JP3239340B2 - Scale adhesion inhibitor and scale adhesion prevention method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a scale-adhering agent capable of preventing scale from adhering to a wall surface of a toilet or a pipe to which urine comes into contact, and masking an unpleasant odor due to urine and urine decomposition products.

[0002]

2. Description of the Related Art A scale originating in urine contains a main component of a calcium-containing inorganic compound and an organic compound based on decomposition of urine alone or urine diluted with washing water, and is usually called urolith. It has long been known that sulfamic acid not only dissolves scale well, but also prevents scale formation by dissolving sulfamic acid in water containing scale components such as calcium ions. Sulfamic acid is a strong acid almost equivalent to hydrochloric acid, sulfuric acid, etc.
Since it is also known that they are much lower than these, there are many proposals regarding a descaling agent containing sulfamic acid, a scale adhesion inhibitor and the like.

[0003] For example, Japanese Patent Publication No. 3-60359 proposes a spherical molded article containing sulfamic acid or a chelating agent and paradichlorobenzene. JP-A-2-147699 proposes a disk-shaped molded article containing an organic carboxylic acid, cyanuric acid, metaphosphoric acid, boric acid or a mixture thereof and a fragrance.

As a method of microencapsulating or coating a drug for the purpose of improving the stability of the drug and controlling the dissolution, for example, JP-A-61-1637 discloses that an organic acid is coated with polyethylene glycol. Proposed.

[0005]

The scale called urinary stone is easily generated near the urinal outlet of a urinal in a men's toilet with a relatively small drainage pipe diameter, and near the pipe inlet. It may cause passage blockage. For this reason, the work of removing the scale is usually performed at intervals of about one to two years. However, the work of removing the scale is not only troublesome in itself, but in order to give the worker an unsanitary feeling, instead of this, it is desired to provide an anti-urine adhesion agent which does not generate the scale itself. I have.

The above-mentioned spherical molded article containing sulfamic acid or a chelating agent and paradichlorobenzene is excellent in the effect of preventing scale adhesion and can also remove ammonia in urine or its decomposed product. It is not effective in removing or masking unpleasant odors. The disk-shaped molded article containing an organic carboxylic acid, cyanuric acid, metaphosphoric acid, boric acid or a mixture thereof and a fragrance as described above is excellent in masking an unpleasant odor. Calcium salts such as acids, cyanuric acid, metaphosphoric acid, boric acid, and the like have a very low solubility in water, and may cause scale formation.

[0007] A molded article of a mixture of sulfamic acid and a fragrance is poor in stability because the fragrance is gradually decomposed by the sulfamic acid during storage. Molded articles from a mixture of sulfamic acid and fragrance coated with the polyethylene glycol cited above show improved storage stability, but in actual use, this coating film is hydrophilic, An aqueous solution of the acid passes through the film and comes into contact with the fragrance, causing gradual decomposition of the fragrance.

When coated with a non-volatile lipophilic polymer, for example, polyethylene, polyvinyl acetate, paraffin wax, etc., the stability of the fragrance during storage and in use is good, but the coating agent is water-soluble. Since it is insoluble, it has a drawback that sulfamic acid and fragrances remain after they disappear, and they adhere to the walls of toilet bowls and pipes and cause scale.

[0009] The present invention prevents the adhesion of scale to the wall of a toilet or a pipe to which urine comes into contact, and further provides the masking property of an unpleasant odor due to urine and urine decomposition products to prevent the adhesion of aromatic scale with good storage stability. To provide an agent.

[0010]

The scale adhesion inhibitor of the present invention comprises 100 parts by weight of a sulfamic acid powder, 0.1 to 200 parts by weight of a fragrance-containing carrier powder, and the surface of the particles of the sulfamic acid powder and the fragrance-containing carrier powder. An amount of the following general formula [1] sufficient to prevent direct contact with the particle surface:

[0011]

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(Wherein n represents an integer of 0 to 10, and R ₁
To R ₈ may be the same or different and each may be a methyl group, an ethyl group,
A phenyl group or a phenyl group. )
Polysiloxane, the following general formula [2]

[0013]

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(Wherein m represents an integer of 2 to 8, and R ₉ to
R ₁₂ may be the same or different and may be a methyl group, ethyl
Group or phenyl group. )
Polysiloxane, triisopropyl-S-trioxane and
And tritertiary butyl-S-trioxane
It is obtained by molding a composition obtained by mixing with a volatile and lipophilic substance selected from the group .

The scale can be suitably prevented from being adhered by installing the molded body in the urinal of the men's toilet, in the trap of the urinal of the men's toilet, in the high tank of the men's toilet, or in the washing water pipe. . The sulfamic acid used in the present invention may be any powder as long as it is powder.
Those having a particle size of 2 mesh or less are preferred.

The fragrance used in the present invention is not particularly limited, but is preferably a liquid.
Natural and synthetic fragrances such as flower scents such as gardenia and quince, scents of fruits such as citrus and peach, and scents of trees such as hinoki and mint. Examples of the carrier of the liquid fragrance include magnesium sulfate, silicates such as calcium silicate, silica gel, colloidal silica, alumina, zeolite, clay minerals such as bentonite, crystalline cellulose, cellulose derivatives such as carboxymethyl cellulose salt and hydroxypropyl cellulose, Examples include gums such as gum arabic and guar gum, powders of starch and derivatives thereof, dextrin, cyclodextrin, agar, gelatin and the like, and those having a particle size of 42 mesh or less are preferred. Further, as the carrier powder, those having a large oil absorbing ability such as calcium silicate, silica gel, dextrin, cyclodextrin and the like are preferable, and those which dissolve in water such as dextrin and cyclodextrin are more preferable.

The mixing ratio of the carrier powder and the fragrance is preferably about 10 to 500 parts by weight per 100 parts by weight of the carrier powder, and particularly preferably 20 to 200 parts by weight. The amount of the fragrance-containing carrier added may be about 0.1 to 200 parts by weight per 100 parts by weight of sulfamic acid, but is particularly preferably 0.1 to 200 parts by weight.
5 to 100 parts by weight are preferred. Examples of the volatile and lipophilic substances used in the present invention include naphthalene, paradichlorobenzene, camphor, adamantane and its derivatives, norbornene and its derivatives, tricyclo [5,2,1,0 ^2,6 ] decane , Cyclododecane, triisopropyl-S-trioxane, tritert-butyl-S-trioxane, 2,2,3-trimethylbicyclo [2,2,1] heptane, 3a, 4,4a, 5,
8,8a, 9,9a-octahydro-4,9,8-dimethano-benz [f] indene, endo-trimethylnorbornane, dimethyl fumarate, tetramethylcyclobutane-1,3-dione, the following general formula [1]

[0018]

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(Wherein n represents an integer of 0 to _10;
To R ₈ may be the same or different and represent any of a methyl group, an ethyl group and a phenyl group. A) a linear polysiloxane represented by the following general formula [2]:

[0020]

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[0021] (m in the formula represents an integer of 2 to 8, R ₉ ~
R ₁₂ may be the same or different and represents any one of a methyl group, an ethyl group, and a phenyl group. )), And particularly, for example, the above-mentioned one
The linear polysiloxane of the general formula [1] and the linear polysiloxane of the above general formula [2]
Polysiloxane represented by the cyclic polysiloxane, triisopropyl -S- trioxane, it is preferable odorless and triethylene tertiary butyl -S- trioxane.

The composition used for molding the scale inhibitor of the present invention contains the above-mentioned volatile and lipophilic substances in addition to the above-mentioned sulfamic acid powder, perfume-containing carrier powder and the like. The amount of the composition of the volatile and lipophilic substances in this composition, when this composition is molded, the surface of the sulfamic acid particles and the surface of the perfume-containing carrier particles in the obtained molded body May be used in such an amount that a portion that directly comes into contact does not occur. The composition preferably comprises
It is prepared by sufficiently mixing the sulfamic acid powder, the flavor-containing carrier powder, and the volatile and lipophilic substance. The amount of the volatile and lipophilic substances used in the mixing is such that the surfaces of the sulfamic acid particles and the surfaces of the fragrance-containing carrier particles are completely covered with the volatile and lipophilic substances by this mixing. An amount greater than the amount is preferred, and an amount less than the amount that fills the particles and voids of the particles resulting from the molding.

The amount of the volatile and lipophilic substances used in this mixing depends on the type of the carrier powder, the particle size distribution of the sulfamic acid and the powder carrier, the surface area, the crushability of the powder during molding, Although it may vary depending on the viscosity and the like of the volatile and lipophilic substances, usually the preferred amount can be easily known by testing the stability of the molded product of the mixture. For example, from 60 mesh to 15
100 parts by weight of sulfamic acid in the range of 0 mesh;
0 to 200 mesh cyclodextrin 6
When tetradecamethylhexasiloxane is mixed with 0 parts by weight and a carrier powder composed of 20 parts by weight of the mint-based mixed flavor, the content of tetradecamethylhexasiloxane is 0.1 to 0.1 parts by weight.
20 parts by weight are mixed.

A composition can also be obtained by simultaneously charging the above-mentioned sulfamic acid powder, the flavor-containing carrier powder and the above-mentioned volatile and lipophilic substances into a container and mixing them. By mixing a fragrance-containing carrier powder with a pre-mixed substance having a lipophilic substance, or by mixing a sulfamic acid powder with a pre-mixed fragrance-containing carrier powder and the volatile and lipophilic substance. The composition used in the molding can be obtained by mixing the sulfamic acid powder mixed with the volatile and lipophilic substances and the fragrance-containing carrier powder.
Particularly preferred are compositions obtained by mixing these sulfamic acid powders mixed with these volatile and lipophilic substances with fragrance-containing carrier powders.

In the composition before molding, besides the above-mentioned components, various additives such as extenders, melt casting aids, surfactants, coloring agents, dissolution rate regulators, binders, corrosion inhibitors may be added as required. , Disinfectants, may be blended with components such as lubricants,
These components are pre-mixed with a sulfamic acid powder, a fragrance-containing carrier powder, and a volatile and lipophilic substance,
Mixing is preferred.

As a method for molding the composition, a method in which a powder mixture of each of the above components is molded under pressure, a method in which the powder mixture is extruded and granulated by a method such as granulation, and then molded under pressure,
A method in which the powder mixture is heated and melted, cast, and molded is exemplified. The shape of the molded body may be any shape such as a sphere, a disk, a cone, and a perforated disk.

[0027]

The molded product of the scale inhibitor of the present invention can be obtained as described above. It is presumably that the surface of the particles of the sulfamic acid powder and the surface of the particles of the flavor-containing carrier powder are volatile during the molding. For bonding through a substance having lipophilicity and lipophilicity, that is, the surface of the particles of the sulfamic acid powder and the surface of the particles of the fragrance-containing carrier powder are bonded as particles coated with a substance having a volatile and lipophilic property. The direct contact between the sulfamic acid and the perfume is suppressed,
Further, even when the molded body comes into contact with water, the direct contact between the aqueous solution of sulfamic acid generated by this contact and the fragrance is suppressed, thereby improving the stability of the fragrance during storage and use. it is conceivable that.

At the time of mixing the carrier powder and the fragrance, if the fragrance is too much, the mixture becomes a paste, and bleeding of the fragrance occurs from the molded article at the time of molding. Conversely, if the fragrance is too small, the fragrance is contained in the molded article. Insufficient amount of fragrance and poor masking performance. When the proportion of the fragrance-containing carrier powder is too small, the masking performance becomes insufficient.On the contrary, when the proportion is too large, the odor of the fragrance is too strong, which is not preferable, and also, the sulfamic acid which is a scale adhesion preventing component in the molded product. And the scale adhesion prevention performance becomes poor.

The substance having volatility and lipophilicity intervenes between the sulfamic acid particles and the particles of the fragrance-containing carrier powder, and acts not only as a coating agent for forming a lipophilic film, but also due to its volatility. Sulfamic acid and fragrance do not remain after disappearing, and do not adhere to toilet bowls, pipes and the like. If the volatile and lipophilic substances are used in an excessively large amount, they will bleed out of the molded body during production of the molded body, leading to deterioration in moldability.

[0030]

【Example】

[0031]

Example 1 25 g of sulfamic acid having a mesh of 60 to 150 mesh and 5 g of a blended flavor were added to a mixture of 2 to 60 mesh.
A mixture of the perfume-containing carrier powder obtained by mixing with 15 g of 00 mesh cyclodextrin and the amount of tetradecamethylhexasiloxane (A) shown in Table 1 was press-molded to a diameter of 35 mm and a weight of 45 to 45. 50 g of disk-shaped molded products No. 1 to 14 were obtained.

The molded product was kept at 70 ° C. for one week, and the change in odor was tested by a sensory test. In Table 1, those with no change in odor were indicated by Δ, and those with odor change were indicated by X.

[0033]

[Table 1]

As shown in Table 1, molded articles Nos. 1 to 4,
7, 9, 11, and 13 were good without any change in odor even in the abuse test at 70 ° C. for 1 week.

By using 0.1 to 10 parts by weight of tetradecamethylhexasiloxane with respect to 100 parts by weight of the total of sulfamic acid and the fragrance-containing carrier, it is possible to obtain a scale adhesion inhibitor having good storage stability. Indicates that you can do it.

[0036]

Example 2 A perfume-containing carrier obtained by mixing 20 g of sulfamic acid of 60 mesh to 150 mesh, 5 g of a mint blended flavor and 15 g of cyclodextrin of 60 mesh to 200 mesh, and the amount shown in Table 2 The mixture with the tetradecamethylhexasiloxane (A) was molded under pressure to obtain disk-shaped molded products No. 15 to 20 having a diameter of 35 mm and a weight of 45 to 50 g.

The molded body was placed in a urinal of a male toilet which emits a bad odor, and a test for an effect of preventing adhesion of scale and a masking performance of an unpleasant odor were performed. The effect of preventing scale adhesion was evaluated by visually observing the pipes, and those with no scale adhesion were rated as Δ, and those with scale adhesion were rated as x. The test of the masking performance was carried out by a sensory test, and was evaluated as “x” where an unpleasant odor was felt and “Δ” where no unpleasant odor was felt. The test results are shown in Table 2.

[0038]

[Table 2]

As shown in Table 2, when sulfamic acid was used, the effect of preventing scale adhesion was all good, but the molded articles Nos. 19 and 20 had an unpleasant odor due to a change in odor during use. Had insufficient masking effect.

[0040]

As described in the above embodiment, the scale adhesion preventive agent of the present invention can prevent scale adhesion and mask unpleasant odors simply by being installed in a urinal of a men's toilet. .

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-61-21200 (JP, A) JP-A-1-185399 (JP, A) JP-A-1-1933397 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C11D 7/22 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. Sulfamic acid powder (100 parts by weight), perfume-containing carrier powder (0.1 to 200 parts by weight), and an amount sufficient to prevent direct contact between the particle surface of the sulfamic acid powder and the particle surface of the perfume-containing carrier powder. of the following general formula [1] [formula 1] (In the formula, n represents an integer of 0 to 10, and R _{1 to} R ₈ represent the same.
May be one or different, methyl, ethyl, phenyl
Represents one of the following groups: ) Linear polysiloxane
And the following general formula [2] (Wherein m represents an integer of 2 to 8, and R _{9 to} R ₁₂ are the same.
Or may be different methyl group, ethyl group, phenyl
Represents any of the groups. The cyclic polysiloxa represented by)
, Triisopropyl-S-trioxane and triter
Selected from the group consisting of shaributyl-S-trioxane
A scale adhesion inhibitor obtained by molding a composition obtained by mixing with a volatile and lipophilic substance. 2. The scale adhesion preventive agent according to claim 1, which is installed in a urinal of a men's toilet, in a trap of a urinal of a men's toilet, in a high tank of a men's toilet, or in a flush water pipe. A method for preventing scale from adhering to these urinals or their traps.