JP5924835B2 - Cleaning composition for hard surface - Google Patents

Description

  The present invention relates to a cleaning composition, and more particularly to a hard surface cleaning composition having good antifouling properties.

  In general households, kitchen fan, gas range, bath tub, toilet, dishes, vehicles, buildings, etc. are made of hard materials such as metal, plastic, glass, ceramics, concrete. Various stains adhere to these hard surfaces due to wind and rain, foods, effluents, oils, exhaust gases, and the like, and various cleaning agents are used to remove these stains. The main purpose of the cleaning agent is to remove dirt, but in recent years, the effect of preventing the reattachment of dirt (antifouling effect) has been attracting attention as an important effect in order to reduce the number of washings.

  In order to prevent the reattachment of dirt after cleaning, a cleaning agent in which a polymer, a fluorine compound, or the like is blended with the cleaning agent is known. For example, Patent Document 1 includes (a) one or more surfactants selected from nonionic surfactants and amphoteric surfactants, and (b) a monomer unit having a quaternary ammonium group or a tertiary amino group. Disclosed is a hard surface cleaning composition containing a polymer containing a weight ratio of (a) / (b) = 1/10 to 50/1. Patent Document 2 discloses that in a method of using a water-soluble or water-dispersible copolymer for imparting hydrophilicity to a hard surface, (a) a quaternary ammonium group and an ethylenic group in the form of polymerized units. A monomer compound having two saturated groups, (b) at least one hydrophilic monomer copolymerizable with (a) and capable of being ionized in the application medium, (c) ethylene At least one optional component containing a photo-unsaturated group, having a neutral charge, having one or more hydrophilic groups and copolymerizable with (a) and (b) A method of using a water-soluble or water-dispersible polymer comprising a hydrophilic monomer compound and having a (a) / (b) molar ratio of 60/40 to 5/95 is disclosed. Furthermore, Patent Document 3 discloses that liquid petroleum hydrocarbons having a boiling point at a pressure of 0.1 MPa of 150 ° C. or higher and a flash point of 40 ° C. or higher at a pressure of 0.1 MPa; 3 to 30% by weight of a metal oxide; 0.1 to 3% by weight of an anionic surfactant; 0.5 to 10% by weight of a nonionic surfactant; 0.1 to 4% by weight of an amphoteric acrylic polymer and 30 to 30% of water A resin surface cleaning agent containing 70% by mass is disclosed. Patent Document 4 discloses a water-repellent treatment composition that is used by impregnating a fabric containing ultrafine fibers as a constituent component when used, and includes the following (A) and (B): Water repellent treatment composition: (A) Fluorine alkoxysilane: 0.05 to 10% by mass, (B) Catalyst: 0.01 to 5% by mass (in the case of acid catalyst or base catalyst, monovalent conversion) (invoice) Item (1); Further, (C) the water-repellent treatment composition for glass containing the insoluble fine powder (claim 2) is disclosed.

JP 2002-146395 A Special table 2003-505535 gazette JP 2008-169361 A JP 2010-138210 A

  However, the cleaning agent containing the polymer as described above is excellent in the effect of preventing the reattachment of lipophilic soil such as oil because the surface to be cleaned is modified to be hydrophilic (oil repellent), The effect of preventing the re-deposition of hydrophilic soil was not so high. Similarly, when the surface to be cleaned is modified to be oleophilic (water repellent), the effect of preventing the reattachment of hydrophilic dirt is excellent, but the effect of preventing the reattachment of lipophilic dirt such as oil is not high. It was. Further, in Patent Document 4, since the surface to be cleaned is treated with water repellency, the effect of preventing the reattachment of hydrophilic dirt is not high, and when an insoluble fine powder is used as a cleaning agent, the fine powder flows down by rinsing. A continuous antifouling effect was not obtained.

  As described above, there are two types of stains, such as oil and other lipophilic stains, and water and other hydrophilic stains.If the surface to be cleaned is water-repellent, hydrophilic stains are difficult to adhere. Dirt becomes easy to adhere. Conversely, if the surface to be cleaned is oil-repellent, lipophilic stains are difficult to adhere, but hydrophilic stains tend to adhere. For these reasons, it can be easily imagined that if the surface to be cleaned can be made water- and oil-repellent at the same time, a great effect can be obtained in preventing the reattachment of dirt, but this is not the case with conventional cleaning compositions. It has been very difficult to balance performance.

  Accordingly, the problem to be solved by the present invention is to provide a hard surface that effectively prevents the reattachment of dirt by simultaneously making the surface to be cleaned water and oil repellent while maintaining the function as a cleaning composition. It is in providing the cleaning composition for water.

Accordingly, the present inventors have intensively studied, and have found a cleaning composition capable of making the surface to be cleaned after being cleaned have water repellency and oil repellency, leading to the present invention.
That is, the present invention is a fluorine compound having one or more groups selected from cationic groups, zwitterionic group and a silyl group (A), full Tsu atom having no surfactant (B) and amino-modified silicone compounds It is a hard surface cleaning composition containing (C) .

  ADVANTAGE OF THE INVENTION According to this invention, the to-be-washed | cleaned surface after washing | cleaning can be made water-repellent and oil-repellent simultaneously, and the cleaning composition for hard surfaces which prevents the reattachment of a stain | pollution | contamination effectively can be provided.

The fluorine compound (A) of the present invention is not particularly limited as long as it is a compound having one or more groups selected from a cationic group, a zwitterionic group and a silyl group, but the following general formula (1) A compound represented by:
R _f − (X) _n −Y (1)
(In the formula, R _f represents a C 3-20 perfluoroalkyl group, and X represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a sulfoamide having 1 to 5 carbon atoms. Any group selected from the group consisting of an alkylene group, a carbonyl group, an alkylenesulfamidoalkylene group having 2 to 8 carbon atoms, an alkyleneoxyalkylene group having 2 to 10 carbon atoms and an alkylenethioalkylene group having 2 to 10 carbon atoms Y represents any group selected from a cationic group, a zwitterionic group, and a silyl group, and n represents a number of 0 or 1.)

The compound represented by the general formula (1) is a compound in which a perfluoroalkyl group represented by R _f and a cation group represented by Y are bonded by X which is a bonding group. X may not be present (in the case of n = 0), and in that case, a compound in which R _f and Y are directly bonded is obtained.

R _f represents a C 3-20 perfluoroalkyl group, and the aliphatic chain may be linear, branched or cyclic, but is preferably a linear perfluoroalkyl group because it can be easily obtained. . Moreover, although carbon number is 3-20, since the effect of reattachment prevention is high, it is preferable that carbon number is 4-12. When the number of carbon atoms is less than 3 or higher than 20, the structural balance between R _f and Y is lost, and a sufficient effect of preventing reattachment of dirt may not be obtained.

Y represents any group selected from a cationic group, a zwitterionic group and a silyl group. The cationic group is not particularly specified as long as it is a quaternary ammonium group, but preferably has a structure represented by the following general formula (2) because it is excellent in the effect of preventing redeposition of dirt.

R ^{1 to} R ^{3 in} the general formula (2) are each an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. Is mentioned. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

Z represents a halogen atom, and examples thereof include a chloro atom, a bromine atom, and an iodine atom. Among these, a chloro atom and a bromine atom are preferable, and a chloro atom is more preferable. Z ⁻ is a counter ion of a quaternary amine.

  Examples of the zwitterionic group include a betaine group, a sulfobetaine group, and an amine oxide group. Among these, a betaine group and an amine oxide group are preferred because they are excellent in the effect of preventing the reattachment of dirt. In addition, although amine oxide may be classified into nonion (neutral), it is classified as a zwitterionic group in the present invention.

Examples of the silyl group include a trialkylsilyl group, a dialkylmonoalkoxysilyl group, a monoalkyldialkoxysilyl group, and a trialkoxysilyl group. Among these, trialkoxysilyl groups are preferable, and trialkoxysilyl groups represented by the following general formula (3) are more preferable:

R ^{4 to} R ^{6 in} the general formula (3) are each an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. Can be mentioned. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

X is a group for bonding R _f and Y, and is selected from an alkylene group, an arylene group, a sulfoamidoalkylene group, a carbonyl group, an alkylenesulfamidoalkylene group, an alkyleneoxyalkylene group, and an alkylenethioalkylene group. . All of the above groups have 1 to 10 carbon atoms, and if the number of carbon atoms is larger than 10, the molecular weight of the linking group becomes too large, and the effect obtained from R _f and Y becomes relatively small. In some cases, the effect of preventing the re-adhesion of dirt is not obtained. Further, X is a group having a role as a linking group, so it does not have to be as long as R _f and Y can be directly bonded.

(B) component of this invention is a surfactant which does not have a fluorine atom, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant are mentioned. Among these, anionic surfactants and nonionic surfactants are preferable because of good detergency, and anionic surfactants are more preferable because of particularly good detergency.
Examples of the anionic surfactant include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, higher alkyl sulfonates, α-olefin sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, and phosphate ester salts. , Fatty acid ester sulfate ester salt, glyceride sulfate ester salt, fatty acid ester sulfonate salt, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxyalkylene Alkyl ether carboxylate, acylated peptide, sulfate ester salt of fatty acid alkanolamide or its alkylene oxide adduct, sulfosuccinate ester, alkylbenzene sulfonate, alkyl naphthalene sulfonate Salt, alkylbenzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N-acyl-N-methyltaurine salt, N-acyl glutamic acid or salt thereof, acyloxyethane sulfonate, alkoxyethane sulfonate, N-acyl -Β-alanine or salt thereof, N-acyl-N-carboxyethyltaurine or salt thereof, N-acyl-N-carboxymethylglycine or salt thereof, acyl lactate, N-acyl sarcosine salt, and alkyl or alkenylaminocarboxy One type or a mixture of two or more types such as methyl sulfate can be mentioned.

  Nonionic surfactants include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether (addition form of ethylene oxide and propylene oxide may be random or block) .), Polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid ester or ethylene oxide adduct thereof, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or ethylene oxide thereof Adduct, fatty acid-N-methylmonoethanolamide or its ethylene oxide adduct, fatty acid dietano Examples thereof include amide or its adduct, sucrose fatty acid ester, alkyl (poly) glycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl ester ethoxylate, N-long chain alkyldimethylamine oxide, and the like. .

  Examples of the cationic surfactant include alkyl (alkenyl) trimethyl ammonium salt, dialkyl (alkenyl) dimethyl ammonium salt, alkyl (alkenyl) quaternary ammonium salt, mono- or dialkyl (alkenyl) containing ether group, ester group or amide group. ) Quaternary ammonium salt, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzyl ammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (alkenyl) amine, alkyl (alkenyl) amine Examples thereof include salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride.

  Examples of amphoteric surfactants include carboxybetaine, sulfobetaine, phosphobetaine, amide amino acids, imidazolinium betaine surfactants, and the like.

  The hard surface cleaning composition of the present invention can provide a certain effect if it contains the above components (A) and (B), but it is preferable to add amino-modified silicone as the component (C). By adding the component (C), the water repellency can be further improved without degrading the oil repellency, and the effect of preventing the reattachment of dirt is improved.

（式中、Ａは、−Ｒ^７ＮＨ_２または−Ｒ^８ＮＨＲ^９ＮＨ_２のいずれかの基を表し、ｑは１〜１００の数を表し、ｒは１〜１００の数を表し、Ｒ^７〜Ｒ^９はそれぞれ炭素数１〜６のアルキレン基を表す。） The amino-modified silicone is not particularly limited as long as the methyl group in the silicone molecule is substituted with an amino group or a group containing an amino group, but is represented by the following general formula (4) because of its good water-repellent effect. Amino-modified silicones are preferred:

(In the formula, A represents a group of -R ⁷ NH ₂ or -R ⁸ NHR ⁹ NH ₂ , q represents a number of 1 to 100, r represents a number of 1 to 100, and R ⁷ to R ⁹ each represents an alkylene group having 1 to 6 carbon atoms.)

R ^{7 to} R ⁹ all represent an alkylene group having 1 to 4 carbon atoms. Examples of such a group include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, Examples thereof include an isopentylene group, a hexylene group, and an isohexylene group. Among these, a methylene group, an ethylene group, and a propylene group are preferable.

  q and r each represent a number of 1 to 100, but the total amount of q and r is preferably 2 to 150, and more preferably 2 to 100. If the total amount of q and r exceeds 200, the viscosity of the amino-modified silicone may increase and handling may be difficult, or precipitation may occur in the cleaning composition. In addition, although the compound of General formula (4) looks like a block copolymer on a display, either a block copolymer or a random copolymer may be sufficient.

  A in the amino-modified silicone is determined by the number of r. The amount of A is not particularly defined, but since it is effective for improving water repellency, the mass of amino-modified silicone (A equivalent) per mole of A is preferably 300 to 50000 g / mol, and 300 to 10000 g. / Mol is more preferable, and 300 to 3000 g / mol is still more preferable. When the equivalent of A is smaller than 300 g / mol or larger than 50000 g / mol, the water repellency improving effect may not be obtained, which is not preferable.

  Although the compounding quantity of the said (A) component and (B) component in the cleaning composition for hard surfaces of this invention is not specifically limited, Since a high effect can be expected, it is 1 mass part of (A) component. On the other hand, the component (B) is preferably 0.1 to 20000 parts by mass, more preferably 1 to 5000 parts by mass, still more preferably 10 to 1000 parts by mass, and most preferably 30 to 300 parts by mass. When the component (B) is less than 0.1 parts by mass or more than 20000 parts by mass, the cleaning property is inferior, the antifouling film formed on the hard surface after cleaning is inferior in uniformity, or the There is a case where the durability of the dirty film is inferior. If the antifouling film is inferior in uniformity, dirt is likely to be reattached, and if it is inferior in durability, the effect of preventing reattachment is not sustained.

  Even when the component (C) is added, the blending amount is not particularly limited, but since a high effect can be expected, the component (C) is 0.001 to 1000 parts per 1 part by mass of the component (A). It is preferable that it is a mass part, 0.01-100 mass parts is more preferable, 0.1-10 mass parts is still more preferable. When the component (C) is less than 0.001 part by mass or more than 1000 parts by mass, the effect of further improving the water repellency may not be obtained.

  When the hard surface cleaning composition of the present invention is actually used, its method of use is not particularly limited. Usually, however, the stock solution or a solution obtained by diluting the stock solution with water is directly sprayed onto the hard surface. And a method of washing a stock solution or a solution obtained by diluting the stock solution with water using a sponge or the like. In these uses, if the viscosity of the hard surface cleaning composition of the present invention is too high, it is difficult to spray or take out from the container. Therefore, it is preferably diluted with water so as to have a constant viscosity. . Further, it is troublesome to use the detergent composition for hard surface of the present invention diluted with water after further diluting with water, and at a concentration that is too high or too low, an antifouling film is used. It may be inferior in uniformity and sustainability. Therefore, the component (A) is preferably 0.001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the hard surface cleaning composition of the present invention containing water. 0.005 to 0.5 mass% is more preferable, and 0.01 to 0.1 mass% is most preferable. Similarly, the component (B) is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass. Moreover, if adding (C) component, 0.001-1 mass% is similarly preferable, 0.005-0.5 mass% is more preferable, 0.01-0.1 mass% is still more preferable. By using aqueous solutions having these preferable concentrations, it is possible to directly clean the hard surface with a cleaning agent having the most effective concentration without further diluting with water.

In order to improve the cleaning effect, it is preferable to add an alkali agent, a monohydric alcohol having 4 or less carbon atoms, or a glycol solvent to the hard surface cleaning composition of the present invention.
Examples of the alkali agent include strong alkalis such as sodium hydroxide and potassium hydroxide; weak alkalis such as monoethanolamine, diethanolamine, triethanolamine and ammonia. Among these, strong alkali is preferable because of its high cleaning effect. The alkali agent is preferably added in an amount of 1 to 20% by mass, more preferably 3 to 15% by mass, based on the total amount of the composition. The alkaline agent has an effect of further improving the cleaning property.

  Examples of the monohydric alcohol having 4 or less carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, and tertiary butanol. Examples of glycol solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol. Monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, (mono, di, tri) ethylene glycol (mono, di, tri) propylene glycol monomethyl ether, (mono, Di, tri) ethylene glycol (mono, di) Tri) propylene glycol monoethyl ether, (mono, di, tri) ethylene glycol (mono, di, tri) propylene glycol monopropyl ether, (mono, di, tri) ethylene glycol (mono, di, tri) propylene glycol monobutyl ether Etc. These monohydric alcohols having 4 or less carbon atoms and glycol solvents are preferably added in an amount of 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the total amount of the composition. The above solvent has an effect of further improving the uniformity of the antifouling film.

In addition, the hard surface cleaning composition of the present invention can be blended with other components such as a chelating agent, a builder, an antiseptic, a coloring matter, and a fragrance as long as the effects of the present invention are not impaired.

Hereinafter, the present invention will be described more specifically with reference to examples.
1. Test Method <Test 1: Water and Oil Repellency Confirmation Test>
One side of a test piece (2 × 5 cm) of a stainless steel plate is scrubbed 5 times with a sponge sufficiently impregnated with the liquid detergent composition of the present invention and comparative product described later, rinsed with running water for 30 seconds, and then dried. It was. Then, using a contact angle meter (FACE Contact Angle Meter, manufactured by Kyowa Interface Science Co., Ltd.), the contact angle on the test piece of ion-exchanged water and hexadecane was measured at 10 points, and the average values were made water and oil repellency. . The greater the contact angle of ion exchange water, the better the water repellency, and the greater the contact angle of hexadecane, the better the oil repellency. The obtained results are shown in Table 1 (Product of the present invention) and Table 2 (Comparative product).

<Test 2: Detergency test>
Soybean oil was uniformly applied on one side of a test piece (10 × 5 cm) of a stainless steel plate so as to be 0.1 ± 0.01 g, and left at room temperature for 1 day. This stainless steel plate was immersed in 10 ml of the liquid detergent composition of the present invention and comparative product described later, and left for 10 minutes. Thereafter, it was rinsed with running water for 30 seconds and then dried, and the washing rate was calculated by the following formula from the change in weight before and after washing.
Washing rate (%) = [(mass of stainless steel plate after applying soybean oil and leaving it to stand) − (mass of stainless steel plate after washing) / actual mass of applied soybean oil] × 100
The obtained results are shown in Table 1 (Product of the present invention) and Table 2 (Comparative product).

<Test 3: Anti-reattachment test>
One side of a test piece (15 × 15 cm) of a stainless steel plate is scrubbed 5 times with a sponge sufficiently impregnated with the liquid detergent composition of the present invention and a comparative product to be described later, rinsed with running water for 30 seconds, and then dried. I let you. Thereafter, 2 ml of soybean oil was uniformly applied to the test piece, baked in an oven at 200 ° C. for 30 minutes, and then rubbed 5 times with a sponge. The surface condition of the test piece after completion was visually evaluated according to the following index. The obtained results are shown in Table 1 (Product of the present invention) and Table 2 (Comparative product).
(Evaluation method)
◎: Dirt is not found ○: Dirt is less than 10% of the area of the test piece, but the dirt can be visually confirmed x: Dirt is adhered to more than 10% of the area of the test piece

<Test 4: Rinseability test>
One side of a test piece (15 × 15 cm) of a stainless steel plate was scrubbed 5 times with a sponge sufficiently impregnated with the liquid detergent composition of the present invention and a comparative product described later, and then wetted with water. (Kimwipe S-200: manufactured by Nippon Paper Crecia Co., Ltd.) was subjected to one reciprocal water wiping per second and evaluated according to the time required for the test piece to have no residue. The obtained results are shown in Table 1 (Product of the present invention) and Table 2 (Comparative product).
(Evaluation method)
◎: Less than 15 seconds ○: Less than 15-30 seconds ×: More than 30 seconds

<Test 5: Uniformity confirmation test of antifouling film>
One side of a test piece (15 × 15 cm) of a stainless steel plate is scrubbed 5 times with a sponge sufficiently impregnated with the liquid detergent composition of the present invention and a comparative product to be described later, rinsed with running water for 30 seconds, and then dried. I let you. The subsequent appearance of the stainless steel surface was visually evaluated according to the following indices. The obtained results are shown in Table 1 (Product of the present invention) and Table 2 (Comparative product).
(Evaluation method)
◎: There is no unevenness and the surface is finished on a uniform and clean surface. ○: There is almost no unevenness and the surface is finished on an almost uniform and clean surface. ×: There is unevenness and the surface is dull.

<Test 6: Sustainability test of antifouling film>
One side of a test piece (15 × 15 cm) of a stainless steel plate is scrubbed 5 times with a sponge sufficiently impregnated with the liquid detergent composition of the present invention and a comparative product to be described later, rinsed with running water for 30 seconds, and then dried. I let you. Then, the running water rinse / drying process for 30 seconds was repeated 10 times. Thereafter, 2 ml of soybean oil was uniformly applied to the test piece, baked in an oven at 200 ° C. for 30 minutes, and then rubbed 5 times with a sponge. The surface condition of the test piece after completion was visually evaluated according to the following index. The obtained results are shown in Table 1 (Product of the present invention) and Table 2 (Comparative product).
(Evaluation method)
◎: Dirt is not found ○: Dirt is less than 10% of the area of the test piece, but the dirt can be visually confirmed x: Dirt is adhered to more than 10% of the area of the test piece

The compounds used in the preparation of the following products of the present invention and comparative products are as follows:
(A) Component A-1: Perfluoroalkylalkoxysilane:

A-2: Perfluoroalkylamine oxide:

A-3: Perfluoroalkyltrialkylammonium salt:

A-4: Perfluoroalkyltrialkylbetaine:

(B) Component B-1: Sodium dodecylbenzenesulfonate B-2: Polyoxyethylene (10) Lauryl ether

(C) Component C-1: amino-modified silicone [in the general formula (4)
A is —C ₂ H ₄ NHC ₂ H ₄ NH ₂ , q is 40, and r is 15. The A equivalent is 354 g / mol)

Other components D-1: polytetrafluoroethylene (powder)
D-2: Fluorine-modified acrylic resin (powder)
D-3: perfluoroalkyl _carboxylate: C ₆ F ₁₃ -CH 2 -COONa
D-4: Silicone oil (KF96, manufactured by Shin-Etsu Chemical Co., Ltd.)
D-5: Polyether-modified silicone (KF353, manufactured by Shin-Etsu Chemical Co., Ltd.)
E-1: Sodium hydroxide E-2: Diethylene glycol monobutyl ether

  Liquid detergent compositions of the present invention and comparative products were prepared at the blending ratios described in Tables 1 and 2 using the above components.

Claims (7)

Cationic group, a fluorine compound having a group selected from zwitterionic group and a silyl group one or more (A), full Tsu atom having no surfactant (B) and amino-modified silicone compounds that contain (C) A cleaning composition for hard surfaces, which is characterized. The cleaning composition for hard surfaces according to claim 1, wherein the fluorine compound (A) is a compound represented by the following general formula (1):
R _f − (X) _n −Y (1)
(In the formula, R _f represents a C 3-20 perfluoroalkyl group, and X represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a sulfoamide having 1 to 5 carbon atoms. Represents any group selected from an alkylene group, a carbonyl group, an alkylenesulfamidoalkylene group having 2 to 8 carbon atoms, an alkyleneoxyalkylene group having 2 to 10 carbon atoms and an alkylenethioalkylene group having 2 to 10 carbon atoms, Y represents any group selected from a cationic group, a zwitterionic group and a silyl group, and n represents a number of 0 or 1.)   3. The hard surface cleaning composition according to claim 1, wherein the surfactant (B) is an anionic surfactant or a nonionic surfactant. Amino-modified silicone compound (C) is a compound represented by the following general formula (4), according to claim 1, wherein the hard surface cleaning composition:

(In the formula, A represents a group of -R ⁷ NH ₂ or -R ⁸ NHR ⁹ NH ₂ , q represents a number of 1 to 100, r represents a number of 1 to 100, and R ⁷ to R ⁹ represents an alkylene group having 1 to 6 carbon atoms.) The surfactant (B) having no fluorine atom with respect to 1 part by mass of the fluorine compound (A) is 0.1 to 20000 parts by mass, and the amino-modified silicone (C) is 0.001 to 1000 parts by mass. The cleaning composition for hard surfaces according to any one of 1 to 4 . 0.001 to 1% by mass of fluorine compound (A), 0.1 to 20% by mass of surfactant (B) having no fluorine atom, amino-modified silicone (C The hard surface cleaning composition according to any one of claims 1 to 4, wherein 0.001 to 1% by mass is contained. Further, chelating agents, builders, preservatives, one selected from the group consisting of dye and perfume or 請 Motomeko 1 to you containing two or more to a hard surface cleaning composition according to any one of 6 .