JP7555458B2 - Surface smoothing agent - Google Patents

Description

The present invention relates to a surface smoothing agent for sanitary ware. Specifically, the present invention relates to a surface smoothing agent for sanitary ware that can smooth the surface of sanitary ware such as toilet bowls and inhibit the adhesion of dirt.

Conventionally, various cleaning agents have been developed and used with the aim of easily keeping the surface of sanitary ceramics such as toilet bowls clean and maintaining a high level of aesthetic appeal. For example, in the case of flush toilets, cleaning agents for flush toilets are known that can clean the inside of the toilet bowl by mixing with the flush water and flowing into the toilet bowl when flushed (Patent Document 1). Such cleaning agents are widely used because they have high cleaning power and are easy to use.

On the other hand, it is known that the surface of sanitary ware can be smoothed to prevent dirt from adhering to the surface. For example, Patent Document 2 discloses that when the surface roughness of the glaze layer of sanitary ware is below a certain level, dirt is less likely to adhere to the unevenness of the surface, improving the self-cleaning function against adhering dirt.

However, when the surface of the sanitary ware is badly soiled and the above-mentioned cleaning agents are not sufficient to remove the dirt, applying an acidic or alkaline detergent to a scrubbing pad or brush and scrubbing hard can cause small scratches on the surface of the sanitary ware, making it less smooth and making it more susceptible to dirt adhering to it again.

In addition, cationic surfactants such as quaternary ammonium salt surfactants have a disinfecting effect and are incorporated into toilet cleaners to prevent microbial stains such as blackening. However, cationic surfactants have the disadvantage of increasing the water contact angle with hard surfaces, which makes them more susceptible to the adhesion of stains, particularly lipid stains.

JP 2000-273486 A JP 2000-257139 A

One of the objects of the present invention is to provide a surface smoothing agent that can easily smooth the surface of sanitary ware. Another object of the present invention is to provide a surface smoothing agent that contains a cationic surfactant and has an excellent effect of preventing adhesion of dirt to the surface of sanitary ware.

The inventors conducted intensive research to solve the above problems and discovered that by immersing a thin piece of sanitary ware having a surface arithmetic mean roughness Ra of 14 nm in a diluted solution containing at least a nonionic surfactant and prepared so that the surfactant concentration is 14 ppm for 10 seconds, then removing it and holding it there for 50 seconds, and repeating this operation six times, the arithmetic mean roughness of the surface of the thin piece of sanitary ware can be reduced to 10 nm or less. They also discovered that such a surface roughness can suppress the adhesion of dirt.

Furthermore, it was found that when a cationic surfactant is added to a surface smoothing agent that satisfies the above-mentioned arithmetic mean roughness, adhesion of dirt (especially lipid dirt such as feces) to the surface of the sanitary ware can be effectively prevented, even though the water contact angle of the surface of the thin piece of sanitary ware after operation is 65° or more.

The present invention was completed through further investigation based on these findings.

That is, the present invention provides the following aspects.
Item 1. Contains a nonionic surfactant,
A surface smoothing agent for sanitary ware, which has an arithmetic mean roughness (Ra) of the surface of a thin piece of the sanitary ware being 10 nm or less after carrying out the following operations (1) to (4):
[operation]
(1) A diluted solution of a surface-leveling agent is prepared by diluting the surface-leveling agent in water so that the concentration of the surfactant is 14 ppm. Also, a thin piece of sanitary ware having an arithmetic mean roughness Ra of 14 nm is prepared.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the surface smoothing agent for 10 seconds and then removed.
(3) After removing the thin piece of sanitary ware from the diluted solution of the surface-smoothing agent, keep it for 50 seconds. (4) Repeat steps (2) and (3) above a total of six times.
Item 2. The surface-smoothing agent according to Item 1, which contains a cationic surfactant.
Item 3. The surface-smoothing agent according to Item 1, which contains an anionic surfactant.
Item 4. The surface-smoothing agent according to Item 2, wherein after the operations (1) to (4) are carried out, the surface of the thin piece of sanitary ware has a water contact angle of 65° or more.
Item 5. The surface smoothing agent according to any one of Items 1 to 4, wherein the nonionic surfactant is present in an amount of 3 to 100 parts by weight per 100 parts by weight of the total amount of the surfactants.
Item 6. The surface smoothing agent according to any one of Items 1 to 5, which is used to prevent feces from adhering to the surface of a toilet bowl.
Item 7. A method for smoothing a surface of a sanitary ware, comprising running water over the surface of the sanitary ware with a diluted solution of the surface-smoothing agent according to any one of items 1 to 5.

According to the present invention, it is possible to provide a surface smoothing agent capable of smoothing the surface of sanitary ware such as a toilet bowl. In addition, the surface smoothing agent of the present invention can smooth out minute irregularities on the surface of sanitary ware such as a toilet bowl, thereby suppressing adhesion of dirt to the surface.

In addition, according to one aspect of the present invention, even if the water contact angle of the sanitary ware surface increases due to the inclusion of a cationic surfactant, the adhesion of dirt to the sanitary ware surface can be effectively prevented by smoothing the sanitary ware surface, and thus, in addition to preventing the adhesion of dirt to the sanitary ware surface, the disinfecting action based on the cationic surfactant can also be effectively exerted.

1 is an AFM image of the surface of an untreated ceramic panel used in the examples. 1 is an AFM image of the surface of a ceramic panel treated with the surface-leveling agent of Example 1. 1 is an AFM image of the surface of a ceramic panel treated with the surface-leveling agent of Example 2. 1 is an AFM image of the surface of a ceramic panel treated with the surface-leveling agent of Example 3.

1. Surface-Smoothing Agent The surface-smoothing agent for sanitary ware of the present invention contains a nonionic surfactant and is characterized in that, after carrying out the operations (1) to (4) below, the arithmetic mean roughness Ra of the surface of a thin piece of sanitary ware is 10 nm or less.
[operation]
(1) A surface-leveling agent dilution solution is prepared by diluting the surface-leveling agent in water so that the concentration of the surfactant is 14 ppm. Also, a thin piece of sanitary ware having an arithmetic mean roughness Ra of 14 nm is prepared.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the surface smoothing agent for 10 seconds and then removed.
(3) After removing the thin piece of sanitary ware from the diluted solution of the surface-smoothing agent, keep it for 50 seconds. (4) Repeat steps (2) and (3) above a total of six times.
The surface smoothing agent of the present invention will be described in detail below.

[Surfactants]
Nonionic surfactants
The surface smoothing agent of the present invention contains at least a nonionic surfactant as a surfactant. By containing a nonionic surfactant, the surface of sanitary ware such as a toilet bowl can be smoothed.

The nonionic surfactant used in the present invention is not particularly limited as long as it can provide the surface smoothing properties described below, and known nonionic surfactants can be used. Specific examples of nonionic surfactants include glycerin fatty acid esters such as glyceryl monostearate, self-emulsifying glyceryl monostearate, and glyceryl monoisostearate; polyoxyethylene glycerin fatty acid esters such as POE glyceryl monostearate and POE glyceryl monooleate; polyglycerin fatty acid esters such as diglyceryl monostearate, tetraglyceryl tristearate, and decaglyceryl pentastearate; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan sesquistearate, and sorbitan monooleate; POE sorbitan monococonutriate, POE tristearate, and POE glyceryl monooleate; Polyoxyethylene sorbitan fatty acid esters such as POE sorbitan monolaurate and POE sorbitan trioleate; polyoxyethylene sorbit fatty acid esters such as POE sorbit monolaurate and POE sorbit tetraoleate; polyethylene glycol fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate and polyethylene glycol distearate; alkylene glycol mono fatty acid esters such as propylene glycol monolaurate and propylene glycol monomyristate; glycerin monododecyl ether, glycerin monolaurate, glycerin monostearate, glycerin monomyristate, glycerin monostearate ... alkyl polyhydric alcohol ethers such as glycerin monocetyl ether, glycerin monostearyl ether, and pentaerythritol monododecyl ether; polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers (lauryl ether, POE cetyl ether, POE stearyl ether, etc.) and polyoxyethylene polyoxypropylene alkyl ethers (POE·POP cetyl ether, POE·POP decyltetradecyl ether, etc.); polyoxyalkylene block polymers; polyoxyethylene alkyl ethers such as POE nonylphenyl ether, POE octylphenyl ether, and POE branched-chain octylphenyl ether. alkylphenyl ether; polyoxyethylene alkylamines such as POE stearylamine and POE oleylamine; fatty acid alkanolamides such as coconut fatty acid diethanolamide, lauric acid diethanolamide, and palm kernel oil fatty acid diethanolamide; acyl methyl glucamides such as lauric acid methyl glucamide and coconut fatty acid methyl glucamide; and other examples include acetylene glycol, POE acetylene glycol, POE lanolin, POE lanolin alcohol, POE castor oil, POE hydrogenated castor oil, POE phytosterol, POE cholestanol, POE nonylphenyl formaldehyde condensate, and alkyl polyglucosides. These may be used alone or in combination of two or more. POE stands for polyoxyethylene, and POP stands for polyoxypropylene.

Among these, polyoxyalkylene alkyl ethers and polyoxyalkylene block copolymers are preferred as nonionic surfactants in the present invention, since they can effectively smooth the surface of sanitary ware such as toilet bowls by repairing fine scratches on the surface.

Suitable examples of the polyoxyalkylene alkyl ether used in the present invention include compound (A) represented by the following general formula (1) and compound (B) represented by the following general formula (2).

(Compound (A))
R ¹ -O-[(EO)a/(PO)b]-H (1)
[In the general formula (1), ^R1 is a linear or branched alkyl group having 8 to 11 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, a is the average number of moles of EO added and is 5≦a, b is the average number of moles of PO added and is 0≦b, and [(EO)a/(PO)b] represents random addition or block addition of EO and PO.]

In the general formula (1), R ¹ represents a linear or branched alkyl group having 8 to 11 carbon atoms. R ¹ is preferably a linear or branched alkyl group having 9 to 10 carbon atoms, more preferably a linear or branched alkyl group having 10 carbon atoms, particularly preferably a branched alkyl group having 10 carbon atoms, and particularly preferably an isodecyl group.

In general formula (1), EO represents an oxyethylene group. Furthermore, a represents the average number of moles of EO added, and a≧5. The average number of moles of EO added a is preferably 5≦a≦30, and more preferably 5≦a≦15.

In addition, in the general formula (1), PO represents an oxypropylene group. Furthermore, b represents the average number of moles of PO added, and is 0≦b. The average number of moles of PO added, b, is preferably 0≦b≦15, and more preferably 0≦b≦10.

In addition, in general formula (1), [(EO)a/(PO)b] indicates random or block addition of EO and PO.

The HLB value of compound (A) is preferably 14.3 or less, more preferably 12.0 to 14.3, and even more preferably 12.8 to 13.9. In this specification, the HLB value of component (A) is a value calculated by the Griffin method.

Examples of polyoxyalkylene alkyl ether type nonionic surfactants corresponding to compound (A) include commercially available "FINESURF D-1305", "FINESURF D-1307", "FINESURF NDB-1000", "FINESURF D-65", "FINESURF D-85", "Wondersurf ID-1033", "Safetycut ID-1055", "Safetycut ID-1061", "Wondersurf ID-90" (all manufactured by Aoki Oil Industries Co., Ltd.), "Naroacty ID70" (manufactured by Sanyo Chemical Industries Co., Ltd.), "Noigen LF-60X", "Noigen LF-80X", "Noigen SD-70", and "Noigen SD-80" (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and these commercially available products can also be used in the present invention.

(Compound (B))
R ² -O-[(EO) _c /(PO) _d ]-H (2)
[In the general formula (2), ^R2 is a linear or branched alkyl group having 12 to 14 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, c is the average number of moles of EO added and is 1 or less, d is the average number of moles of PO added and is 1 or less, and [(EO) _c /(PO) _d ] represents random addition or block addition of EO and PO.]

In the general formula (2), R ² represents a linear or branched alkyl group having 12 to 14 carbon atoms.
^R2 is preferably a linear or branched alkyl group having 12 to 13 carbon atoms.

In addition, in the general formula (2), EO represents an oxyethylene group. Furthermore, c represents the average number of moles of EO added, and is 1≦c. The average number of moles of EO added c is preferably 1≦c≦30, and more preferably 5≦c≦25.

In addition, in the general formula (2), PO represents an oxypropylene group. Furthermore, d represents the average number of moles of PO added, and is 1≦d. The average number of moles of PO added, d, is preferably 1≦d≦15, and more preferably 1≦d≦10.

In addition, in general formula (2), [(EO)c/(PO)d] indicates random or block addition of EO and PO.

Examples of polyoxyalkylene alkyl ether type nonionic surfactants corresponding to compound (B) include "SANNONIC FN140" (manufactured by Sanyo Chemical Industries, Ltd.), "WONDASURF 140" and "WONDASURF S-1400" (all manufactured by Aoki Oil Industries Co., Ltd.), and "NOIGEN TDX-120D" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and these commercially available products can also be used in the present invention.

A suitable example of the polyoxyalkylene block copolymer used in the present invention is compound (C) represented by the following general formula (2).

(Compound (C))
H-O-[(EO) _e / (BO) _f / (PO) _g / (BO) _h / (EO) _i ]-H (3)
[In the general formula (3), EO is an oxyethylene group, BO is an oxybutylene group, PO is an oxypropylene group, e and i are the average number of moles of EO added, and are 1≦e and 1≦i, f and h are the average number of moles of BO added, and are 1≦f and 1≦h, g is the average number of moles of PO added, and [(EO) _e /(BO) _f /(PO) _g /(BO) _h /(EO) _i ] represents random addition or block addition of EO, BO and PO.]

In general formula (3), EO represents an oxyethylene group. e and i represent the average number of moles of EO added, and 1≦e and 1≦i.

In addition, in general formula (3), BO represents an oxybutylene group. f and h represent the average number of moles of EO added, and 1≦f and 1≦h are satisfied.

In general formula (3), PO represents an oxypropylene group. g represents the average number of moles of PO added, and is 1 or less.

In addition, in the general formula (3), [(EO) _e /(BO) _f /(PO) _g /(BO) _h /(EO) _i ] represents random addition or block addition of EO and PO.

As the nonionic surfactant in the present invention, from the viewpoint of being able to suitably provide the surface smoothing properties described below, at least one selected from the group consisting of the above-mentioned compounds (A), (B), and (C) is preferably used.

The content of the nonionic surfactant in the surface smoothing agent of the present invention may be appropriately set within a range that provides the surface smoothing properties described below depending on the type of nonionic surfactant used and the dilution ratio when applied to the surface of the sanitary ware, but is usually 0.1 to 80% by weight, preferably 1 to 70% by weight, and more preferably 2 to 60% by weight.

Cationic surfactantThe surface-smoothing agent of the present invention may contain a cationic surfactant to the extent that the surface smoothing properties described below are satisfied. Cationic surfactants have a disinfecting effect, and by including a cationic surfactant in the surface-smoothing agent of the present invention, it is possible to provide the effect of suppressing adhesion of microbial stains, such as blackening, to the sanitary ware surface. Since cationic surfactants have the effect of increasing the water contact angle of the sanitary ware surface, in the prior art, the incorporation of a cationic surfactant was actually a factor that made stains more likely to adhere, but the surface-smoothing agent of the present invention has the surface smoothing properties described below, making it possible to effectively suppress adhesion of stains even if the water contact angle of the sanitary ware surface increases.

The type of cationic surfactant used in the present invention is not particularly limited, but examples thereof include quaternary ammonium salt type surfactants such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyltrimethylammonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, benzethonium chloride, benzalkonium chloride, and didecyldimethylammonium adipate; amidoamine salt type cationic surfactants such as stearic acid diethylaminoethylamide glutamate and lanolin fatty acid diethylaminoethylamide glutamate; and lauric acid amidoguanidine hydrochloride. These cationic surfactants may be used alone or in combination of two or more.

Among these, from the viewpoint of optimally combining a disinfecting effect with an effect of preventing dirt adhesion, a quaternary ammonium salt type surfactant is preferable, and didecyldimethylammonium chloride is more preferable. Furthermore, by blending such a quaternary ammonium salt type surfactant, the water contact angle characteristics described below can also be optimally satisfied.

When a cationic surfactant is contained in the surface smoothing agent of the present invention, the content may be appropriately set according to the type of cationic surfactant used and the dilution ratio when applied to the surface of the sanitary ware, within the limit that satisfies the surface smoothness characteristics described below, but is usually 0.01 to 60% by weight, preferably 0.1 to 50% by weight, and more preferably 1 to 40% by weight.

When the surface smoothing agent of the present invention contains a cationic surfactant, the content ratio of the nonionic surfactant to the cationic surfactant is determined according to the content of both surfactants described above, but for example, the cationic surfactant is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and even more preferably 0.1 to 1 part by weight per 1 part by weight of the nonionic surfactant.

Other Surfactants The surface smoothing agent of the present invention may further contain other surfactants in addition to the above-mentioned surfactants, as long as the surface smoothing properties described below are satisfied. Examples of other surfactants include anionic surfactants and amphoteric surfactants. Among these, anionic surfactants are preferred.

Specific examples of anionic surfactants include fatty acid salts such as soap base, sodium laurate, sodium palmitate, and coconut potassium soap; POE lauryl ether carboxylate, POP/POE ether myristate; higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, etc.); alkyl ether sulfate salts such as triethanolamine POE lauryl sulfate and sodium POE lauryl sulfate; sodium lauroyl sarcosine, lauroyl-N-methyl-β-arabinanyl sulfate, etc. N-acylamine salts such as sodium lauroyl glutamate, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, and diethanolamine N-palmitoyl aspartate; higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyl taurate, sodium coconut fatty acid methyl taurate, sodium lauroyl methyl taurate, and sodium POE lauryl amide ether sulfonate; sodium POE oleyl ether phosphate, POE stearyl ether phosphate, and POE lauryl amide ether. Phosphate salts such as sodium phosphate; sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate; alkylbenzene sulfonates such as sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, and linear dodecylbenzene sulfonic acid; sulfated oils such as sodium hydrogenated coconut oil fatty acid glycerin sulfate and turpentine oil, α-olefin sulfonates, and higher fatty acid ester sulfones. Examples of anionic surfactants include higher fatty acid ester sulfates such as sodium lauroyl monoethanolamide succinate and secondary alcohol sulfate salts; higher fatty acid alkylolamide sulfates such as sodium lauroyl monoethanolamide succinate and sodium caseinate; sulfate ester salt or sulfonate salt surfactants such as alkyl sulfate ester salts, polyoxyethylene alkyl sulfate ester salts, fatty acid amide ether sulfate ester salts, acyl isethionate salts, and sulfosuccinate salts; and carboxylic acid surfactants such as ether carboxylates, fatty acid amide ether carboxylates, N-acyliminodiacetic acid, and N-acylamino acid salts. These anionic surfactants may be used alone or in combination of two or more.

Among them, from the viewpoint of satisfying the surface smoothness characteristics described below, the anionic surfactant is preferably a higher fatty acid ester sulfate, and more preferably an α-olefin sulfonate. Specific examples of the α-olefin sulfonate include compound (D) represented by the following general formula (4).
(Compound (D))
C _n H _2n O ₃ SNa, C _n H _2n+1 O ₄ SNa (4)
[In the general formula (4), n is an integer from 12 to 18.]

In general formula (4), n is preferably an integer from 12 to 14.

Examples of amphoteric surfactants include betaine-type amphoteric surfactants such as coconut oil fatty acid amidopropyl dimethylaminoacetate betaine, lauryl dimethylaminoacetate betaine, lauric acid amidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, and lauryl hydroxysulfobetaine; amino acid-type amphoteric surfactants such as sodium β-laurylaminopropionate and sodium lauryl diaminoethyl glycine; and amine oxide-type amphoteric surfactants such as decyl dimethylamine oxide and lauryl dimethylamine oxide. These amphoteric surfactants may be used alone or in combination of two or more.

These surfactants may be used alone or in combination of two or more.

When an anionic surfactant is contained in the surface smoothing agent of the present invention, the content may be appropriately set according to the type of anionic surfactant used and the dilution ratio when applied to the surface of the sanitary ware, within the limit that satisfies the surface smoothness characteristics described below, but is usually 0.1 to 70% by weight, preferably 1 to 60% by weight, and more preferably 1 to 50% by weight.

When the surface smoothing agent of the present invention contains an anionic surfactant, the content ratio of the nonionic surfactant to the anionic surfactant is determined according to the content of both surfactants described above, but for example, the content of the anionic surfactant is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and even more preferably 0.1 to 1 part by weight, per 1 part by weight of the nonionic surfactant.

When an amphoteric surfactant is contained in the surface smoothing agent of the present invention, the content may be appropriately set according to the type of amphoteric surfactant used and the dilution ratio when applied to the surface of the sanitary ware, within the limit that satisfies the surface smoothness characteristics described below, but is usually 0.01 to 50% by weight, preferably 0.1 to 40% by weight, and more preferably 1 to 30% by weight.

When the surface smoothing agent of the present invention contains an amphoteric surfactant, the content ratio of the nonionic surfactant to the amphoteric surfactant is determined according to the content of both surfactants described above, but for example, the content of the amphoteric surfactant is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, and even more preferably 0.01 to 0.5 parts by weight per 1 part by weight of the nonionic surfactant.

Total content of surfactants, etc. In the surface smoothing agent of the present invention, the total content of surfactants (total content of surfactants) is determined depending on the types and combination of surfactants used, the content of each surfactant described above, and the like, but is, for example, 0.1 to 80% by weight, preferably 1 to 70% by weight, and more preferably 2 to 60% by weight.

In the surface smoothing agent of the present invention, the ratio of the nonionic surfactant to the total amount of surfactants is determined according to the types and combinations of surfactants used, the contents of each surfactant described above, etc., but from the viewpoint of suitably satisfying the surface smoothness characteristics described below, the nonionic surfactant is 3 to 100 parts by weight, preferably 30 to 100 parts by weight, and more preferably 50 to 100 parts by weight per 100 parts by weight of the total amount of surfactants contained.

[Other ingredients]
The surface-smoothing agent of the present invention may contain other components, if necessary, in addition to the above-mentioned surfactant.

(Fragrance)
The surface-smoothing agent of the present invention may further contain a fragrance component as long as it satisfies the surface smoothing properties described below. By containing a fragrance component, a desired fragrance can be imparted to a space in which the surface-smoothing agent of the present invention is used, such as a toilet.

The fragrance component to be included in the surface smoothing agent of the present invention is not particularly limited as long as it is a fragrance that is normally used in cleaning compositions for flush toilets, etc., and the fragrance component to be blended may be appropriately selected depending on the fragrance to be provided. Examples of the fragrance components used in the present invention include natural fragrances as well as synthetic fragrances such as hydrocarbon-based fragrances, ether-based fragrances, ester-based fragrances, alcohol-based fragrances, aldehyde-based fragrances, and ketone-based fragrances.

Specific examples of natural fragrances include lemon oil, orange oil, bergamot oil, ylang-ylang oil, patchouli oil, citronella oil, lemongrass oil, boerose oil, clove oil, eucalyptus oil, cedar oil, lavender oil, sandalwood oil, vetiver oil, geranium oil, labdanum oil, mint oil, peppermint oil, rose oil, jasmine oil, and litz acubeba oil. Examples of hydrocarbon fragrances include limonene, α-pinene, camphene, p-cymene, and fenchene. Examples of ether fragrances include tetrahydro-2,4-dimethyl-4-phenylfuran, 1,8-cineole, rose oxide, cedrol methyl ether (cedrumber), p-cresyl methyl ether, isoamylphenyl ethyl ether, 4-phenyl-2,4,6-trimethyl-1,3-dioxane, and anethole. Examples of ester-based fragrances include geranyl acetate, ethyl acetate, ethyl propionate, methyl butyrate, ethyl isobutyrate, ethyl butyrate, butyl acetate, ethyl 2-methylbutyrate, isoamyl acetate, ethyl 2-methylpentanoate (manzanate), hexyl acetate, allyl hexanoate, tricyclodecenyl propionate (VERTOPRO; fluorocyclen), allyl heptanoate, isobornyl acetate, linalyl acetate, citronellyl acetate, 2-ter-butylcyclohexyl acetate (narcidol), and the like. Examples of alcohol-based fragrances include linalool, 3-octanol, 2,6-dimethyl-heptanol, 10-undecenol, geraniol, nerol, citronellol, rhodinol, myrcenol, tetrahydrolinalool, terpineol, cedrol, 2,4-dimethyl-3-cyclohexane-1-methanol, 4-isopropylcyclohexanol, nerolidol, 9-decenol, cis-3-hexenol, trans-2-hexenol, and eugenol. Examples of aldehyde fragrances include citronellal, octanal, paraldehyde, benzaldehyde, aldehyde C-6, aldehyde C-7, aldehyde C-8, aldehyde C-9, aldehyde C-10, triplal, p-ethyldimethylhydrocinnamic aldehyde (florazone), 2-tridecenal, and aldehyde C11. Examples of ketone-based fragrances include 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, acetoin, methyl amyl ketone, ethyl amyl ketone, methyl hexyl ketone, methyl nonyl ketone, methylheptenone, coavone, camphor, carvone, menthone, d-pulegone, piperitone, fenchone, geranyl acetone, maltol, ethyl maltol, 2,5-dimethyl-4-hydroxyfuranone, plicatone, acetophenone, p-methylacetophenone, benzyl acetone, and benzyl ketone.

These fragrance ingredients may be used alone as a single fragrance, or in combination of two or more as a blended fragrance.

In the surface smoothing agent of the present invention, the content of the fragrance component is not particularly limited as long as the surface smoothness characteristics described below can be satisfied, and may be set appropriately depending on the type of fragrance component and the strength of the fragrance to be provided, for example, 0.1 to 20% by weight, preferably 1 to 15% by weight, and more preferably 2 to 15% by weight.

(Base)
The surface smoothing agent of the present invention may contain water and a solvent as a base, as necessary, depending on its form and use. The type of solvent is not particularly limited, and examples thereof include monohydric lower alcohols such as ethanol, propanol, and butanol; and polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, and glycerin. The content of the base is not particularly limited as long as the surface smoothness characteristics described below can be satisfied, and can be appropriately designed depending on the type of base, and examples thereof include 20 to 99.9% by weight, preferably 30 to 99% by weight, and more preferably 40 to 98% by weight, in the case of water.

In addition, the surface smoothing agent of the present invention may further contain, as necessary, appropriate amounts of additives such as enzymes, bactericides, chelating agents, colorants, pigments, deodorants, emulsifying and solubilizing agents for oily components, bulking agents, solubility regulators, bleaching agents, water repellents, hydrophilic agents, fillers, pH regulators, thickeners, moldability improvers, lubricants, buffers, opacifying agents, and defoamers, so long as the surface smoothing agent satisfies the surface smoothing characteristics described below.

[form]
The surface-smoothing agent of the present invention may be in any form of solid, gel, semi-solid, or liquid, and may be appropriately selected depending on the application.

[Surface smoothness characteristics]
The surface smoothing agent of the present invention is characterized in that, after carrying out the following operations (1) to (4), the arithmetic mean roughness Ra of the surface of a thin piece of sanitary ware becomes 10 nm or less.
[operation]
(1) A diluted solution of a surface-leveling agent is prepared by diluting the surface-leveling agent in water so that the concentration of the surfactant is 14 ppm. Also, a thin piece of sanitary ware having an arithmetic mean roughness Ra of 14 nm is prepared.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the surface smoothing agent for 10 seconds and then removed.
(3) After removing the thin piece of sanitary ware from the diluted solution of the surface-smoothing agent, keep it for 50 seconds. (4) Repeat steps (2) and (3) above a total of six times.

The surface smoothing agent of the present invention has the property of making the arithmetic mean roughness Ra of the surface of the sanitary ware 10 nm or less when the above operations (1) to (4) are carried out, and the surface of the sanitary ware can be smoothed. Smoothing the surface of the sanitary ware can inhibit adhesion of dirt to the surface. From the viewpoint of further enhancing the effect of inhibiting adhesion of dirt, the arithmetic mean roughness Ra is preferably 1 to 10 nm, and more preferably 2 to 8 nm.

In the present invention, the arithmetic mean roughness Ra is the arithmetic mean roughness Ra defined in JIS B 0601: 2001. In the present invention, the arithmetic mean roughness Ra is a value determined by measurement using an atomic force microscope (AFM) under the following conditions.
(Analysis conditions)
Test equipment: SIMADZU SPM-9700 (manufactured by Shimadzu Corporation)
Measurement probe: NanoWorld NCH
Mode: Phase scanner: 30 μm
Range: 10 μm
Vibration: 0.25Hz

The steps (1) to (4) for measuring the arithmetic mean roughness Ra are explained below.

In the operation (1), the surface smoothing agent of the present invention is diluted with water so that the total concentration of the surfactants contained in the surface smoothing agent (total concentration of all surfactants) is 14 ppm to prepare a diluted solution. There are no particular limitations on the water used for dilution, and it may be distilled water, ion-exchanged water, or pure water, but distilled water is preferred.

In addition, in the step (1), a thin piece of sanitary ware with an arithmetic mean roughness Ra of 14 nm is prepared. The thin piece of sanitary ware is a thin piece having a ceramic surface used for sanitary ware. Sanitary ware is a ceramic device used in sanitary facilities such as toilets, washbasins, bathtubs, and bidets. The thin piece of sanitary ware prepared in the step (1) may have a surface arithmetic mean roughness Ra of 14 nm, and specifically, a ceramic tile (KY Tile P4-100, manufactured by Nippon Test Panel Co., Ltd.) can be used.

In operation (2), a thin piece of sanitary ware is immersed in the diluted surface-smoothing agent for 10 seconds and then removed. In operation (2), the thin piece of sanitary ware is immersed in the diluted surface-smoothing agent prepared in operation (1) for 10 seconds, for example, with the surface of the thin piece at approximately 70° to the horizontal, and then removed. The temperature of the diluted surface-smoothing agent during operation (2) is not particularly limited as it is not thought to affect the measured values, but a temperature of around 25°C is preferable.

In step (3), the removed thin piece of sanitary ware is dried by holding it in the air for 50 seconds. The temperature during step (2) is not particularly limited as it is not thought to affect the measured values, but a temperature of around 25°C is preferable.

In operation (4), operations (2) and (3) are counted as one cycle, and a total of six cycles are performed.

After completing operation (4), the surface of the thin piece of sanitary ware is thoroughly dried, and then the arithmetic mean roughness Ra of the surface is measured.

[Water contact angle characteristics]
One embodiment of the surface smoothing agent of the present invention includes one that contains a cationic surfactant together with a nonionic surfactant, and that has a water contact angle of 65° or more on the surface of a thin piece of sanitary ware after carrying out the same operations (1) to (4) as in the measurement of the arithmetic mean roughness Ra. The surface smoothing agent of the present invention thus contains a cationic surfactant, and even if the water contact angle becomes large, by being endowed with the above-mentioned surface smoothing properties, it can effectively inhibit adhesion of dirt (particularly feces) to the sanitary ware surface.

In a preferred embodiment when the surface smoothing agent of the present invention contains a cationic surfactant, the water contact angle of the surface of the thin piece of sanitary ware after the steps (1) to (4) is preferably 65 to 100°, more preferably 70 to 95°, and even more preferably 70 to 90°.

The water contact angle is measured after carrying out the same steps (1) to (4) as in the measurement of the arithmetic mean roughness Ra, and then thoroughly drying the surface of the thin piece of sanitary ware. In the present invention, the water contact angle is a value measured using a contact angle meter that uses the sessile drop method.

[Usage]
The surface smoothing agent of the present invention is for sanitary ware, and can smooth the surface of the sanitary ware to suppress adhesion of dirt. Sanitary ware is not particularly limited, and examples thereof include ceramic toilet bowls, wash basins, bathtubs, bidets, etc. Among them, the surface smoothing agent of the present invention is preferably applied to toilet bowls, since it is excellent in suppressing adhesion of feces to the surface of the toilet bowl and the occurrence of blackening.

The surface-smoothing agent of the present invention may be applied directly to a sanitary container such as a toilet bowl to be cleaned, or, for example, when the surface-smoothing agent of the present invention is used in a flush toilet, it may be applied to the toilet bowl by being diluted with the flush water and flowing when the toilet is flushed. When the surface-smoothing agent of the present invention is used diluted with the flush water of a flush toilet, the dilution ratio is not particularly limited, but may be, for example, about 10,000 to 1,000,000 times, and preferably about 20,000 to 500,000 times.

When the surface smoothing agent of the present invention is used by diluting it in flush water, it may be used on the tank of a flush toilet or on the rim. The on-tank version is used by placing it on the hand washing section of a flush toilet, and is applied by contacting a container containing the surface smoothing agent with flush water for cleaning supplied to the hand washing section, causing the surface smoothing agent to flow out of the container and discharging the flush water with the surface smoothing agent dissolved in it into the toilet bowl. The rim version is used by attaching it to the rim of a flush toilet, and is applied by contacting a container containing the surface smoothing agent with flush water discharged into the toilet bowl, causing the surface smoothing agent to flow out of the container and discharging the flush water with the surface smoothing agent dissolved in it into the toilet bowl.

When the surface smoothing agent of the present invention is applied to a flush toilet, it may be applied to any flushing system, such as wash-off, siphon, siphon jet, blow-out, siphon vortex, power drive, or tornado. However, it is preferable to apply the agent to a flush toilet with a vortex flow (tornado) flushing system, in which flush water is forcefully sprayed in a vortex shape from a rim outlet, because it can be applied to a wider range of the toilet surface.

As described above, the surface smoothing agent of the present invention can smooth the surface of sanitary ware and prevent dirt from adhering.

2. Method for smoothing a sanitary ware surface The method for smoothing a sanitary ware surface of the present invention is characterized by running a diluted solution of the above-mentioned surface smoothing agent over the sanitary ware surface.

The surface of the sanitary ware can be smoothed by running a diluted solution of the above-mentioned surface smoothing agent over the surface of the sanitary ware. If the surface of the sanitary ware has minute irregularities such as scratches, dirt will easily adhere to it. By applying the above-mentioned surface smoothing agent to such a sanitary ware surface, the surface can be smoothed and the adhesion of dirt can be suppressed.

The surface smoothing agent, its dilution, and sanitary ware of the present invention are as described above in "1. Surface smoothing agent."

The flushing method is as described above in "1. Surface smoothing agent," for example, by diluting the surface smoothing agent with flush water from a flush toilet and flushing the diluted water.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

Experimental Example 1
(Preparation of Surface-Smoothing Agent)
A surface-smoothing agent was prepared by mixing the components so as to obtain the formulation shown in Table 1. The specific surfactants shown in Table 1 were as follows:
Polyoxyalkylene alkyl ether 1: "Noigen LF-80X", manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Polyoxyalkylene alkyl ether 2: "Sannonic FN140", manufactured by Sanyo Chemical Industries, Ltd. Polyoxyalkylene tridecyl ether 3: a compound represented by the following general formula (A): R ² -O-[(EO) _c /(PO) _d ]-H (A)
[In the general formula (A), ^R2 represents a linear or branched alkyl group having a molecular weight of 12 to 14, EO represents an oxyethylene group, PO represents an oxypropylene group, c represents the average number of moles of EO added and is 1 or less, d represents the average number of moles of PO added and is 1 or less, and [(EO) _c /(PO) _d ] represents the random addition or block addition of EO and PO.]
Polyoxyethylene polyoxypropylene block polymer: a compound represented by the following general formula (B): H-O-[(EO) _e /(BO) _f /(PO) _g /(BO) _h /(EO) _i ]-H (B)
[In the general formula (B), EO is an oxyethylene group, BO is an oxybutylene group, PO is an oxypropylene group, e and i are the average number of moles of EO added, and are 1≦e and 1≦i, f and h are the average number of moles of BO added, and are 1≦f and 1≦h, g is the average number of moles of PO added, and [(EO) _e /(BO) _f /(PO) _g /(BO) _h /(EO) _i ] represents random addition or block addition of EO, BO and PO.]
- Sodium α-olefin sulfonate: "Neogen AO-90", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

(Evaluation of ceramic tile surface smoothing)
As a thin piece of sanitary ware, a ceramic tile (KY Tile P4-100, manufactured by Nippon Test Panel Co., Ltd.) having a length of 15 mm, a width of 15 mm, and a thickness of 5 mm was prepared.
The surface smoothing agent prepared above was appropriately diluted with distilled water to prepare a diluted solution so that the total amount of surfactant contained in the surface smoothing agent was 14 ppm. The ceramic tile was immersed in this diluted solution (25°C) for 10 seconds in a state in which the ceramic surface was approximately 70°C relative to the horizontal surface, and then pulled out of the test solution and held at 25°C for 50 seconds to dry, which constitutes one cycle, for a total of six cycles of immersion and drying. After that, it was confirmed that the surface was completely dry (left overnight), and the surface of the ceramic tile was measured under the following conditions using an atomic force microscope (AFM) (SPM-9700, manufactured by Shimadzu Corporation) to determine the arithmetic mean roughness Ra. In addition, the arithmetic mean roughness Ra of the surface of the ceramic tile in an untreated state without performing the above operation was also determined.
(Analysis conditions)
Test equipment: SIMADZU SPM-9700
Measurement probe: NanoWorld NCH
Mode: Phase scanner: 30 μm
Range: 10 μm
Vibration: 0.25Hz

The results are shown in Table 2. Figures 1 to 4 show AFM images of an untreated ceramic panel and a ceramic panel treated with the surface smoothing agents of Examples 1 to 3, respectively. Table 2 shows that by immersing a ceramic panel with an arithmetic mean roughness of the surface of the ceramic panel, which is 14 nm in diameter, a specified number of times in a diluted solution in which a surface smoothing agent containing a nonionic surfactant is diluted to a surfactant concentration of 14 ppm, the arithmetic mean roughness of the surface of the ceramic panel becomes 10 nm or less. This result confirms that a surface smoothing agent containing a nonionic surfactant can smooth ceramic surfaces.

Experimental Example 2
For the surface smoothing agents of Examples 1 to 3, a thin piece of sanitary ware (KY Tile P4-100, manufactured by Nippon Test Panel Co., Ltd.) was subjected to a total of six cycles of immersion and drying in the same manner as in "Evaluation of Surface Smoothing of Ceramic Tile" in Experimental Example 1. Thereafter, it was confirmed that the surface was completely dry (left overnight), and the contact angle of a water droplet (water contact angle) when distilled water was dropped onto the surface of the thin piece of sanitary ware was measured using a contact angle meter (DropMaster500 manufactured by Kyowa Interface Science Co., Ltd., measurement and analysis integrated software: FAMAS, water droplet amount: 6 μl, measurement waiting time: 1000 ms). The measurement results of the water contact angle are shown in Table 3.

The surface smoothing agents of Examples 1 and 2 were also placed in containers for on-tank toilet cleaners, and the following practical use tests were carried out. The containers in question are those commonly used for on-tank toilet cleaners, and the containers containing the surface smoothing agents are installed in the hand washing section above the water tank of a flush toilet, and are configured so that when water is supplied after flushing, the agent is diluted approximately 70,000 times with the supplied water and stored in the water tank as flush water.

(Actual use test)
In a flush toilet in a general household, the number of times that feces adhered to the toilet bowl was counted for 30 days without the surface smoothing agents of Examples 1 and 2. While the number of times that feces adhered was being counted, the toilet bowl was polished and cleaned whenever feces were found to adhere. Next, in households where feces were found to adhere, the surface smoothing agent (Example 1 or 2) contained in a container for on-tank toilet cleaner was placed in the hand washing section above the water tank of the flush toilet, and the number of times that feces adhered to the toilet bowl was counted under the same conditions as above for 30 days.

The results are shown in Table 4. When the surface smoothing agents of Examples 1 and 2 were used, fecal adhesion was effectively suppressed. In particular, when the surface smoothing agent of Example 2, which contains a nonionic surfactant and a cationic surfactant, was used, the water contact angle after the above operation was 65° or more, and the frequency of fecal adhesion was significantly reduced, even though the surface environment was one in which dirt easily adhered.

Claims (5)

Contains a nonionic surfactant and a cationic surfactant ,
the nonionic surfactant is a polyoxyalkylene alkyl ether,
the cationic surfactant is a quaternary ammonium salt surfactant,
After carrying out the following operations (1) to (4), the arithmetic mean roughness Ra of the surface of the sanitary ware thin plate piece is 10 nm or less , and the water contact angle of the surface of the sanitary ware thin plate piece is 65° or more .
A surface smoothing agent for sanitary ware.
[operation]
(1) A diluted solution of a surface-leveling agent is prepared by diluting the surface-leveling agent in water so that the concentration of the surfactant is 14 ppm. Also, a thin piece of sanitary ware having an arithmetic mean roughness Ra of 14 nm is prepared.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the surface smoothing agent for 10 seconds and then removed.
(3) After being removed from the diluted surface-smoothing agent solution, the thin sanitary ware piece is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of six times. The surface smoothing agent according to claim 1, which contains an anionic surfactant. 3. The surface smoothing agent according to claim 1, wherein the nonionic surfactant is contained in an amount of 3 to 100 parts by weight per 100 parts by weight of the total amount of the surfactants. The surface smoothing agent according to any one of claims 1 to 3 , which is used to prevent adhesion of feces to the surface of a toilet bowl. A method for smoothing a surface of a sanitary ware, comprising running water over the surface of the sanitary ware with a diluted solution of the surface smoothing agent according to any one of claims 1 to 3 .