JP7496401B2 - Friction resistance reducing agent for sanitary ware - Google Patents

Description

The present invention relates to a frictional resistance reducer for sanitary ware. Specifically, the present invention relates to a frictional resistance reducer for sanitary ware that can reduce the frictional resistance of the surface of sanitary ware such as a toilet bowl and inhibit the adhesion of dirt.

Conventionally, various cleaning agents have been developed and used to easily keep the surfaces of sanitary ceramics such as toilet bowls clean and to maintain 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.

In addition, cationic surfactants such as quaternary ammonium salt surfactants have a disinfecting effect and are used in cleaning agents for sanitary ware to prevent microbial stains such as blackening.

On the other hand, it is known that when the surface of sanitary ware becomes water repellent, dirt becomes more likely to adhere to it, and it is therefore desirable that cleaning agents for sanitary ware be designed to reduce the water contact angle of the sanitary ware surface and impart high hydrophilicity. However, while cationic surfactants have a disinfecting effect, they also have the effect of increasing the water contact angle of the sanitary ware surface and reducing its hydrophilicity, and cleaning agents containing cationic surfactants have the disadvantage of making it easier for dirt to adhere to the sanitary ware surface.

Therefore, there is a need to develop a formulation that can prevent the adhesion of dirt to the surface of sanitary ware, regardless of the degree of hydrophilicity imparted to the surface of the sanitary ware.

JP 2000-273486 A

Until now, the relationship between the adhesion of dirt to the surface of sanitary ware and the frictional resistance of the surface of sanitary ware has not been known. Under these circumstances, the inventors have conducted intensive research and have obtained the new knowledge that there is a correlation between the adhesion of dirt to the surface of sanitary ware and the frictional resistance of the surface of sanitary ware, and that the smaller the frictional resistance, the more difficult it is for dirt to adhere to the surface of sanitary ware.

Therefore, one object of the present invention is to provide a frictional resistance reducer for sanitary ware that can reduce the frictional resistance of the surface of the sanitary ware and inhibit adhesion of dirt. Another object of the present invention is to provide a frictional resistance reducer for sanitary ware that can prevent adhesion of dirt to the surface of the sanitary ware by reducing the frictional resistance of the surface of the sanitary ware, even while containing a cationic surfactant.

The present inventors have conducted intensive research to solve the above-mentioned problems and have found that a frictional resistance reducer which contains at least a nonionic surfactant and can reduce the average coefficient of friction (MIU) of the surface of a thin piece of sanitary ware to 1.25 or less under the following operating conditions can effectively suppress adhesion of dirt to the surface of the sanitary ware.
[operation]
(1) A diluted solution of the frictional resistance reducing agent was prepared by diluting the frictional resistance reducing agent in water so that the concentration of the surfactant was 14 ppm. In addition, a thin piece of sanitary ware (1 cm x 5 cm, thickness 0.5 cm) with an average coefficient of friction (MIU) of 1.40 was washed with acetone and air-dried.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the frictional resistance reducing agent for 10 seconds and then removed.
(3) After being removed from the diluted solution of the frictional resistance reducing agent, the thin piece of sanitary ware is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of 12 times.

Furthermore, it was found that a frictional resistance reducer that satisfies the above-mentioned average coefficient of friction (MIU) contains a cationic surfactant, and can effectively prevent adhesion of dirt (especially lipid dirt such as feces) to the surface of the sanitary ware, even when the water contact angle of the surface of the thin piece of sanitary ware under the above-mentioned operating conditions is 65° or more.

The present invention has been completed through further investigation based on these findings. That is, the present invention provides the following aspects.
Item 1. Contains a nonionic surfactant,
A frictional resistance reducer for sanitary ware, which reduces the average coefficient of friction (MIU) of the surface of a thin piece of sanitary ware to 1.25 or less after carrying out the following operations (1) to (4):
[operation]
(1) A diluted solution of the frictional resistance reducing agent was prepared by diluting the frictional resistance reducing agent in water so that the concentration of the surfactant was 14 ppm. In addition, a thin piece of sanitary ware (1 cm x 5 cm, thickness 0.5 cm) with an average coefficient of friction (MIU) of 1.40 was washed with acetone and air-dried.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the frictional resistance reducing agent for 10 seconds and then removed.
(3) After being removed from the diluted solution of the frictional resistance reducing agent, the thin piece of sanitary ware is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of 12 times.
Item 2. The frictional resistance reducing agent according to Item 1, which contains a cationic surfactant.
Item 3. The frictional resistance reducer according to Item 1, which contains an anionic surfactant.
Item 4. The frictional resistance reducing 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 frictional resistance reducing agent according to any one of Items 1 to 4, wherein the nonionic surfactant is 3 to 100 parts by weight per 100 parts by weight of the total amount of the surfactants.
Item 6. The frictional resistance reducer according to any one of Items 1 to 5, which is used to prevent feces from adhering to a surface of a toilet bowl.
Item 7. A method for reducing frictional resistance on a surface of sanitary ware, comprising running water over the surface of the sanitary ware containing a diluted solution of the frictional resistance reducer according to any one of items 1 to 6.

According to the present invention, by reducing the frictional resistance of the surface of sanitary ceramics such as toilets, it is possible to effectively prevent the adhesion of dirt to said 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 frictional resistance of the sanitary ware surface is reduced, thereby effectively preventing adhesion of dirt. In addition to preventing adhesion of dirt to the sanitary ware surface, the cationic surfactant can also effectively exert a disinfecting effect.

The friction reducer 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 average coefficient of friction (MIU) of the surface of a thin piece of sanitary ware becomes 1.25 or less. The friction reducer of the present invention will be described in detail below.
[operation]
(1) A diluted solution of the frictional resistance reducing agent was prepared by diluting the frictional resistance reducing agent in water so that the concentration of the surfactant was 14 ppm. In addition, a thin piece of sanitary ware (1 cm x 5 cm, thickness 0.5 cm) with an average coefficient of friction (MIU) of 1.40 was washed with acetone and air-dried.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the frictional resistance reducing agent for 10 seconds and then removed.
(3) After being removed from the diluted solution of the frictional resistance reducing agent, the thin piece of sanitary ware is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of 12 times.

[Surfactants]
Nonionic surfactants
The friction reducer of the present invention contains at least a nonionic surfactant as a surfactant. By containing a nonionic surfactant, it is possible to reduce the friction resistance of the surface of sanitary ware such as a toilet bowl.

The nonionic surfactant used in the present invention is not particularly limited as long as it can provide the friction resistance 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 sorbitan 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 nonionic surfactants, polyoxyalkylene alkyl ethers and polyoxyalkylene block copolymers are preferred from the viewpoint of providing suitable friction resistance, which will be described later.

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), ^R2 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 Daiichi 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 are satisfied.

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 friction resistance 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 frictional resistance reducing agent of the present invention may be appropriately set within a range that provides the frictional resistance 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 frictional resistance reducer of the present invention may contain a cationic surfactant to the extent that the frictional resistance described below is satisfied. Cationic surfactants have a disinfecting effect, and by including a cationic surfactant in the frictional resistance reducer 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 conventional technology, the incorporation of a cationic surfactant was actually a factor that made stains more likely to adhere, but the frictional resistance reducer of the present invention has the frictional resistance described below, so that even if the water contact angle of the sanitary ware surface increases, it is possible to effectively suppress the adhesion of stains.

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 a dirt-removing effect, a quaternary ammonium salt type surfactant is preferable, and more preferably, didecyl dimethyl ammonium chloride and didecyl dimethyl ammonium methyl sulfate are mentioned. Furthermore, by blending such a quaternary ammonium salt type surfactant, it is also possible to optimally satisfy the water contact angle characteristics described later.

When a cationic surfactant is contained in the frictional resistance reducing 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, etc., up to the limit that satisfies the frictional resistance 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 frictional resistance reducing 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 frictional resistance reducer of the present invention may further contain other surfactants in addition to the above surfactants, as long as the frictional resistance described below is satisfied. Examples of other surfactants include anionic surfactants and amphoteric surfactants. Among these, anionic surfactants are preferable.

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. Examples of the surfactant include phosphate salts such as sodium phosphate; sulfosuccinate salts such as sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, and sodium lauryl polypropylene glycol sulfosuccinate; alkylbenzene sulfonates such as linear dodecylbenzene sodium sulfonate, linear dodecylbenzene triethanolamine sulfonate, and linear dodecylbenzene sulfonic acid; sulfated oils such as hydrogenated coconut oil fatty acid glycerin sodium sulfate and turpentine oil, higher fatty acid ester sulfate salts such as α-olefin sulfonates, higher fatty acid ester sulfonates, and secondary alcohol sulfate salts; higher fatty acid alkylolamide sulfate salts such as sodium lauroyl monoethanolamide succinate and sodium caseinate; sulfate ester salt or sulfonate salt type surfactants such as alkyl sulfate salts, polyoxyethylene alkyl sulfate salts, fatty acid amide ether sulfate salts, acyl isethionate salts, and sulfosuccinate salts; and carboxylic acid type 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 these anionic surfactants, from the viewpoint of satisfying the friction resistance described below, preferred are higher fatty acid ester sulfates, and more preferred are α-olefin sulfonates. Specific examples of α-olefin sulfonates include compound (D) represented by the following general formula (4).
(Compound (D))
_{CnH2nO3SNa , CnH2n+ 1O4SNa ( 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 frictional resistance reducer 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, etc., up to the limit that satisfies the frictional resistance 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 frictional resistance reducer 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 frictional resistance reducing 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, as long as the frictional resistance described below is satisfied, 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 frictional resistance reducing 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 frictional resistance reducer of the present invention, the total content of surfactants (total surfactant content) 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 frictional resistance reducing agent of the present invention, the ratio of the nonionic surfactant to the total amount of surfactants is determined according to the type and combination of surfactants used, the content of each surfactant described above, etc., but from the viewpoint of suitably satisfying the frictional resistance 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 frictional resistance reducer of the present invention may contain other components, if necessary, in addition to the above-mentioned surfactant.

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

The fragrance component to be included in the frictional resistance reducing 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 frictional resistance reducing agent of the present invention, the content of the fragrance component is not particularly limited as long as the frictional resistance 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 frictional resistance reducer of the present invention may contain a base such as water or a solvent depending on its form, use, etc. The type of solvent is not particularly limited, and examples thereof include monohydric lower alcohols such as ethanol, propanol, butanol, etc.; polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, etc. The content of the base is not particularly limited as long as the frictional resistance described below can be satisfied, and can be appropriately designed depending on the type of base, etc. For example, in the case of water, the content is 20 to 99.9% by weight, preferably 30 to 99% by weight, more preferably 40 to 98% by weight.

In addition, the frictional resistance reducer 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 adjusters, thickeners, moldability improvers, lubricants, buffers, opacifying agents, and defoamers, so long as the frictional resistance described below is satisfied.

[form]
The frictional resistance reducing agent of the present invention may be in any form of solid, gel, semi-solid or liquid, which may be appropriately selected depending on the application.

[Friction resistance]
The frictional resistance reducer of the present invention is characterized in that the average coefficient of friction (MIU) of the surface of a thin piece of sanitary ware is 1.25 or less after carrying out the following operations (1) to (4).
[operation]
(1) A diluted solution of the frictional resistance reducing agent was prepared by diluting the frictional resistance reducing agent in water so that the concentration of the surfactant was 14 ppm. In addition, a thin piece of sanitary ware (1 cm x 5 cm, thickness 0.5 cm) with an average coefficient of friction (MIU) of 1.40 was washed with acetone and air-dried.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the frictional resistance reducing agent for 10 seconds and then removed.
(3) After being removed from the diluted solution of the frictional resistance reducing agent, the thin piece of sanitary ware is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of 12 times.

The surface smoothing agent of the present invention has the property that, when the operations (1) to (4) described above are carried out, the average coefficient of friction (MIU) of the surface of the sanitary ware becomes 1.25 or less, and based on this, it is possible to prevent adhesion of dirt to the surface of the sanitary ware. From the viewpoint of further enhancing the effect of preventing adhesion of dirt, the average coefficient of friction (MIU) is preferably 1.20 or less, more preferably 1.15 or less, and particularly preferably 1.10 or less. In addition, there is no particular restriction on the lower limit of the average coefficient of friction (MIU), but examples thereof include 0.01 or more, preferably 0.1 or more, and more preferably 0.5 or more.

In the present invention, the average coefficient of friction (MIU) is a value determined using a friction tester KES-SE (manufactured by Kato Tech Co., Ltd.) with a 10 mm square silicon sensor, a sensor weight of 25 g, and a speed of 1 mm/sec.

The steps (1) to (4) for measuring the average coefficient of friction (MIU) are explained below.

In the operation (1), the frictional resistance reducer is diluted with water so that the total concentration of the surfactants contained in the frictional resistance reducer (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 average coefficient of friction (MIU) of 1.40 is prepared. The thin piece of sanitary ware is a thin piece with 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 (1 cm x 5 cm, thickness 0.5 cm) prepared in the step (1) may have an average coefficient of friction (MIU) of 1.40 on the surface after washing with acetone, 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 frictional resistance reducing agent for 10 seconds and then removed. In operation (2), the thin piece of sanitary ware is immersed in the diluted frictional resistance reducing 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 frictional resistance reducing agent during operation (2) is not particularly limited as it is not thought to affect the measured value, 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 12 cycles are performed.

After completing step (4), the surface of the thin piece of sanitary ware is thoroughly dried, and the average coefficient of friction (MIU) of the surface is then measured.

[Water contact angle characteristics]
One embodiment of the frictional resistance reducer of the present invention includes one that contains a cationic surfactant together with a nonionic surfactant, and that, after carrying out the same operations (1) to (4) as in the measurement of the average coefficient of friction (MIU), has a water contact angle of 65° or more on the surface of a thin piece of sanitary ware. The frictional resistance reducer of the present invention thus contains a cationic surfactant, and even if the water contact angle becomes large, by having the low frictional resistance property described above, it is possible to effectively suppress adhesion of dirt (particularly feces) to the surface of the sanitary ware.

In a preferred embodiment when the frictional resistance reducer 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 steps (1) to (4) similar to those for measuring the average coefficient of friction (MIU) 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 frictional resistance reducer of the present invention is for sanitary ware, and can reduce the frictional resistance of 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 these, the frictional resistance reducer 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 frictional resistance reducing agent of the present invention may be applied directly to a sanitary container such as a toilet bowl to be flushed, or, for example, when the frictional resistance reducing 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 frictional resistance reducing 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 frictional resistance reducer 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 top of the hand washing section of a flush toilet, and is applied by contacting a container containing the frictional resistance reducer with flush water for washing supplied to the hand washing section, causing the frictional resistance reducer to flow out of the container and discharging the flush water with the frictional resistance reducer 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 frictional resistance reducer with flush water discharged into the toilet bowl, causing the frictional resistance reducer to flow out of the container and discharging the flush water with the frictional resistance reducer dissolved in it into the toilet bowl.

When the frictional resistance reducing agent of the present invention is applied to a flush toilet, the toilet may be of any flushing type, such as a wash-off type, a siphon type, a siphon jet type, a blow-out type, a siphon vortex type, a power drive type, or a tornado type (a vortex flushing type in which flush water is forcefully ejected in a vortex from a rim outlet). In a tornado type toilet, the flush water is forcefully ejected in a vortex from a rim outlet, so turbulence of the flush water tends to occur easily in the toilet, but by using the frictional resistance reducing agent of the present invention in a tornado type flush toilet, the frictional resistance of the toilet surface can be effectively suppressed, the turbulence of the flush water can be reduced, and the flush water can be ejected in the set direction. In view of the effects of the present invention, it can be said that a tornado type flush toilet is suitable as a flush toilet to which the frictional resistance reducing agent of the present invention can be applied.

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

2. Method for Reducing Friction on a Sanitary Ware Surface The method for reducing friction on a sanitary ware surface of the present invention is characterized by running a diluted solution of the above-mentioned frictional resistance reducing agent over the sanitary ware surface.

By running a diluted solution of the friction resistance reducing agent described above over the surface of the sanitary ware, the friction resistance of the sanitary ware surface can be reduced, thereby preventing the adhesion of dirt to the surface of the sanitary ware.

In the friction reduction method of the present invention, the friction reducer used, its dilution solution, the method of running the dilution solution through the sanitary ware to which it is applied, etc. are as described in the above section "1. Friction reducer."

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.

Test Example 1
1. Preparation of Frictional Resistance Reducer The components shown in Table 1 were mixed together to prepare a frictional resistance reducer.

2. Evaluation of Friction Resistance and Water Contact Angle of Ceramic Tile Surface As a thin piece of sanitary ware, a ceramic tile (KY Tile P4-100, manufactured by Nippon Test Panel Co., Ltd.) measuring 1 cm x 5 cm and 0.5 cm in thickness was prepared by washing with acetone and air-drying.

The frictional resistance reducing agent prepared above was appropriately diluted with distilled water to prepare a diluted solution so that the total amount of surfactants contained in the frictional resistance reducing agent was 14 ppm. The ceramic tile was immersed in this diluted solution (25°C) for 10 seconds in a state where the ceramic surface was at approximately 70° to the horizontal plane, and then removed from the diluted solution and held at 25°C for 50 seconds and dried, which constitutes one cycle. A total of 12 cycles of immersion and drying were performed. After that, it was confirmed that the surface was completely dry (left overnight), and the average friction coefficient (MIU) and water contact angle were measured. In addition, the average friction coefficient (MIU) and water contact angle of the ceramic tile surface in an untreated state without performing the above operations were also determined.

The average coefficient of friction (MIU) was measured using a friction tester KES-SE (manufactured by Kato Tech Co., Ltd.) with a 10 mm square silicon sensor, with the sensor weight set to 25 g and the speed set to 1 mm/sec. The average value was calculated from a total of 20 measurements (i.e., the silicon sensor was moved 20 times).

The water contact angle was measured by placing a drop of distilled water on the surface of a thin piece of sanitary ware using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.; measurement and analysis integrated software: FAMAS; water drop volume: 6 μl; measurement wait time: 1000 ms).

The results are shown in Table 2. As a result, it was confirmed that the friction reducer (Example 1) was able to reduce the average coefficient of friction (MIU) of the sanitary ware surface to 1.25 or less by the above-mentioned operation. In addition, because the friction reducer (Example 1) contains a cationic surfactant (sodium alpha-olefin sulfonate), the water contact angle of the sanitary ware surface reached a high value of 65° or more by the above-mentioned operation.

Test Example 2
The friction reducer (Example 1) was placed in a container for on-tank toilet cleaners, and the following practical use test was carried out. The container in question is one that is commonly used for on-tank toilet cleaners, and the container containing the friction reducer is placed in the hand-washing section above the water tank of a flush toilet, and is configured so that when water is supplied after flushing, the friction reducer is diluted about 70,000 times with the supply 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 friction reducer (Example 1). While the number of times that feces adhered was being counted, the toilet bowl was scrubbed and cleaned whenever feces were found to adhere. Next, in a household where feces were found to adhere, the friction reducer (Example 1) 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 for 30 days under the same conditions as above.

<Results>
The average number of fecal deposits before and during installation of the friction reducer (Example 1) was calculated for households where fecal deposits were observed, and the results are shown in Table 3. The friction reducer (Example 1) contains a cationic surfactant and has the property of increasing the water contact angle of the toilet surface, so even though it was predicted that dirt would be more likely to adhere to the toilet surface, the number of fecal deposits was significantly reduced. In other words, this result makes it clear that a friction reducer that can reduce the average friction coefficient (MIU) evaluated in Test Example 1 to 1.25 or less can effectively prevent dirt from depositing, regardless of the degree of hydrophilicity that can be imparted to the toilet surface.

Claims (10)

Contains a nonionic surfactant,
A friction resistance reducer for tornado-type flush toilets (excluding those used in foam-flush toilets ) that reduces the average coefficient of friction (MIU) of the surface of a thin piece of sanitary ware to 1.25 or less after carrying out the following operations (1) to (4):
[operation]
(1) A diluted solution of the frictional resistance reducing agent was prepared by diluting the frictional resistance reducing agent in water so that the concentration of the surfactant was 14 ppm. In addition, a thin piece of sanitary ware (1 cm x 5 cm, thickness 0.5 cm) with an average coefficient of friction (MIU) of 1.40 was washed with acetone and air-dried.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the frictional resistance reducing agent for 10 seconds and then removed.
(3) After being removed from the diluted solution of the frictional resistance reducing agent, the thin piece of sanitary ware is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of 12 times. The frictional resistance reducer according to claim 1, which contains a cationic surfactant. 3. The frictional resistance reducing agent according to claim 2, wherein after the steps (1) to (4) are carried out, the surface of the thin piece of sanitary ware has a water contact angle of 65 to 100° . Contains a nonionic surfactant and a cationic surfactant ,
A friction resistance reducer for sanitary ware (excluding those used in foam-wash toilets) which, after carrying out the following operations (1) to (4), results in an average coefficient of friction (MIU) of 1.25 or less on the surface of a thin piece of sanitary ware and a water contact angle of 65 to 100° on the surface of the thin piece of sanitary ware.
[operation]
(1) A diluted solution of the frictional resistance reducing agent was prepared by diluting the frictional resistance reducing agent in water so that the concentration of the surfactant was 14 ppm. In addition, a thin piece of sanitary ware (1 cm x 5 cm, thickness 0.5 cm) with an average coefficient of friction (MIU) of 1.40 was washed with acetone and air-dried.
(2) A thin piece of sanitary ware is immersed in the diluted solution of the frictional resistance reducing agent for 10 seconds and then removed.
(3) After being removed from the diluted solution of the frictional resistance reducing agent, the thin piece of sanitary ware is kept in that state for 50 seconds.
(4) The above steps (2) and (3) are repeated a total of 12 times. The nonionic surfactant is at least one selected from the group consisting of a compound (A) represented by the following general formula (1), a compound (B) represented by the following general formula (2), and a compound (C) represented by the following general formula (3). The frictional resistance reducer according to any one of claims 1 to 4.
[Chemical formula 1]
R ¹ -O-[(EO) _a / (PO) _b ］-H (1)
[In the general formula (1), R ¹ 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, [(EO) _a / (PO) _b ] indicates random or block addition of EO and PO.]
[Chemical formula 2]
R ² -O-[(EO) _c / (PO) _d ］-H (2)
[In the general formula (2), R ² 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≦c, d is the average number of moles of PO added and is 1≦d, [(EO) _c / (PO) _d ] indicates random or block addition of EO and PO.]
[Chemical formula 3]
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 1≦e, 1≦i, f and h are the average number of moles of BO added, and 1≦f, 1≦h, and g is the average number of moles of PO added, and 1≦g, [(EO) _e / (BO) _f / (PO) _g / (BO) _h / (EO) _i ] indicates random or block addition of EO, BO, and PO.] The frictional resistance reducing agent according to any one of claims 2 to 5, wherein the cationic surfactant is at least one selected from the group consisting of didecyl dimethyl ammonium chloride and didecyl dimethyl ammonium methyl sulfate. 7. The frictional resistance reducing agent according to claim 2, wherein the content of said cationic surfactant is 0.01 to 5 parts by weight per 1 part by weight of said nonionic surfactant . The frictional resistance reducer according to any one of claims 1 to 7 , which contains an anionic surfactant. The frictional resistance reducer according to any one of claims 1 to 8 , which is used to prevent adhesion of feces to the surface of a toilet bowl. A method for reducing frictional resistance on a tornado type flush toilet surface or a sanitary ware surface, comprising running a diluted solution of the frictional resistance reducer according to any one of claims 1 to 9 over the tornado type flush toilet surface or the sanitary ware surface.