferably 6 or less, more preferably 4 or less, still more preferably 3 or less, and even more preferably 1.5 or less, from the viewpoint of detergency. Is the number of N may be 0.
In the general formula (c4-2), when R ^44c is an ethylene group, n is preferably 0.1 or more, more preferably 0.5 or more, and preferably 6 or less, from the viewpoint of detergency. More preferably, the number is 3 or less.
In the general formula (c4-2), when R ^44c is a propylene group, n is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.8 from the viewpoint of detergency. The number is 4 or more, preferably 1.5 or less, more preferably 1.0 or less, and still more preferably 0.8 or less.
In the general formula (c4-2), when R ^44c is an ethylene group or a propylene group, n can be selected from these ranges.

In the general formula (c4-2), M ² represents a hydrogen atom or an inorganic cation such as sodium ion, ammonium ion, potassium ion, magnesium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, morpholine. Examples thereof include organic cations such as nium ions, and preferred are inorganic cations selected from sodium ions, potassium ions, ammonium ions, and magnesium ions.

In formula ^{(C4-2), when R 43c} to obtain a compound containing a branched alkyl group as the alcohol represented by the raw material ^R 43c -OH, the number 8 to 14 of the 1-alkene carbon After condensing an alcohol obtained by hydroformylation (containing 15 mol% to 70 mol% of an alkyl group having a methyl group branched at the β position relative to the OH group), an aldehyde having 4 to 8 carbon atoms, Obtained by hydroformylation of a Gerber type alcohol obtained by reduction (containing 100 mol% of a structure in which an alkyl group having 3 to 6 carbon atoms is branched at the β-position relative to the OH group) and isobutene 3,5,5-trimethylhexanol obtained by hydroformylation of isobutene trimer (branching rate is 100 mol%), stone Examples thereof include synthetic alcohols derived from oil and coal (which are alkyl groups having a branching ratio of about 20 mol% to 100 mol%).

The component (c4-3) used in the present invention is an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a carboxy group.
Specific examples include higher fatty acids or salts thereof, polyoxyethylene alkyl ether carboxylic acids or salts thereof, and N-acyl amino acids or salts thereof.

As the higher fatty acid or a salt thereof, one represented by the following general formula (c4-3-1) is preferable.
R ^45c -COOX ^1c (c4-3-1)
[Wherein, R ^45c represents an alkyl group or alkenyl group having 8 to 21 carbon atoms, and X ^1c represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkanol ammonium, or a basic amino acid. ]

The polyoxyethylene alkyl ether carboxylic acid or a salt thereof is preferably one represented by the following general formula (c4-3-2).
R ^46c —O— (CH ₂ CH ₂ O) _g COOX ^2c (c4-3-2)
[In the formula, R ^46c represents an alkyl group or alkenyl group having 8 to 21 carbon atoms, g represents an average addition mole number of ethylene oxide, represents a number of 0.5 to 10 and X ^2c represents a hydrogen atom, (Indicates alkali metal, alkaline earth metal, ammonium, alkanol ammonium or basic amino acid)

In general formula (c4-3-2), R ^46c is preferably a straight or branched chain having 10 or more carbon atoms, and preferably 16 or less carbon atoms, more preferably 14 or less carbon atoms, from the viewpoint of detergency. Alkyl groups are preferred. The average added mole number g of ethylene oxide is preferably 1 or more and 6 or less from the viewpoint of detergency.
Moreover, as ^X2c , what was described in the above-mentioned ^X1c is mentioned preferably.

N-acylamino acids or salts thereof include N-acylglycine salts and N-acyl-β-alanine salts, and those represented by the following general formula (c4-3-3) are preferred.
R ^47c CONH (CH ₂ ) _h COOX ^3c (c4-3-3)
[Wherein, R ^47c represents an alkyl group or alkenyl group having 8 to 21 carbon atoms, h represents a number of 1 or 2, and X ^3c represents a hydrogen atom, an alkali metal, ammonium, an alkanol ammonium, or a basic amino acid. Show

In General Formula (c4-3-3), R ^47c is preferably an alkyl group or an alkenyl group of 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less, from the viewpoint of detergency. It may be either linear or branched. R ^27c CO is preferably a lauroyl group, a myristoyl group, or a coconut oil fatty acid acyl group mainly composed of a lauroyl group.

<Composition, optional components, etc.>
In the liquid detergent composition for hard surface of the present invention, the content of the component (a) is preferably 0.01% by mass or more, more preferably 0.8% from the viewpoint of making the hard surface hydrophilic and preventing soil adhesion. From the viewpoint of excellent foaming and detergency after storage at room temperature, it is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass. % Or less, more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less, and still more preferably 0.4% by mass or less.

  The hard surface liquid detergent composition of the present invention is preferably 0.1% by mass or more, more preferably 0, from the viewpoint that the content of the component (b) is excellent in foaming and detergency after storage at room temperature. .3% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of excellent bubbling after low-temperature storage and cleaning power, more preferably 0.7% by mass or more, still more preferably 0.9% by mass or more, From the viewpoint of foaming properties, it is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less, still more preferably 3% by mass or less, and still more preferably 2.5% by mass or less. It is.

Further, in the liquid detergent composition for hard surface of the present invention, the content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass, from the viewpoints of detergency and foaming power. % Or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and from the viewpoint of economy, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass. % Or less, more preferably 5% by mass or less.
When the component (c) includes a cationic surfactant, the content of the cationic surfactant in the liquid detergent composition for hard surface of the present invention is preferably 0.01 mass from the viewpoint of sterilizing power. % Or more, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, still more preferably 0.2% by weight or more, and from the viewpoint of blending stability, preferably 5% by weight or less, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1.5 mass% or less.
When the component (c) includes a surfactant selected from an anionic surfactant, an amphoteric surfactant and a nonionic surfactant, the anionic surfactant in the liquid detergent composition for hard surface of the present invention, The total content of surfactants selected from amphoteric surfactants and nonionic surfactants is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of foaming power and detergency. Further, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and from the viewpoint of economy, it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less. More preferably, it is 5 mass% or less.

When component (c) contains an amphoteric surfactant, the content of the amphoteric surfactant in the liquid detergent composition for hard surface of the present invention is preferably 0.05 from the viewpoint of foamability. From the viewpoint of economy (low cost), preferably 10% by mass or less, more preferably 8% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.
When the component (c) contains a nonionic surfactant, the content of the nonionic surfactant in the liquid detergent composition for hard surface of the present invention is preferably 0 from the viewpoint of foamability. .05 mass% or more, more preferably 0.1 mass% or more, still more preferably 0.15 mass% or more, and from the viewpoint of economy (low cost), preferably 10 mass% or less, more preferably 8 mass%. % Or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
Further, when the component (c) contains an anionic surfactant, the content of the anionic surfactant in the hard surface liquid detergent composition of the present invention is preferably 0 from the viewpoint of foamability. 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and from the viewpoint of economy (low cost) and blending stability, preferably 10% by mass or less, more Preferably it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.

  The liquid detergent composition for hard surface of the present invention preferably has a mass ratio of (b) / (a) of 0.1 or more, more preferably from the viewpoint of excellent foaming and detergency after low-temperature storage. 3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, still more preferably 1 or more, still more preferably 1.3 or more, still more preferably 1.5 or more, and even more preferably 2 From the viewpoint of foaming power, it is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, still more preferably 25 or less, and still more preferably 20 or less.

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

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

  The liquid detergent composition for hard surfaces of the present invention can contain a chelating agent. Preferred chelating agents include (i) tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, and alkali metal salts thereof, (ii) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediamine Triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and alkali metal salts or alkaline earth metal salts thereof, (iii) aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylene Phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, and alkali metal or alkaline earth metal salts thereof; (iv) acrylic acid and methacrylic acid; Nomer homopolymer or copolymer, acrylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid, and alkali metal salts thereof, (v) citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, One or more polyvalent carboxylic acids selected from malonic acid and maleic acid and alkali metal salts thereof; (vi) alkylglycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine- Examples thereof include N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid, and salts thereof. Among these, one or more chelating agents selected from (ii), (iii), and (v) are preferable, and ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, One or more chelating agents selected from citric acid, succinic acid and salts thereof are preferred. Further, one or more chelating agents selected from ethylenediaminetetraacetic acid, citric acid, and salts thereof are preferred.

  When the liquid detergent composition for hard surfaces of the present invention contains a chelating agent, the content thereof is preferably 0.01% by mass or more, more preferably 0 in the composition from the viewpoint of improving the detergency. .2% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass from the viewpoint of excellent storage stability at low temperatures. % Or less, more preferably 5% by mass or less. In addition, the mass of a chelating agent is an acid conversion value.

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

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

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

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

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

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

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

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

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

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

<1>
(A) including the structural unit (a1) represented by the following formula (1) and the structural unit (a2) represented by the following formula (2), the molar ratio of the structural unit (a1) and the structural unit (a2) A copolymer in which structural unit (a1) / structural unit (a2) is 30/70 or more and 99.9 / 0.1 or less (hereinafter referred to as component (a)), (b) an alkali metal halide, And an inorganic salt selected from halides of alkaline earth metals (hereinafter referred to as component (b)) and (c) a surfactant (hereinafter referred to as component (c)). object.

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

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

<2>
The weight average molecular weight of the component (a) is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, and preferably 200,000 or less, more preferably 15 The liquid detergent composition for hard surfaces according to <1>, which is 10,000 or less, more preferably 100,000 or less.

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

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

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

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

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

<8>
(B) The hard surface liquid cleaning composition according to any one of <1> to <7>, wherein the component is an alkali metal chloride.

<9>
<1> to <8>, wherein the component (b) is one or more compounds selected from the group consisting of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, and potassium iodide, preferably sodium chloride. The liquid detergent composition for hard surfaces in any one of.

<10>
<1> to <9>, wherein the component (c) is one or more surfactants selected from cationic surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants The liquid detergent composition for hard surfaces in any one.

<11>
(C) As a component, it contains a cationic surfactant and one or more surfactants selected from anionic surfactants, amphoteric surfactants, and nonionic surfactants. The liquid detergent composition for hard surfaces according to any one of <1> to <10>, comprising an agent, and one or more surfactants selected from amphoteric surfactants and nonionic surfactants.

<12>
The liquid detergent composition for hard surfaces according to <10> or <11>, wherein the cationic surfactant is a mono- or di-long alkyl quaternary ammonium salt.

<13>
<10> to <12, wherein the cationic surfactant is a cationic surfactant selected from a compound represented by the following general formula (c1-1) and a compound represented by the general formula (c1-2). > The liquid detergent composition for hard surfaces according to any one of the above.

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

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

<14>
The amphoteric surfactant is one or more amphoteric surfactants selected from amine oxide, sulfobetaine and carbobetaine, preferably one or more amphoteric surfactants selected from sulfobetaine and carbobetaine, The liquid detergent composition for hard surfaces according to any one of <10> to <13>, which is preferably carbobetaine.

<15>
Nonionic surfactant is (c3-1) monoalkyl glyceryl ether, (c3-2) polyoxyalkylene monoalkyl or alkenyl ether, (c3-3) alkyl polyglycoside (glycoside type nonionic surfactant), ( one or more nonions selected from the group consisting of c3-4) sorbitan nonionic surfactants, (c3-5) aliphatic alkanolamides, (c3-6) fatty acid monoglycerides, and (c3-7) sucrose fatty acid esters The liquid detergent composition for hard surfaces according to any one of <10> to <14>, which is a surfactant.

<16>
The anionic surfactant is (c4-1) a sulfosuccinic acid ester or a salt thereof having a hydrocarbon group having 5 to 18 carbon atoms, (c4-2) a hydrocarbon group having 8 to 21 carbon atoms, and sulfuric acid. Anionic surfactant having an ester group or a sulfonic acid group (excluding (c4-1)), (c4-3) an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a carboxy group A surfactant, and (c4-4) one or more anionic surfactants selected from the group consisting of an anionic surfactant having a hydrocarbon group having 8 to 21 carbon atoms and a phosphoric acid ester group. The liquid detergent composition for hard surfaces according to any one of <10> to <15>.

<17>
The content of the component (a) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2% or less, more preferably 1% or less, even more preferably 0.8% or less, even more preferably 0.5% or less, and still more preferably 0.4% or less, <1 The liquid detergent composition for hard surfaces according to any one of> to <16>.

<18>
The content of the component (b) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.7% by mass or more, and even more. Preferably 0.9% by weight or more, and preferably 10% by weight or less, more preferably 8% by weight or less, still more preferably 5% by weight or less, still more preferably 3% by weight or less, and even more preferably 2.5%. The liquid detergent composition for hard surfaces according to any one of <1> to <17>, which is not more than mass%.

<19>
The content of the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably Is 20% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and still more preferably 5% by mass or less, and the liquid for hard surface according to any one of <1> to <18> Cleaning composition.

<20>
(C) A cationic surfactant is included as a component, and the content of the cationic surfactant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass. Or more, more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and even more preferably. Is 1.5 mass% or less, The liquid detergent composition for hard surfaces in any one of <1>-<19>.

<21>
The component (c) includes a surfactant selected from anionic surfactants, amphoteric surfactants and nonionic surfactants, and is selected from anionic surfactants, amphoteric surfactants and nonionic surfactants. The total surfactant content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably Is 20% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and still more preferably 5% by mass or less, and the liquid for hard surface according to any one of <1> to <20> Cleaning composition.

<22>
The mass ratio of (b) / (a) is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 0.7 or more, and even more preferably 1 or more. More preferably 1.3 or more, still more preferably 1.5 or more, still more preferably 2 or more, and preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 25. Hereinafter, the liquid detergent composition for hard surfaces according to any one of <1> to <21>, more preferably 20 or less.

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

<24>
A chelating agent is contained, and the content of the chelating agent is preferably 0.01% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. And the liquid detergent composition for hard surfaces according to any one of <1> to <23>, preferably 10% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less.

<25>
The liquid detergent composition for hard surfaces according to any one of <1> to <24>, wherein the hard surface is a hydrophilic hard surface.

<26>
<1>-<25> The dirt adhesion prevention method of a hard surface which treats a hard surface with the liquid cleaning composition for hard surfaces in any one of.

<27>
Hard surface is glass, earthenware, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP; cotton, silk, wool, etc. The method for preventing adhesion of soil on a hard surface according to <26>, which is a solid hard surface such as a natural fiber; synthetic fibers such as polyester, nylon, and rayon.

<28>
<26> or <27> The method for preventing adhesion of dirt on a hard surface according to <26> or <27>, wherein the hard surface is one or more hard surfaces selected from glass, ceramics, porcelain, plastic, stainless steel and silicon wafer.

<29>
An article having a hard surface, and further treating an article having a hard surface selected from a toilet bowl, a bathtub, a kitchen sink, a window glass, a mirror, and a faucet, according to any one of <26> to <28> Adhesion prevention method.

<30>
The static contact angle with respect to water of the glass surface treated with the liquid detergent composition for hard surfaces is preferably 20 ° or less, more preferably 15 ° or less, still more preferably 10 ° or less, and even more preferably 8 ° or less. Yes, preferably 1 ° or more, <26> to <29> The method for preventing soil adhesion on a hard surface according to any one of <26> to <29>.

<35>
Use of the composition according to any one of <1> to <25> as a liquid detergent for hard surfaces.

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

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

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

Production Example 2 [Production of Copolymer A2]
(Process 1)
33.27 g of ethanol was placed in a four-necked flask with an internal volume of 1000 mL, and the mixture was heated to 78 ° C. and refluxed. A solution prepared by mixing 81.13 g of 2- (dimethylamino) ethyl methacrylate, 76.52 g of 2- (dimethylamino) ethyl diethylsulfate and 29.76 g of ethanol, and 2,2′-azobis (2 -Methylbutyronitrile) A solution in which 1.42 g and 3.31 g of ethanol were mixed was dropped separately over 2 hours for polymerization. After aging for 4 hours, the mixture was cooled to obtain a polymer solution.
(Process 2)
270.77 g of the obtained polymer solution, 4.34 g of sodium bicarbonate, and 285.67 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. 1,3-propane sultone 67.45g was dripped there over 1 hour, and reaction was performed. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing a copolymer.

In the copolymer A2, the structural units (a1) and (a2) are the same as the copolymer A1, and the molar ratio of the structural unit (a1) / the structural unit (a2) is 70/30.
Further, the copolymer A2 had a weight average molecular weight of 81,000.

In addition, the weight average molecular weights of the copolymers A1 to A2 were measured by gel permeation chromatography (pullulan) under the following conditions.
Column: Two TSKgel α-M (manufactured by Tosoh Corporation) were connected in series.
Column temperature: 40 ° C
Eluent: 0.15 mol Na ₂ SO ₄ /1% CH ₃ COOH / water Flow rate: 1.0 ml / min Detector: Differential refractometer

Examples 1-9 and Comparative Examples 1-3
Using the following blending components, the hard surface liquid detergent composition shown in Table 1 was prepared, and the following items were evaluated. The results are shown in Table 1. In addition, all the mass% of the mixing | blending component in Table 1 is a numerical value based on an effective part. In the table, the (b) / (a) mass ratio is shown with the component (b ′) [comparison compound of the component (b)] as the component (b) for convenience.

<Blending ingredients>
(A) Component and copolymer A1-A2 were used.
(B) Component-The compounds shown in Table 1 were used.
(C) Ingredients / Amphoteric surfactant: Lauramidopropylcarbobetaine (product name “Amphithol 20AB”, manufactured by Kao Corporation)
Cationic surfactant: alkyldimethylbenzylammonium chloride: alkyl group having 8 carbon atoms (product name “Sanisol 08”, manufactured by Kao Corporation)
Nonionic surfactant: alkyl polyglycoside: alkyl (carbon number 12 to 16) polyglucose (average sugar condensation degree 1 to 2) (product name “AG124”, manufactured by Kao Corporation)
Other components: EDTA: ethylenediaminetetraacetic acid, tetrasodium salt (in the table, mass% based on the apparent blending amount is shown)

<Bubbling>
The liquid cleaning composition for hard surfaces was tested using the liquid cleaning composition for hard surfaces after preparation and storage for 3 days at 20 ° C. or 3 days at −5 ° C., respectively. The liquid detergent composition for hard surfaces after storage at each temperature is filled into a trigger spray container (toilet magic phosphorus deodorizing and cleaning spray, manufactured by Kao Corporation), and a 200 mL graduated cylinder (in a wide foam mode of the container) (Inner diameter 40 mm) was sprayed 10 times. The mass of the 200 mL graduated cylinder after spraying was measured using a 4-digit balance, and the difference from the mass of the graduated cylinder before spraying was defined as the foam application amount (g) (a). The volume (mL) of foam in the graduated cylinder after spraying was visually read (b). The foam specific volume was calculated by the following formula. The results are shown in Table 1.
Foam specific volume (mL / g) = (b) / (a)
It shows that it is excellent in foaming, so that foam specific volume is large.

<Detergency>
The liquid cleaning composition for hard surfaces was tested using the liquid cleaning composition for hard surfaces after preparation and storage for 3 days at 20 ° C. or 3 days at −5 ° C., respectively. Using the hard surface liquid detergent composition after storage at each temperature, the detergency against model soil was evaluated. A method for producing model dirt and a method for evaluation are shown below.
* Model dirt production method and evaluation method As a dirt model, 0.4 g of rapeseed oil was uniformly applied to an iron plate (SUS304, 100 cm ² ) and baked at a temperature of 180 ° C. for 60 minutes to form an almost dry film. A plate was prepared and used to test the cleaning power. In the detergency test, 0.3 ml of the composition was dropped on the above-mentioned model stain plate fixed horizontally and left for 1 minute, and then lightly removed dirt was removed with absorbent cotton. The degree of detergency (detergency) was as follows: The evaluation was performed by the method.
Take an image with the same shooting conditions, such as brightness, for the uncoated stain iron plate, the unwashed iron plate after the stain application, and the washed iron plate. It was measured. The cleaning rate of the iron plate was calculated by comparing the state of the iron plate after the cleaning with the cleaning rate of 0% for the iron plate before the soil cleaning and the cleaning rate of 100% for the iron plate not coated with the soil. From the cleaning rate, the cleaning power was evaluated according to the following criteria. Note that the image processing software ImageJ1.47v was used for the gray scale measurement.
* Evaluation criteria of cleaning power 1: Cleaning rate of less than 20% 2: Cleaning rate of 20% or more and less than 40% 3: Cleaning rate of 40% or more and less than 60% 4: Cleaning rate of 60% or more and less than 80% 5: Cleaning rate 80% or more

<Anti-fouling property (anti-fouling property)>
The liquid detergent composition for hard surfaces was tested using the liquid detergent composition for hard surfaces after preparation and storage at −5 ° C. for 3 days.
A glass plate (Matsunami Glass Industry Co., Ltd., shape: 76 mm × 26 mm × 1 mm) is coated with 1 mL of the hard surface liquid detergent composition on one side and allowed to stand for 5 minutes, and then 25 ° C. tap water (flow rate 50 mL) / Second) was used for the following evaluation.
450 ml of water and 50 ml of a model oil solution (model oil: oleic acid, pigment: Sudan III (0.1 part by mass with respect to 100 parts by mass of oleic acid)) are mixed in a 500 ml beaker having a diameter of 10 cm, and the lower layer is water. The liquid which the upper layer isolate | separated into two layers of oil was prepared.
The glass plate was passed through the upper layer and immersed in the lower layer for 10 seconds so that the entire plate was immersed, and then pulled up.
Then, after drying the glass plate after soaking, take a picture of the glass plate, image it (using ImageJ) to measure the residual area of the oil on the glass plate, and based on the processing area of the glass plate, The residual ratio of was calculated. Residual rate (%) was calculated based on how much oil was coated on the surface (degree of coating), where the treated area of the glass was 100.

Claims (6)

(A) including the structural unit (a1) represented by the following formula (1) and the structural unit (a2) represented by the following formula (2), the molar ratio of the structural unit (a1) and the structural unit (a2) A copolymer in which structural unit (a1) / structural unit (a2) is 30/70 or more and 99.9 / 0.1 or less (hereinafter referred to as component (a)), (b) an alkali metal halide, And an inorganic salt selected from halides of alkaline earth metals (hereinafter referred to as component (b)) and (c) a surfactant (hereinafter referred to as component (c)). object.

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

[Where,
R ⁸ to R ^10: the same or different, the number of hydrogen atom or a C 1 or 2 alkyl groups ^X 3: O
R ^{11 is} an alkylene group having 1 to 4 carbon atoms, X ^{4 is} N ⁺ R ¹² R ¹³ R ¹⁴ X ⁵ or NR ¹⁵ R ¹⁶ , and R ^{12 to} R ¹⁶ are the same or different and have a hydrogen atom or carbon number 1 to 4 hydrocarbon groups, X ⁵ represents an anion. ]   The liquid detergent composition for hard surfaces according to claim 1, wherein the mass ratio of (b) / (a) is 0.1 or more.   The liquid detergent composition for hard surfaces according to claim 1 or 2, wherein the content of the component (a) is 0.01% by mass or more, and the content of the component (b) is 0.1% by mass or more.   The component (c) is one or more surfactants selected from a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant. The liquid detergent composition for hard surfaces according to 1.   The liquid cleaning composition for hard surfaces according to any one of claims 1 to 4, wherein the hard surface is a hydrophilic hard surface.   A method for preventing adhesion of dirt on a hard surface, wherein the hard surface is treated with the liquid detergent composition for hard surface according to any one of claims 1 to 5.