JPH0873837A - Antifoulant and antifouling of toilet bowl - Google Patents

Abstract

PURPOSE: To obtain an antifoulant capable of preventing filth from being attached to a toilet bowl for a long period, and capable of simplifying toilet bowl cleaning owing to easily removing such attached filth by using the antifoulant which is, essentially comprises a siloxane derivative and an acid catalyst. CONSTITUTION: This antifoulant essentially comprises pref. a total of 100 pts.wt. of (A) 1-99 pts.wt. of a siloxane derivative and (B) 99-1 pts.wt. of an acid catalyst (e.g. aluminum chloride, sulfuric anhydride). The component A is e.g. a linear siloxane of formula I (R1 -R3 are each H, a halogen, etc.; R4 is an alkyl, amino, etc.; (n) is >=1), a cyclic siloxane having recurring unit of formula II ((n) is >=2). When the component A is liquid, its viscosity is pref. 500-2000cst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent for preventing or reducing adhesion of filth to a toilet bowl, an antifouling method, and an antifouling treated toilet bowl.

[0002]

2. Description of the Related Art Regardless of Western style or Japanese style, urine for urine and urine is repeatedly swept with filth such as urine and stool, and thus filth is gradually deposited. In the case of washing with water, the filth is washed off each time, but as the number of times of use increases, the portion where water flows gradually becomes contaminated. Moreover, in the peripheral portion of the toilet bowl, which is not involved in cleaning with water, the degree of contamination increases dramatically. For example, in Japanese style urinals and western style urinals, droplets of urine are scattered on the peripheral portion of the toilet bowl and the like, so that these are dried and soiled. In addition, even in a Japanese style toilet for stool, dirt adheres to the interface of the water flow and the part where the water does not flow.

Since cleaning of toilet bowls is disliked, there has been a demand for measures to prevent dirt from adhering and to make toilet bowl cleaning intervals as long as possible. For example, a method of cleaning with water containing a cleaning agent has been devised, but it cannot be said to be perfect, and these stains have been cleaned with a brush or the like at regular intervals without finding an effective method. It was the actual situation.

[0004]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide an antifouling agent and a method for treating the same, which can prevent filth from adhering to toilet bowls and can greatly extend the interval for cleaning toilet bowls. .

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventor has found that a composition containing a siloxane derivative together with an acidic catalyst or active siloxane is simply applied to the surface of a toilet bowl or the like. It has been found that the hydroxyl group or other reactive site of silanol (-Si-OH) existing on the surface of a toilet bowl or the like can be modified by a covalent bond to prevent the attachment of filth to the surface of the toilet bowl for a long time.

That is, the present invention provides the following antifouling agent, antifouling method, and antifouling-treated toilet bowls.

Item 1. An antifouling agent for toilet bowls containing a siloxane derivative and an acidic catalyst as essential components (hereinafter referred to as the first antifouling agent).

Item 2. An antifouling agent for toilet bowls (hereinafter, referred to as a second antifouling agent) containing at least one selected from the group consisting of activated siloxanes and activated silanes as an essential component.

Item 3. Item 3. A method for antifouling a toilet bowl, which comprises contacting the toilet bowl with the antifouling agent according to Item 1 or 2.

Item 4. Toilet bowls that have undergone antifouling treatment by the method of paragraph 3.

In the present invention, the siloxane derivative is "S
The compound having an iO "structure is not particularly limited and may be a monomer or a polymer. Specific examples of the siloxane derivative include cyclic siloxane, chain siloxane, and cyclic siloxane and chain siloxane. Examples of the combined product include those that can be used alone or in combination of two or more.

The chain siloxane has the general formula (1)

[0013]

Embedded image

[In the formula, R ₁ , R ₂ and R ₃ are the same or different and each is a hydrogen atom, a halogen atom, an amino group, an aminoalkyl group, an epoxy group, a polyether group, an alkyl group, a halogenated alkyl group, an alkenyl group. Group, alkynyl group, alkoxy group, phenyl group which may have a substituent, styryl group which may have a substituent, mercaptoalkyl group, epoxyalkyl group, carboxyalkyl group, hydroxyalkyl group, acrylalkyl And a methacrylalkyl group, an aralkyl group which may have a substituent, and a polyether group. R ₄ is an alkyl group, an aminoalkyl group, an epoxy group, a halogenated alkyl group, an alkenyl group, an alkynyl group, a phenyl group which may have a substituent, a mercaptoalkyl group, an epoxyalkyl group, a carboxyalkyl group, a hydroxy group. An alkyl group, an acrylalkyl group, a methacrylalkyl group or an aralkyl group which may have a substituent is shown. n represents an integer of 1 or more. ] The chain-like siloxane represented by these is illustrated.

The cyclic siloxane has the general formula (2)

[0016]

Embedded image

[In the formula, R ₁ and R ₂ are the same as defined above. m represents an integer of 2 or more. And a siloxane having a repeating unit of

The activated siloxane and activated silane used in the present invention mean a compound having at least one leaving group bonded to a silicon atom (Si) and reacting with Si-OH of a toilet bowl to form a siloxane. . As the leaving group bonded to the activated siloxane and the activated silane, a halogen atom,
-OTs group (Ts is p-toluenesulfonyl), -OMs group (Ms is methanesulfonyl)
However, the present invention is not limited to these. Specific examples of the activated siloxane include the following compounds.

* Vinylsilanes such as vinyltrichlorosilane, vinyltriethoxysilane, etc. * Acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, * β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-gly Epoxysilanes such as cidoxypropyltrimethoxysilane, * Aminosilanes such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, * Methyltrichlorosilane, methyl Chlorosilanes such as dichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, * silazanes such as hexamethyldisilazane, * N, N'-bis (trimethylsilyl) urea, N , O
-Amidosilanes such as (bistrimethylsilyl) acetamide.

The first antifouling agent of the present invention includes those which are stored and sold in a state where the siloxane derivative and the acidic catalyst are mixed, but in addition to this, the siloxane derivative and the acidic catalyst are separately sold and stored. Etc., including mixing these when applied to a toilet bowl, or separately applying siloxane and a catalyst to a toilet bowl and mixing these on the surface of the toilet bowl to form a composition. The second antifouling agent of the present invention includes a case where the activated siloxane and / or the activated silane alone is subjected to antifouling treatment by a treatment such as heating without containing an acidic catalyst.

In the present invention, "toilet bowl" means a Western-style toilet bowl, a Japanese-style toilet bowl for urine and stool, a washbasin (sink) of a washbasin, and a flushing part of a water bowl for an integrated flush toilet, And bathroom tiles, both of which are made of earthenware. The various toilets may be of a flush type or a flush type, but are particularly applied to flush toilets.

The antifouling-treated toilet bowl of the present invention is specifically as follows.

* Western style toilet treated with the first antifouling agent or the second antifouling agent.

* Japanese style urinals treated with the first antifouling agent or the second antifouling agent.

* Japanese style toilet bowl treated with the first antifouling agent or the second antifouling agent.

* The washbasin part of the washbasin treated with the first antifouling agent or the second antifouling agent.

* The water-surrounding portion of the water tank for a flush toilet integrated with the hand wash treated with the first antifouling agent or the second antifouling agent.

* Bathroom tile treated with the first antifouling agent or the second antifouling agent.

The siloxane derivative, the activated siloxane and the activated silane can be widely used from a gaseous form to a liquid form, and particularly in the liquid form, the viscosity is 0.65 to 0.65.
100,000 centistokes, preferably 100-2
0000 centistokes, more preferably 500-2
The one having 0000 centistokes shows good physical properties.

In the chain or cyclic siloxane of the general formula (1) or (2), the halogen atom represented by R ₁ , R ₂ , R ₃ and R ₄ is a fluorine atom, a chlorine atom, a bromine atom, The iodine atom is exemplified.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, se
a straight-chain or branched alkyl group having 1 to 22 carbon atoms such as a c-butyl group, a t-butyl group, a pentyl group, a hexyl group, a hexadecyl group, an octadecyl group, an eicosanyl group, and a docosanyl group, preferably a carbon number 1 -8 straight-chain or branched alkyl groups.

The halogenated alkyl group includes monofluoromethyl group, difluoromethyl group, trichloromethyl group, trifluoromethyl group, chloroethyl group, 1,1,1.
1-trifluoroethyl group, 1,1,1-trifluoronormalpropyl group, trichloro-t-butyl group, ω-
Examples thereof include linear or branched halogenated alkyl groups having 1 to 22 carbon atoms such as fluorohexadecyl group, ω-fluorooctadecyl group, ω-fluoroeicosanyl group, and ω-chlorodocosanyl group. Preferred halogenated alkyl groups include linear or branched fluorinated alkyl groups having 1 to 22 carbon atoms.

As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, a dodecyloxy group,
Examples thereof include linear or branched alkoxy having 1 to 22 carbon atoms such as octadecyloxy group, eicosanyloxy group, and docosanyloxy group.

Examples of the polyether group include polyoxyethylene, polyoxypropylene and polyoxytetramethylene containing two or more repeating units.

The aminoalkyl group includes aminomethyl group, aminoethyl group, aminopropyl group, aminobutyl group, aminopentyl group, aminohexyl group, aminohexadecyl group, aminooctadecyl group, aminoeicosanyl group, aminodocosa group. A linear or branched aminoalkyl group having 1 to 22 carbon atoms such as a nyl group, preferably 1 to 8 carbon atoms
And a linear or branched aminoalkyl group.

As the alkenyl group, vinyl group, propionyl group, butenyl group, pentenyl group, hexenyl group,
Heptenyl group, octenyl group, nonel group, decenyl group,
Hexadecenyl group, octadecenyl group, eicosenyl group, docosenyl group and the like having 1 to 22 carbon atoms, preferably 1 to
8, more preferably 1 to 4 straight chain or branched alkenyl groups.

The alkynyl group includes ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group,
A straight-chain or branched alkynyl group having 1 to 22 carbon atoms such as a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a hexadecynyl group, an octadecynyl group, an eicosinyl group, and a docosinyl group, preferably a straight chain having 1 to 8 carbon atoms. Examples include chain or branched alkynyl groups.

The phenyl group which may have a substituent is
An unsubstituted phenyl group and a phenyl group having a substituent are meant, and examples of the styryl group which may have a substituent include an unsubstituted styryl group and a styryl group having a substituent on the benzene ring. The substituent of the phenyl group having a substituent and the styryl group having a substituent is a substituent which is usually substituted on an aromatic nucleus such as an alkyl group, an alkoxy group, a hydroxy group, an amino group, a trifluoromethyl group, a nitro group and a carboxyl group. It is at least one selected from the group consisting of, and the number of substituents is 1 to 3, preferably 1 or 2, and more preferably 1.

As the mercaptoalkyl group, a mercaptomethyl group, a 2-mercaptomethyl group, a 3-mercaptopropyl group, a 4-mercaptobutyl group and the like having 1 to 1 carbon atoms can be used.
8, preferably 1 to 4 mercaptoalkyl groups.

Examples of the epoxyalkyl group include 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 5,6-epoxyhexyl and 6,7-.
Epoxy heptyl, 7,8-epoxy octyl, 8,9
Examples thereof include groups having an ethylene oxide residue at the end of an alkylene group having 1 to 8 carbon atoms such as -epoxynonyl and 9,10-epoxydecyl.

As the carboxyalkyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 5-carboxypentyl group, 6-carboxyhexyl group, 7-carboxyheptyl group, 8 Examples thereof include a group having COOH at the end of an alkylene group having 1 to 8 carbon atoms such as a carboxyoctyl group.

Examples of the hydroxyalkyl group include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group,
1 to 22 carbon atoms such as hydroxyheptyl group, hydroxyoctyl group, hydroxydecyl group, ω-hydroxyhexadecyl group, ω-hydroxyoctadecyl group, ω-hydroxyeicosanyl group, ω-hydroxydocosanyl group
And a hydroxyalkyl group having a straight chain or a branch.

The acrylalkyl group and methacrylalkyl group are represented by the following formulas (I) and (II)

[0044]

[Chemical 3]

(In the formula, p represents an integer of 1 to 8).

As the aralkyl group which may have a substituent, Ar- (CH ₂ ) _q- [wherein, Ar represents a phenyl group which may have a substituent, and q is 1 Indicates an integer of ˜8. ] Is given. A
The phenyl group having a substituent represented by r is the same as above.

N is an integer of 1 or more, preferably 13 to 3
Represents an integer of 00.

M is an integer of 2 or more, preferably 13 to 3
Represents an integer of 00.

The "acidic catalyst" mixed in the first antifouling agent of the present invention is aluminum chloride, boron trifluoride, sulfuric acid anhydride, nitric acid, concentrated hydrochloric acid, concentrated sulfuric acid, phosphoric acid, polyphosphoric acid, aromatic sulfonic acid. And any one selected from the group consisting of organic acids such as aliphatic sulfonic acids and mixed acids thereof.

The first antifouling agent of the present invention is not particularly limited, but can be used, for example, as follows. First,
Wipe off water adhering to the surfaces of toilet bowls with a piece of paper or cloth. At this time, the water on the surface of the toilet bowl may be completely removed and dried by a dryer, but even if a small amount of water adheres to the surface, there is virtually no problem.For example, separate siloxane and acidic catalyst. Alternatively, the composition may be contacted with a toilet bowl and allowed to react at room temperature for several minutes. The method of contact is not particularly limited as long as the composition of the present invention is present on the surface of the toilet bowl, but may be applied or sprayed with, for example, cloth, paper, a brush or the like. The toilet bowl before being installed in the toilet, washroom, etc. can be easily subjected to antifouling treatment by contacting it with the first antifouling agent by dipping, coating, spraying or the like.

When the second antifouling agent is in a liquid state, it is brought into contact with the surface of the toilet bowl by coating or spraying, and when it is in a gaseous state, it is brought into contact with the surface of the toilet bowl by an adsorption treatment, The surface can be subjected to an antifouling treatment by a treatment such as standing at room temperature for about several minutes to several tens of minutes or by heating.

The first antifouling agent of the present invention comprises siloxanes 1 to 99 based on 100 parts by weight of the total amount of siloxane and acidic catalyst.
Parts by weight, 99-1 parts by weight of catalyst. The first antifouling agent and the second antifouling agent may be used after being dissolved in a solvent. Examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol and butanol, halogenated hydrocarbons such as chloroform and methylene chloride,
Aromatic hydrocarbons such as benzene and toluene, linear or cyclic aliphatic hydrocarbon solvents such as hexane and cyclohexane, esters such as ethyl acetate and butyl acetate,
Examples thereof include ketones such as acetone, glycols such as ethylene glycol and polyethylene glycol, and polyethers, and aprotic polar solvents such as DMSO and DMF.

[0053]

By using the antifouling agent of the present invention, it is possible to suppress the attachment of filth to toilet bowls for several months.
Further, since the attached dirt can be easily removed, the toilet bowls can be easily cleaned. In addition, the toilet bowls treated by the antifouling method of the present invention are preferable because dirt hardly adheres to them.

After a few months of use, the surface becomes a little soiled because dirt is deposited on the surface of the antifouling film. In this case as well, by removing dirt on the surface with paper or cloth, the antifouling film reappears on the surface, so that the initial antifouling effect is reproduced. At this time, if the surface treatment is performed again with the antifouling treatment agent of the present invention, the effect is further improved.

[0055]

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of Antifouling Agent The following ingredients were mixed to obtain an antifouling agent of the present invention.

* Formulation 1 Dimethyl silicone (Shin-Etsu Silicone KF96-500) 5.0 g Concentrated sulfuric acid 1.5 g Isopropanol 40.0 g Benzene 53.5 g * Formulation 2 Dimethyl silicone (Shin-Etsu Silicone KF96-1000) 15.0 g Concentrated sulfuric acid 2. 5 g Isopropanol 100.0 ml Benzene 200.0 ml Formulations 1 and 2 were prepared according to the following method.

First, concentrated sulfuric acid was added to isopropanol,
A homogeneous solution was obtained. Dimethylsilcorn oil was added to this, and after stirring well, benzene was added to prepare compositions 1 and 2 as clear solutions.

(2) Test method (2-1) Method A The antifouling agents of the above formulations 1 and 2 were divided into the left and right sides from the inner side of the flush toilet bowl for men's urine where water flows to the left and right, and the antifouling agent was provided on one side. (Prescription 1 or 2) was applied, while the other was left untreated, the degree of contamination on the left and right was compared and examined. The men's flush urinal used was used by 7 to 8 persons, and the implementation period was one month in the summer July period.

The results are shown in Tables 1 and 2 below.

[0061]

[Table 1]

[0062]

[Table 2]

In Tables 1 and 2, ◯ indicates that no contamination was observed.

Δ indicates that there is a slight urine trace adherence.

X indicates that there is obvious contamination or urine trace adherence.

XX indicates the degree of contamination that causes discomfort.

As is clear from the results shown in Tables 1 and 2, the contamination of the portion of the toilet bowl that was washed away with water was slightly contaminated in the untreated portion after 1 week, and was apparent after 1 month. Contamination is observed.

On the other hand, in the treated portion of the same toilet bowl, the portion washed away with water showed no contamination even after one month, and it was proved that the antifouling effect was maintained.

Further, since the peripheral portion of the toilet bowl is not exposed to water, the degree of contamination is high. In the untreated portion, contamination is already recognized after 1 day has passed, and after 2 days, it is required to be cleaned as clear contamination. On the other hand, in the peripheral portion coated with the antifouling agent, almost no contamination was observed even after one month, and it was proved that the antifouling effect was maintained.

This is because the surface of the urine was covered with the siloxane coating due to the application of the chemicals, and the water-repellent effect was exhibited, so that the urine drops formed into water drops and rolled off, and as a result, the peripheral portion of the toilet bowl was not contaminated.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kensuke Fujii 1-33 Toyotsu-cho, Suita-shi, Osaka Das Kin Co., Ltd. (72) Inventor Dai Hirayama 1-33 Toyotsu-cho, Suita-shi, Osaka Das Kin Co., Ltd. (72) Inventor Takehisa Kinoyama 1-33 Toyotsucho, Suita City, Osaka Prefecture Daskin Co., Ltd.

Claims (4)

[Claims] 1. An antifouling agent for toilet bowls, which comprises a siloxane derivative and an acidic catalyst as essential components. 2. An antifouling agent for toilet bowls comprising at least one selected from the group consisting of activated siloxanes and activated silanes as an essential component. 3. An antifouling method for toilet bowls, which comprises contacting the toilet bowl with the antifouling agent according to claim 1 or 2. 4. Toilet bowls which are antifouling treated by the method of claim 3.