JP6231364B2 - Hard surface treatment composition - Google Patents

Description

  The present invention relates to a hard surface treating agent composition, a method for improving the hydrophilicity of a hydrophobic hard surface, and a method for treating a hydrophobic hard surface.

  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 causes is that many hard surfaces such as polyvinyl chloride, polypropylene, and stainless steel used in the residential environment have hydrophobic properties. In other words, since the hydrophobic hard surface has a high affinity with hydrophobic dirt, the dirt is likely to remain and accumulate, and it is difficult to wash or remove the hydrophobic dirt once adhered. Yes.

  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. It is conceivable to modify the surface of the hydrophilic hard surface so as to have hydrophilic properties. However, the coating operation itself becomes a burden as an additional operation, and unless the surface modification is permanent, it is necessary to repeat the modification treatment. For this reason, it is desirable to maintain the effect in addition to the effect of imparting hydrophilicity to the hydrophobic hard surface.

  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.

  Patent Document 3 discloses that a copolymer having a specific structure that can contain a unit of a sulfobetaine monomer is used as a detergent composition, a fabric management composition, or a composition for skin and / or hair.

JP 2001-181601 A JP 2010-1000086 A JP 2006-505686 A

  However, from the viewpoint of the antifouling effect of the hydrophobic hard surface, a further high antifouling effect that is expected to satisfy consumers has been expected. Furthermore, the technique which can maintain antifouling property with respect to the hydrophobic hard surface which hot water touches like a bathtub is desired.

The present invention provides a hard surface treatment composition that can modify a hard surface, preferably a hydrophobic hard surface, to impart excellent antifouling properties and improve antifouling durability. The present invention is for use in a hard surface that removes hydrophobic dirt from a hydrophobic hard surface and imparts excellent antifouling property and antifouling durability to the hydrophobic hard surface by using it in a cleaning operation of a hydrophobic hard surface. A treating agent composition is included.
In the present invention, “antifouling property” means an effect of suppressing dirt from remaining on a hard surface. In the present invention, the term “antifouling durability” means an effect of maintaining the antifouling property, and preferably has an antifouling effect even in a high temperature environment, for example, when it is in contact with hot water for a long time. Means lasting.

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 block type polymer compound (hereinafter referred to as component (a)) containing an alkyl group-containing monomer unit (a-2) in a total monomer unit of 5 mol% or more and 50 mol% or less, 0.01 mass% or more 10% by mass or less,
(B) Surfactant [hereinafter referred to as (b) component] is 0.5 mass% or more and 30 mass% or less,
It is related with the processing agent composition for hard surfaces to contain.

  Moreover, this invention relates to the method of apply | coating the processing agent composition for hard surfaces of the said invention on the hydrophobic hard surface, and improving the hydrophilic property of this hydrophobic hard surface.

  In addition, the present invention provides a treatment for hard surfaces according to the present invention, which is applied to a hydrophobic hard surface to which dirt has adhered, and is then rinsed with water to remove dirt from the hydrophobic hard surface and The present invention relates to a method for treating a hydrophobic hard surface, which both imparts hydrophilicity to the hydrophobic hard surface.

  According to the present invention, there is provided a hard surface treatment composition capable of imparting excellent antifouling properties to hard surfaces such as bathrooms, kitchens and toilets, preferably hydrophobic hard surfaces, and improving antifouling durability. Is done. Further, according to the present invention, the hard surface, preferably a hydrophobic hard surface, exhibits high detergency when cleaning dirt generated on the hard surface, and provides excellent antifouling property and antifouling durability. A treating agent composition is provided.

<(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 block type polymer compound containing 5 mol% or more and 50 mol% or less of monomer units (a-2) having 18 or less alkyl groups in all monomer units.

  In the present invention, the block type polymer compound of component (a) is efficiently adsorbed on the hydrophobic hard surface by the hydrophobic block (a-2), and hydrophobic by the hydrophilic block (a-1). It is considered that the hard surface is hydrophilized and exhibits high antifouling performance. 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. Compared to the random polymer compound, it is considered that the block polymer compound is likely to adsorb the hydrophobic block near the hydrophobic hard surface. Moreover, it is thought that the hard surface is hydrophilized by the hydrophilic blocks assembled in the opposite direction to the adsorption site. Furthermore, it is thought that the antifouling durability can be expressed because the adsorption residual property is enhanced by the effect of the adsorbed hydrophobic block.

  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 (1) from the viewpoint of imparting antifouling properties.

[Wherein, R ¹¹ is an alkylene group having 1 to 5 carbon atoms, and R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there. X is a group selected from —COO—, —CONH—, and OCO—. R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ¹⁷ is an alkylene having 1 to 10 carbon atoms. Or a hydroxyalkylene group having 1 to 10 carbon atoms. ]

In the general formula (1), R ¹¹ is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms, An alkylene group having 2 carbon atoms is more preferable.

In the general formula (1), R ¹³ and R ¹⁴ 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 more preferable.

In general formula (1), R ¹⁵ and R ¹⁶ 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. Preferably, a methyl group is more preferable.

In the general formula (1), R ¹⁷ is preferably an alkylene group having 1 to 5 carbon atoms or a hydroxy alkylene group having 1 to 5 carbon atoms, and 2 to 4 carbon atoms in terms of imparting antifouling properties. An alkylene group having 2 or more and 4 or less carbon atoms is more preferable, an alkylene group having 3 carbon atoms or a hydroxyalkylene group having 3 carbon atoms is more preferable, and an alkylene group having 3 carbon atoms is more preferable.

  In the general formula (1), X 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 (2) from the viewpoint of imparting antifouling properties.

[Wherein, R ²¹ 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 ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is —COO—, —CONH—, —OCO—, or a divalent aromatic hydrocarbon group. However, when R ²¹ is a hydrogen atom or — (C ₂ H ₄ O) _n —H, at least one of R ²² , R ²³ , and R ²⁴ is an alkyl group having 1 to 3 carbon atoms. ]

In the general formula (2), R ²¹ 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 general formula (2), R ²² is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, from the viewpoint of ease of production of component (a). A methyl group is more preferable.

In the general formula (2), R ²³ and R ²⁴ 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 more preferable.

  In the general formula (2), Y is preferably —COO— or —OCO—, more preferably —COO— from the viewpoint of imparting antifouling properties. The divalent aromatic hydrocarbon group for Y 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, 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 imparting antifouling properties 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 The content is preferably 10 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, more preferably 20 mol% or less, 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 more preferable, 95 mol% or more is more preferable, 97 mol% or more is more preferable, and 99 mol% or more is 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 more preferably 10 mol% or less in all monomer units. Preferably, 5 mol% or less is more preferable, 3 mol% or less is more preferable, and 1 mol% or less is 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 more preferable.

  The weight average molecular weight of the component (a) is preferably 1,000 or more and 5,000,000 or less. The weight average molecular weight of the component (a) is preferably 2,000 or more, more preferably 3,000 or more, more preferably 5,000 or more, and 10,000 or more because the adsorption residual property of the component (a) increases. Is more preferable, 50,000 or more is more preferable, and 100,000 or more is more preferable. Further, since the hydrophilicity of the hard surface can be enhanced, the weight average molecular weight of the component (a) is preferably 3,000,000 or less, more preferably 1,500,000 or less, and more preferably 1,000,000 or less. Preferably, 500,000 or less is more preferable, 400,000 or less is more preferable, 300,000 or less is more preferable, 200,000 or less is more preferable, and 150,000 or less is more preferable.

  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

  Among the polymer compounds used in Comparative Examples described later, Comparative Polymer Compound 5 was measured for weight average molecular weight in the same manner as described above except that the solvent was ethanol.

Of the polymer compounds used in Comparative Examples described later, Comparative Polymer Compound 4 was measured by gel permeation chromatograph (GPC) under the following conditions.
<Method for Measuring Molecular Weight of Comparative Polymer Compound 4>
Column: Tosoh Corporation G4000PWXL + G2500PWXL
Eluent: 0.2M phosphate buffer / acetonitrile (9/1)
Flow rate: 1.0 mL / min
Detector: RI
Sample concentration: 5 mg / mL
Reference material: Polyethylene glycol

  The component (a) is a block type polymer compound. That is, it 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. The block type for the component (a) means having a block structure of the monomer unit (a-1) and a block structure of the monomer unit (a-2).

  More specifically, the block type polymer compound of component (a) has at least one block of monomer unit (a-1) in which two or more monomer units (a-1) are bonded, and two or more blocks. It has at least one block of the monomer unit (a-2) to which the monomer unit (a-2) is bonded.

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 (2), 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.
In the present invention, the component (a) may be any type of block copolymer of the above (1) to (5).

<(B) component>
The hard surface treating agent composition of the present invention contains a surfactant as the component (b). Although it is presumed that the dissolved state of the component (a) has an influence on the expression of the antifouling property of the present invention, the high antifouling performance expressed in the present invention includes the component (b) in the component (a). It is thought that it improves more by using together. Further, by using the component (b), a high cleaning effect can be exhibited when cleaning the hydrophobic hard surface.

  Examples of the component (b) 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 (b1) and (b2).
(B1) 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 (b2): 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 (b1) 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 even more preferably 12 or less. As the salt, sodium salt, potassium salt, and alkanolamine salt are preferable. The component (b1) preferably has one or two chain hydrocarbon groups having 8 or more and 18 or less carbon atoms, and further one. The component (b1) preferably has one or two carboxylic acid groups or salts thereof, and further one. (B1) As for a component, what has a salt of a carboxylic acid group is 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. The chain hydrocarbon group is preferably a straight chain, and more preferably a straight chain alkyl group. The chain hydrocarbon group is preferably primary and more preferably a primary alkyl group. The chain hydrocarbon group is preferably a linear primary alkyl group.

  Preferred component (b1) 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 (b1) 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, 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 (b2) 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. Examples of the chain hydrocarbon group include a hydrocarbon group selected from a linear hydrocarbon group and a branched chain hydrocarbon group. Preferred chain hydrocarbon groups include alkyl groups and alkenyl groups, with alkyl groups being more preferred. The chain hydrocarbon group is preferably a straight chain, and more preferably a straight chain alkyl group. The chain hydrocarbon group is preferably primary and more preferably a primary alkyl group. The chain hydrocarbon group is preferably a linear primary alkyl group. (B2) 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, 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 more preferable. As the salt, sodium salt, potassium salt, and alkanolamine salt are preferable. The component (b2) preferably has 1 or 2 and further 1 chain hydrocarbon group having 7 to 18 carbon atoms. In addition, the component (b2) preferably has one or two or more groups selected from sulfonic acid groups, sulfuric acid groups, phosphoric acid groups, 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.

  Preferred examples of the component (b2) in terms of improving detergency include alkyl having 7 to 18 carbon atoms or alkyl or alkenylbenzene sulfonate having an alkenyl group, alkyl having 7 to 18 carbon atoms, Polyoxyalkylene alkyl or alkenyl ether sulfate having an alkenyl group, alkyl group having 7 to 18 carbon atoms or alkyl or alkenyl sulfate having an alkenyl group, α-olefin sulfonic acid having 7 to 18 carbon atoms Salt, lower alkyl ester salt having an alkyl group having 1 or 2 carbon atoms of α-sulfo fatty acid having 7 to 18 carbon atoms, primary alkanesulfonate having 7 to 18 carbon atoms, 7 to 18 carbon atoms, 18 The following secondary alkane sulfonate, alkyl group having 7 to 18 carbon atoms, or alkene Examples thereof include alkyl or alkenyl phosphate esters having a nyl 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 to 6 An anionic surfactant selected from certain polyoxyethylene alkyl ether sulfates is preferred. These anionic surfactant salts are also preferably alkali metal salts, ethanolamine salts, or ammonium salts.

  When the component (b1) and the component (b2) are used in combination as the component (b), good foaming is obtained at the time of washing, while the rinsing property is good. Therefore, in this invention, it is preferable to contain (b1) component and (b2) component as (b) component. In this case, the mass ratio of the component (b1) / (b2) 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. The alkyl group possessed by the nonionic surfactant is preferably a linear alkyl group. Further, the alkyl group possessed by the nonionic surfactant is preferably a primary alkyl group. Further, the alkyl group possessed by the nonionic surfactant is preferably a linear primary alkyl group.

  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. The alkyl group possessed by the cationic surfactant is preferably a linear alkyl group. The alkyl group possessed by the cationic surfactant is preferably a primary alkyl group. The alkyl group possessed by the cationic surfactant is preferably a linear primary alkyl group.

  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.

  Of these, alkyldimethylamine oxide having 10 to 16 carbon atoms and fatty acid amidopropyl-N, N-dimethylacetic acid having 10 to 16 carbon atoms from the viewpoint of detergency against foaming during washing and scum stains such as soap residue. Betaine is preferred.

  As the component (b), it is preferable to contain one or more surfactants selected from anionic surfactants, nonionic surfactants and amphoteric surfactants from the standpoint of preventing the effect of imparting antifouling properties. Among these, it is preferable to contain an anionic surfactant. Moreover, it is preferable to contain 1 or more types of anionic surfactant chosen from (b1) component and (b2) component as (b) component, and to contain both (b1) component and (b2) component Is more preferable.

<Composition of hard surface treatment composition>
The content of the component (a) in the hard surface treating agent 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 05 mass% or more is more preferable. 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 more preferably 1% by mass or less.

  Content of (b) component in the processing agent composition for hard surfaces of this invention is 0.5 mass% or more and 30 mass% or less. The content of the component (b) is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably 7% by mass or more in the composition from the viewpoint of improving detergency. And 25 mass% or less is preferable, 20 mass% or less is more preferable, 15 mass% or less is more preferable, 12 mass% or less is more preferable, 10 mass% or less is more preferable, 9 mass% or less is more preferable. In addition, in this invention, about the anionic surfactant of (b) component, let the mass as a sodium salt be the mass of (b) component in a composition.

  In the hard surface treating agent composition of the present invention, from the viewpoint of imparting antifouling properties, the mass ratio of the component (a) to the component (b) is (b) / (a) and is 5 or more and 500 or less. It is preferable. From the viewpoint of imparting antifouling properties, the mass ratio of (b) / (a) is preferably 7 or more, more preferably 10 or more, more preferably 15 or more, more preferably 30 or more, more preferably 50 or more, and 400 or less, 300 or less is more preferable, 200 or less is more preferable, and 100 or less is more preferable.

  The hard surface treating agent composition of the present invention can contain the following components in addition to the component (a) and the component (b).

<(C) component>
The hard surface treating agent composition of the present invention preferably contains an organic solvent as the component (c).

  The component (c) is preferably an organic solvent having an inorganic / organic ratio of 0.6 or more and 2.2 or less in the organic conceptual diagram.

  The organic solvent is usually a component that is often blended for the purpose of keeping the liquid property of the liquid composition uniform and maintaining the liquid property even after long-term storage and improving the washability. (C) component which is an organic solvent of this is selected, The composition which provides high antifouling property to a hydrophobic hard surface can be obtained by making it contain a specific quantity with (a) component.

  The “organic conceptual diagram” used to identify the organic solvent in the present invention is a method for grasping the outline of the properties of the organic compound, and is mainly based on organicity (covalent bonding) based on the number of carbon atoms and substitution. It is divided into inorganicity (ionic bondability) based on the nature and tendency of the group, and the organic compound is positioned one by one on the Cartesian coordinates named the organic axis and the inorganic axis, and the outline of the nature is understood. . The inorganic / organic values of organic solvents in the organic conceptual diagram are listed in “New edition organic conceptual diagram: Basics and applications” (Yoshio Koda, Shiro Sato, Yoshio Honma, Sankyo Publishing, 2008, page 15, Table 1.1). It can be calculated from what is described.

  From the viewpoint of imparting antifouling properties, the inorganic / organic ratio in the organic conceptual diagram of the component (c) is preferably 0.7 or more, more preferably 1.0 or more, and more preferably 1.2 or more. .4 or more is more preferable, 1.5 or more is more preferable, 2.0 or less is preferable, 1.9 or less is more preferable, 1.8 or less is more preferable, and 1.7 or less is more preferable.

  Examples of the organic solvent used as the component (c) include various mono-, di- or tri-alkylene glycol monoethers and mono-, di- or tri-alkylene glycol diethers. Specifically, mono-, di- or tri-ethylene glycol monoether, and mono-, di- or tri-ethylene glycol diether, and mono-, di- or tri-propylene glycol monoether, and mono-, Di- or tri-propylene glycol diether is suitable. Such glycol monoether and glycol diether preferably have an alkyl group, and the alkyl group can be selected from alkyl groups having various carbon numbers. For example, methyl, ethyl, propyl, butyl, hexyl and the like. These glycol ethers and glycol diethers preferably have a total carbon number of 4 or more, more preferably 6 or more, more preferably 8 or more, and preferably 14 or less, more preferably 12 or less, more preferably 10 or less. It is.

  As the component (c), from the viewpoint of imparting antifouling properties, ethylene glycol mono-butyl ether (1.5), diethylene glycol mono-butyl ether (1.6), ethylene glycol mono-isobutyl ether (1.6), diethylene glycol mono -Isobutyl ether (1.7), ethylene glycol mono-hexyl ether (1.1), diethylene glycol mono-hexyl ether (1.2), propylene glycol mono-butyl ether (0.9), dipropylene glycol mono-butyl ether ( 0.7), dipropylene glycol mono-methyl ether (1.0), tripropylene glycol mono-methyl ether (0.8), ethylene glycol mono-isopropyl ether (2.0), 2-propanol (2.0 ), Ethile One or more organic solvents selected from glycol mono-2-ethylhexyl ether (0.8), propylene glycol mono-n-propyl ether (1.0) and dipropylene glycol mono-n-propyl ether (0.8) Is mentioned. Among these, one or more organic solvents selected from ethylene glycol mono-butyl ether (1.5) and diethylene glycol mono-butyl ether (1.6) are preferable, and diethylene glycol mono-butyl ether (1.6) is more preferable. Here, the numbers in () are inorganic / organic values.

  The content of the component (c) in the hard surface treating agent composition of the present invention is preferably 1% by mass or more. From the viewpoint of imparting antifouling properties, the content of component (c) is 1% by mass or more in the composition, preferably 1.5% by mass or more, more preferably 3% by mass or more, and more preferably 4% by mass or more. 5 mass% or more is more preferable, 6 mass% or more is more preferable, 7 mass% or more is more preferable, and 7.5 mass% or more is more preferable. In addition, the content of the component (c) is preferably 30% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 9% by mass or less in the composition.

  The hard surface treating agent composition of the present invention comprises (a) component, (b) component, and (c) component, preferably in combination with predetermined conditions, so that (a) component is a hydrophobic hard surface. It is presumed that it imparts higher antifouling properties.

  When the hard surface treating agent composition of the present invention contains the component (c), the mass ratio of the component (b) to the component (c) is (b) / (c) from the viewpoint of imparting antifouling properties. 0.1 or more and 10 or less. From the viewpoint of imparting antifouling properties, the mass ratio of (b) / (c) is preferably 0.2 or more, more preferably 0.5 or more, more preferably 0.8 or more, and preferably 8 or less, 5 or less is more preferable, 3 or less is more preferable, 2 or less is more preferable, and 1.5 or less is more preferable.

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

  The content of the component (d) in the hard surface treating agent composition of the present invention is 1% by mass or more in the composition from the viewpoint of making the liquid property uniform and maintaining the liquid property even after long-term storage. 1.2 mass% or more is more preferable, 1.5 mass% or more is more preferable, 2 mass% or more is more preferable, 5 mass% or less is preferable, 4 mass% or less is more preferable, 3 mass% or more % Or less is more preferable, and 2.5 mass% or less is more preferable.

<(E) component>
The hard surface treating agent composition of the present invention can contain a chelating agent as the component (e). Preferable chelating agents include (e1) tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and alkali metal salts thereof, (e2) ethylenediaminetetraacetic acid, hydroxyiminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, hydroxyethylenediamine Triacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and alkali metal salts or alkaline earth metal salts thereof, (e3) 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, (e4) acrylic acid and methacrylic acid Monomers or copolymers of monomers, acrylic acid-maleic acid copolymer, poly α-hydroxyacrylic acid, and alkali metal salts thereof, (e5) citric acid, succinic acid, malic acid, fumaric acid, tartaric acid , One or more selected from polycarboxylic acids selected from malonic acid and maleic acid and alkali metal salts thereof, (e6) 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 (e2), (e3), and (e5) are preferable, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, citric acid One or more chelating agents selected from succinic acid and salts thereof are more preferable. One or more chelating agents selected from ethylenediaminetetraacetic acid, citric acid, and salts thereof are more preferable.

  The content of the component (e) in the hard surface treating agent 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 from the viewpoint of excellent storage stability at low temperatures, 10% by mass or less is preferable, 7% by mass or less is more preferable, and 5% by mass or less is more preferable. In addition, about the chelating agent of (e) component, let the mass as a sodium salt be the mass of (e) component in a composition.

<Component (f)>
The hard surface treating agent composition of the present invention preferably contains water as the component (f). 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 (f) in the composition is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass. % Or more is more preferable. And 95 mass% or less is preferable in a composition, and, as for content of (f) component, 90 mass% or less is more preferable, and 85 mass% or less is more preferable.

  Furthermore, the hard surface treating agent composition of the present invention contains antiseptics, hydrotropes, dyes, viscosity modifiers, antioxidants, fragrances, etc., as long as the antifouling property imparting effect and cleaning performance are not impaired. I can do it.

  Further, in the hard surface treating agent composition of the present invention, the pH at 20 ° C. is preferably 3 or more, more preferably 5 or more, and more preferably 6 or more, from the viewpoint of increasing detergency. Preferably, it is 7 or more. And from the viewpoint of excellent storage stability, the pH at 20 ° C. is preferably 11 or less, more preferably 10 or less, more preferably 9 or less, and more preferably 8.5 or less. preferable. As the pH adjuster, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids other than the components (b) and (e) 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 treating agent composition of the present invention is intended for hard surfaces, preferably hydrophobic hard surfaces, and by imparting antifouling properties by modifying the hydrophobic surface to a hydrophilic surface. It is estimated that

  The hydrophobic hard surface that is the target of the hard surface treating agent 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 more preferable, and what is 80 degrees or more is 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 processing agent composition for hard surfaces of the present invention can impart excellent antifouling properties to the hydrophobic hard surfaces of kitchens, bathrooms and toilets. Therefore, it is preferable that the processing agent composition for hard surfaces of this invention is 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 hard surface cleaning composition for bathrooms.

  Moreover, it is preferable to use the processing agent composition for hard surfaces of this invention as a spray type hard surface processing agent article | item formed by filling a spray type container. Such articles can also be used as spray-type hard surface cleaning articles and spray-type hard surface modifier articles. 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 processing agent 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 the liquid processing agent 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, sucks up the liquid processing agent composition through a vertical pipe immersed in the liquid processing agent 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 for applying the treatment composition of the present invention to the hydrophobic hard surface can be selected according to the width (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 treating agent 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 remarkably reduced by treating the hard surface with the hard surface treating agent 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 processing agent composition for hard surfaces of this invention, the static contact angle with respect to the 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 more preferable, and 50 ° or more is more preferable.

  In the hard surface treating agent composition of the present invention, after being applied to a hydrophobic hard surface, a coating film containing the component (a) is formed to coat the hard surface, thereby preventing the PVC plate against ion-exchanged water. It is estimated that the static contact angle can be 60 ° or less.

  The present invention includes a hard surface cleaning composition comprising the hard surface treating composition of the present invention. That is, this invention relates to the cleaning composition for hard surfaces which contains (a) component 0.01 mass% or more and 10 mass% or less, and (b) component 0.5 mass% or more and 30 mass% or less. The preferable aspect of the cleaning composition for hard surfaces of this invention can be selected from what was described in the processing agent composition for hard surfaces of this invention. When used as a hard surface cleaning composition, it is preferable to contain a component selected from the component (c), the component (d), the component (e) and the component (f). Moreover, when using as a cleaning composition for hard surfaces, it is preferable to contain 5 mass% or more of (b) component.

  Moreover, this invention includes the modifier composition for hard surfaces which consists of the processing agent composition for hard surfaces of this invention. That is, this invention relates to the hard surface modifier composition which contains (a) component 0.01 mass% or more and 10 mass% or less, and (b) component 0.5 mass% or more and 30 mass% or less. . The preferable aspect of the modifier composition for hard surfaces of this invention can be selected from what was described by the processing agent composition for hard surfaces of this invention.

<How to use>
The treatment agent composition for hard surface of the present invention comprises a step of applying the composition to a hydrophobic hard surface, and a surface on which the composition of the hydrophobic hard surface is coated with 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 hard surface treating agent composition of the present invention to a hydrophobic hard surface, a step of thinly spreading using a sponge or the like, and then a method of treating a 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 above-described hard surface treating agent composition of the present invention is filled in a spray-type container as described above. It is preferable to use a spray type hard surface treating agent article. The temperature of water used for rinsing after washing is preferably 5 ° C. or higher, more preferably 15 ° C. or higher, so that the hydrophilic modification component (a) remains on the hydrophobic hard surface. 50 ° C. or lower is preferable, and 35 ° C. or lower is more preferable.

<Aspect of the Present Invention>
Examples of the present invention are illustrated below.
<1> (a) 50 mol% or more and 95 mol% or less of the monomer unit (a-1) having a sulfobetaine structure and 1 or more carbon atoms other than the monomer unit (a-1), A block type polymer compound [hereinafter referred to as component (a)] containing a monomer unit (a-2) having 18 or less alkyl groups in an amount of 5 mol% to 50 mol% in all monomer units, Mass% or more, 10 mass% or less, and
(B) Surfactant [hereinafter referred to as (b) component] is 0.5 mass% or more and 30 mass% or less,
Containing hard surface treatment composition.

<2> The hard surface treating agent composition according to <1>, wherein the monomer unit (a-1) is a monomer unit obtained from a monomer represented by the following general formula (1).

[Wherein, R ¹¹ is an alkylene group having 1 to 5 carbon atoms, and R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there. X is a group selected from —COO—, —CONH—, and OCO—. R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ¹⁷ is an alkylene having 1 to 10 carbon atoms. Or a hydroxyalkylene group having 1 to 10 carbon atoms. ]

<3> In the general formula (1), R ¹¹ is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, more preferably a carbon number. The hard surface treating agent composition according to <2>, which is an alkylene group having 1 or 2 carbon atoms, more preferably an alkylene group having 2 carbon atoms.

<4> In the general formula (1), R ¹³ and R ¹⁴ are preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom or a methyl group. The hard surface treating agent composition according to <2> or <3>, which is preferably a hydrogen atom.

<5> In the general formula (1), R ¹⁵ and R ¹⁶ are each independently preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. The treatment composition for hard surface according to any one of <2> to <4>, more preferably a methyl group.

<6> In the general formula (1), R ¹⁷ is preferably an alkylene group having 1 to 5 carbon atoms or a hydroxyalkylene group having 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms. Or an alkylene group having 2 or more and 4 or less carbon atoms, more preferably an alkylene group having 3 carbon atoms or a hydroxyalkylene group having 3 carbon atoms, more preferably an alkylene group having 3 carbon atoms. 2>-<5> Hard surface treating agent composition in any one of.

<7> In the general formula (1), X is preferably —COO— or —OCO—, more preferably —COO—, the hard surface according to any one of <2> to <6>. Treatment composition.

<8> The alkyl group of the monomer unit (a-2) is preferably an alkyl group having 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 5 or less carbon atoms, more preferably 4 or less carbon atoms. The treatment composition for hard surface according to any one of <1> to <7>, which is more preferably an alkyl group having 4 carbon atoms.

<9> The hard surface treating agent composition according to any one of <1> to <8>, wherein the monomer unit (a-2) is a monomer unit obtained from a monomer represented by the following general formula (2). object.

[Wherein, R ²¹ 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 ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is —COO—, —CONH—, —OCO—, or a divalent aromatic hydrocarbon group. However, when R ²¹ is a hydrogen atom or — (C ₂ H ₄ O) _n —H, at least one of R ²² , R ²³ , and R ²⁴ is an alkyl group having 1 to 3 carbon atoms. ]

<10> In the general formula (2), R ²¹ is preferably an alkyl group having 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 5 or less carbon atoms, more preferably 4 or less carbon atoms. More preferably, the hard surface treating agent composition according to <9>, which is an alkyl group having 4 carbon atoms.

<11> In the general formula (2), R ²² is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, more preferably a methyl group. The hard surface treating agent composition according to <9> or <10>.

<12> In the general formula (2), R ²³ and R ²⁴ are each independently preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom or a methyl group. The hard surface treating agent composition according to any one of <9> to <11>, which is preferably a hydrogen atom.

<13> In the general formula (2), Y is preferably —COO— or —OCO—, more preferably —COO—, the hard surface according to any one of <9> to <12> Treatment composition.

<14> 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, more preferably 80 mol% or more, more preferably 85. The hard surface treatment according to any one of <1> to <13>, which is contained in an amount of not less than mol%, and preferably not more than 94 mol%, more preferably not more than 92 mol%, more preferably not more than 90 mol%. Agent composition.

<15> The component (a) contains the monomer unit (a-2) in all monomer units, preferably 6 mol% or more, more preferably 8 mol% or more, more preferably 10 mol% or more, and The hard surface treatment according to any one of <1> to <14>, preferably 40 mol% or less, more preferably 30 mol% or less, more preferably 20 mol% or less, more preferably 15 mol% or less. Agent composition.

<16> 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, more preferably, in all monomer units of the component (a). 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, more preferably 97 mol% or more, more preferably 99 mol% or more, and preferably 100 mol% or less. Hard surface treating agent composition in any one of <1>-<15> which is mol%.

<17> The molar ratio of the monomer unit (a-1) to the monomer unit (a-2) in the component (a) is (a-1) / (a-2), preferably 50/50 or more, more preferably. Is 60/40 or more, more preferably 70/30 or more, more preferably 80/20 or more, more preferably 85/15 or more, and preferably 95/5, more preferably 93/7 or less, more preferably Is a hard surface treating agent composition according to any one of <1> to <16>, which is 90/10 or less.

<18> The weight average molecular weight of the component (a) is preferably 1,000 or more, more preferably 5,000 or more, more preferably 10,000 or more, more preferably 50,000 or more, more preferably 100,000. And preferably 5,000,000 or less, more preferably 3,000,000 or less, more preferably 1,500,000 or less, more preferably 1,000,000 or less, more preferably 500,000 or less. 000 or less, more preferably 400,000 or less, more preferably 300,000 or less, more preferably 200,000 or less, more preferably 150,000 or less, according to any one of <1> to <17> Hard surface treatment composition.

<19> The hard surface according to any one of <1> to <18>, which contains at least one anionic surfactant selected from the following (b1) component and (b2) component as the (b) component: Treatment agent composition.
(B1) 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 (b2): 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

<20> The component (b1) and the component (b2) are contained as the component (b), and the mass ratio of the component (b1) / (b2) is preferably 0.05 or more, more preferably 0.1 or more. The hard surface treating agent composition according to <19>, more preferably 0.3 or more, and preferably 1 or less, more preferably 0.8 or less, more preferably 0.7 or less.

<21> The content of the component (a) in the composition is preferably 0.02% by mass or more, more preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and preferably Is 5 mass% or less, More preferably, it is 2.5 mass% or less, More preferably, it is 1 mass% or less, The processing agent composition for hard surfaces in any one of <1>-<20>.

<22> The content of the component (b) is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 5% by mass or more, in the composition in terms of the mass as the sodium salt. Preferably, it is 7% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 12% by mass or less, more preferably 10% by mass or less, More preferably, it is 9 mass% or less, The hard surface treating agent composition in any one of <1>-<21>.

<23> The mass ratio of the component (a) to the component (b) is (b) / (a), preferably 5 or more, more preferably 7 or more, more preferably 10 or more, more preferably 15 or more. Preferably it is 30 or more, more preferably 50 or more, and preferably 500 or less, more preferably 400 or less, more preferably 300 or less, more preferably 200 or less, more preferably 100 or less, <1> to <22> The hard surface treating agent composition according to any one of <22>.

<24> As the component (c), the organic solvent, preferably the inorganic / organic ratio in the organic conceptual diagram is 0.6 or more, preferably 0.7 or more, more preferably 1.0 or more, more preferably 1.2 or more, more preferably 1.4 or more, more preferably 1.5 or more, and 2.2 or less, more preferably 1.9 or less, more preferably 1.8 or less, more preferably 1.7. The processing agent composition for hard surfaces as described in any one of <1>-<23> containing the organic solvent which is the following.

<25> The component (c) is an organic solvent selected from mono-, di- or tri-alkylene glycol monoethers and mono-, di- or tri-alkylene glycol diethers, preferably mono-, di- Or selected from tri-ethylene glycol ether, and mono-, di- or tri-ethylene glycol diether, and mono-, di- or tri-propylene glycol ether, and mono-, di- or tri-propylene glycol diether Organic solvents, more preferably mono-, di- or tri-ethylene glycol monoalkyl ethers, and mono-, di- or tri-ethylene glycol diethers, and mono-, di- or tri-propylene glycol monoethers, And mono-, di- or tri-propylene glycol die An organic solvent selected from tellurium, wherein the total number of carbon atoms in the compound is 4 or more, preferably 6 or more, more preferably 8 or more, and 14 or less, preferably 12 or less, more preferably 10 or less. <24> The hard surface treatment composition according to <24>.

<26> The content of the component (c) is preferably 1% by mass or more, more preferably 1.5% by mass or more, more preferably 3% by mass or more, more preferably 4% by mass or more, in the composition. Preferably it is 5% by weight or more, more preferably 6% by weight or more, more preferably 7% by weight or more, more preferably 7.5% by weight or more, and preferably 30% by weight or less, more preferably 20% by weight. Hereinafter, the hard surface treatment composition according to <24> or <25>, more preferably 15% by mass or less, and more preferably 9% by mass or less.

<27> The mass ratio of the component (b) to the component (c) is (b) / (c), preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.5 or more, and more. Preferably it is 0.8 or more, and preferably 10 or less, more preferably 8 or less, more preferably 5 or less, more preferably 3 or less, more preferably 2 or less, more preferably 1.5 or less. <24>-<26> Hard surface treating agent composition in any one of <26>.

<28> As component (d), an inorganic salt selected from alkali metal halides and alkaline earth metal halides is contained. Preferably, as component (d), sodium chloride, potassium chloride, calcium chloride, magnesium chloride is used. And a hard surface treating agent composition according to any one of <1> to <27>, which contains at least one compound selected from the group consisting of potassium iodide.

<29> The content of the component (d) is preferably 1% by mass or more, more preferably 1.2% by mass or more, more preferably 1.5% by mass or more, more preferably 2% by mass or more in the composition. The hard surface treatment composition according to <28>, preferably 5% by mass or less, more preferably 4% by mass or less, more preferably 3% by mass or less, and more preferably 2.5% by mass or less. object.

<30> As component (f), water is contained, preferably water is contained in the composition in an amount of 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more. And the processing agent composition for hard surfaces in any one of <1>-<29> containing 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.

<31> The pH at 20 ° C. is preferably 3 or more, more preferably 5 or more, more preferably 6 or more, more preferably 7 or more, and preferably 11 or less, more preferably 10 or less, more preferably The hard surface treating agent composition according to any one of <1> to <30>, which is 9 or less, more preferably 8.5 or less.

<32> A method of improving the hydrophilicity of the hydrophobic hard surface by applying the hard surface treating agent composition according to any one of <1> to <31> to the hydrophobic hard surface.

<33> After applying the hard surface treating agent composition according to any one of <1> to <31> to a hydrophobic hard surface to which dirt is attached, rinsing with water allows the treatment from the hydrophobic hard surface. A method for treating a hydrophobic hard surface, wherein both removal of soil and imparting hydrophilicity to the hydrophobic hard surface are performed.

<Examples and Comparative Examples>
The hard surface treating agent compositions described in Tables 1 to 3 were prepared. The pH (20 ° C.) of each composition was adjusted to the values in the table with sodium hydroxide and hydrochloric acid. About these compositions, the following item was evaluated. Details are shown below. The results are shown in Table 1. In some examples in the table, the mass ratio (b) / (a) is shown with the component (a ′) as the component (a).

<Contact angle>
After applying 1 mL of the hard surface treatment composition to a PVC plate (Engineering Test Service Co., Ltd., shape: 25 mm × 75 mm × 1 mm) and let 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 measurement, a fully automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used, and 20 μl of ion-exchanged water droplets were deposited on the treated surface and contacted 10 times at 1-second intervals after 3 seconds of deposition. The angle was measured and the average value was recorded as data. In addition, the static contact angle of the PVC board before a process was 85 degrees.

<Anti-fouling>
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, the amount of sebum (y) remaining on the surface of the PVC plate treated with the composition not containing the component (a) (replace the component (a) with ion-exchanged water) 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 Apply 1 ml each of the hard surface treating agent composition to both sides of a PVC plate (Engineering Test Service Co., Ltd., shape: 80 mm x 250 mm x 1 mm) and spread with a sponge. After being allowed to stand for 30 minutes, rinsed with tap water (50 mL / second) at 25 ° C. for 20 seconds.

<Anti-fouling durability>
A plurality of PVC plates ^* and untreated PVC plates treated with each composition were fixed to a draft portion of a bath containing 40 ° C. hot water. Four men evaluated the adhesion state of the stain | pollution | contamination with respect to a PVC board after taking a bath one by one. The bathing time was 10 minutes per person. Moreover, the PVC board was fixed so that the center of a PVC board might be located in a draft part, when a man entered the bathtub. In addition, an untreated PVC board is a PVC board processed with the composition which does not mix | blend (a) component in the composition of each composition [Replace the component of (a) with ion-exchange water].

  After the first man has taken a bath, take out one PVC board, leave it at 40 ° C for 30 minutes, wash it with shower water only for 10 seconds, and visually observe the state of dirt on the PVC board. Evaluation based on the criteria. Furthermore, this operation was repeated, and the PVC board after the second male bathed, the PVC board after the third male bathed, and the PVC board after the fourth male bathed were each evaluated. In addition, evaluation was performed by replacing hot water for each composition. In some of the comparative examples, evaluation after the second and third bathing was not performed.

* PVC plate treated with each composition Apply 1 ml each of the hard surface treating agent composition to both sides of a PVC plate (Engineering Test Service Co., Ltd., shape: 80 mm x 250 mm x 1 mm) and spread with a sponge. After being allowed to stand for 30 minutes, rinsed with tap water (50 mL / second) at 25 ° C. for 20 seconds.

Evaluation criteria 5: No dirt adherence 4: Slightly dirt adheres 3: 1/4 dirt adheres compared to untreated PVC board 2: Untreated PVC board Compared with half amount of dirt, 1: Same level of dirt as untreated PVC board is attached.

The components in Table 1 are as follows.
Block type polymer compound 1: block type obtained in Synthesis Example 1 below and having a monomer unit (a-1) / monomer unit (a-2) = 90/10 (molar ratio) and a weight average molecular weight of 130,000 Polymer compound / block polymer compound 2: monomer unit (a-1) / monomer unit (a-2) = 85/15 (molar ratio) obtained in Synthesis Example 2 below, weight average molecular weight 140,000 Block polymer compound

Comparative polymer compound 1: polymer obtained in the following Comparative Synthesis Example 1 and having a monomer unit (a-1) / monomer unit (a-2) = 80/20 (molar ratio) and a weight average molecular weight of 150,000 Compound

Comparative polymer compound 2: Polymer compound having a weight average molecular weight of 160,000 obtained in Comparative Synthesis Example 2 below

Comparative polymer compound 3: Polymer compound having a weight average molecular weight of 110,000 obtained in Comparative Synthesis Example 3 below

Comparative polymer compound 4: Polymer compound having a weight average molecular weight of 130,000 obtained in Comparative Synthesis Example 4 below

Comparative polymer compound 5: polymer compound having a weight average molecular weight of 55,000 obtained in Comparative Synthesis Example 5 below

Sodium polyoxyethylene alkyl ether sulfate: alkyl group having 12 to 16 carbon atoms, ethylene oxide average addition mole number of 4.0
Polyoxyethylene alkyl ether: alkyl group having 12 to 16 carbon atoms, ethylene oxide average addition mole number 10
Alkyl polyglycoside: alkyl (C12-16) polyglucose (average degree of sugar condensation 1-2)
Alkylamidopropylbetaine: fatty acid (carbon number 12) amidopropyl-N, N-dimethyl-acetic acid betainealkyldimethylbenzylammonium chloride: alkyl group having 12 to 16 carbon atoms

<Synthesis Example 1>
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 purged with nitrogen. 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 dropped while stirring 500 mL of methanol to precipitate a polymer, and the solid of block type polymer compound 1 was obtained by filtration and drying.
In the block polymer compound 1, the monomer unit is a monomer unit (a-1) obtained from N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium. Monomer unit formed by reaction of 2- (dimethylamino) ethyl methacrylate with 1,3-propane sultone] and monomer unit (a-2) obtained from n-butyl methacrylate, the molar ratio of which is monomer Unit (a-1) / monomer unit (a-2) = 90/10. In the block type polymer compound 1, the arrangement of the monomer units was a block. Further, the block type polymer compound 1 had a weight average molecular weight of 130,000.

<Synthesis Example 2>
Put an eggplant flask with 30 g of n-butyl methacrylate, 0.514 g of ethyl 2-bromoisobutyrate, 1.62 g of 4,4-dinonyl-2,2-dipyridyl, and 45 g of anisole, stopper with a three-way cock and perform nitrogen bubbling for 15 minutes. A monomer solution was prepared. Next, a stirrer chip, 0.131 g of copper (I) chloride and 0.0886 g of copper (II) chloride were placed in another eggplant flask, and the inside was replaced by nitrogen with a three-way cock, and then the monomer solution was added. Nitrogen bubbling was performed for 10 minutes, followed by polymerization by heating to 70 ° C. After 15 hours, the polymerization solution was cooled with ice 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, 5.66 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. It was stoppered with a three-way cock and 1.98 g of 1,3-propane sultone was added dropwise while heating to 50 ° C. After cooling for 5 hours, the polymer solution was dropped while stirring 500 mL of methanol to precipitate the polymer, and a solid of block type polymer compound 2 was obtained by filtration and drying.
In the block type polymer compound 2, the monomer unit is a monomer unit (a-1) obtained from N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium. Monomer unit formed by reaction of 2- (dimethylamino) ethyl methacrylate with 1,3-propane sultone] and monomer unit (a-2) obtained from n-butyl methacrylate, the molar ratio of which is monomer Unit (a-1) / monomer unit (a-2) = 85/15. Further, in the block type polymer compound 2, the arrangement of the monomer units was a block. Further, the block type polymer compound 2 had a weight average molecular weight of 140,000.

<Comparative Synthesis Example 1>
A 300 mL four-necked separable flask equipped with a stirrer (using a 60 mm crescent blade made of Teflon (registered trademark)), a nitrogen inlet tube, and a thermometer was added to N, N-dimethyl-N- (3-sulfonatopropyl) -2- (Methacryloyloxy) ethane-1-aminium (Sigma Aldrich) 26.6 g, n-butyl methacrylate (Wako Pure Chemical Industries, Ltd.) 3.39 g, ethanol 48 g, and ion-exchanged water 68 g were added and stirred at 200 rpm. Then, nitrogen substitution was performed by blowing nitrogen gas at 100 mL / min for 30 minutes. Next, the temperature was raised to 80 ° C., 5.0 g of ion-exchanged water and 0.544 g of ammonium persulfate (APS, Sigma-Aldrich) were added to initiate polymerization. After 4 hours, the mixture was cooled and dried under reduced pressure at 80 ° C. for 17 hours to obtain a white solid of comparative polymer compound 1.
Comparative polymer compound 1 was produced by a production method in which a block-type polymer compound was not obtained.
Comparative polymer compound 1 has monomer units (a-1) obtained from N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium and methacrylic monomer units. It was a monomer unit (a-2) obtained from acid n-butyl, and the molar ratio was monomer unit (a-1) / monomer unit (a-2) = 80/20. Comparative polymer compound 1 had a weight average molecular weight of 150,000.

<Comparative Synthesis Example 2>
In a separable flask made of glass with an internal volume of 300 mL, 20.0 g of N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium (Sigma Aldrich), trifluoroethanol 170 g (manufactured by Sigma Aldrich) was added, mixed uniformly, and stirred for 30 minutes in a nitrogen atmosphere. After this solution was heated to about 70 ° C., 0.18 g of a polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) and 10.0 g of trifluoroethanol were added and polymerization was carried out by maintaining for 6 hours. It was. Next, the polymer solution was dropped while stirring 4 L of methanol to precipitate a polymer, and a solid of comparative polymer compound 2 was obtained by filtration and drying.
Comparative polymer compound 2 was a homopolymer of N, N-dimethyl-N- (3-sulfonatopropyl) -2- (methacryloyloxy) ethane-1-aminium. Comparative polymer compound 2 had a weight average molecular weight of 160,000.

<Comparative Synthesis Example 3>
In a separable flask equipped with a cooling reflux tube, a dropping funnel, a thermometer, a nitrogen inlet tube and a stirring device, dimethylaminoethyl methacrylate 49 g, t-butyl acrylate 1.9 g, 2,2′-azobis (2-methylbutyro (Nitrile) 0.31 g and ethyl alcohol 100 g were charged and reacted at 80 ° C. for 4 hours while blowing nitrogen. Next, a solution obtained by dissolving 67.5 g of sodium 2-hydroxy-3-propanesulfonate in 70 g of ethanol / water (= 50/50 mass ratio) was added to the obtained polymerization reaction solution, and after sufficient stirring, Further, the amphoteric reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. After the reaction, the mixture was allowed to cool to room temperature and filtered to remove precipitates, the solvent was removed by drying under reduced pressure, and 93 g of Comparative Polymer Compound 3 was obtained as a solid content. The weight average molecular weight of the obtained comparative polymer compound 3 was 110,000. Further, in this comparative polymer compound 3, the binding rate of the sulfobetaine moiety was 100% in terms of a molar ratio based on all nitrogen atoms contained in the copolymer.
In Comparative Polymer Compound 3, the monomer units were N-methacryloyloxyethyl N, N-dimethylammonium N- (hydroxy) propanesulfonate and t-butyl methacrylate, and the arrangement of the monomer units was a block. Further, the molar ratio of the monomer units of the comparative polymer compound 3 was N-methacryloyloxyethyl N, N-dimethylammonium N- (hydroxy) propanesulfonate / t-butyl methacrylate = 96/4. The comparative polymer compound 3 had a weight average molecular weight of 110,000.

<Comparative Synthesis Example 4>
In a separable flask made of glass having an internal volume of 300 mL, 17.1 g of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Sigma Aldrich), 2.93 g of n-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), methanol 38.5 g and ion-exchanged water 23.4 g were added, mixed uniformly, and stirred for 30 minutes in a nitrogen atmosphere. Thereafter, the temperature of the solution was raised to about 70 ° C., and then 0.13 g of a polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) and 5.0 g of methanol were added, and polymerization was carried out by maintaining for 6 hours. It was. Thereafter, an aqueous sodium hydroxide solution was added to neutralize to pH 7. Next, the polymer solution was dropped while stirring 4 L of 2-propanol to precipitate a polymer, and a solid of comparative polymer compound 4 was obtained by filtration and drying.
Comparative polymer compound 4 is a monomer unit obtained from 2-acrylamido-2-methylpropanesulfonic acid and a monomer unit (a-2) obtained from n-butyl methacrylate, and the molar ratio thereof is 2 -Monomer unit / monomer unit (a-2) = 80/20 obtained from acrylamido-2-methylpropanesulfonic acid. Comparative polymer compound 4 had a weight average molecular weight of 130,000.

<Comparative Synthesis Example 5>
In a separable flask made of glass having an internal volume of 300 mL, 44.4 g of methacryloyloxyethyltrimethylammonium chloride (QDM, manufactured by MRC Unitech Co., Ltd.), 4.46 g of styrene (manufactured by Wako Pure Chemical Industries, Ltd.), a polymerization initiator ( Parroyl L (manufactured by NOF Corporation) 8.53 g, ion-exchanged water 2.52 g, and ethanol 103 g were added, mixed uniformly, and stirred for 30 minutes in a nitrogen atmosphere. The solution was heated to about 90 ° C. and then held for 6 hours for polymerization. Next, the polymer solution was dropped while stirring 4 L of acetone to precipitate a polymer, and a solid of comparative polymer compound 5 was obtained by filtration and drying.
Comparative polymer compound 5 is a monomer unit obtained from methacryloyloxyethyltrimethylammonium chloride and a monomer unit (a-2) obtained from styrene, and the molar ratio is obtained from methacryloyloxyethyltrimethylammonium chloride. Monomer unit / monomer unit (a-2) = 80/20. Comparative polymer compound 5 had a weight average molecular weight of 55,000.

From the results of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-7 in Table 1, by including the component (a) and the component (b), the effect of imparting antifouling properties is excellent. I understand.
Further, from the results of Example 1-3 and Comparative Example 1-1 in Table 1, by using a block-type polymer compound that satisfies the structure and ratio of the component (a) of the present invention as the polymer compound, It can be seen that the effect of imparting dirtiness is excellent.
Moreover, it can be seen from the results in Table 2 that the effects of the present invention can also be obtained when various organic solvents are used as the component (c). The composition of Table 2 was excellent in antifouling durability.
Moreover, it can be seen from the results in Table 3 that when the component (c) is used, the mass ratio of the component (b) to the component (c) has a suitable range. The composition of Table 3 was excellent in antifouling durability.

Claims (8)

(A) 50 mol% or more and 95 mol% or less of the monomer unit (a-1) having a sulfobetaine structure and 2 or more and 5 or less carbon atoms other than the monomer unit (a-1) A block unit that is a monomer unit having an alkyl group, and that contains a monomer unit (a-2) obtained from a monomer represented by the following general formula (2) in an amount of 5 mol% to 50 mol% in all monomer units A polymer compound (hereinafter referred to as component (a)) is 0.01% by mass or more and 10% by mass or less, and
(B) 0.5% by mass or more and 30% by mass or less of a surfactant [hereinafter referred to as component (b)],
The processing agent composition for hard surfaces whose mass ratio of (a) component and (b) component is (b) / (a) and is 5 or more and 100 or less .

[Wherein R ²¹ represents an alkyl group having 2 to 5 carbon atoms. R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is —COO— or —OCO—. ] Monomer units (a-1) is a monomer unit derived from a monomer represented by the following general formula (1), according to claim 1 Symbol placement hard surface treating agent composition.

[Wherein, R ¹¹ is an alkylene group having 1 to 5 carbon atoms, and R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there. X is a group selected from —COO—, —CONH—, and —OCO—. R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ¹⁷ is an alkylene having 1 to 10 carbon atoms. Or a hydroxyalkylene group having 1 to 10 carbon atoms. ] (A) The hard surface use of Claim 1 or 2 whose sum total of a monomer unit (a-1) and a monomer unit (a-2) is 60 mol% or more and 100 mol% or less in all the monomer units of a component. Treatment agent composition. 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 processing agent composition for hard surfaces in any one of Claims 1-3 . Furthermore, the hard of any one of Claims 1-4 which contains the organic solvent whose inorganic / organic ratio in an organic conceptual diagram is 0.6 or more and 2.2 or less as (c) component Surface treating agent composition. The hard surface treatment composition according to any one of claims 1 to 5 , which is for bathroom, kitchen or toilet. A method for improving the hydrophilicity of a hydrophobic hard surface by applying the hard surface treating agent composition according to any one of claims 1 to 6 to a hydrophobic hard surface. The removal of dirt from the hydrophobic hard surface by applying the treatment composition for hard surface according to any one of claims 1 to 6 to the hydrophobic hard surface to which dirt has adhered, and then rinsing with water. And a method for treating a hydrophobic hard surface, wherein both hydrophilicity is imparted to the hydrophobic hard surface.