JP4463521B2 - Antifouling detergent composition for hard surfaces around water - Google Patents

Abstract

To provide an anti-soiling detergent composition that has excellent detergency, endows cleaned surfaces with a pronounced anti-soiling effect, effectively sustains the anti-staining effect, possesses superb storage stability, and can be used on restrooms, sinks, baths, and other damp, hard surfaces. The anti-soiling detergent composition contains (A) 0.05 to 10 mass% of a polyetheramide-modified organopolysiloxane and/or amino-modified organopolysiloxane, (B) 0.1 to 30 mass% of a specific surfactant, (C) 0.1 to 20 mass% of a metal chelating agent, and (D) water.

Description

The present invention relates to an antifouling detergent composition for hard surfaces around water , which has an excellent detergency, a continuous antifouling effect on the surface to be cleaned, and also excellent storage stability. For more information, toilets, washing and antifouling for washstand, the Ri water times such bath such as plastic, stainless steel, enamel, tile, glass, ceramics, hard surfaces natural material stone such as granite, terrazzo, in particular, toilet basin The present invention relates to an antifouling detergent composition for hard surfaces around water, which is suitably used for cleaning hard surfaces such as tiles, glass, ceramics, etc., and for preventing dirt stains.

Bathroom or washbasin, water once Riniokeru hard surfaces such as toilets, various dirt adheres in accordance with the usage situation. For example, stains in the bathroom are nitrogen-containing compounds such as proteins and fatty acid metal salts, stains in the washstand are fatty acid metal salts, etc., and stains in the toilet are dirt and urine from excrement such as feces and urine. Stones. In addition, these hard surfaces are constantly contacted with tap water and repeatedly dried, so the silicate scale and carbonate scale derived from tap water are locally concentrated and adhered, and are generally called water spots or scales. It becomes. In particular, since glass surfaces of pottery and mirrors such as flush toilets and washstands in the toilet space are hydrophilic, scale dirt tends to adhere.
If this scale dirt accumulates over a long period of time, it will not only be difficult to remove because the scale dirt will be firmly bonded to the hard surface, but the scale dirt will easily become a hotbed of mold and germs along with other dirt. The problem also arises. The initial scale dirt can be removed relatively easily by frequent cleaning, but the current situation is that the frequency of cleaning tends to decrease due to the efficiency of the cleaning work.

  Therefore, in order to prevent scale dirt from sticking firmly to the hard surface, there is a demand for a cleaning agent having a performance (anti-stain effect) that makes it difficult to attach scale dirt and other dirt. On the other hand, the development of a cleaning agent that imparts an antifouling effect has been made. As a cleaning agent having such an antifouling effect, there has been proposed a cleaning agent that imparts an antifouling effect by forming a film on the surface to be cleaned by containing a specific organopolysiloxane in the cleaning composition. Yes.

  As a cleaning agent containing such an organopolysiloxane and having an antifouling effect, for example, it contains an amino-modified organopolysiloxane and a nonionic surfactant, suppresses the reattachment of scale, and protects the bathtub material. (For example, refer to Patent Document 1), and a cleaning composition containing a specific organopolysiloxane for protecting and polishing the surface of bathroom utensils is disclosed. (For example, refer to Patent Document 2). Furthermore, a hard surface antifouling antibacterial detergent composition having an antifouling effect and an antibacterial action, containing a specific cationic surfactant, a cationic fungicide and a hydrophilic organopolysiloxane is disclosed (for example, (See Patent Document 3).

However, in the above Patent Document 1 and Patent Document 2, although a detergent composition having an excellent detergency and antifouling effect against scale dirt is disclosed, there is no description of the antifouling effect against scale dirt, Further, there is no disclosure of a continuous antifouling effect and storage stability considered to be important in practical use. Further, Patent Document 3 discloses a detergent composition having an excellent antifouling effect against scale dirt, but does not disclose storage stability and specific cleaning power, and has excellent cleaning power. In addition, no detergent has been developed that satisfies all of the continuous antifouling effects and storage stability at the same time.
Therefore, in addition to excellent cleaning power, it has been desired to develop a cleaning agent that maintains antifouling effects and has excellent storage stability even in places where it comes into contact with tap water repeatedly such as toilets, washstands, and bathrooms. .

JP-A-51-83608 Japanese Patent Laid-Open No. 3-197596 JP 2000-198999 A

In addition to having excellent cleaning power, the present invention has an excellent antifouling effect on the surface to be cleaned and the sustainability of the antifouling effect, and further for water-based hard surfaces with excellent storage stability. An object is to provide a cleaning composition. For more information, toilets, washing and antifouling for washstand, the Ri water times such bath such as plastic, stainless steel, enamel, tile, glass, ceramics, hard surfaces natural material stone such as granite, terrazzo, in particular, toilet basin It is an object of the present invention to provide an antifouling detergent composition for hard surfaces around water, which is suitably used for cleaning hard surfaces such as tiles, glass, ceramics, etc., and for preventing dirt stains.

The present inventors have made intensive studies to achieve the above object, a polyetheramide-modified organopolysiloxane down, a surfactant, a metal chelating agent, by combining the water, excellent In addition to having a detergency, the antifouling detergent composition for hard surfaces around water is excellent in the antifouling effect on the surface to be cleaned, and also in the durability of the antifouling effect and the storage stability of the composition. The knowledge that is obtained. The present invention has been completed based on such findings.
That is, the present invention provides the following antifouling detergent composition for hard surfaces around water .

1. (A) 0.05-10% by mass of polyetheramide-modified organopolysiloxane,
(B) 0.1-30% by mass of at least one surfactant selected from nonionic surfactants, amphoteric surfactants and cationic surfactants,
(C) Metal chelating agent 0.1-20 mass% and (D) Antifouling detergent composition for hard surface around water, comprising water.
2 . ( A) component is the following average composition formula (1)
R ¹ _a R ² _b Q ¹ _c Q ² _d SiO _{(4-abcd) / 2} (1)
[Wherein, a and d are 0 or a positive number, b and c are positive numbers, and 1.9 ≦ a + b + c + d ≦ 2.2. R ¹ is a hydrogen atom, a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is represented by the following general formula (2 Or (3)

R ³ and R ⁵ are divalent hydrocarbon groups having 2 to 18 carbon atoms, R ⁴ and R ⁶ are hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms, X Is the following general formula (4)
_{^{-R 7 e O f - (C}} 2 H 4 O) g - (R 8 O) h -Y (4)
E and f are each 0 or 1, g and h are 0 or a positive integer of 1 or more, R ⁷ is a divalent hydrocarbon group having 2 to 18 carbon atoms, and R ⁸ is carbon. A divalent hydrocarbon group having 3 to 10 atoms, Y represents a monovalent hydrocarbon group having 1 to 18 carbon atoms. Q ² is the following general formula (5)
_{^{-R 9 i O j - (C}} 2 H 4 O) k - (R 10 O) m -Z (5)
I and j are each 0 or 1, k is a positive integer of 1 or more, m is 0 or a positive integer of 1 or more, and R ⁹ is a divalent carbon atom having 2 to 18 carbon atoms. A hydrogen group, R ¹⁰ is a divalent hydrocarbon group having 3 to ¹⁰ carbon atoms, and Z is a monovalent hydrocarbon group having 1 to 18 carbon atoms. However, d and g are not 0 at the same time. ]
The antifouling detergent composition for hard surfaces around water as described in 1 above, which is a polyetheramide-modified organopolysiloxane represented by the formula:

3 . (A) component is the following average composition formula (6)
R ¹ _a R ² _b Q ¹ _c Q ² _d Q ³ _e1 SiO _{(4-abcd-e1) / 2} (6)
[Wherein, a and d are 0 or a positive number, b, c and e1 are positive numbers, and 1.9 ≦ a + b + c + d + e1 ≦ 2.2. R ¹ is a hydrogen atom, a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is represented by the following general formula (2 Or (3)

R ³ and R ⁵ are divalent hydrocarbon groups having 2 to 18 carbon atoms, R ⁴ and R ⁶ are hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms, X Is the following general formula (4)
_{^{-R 7 e O f - (C}} 2 H 4 O) g - (R 8 O) h -Y (4)
E and f are each 0 or 1, g and h are 0 or a positive integer of 1 or more, R ⁷ is a divalent hydrocarbon group having 2 to 18 carbon atoms, and R ⁸ is carbon. divalent hydrocarbon radical having the number of atoms of 3 to 10, Y denotes a monovalent hydrocarbon group having carbon atom number of 1 to 18. Q ² is the following general formula (5)
_{^{-R 9 i O j - (C}} 2 H 4 O) k - (R 10 O) m -Z (5)
I and j are each 0 or 1, k is a positive integer of 1 or more, m is 0 or a positive integer of 1 or more, and R ⁹ is a divalent carbon atom having 2 to 18 carbon atoms. hydrogen radical, R ¹⁰ represents a divalent hydrocarbon group, Z is a carbon atom number from 1 to 18 monovalent hydrocarbon group having 3 to 10 carbon atoms. However, d and g are not 0 at the same time. Q ³ represents the following general formula (7) or (8)

R ³ and R ⁵ represent a divalent hydrocarbon group having 2 to 18 carbon atoms, R ⁴ and R ⁶ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. . ]
The antifouling detergent composition for hard surfaces around water as described in 1 above, which is a polyetheramide-modified organopolysiloxane represented by the formula:
4). In addition to the components (A) to (D), (E) the antifouling detergent composition for hard surface around water according to any one of the above 1 to 3 containing 0.01 to 5% by mass of a thickener.
5 . (E) component of the thickener, thickening polysaccharides, carboxyvinyl polymers, crosslinked polyacrylic acid or at least one is intended water around the four hard surfaces antifouling detergent selected from a salt thereof Composition.
6). In addition to the said component, (F) The antifouling detergent composition for hard surfaces around water in any one of said 1-5 containing 0.1-20 mass% of water-soluble solvents.
7). (6) The antifouling detergent composition for hard surfaces around water as described in 6 above, wherein the water-soluble solvent as component (F) is at least one selected from alcohols, glycol ethers and terpene hydrocarbon solvents.

The antifouling detergent composition for hard surfaces around the water of the present invention (hereinafter simply referred to as “antifouling detergent composition”) comprises a specific organopolysiloxane (component A), a surfactant (component B), Since it has a specific composition containing a metal chelating agent (component C) and water (component D) in a specific ratio, it has excellent detergency and also has excellent protection against the surface to be cleaned. In addition to having an antifouling effect, it also has the effect of exhibiting an excellent antifouling effect. And it is excellent also in the storage stability of a composition. Accordingly, toilet, wash basin, water times Ri plastic such bathrooms, etc., stainless steel, enamel, tile, glass, ceramics, cleaning and soil for hard surfaces natural material stone such as granite, terrazzo, in particular, toilet, washbasin It can be suitably used for cleaning hard surfaces such as glass and ceramics, and for preventing dirt contamination.

First, the antifouling detergent composition of the present invention contains the above component (A), component (B), component (C) and component (D) as essential components.
Component (A) used in the present invention is a polyetheramide-modified organopolysiloxane down and added for imparting antifouling effect on cleaned surface.

As the polyether amide-modified organopolysiloxane (A) used in the present invention, the following average composition formula (1)
R ¹ _a R ² _b Q ¹ _c Q ² _d SiO _{(4-abcd) / 2} (1)
And an organopolysiloxane having an amide group and a polyoxyethylene group represented by the formula:
In the average composition formula (1), a and d are 0 or a positive number, b and c are positive numbers, and 1.9 ≦ a + b + c + d ≦ 2.2. R ¹ represents a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, an aryl group such as a phenyl group, a tolyl group, and a xylyl group, and a benzyl group. And an aralkyl group such as a phenethyl group, a halo-substituted alkyl group such as a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group.
In the above average composition formula (1), R ² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. , Vinyl group, phenyl group and the like.
In the average composition formula (1), Q ¹ represents the following general formula (2) or (3)

The bivalent organic group which has an amide group represented by these is shown. In the above general formulas (2) and (3), R ³ and R ⁵ represent a divalent hydrocarbon group having 2 to 18 carbon atoms, specifically, an ethylene group, a propylene group, a butylene group, an isobutylene group, Examples include pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, cyclohexyl group, and the like. In the above formula, R ⁴ and R ⁶ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, Alkyl groups such as xyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, aralkyl groups such as benzyl groups and phenethyl groups, halo substitutions such as 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, etc. Examples include alkyl groups.

In the general formulas (2) and (3), X represents the following general formula (4).
^{_{-R 7 e O f - (C}} 2 H 4 O) g - (R 8 O) h -Y (4)
It is a monovalent organic group represented by e and f are each 0 or 1, and g and h are 0 or a positive integer of 1 or more. R ⁷ represents a divalent hydrocarbon group having 2 to 18 carbon atoms, specifically, ethylene group, propylene group, butylene group, isobutylene group, pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, Examples include a cyclohexyl group. R ⁸ represents a divalent hydrocarbon group having 3 to 10 carbon atoms, and specific examples include a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Y is A alkyl group, a methyl group, an ethyl group, etc. propyl groups.

In the average composition formula (1), Q ² represents the following general formula (5).
_{^{-R 9 i O j - (C}} 2 H 4 O) k - (R 10 O) m -Z (5)
It is a monovalent organic group having a polyoxyalkylene group represented by i and j are each 0 or 1, k is a positive integer of 1 or more, and m is 0 or a positive integer of 1 or more. R ⁹ represents a divalent hydrocarbon group having 2 to 18 carbon atoms, specifically, ethylene group, propylene group, butylene group, isobutylene group, pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, Examples include a cyclohexyl group. R ¹⁰ represents a divalent hydrocarbon group having 3 to ¹⁰ carbon atoms, and specific examples thereof include a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Z is A alkyl group, a methyl group, an ethyl group, etc. propyl groups.
The molecular structure of the polyetheramide-modified organopolysiloxane may be not only linear but also branched, cyclic, and network.
Examples of the polyetheramide-modified organopolysiloxane having such an amide group and a polyoxyethylene group include compounds represented by the following general formula.

Wherein, R ¹¹ is _{- (CH 2) 3 NHCO (} CH 2) q O (CH 2 CH 2 O) r (CH 2) shows the _s H, n is 10 to 1000, p is 1 to 100, q Is 1 to 100, r is 2 to 20, and s is 0 to 20. ]

[Wherein, R ¹² represents — (CH ₂ ) ₃ NH (CH ₂ ) ₂ NHCO (CH ₂ ) _w H, R ¹³ represents — (CH ₂ ) ₃ O (CH ₂ CH ₂ O) _x (CH ₂ CHCH ₃ O) _y (CH ₂ ) _z H, t is 10 to 1000, u is 1 to 100, v is 1 to 100, w is 1 to 20, x is 2 to 20, y is 0 to 20, z is 0-20. ]

Wherein, R ^c1 is _{- (CH 2) 3 NHCO (} CH 2) m4 O m5 (CH 2 CH 2 O) m6 (CH 2 CHCH 3 O) m7 (CH 2) m8 H, R c2 is - (CH _{2) 3 O (CH 2 CH} 2 O) m9 (CH 2 CHCH 3 O) m10 (CH 2) illustrating the _m11 D ^1. E ¹ and E ² may be the same or different and each represents R ^c1 , R ^c2 , —OH, — (CH ₂ ) _p1 H, preferably —CH ₃ . D ¹ represents —H or —COCH ₃ . m1 is 10 to 1000, m2 is 1 to 100, m3 is 0 to 100, m4 is 1 to 100, m5 is 0 or 1, m6 is 0 to 20, m7 is 0 to 20, m8 is 0 to 20, m9 is 2-20, m10 is 0-20, m11 is 0-20, and p1 is 0-20. However, m3 and m6 are not 0 at the same time. ]

[Wherein, R ^c3 represents — (CH ₂ ) ₃ NH (CH ₂ ) ₂ NHCO (CH ₂ ) _{m 15} O _{m 16} (CH ₂ CH ₂ O) _{m 17} (CH ₂ CHCH ₃ O) _{m 18} (CH ₂ ) _{m 19} H, R ^c4 is - shows the _{(CH 2) 3 O (CH} 2 CH 3 O) m20 (CH 2 CHCH 3 O) m21 (CH 2) m22 D 2. E ³ and E ⁴ may be the same or different and each represents R ^c3 , R ^c4 , —OH, — (CH ₂ ) _p2 H, preferably —CH ₃ . D ² represents —H or —COCH ₃ . m12 is 10 to 1000, m13 is 1 to 100, m14 is 0 to 100, m15 is 1 to 100, m16 is 0 or 1, m17 is 0 to 20, m18 is 0 to 20, m19 is 0 to 20, m20 is 2-20, m21 is 0-20, m22 is 0-20, p2 is 0-20. However, m14 and m17 are not 0 at the same time. ]

  Specifically, a compound having a chemical structure as shown below is exemplified.

[Wherein, G ¹ represents (CH ₂ ) ₃ NHCOCH ₂ O (CH ₂ CH ₂ O) ₄ C ₁₂ H ₂₅ . ]

Wherein, G ² represents a _{(CH 2) 3 NH (CH} 2) 2 NHCO (CH 2) 3 O (CH 2 CH 2 O) 10 C 12 H 25. ]

[Wherein G ³ represents (CH ₂ ) ₃ O (CH ₂ CH ₂ O) ₁₀ (CH ₂ CHCH ₃ O) ₁₀ H, and G ⁴ represents (CH ₂ ) ₃ NHCO (CH ₂ ) ₃ O (CH It shows a _{2 CH 2 O) 6 C 10} H 21. ]

[Wherein, G ⁵ represents (CH ₂ ) ₃ O (CH ₂ CH ₂ O) ₁₀ COCH ₃ , and G ⁶ represents (CH ₂ ) ₃ NH (CH ₂ ) ₂ NHCOC ₁₆ H ₃₃ . ]

The polyether amide-modified organopolysiloxane (A) used in the present invention includes the following average composition formula (6)
R ¹ _a R ² _b Q ¹ _c Q ² _d Q ³ _e1 SiO _{(4-abcd-e1) / 2} (6)
An organopolysiloxane having an amide group, a polyoxyethylene group and an amino group represented by
In the average composition formula (6), a and d are 0 or a positive number, b, c and e1 are positive numbers, and 1.9 ≦ a + b + c + d + e1 ≦ 2.2. R ¹ represents a hydrogen atom, a hydroxyl group, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, an aryl group such as a phenyl group, a tolyl group, and a xylyl group, and a benzyl group. And an aralkyl group such as a phenethyl group, a halo-substituted alkyl group such as a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group.
In the above average composition formula (6), R ² represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group. , Vinyl group, phenyl group and the like.
In the average composition formula (6), Q ¹ represents the following general formula (2) or (3)

The bivalent organic group which has an amide group represented by these is shown. In the above general formulas (2) and (3), R ³ and R ⁵ represent a divalent hydrocarbon group having 2 to 18 carbon atoms, specifically, an ethylene group, a propylene group, a butylene group, an isobutylene group, Examples include pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, cyclohexyl group, and the like. In the above formula, R ⁴ and R ⁶ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, Alkyl groups such as xyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, aralkyl groups such as benzyl groups and phenethyl groups, halo substitutions such as 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, etc. Examples include alkyl groups.

In the general formulas (2) and (3), X represents the following general formula (4).
^{_{-R 7 e O f - (C}} 2 H 4 O) g - (R 8 O) h -Y (4)
It is a monovalent organic group represented by e and f are each 0 or 1, and g and h are 0 or a positive integer of 1 or more. R ⁷ represents a divalent hydrocarbon group having 2 to 18 carbon atoms, specifically, ethylene group, propylene group, butylene group, isobutylene group, pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, Examples include a cyclohexyl group. R ⁸ represents a divalent hydrocarbon group having 3 to 10 carbon atoms, and specific examples include a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Y is A alkyl group, a methyl group, an ethyl group, etc. propyl groups.

In the average composition formula (6), Q ² represents the following general formula (5).
_{^{-R 9 i O j - (C}} 2 H 4 O) k - (R 10 O) m -Z (5)
It is a monovalent organic group having a polyoxyalkylene group represented by i and j are each 0 or 1, k is a positive integer of 1 or more, and m is 0 or a positive integer of 1 or more. R ⁹ represents a divalent hydrocarbon group having 2 to 18 carbon atoms, specifically, ethylene group, propylene group, butylene group, isobutylene group, pentamethylene group, octamethylene group, decamethylene group, dodecamethylene group, Examples include a cyclohexyl group. R ¹⁰ represents a divalent hydrocarbon group having 3 to ¹⁰ carbon atoms, and specific examples thereof include a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Z is A alkyl group, a methyl group, an ethyl group, etc. propyl groups.
In the average composition formula (6), Q ³ represents the following general formula (7) or (8).

The bivalent organic group which has an amino group represented by these is shown. In the general formulas (7) and (8), R ^{3 to} R ⁶ are the same as described above.
From the viewpoint of durability of the antifouling effect, the total amount of the primary and secondary amino groups of the general formula (7) or (8) contained in the polyetheramide-modified organopolysiloxane molecule is 0.15. It is preferable to be in the range of ˜0.45 mass%. When the total content of the primary and secondary amino groups is less than 0.15% by mass, the adsorptivity of the polyetheramide-modified organopolysiloxane on the surface to be cleaned is poor, so that the antifouling effect is not long-lasting. When the content exceeds .45 mass%, the storage stability of the composition becomes poor.
The molecular structure of the polyetheramide-modified organopolysiloxane may be not only linear but also branched, cyclic, and network.
Examples of the polyetheramide-modified organopolysiloxane having such an amide group, polyoxyethylene group, and amino group include compounds represented by the following general formula.

Wherein, R ¹⁴ is _{- (CH 2) 3 O (} CH 2 CH 2 O) n5 (CH 2 CHCH 3 O) n6 (CH 2) n7 D 3, R 15 is _{- (CH 2) 3 NH 2} , R ¹⁶ is _{- (CH 2) 3 NHCO (} CH 2) n8 O n9 (CH 2 CH 2 O) n10 (CH 2 CHCH 3 O) n11 (CH 2) illustrating the _n12 H. E ⁵ and E ⁶ may be the same or different and each represents R ¹⁴ , R ¹⁵ , R ¹⁶ , —OH, — (CH ₂ ) _p3 H, preferably —CH ₃ . D ³ represents —H or —COCH ₃ . n1 is 10 to 1000, n2 is 0 to 100, n3 is 1 to 100, n4 is 1 to 100, n5 is 2 to 20, n6 is 0 to 20, n7 is 0 to 20, n8 is 1 to 100, and n9 is 0 or 1, n10 is 0 to 20, n11 is 0 to 20, n12 is 0 to 20, and p3 is 0 to 20. However, n2 and n10 are not 0 at the same time. ]

Wherein, R ¹⁷ is _{- (CH 2) 3 O (} CH 2 CH 2 O) n17 (CH 2 CHCH 3 O) n18 (CH 2) n19 D 4, R 18 is _{- (CH 2) 3 NH (} CH It is ^{_{2) 2 NH 2, R 19}} - (CH 2) 3 NH (CH 2) 2 NHCO (CH 2) n20 O n21 (CH 2 CH 2 O) n22 (CH 2 CHCH 3 O) n23 (CH 2) n24 H is shown. E ⁷ and E ⁸ may be the same or different and each represents R ¹⁷ , R ¹⁸ , R ¹⁹ , —OH, — (CH ₂ ) _p4 H, preferably —CH ₃ . D ⁴ represents —H or —COCH ₃ . n13 is 10 to 1000, n14 is 0 to 100, n15 is 1 to 100, n16 is 1 to 100, n17 is 2 to 20, n18 is 0 to 20, n19 is 0 to 20, n20 is 1 to 100, and n21 is 0 or 1, n22 is 0 to 20, n23 is 0 to 20, n24 is 0 to 20, and p4 is 0 to 20. However, n14 and n22 are not 0 at the same time. ]

  Specifically, a compound having a chemical structure as shown below is exemplified.

Wherein, G ¹⁴ is _{- (CH 2) 3 O (} CH 2 CH 2 O) 5 C 12 H 25, G 15 is _{- (CH 2) 3 NH 2} , G 16 is - (CH _{2) 3} NHCOCH ₂ O (CH ₂ CH ₂ O) ₅ C ₁₂ H ₂₅ is shown. ]

[In the formula, G ¹⁷ is — (CH ₂ ) ₃ O (CH ₂ CH ₂ O) ₁₀ C ₁₀ H ₂₁ , G ¹⁸ is — (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ , G ¹⁹ is — ( It shows the _{CH 2) 3 NH (CH 2} ) 2 NHCOCH 2 O (CH 2 CH 2 O) 4 C 10 H 21. ]

The amount of the component (A) This is selected in the range of 0.05 to 10 weight percent based on the total weight of the composition. If this amount is less than 0.05% by mass, the antifouling effect is poor, and even if it exceeds 10% by mass, the improvement of the antifouling effect is saturated and disadvantageous from an economical viewpoint. The blending amount of the component (A) is preferably in the range of 0.1 to 8% by mass from the viewpoint of antifouling effect and storage stability, and more preferably in the range of 0.1 to 5% by mass from the viewpoint of economy. preferable. This (A) component may be used independently or may be used in combination of 2 or more type.

Used in the present invention component (B) of the surfactant is formulated for the purpose of washing the dirt adhering to the surface to be cleaned, and a polyetheramide-modified organopolysiloxane down solubilized as component (A) .
The component (B) surfactant is at least selected from nonionic surfactants, amphoteric surfactants, and cationic surfactants from the viewpoint that the antifouling effect that is the effect of the component (A) is not impaired. One surfactant is used.
Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyal polyglucosides, fatty acid polyglycerol esters, fatty acid sucrose esters, fatty acid alkanolamides, and the like. In the present invention, among these nonionic surfactants, polyoxyalkylene alkyl ethers, alkyl polyglucosides, and fatty acid alkanolamides are preferable from the viewpoint of detergency, and further, polyoxyalkylene alkyl ethers from the viewpoint of economy. Alkyl polyglucoside is preferred.
Amphoteric surfactants include alkylcarboxybetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidobetaines, imidazolinium betaines, alkyldiaminoethylglycines, dialkyldiaminoethylglycines, alkylamine oxides, alkyl ether amine oxides, amidoamine oxides Etc. In the present invention, among these amphoteric surfactants, alkylcarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidobetaine, alkylamine oxide, alkyletheramine oxide, and amidoamine oxide are preferable from the viewpoint of detergency. Furthermore, alkylamide betaines and alkylamine oxides are preferred from the viewpoint of economy.
Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl trimethyl ammonium salt, alkyl dimethyl ammonium adipate, benzalkonium salt, benzethonium salt, pyridinium salt, imidazolinium salt, biguanide compound and the like. . The counter ion of these cationic surfactants is a halogen ion or the like. In the present invention, among these cationic surfactants, dialkyldimethylammonium salt, alkyldimethylammonium adipate, benzalkonium salt, benzethonium salt, and biguanide compound are preferable from the viewpoint of bactericidal property and economical efficiency. From the viewpoint of improving the fouling effect, benzalkonium chloride and dialkyldimethylammonium chloride are preferred.

These surfactants may be used singly or in combination of two or more, and include a detergency against dirt, foaming properties, rinsing properties, mildness to skin, damage to materials, wiping properties, etc. Can be appropriately selected according to the required performance.
The compounding quantity of this (B) component is chosen in the range of 0.1-30 mass% in a composition. If this amount is less than 0.1% by mass, the detergency and solubilizing effect of the component (A) are poor. Even if it exceeds 30% by mass, the improvement in the detergency becomes saturated, which is economically disadvantageous. Become. The blending amount of the surfactant is preferably in the range of 1 to 30% by mass from the viewpoint of detergency, and more preferably in the range of 1 to 15% by mass based on the total mass of the composition. .

Examples of the metal chelating agent of component (C) used in the present invention include hydroxycarboxylic acids, aminocarboxylic acids, phosphoric acids, phosphonic acids, phosphonocarboxylic acids, water-soluble polymer polymers, and salts thereof. The thing which shows water-soluble chelate ability is mentioned, It may be used independently or may be used in combination of 2 or more type. The metal chelating agent is blended for the purpose of improving detergency.
Examples of hydroxycarboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid Citric acid, malic acid, gluconic acid, or a salt thereof.
Examples of aminocarboxylic acids include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionic acid, methylglycinediacetic acid, triethylenetetraminehexaacetic acid, ethylene glycol dietherdiamine. Examples include tetraacetic acid, hydroxyethyliminodiacetic acid, cyclohexane-1,2-diaminetetraacetic acid, diencoric acid, or salts thereof.

Examples of phosphoric acids include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, condensed phosphoric acid such as phytic acid, and salts thereof.
Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and its derivatives, 1-hydroxyethane-1,1. , 2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, or a salt thereof.
Examples of the phosphonocarboxylic acids include 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, and salts thereof.
Examples of the water-soluble polymer include polyacrylic acid, polymaleic acid, a copolymer of acrylic acid and maleic acid, polyaconitic acid, poly-α-hydroxyacrylic acid, polymethacrylic acid, or salts thereof. .

These metal chelating agents may be used in an acid form, or a part or all of them may be in a salt form. Examples of the salt include alkali metal salts such as potassium and sodium, alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine, and ammonium salts.
Among these metal chelating agents, hydroxycarboxylic acids, aminocarboxylic acids, or alkali metal salts and alkanolamine salts thereof are preferable from the viewpoint of environmental influences, and from the economical viewpoint, hydroxycarboxylic acids, Aminocarboxylic acids or their sodium salts are preferred.
The compounding quantity of this (C) component is chosen in the range of 0.1-20 mass% in a composition. If this amount is less than 0.1% by mass, the effect of improving the detergency is poor, and if it exceeds 20% by mass, the effect of improving the detergency becomes saturated and the storage stability of the composition becomes poor. Rather, it is economically disadvantageous. The compounding amount of the metal chelating agent is preferably in the range of 1 to 20% by mass from the viewpoint of detergency based on the total mass of the composition, and more preferably in the range of 1 to 15% by mass from the viewpoint of economy. .

Examples of the water (D) used in the present invention include pure water, ion exchange water, soft water, distilled water, and tap water. These may be used alone or in combination of two or more. Of these, tap water and ion-exchanged water are preferably used from the viewpoint of economy and storage stability.
The “water” is the sum of water contained in the form of crystallization water or aqueous solution derived from each component constituting the antifouling detergent composition of the present invention and water added from the outside, and is antifouling. It mix | blends so that the whole cleaning composition may be 100%.
A thickener can be mix | blended with this invention as an (E) component with the essential component of said (A)-(D) as needed. This component (E) improves the usability of the antifouling detergent composition of the present invention, particularly when sprayed or when cleaning a non-horizontal surface, and thus the detergency on the non-horizontal surface due to the thickening effect. It is blended for the purpose of improving.

Examples of the thickener of component (E) used in the present invention include thickening polysaccharides such as xanthan gum, carrageenan, guar gum, gum arabic, locust bean gum, alginate, carboxymethylcellulose, carboxyvinyl polymer, and crosslinked type. Examples include polyacrylic acid or a salt thereof. In the present invention, among these, xanthan gum and carboxyvinyl polymer are preferable from the viewpoint of the stability of the composition.
The compounding quantity of this (E) component is chosen in the range of 0.01-5 mass% in a composition. If this amount is less than 0.01% by mass, the effect of thickening is poor, and even if it exceeds 5% by mass, it will be too thick and difficult to handle, rather it is economically disadvantageous. The blending amount of the thickener is preferably in the range of 0.05 to 2% by mass from the viewpoint of workability based on the total mass of the composition, and more preferably 0.05 to 1% by mass from the viewpoint of economy. A range is more preferred.

In the present invention, a water-soluble solvent can be blended as the component (F) as necessary together with the essential components (A) to (D). This (F) component contributes to the improvement of the further cleaning power, especially the cleaning power with respect to organic dirt.
As the water-soluble solvent of component (F),
(1) Monohydric alcohols such as ethanol, propanol, isopropanol and butanol, Alcohols such as ethylene glycol, diethylene glycol, isoprene glycol and propylene glycol, and alcohols such as polyhydric alcohols such as glycerin, polyglycerin and 1,3-butanediol Kind,
(2) Ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol Alkylene glycol such as monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, tripropylene glycol dimethyl ether Le (mono, di) glycol ethers such as alkyl ethers,
(3) terpene hydrocarbon solvents such as limonene, pinene, terpinolene, myrcene, terpinene, ferrandrene,
Etc.

These water-soluble solvents may be used alone or in combination of two or more, and are appropriately selected and used according to the required performance such as detergency against dirt, damage to materials, and wiping properties. be able to.
Among these water-soluble solvents, lower alcohols having 1 to 5 carbon atoms, glycol ethers, and terpene hydrocarbon solvents are preferable from the viewpoint of detergency, and moreover, from the viewpoint of detergency, safety, and water solubility, the number of carbon atoms. 1-5 lower alcohols, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether and limonene are preferred.
The compounding quantity of this (F) component is chosen in the range of 0.1-20 mass% in a composition. If this amount is less than 0.1% by mass, the detergency is poor, and even if it exceeds 20% by mass, the improvement of the detergency becomes saturated, rather disadvantageous economically, and the storage stability of the composition Becomes scarce. The blending amount of the water-soluble solvent is preferably in the range of 1 to 15% by mass based on the total mass of the composition, from the viewpoint of the balance between detergency and storage stability, and further from the point of economy, 1 to 10% by mass. % Range is more preferred.

The stock solution of the antifouling detergent composition of the present invention has a pH of 5 to 9, preferably 6 to 8 in consideration of not adversely affecting the material of the object to be cleaned and safety to the human body and the environment. It is adjusted to the range. The pH is adjusted using a substance exhibiting alkalinity and a substance exhibiting acidity.
Examples of alkaline substances used for pH adjustment include alkali hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, silicates such as sodium silicate and potassium silicate, Amines such as ethanolamine and diethanolamine, ammonia, and the like are used, and as an acidic substance used for pH adjustment, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid and acetic acid are used.
In addition, when the organic acid applicable to (C) component is used for the said pH adjuster, it is necessary to consider so that the mixture ratio of (C) component may not remove | deviate from the range of 0.1-20 mass%.

In addition to the above-mentioned components, the antifouling detergent composition of the present invention may further contain a fragrance, a dye, a pigment, a bactericidal agent, a preservative, and the like as long as the purpose of the present invention is not impaired. it can.
The antifouling detergent composition of the present invention is suitably used for cleaning and antifouling hard surfaces that repeatedly come into contact with tap water and easily adhere to scale dirt, particularly hard surfaces such as toilets, washstands, and bathrooms. The materials of these surfaces to be cleaned are plastics, stainless steel, enamel, tiles, glass, ceramics, natural stone materials such as Mikage and Terrazzo.
The antifouling detergent composition of the present invention is used by diluting with an undiluted solution or water or lukewarm water according to the degree of dirt on the surface to be cleaned. The magnification at the time of dilution is preferably up to 50 times from the viewpoint of cleaning power and antifouling effect.

The cleaning method using the antifouling detergent composition of the present invention is, for example,
(1) A method of rinsing a hard surface with a sponge or the like after impregnating the antifouling detergent composition of the present invention and scrubbing the hard surface,
(2) A method in which the antifouling detergent composition of the present invention is directly sprinkled on the surface to be cleaned, rubbed with a sponge, and then rinsed with water.
(3) A method of spraying the antifouling detergent composition of the present invention onto the surface to be cleaned, leaving it for a while and rinsing with water,
(4) A method of impregnating a non-woven fabric or the like with the antifouling detergent composition of the present invention on an upright surface, sticking and standing for a while, and rinsing with water,
(5) A method in which a towel or duster is impregnated with the antifouling detergent composition of the present invention, and after wiping off the dirt, wiping with a towel soaked with water,
Etc.

  Hereinafter, the antifouling detergent composition of the present invention will be described in detail with reference to examples and comparative examples. In addition, this invention is not limited to these.

Examples 1-25 , Reference Examples 1-3 and Comparative Examples 1-18
Antifouling detergent compositions shown in Tables 1 to 8 were prepared and subjected to various tests. In addition, the numerical value of each component in a table | surface is content (mass%) of each component. And if necessary, the pH is adjusted using a pH adjusting agent such as acetic acid, sulfuric acid, sodium hydroxide, etc., but the sum of the components (A) to (F), the pH adjusting agent, and the optional components is as a whole. It is 100% by mass. In Tables 1 to 8, “ ◯ ” in the column of the pH adjuster means that the pH adjuster was used.
And about each obtained antifouling detergent composition, about each test item of pH, detergency, antifouling effect, antifouling effect sustainability, storage stability, it is evaluated by the following test method and criteria, The results are shown in Tables 1 to 8 below.

(1) pH
Using a pH meter (Horiba, Ltd .: pH METER F-12), the pH value at 25 ° C. of the stock solution of the prepared antifouling detergent composition was measured according to JIS Z-8808: 1984.

(2) Detergency test 1: Toilet model dirt [Preparation of toilet model dirt]
Lanolin (0.5 g) was dissolved in chloroform (5 ml) and further diluted with ethanol (495 ml) to prepare an ethanol solution. Ferric 10g chloride dissolved in 500 ml of water, those added to the ethanol solution, pre sandpaper (Nippon Coated Abrasive Co.: No.120) to the aspect 10 reciprocating, 20 laps circle drawing memorial Then, it was applied in an amount of 1 milliliter to a porcelain tile (INAX: SPKC-100 / L00: white: 10 cm × 10 cm) having a rough surface. After baking this at 145 degreeC for 1 hour, it stood to cool at room temperature to make a test piece.
[Test method]
To the test piece, 5 ml of the stock solution of each composition was dropped, and a detergency test was performed by reciprocating a sponge (4 cm × 8 cm) 15 times using a washability tester (manufactured by Tester Sangyo Co., Ltd.). After the test, it was rinsed with a constant amount of tap water for 10 seconds and dried at room temperature. At this time, the whiteness of the test pieces before and after the test was measured, and the cleaning rate was obtained using the following formula. For the measurement of whiteness, a color difference meter (manufactured by Minolta: model CR-331) was used.
Washing rate (%) = (whiteness after washing−whiteness before washing) / (whiteness before adhesion of dirt−whiteness before washing) × 100
Using the value of the washing rate, the evaluation was made according to the following criteria.
[Criteria]
◎: Cleaning rate of 80% or more ○: Cleaning rate of 60% or more △: Cleaning rate of 40% or more ×: Cleaning rate of less than 40%

(3) Detergency test 2: Soap residue model stain [Preparation of soap residue model stain]
A solution obtained by dissolving 2.5 g of oleic acid, 2.5 g of triolein, 0.25 g of albumin and 4.75 g of calcium stearate in 60 g of chloroform was added to a slide glass (7.6 cm × 2.6 cm) in an amount of 1 ml, It was applied evenly. This was dried overnight at room temperature to obtain a test piece.
[Test method]
A stock solution of each composition was dropped on the test piece, and a tissue paper (trade name “Kimwipe”, manufactured by Crecia Co., Ltd.) was wrapped around a congeal rod, and was reciprocated 15 times to perform scrubbing, and a detergency test was performed. It was. After the test, it was rinsed with a constant amount of tap water for 10 seconds and dried at room temperature. At this time, the mass of the test piece before and after the test was measured, and the cleaning rate was obtained using the following formula.
Cleaning rate (%) = (mass of dirt removed by detergency test / before detergency test
Mass of dirt attached) × 100
Using the value of the washing rate, the evaluation was made according to the following criteria.
[Criteria]
◎: Cleaning rate of 80% or more ○: Cleaning rate of 60% or more △: Cleaning rate of 40% or more ×: Cleaning rate of less than 40%

(4) Antifouling effect test [Test method]
Porcelain tiles (manufactured by INAX: SPKC-100 / L00: white: 10 cm × 10 cm) are washed with 2 ml of the stock solution of each composition using a sponge (4 cm × 8 cm) and rinsed with a constant amount of tap water for 20 seconds. The test piece was dried at room temperature. To this test piece, 1 g of ferric chloride dissolved in 100 g of water was dropped into a spot using a dropper, and then 5 drops were fired at 105 ° C. for 3 hours and allowed to cool at room temperature. The test piece was scrubbed with a tissue paper (trade name “Kimwipe” manufactured by Crecia Co., Ltd.) moistened with water, and the removal of the stain was visually determined.
[Criteria]
A: All 5 spots are removed by rubbing lightly.
○: All five spots are removed by rubbing with force.
Δ: Four points of dirt are removed by rubbing with force.
X: Two or more stains remain even when rubbed with force.

(5) Sustainability test 1 for antifouling effect
[Test method]
The durability test of the antifouling effect in actual use was conducted on urinals, toilets (Western and Japanese styles) and washstands of public men's toilets that are cleaned once a day.
First, on the first day of the test, the undiluted solution of each composition was used for the urinal, urinal and wash basin, and was washed with a sponge and rinsed with water. For the next 6 days, after scrubbing with a sponge soaked in water, only water was rinsed, and no detergent was used. When cleaning on the 7th day, the stock solutions of the respective compositions were used in the same way as on the first day, and after rubbed with a sponge, rinsed with water.
As described above, the cleaning using the stock solution of each composition is continued once a week for one month (four cycles), and the condition of dirt is visually observed one month after the start of the test (after four cycles). And evaluated according to the following criteria.
[Criteria]
◎: Same clean as the previous month, with less dirt and less cleaning time.
○: Although it was in the same state as one month ago, there were occasional dirt deposits.
Δ: It was dirty compared to 1 month ago.
×: It was very dirty compared to 1 month ago.

(6) Sustainability test 2 for antifouling effect
[Test method]
The durability test of the antifouling effect in actual use was conducted on urinals, toilets (Western and Japanese styles) and washstands of public men's toilets that are cleaned once a day.
First, on the first day of the test, the undiluted solution of each composition was used for the urinal, urinal and wash basin, and was washed with a sponge and rinsed with water. For 13 days from the next day, after washing with a sponge soaked in water, it was rinsed with water only, and no detergent was used. At the time of cleaning on the 14th day, the stock solution of each composition was used in the same manner as on the first day, and after scrubbing with a sponge, it was rinsed with water.
As described above, the cleaning using the stock solution of each composition is continued once every two weeks for one month (two cycles), and the state of dirt is visually observed one month after the start of the test (after two cycles). And evaluated according to the following criteria.
[Criteria]
◎: Same clean as the previous month, with less dirt and less cleaning time.
○: Although it was in the same state as one month ago, there were occasional dirt deposits.
Δ: It was dirty compared to 1 month ago.
×: It was very dirty compared to 1 month ago.

(7) Storage stability test 1: High temperature stability [Test method]
Each composition was placed in an incubator set at 50 ° C. (manufactured by Yamato Kagaku Co., Ltd .: Model IS82) for 3 months, and visually observed for precipitation, discoloration, and separation. Evaluation was performed according to the following criteria.
[Criteria]
A: No precipitation, discoloration, or separation is observed in the composition.
○: Precipitation, discoloration, and separation are slightly observed in the composition.
Δ: Precipitation, discoloration, and separation are clearly seen in the composition.
X: Precipitation, discoloration, and separation are remarkably observed in the composition.

(8) Storage stability test 2: Freezing / restoring property [Test method]
Each composition was frozen overnight by placing it in a freezer refrigerator (Hoshizaki: Model HRF-90P) set at −15 ° C. and then thawed at room temperature five times. The appearance of each composition after 8 hours was visually observed. Evaluation was performed according to the following criteria. [Criteria]
A: No precipitation, discoloration, or separation is observed in the composition even after 5 freeze / thaw cycles.
○: No precipitation, discoloration, or separation is observed in the composition even after 4 times of freezing / thawing, but precipitation, discoloration, and separation are observed in the fifth time.
Δ: Precipitation, discoloration, and separation are not observed in the composition even after freezing / thawing three times, but precipitation, discoloration, and separation are observed in the fourth time.
X: Precipitation, discoloration, and separation are observed in the composition by three freeze / thaw cycles.

In addition, the detail of the component shown to the following Tables 1-8 is as follows.
* Organopolysiloxane 1: Polyetheramide-modified organopolysiloxane represented by the following chemical formula

Wherein, G ⁷ shows a _{(CH 2) 3 NHCOCH 2 O} (CH 2 CH 2 O) 4 C 12 H 25. ]

* Organopolysiloxane 2: Polyetheramide-modified organopolysiloxane represented by the following chemical formula

[In the formula, G ⁸ represents (CH ₂ ) ₃ NHCOCH ₂ O (CH ₂ CH ₂ O) ₅ C ₁₂ H ₂₅ . ]

* Organopolysiloxane 3: Polyetheramide-modified organopolysiloxane represented by the following chemical formula

[Wherein, G ⁹ is (CH ₂ ) ₃ O (CH ₂ CH ₂ O) ₁₀ C ₁₂ H ₂₅ , G ¹⁰ is (CH ₂ ) ₃ NH ₂ , and G ¹¹ is (CH ₂ ) ₃ NHCOCH ₂ O (CH ₂ CH ₂ O) ₅ C ₁₂ H ₂₅ is shown. ]

* Organopolysiloxane 4: Polyetheramide-modified organopolysiloxane represented by the following chemical formula

Wherein, G ¹² _{is, (CH 2) 3 O (} CH 2 CH 2 O) 8 C 12 H 25, G 13 _{is, (CH 2) 3 NHCOCH 2} O (CH 2 CH 2 O) 4 C 12 H ₂₅ is shown. ]

* Organopolysiloxane 5: Amino-modified organopolysiloxane (manufactured by Dow Corning Silicone, Inc./trade name: SF8417)
* Organopolysiloxane 6: Polyether-modified organopolysiloxane (manufactured by Shin-Etsu Silicone / trade name: KF-6011)
* Organopolysiloxane 7: Dimethylpolysiloxane (Toray Dow Corning Silicone Co., Ltd./Brand name: BY22-007)
* Nonionic surfactant 1: Alkyl polyglucoside (manufactured by Cognis Japan / trade name: Glucopon 215CSUP)
* Nonionic surfactant 2: Polyoxyethylene alkyl ether (manufactured by Sanyo Kasei Kogyo Co., Ltd./Brand name: NAROACTY ID70)
* Nonionic surfactant 3: polyoxyethylene alkyl ether (BASF / trade name: Lutensol TO8)
* Amphoteric surfactant 1: alkylamidopropyl betaine (Gold Schmidt / trade name: TegoBetain L10S)
* Amphoteric Surfactant 2: Alkylamine Oxide (Lonza / Brand: Barlox12)
* Cationic surfactant 1: benzalkonium chloride (manufactured by Sanyo Chemical Industries, Ltd./trade name: Cation G-50)
* Cationic surfactant 2: Didecyldimethylammonium chloride (Lonza / Brandac2280)
* Anionic surfactant 1: Sodium alkyl ether sulfonate (manufactured by Toho Chemical Co., Ltd./Trade name: ALSCOPE TH-330)
* Anionic surfactant 2: Sodium linear alkylbenzene sulfonate (manufactured by Teika / Brand name: Teica Power LN2450)
* Thickener 1: Carboxyvinyl polymer (Wako Pure Chemical Industries, Ltd./trade name: Hibiswako 105)
* Thickener 2: Xanthan gum (manufactured by Kelco / Brand name: Kelzan)

From the above results, it can be seen that the compositions of Examples 1 to 25 exhibit good performance in any of the test items of detergency, antifouling effect, durability of the antifouling effect, and storage stability. On the other hand, (A) of the composition and Comparative Examples 1 to 6 without the polyetheramide-modified organopolysiloxane down components, the (A) the composition of Comparative Example 7 the content of the component is too small, the antifouling It turns out that it is inferior to the sustainability of an effect and an antifouling effect. Moreover, it turns out that the composition of the comparative examples 8 and 9 with which (A) component was mix | blended exceeding 10 mass% is inferior in storage stability. Furthermore, it can be seen that the compositions of Reference Examples 1 to 3 which contain an amino-modified organopolysiloxane and do not contain the polyetheramide-modified organopolysiloxane (A) are also inferior in storage stability.

And the composition of the comparative example 10 which does not contain the surfactant of (B) component, and the composition of the comparative example 11 in which the compounding quantity of this (B) component is too small, It turns out that it is inferior in storage stability. Moreover, it turns out that the composition of the comparative example 12 in which (B) component was mix | blended exceeding 30 mass% is inferior to the antifouling effect, the durability of an antifouling effect, and the storage stability. Furthermore, it turns out that the composition of the comparative examples 13 and 14 containing the anionic surfactant which is surfactant other than (B) component is inferior to the antifouling effect and the durability of the antifouling effect.
Furthermore, it turns out that the composition of the comparative examples 15 and 16 which does not contain the metal chelating agent of (C) component, and the composition of the comparative example 17 with too little compounding quantity of this (C) component are inferior to a cleaning power. Moreover, it turns out that the composition of the comparative example 18 in which (C) component was mix | blended exceeding 20 mass% is inferior in storage stability.

Further, by using the composition of Example 7-9, 19 and 23-25, shops, offices, toilets such as a house, as a target washbasin-mirror, as in the persistence test antifouling effect cleaning As a result, good detergency was exhibited, and good results were obtained for the durability of the antifouling effect.

Claims (7)

(A) 0.05-10% by mass of polyetheramide-modified organopolysiloxane,
(B) 0.1-30% by mass of at least one surfactant selected from nonionic surfactants, amphoteric surfactants and cationic surfactants,
(C) Metal chelating agent 0.1-20 mass% and (D) Antifouling detergent composition for hard surface around water, comprising water. (A) component is the following average composition formula (1)
R ¹ _a R ² _b Q ¹ _c Q ² _d SiO _{(4-abcd) / 2} (1)
[Wherein, a and d are 0 or a positive number, b and c are positive numbers, and 1.9 ≦ a + b + c + d ≦ 2.2. R ¹ is a hydrogen atom, a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is represented by the following general formula (2 Or (3)
R ³ and R ⁵ are divalent hydrocarbon groups having 2 to 18 carbon atoms, R ⁴ and R ⁶ are hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms, X Is the following general formula (4)
_{^{-R 7 e O f - (C}} 2 H 4 O) g - (R 8 O) h -Y (4)
E and f are each 0 or 1, g and h are 0 or a positive integer of 1 or more, R ⁷ is a divalent hydrocarbon group having 2 to 18 carbon atoms, and R ⁸ is carbon. A divalent hydrocarbon group having 3 to 10 atoms, Y represents a monovalent hydrocarbon group having 1 to 18 carbon atoms. Q ² is the following general formula (5)
_{^{-R 9 i O j - (C}} 2 H 4 O) k - (R 10 O) m -Z (5)
I and j are each 0 or 1, k is a positive integer of 1 or more, m is 0 or a positive integer of 1 or more, and R ⁹ is a divalent carbon atom having 2 to 18 carbon atoms. A hydrogen group, R ¹⁰ is a divalent hydrocarbon group having 3 to ¹⁰ carbon atoms, and Z is a monovalent hydrocarbon group having 1 to 18 carbon atoms. However, d and g are not 0 at the same time. ]
The antifouling detergent composition for hard surfaces around water according to claim 1, which is a polyetheramide-modified organopolysiloxane represented by the formula: (A) component is the following average composition formula (6)
R ¹ _a R ² _b Q ¹ _c Q ² _d Q ³ _e1 SiO _{(4-abcd-e1) / 2} (6)
[Wherein, a and d are 0 or a positive number, b, c and e1 are positive numbers, and 1.9 ≦ a + b + c + d + e1 ≦ 2.2. R ¹ is a hydrogen atom, a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, R ² is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is represented by the following general formula (2 Or (3)
R ³ and R ⁵ are divalent hydrocarbon groups having 2 to 18 carbon atoms, R ⁴ and R ⁶ are hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms, X Is the following general formula (4)
_{^{-R 7 e O f - (C}} 2 H 4 O) g - (R 8 O) h -Y (4)
E and f are each 0 or 1, g and h are 0 or a positive integer of 1 or more, R ⁷ is a divalent hydrocarbon group having 2 to 18 carbon atoms, and R ⁸ is carbon. A divalent hydrocarbon group having 3 to 10 atoms, Y represents a monovalent hydrocarbon group having 1 to 18 carbon atoms. Q ² is the following general formula (5)
_{^{-R 9 i O j - (C}} 2 H 4 O) k - (R 10 O) m -Z (5)
I and j are each 0 or 1, k is a positive integer of 1 or more, m is 0 or a positive integer of 1 or more, and R ⁹ is a divalent carbon atom having 2 to 18 carbon atoms. A hydrogen group, R ¹⁰ is a divalent hydrocarbon group having 3 to ¹⁰ carbon atoms, and Z is a monovalent hydrocarbon group having 1 to 18 carbon atoms. However, d and g are not 0 at the same time. Q ³ represents the following general formula (7) or (8)
R ³ and R ⁵ represent a divalent hydrocarbon group having 2 to 18 carbon atoms, R ⁴ and R ⁶ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. . ]
The antifouling detergent composition for hard surfaces around water according to claim 1, which is a polyetheramide-modified organopolysiloxane represented by the formula: In addition to the above-mentioned components (A) to (D), (E) a thickener 0.01 to 5% by mass for water-based hard surfaces according to any one of claims 1 to 3 Antifouling detergent composition. The thickening agent for the hard surface around water according to claim 4 , wherein the thickener of component (E) is at least one selected from thickening polysaccharides, carboxyvinyl polymers, cross-linked polyacrylic acid or salts thereof. Stain cleaner composition. The antifouling detergent composition for hard surfaces around water according to any one of claims 1 to 5, comprising 0.1 to 20% by mass of (F) a water-soluble solvent in addition to the above components. 7. The antifouling detergent composition for hard surfaces around water according to claim 6 , wherein the water-soluble solvent of component (F) is at least one selected from alcohols, glycol ethers, and terpene hydrocarbon solvents. .