JP5957247B2 - Hard surface treatment composition - Google Patents

Description

  The present invention relates to a hard surface treating agent composition capable of imparting antifouling properties to 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 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.

  Patent Document 1 discloses a cleaning agent that performs an initial cleaning of a hard surface using a cleaning composition containing a hydrophilic polymer and a nonionic surfactant, and then can easily remove dirt from the treated surface. ing. Patent Document 2 discloses a hydrophilicity imparting agent that contains an amphoteric polymer containing a large amount of anionic groups and a nonionic surfactant, and imparts antifouling properties to a hard surface. Further, Patent Document 3 discloses a treatment of a hydrophobic surface performed at home in order to prevent accumulation of soil residues using a composition containing an amphiphilic block copolymer and a cation and a nonionic surfactant. .

  On the other hand, Patent Document 4 discloses a detergent composition for hydrophilic hard surfaces such as ceramic tiles and toilet bowls having detergency and antifouling properties. Patent Document 5 discloses a composition containing a specific polymer, a bactericidal compound, and a surfactant under predetermined conditions, and results in excellent antifouling property to hydrophilic hard surfaces such as ceramic tiles and toilet bowls. However, there is a limitation that anionic surfactants should be used in unaffected amounts to reduce bactericidal and antifouling properties.

  It is also known that surface modification is performed with a composition containing a coacervate such as a polymer. In Patent Document 6, an aqueous dispersion or solution of a coacervate having a core-shell structure, in which a core is a predetermined inorganic particle and a shell is a predetermined polymer shell, has properties such as prevention of soil adhesion to a hard surface. It is described to be used for giving.

JP 2010-536950 A Special table 2003-505535 gazette Special table 2009-545642 JP-A-9-169995 JP 2003-096493 A Special table 2009-542894 gazette

  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.

  The subject of this invention is providing the processing agent composition for hydrophobic hard surfaces which can modify | reform hydrophobic hard surfaces and can provide the outstanding antifouling property. Furthermore, the problem of the present invention is to remove the hydrophobic dirt from the hydrophobic hard surface and to impart excellent antifouling property to the hydrophobic hard surface by using it in the cleaning operation of the hydrophobic hard surface. It is providing the processing agent composition.

  The present inventor conducted a technical study on coacervation, which will be described later, with respect to a treatment agent composition that imparts excellent antifouling properties to a hydrophobic hard surface and can further remove dirt from the hydrophobic hard surface. It came to complete.

The present invention provides (a) 20 to 100 mol% of a monomer unit having a cationic group, 0 to 80 mol% of a monomer unit having a nonionic group, and 0 to 0 of a monomer unit having an anionic group in the molecule. A cationic polymer compound containing 40 mol%, having a molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group of 0.3 or less and a weight average molecular weight of 1,000 to 300,000 [ Hereinafter referred to as component (a)] 0.05 to 10% by mass, and (b) one or more anionic surfactants selected from the following components (b1) and (b2) [hereinafter referred to as component (b) 0.5 to 30% by mass,
The ratio A / B between the number of moles A of the cationic group in the component (a) and the number of moles B of the anionic group in the component (b) is 0.04 or more and 2 or less.
The present invention relates to a hydrophobic hard surface treating agent composition.
(B1) component: an anionic surfactant (b2) component having a chain hydrocarbon group having 8 to 18 carbon atoms and a carboxylic acid group or a salt thereof; a chain hydrocarbon group having 7 to 18 carbon atoms and a sulfonic acid Anionic surfactant having one or more selected from a group, a sulfate group, a phosphate group, and a salt thereof

  In the present invention, the step of applying the hydrophobic hard surface treating agent composition of the present invention to a hydrophobic hard surface and the surface on which the composition of the hydrophobic hard surface is applied are at least 5 times the coating mass. And a method of treating a hydrophobic hard surface having a step of rinsing with water of a mass of

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

  In the present invention, the treatment composition for a hydrophobic hard surface of the present invention is applied to a hydrophobic hard surface to which dirt has adhered, and then rinsed with water to remove the 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.

  The present invention is a hydrophobic hard surface treatment method using the hydrophobic hard surface treating agent composition of the present invention, wherein the turbidity of the composition is 10 or less, and Treatment of a hydrophobic hard surface that is applied to an attached hydrophobic hard surface and then rinsed with water to both remove soil from the hydrophobic hard surface and impart hydrophilicity to the hydrophobic hard surface Regarding the method.

  ADVANTAGE OF THE INVENTION According to this invention, the processing agent composition for hydrophobic hard surfaces which provides the outstanding antifouling property to hydrophobic hard surfaces, such as a bathroom and a kitchen, is provided. Furthermore, according to the present invention, there is provided a treatment composition for a hydrophobic hard surface that exhibits high detergency and provides excellent antifouling properties when cleaning dirt generated on these hydrophobic hard surfaces. The

<(A) component>
Component (a) contains 20 to 100 mol% of a monomer unit having a cationic group, 0 to 80 mol% of a monomer unit having a nonionic group, and 0 to 40 mol of a monomer unit having an anionic group in the molecule. It is a cationic polymer compound containing a mol%, wherein the molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group is 0.3 or less and the weight average molecular weight is 1,000 to 300,000. It is presumed that a high antifouling property is imparted by forming a complex with the component (b) by rinsing after being applied to the hydrophobic hard surface and forming an adsorption layer on the hydrophobic hard surface.

  The monomer unit (a) having a cationic group is preferably a monomer unit having at least one group selected from an amino group and a quaternary ammonium group from the viewpoint of imparting antifouling properties.

  Furthermore, the monomer unit (a) having a cationic group is obtained by polymerizing one or more compounds selected from the compound represented by the general formula (1) and the compound represented by the general formula (2). The structural unit obtained is preferable from the viewpoint of imparting high antifouling properties.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom or a C1-C3 alkyl group. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - R 12 -OCO-R 13 - group selected from, preferably -COOR ¹² - is. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—, preferably an alkyl group having 1 to 3 carbon atoms. R ⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably an alkyl group having 1 to 3 carbon atoms, R ⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, Preferably it is a C1-C3 alkyl group, Z < ^- > shows an anion, Preferably a chlorine ion. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—, preferably an alkyl group having 1 to 3 carbon atoms. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably an alkyl group having 1 to 3 carbon atoms. ]

  Specific monomer compounds derived from the monomer unit having a cationic group include diallyldialkylammonium salts in which the alkyl group has 1 to 3 carbon atoms, and N- in which the alkyl group has 1 to 5 carbon atoms. (Meth) acryloylaminoalkyl-N, N-dialkylamine, N- (meth) acryloylaminoalkyl-N, N, N-trialkylammonium salt whose alkyl group has 1 to 5 carbon atoms, carbon number of alkyl group N- (meth) acryloyloxyalkyl-N, N, N-trialkylammonium salt in which is 1 to 5 and the alkenyl group have 2 to 10 carbon atoms, and the alkyl group has 1 to 3 carbon atoms. A compound selected from N- (ω-alkenyl) -N, N-dialkylamine is a preferred example from the viewpoint of imparting antifouling properties. More preferably, it is a diallyldialkylammonium salt in which the alkyl group has 1 to 3 carbon atoms or an N- (meth) acryloyloxyalkyl-N, N, N-trialkylammonium salt in which the alkyl group has 1 to 5 carbon atoms. Particularly preferred is a diallyldialkylammonium salt in which the alkyl group has 1 to 3 carbon atoms. Here, “(meth) acryloyl” means “acryloyl or methacryloyl”.

  Specific monomer compounds derived from the monomer unit having a nonionic group as the component (a) include acrylamide, methacrylamide, t-butylacrylamide, vinyl acetate, vinyl alcohol, styrene, hydroxyethyl methacrylate, methacryl A compound selected from methyl acrylate, butyl acrylate, and stearyl methacrylate is preferable from the viewpoint of imparting antifouling properties. More preferred are acrylamide, styrene, and methyl methacrylate.

  Moreover, (a) component can contain the monomer unit which has an anionic group. Specific monomer compounds derived from the monomer unit having an anionic group include methacrylic acid and its salt, acrylic acid and its salt, maleic anhydride, maleic acid and its salt, styrenesulfonic acid and its salt, Examples include acrylamido-2-methylpropanesulfonic acid and its salt, and 2 (methacryloyloxy) ethanesulfonic acid and its salt.

The abundance ratio of the monomer unit having a cationic group, the monomer unit having a nonionic group and the monomer unit having an anionic group among the constituent units of the component (a) is obtained by measurement of ¹ H-NMR and ¹³ C-NMR. It can be obtained from the peak obtained. Moreover, although it is possible to calculate from the charging ratio of the monomer constituting the component (a), that is, the polymerization ratio, priority is given to a method obtained from peaks obtained by measurement of ¹ H-NMR and ¹³ C-NMR. .

  The component (a) contains 20 to 100 mol% of a monomer unit having a cationic group in the molecule, but preferably 40 mol because the effect of imparting antifouling property to the hydrophobic hard surface is enhanced above the lower limit. % Or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more. The component (a) is a monomer compound having a cationic group, for example, a homopolymer of one or more compounds selected from the compound represented by the general formula (1) and the compound represented by the general formula (2). However, from the viewpoint of imparting antifouling properties, a homopolymer of the compound represented by the general formula (1) is preferable.

  In addition, the component (a) contains 0 to 80 mol% of a monomer unit having a nonionic group in the molecule. However, since the effect of imparting antifouling property to the hydrophobic hard surface is enhanced below the upper limit, 60 mol % Or less, more preferably 40 mol% or less, still more preferably 20 mol% or less, still more preferably 10 mol% or less. Most preferably, it is 0 mol%.

  Moreover, (a) component contains 0-40 mol% of monomer units which have an anionic group in a molecule | numerator. In order to enhance the antifouling effect, the content of the monomer unit having an anionic group is preferably 30 mol% or less in the molecule, more preferably 10 mol% or less, still more preferably 5 mol% or less, Even more preferably not.

  In order to enhance the antifouling effect, the component (a) is a molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group, that is, [monomer unit having an anionic group / cationic group. Monomer unit] is 0.3 or less, preferably 0.2 or less, more preferably 0.15 or less, still more preferably 0.1 or less, and 0.02 More preferably, it is as follows. As described above, since component (a) preferably does not contain a monomer unit having an anionic group, the molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group is more preferably 0.

  As the component (a), particularly preferably, a homopolymer of diallyldialkylammonium salt in which the alkyl group has 1 to 3 carbon atoms, or an N- (meth) acryloyloxyalkyl-N in which the alkylene group has 1 to 5 carbon atoms. , N, N-trialkylammonium salt homopolymer, and a cationic polymer compound selected from a copolymer of diallyldialkylammonium salt and acrylamide having an alkyl group with 1 to 3 carbon atoms.

  The weight average molecular weight of the cationic polymer compound as the component (a) is 1,000 to 300,000, but the component (a) or the complex of the component (a) and the component (b) above the lower limit value. Adsorption persistence is increased, and the hydrophilicity of the hard surface is increased below the upper limit value. Therefore, 2,000 to 200,000 is preferable, 3,000 to 150,000 is more preferable, and 5,000 to 100,000 is more preferable. 000, more preferably 5,000 to 50,000, and most preferably 5,000 to 10,000.

Here, the weight average molecular weight of the component (a) is measured by gel permeation chromatography using polyethylene glycol as a standard sample. (Column: TSK-GEL α-M manufactured by Tosoh Corporation, eluent [50 mmol / L LiBr 1% CH ₃ COOH / ethanol]: water = 3: 7, detector: RI, sample concentration: 5 mg / mL)

  The content of the component (a) in the hydrophobic hard surface treating agent composition of the present invention improves the antifouling property at the lower limit or higher, and improves the hydrophilic property of the hard surface below the upper limit. It is 0.05-10 mass%, 0.05-5 mass% is preferable, 0.08-2.5 mass% is more preferable, 0.1-1 mass% is still more preferable.

<(B) component>
The component (b) is one or more anionic surfactants selected from the following components (b1) and (b2). The component (b) is applied to the hydrophobic hard surface and then preferably diluted with rinsing or the like to form a complex with the component (a) and adsorb to the hydrophobic hard surface, thereby providing high antifouling properties. It is estimated that Moreover, when the component (b) is used together with the component (a), a high cleaning effect can be exhibited when cleaning the hydrophobic hard surface.
(B1) component: an anionic surfactant (b2) component having a chain hydrocarbon group having 8 to 18 carbon atoms and a carboxylic acid group or a salt thereof; a chain hydrocarbon group having 7 to 18 carbon atoms and a sulfonic acid Anionic surfactant having one or more selected from a group, a sulfate group, a phosphate group, and a salt 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, but the residual number of carbon atoms in the chain hydrocarbon group remains below the lower limit. 9-18 are preferred, 9-15 are more preferred, 9-13 are still more preferred, and 10-12 are even more preferred, since the property increases and the antifouling property imparting effect is enhanced below the upper limit. As the salt, sodium salt, potassium salt, and alkanolamine salt are preferable. The component (b1) preferably has 1 to 2 and further 1 chain hydrocarbon group having 8 to 18 carbon atoms. Further, the component (b1) preferably has 1 to 2 carboxylic acid groups or salts thereof, and further one. Furthermore, what has the salt of a carboxylic acid group is preferable.

  Preferred component (b1) from the viewpoint of imparting antifouling properties is a higher fatty acid salt having a chain hydrocarbon group having 8 to 18 carbon atoms, and a polyoxyethylene alkyl ether carboxylate having an alkyl group having 8 to 18 carbon atoms. And a polyoxyethylene amide alkyl ether carboxylate having 8 to 18 carbon atoms in the alkyl group. From the viewpoint of imparting antifouling property, the 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, and more preferably It is a linear higher fatty acid salt having 9 to 19 carbon atoms. More preferable compounds from the viewpoint of imparting antifouling properties 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. (B2) The chain hydrocarbon group of the component (b2) has 7 to 18 carbon atoms. However, the carbon residue of the chain hydrocarbon group has an adsorbing residual property that is higher than the lower limit value and an antifouling property imparting effect when the carbon number is lower than the upper limit value. Since it increases, 8-16 are preferable, 10-15 are more preferable, and 12-14 are still more preferable. As the salt, sodium salt, potassium salt, and alkanolamine salt are preferable. The component (b2) preferably has 1 to 2 and further 1 chain hydrocarbon group having 7 to 18 carbon atoms. In addition, the component (b2) preferably has 1 to 2 or more one selected from sulfonic acid groups, sulfuric acid groups, phosphoric acid groups, and salts thereof. Furthermore, what has 1 or more types selected from the salt of a sulfonic acid group, the salt of a sulfuric acid group, and the salt of a phosphoric acid group is preferable.

  Examples of the component (b2) that are preferable in terms of imparting antifouling properties and improving detergency include alkyl or alkenylbenzene sulfonates having a chain hydrocarbon group having 7 to 18 carbon atoms or alkenyl groups, carbon Polyoxyalkylene alkyl or alkenyl ether sulfate having an alkyl group or alkenyl group having 7 to 18 carbon atoms, alkyl or alkenyl sulfate having an alkyl group or alkenyl group having 7 to 18 carbon atoms, α having 7 to 18 carbon atoms -Olefin sulfonate, lower alkyl ester salt having an alkyl group having 1 to 2 carbon atoms of [alpha] -sulfo fatty acid having 7 to 18 carbon atoms, primary alkane sulfonate having 7 to 18 carbon atoms, 7 to 18 carbon atoms Secondary alkane sulfonate, alkyl having 7 to 18 carbon atoms or alkyl or alkenyl having alkenyl group And luric acid ester salts. Among them, an alkyl or alkenylbenzene sulfonate having an alkyl group having 7 to 18 carbon atoms or an alkenyl group, polyoxyethylene alkyl having 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 ether sulfate ester salts is preferred. These anionic surfactant salts are also preferably alkali metal salts, ethanolamine salts, or ammonium salts.

  In the present invention, it is preferable that the component (b1) and the component (b2) are used in combination as the component (b) from the viewpoint of good foaming during washing and good rinsing properties. In this case, the mass ratio of (b1) component / (b2) component is preferably 0.05 to 1, more preferably 0.1 to 0.8, and still more preferably 0.3 to 0.7.

  In addition, the content of the component (b) in the hydrophobic hard surface treating agent composition of the present invention is such that the detergency increases when the lower limit value is exceeded, and the effect of imparting adsorption residue and antifouling properties is enhanced below the upper limit value. From 0.5 to 30% by mass, preferably from 0.5 to 15% by mass, more preferably from 0.5 to 10% by mass, still more preferably from 0.5 to 5% by mass, and from 0.5 to 2% by mass. % Is even more preferred. In addition, about the anionic surfactant of (b) component, let the mass as a sodium salt be the mass of (b) component in a composition.

<Hydrophobic hard surface treatment composition>
The treating agent composition for hydrophobic hard surface of the present invention uses the component (a) and the component (b) in combination under predetermined conditions, so that in the rinsing step after being applied to the hydrophobic hard surface (a) It is presumed that the component and the component (b) form a complex and are adsorbed on the hydrophobic hard surface, thereby imparting high antifouling properties. Further, when used for cleaning a hydrophobic hard surface, a high detergency due to the component (b) is expressed.

  When the ratio A / B of the number of moles A of the cationic groups in the component (a) to the number of moles B of the anionic groups in the component (b) is equal to or higher than the lower limit, the detergency increases. Since the imparting effect is enhanced, A / B is 0.04 or more and 2 or less, preferably 0.1 or more and 2 or less, more preferably 0.3 or more and 2 or less, and more preferably 0.5 or more and 2 or less. Further preferred.

  The number of moles A is based on the total amount of the component (a) in the composition, the weight average molecular weight of the component (a), the mole percentage of the monomer unit having a cationic group in the component (a), and It can obtain | require by calculating from content in the composition of (a) component. Moreover, the number A of moles when a plurality of types of component (a) are used can be determined from the content in each composition, the weight average molecular weight, and the mol% of the monomer unit having a cationic group.

  The number of moles B is based on the total amount of component (b) in the composition, and is calculated by calculating from the weight average molecular weight of component (b) and the content of component (b) in the composition. I can do it. Moreover, the number of moles B in the case of using a plurality of types of component (b) can be determined from the content and weight average molecular weight in each composition.

  The processing agent composition for hydrophobic hard surfaces of the present invention can contain the following components in addition to the component (a) and the component (b).

<(C) component>
The hydrophobic hard surface treating agent composition of the present invention preferably contains water as the component (c). 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 component (c) is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more in the composition. It is still more preferable, and it is still more preferable that it is 80 mass% or more.

<(D) component>
Since the hydrophobic hard surface treating agent composition of the present invention is also suitable for cleaning a hydrophobic hard surface, it is possible to improve the cleaning power by containing a surfactant other than the component (b) as the component (d). From the point of view, it is preferable. Examples of the component (d) include one or more surfactants selected from nonionic surfactants, cationic surfactants, and amphoteric surfactants.

  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, and 10 to 10 carbon atoms. Polyoxyalkylene sorbitan fatty acid ester having 18 fatty acid groups, alkyl polyglycoside having an alkyl group having 8 to 18 carbon atoms, sucrose fatty acid ester having an aliphatic group having 8 to 18 carbon atoms, alkyl group having 8 to 18 carbon atoms And alkyl polyglyceryl ethers having Among these, from the viewpoint of detergency against oily dirt, polyoxyethylene alkyl ether having an alkyl group having 10 to 14 carbon atoms and an ethylene oxide average addition mole number of 5 to 20 is preferable, and from the viewpoint of foaming during use. Alkyl polyglycosides having an alkyl group of 8 to 18 carbon atoms and a sugar condensation degree of 1 to 3 are preferred.

  Preferred cationic surfactants from the viewpoint of improving detergency include alkyltrimethylammonium salts having 10 to 20 carbon atoms in the alkyl group, dialkyldimethylammonium salts having 6 to 14 carbon atoms in the alkyl group, and carbons in the alkyl group. Examples thereof include alkyl dimethyl benzyl ammonium salts and benzethonium salts having 6 to 18 numbers.

  Preferred amphoteric surfactants from the viewpoint of improving detergency include alkyldimethylamine oxide, fatty acid amidopropylamine oxide, alkyl-N, N-dimethylacetic acid betaine, fatty acid amidopropyl-N, N-dimethylacetic acid betaine, and alkyl-N. , N-dimethylethanesulfobetaine, fatty acid amidopropyl-N, N-dimethyl-2-hydroxypropylsulfobetaine, and betaines such as 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.

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

  (D) When containing one or more surfactants selected from nonionic surfactants and amphoteric surfactants as component, in order to increase the rinsing properties in the rinsing step after washing, the cation in component (a) The monomer unit having a functional group is preferably 20 to 90 mol%, more preferably 20 to 60 mol%, still more preferably 20 to 40 mol%, still more preferably 20 to 35 mol%.

  In addition, in the case of containing one or more surfactants selected from nonionic surfactants and amphoteric surfactants as component (d), in addition to imparting detergency and antifouling properties, rinsing in the rinsing step after washing It is desirable to increase the nature. In order to enhance rinsing properties, the monomer unit having a nonionic group in component (a) is preferably 10 to 80 mol%, more preferably 30 to 80 mol%, still more preferably 50 to 80 mol%, 70-80 mol% is still more preferable.

  The content of the component (d) in the hydrophobic hard surface treating agent composition of the present invention is preferably from 0.1 to 20% by mass, and from 0.5 to 10% by mass from the viewpoint of improving detergency. More preferably, it is 1 to 6% by mass, and further preferably 3 to 5% by mass.

  Moreover, since the antifouling property-improving effect is improved above the lower limit value and the cleaning power is increased below the upper limit value, the mass ratio of the content of the (b) component to the total content of the (b) component and the (d) component Is (b) / [(b) + (d)], preferably 0.05 or more, more preferably 0.05 to 0.9, and more preferably 0.1 to 0.5. Is more preferable, and it is still more preferable that it is 0.15-0.3.

<(E) component>
The hydrophobic 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, 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 (e) in the hydrophobic hard surface treating agent composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.2 to 7% by mass, and More preferably, it is 5-5 mass%. (E) When the content of the component is not less than the lower limit, the detergency is improved. When the content is not more than the upper limit, the storage stability at low temperature is excellent, and the detergency and sprayability using a spray-type container after storage at low temperature Can be compatible. 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 hydrophobic hard surface treating agent composition of the present invention preferably further contains an organic solvent as the component (f) from the viewpoint of maintaining the liquid property and improving the cleaning property of the treating agent composition.

  A variety of mono-, di- or tri-alkylene glycol ethers and mono-, di- or tri-alkylene glycol diethers are suitable for use as organic solvents, specifically mono-, di- or tri-alkylene ethers. -Ethylene glycol ethers and mono-, di- or tri-ethylene glycol diethers, and mono-, di- or tri-propylene glycol ethers and mono-, di- or tri-propylene glycol diethers are suitable. The alkyl group possessed by such glycol ether and glycol diether 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 4 to 14, more preferably 6 to 12, and even more preferably 8 to 10 carbon atoms in the entire compound.

  Preferred organic solvents for use include ethylene glycol mono-butyl ether, diethylene glycol mono-butyl ether, propylene glycol mono-butyl ether, dipropylene glycol mono-butyl ether, and dipropylene glycol mono-n-propyl ether.

  1-10 mass% is preferable, as for content of the (f) component in the processing agent composition for hydrophobic hard surfaces of this invention, 3-10 mass% is more preferable, and 5-9 mass% is still more preferable.

  Furthermore, the hydrophobic hard surface treating agent composition of the present invention includes an antiseptic, a hydrotrope, a dye, a viscosity modifier, an antioxidant, a fragrance, etc. within a range that does not impair the antifouling property and the cleaning performance. Can be blended.

  Moreover, the hydrophobic hard surface treating agent composition of the present invention preferably has a pH of 3 to 11 at 20 ° C. because the detergency is increased above the lower limit and the storage stability is excellent below the upper limit. It is more preferably 5 to 10, more preferably 6 to 9, and still more preferably 7 to 8. 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 treatment composition for hydrophobic hard surface of the present invention is intended for a hydrophobic hard surface, and the antifouling effect is expressed by modifying the hydrophobic surface to a hydrophilic surface. Estimated.

  The hydrophobic hard surface that is the target of the treatment composition for hydrophobic hard surface of the present invention preferably has a static contact angle with respect to ion-exchanged water of 50 ° or more, more preferably 60 ° or more, and 70 More preferably, the angle is more than 80 °, more preferably more than 80 °. Therefore, in the present invention, a hard surface satisfying this contact angle can be a hydrophobic hard surface.

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

  In kitchens and bathrooms, materials that give the above-mentioned 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, it is significant to impart antifouling properties to hydrophobic stains. . The treatment agent for hydrophobic hard surfaces of the present invention can impart excellent antifouling properties to the hydrophobic hard surfaces of kitchens and bathrooms, and is also excellent in cleanability. Accordingly, the hydrophobic hard surface treating agent composition of the present invention is preferably used for kitchens or bathrooms. 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. Among them, it is more preferably used as a hydrophobic hard surface cleaning composition for bathrooms.

  The hydrophobic hard surface treating agent composition of the present invention is preferably used as a spray-type hydrophobic hard surface treating agent article formed by filling a spray container. Such articles can also be used as spray-type hydrophobic hard surface cleaner articles and spray-type hydrophobic 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 lower position of 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 liquid and pulling the trigger again, the liquid in the cylinder is pushed out and led 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 hydrophobic hard surface treating agent composition of the present invention can impart good hydrophilicity to the 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 hard surface is treated (applied, rinsed) with the treating agent composition for hard surface of the present invention. It has been confirmed that the corners are remarkably reduced, and it is suggested that this hydrophilic effect exhibits a high antifouling property imparting effect.

  Hydrophobic soil solubilized by the treatment composition for hydrophobic hard surface of the present invention is removed from the hydrophobic hard surface in the rinsing step after washing, but has a cationic group as component (a). The polymer compound and the anionic surfactant of the component (b) can form a hydrophilic modification component and adsorb and remain on the hard surface, and can achieve both a cleaning effect and hydrophilic modification. The hydrophilization-modifying component comprising the component (a) and the component (b) is adsorbed and retained on the hard surface due to a coacervation phenomenon that is deposited in layers on the hard surface due to a decrease in hydration in the rinsing step. It is thought that it functions as a surface modifier. That is, the hydrophobic hard surface treating agent composition of the present invention is diluted with water in the rinsing step after washing so that the component (a) and the component (b) form a hydrophilic modification component, and the Solubility phenomenon reduces solubility and adsorbs on hard surface. From the viewpoint of enhancing the adsorption effect, a composition that produces turbidity when diluted with water is preferred. Moreover, when using as a spray article, in order to improve sprayability, it is preferable that it is transparent and uniform, and the composition which has the characteristic which becomes cloudy by water dilution is more preferable.

The treatment composition for hydrophobic hard surface of the present invention is a solution obtained by diluting the composition with water 20 times with respect to the turbidity T ₁ of the composition in order to improve the hydrophilic modification property of the hydrophobic hard surface. It is preferable that T ₂₀ / T _1, which is a ratio to the turbidity T ₂₀ , is 2 or more, more preferably 10 or more, and even more preferably 50 or more. When measuring turbidity, the insolubilized material may be separated. Therefore, 100 ml of the stock solution or 20-fold diluted solution of the composition is placed in a 200 ml beaker and used for 5 minutes at 25 ° C. and 150 rpm using a stirrer bar (8 mm × 20 mm). After stirring, the above T ₁ or T ₂₀ is measured within 3 minutes. It can be measured using a Haze Meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. as a turbidity meter.

It is assumed that the increase in turbidity is caused by the dispersion of insoluble components, and the insoluble dispersion causes clogging in the trigger during spraying. On the other hand, after diluting with water, a state in which insoluble components are precipitated is adsorbed and retained on the hydrophobic hard surface in view of function expression. In order to improve sprayability and detergency, the turbidity of the composition, that is, T ₁ is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less. On the other hand, in order to enhance the hydrophilic modification property of the hard surface, T ₂₀ is preferably 20 or more, more preferably 50 or more, and further preferably 100 or more.

The property that T ₂₀ / T ₁ is 2 or more can be imparted to the hydrophobic hard surface treating agent composition of the present invention by containing the component (a) and the component (b) at a specific ratio.

  Further, the hydrophobic hard surface treating agent composition of the present invention has a static contact angle of 60 ° or less with respect to ion-exchanged water of a treated PVC plate (manufactured by Engineering Test Service Co., Ltd.) measured by the method described in the Examples. From the viewpoint of imparting antifouling properties, it is preferably 50 ° or less, more preferably 45 ° or less, and even more preferably 40 ° 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 treatment composition for hydrophobic hard surface of the present invention, after applying to the hydrophobic hard surface, a coating film containing (a) component and (b) component is formed to coat the hard surface, It is estimated that the static contact angle of the PVC plate with respect to the ion exchange water can be set to 60 ° or less.

  The present invention includes a hydrophobic hard surface cleaning composition comprising the hydrophobic hard surface treatment composition of the present invention. That is, the present invention contains (a) component 0.05 to 10% by mass, and (b) component 0.5 to 30% by mass, and (a) the number of moles A of the cationic groups in component (b) ) It relates to a hydrophobic hard surface cleaning composition, wherein the ratio A / B with the number of moles B of anionic groups in the component is 0.04 or more and 2 or less. The preferable aspect of the cleaning composition for hydrophobic hard surfaces of the present invention can be selected from those described in the treatment composition for hydrophobic hard surfaces of the present invention. When used as a cleaning composition for hydrophobic hard surfaces, it is preferable to contain components (c) to (f).

  Moreover, this invention includes the modifier composition for hydrophobic hard surfaces which consists of the processing agent composition for hydrophobic hard surfaces of this invention. That is, the present invention contains (a) component 0.05 to 10% by mass, and (b) component 0.5 to 30% by mass, and (a) the number of moles A of the cationic groups in component (b) ) It relates to a hydrophobic hard surface modifier composition in which the ratio A / B with the number of moles B of anionic groups in the component is 0.04 or more and 2 or less. The preferable aspect of the modifier composition for hydrophobic hard surfaces of this invention can be selected from what was described in the processing agent composition for hydrophobic hard surfaces of this invention.

<How to use>
The treatment agent composition for hydrophobic hard surface of the present invention comprises a step of applying the composition to the hydrophobic hard surface, and a surface on which the composition of the hydrophobic hard surface is coated with water, preferably with a coating mass. It is preferable to use for the processing method of the hard surface which has a process of rinsing with 5 times or more of water. In addition, after the step of applying the hydrophobic hard surface treating agent composition of the present invention to the hydrophobic hard surface, a step of thinly spreading using a sponge or the like, followed by a step of rinsing with water is performed. More preferably it is used as a method. 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 known methods, but for application to a hydrophobic hard surface, the above-mentioned treatment agent for hydrophobic hard surface of the present invention is filled in a spray-type container as described above. It is preferable to use a spray-type hydrophobic hard surface treatment agent article. Further, the temperature of water used for rinsing after washing is preferably 5 to 50 ° C. in order to leave the hydrophilic modification component composed of the components (a) and (b) on the hydrophobic hard surface. -35 degreeC is more preferable.

<Aspect of the Present Invention>
Examples of the present invention are illustrated below.

[1-1] (a) In the molecule, the monomer unit having a cationic group is 20 to 100 mol%, the monomer unit having a nonionic group is 0 to 80 mol%, and the monomer unit having an anionic group is 0. Cationic polymer compound containing ˜40 mol%, wherein the molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group is 0.3 or less, and the weight average molecular weight is 1,000 to 300,000 [Hereinafter referred to as component (a)] 0.05 to 10% by mass, and (b) one or more anionic surfactants selected from the following components (b1) and (b2) [hereinafter referred to as component (b) Containing 0.5 to 30% by mass,
The ratio A / B between the number of moles A of the cationic group in the component (a) and the number of moles B of the anionic group in the component (b) is 0.04 or more and 2 or less.
Hydrophobic hard surface treatment composition.
(B1) component: an anionic surfactant (b2) component having a chain hydrocarbon group having 8 to 18 carbon atoms and a carboxylic acid group or a salt thereof; a chain hydrocarbon group having 7 to 18 carbon atoms and a sulfonic acid Anionic surfactant having one or more selected from a group, a sulfate group, a phosphate group, and a salt thereof

[1-2] (a) One or more compounds selected from a compound represented by formula (1) and a compound represented by formula (2), wherein the monomer unit having a cationic group as component (a) The hydrophobic hard surface treating agent composition according to [1-1], which is a structural unit obtained by polymerization.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom or a C1-C3 alkyl group. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - R 12 -OCO-R 13 - a group selected from. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, R ⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and Z ⁻ represents an anion. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]

[1-3] A monomer compound derived from a monomer unit having a cationic group is a diallyldialkylammonium salt having an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. -(Meth) acryloylaminoalkyl-N, N-dialkylamine, N- (meth) acryloylaminoalkyl-N, N, N-trialkylammonium salt in which the alkyl group has 1 to 5 carbon atoms, carbon of the alkyl group The N- (meth) acryloyloxyalkyl-N, N, N-trialkylammonium salt having 1 to 5 carbon atoms and the alkenyl group have 2 to 10 carbon atoms, and the alkyl group has 1 to 3 carbon atoms. The treatment composition for a hydrophobic hard surface according to the above [1-1] or [1-2], which is a compound selected from a certain N- (ω-alkenyl) -N, N-dialkylamine object.

[1-4] The component (a) contains a monomer unit having a cationic group in the molecule of 40 mol% or more, further 60 mol% or more, further 70 mol% or more, and further 90 mol% or more. Is contained in 40 to 100 mol%, further 60 to 100 mol%, further 70 to 100 mol%, and further 90 to 100 mol%, according to any one of the above [1-1] to [1-3]. Hydrophobic hard surface treatment composition.

[1-5] The molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group in the component (a), that is, the mole of [monomer unit having an anionic group / monomer unit having a cationic group]. The hydrophobic hard material according to any one of [1-1] to [1-4], wherein the ratio is 0.2 or less, further 0.15 or less, further 0.1 or less, further 0.02 or less, and further 0. Surface treating agent composition.

[1-6] The weight average molecular weight of the component (a) is 2,000 or more, further 3,000 or more, further 5,000 or more, 200,000 or less, further 150,000 or less, and further 100,000 or less. Further, 50,000 or less, further 10,000 or less, specifically, 2,000 to 200,000, further 3,000 to 150,000, further 5,000 to 100,000, further 5,000. The processing agent composition for hydrophobic hard surfaces according to any one of [1-1] to [1-5], which is ˜50,000, and further 5,000 to 10,000.

[1-7] The content of the component (a) in the composition is 0.05% by mass or more, further 0.08% by mass or more, further 0.1% by mass or more, 5% by mass or less, and further 2 .5% by mass or less, further 1% by mass or less, for example, 0.05 to 5% by mass, further 0.08 to 2.5% by mass, and further 0.1 to 1% by mass. 1]-[1-6] The hydrophobic hard surface treating agent composition according to any one of [1-6].

[1-8] Any one of [1-1] to [1-7] above, wherein the component (b1) is an anionic surfactant having 1 or 2 carboxylic acid groups or salts thereof. Treatment composition for hydrophobic hard surface.

[1-9] Hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-8], wherein the component (b1) is an anionic surfactant having a carboxylic acid group salt. object.

[1-10] The component (b2) is an anionic surfactant having one or more selected from sulfonic acid groups, sulfuric acid groups, phosphoric acid groups, and salts thereof, and one more. The treatment agent composition for hydrophobic hard surfaces according to any one of [1-1] to [1-9].

[1-11] [1-1] The component (b2) is an anionic surfactant having one or more selected from a sulfonic acid group salt, a sulfuric acid group salt, and a phosphoric acid group salt. -The processing agent composition for hydrophobic hard surfaces in any one of [1-10].

[1-12] (b1) a higher fatty acid salt having a chain hydrocarbon group having 8 to 18 carbon atoms, and (b2) an alkyl or alkenyl having an alkyl group or alkenyl group having 7 to 18 carbon atoms Selected from benzene sulfonate, polyoxyalkylene alkyl or alkenyl ether sulfate ester having an alkyl group or alkenyl group having 7 to 18 carbon atoms, alkyl or alkenyl sulfate ester salt having an alkyl group or alkenyl group having 7 to 18 carbon atoms The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-11], which is one or more of the above.

[1-13] As component (b), both component (b1) and component (b2) are contained, and component (b1) and component (b2) are further replaced by component (b1) / component (b2) = 0. 0.05 or more, further 0.1 or more, further 0.3 or more, 1 or less, further 0.8 or less, and further 0.7 or less, for example, 0.05 to 1, The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-12], which is contained in a mass ratio of 0.1 to 0.8, and further 0.3 to 0.7. .

[1-14] The content of the component (b) is 0.5% by mass or more, 15% by mass or less, further 10% by mass or less, further 5% by mass or less, and further 2% by mass or less in the composition. [1-1] to [1], for example, 0.5 to 15% by mass, further 0.5 to 10% by mass, further 0.5 to 5% by mass, and further 0.5 to 2% by mass. -13] The hydrophobic hard surface treating agent composition according to any one of [13].

[1-15] The ratio A / B between the number of moles A of the cationic group in the component (a) and the number of moles B of the anionic group in the component (b) is 0.1 or more, more preferably 0.3 or more. Further, the ratio is 0.5 or more and 2 or less. For example, the ratio is 0.1 or more and 2 or less, further 0.3 or more and 2 or less, and further 0.5 or more and 2 or less. -1] to [1-14] The hydrophobic hard surface treatment agent composition according to any one of [1-14].

[1-16] Water is contained as component (c), and the content of component (c) is 50% by mass or more, further 60% by mass or more, further 70% by mass or more, and further 80% by mass in the composition. The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-15], which is described above.

[1-17] Surfactant other than component (b) as component (d), one or more surfactants selected from nonionic surfactants, cationic surfactants and amphoteric surfactants, and nonion The hydrophobic hard surface treatment agent composition according to any one of [1-1] to [1-16], which contains one or more surfactants selected from surfactants and amphoteric surfactants.

[1-18] As component (d), one or more surfactants selected from nonionic surfactants and amphoteric surfactants are contained, and the monomer unit having a cationic group in component (a) is 20 mol%. Or more, 90 mol% or less, further 60 mol% or less, further 40 mol% or less, further 35 mol% or less, for example, 20 to 90 mol%, further 20 to 60 mol%, further 20 to 40 mol% Furthermore, the treatment agent composition for hydrophobic hard surfaces according to the above [1-17], which is further 20 to 35 mol%.

[1-19] (d) One or more surfactants selected from nonionic surfactants and amphoteric surfactants are contained as component, and the monomer unit having a nonionic group in component (a) is 10 mol%. Or more, further 30 mol% or more, further 50 mol% or more, further 70 mol% or more, and 80 mol% or less, for example, 10 to 80 mol%, further 30 to 80 mol%, further 50 to 80 mol% Furthermore, it is 70-80 mol%, The processing agent composition for hydrophobic hard surfaces of the said [1-17] or [1-18] description.

[1-20] The content of the component (d) in the composition is 0.1% by mass or more, further 0.5% by mass or more, further 1% by mass or more, further 3% by mass or more, and 20% by mass. Hereinafter, it is further 10% by mass or less, further 6% by mass or less, and further 5% by mass or less, for example, 0.1 to 20% by mass, further 0.5 to 10% by mass, further 1 to 6% by mass, and further 3 The treatment composition for hydrophobic hard surfaces according to any one of [1-17] to [1-19], which is ˜5 mass%.

[1-21] The mass ratio of the content of the component (b) to the total content of the component (b) and the component (d) is 0.05 or more in (b) / [(b) + (d)], Furthermore, it is 0.1 or more, further 0.15 or more, 0.9 or less, further 0.5 or less, and further 0.3 or less, for example, 0.05 to 0.9, further 0.1 to 0. 5, Furthermore, it is 0.15-0.3, The processing agent composition for hydrophobic hard surfaces in any one of said [1-17]-[1-20].

[1-22] A chelating agent is contained as the component (e), and the content of the component (e) is 0.01% by mass or more, further 0.2% by mass or more, and further 0.5% by mass in the composition. % Or more, 10 mass% or less, further 7 mass% or less, further 5 mass% or less, for example, 0.01 to 10 mass%, further 0.2 to 7 mass%, further 0.5 to 5 mass % [1-1] to [1-21], the treatment composition for a hydrophobic hard surface according to any one of the above.

[1-23] An organic solvent is contained as the component (f), and the content of the component (f) in the composition is 1% by mass or more, further 3% by mass or more, further 5% by mass or more, and 10%. Any one of the above [1-1] to [1-22], which is not more than mass%, further not more than 9 mass%, for example, 1 to 10 mass%, further 3 to 10 mass%, and further 5 to 9 mass%. The treatment composition for hydrophobic hard surfaces as described above.

[1-24] The pH at 20 ° C. is 3 or more, 5 or more, 6 or more, 7 or more, 11 or less, 10 or less, 9 or less, or 8 or less, for example, 3 to 11, The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-23], further 5 to 10, further 6 to 9, and further 7 to 8.

[1-25] The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-24], which is used for a kitchen or a bathroom.

[1-26] The above-mentioned [1-1] to [1-] for a hydrophobic hard surface having a static contact angle with respect to ion-exchanged water of 50 ° or more, further 60 ° or more, further 70 ° or more, and further 80 ° or more. 25] The hydrophobic hard surface treating agent composition according to any one of [25].

[1-27] The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-26], wherein the turbidity T ₁ is 10 or less, 8 or less, or 5 or less.

[1-28] The ratio according to any one of [1-1] to [1-27] above, wherein T ₂₀ / T ₁ which is a ratio to turbidity T ₂₀ is 2 or more, further 10 or more, and further 50 or more. Hydrophobic hard surface treatment composition.

[2-1] Spray-type hydrophobic hard surface cleaning article, which is obtained by filling a spray-type container with the hydrophobic hard surface treatment composition according to any one of [1-1] to [1-28]. .

[2-2] The cleaning article for a hydrophobic hydrophobic hard surface according to [2-1], wherein the spray container is a spray container equipped with a trigger sprayer.

[3-1] (a) Component 0.05 to 10% by mass, (b) Component 0.5 to 30% by mass, (a) Number of moles A of the cationic group in component and (b) The detergent composition for hydrophobic hard surfaces whose ratio A / B with the number of moles B of the anionic group in a component is 0.04 or more and 2 or less.

[4-1] (a) 0.05 to 10% by mass of component, and (b) 0.5 to 30% by mass of component, and (a) the number of moles A of the cationic groups in component and (b) The modifier composition for hydrophobic hard surfaces whose ratio A / B with the number of moles B of the anionic group in a component is 0.04 or more and 2 or less.

[5-1] A step of applying the hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-28] to a hydrophobic hard surface, and a composition of the hydrophobic hard surface A method for treating a hydrophobic hard surface, comprising rinsing a surface on which an object is applied with water having a mass of 5 times or more, further 20 times or more, and even 50 times or more the coating mass.

[6-1] The hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-28] is applied to a hydrophobic hard surface to improve the hydrophilicity of the hydrophobic hard surface. How to make.

[7-1] After applying the hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-28] to the hydrophobic hard surface to which dirt has adhered, water, preferably By rinsing with water having a mass of 5 times or more, further 20 times or more, and even 50 times or more the appropriate amount of the composition, removal of dirt from the hydrophobic hard surface and hydrophilicity to the hydrophobic hard surface A method for treating a hydrophobic hard surface, both of which is applied.

[8-1] A method for treating a hydrophobic hard surface using the hydrophobic hard surface treating agent composition according to any one of [1-1] to [1-28], wherein the composition is cloudy The degree is 10 or less, and after applying the composition to a hydrophobic hard surface to which dirt is attached, water, preferably 5 times or more, more preferably 20 times or more, and further 50 times or more of the appropriate amount of the composition. A method for treating a hydrophobic hard surface, wherein both removal of dirt from the hydrophobic hard surface and imparting hydrophilicity to the hydrophobic hard surface are performed by rinsing with water having a mass of This turbidity is T ₁ described above.

[9-1] A cleaning composition for a hydrophobic hard surface, comprising the hydrophobic hard surface treatment composition according to any one of [1-1] to [1-28].

<Examples and Comparative Examples>
The processing agent composition for hydrophobic hard surfaces of Tables 1-3 was prepared. Table 3 shows compositions with further enhanced detergency, and the compositions in Table 3 are more suitable as hydrophobic hard surface detergent compositions. The pH (20 ° C.) of each composition was adjusted to 8 with sodium hydroxide and hydrochloric acid. About these compositions, the following item was evaluated. Details are shown below. In the table, Mw is the weight average molecular weight, and EOp is the average added mole number of ethylene oxide.

<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.

<Dirt residual rate>
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 board after immersion was rinsed with tap water (50 mL / second) at 25 ° C. for 10 seconds each on the front and back sides, and after drying, the mass was measured to determine the amount of residual sebum. In the composition of each composition, the amount of sebum remaining on the surface of the PVC plate treated with the composition not containing component (a) [replacement of component (a) with ion-exchanged water] is defined as 100%, and the corresponding composition The ratio of the amount of sebum remaining on the surface of the PVC plate treated with the product was calculated.
* 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.

<Appearance>
The stock solution, the 2-fold diluted solution, the 5-fold diluted solution, and the 20-fold diluted solution of the hard surface treating agent composition were visually observed to evaluate the compatibility. Ion exchange water at 25 ° C. was used for dilution of the composition.
Transparent: No precipitate or turbidity occurred, and it dissolved transparently.
Cloudiness: Precipitation and turbidity occurred.

<Cleanability>
0.05 mL of the hard surface treating agent composition was applied to a bathroom chair used for one month in a general household and allowed to stand at room temperature for a certain time (5 minutes or 10 minutes). Thereafter, it was washed off with water, and the stain was visually judged according to the following criteria.
A: Dirt is removed cleanly by standing for 5 minutes.
◯: Dirt does not fall cleanly after standing for 5 minutes, but cleanly falls after standing for 10 minutes.
X: Dirt does not come off cleanly after standing for 10 minutes.

* 1 Ratio A / B between the number of moles A of the cationic group in component (a) and the number of moles B of the anionic group in component (b), and the value using the number of anionic groups in component (b ′) Are shown in parentheses as reference values (the same applies to Table 2).

From the results of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-6, it can be seen that the inclusion of the component (a) and the component (b) is excellent in antifouling property.
Further, from the results of Examples 1-1 to 1-5 and Comparative Examples 1-7 to 1-12, the component (a) contains the component (b), and the A / B ratio is within the scope of the present invention. When it exists, it turns out that it is excellent in the antifouling property provision effect.

From the results of Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-4 and 2-11, by containing the component (a) and the component (b), the effect of imparting antifouling properties is excellent. I understand that.
Moreover, from the results of Examples 2-1 to 2-8 and Comparative Examples 2-5 to 2-10, the component (a) contains the component (b), and the A / B ratio is within the scope of the present invention. When it exists, it turns out that it is excellent in the antifouling property provision effect.

* 2 Ratio A / B between the number of moles A of the cationic group in the component (a) and the number of moles B of the anionic group in the component (b), and the value using the number of cationic groups in the component (a ′) Are shown in parentheses as reference values.

The components in Table 3 are as follows.
Polymer 1: Polymethacryloyloxyethyltrimethylammonium chloride [Mw = 8,000, molar ratio of monomer unit having an anionic group to monomer unit having a cationic group (hereinafter referred to as a molar ratio of an anionic monomer unit) 0 ]
Polymer 2: copolymer of methacryloyloxyethyltrimethylammonium chloride / acrylamide = 60/40 (molar ratio) (Mw = 7,000, molar ratio of anionic monomer unit 0)
Polymer 3: methacryloyloxyethyltrimethylammonium chloride / styrene = 70/30 (molar ratio) copolymer (Mw = 10,000, anionic monomer unit molar ratio 0)
Polymer 4: copolymer of methacryloyloxyethyltrimethylammonium chloride / methyl methacrylate = 80/20 (molar ratio) (Mw = 6,000, molar ratio of anionic monomer unit 0)
Polymer 5: copolymer of diallyldimethylammonium chloride / acrylamide = 24/76 (molar ratio) (Mw = 120,000, molar ratio of anionic monomer unit 0)

Polymer 6: methacryloyloxyethyltrimethylammonium chloride / acrylamido-2-methylpropanesulfonic acid sodium salt / butyl methacrylate = 45/45/10 (molar ratio) copolymer (Mw = 7,000, anionic monomer) Unit molar ratio 1.22)

  The average molecular weight of polyoxyethylene alkyl (carbon number 12) ether sulfate sodium salt (EOp4.0) is 466.2, and the average molecular weight of alkyl (carbon number 10-14) sodium benzenesulfonate is 342.8. .

  From the results of Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-4, by combining the component (a) and the component (b) of the present invention, the antifouling property is excellent, and It turns out that the modifier composition for hard surfaces excellent also in the washing | cleaning performance is obtained. In addition, in the compositions of the examples, a phenomenon of white turbidity was observed by dilution with water, particularly 5 times dilution and 20 times dilution, suggesting adsorption of the hydrophilization modifying component to the hydrophobic hard surface in the rinsing step. .

Claims (10)

(A) 20 to 100 mol% of a monomer unit having a cationic group, 0 to 80 mol% of a monomer unit having a nonionic group, and 0 to 40 mol% of a monomer unit having an anionic group in the molecule And a cationic polymer compound wherein the molar ratio of the monomer unit having an anionic group to the monomer unit having a cationic group is 0.3 or less and the weight average molecular weight is 1,000 to 300,000 [hereinafter, (a ) Component] 0.05 to 10% by mass, and (b) one or more anionic surfactants selected from the following components (b1) and (b2) [hereinafter referred to as component (b)] 0.5 Contains ~ 30% by weight,
The ratio A / B between the number of moles A of the cationic group in the component (a) and the number of moles B of the anionic group in the component (b) is 0.04 or more and 2 or less.
Hydrophobic hard surface treatment composition.
(B1) component: an anionic surfactant (b2) component having a chain hydrocarbon group having 8 to 18 carbon atoms and a carboxylic acid group or a salt thereof; a chain hydrocarbon group having 7 to 18 carbon atoms and a sulfonic acid Anionic surfactant having one or more selected from a group, a sulfate group, a phosphate group, and a salt thereof The monomer unit (a) having a cationic group is obtained by polymerizing one or more compounds selected from the compound represented by the general formula (1) and the compound represented by the general formula (2). The processing agent composition for hydrophobic hard surfaces according to claim 1, which is a structural unit.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom or a C1-C3 alkyl group. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - R 12 -OCO-R 13 - a group selected from. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, R ⁶ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and Z ⁻ represents an anion. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]   (B1) a higher fatty acid salt having a chain hydrocarbon group having 8 to 18 carbon atoms, and (b2) an alkyl or alkenylbenzene sulfonate having an alkyl group or alkenyl group having 7 to 18 carbon atoms, One or more selected from polyoxyalkylene alkyl or alkenyl ether sulfates having an alkyl group or alkenyl group having 7 to 18 carbon atoms, and alkyls or alkenyl sulfates having an alkyl group or alkenyl group having 7 to 18 carbon atoms The treatment composition for hydrophobic hard surfaces according to any one of claims 1 and 2.   The treatment composition for hydrophobic hard surfaces according to any one of claims 1 to 3, which is used for kitchens or bathrooms.   A cleaning article for a hydrophobic hydrophobic hard surface, comprising a spray-type container filled with the treatment composition for hydrophobic hard surface according to any one of claims 1 to 4.   The process of apply | coating the processing agent composition for hydrophobic hard surfaces in any one of Claims 1-4 to a hydrophobic hard surface, and the surface by which the composition of this hydrophobic hard surface was apply | coated is applied mass. A method for treating a hydrophobic hard surface, comprising a step of rinsing with water having a mass 5 times or more of water.   A method for improving the hydrophilicity of the hydrophobic hard surface by applying the treatment composition for hydrophobic hard surface according to any one of claims 1 to 4 to the hydrophobic hard surface.   After applying the treatment composition for hydrophobic hard surface according to any one of claims 1 to 4 to the hydrophobic hard surface to which dirt has adhered, the dirt from the hydrophobic hard surface is obtained by rinsing with water. A method for treating a hydrophobic hard surface, wherein both removal of water and imparting hydrophilicity to the hydrophobic hard surface are performed.   A method for treating a hydrophobic hard surface using the hydrophobic hard surface treating agent composition according to any one of claims 1 to 4, wherein the turbidity of the composition is 10 or less, and the composition Is applied to a hydrophobic hard surface with dirt attached thereto, and then rinsed with water to both remove the soil from the hydrophobic hard surface and impart hydrophilicity to the hydrophobic hard surface. Hard surface treatment method.   The cleaning composition for hydrophobic hard surfaces which consists of the processing agent composition for hydrophobic hard surfaces in any one of Claims 1-4.