JP6368132B2 - Cleaning composition for hard surface - Google Patents

Description

  The present invention relates to a hard surface cleaning composition.

  The living environment equipment that surrounds us has various hard surfaces made of plastic, metal, etc., and these hard surfaces are exposed to an environment where various types of dirt adhere in daily life. In particular, in water-related facilities, dirt that tends to remain on a daily basis, such as sebum and scale stains in the bathroom, range hoods, gas stoves, and oil stains around the sink, has been generated. Is a heavy burden on consumers.

  Among them, it is generally known that hydrophobic dirt is difficult to remove and is likely to remain. One of the reasons that hydrophobic dirt is likely to adhere and remain and is difficult to remove is that many hard surfaces such as polyvinyl chloride, polypropylene, and stainless steel used in living environments have hydrophobic properties. . That is, since the hydrophobic hard surface has a high affinity with the hydrophobic dirt, the dirt is likely to remain and accumulate, and it is difficult to wash and remove.

  As a method to obtain a higher effect in removing hydrophobic dirt from the hydrophobic hard surface and preventing soil residue or dirt reattachment to the hydrophobic hard surface, a modifier is applied to the hard surface to make it hydrophobic. Although it is conceivable to modify the surface of the hard surface so that it has hydrophilic properties, the application work itself becomes a burden as an additional housework action, and unless the surface modification is permanent In this case, it is necessary to repeat the reforming process. Therefore, it is desirable that the effect of imparting hydrophilicity to the hydrophobic hard surface is high from the viewpoint of continuing the antifouling performance.

  Patent Document 1 describes an aqueous antifouling composition that adsorbs on a target surface and exhibits antifouling properties, and exemplifies many types of amphoteric polymer electrolytes.

  Patent Document 2 describes a cleaning or rinsing composition containing a surfactant and a specific polybetaine. Patent Document 2 describes a composition intended to be treated for the purpose of imparting persistent adhesion prevention and adhesion prevention properties to a hard surface with respect to pollutant substances. The use of agents, polymers and other optional ingredients is illustrated.

JP 2001-181601 A JP 2010-1000086 A

However, from the viewpoint of the antifouling effect of the hard surface, especially the hydrophobic hard surface, a further high antifouling effect at a level that is satisfied by consumers has been expected. Patent Document 1 describes that even in a cleaning process involving rinsing with water, an active ingredient in the composition system is not washed away by rinsing and is adsorbed on the target surface to exhibit antifouling properties. Even when used together with a cleaning agent, a higher level of hydrophilization performance is desired from the viewpoint of imparting antifouling properties by leaving many active ingredients on the target surface.
In addition, Patent Document 2 describes that, for example, a long-lasting adhesion preventing property is maintained over many rinsing cycles such as a toilet. However, when used together with a cleaning agent, the antifouling property is imparted. From this viewpoint, a higher level of hydrophilization performance is desired.

  The subject of this invention is providing the cleaning composition for hard surfaces which provides the outstanding antifouling property by using in the washing | cleaning operation | work of a hard surface.

The present invention
(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 1 to 18 carbon atoms other than the monomer unit (a-1). A polymer compound containing an alkyl group-containing monomer unit (a-2) in an amount of 5 mol% to 50 mol% in all monomer units [hereinafter referred to as component (a)] is 0.01 mass% to 10 mass%. Less than,
(B) at least 0.1% by mass of at least one compound selected from the compound represented by the following general formula (1) and the compound represented by the general formula (2) [hereinafter referred to as component (b)], 30% by mass or less,
(C) 0.5% by mass or more and 30% by mass or less of surfactant (hereinafter referred to as component (c)),
The present invention relates to a hard surface cleaning composition to be contained.

[Where,
m is 1 or more and 3 or less, and shows that a benzene ring or a cyclohexane ring has m substituents-[(R) _n -X].
When m is 2 or more, m pieces of-[(R) _n -X] may be the same or different.
R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number of 0 or 1.
X represents an amino group, a formyl group, a carbamoyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. And a group or atom selected from a mono- or dialkylamino group, an alkanoyl group having 2 to 6 carbon atoms, an alkylamide group having an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom.
X is a mono- or dialkylamino group having at least one amino group or an alkyl group having 1 to 6 carbon atoms. ]

  The present invention also relates to a method for improving the hydrophilicity of the hydrophobic hard surface by applying the hard surface cleaning composition of the present invention to a hydrophobic hard surface.

  The present invention also provides a method for removing dirt from the hydrophobic hard surface by applying the detergent composition for hard surface of the present invention to a hydrophobic hard surface to which dirt has adhered, and rinsing with water. The present invention relates to a method for treating a hydrophobic hard surface, which both imparts hydrophilicity to the hydrophobic hard surface.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for hard surfaces which provides the outstanding antifouling property to hard surfaces, such as a bathroom, a kitchen, a toilet, especially a hydrophobic hard surface is provided. Furthermore, according to the present invention, there is provided a hard surface cleaning composition that achieves improvement in finish by leaving a water film on a hydrophobic hard surface.

<(A) component>
Component (a) is a monomer unit (a-1) having a sulfobetaine structure of 50 mol% or more and 95 mol% or less of all monomer units, and 1 or more carbon atoms other than the monomer unit (a-1), It is a high molecular compound which contains 5 mol% or more and 50 mol% or less of monomer units (a-2) having 18 or less alkyl groups in all monomer units. The component (a) is presumed to impart high antifouling properties by forming an adsorption layer on the hydrophobic hard surface even after rinsing after being applied to the hydrophobic hard surface.

  The monomer unit (a-1) having a sulfobetaine structure contains a cationic group and a sulfonic acid anion group in one monomer unit. The monomer unit (a-1) constituting the component (a) is preferably a monomer unit obtained from a monomer represented by the following general formula (3) from the viewpoint of imparting antifouling properties.

[Wherein R ³¹ is an alkylene group having 1 to 5 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there. Y is a group selected from -COO-, -CONH-, and -OCO-. R ³⁵ and R ³⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ³⁷ is an alkylene having 1 to 10 carbon atoms. Or a hydroxyalkylene group having 1 to 10 carbon atoms. ]

In the general formula (3), R ³¹ is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and further preferably an alkylene group having 1 or 2 carbon atoms, Even more preferred is an alkylene group having 2 carbon atoms.

In General Formula (3), R ³² is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and a methyl group being more preferable from the viewpoint of ease of production of the component (a). Further preferred.

In the general formula (3), R ³³ and R ³⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms from the viewpoint of ease of production of the component (a). A methyl group is more preferable, and a hydrogen atom is still more preferable.

In general formula (3), R ³⁵ and R ³⁶ are each independently preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, from the viewpoint of imparting antifouling properties. A methyl group is more preferable.

In the general formula (3), R ^37, from the viewpoint of anti-smudge, number 1 or more carbon atoms, 5 or less alkylene group or having 1 or more carbon atoms, 5 or less hydroxyalkylene group are preferred, the number 2 or more carbon atoms, 4 or less Are more preferable, a C3 alkylene group or a C3 hydroxyalkylene group is more preferable, and a C3 alkylene group is still more preferable.

  In the general formula (3), Y is preferably —COO— or —OCO—, more preferably —COO— from the viewpoint of imparting antifouling properties.

  The alkyl group contained in the monomer unit (a-2) constituting the component (a) is preferably an alkyl group having 2 or more carbon atoms, more preferably an alkyl group having 3 or more carbon atoms, and an alkyl group having 5 or less carbon atoms. Is preferable, an alkyl group having 4 or less carbon atoms is more preferable, and an alkyl group having 4 carbon atoms is more preferable.

  The monomer unit (a-2) constituting the component (a) is preferably a monomer unit obtained from a monomer represented by the following general formula (4) from the viewpoint of imparting antifouling properties.

[Wherein, R ⁴¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or — (C ₂ H ₄ O) _n —H. n is a number of 1 or more and 30 or less. R ⁴² , R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z is —COO—, —CONH—, —OCO—, or a divalent aromatic hydrocarbon group. However, when R ⁴¹ is a hydrogen atom or — (C ₂ H ₄ O) _n —H, at least one of R ⁴² , R ⁴³ and R ⁴⁴ is an alkyl group having 1 to 3 carbon atoms. ]

In the general formula (4), R ⁴¹ is preferably an alkyl group having 2 or more carbon atoms, more preferably an alkyl group having 3 or more carbon atoms, from the viewpoint of adsorption of the component (a) on the hard surface, An alkyl group having 5 or less is preferable, an alkyl group having 4 or less carbon atoms is more preferable, and an alkyl group having 4 carbon atoms is more preferable.

In the general formula (4), R ^42, from the viewpoint of production easiness of the component (a), preferably a hydrogen atom or an alkyl group having a carbon number of 1 or 2, more preferably an alkyl group having 1 or 2 carbon atoms A methyl group is more preferred.

In the general formula (4), R ⁴³ and R ⁴⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms from the viewpoint of ease of production of the component (a). A methyl group is more preferable, and a hydrogen atom is still more preferable.

  In the general formula (4), Z is preferably —COO— or —OCO—, more preferably —COO— from the viewpoint of imparting antifouling properties. The divalent aromatic hydrocarbon group for Z preferably has 3 to 20 carbon atoms. Specific examples include a phenylene group.

The abundance ratio of each monomer unit in the constituent monomer units of the component (a) can be determined from peaks obtained by ¹ H-NMR and ¹³ C-NMR measurements. Moreover, it is also possible to calculate from the charging ratio of the monomer constituting the component (a), that is, the molar ratio or the mass ratio. Priority is given to the method obtained from the peaks obtained by ¹ H-NMR and ¹³ C-NMR measurements.

  (A) A component contains 50 mol% or more and 95 mol% or less of monomer units (a-1) in all the monomer units in a molecule | numerator. From the viewpoint of imparting antifouling properties to the hydrophobic hard surface, the component (a) is the monomer unit (a-1) in the total monomer units, preferably 60 mol% or more, more preferably 70 mol% or more. The content is preferably 80 mol% or more, more preferably 85 mol% or more, and preferably 94 mol% or less, more preferably 92 mol% or less, still more preferably 90 mol% or less.

  (A) A component contains 5 mol% or more and 50 mol% or less of monomer units (a-2) in all the monomer units in a molecule | numerator. From the viewpoint of the adsorption of the component (a) to the hydrophobic hard surface, the component (a) is the monomer unit (a-2) in the total monomer units, preferably 6 mol% or more, more preferably 8 mol% or more, more preferably 10 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and even more preferably 15 mol% or less. .

  The total of the monomer unit (a-1) and the monomer unit (a-2) is preferably 60 mol% or more, more preferably 70 mol% or more, from the viewpoint of imparting antifouling properties, in all monomer units of the component (a). 80 mol% or more is more preferable, 90 mol% or more is further more preferable, 95 mol% or more is more preferable, 97 mol% or more is further more preferable, and 99 mol% or more is still more preferable. Moreover, it is preferable that it is 100 mol% or less, and 100 mol% may be sufficient.

  The component (a) contains 0 mol% or more and 45 mol% or less of one or more types of monomer units (a-3) different from the monomer unit (a-1) and the monomer unit (a-2) in the molecule. I can do it. From the viewpoint of imparting antifouling properties, the monomer unit (a-3) contained in the component (a) is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less in all monomer units. Preferably, 5 mol% or less is more preferable, 3 mol% or less is further more preferable, and 1 mol% or less is still more preferable. Examples of the monomer unit (a-3) include those obtained from a monomer having a cationic group or a monomer having an anionic group.

  The molar ratio of the monomer unit (a-1) to the monomer unit (a-2) in the component (a) is (a-1) / from the viewpoint of imparting antifouling properties and adsorption of the component (a) on the hard surface. In (a-2), 50/50 or more is preferable, 60/40 or more is more preferable, 70/30 or more is more preferable, 80/20 or more is more preferable, 85/15 or more is more preferable, and 95/5 or less is preferable, 93/7 or less is more preferable, and 90/10 or less is still more preferable.

  The weight average molecular weight of the component (a) is preferably 1,000 or more and 5,000,000 or less. (A) Since the adsorption residual property of component increases, the weight average molecular weight of component (a) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and further 10,000. More preferably, 50,000 or more, and more preferably 100,000 or more. Moreover, since the hydrophilic property of a hard surface can be improved, 3,000,000 or less is preferable, 1,500,000 or less is more preferable, 1,000,000 or less is more preferable, and 500,000 or less is more preferable. Further, it is preferably 400,000 or less, more preferably 300,000 or less, further 200,000 or less, and further preferably 150,000 or less.

  Here, the weight average molecular weight of the component (a) can be measured by a conventional method adapted to the type of polymer, and specifically, can be measured by the following molecular weight measurement method. The polymer compounds of Examples described later were also measured for weight average molecular weight by this method.

<Method for measuring molecular weight of component (a)>
The molecular weight is measured by SLS (Static Light Scattering Method). The weight average molecular weight (Mw) is calculated by measuring static light scattering under the following conditions using a light scattering photometer (DLS-7000, manufactured by Otsuka Electronics Co., Ltd.) to produce Zimm-plot. Moreover, the refractive index increment required for calculation of molecular weight is measured using a differential refractometer (DRM3000, manufactured by Otsuka Electronics Co., Ltd.).
Wavelength: 632.8 nm (helium-neon laser)
Scattering angle: measured every 10 ° from 30 ° to 150 °.
Average temperature: 25 ° C
Solvent: trifluoroethanol

  The component (a) may be a block polymer compound or a random polymer compound, but is preferably a block polymer compound. That is, a polymer compound having a structure in which constituent monomer units such as the monomer unit (a-1) and the monomer unit (a-2) are bonded in a block form is preferable.

For example, when the monomer unit constituting each block is a monomer unit (a-1) and a monomer unit (a-2), the block polymer compound represents the monomer unit (a-1) with X, and the monomer unit When (a-2) is represented by Y, X and Y are arranged as shown in (1) to (5) below. In the following (1) to (5), p, p ′, q, q ′, and r are each an integer of 2 or more, and “/” indicates the order of bonding of (X) p and (Y) q. It is a symbol that means not.
(1)-(X) p- (Y) q-
(2)-(Y) q- (X) p-
(3)-(X) p- (Y) q- (X) p'-
(4)-(Y) q- (X) p- (Y) q'-
(5)-[(X) p-/-(Y) q] r-

In addition, when the block type high molecular compound of (a) component has a monomer unit (a-3), when the monomer unit (a-3) is represented by Z, Z is, for example, the above (1) to (5) It may be bonded to any position.
When the component (a) is a block copolymer, it may be any type of block copolymer of the above (1) to (5).

<(B) component>
The component (b) is one or more compounds selected from the compound represented by the following general formula (1) and the compound represented by the general formula (2).

[Where,
m is 1 or more and 3 or less, and shows that a benzene ring or a cyclohexane ring has m substituents-[(R) _n -X].
When m is 2 or more, m pieces of-[(R) _n -X] may be the same or different.
R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number of 0 or 1.
X represents an amino group, a formyl group, a carbamoyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. And a group or atom selected from a mono- or dialkylamino group, an alkanoyl group having 2 to 6 carbon atoms, an alkylamide group having an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom.
X is a mono- or dialkylamino group having at least one amino group or an alkyl group having 1 to 6 carbon atoms. ]

  In this invention, the composition which provides high antifouling property to a hydrophobic hard surface can be obtained by selecting specific (b) component and making it contain a specific amount with (a) component.

In general formula (1) or (2), from the viewpoint of imparting antifouling properties, R is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, and carbon. The alkylene group of Formula 1 is more preferable.
In general formula (1) or general formula (2), n is preferably 0.

Examples of the alkoxy group having 1 to 6 carbon atoms for X include a group represented by -OR (R is an alkyl group having 1 to 6 carbon atoms).
Examples of the alkyl ester group having an alkyl group having 1 to 6 carbon atoms for X include a group represented by —COOR (R is an alkyl group having 1 to 6 carbon atoms).
The mono- or dialkylamino group having an alkyl group having 1 to 6 carbon atoms in X includes —N (R) ₂ (R is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one Is an alkyl group having 1 to 6 carbon atoms.).
Examples of the alkanoyl group having 2 or more and 6 or less carbon atoms of X include a group represented by —COR (where R is an alkyl group having 1 to 5 carbon atoms).
The alkylamide group having an alkyl group having 1 or more and 6 or less carbon atoms of X includes —CON (R) ₂ (R is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, at least one of which is carbon A group represented by formula (1) to (6).

  In general formula (1) or (2), X is an alkyl ester having an amino group, an alkoxy group having 1 to 2 carbon atoms, and an alkyl group having 1 to 2 carbon atoms from the viewpoint of imparting antifouling properties. A mono- or dialkylamino group having a group or an alkyl group having 1 to 2 carbon atoms is preferred, and an amino group is more preferred.

  X is a mono- or dialkylamino group having at least one amino group or an alkyl group having 1 to 6 carbon atoms.

  As the component (b), aniline or p-anisidine is preferable and p-anisidine is more preferable from the viewpoint of imparting antifouling properties.

  The composition preferably has a high pH, which is presumed to be because the component (b) functions effectively at a high pH. In blending the composition, the pH may be adjusted after adding the above-mentioned salt.

<(C) component>
The component (c) is a surfactant. Although it is presumed that the dissolved state of the component (a) has an influence on the expression of antifouling properties, the high antifouling performance expressed in the present invention is the (a) component, the (b) component and (C) It implement | achieves by using a component together. In addition, by using the component (c), a high cleaning effect can be exhibited when cleaning the hydrophobic hard surface.
Note that the component (a), the component (b), the component (d) and the component (f) described later do not correspond to the component (c).

  Examples of the component (c) include one or more surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

Preferred anionic surfactants from the viewpoint of imparting antifouling properties and improving detergency include one or more anionic surfactants selected from the following components (c1) and (c2).
(C1) component: an anionic surfactant having a chain hydrocarbon group having 8 to 18 carbon atoms and a carboxylic acid group or a salt thereof,
Component (c2): an anionic surfactant having a chain hydrocarbon group having 7 to 18 carbon atoms and one or more selected from sulfonic acid groups, sulfuric acid groups, phosphoric acid groups, and salts thereof

  The component (c1) is an anionic surfactant having a chain hydrocarbon group having 8 to 18 carbon atoms and a carboxylic acid group or a salt thereof. From the viewpoint of detergency, the chain hydrocarbon group preferably has 9 or more carbon atoms, more preferably 10 or more, and preferably 15 or less, more preferably 13 or less, and still more preferably 12 or less. As the salt, sodium salt, potassium salt, and alkanolamine salt are preferable. The component (c1) preferably has 1 or 2 and further 1 chain hydrocarbon group having 8 to 18 carbon atoms. The component (c1) preferably has one or two carboxylic acid groups or salts thereof, and further one. Furthermore, what has the salt of a carboxylic acid group is preferable. Examples of the chain hydrocarbon group include a hydrocarbon group selected from a linear hydrocarbon group and a branched chain hydrocarbon group. Furthermore, examples of the chain hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable.

  Preferred component (c1) is a higher fatty acid salt having a chain hydrocarbon group having 8 to 18 carbon atoms, a polyoxyethylene alkyl ether carboxylate having an alkyl group having 8 to 18 carbon atoms, an alkyl group Is a polyoxyethylene amide alkyl ether carboxylate having 8 to 18 carbon atoms. More preferable component (c1) is a higher fatty acid salt having a chain hydrocarbon group having 8 to 18 carbon atoms, that is, a higher fatty acid salt having 9 to 19 carbon atoms, and more preferably 9 carbon atoms. The above are 19 or less linear higher fatty acid salts. More preferable compounds include sodium decanoate, sodium laurate, and sodium myristate.

  The component (c2) is an anionic surfactant having a chain hydrocarbon group having 7 to 18 carbon atoms and one or more selected from a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, and salts thereof. is there. (C2) The chain hydrocarbon group of the component has 7 or more and 18 or less carbon atoms, preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and 16 or less from the viewpoint of detergency. Preferably, 15 or less is more preferable, and 14 or less is still more preferable. Examples of the chain hydrocarbon group include a hydrocarbon group selected from a linear hydrocarbon group and a branched chain hydrocarbon group. Furthermore, examples of the chain hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable. As the salt, sodium salt, potassium salt, and alkanolamine salt are preferable. The component (c2) preferably has 1 or 2 and further 1 chain hydrocarbon group having 7 to 18 carbon atoms. In addition, the component (c2) preferably has one or two, or even one salt of a group selected from a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, and salts thereof. Still further, those having one or two, and further one salt selected from a salt of a sulfonic acid group, a salt of a sulfuric acid group, and a salt of a phosphoric acid group are preferred.

  Further, examples of the component (c2) that is preferable in terms of improving detergency include alkyl having a chain hydrocarbon group of 7 or more and 18 or less alkyl group or alkenyl group having an alkenyl group or alkenylbenzene sulfonate, and having 7 or more carbon atoms. , Polyoxyalkylene alkyl or alkenyl ether sulfate ester salt having an alkyl group or alkenyl group of 18 or less, alkyl group or alkenyl sulfate salt having an alkyl group or alkenyl group of 18 or less carbon atom, 7 or more carbon atoms, 18 The following α-olefin sulfonates, lower alkyl ester salts having an alkyl group having 1 or 2 carbon atoms of α-sulfo fatty acids having 7 to 18 carbon atoms, and primary alkane sulfonates having 7 to 18 carbon atoms , Secondary alkane sulfonate having 7 to 18 carbon atoms, 7 to 18 carbon atoms Examples thereof include alkyl or alkenyl phosphate ester salts having an alkyl group or an alkenyl group. Among them, an alkyl or alkenylbenzene sulfonate having an alkyl group or an alkenyl group having 7 to 18 carbon atoms, and an alkyl group having 7 to 18 carbon atoms and an ethylene oxide average addition mole number of 1 or more, 6 An anionic surfactant selected from the following polyoxyethylene alkyl ether sulfates is preferred. These anionic surfactant salts are also preferably alkali metal salts, ethanolamine salts, or ammonium salts.

  When the component (c1) and the component (c2) are used in combination as the component (c), good foaming is obtained at the time of washing, while the rinsing property is good. Therefore, in this invention, it is preferable to contain (c1) component and (c2) component as (c) component. In this case, the mass ratio of the component (c1) / the component (c2) is preferably 0.05 or more, preferably 0.1 or more, more preferably 0.3 or more, and preferably 1 or less, 0.8 or less. Is preferable, and 0.7 or less is more preferable.

  Preferred nonionic surfactants from the viewpoint of improving detergency include polyoxyalkylene alkyl ethers having an alkyl group having 10 to 18 carbon atoms, polyoxyalkylene alkenyl ethers having an alkenyl group having 10 to 18 carbon atoms, Polyoxyalkylene sorbitan fatty acid ester having a fatty acid group of 10 to 18 carbon atoms, alkyl polyglycoside having an alkyl group of 8 to 18 carbon atoms, sucrose fatty acid having a fatty acid group of 8 to 18 carbon atoms Examples thereof include esters and alkyl polyglyceryl ethers having an alkyl group having 8 to 18 carbon atoms. Among these, from the viewpoint of detergency against oily soils, polyoxyethylene alkyl ethers having an alkyl group having 10 to 14 carbon atoms and an average added mole number of ethylene oxide of 5 or more and 20 or less are preferable. From the viewpoint of foaming, an alkyl polyglycoside having an alkyl group having 8 to 18 carbon atoms and having a sugar condensation degree of 1 to 3 is preferred.

  Preferred cationic surfactants from the viewpoint of improving sterilization performance and detergency include alkyltrimethylammonium salts having an alkyl group having 10 to 20 carbon atoms, and dialkyls having an alkyl group having 6 to 14 carbon atoms. Examples thereof include dimethylammonium salts, alkyldimethylbenzylammonium salts having an alkyl group having 6 to 18 carbon atoms, and benzethonium salts.

  Preferred amphoteric surfactants from the viewpoint of foam control and improvement in detergency include alkyldimethylamine oxide, fatty acid amidopropylamine oxide, alkyl-N, N-dimethylacetic acid betaine, fatty acid amidopropyl-N, N-dimethylacetic acid betaine, Examples include betaine such as alkyl-N, N-dimethylethanesulfobetaine, fatty acid amidopropyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, and alkylcarboxymethylhydroxyethylimidazolium betaine.

  Among them, from the viewpoint of detergency against foaming during washing and scum dirt such as soap residue, alkyldimethylamine oxide having an alkyl group of 10 to 16 carbon atoms, fatty acid amidopropyl-N, having 12 to 14 carbon atoms, N-dimethyl acetate betaine is preferred.

  (C) As a component, it is preferable to contain 1 or more types of surfactant chosen from an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant from the point which does not hinder the effect of imparting antifouling property. (C) As a component, it is more preferable to contain a nonionic surfactant.

<Composition of detergent composition for hard surface>
The content of the component (a) in the hard surface cleaning composition of the present invention is 0.01% by mass or more and 10% by mass or less. In view of the effect of imparting antifouling property, the content of the component (a) is 0.01% by mass or more in the composition, preferably 0.02% by mass or more, more preferably 0.03% by mass or more, and More preferably, it is at least 05% by mass. From the viewpoint of enhancing the hydrophilicity of the hard surface, it is 10% by mass or less, preferably 5% by mass or less, more preferably 2.5% by mass or less, and still more preferably 1% by mass or less.

Content of the (b) component in the cleaning composition for hard surfaces of this invention is 0.1 mass% or more and 30 mass% or less. From the viewpoint of imparting antifouling properties, 0.3% by mass or more is preferable in the composition, 0.5% by mass or more is more preferable, 1% by mass or more is further preferable, 2% by mass or more is more preferable, and 25 mass% or less is preferable, 20 mass% or less is more preferable, 18 mass% or less is further more preferable, and 15 mass% or less is still more preferable.

Content of (c) component in the cleaning composition for hard surfaces of this invention is 0.5 mass% or more and 30 mass% or less. The content of the component (c) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and more preferably 7% by mass or more in the composition from the viewpoint of improving detergency. It is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 17% by mass or less, and still more preferably 15% by mass or less. In addition, about the anionic surfactant of (c) component, let the mass as a sodium salt be the mass of (c) component in a composition.

  The detergent composition for hard surfaces of the present invention uses component (a), component (b) and component (c) in combination under predetermined conditions, so that component (a) is adsorbed on the hydrophobic hard surface. Therefore, it is estimated that high antifouling property is imparted.

  In the hard surface cleaning composition of the present invention, the mass ratio of the component (a) to the component (c) is 5 or more in terms of (c) / (a) from the viewpoint of providing both antifouling properties and cleaning properties. 500 or less. The mass ratio of (c) / (a) is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, still more preferably 30 or more, still more preferably 50 or more, and preferably 400 or less, 300 or less is more preferable, 200 or less is more preferable, and 150 or less is still more preferable.

  The hard surface cleaning composition of the present invention has a mass ratio of the component (b) to the component (c) of (c) / (b) from the standpoint of both imparting antifouling properties and cleaning properties. It is preferably 1 or more and 10 or less. From the viewpoint of imparting antifouling properties, the mass ratio of (c) / (b) is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.4 or more, and even more preferably 0.5 or more. It is preferably 7 or less, more preferably 5 or less, further preferably 4.5 or less, and still more preferably 4 or less.

According to this invention, the composition which can hydrophilize a hydrophobic hard surface and can provide high antifouling property by containing the compound of the (b) component which has a specific structure more than a specific density | concentration is provided. The expression principle of this function is not necessarily clear, but it is presumed that the adsorption state of the polymer compound (a) is controlled by controlling the dissolved state in the bulk.
The polymer compound (a) used in the present invention is presumed to be adsorbed on the hard surface by hydrophobic interaction, but its adsorption ability is remarkably due to the presence of the component (c) surfactant. Be inhibited. However, it is considered that the component (b) preferentially interacts with the component (c) and alleviates the inhibition of adsorption of the component (a) by the component (c). Therefore, by containing the specific compound of the component (b), the surfactant of the component (c), which is a component that exhibits a cleaning effect, can be obtained without inhibiting the adsorption of the polymer compound of the component (a). It can be dissolved in the bulk. It is presumed that this makes it possible to achieve both the function of removing dirt with the component (c) and the function of adsorbing and remaining the component (a) after washing.

  The hard surface cleaning composition of the present invention may contain the following components in addition to the component (a), the component (b), and the component (c).

<(D) component>
The detergent composition for hard surfaces of the present invention is a water-soluble organic solvent (however, other than the component (b) as the component (d) for the purpose of improving the solubility of the component (b). It is desirable to contain (D) About a component, water solubility means what melt | dissolves 5g or more in 100g of water of 20 degreeC. As component (d), one or more water-soluble substances selected from various alcohols, diols, triols, mono-, di- or tri-alkylene glycol monoethers, mono-, di- or tri-alkylene glycol diethers, etc. An organic solvent is mentioned. The alkyl group can be selected from alkyl groups having various carbon numbers. It is preferable that the alkyl group has 1 or more and 4 or less, further 3 or less, and further 2 or less. As the component (d), from the viewpoint of imparting antifouling properties, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol mono-methyl ether, diethylene glycol mono-methyl ether, ethylene glycol mono-butyl ether, and diethylene glycol mono-butyl ether are preferable. Ethanol, ethylene glycol mono-methyl ether, and diethylene glycol mono-methyl ether are more preferable, and ethanol and diethylene glycol mono-methyl ether are still more preferable.

  From the viewpoint of improving the solubility of the component (b), the content of the component (d) in the hard surface cleaning composition of the present invention is preferably 1% by mass or more, and more preferably 3% by mass or more. 5 mass% or more is further preferable, 7 mass% or more is further preferable, and 50 mass% or less is preferable, 30 mass% or less is more preferable, 20 mass% or less is further preferable, and 15 mass% or less is further more preferable.

<(E) component>
The detergent composition for hard surface of the present invention has an alkali metal halide and an alkaline earth metal as the component (e) for the purpose of making the liquid composition uniform and maintaining the liquid property even after long-term storage. It is preferable to contain an inorganic salt selected from these halides. As the component (e), 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 (e) is more preferably an alkali metal chloride, and even more preferably sodium chloride.

  The content of the component (e) in the hard surface cleaning composition of the present invention is 0.5% in the composition from the viewpoint of making the liquid property of the liquid composition uniform and maintaining the liquid property even after long-term storage. % Or more, more preferably 0.6% by weight or more, more preferably 0.7% by weight or more, still more preferably by weight% or more, and preferably 5% by weight or less, more preferably 3% by weight or less, 2 mass% or less is still more preferable.

<Component (f)>
The hard surface cleaning composition of the present invention can contain a chelating agent as component (f). Preferred chelating agents include (f1) tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid, and alkali metal salts thereof, (f2) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediamine Triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine hexaacetic acid, and alkali metal salts or alkaline earth metal salts thereof, (f3) aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylene From phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, and alkali metal salts or alkaline earth metal salts thereof, (f4) acrylic acid and methacrylic acid Monomers or copolymers of monomers, acrylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid, and alkali metal salts thereof, (f5) citric acid, succinic acid, malic acid, fumaric acid, tartaric acid One or more polycarboxylic acids selected from malonic acid and maleic acid and alkali metal salts thereof, (f6) alkylglycine-N, N-diacetic acid, aspartic acid-N, N-diacetic acid, serine -N, N-diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid, and salts thereof. Among these, one or more chelating agents selected from (f2), (f3), and (f5) 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.

  The content of the component (f) in the hard surface cleaning composition of the present invention is preferably 0.01% by mass or more, more preferably 0.2% by mass or more in the composition from the viewpoint of further improving the cleaning power. Preferably, 0.5% by mass or more is more preferable, and 10% by mass or less is preferable, 7% by mass or less is more preferable, and 5% by mass or less is more preferable from the viewpoint of excellent storage stability at low temperatures. In addition, about the chelating agent of (f) component, let the mass as a sodium salt be the mass of (f) component in a composition.

<(G) component>
The hard surface cleaning composition of the present invention preferably contains water as the component (g). More preferably, it is a liquid composition containing water. In order to ensure the uniformity of the liquid after long-term storage, the content of the component (g) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and 80% by mass in the composition. % Or more is even more preferable. And content of (g) component is 95 mass% or less in a composition, 90 mass% or less is more preferable, 85 mass% or less is still more preferable.

  Furthermore, the hard surface cleaning composition of the present invention contains antiseptics, hydrotropes, dyes, viscosity modifiers, antioxidants, fragrances and the like within a range that does not impair the antifouling property and cleaning performance. I can do it.

  The hard surface cleaning composition of the present invention preferably has a pH at 20 ° C. of 5 or more, more preferably 6 or more, and 6.5 or more from the viewpoint of imparting antifouling properties. Is more preferable, and it is still more preferable that it is 7 or more. Further, the pH at 20 ° C. is preferably 13.5 or less, more preferably 12 or less, still more preferably 11 or less, even more preferably 10 or less, and 9 or less. Is most preferred. As the pH adjuster, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids other than the components (c) and (f) can be used as the acid agent. Moreover, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate can be used as the alkaline agent.

  The hard surface cleaning composition of the present invention is intended for a hard surface, preferably a hydrophobic hard surface, and an antifouling effect is exhibited by modifying the hydrophobic surface to a hydrophilic surface. It is estimated that In addition, it is presumed that the effect of imparting antifouling property to hydrophobic dirt is also exhibited by leaving a water film on the hydrophobic hard surface. The water film here refers to a water layer that does not easily drain after contact with the hydrophobic hard surface, such as after a cleaning operation, and remains on the hydrophobic hard surface. The water film can be recognized as a water film that uniformly covers the hard surface. The anti-fouling property is imparted by leaving a water film on the hydrophobic hard surface, and the finish of hard surfaces such as glass and mirrors is improved.

  The hydrophobic hard surface that is the target of the hard surface cleaning composition of the present invention is preferably such that the static contact angle at 25 ° C. with respect to ion-exchanged water is 50 ° or more, more preferably 60 ° or more, What is 70 degrees or more is still more preferable, and what is 80 degrees or more is still more preferable. In the present invention, a hard surface that satisfies this contact angle can be a hydrophobic hard surface.

  Examples of the material that gives a hydrophobic hard surface include hydrophobic metals such as stainless steel, hydrophobic plastics such as polyvinyl chloride (PVC), ABS resin, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, and 6-nylon, and fibers. It may be a composite material such as reinforced plastic (FRP).

  In kitchens, bathrooms and toilets, the above-mentioned materials that give a hydrophobic hard surface are frequently used, and because it is in an environment where hydrophobic stains derived from food and the human body are likely to adhere, imparting antifouling properties to hydrophobic stains Is significant. The hard surface cleaning composition of the present invention can impart excellent antifouling properties to the hydrophobic hard surfaces of kitchens, bathrooms and toilets. Accordingly, the hard surface cleaning composition of the present invention is preferably used for kitchens, bathrooms, or toilets. Specifically, the composition of the present invention is applied to a hydrophobic hard surface around a kitchen (wall, floor, sink, etc.) and a hydrophobic hard surface of a product used in the kitchen (stove, microwave oven, oven, refrigerator, etc.). It can be applied to. Further, the composition of the present invention can be applied to a hydrophobic hard surface (wall, floor, bathtub, etc.) around the bathroom and a hydrophobic hard surface of a product (bathroom chair, basin, etc.) used in the bathroom. In addition, the composition of the present invention can be applied to hydrophobic hard surfaces (walls, floors, toilets, etc.) of toilets and hydrophobic hard surfaces of products (storage racks, trash cans, etc.) used in toilets. Among them, it is more preferably used as a hydrophobic hard surface cleaning composition for bathrooms.

  Moreover, it is preferable to use the detergent composition for hard surfaces of the present invention as a spray-type hard surface detergent article formed by filling a spray container. Such an article can also be used as a spray-type hard surface treatment agent article or a spray-type hard surface modifier article. Examples of the spray container include a spray container equipped with a trigger sprayer (referred to as a trigger spray container). Examples of the trigger type spray container include a container body containing a liquid detergent composition, and a trigger type liquid ejector attached to the mouth part of the container body, and further, the mouth part of the container body. Is mounted with a trigger sprayer for ejecting a liquid detergent composition, a vertical pipe and a horizontal pipe are formed in the trigger sprayer, and the vertical pipe and the horizontal pipe are formed in the vertical pipe. A spray container (referred to as spray container (I)) in which a valve for blocking communication with the road is provided. The spray container (I) is provided with a cylinder at a position below the horizontal pipe, and a spin element is mounted at the tip of the horizontal pipe, and a nozzle having a nozzle hole is fitted at the tip of the spin element. It is fixed. The spray container (I) pulls the trigger, discharges the air in the cylinder to the outside, and when the trigger is returned, the liquid detergent composition is sucked up through a vertical pipe immersed in the liquid detergent composition of the container body. By filling the cylinder with the liquid and pulling the trigger again, the liquid in the cylinder is pushed out and guided to the vertical pipe, and the liquid flow is spun through the horizontal pipe and the spin element, and finally from the nozzle. It is of the type that erupts. The method of applying the cleaning composition of the present invention to the hydrophobic hard surface can be selected according to the area (area) of the hydrophobic hard surface. For example, it can be carried out by spraying about 0.05 to 5 mL of the stock solution of the composition of the present invention as it is.

  The hard surface cleaning composition of the present invention can impart good hydrophilicity to a hydrophobic hard surface and is excellent in its sustaining effect. Furthermore, it has a cleaning effect on oil stains, protein stains, sebum stains and the like adhering to the hydrophobic hard surface. The hydrophilicity of the hard surface can be evaluated by measuring the contact angle of water on the surface, but the contact angle is significantly reduced by treating the hard surface with the hard surface cleaning composition of the present invention. This is confirmed, and it is suggested that this hydrophilization expresses a high antifouling property imparting effect.

  Moreover, as for the cleaning composition for hard surfaces of this invention, the static contact angle with respect to ion-exchange water of the PVC board (made by Engineering Test Service Co., Ltd.) after the process measured by the method of an Example becomes 70 degrees or less. Is preferably 60 ° or less, more preferably 40 ° or less, and even more preferably 30 ° or less. Furthermore, the difference between the static contact angle of the PVC plate before treatment with respect to the ion exchange water and the static contact angle of the PVC plate after treatment with respect to the ion exchange water is preferably 10 ° or more from the viewpoint of imparting antifouling properties, 30 ° or more is more preferable, 40 ° or more is further preferable, and 50 ° or more is still more preferable.

  In the cleaning composition for hard surface of the present invention, after applying to the hydrophobic hard surface, the coating film containing the component (a) is formed to cover the hard surface, thereby to the ion exchange water of the PVC plate. It is estimated that the static contact angle can be 60 ° or less.

<How to use>
In the hard surface cleaning composition of the present invention, the step of applying the composition to a hydrophobic hard surface and the surface on which the composition of the hydrophobic hard surface is applied are water, preferably 5 times the coating mass. It is preferable to use for the processing method of the hard surface which has a rinse process with the water of the above mass. Further, after the step of applying the detergent composition for hard surface of the present invention to the hydrophobic hard surface, a step of thinly spreading using a sponge or the like, and then a method of treating the hard surface having a step of rinsing with water More preferably it is used. By performing this method on a hydrophobic surface to which dirt is attached, both removal of dirt and imparting antifouling properties can be achieved.

  These steps can be carried out according to a known method. For application to a hydrophobic hard surface, the spray composition is filled with the detergent composition for hard surface of the present invention as described above. It is preferred to use a spray-type hard surface cleaner article. Further, the temperature of water used for rinsing after washing is preferably 5 ° C. or higher in order to leave the hydrophilic modification component composed of the components (a) and (b) on the hydrophobic hard surface, and 15 ° C. The above is more preferable, and 50 ° C. or lower is preferable, and 35 ° C. or lower is more preferable.

<Examples and Comparative Examples>
The cleaning composition for hard surfaces described in Tables 1-2 was prepared. The pH (20 ° C.) of each composition was adjusted with sodium hydroxide and hydrochloric acid. About these compositions, the following item was evaluated. Details are shown below.

<Contact angle>
After applying 1 mL of the hard surface cleaning composition to a PVC plate (Engineering Test Service Co., Ltd., shape: 25 mm × 140 mm × 1 mm) and allowing to stand for 5 minutes, tap water at 25 ° C. (flow rate 50 mL / second) Rinse for 20 seconds. The static contact angle with respect to the ion-exchanged water of the PVC plate subjected to the above-described treatment was measured in a measurement chamber whose temperature was adjusted to 25 ° C. and 40% RH. For the measurement, a fully automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used. A 20 μl drop of ion-exchanged water was deposited on the treated surface, and contacted 5 times at 1-second intervals after 3 seconds of deposition. The angle was measured and the average value was recorded as data. In addition, the static contact angle of the PVC board before a process was 85 degrees.

<Water film retention>
After applying 1 mL of the hard surface cleaning composition to a PVC plate (Engineering Test Service Co., Ltd., shape: 25 mm × 140 mm × 1 mm) and allowing to stand for 5 minutes, tap water at 25 ° C. (flow rate 50 mL / second) Rinse for 20 seconds. Thereafter, the PVC plate was erected in the vertical direction, and the water film retention on the surface of the PVC plate was evaluated according to the following criteria.
A: A water film is maintained on the PVC plate for 10 seconds or more.
Δ: The water film is maintained on the PVC plate for 3 seconds or more and less than 10 seconds. ×: The time that the water film is maintained on the PVC plate is less than 3 seconds.

<Anti-fouling property>
12 g of model sebum solution (model sebum / chloroform = 1, mass ratio) was added and dispersed in 10 L of 40 ° C. hot water, and the PVC plate ^* treated with each composition was immersed for 12 hours. The PVC plate after immersion was rinsed with tap water (50 mL / second) at 25 ° C. for 10 seconds on each side, and after drying, the mass was measured to determine the amount of residual sebum (x). In the composition of each composition, it remained on the surface of the PVC plate treated with the composition in which the component (a) and the component (b) were not blended (replace the component (a) and component (b) with ion-exchanged water). The amount of sebum (y) was measured in the same manner. From the residual sebum amount x and y, the antifouling property was calculated by the following formula.
Antifouling property (%) = [1- (x / y)] × 100
* PVC plate treated with each composition After applying 1 mL of the hard surface cleaning composition on both sides of a PVC plate (Engineering Test Service Co., Ltd., shape: 25 mm × 2140 mm × 1 mm) and allowing to stand for 5 minutes Rinsed with tap water (50 mL / sec) at 25 ° C. for 20 seconds.

The components in Tables 1 and 2 are as follows.
Polymer compound: a block type polymer compound obtained in the following synthesis example and having a monomer unit (a-1) / monomer unit (a-2) = 90/10 (molar ratio) and a weight average molecular weight of 130,000 Polyoxyethylene alkyl ether: 12 carbon atoms of alkyl group, average number of moles of ethylene oxide added 9

<Synthesis example>
Place eggplant flask with 30 g of n-butyl methacrylate, 0.823 g of ethyl 2-bromoisobutyrate, 2.58 g of 4,4-dinonyl-2,2-dipyridyl and 45 g of anisole, stopper with a three-way cock, and bubbling with nitrogen for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.209 g of copper (I) chloride, and 0.141 g of copper (II) chloride were placed in another eggplant flask, and after plugging with a three-way cock and replacing with nitrogen, the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After 6 hours, the polymerization solution was ice-cooled while being exposed to air to complete the polymerization. Subsequently, the polymerization solution was dropped while stirring a mixed solution of 200 mL of water and 600 mL of methanol to precipitate a polymer, and a polymer solid was obtained by filtration and drying. Next, add 30 g of 2- (dimethylamino) ethyl methacrylate, 2.83 g of the polymer solid obtained above, 0.146 g of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and 30 g of anisole to the eggplant flask. The monomer solution was prepared by stoppering with a three-way cock and performing nitrogen bubbling for 15 minutes. Next, a stirrer chip and 0.0629 g of copper (I) chloride were put into another eggplant flask, and the mixture was stoppered with a three-way cock and replaced with nitrogen, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After 7.5 hours, the polymerization solution was cooled with ice while being exposed to air to complete the polymerization. Next, after removing the copper complex by activated alumina column treatment, the polymer solution was dropped while stirring 1 L of hexane to precipitate the polymer, and a polymer solid was obtained by filtration and drying. In a recovery flask, 3 g of the polymer obtained and 12 g of 2,2,2-trifluoroethanol were added to dissolve the polymer. The flask was stoppered with a three-way cock, and 2.08 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After cooling for 5 hours, the polymer solution was added dropwise while stirring 500 mL of methanol to precipitate a polymer, and a polymer compound solid was obtained by filtration and drying.
In the polymer compound, the monomer unit is a monomer unit (a-1) obtained from N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium and n-methacrylate It was a monomer unit (a-2) obtained from -butyl, and the molar ratio thereof was monomer unit (a-1) / monomer unit (a-2) = 90/10. In the polymer compound, the arrangement of the monomer units was a block. The polymer compound had a weight average molecular weight of 130,000.

  From the results of Examples 1-1 to 1-3 and Comparative Example 1-1, it can be seen that the inclusion of the component (a), the component (b), and the component (c) is excellent in the antifouling property imparting effect.

  From the results of Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3, by containing (a) component, (b) component, (c) component and (d) component, antifouling It can be seen that the effect of imparting sex is excellent.

<Prescription example>
A formulation example as a bathroom cleaner is shown below. According to the following prescription, it is possible to achieve both excellent cleaning properties and antifouling properties in bathroom cleaning.
(A) Polymer compound 0.1% by mass
(B) 10% by mass of diethylene glycol monophenyl ether
(C) Polyoxyethylene alkyl ether 1.5% by mass
Sodium myristate 1% by mass
Sodium polyoxyethylene alkyl ether sulfate 1.5% by mass
Alkyl polyglycoside 1.5% by mass
Alkylamidopropylbetaine 2% by mass
Alkyldimethylbenzylammonium chloride 1% by mass
(D) 7.5% by mass of diethylene glycol monomethyl ether
(E) Sodium chloride 0.5% by mass
(F) Citric acid 0.5% by mass
Ethylenediaminetetraacetic acid sodium salt 2.5% by mass
Ion exchange water balance
Total 100% by mass

Claims (11)

(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 1 to 18 carbon atoms other than the monomer unit (a-1). A polymer compound containing an alkyl group-containing monomer unit (a-2) in an amount of 5 mol% to 50 mol% in all monomer units [hereinafter referred to as component (a)] is 0.01 mass% to 10 mass%. Less than,
(B) 0.1% by mass or more, 30% by mass or less of a compound represented by the following general formula (1) [hereinafter referred to as component (b)], and
(C) A detergent composition for a surface of a hydrophobic plastic containing 0.5% by mass or more and 30% by mass or less of a surfactant [hereinafter referred to as component (c)].

[Where,
m is a number of 1 or more and 3 or less, and indicates that the benzene ring has m substituents — [(R) _n —X].
When m is 2 or more, m pieces of-[(R) _n -X] may be the same or different.
R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and n is a number of 0 or 1.
X represents an amino group, a formyl group, a carbamoyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl ester group having an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. And a group or atom selected from a mono- or dialkylamino group, an alkanoyl group having 2 to 6 carbon atoms, an alkylamide group having an alkyl group having 1 to 6 carbon atoms, and a hydrogen atom.
X is a mono- or dialkylamino group having at least one amino group or an alkyl group having 1 to 6 carbon atoms. ] The cleaning composition for hydrophobic plastic surfaces according to claim 1, wherein the mass ratio of the component (a) to the component (c) is (c) / (a) and is 5 or more and 500 or less. The cleaning composition for a hydrophobic plastic surface according to claim 1 or 2, wherein the mass ratio of the component (b) to the component (c) is 0.1 to 10 in terms of (c) / (b). The detergent composition for hydrophobic plastic surfaces according to any one of claims 1 to 3, wherein the monomer unit (a-1) is a monomer unit obtained from a monomer represented by the following general formula (3).

[Wherein R ³¹ is an alkylene group having 1 to 5 carbon atoms, and R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there. Y is a group selected from -COO-, -CONH-, and -OCO-. R ³⁵ and R ³⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ³⁷ is an alkylene having 1 to 10 carbon atoms. Or a hydroxyalkylene group having 1 to 10 carbon atoms. ] The detergent composition for hydrophobic plastic surfaces according to any one of claims 1 to 4, wherein the monomer unit (a-2) is a monomer unit obtained from a monomer represented by the following general formula (4).

[Wherein, R ⁴¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or — (C ₂ H ₄ O) _n —H. n is a number of 1 or more and 30 or less. R ⁴² , R ⁴³ and R ⁴⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z is —COO—, —CONH—, —OCO—, or a divalent aromatic hydrocarbon group. However, when R ⁴¹ is a hydrogen atom or — (C ₂ H ₄ O) _n —H, at least one of R ⁴² , R ⁴³ and R ⁴⁴ is an alkyl group having 1 to 3 carbon atoms. ] Further, (d) a water-soluble organic solvent [however, it is other than the component (b). ] The cleaning composition for hydrophobic plastic surfaces in any one of Claims 1-5 containing 1 mass% or more and 50 mass% or less. The total of monomer unit (a-1) and monomer unit (a-2) is 60 mol% or more and 100 mol% or less in all monomer units of (a) component, Any one of Claims 1-6. The cleaning composition for hydrophobic plastic surfaces as described. The molar ratio of the monomer unit (a-1) to the monomer unit (a-2) in the component (a) is (a-1) / (a-2) and is 50/50 or more and 95/5 or less. The cleaning composition for hydrophobic plastic surfaces according to any one of claims 1 to 7. The detergent composition for hydrophobic plastic surfaces according to any one of claims 1 to 8, which is for bathroom, kitchen or toilet. Method for improving the hydrophilicity of hydrophobic plastic surfaces hydrophobic plastic surface cleaning composition according to any one of claims 1 to 9 is applied to a hydrophobic plastic surface. The any one hydrophobic plastic surface detergent composition according to claims 1-9, after application to a hydrophobic plastic surface which dirt, by rinsing with water, dirt from hydrophobic plastic surface performing both hydrophilic application to remove the hydrophobic plastic surface treatment method of the hydrophobic plastic surfaces.