JPH11335215A - Slime controller molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a slime controller molding which can control the occurrence of the phenomenon such as discoloration, coloration of packed materials or the like and store very stably over a long period of time without change of the quality by including an iodoglycine composite and a moisture absorbent component. SOLUTION: The objective molding is obtained by including (A) an iodoglycine composite (preferably tetraglycinehydroperiodide, potassium tetraglycinetriiodide or the like) and (B) a moisture absorbent component (preferably silica get, sodium sulfate, polyvinyl pyrrolidone or the like) preferably in a proportion of 0.2-2 wt.% in the molding and preferably (C) at least one kind of organic acids selected from benzoic acid, p-hydroxybenzoic acid, salicylic acid or adipic acid preferably in a proportion of 2-20 pts.wt. per 1 pt.wt. of the component A and preferably molding under pressure. In order to retard the dissolution rate of this molding in water, stearic acid, silicone oil or the like is added in a proportion of 0.1-5 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a slimming inhibitor molded article for preventing slime from occurring in places where water is frequently used, such as kitchens, sinks, and baths. More specifically, the present invention relates to an anti-slime agent molded article which uses an iodoglycine complex as an active ingredient for preventing the occurrence of slime and has sufficiently excellent storage stability.

[0002]

2. Description of the Related Art In places where water is used, such as kitchens, sinks, and baths, sliminess such as slimy bottoms, walls or floors is likely to occur. In preventing such slicking from occurring, the present inventors have already found that a slicking inhibitor molded article formed by containing an iodoglycine complex as an active ingredient is very useful, and a patent has been made. Filed (Japanese Patent Application Hei 8-3265)
No. 91).

[0003] The anti-seize agent molded article described above has an accurate effect for preventing the occurrence of slime, and has extremely high safety and a long-term effect as compared with the conventionally known anti-seize agent molded article. It has the characteristic of being excellent in sustainability.

[0004]

As described above, the anti-slip agent molded article formed by using an iodoglycine complex as an active ingredient has various unprecedented advantages. In the subsequent further studies of the present inventors, the obtained molded product itself may be slightly discolored, or the material wrapping it may be discolored little by little depending on manufacturing conditions or storage environment. It turned out that.

[0005] Even if such a phenomenon appears, there is no change in the substantial effect exhibited by the molded product. However, such a molded product may be changed in some cases. It is demanded that the phenomenon give an impression of a decrease in commercial value, and further, from the viewpoint of the nature of use, there is no such phenomenon as described above.

SUMMARY OF THE INVENTION The present invention has been made to eliminate the above-mentioned phenomenon in a molded article containing an iodoglycine complex and containing an iodoglycine complex. It is an object of the present invention to provide a slime preventive molded article which does not change its color without being affected by storage environment and the like and does not give any color to a packaging material or the like.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems. As a result, phenomena such as the discoloration and coloring of the package are particularly moisture and humidity, for example, moisture introduced from raw materials at the time of its manufacture,
It has been found that it depends considerably on the environment during mixing and molding operations of each component, and further on the humidity conditions during storage of the product.

As a result of further research, it was found that a molded article obtained by adding a hygroscopic agent to the anti-sedimentation agent composition containing an iodoglycine complex as an active ingredient and then forming the molded article had a tendency to dissolve in actual use. It does not adversely affect the tendency to generate free iodine and the effect of preventing slimming, and can significantly suppress the occurrence of phenomena such as discoloration of itself and coloring of packaging materials, thereby resulting in any change in quality. Without this, it was found that it can be stored very stably for a long period of time.

Further, when a specific inorganic hygroscopic agent is blended as a hygroscopic component, it also has a feature of giving a constant amount of free iodine constantly over the entire period of use during actual use. And found that
Those using a hygroscopic polymer as a hygroscopic component,
It has also been found that a further binder effect is imparted and the moldability is further improved, and the present invention has been completed.

[0010] That is, the present invention is a molded article of anti-slimming agent comprising (1) an iodoglycine complex and a moisture absorbent component, and (2) an iodoglycine complex, a moisture absorbent component, And in addition, benzoic acid, p
-Containing at least one organic acid selected from the group consisting of hydroxybenzoic acid, salicylic acid, adipic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, citric acid, fumaric acid, malic acid and tartaric acid; (3) a moisture-absorbing agent component is silica gel, sodium sulfate,
Molecular sieve, zeolite, and one or more selected from the group of white carbon, the (1) or (2) is a anti-slip agent molded product according to the present invention, and (4) a moisture absorbent component , Polyvinylpyrrolidone,
Polyamino acid, sodium polyamino acid, polyvinyl acetamide, and one or more selected from the group of carboxymethyl cellulose, the above (1)
Or (2) the anti-slip agent molded product according to
(5) the iodoglycine complex is tetraglycine hydroperiodide, potassium tetraglycine triiodide or diglycine hydroperiodide,
A slime preventive molded article according to any one of the above (1) to (4).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the anti-seize agent molded product of the present invention, the iodoglycine complex as an active ingredient is, for example,
The following formula (1) [Formula 1] which is called by the general name globulin

[0012]

Embedded image A tetraglycine hydroperiodide (hereinafter, referred to as globulin) represented by the general formula (2)

[0013]

Embedded image Potassium tetraglycine triiodide represented by the following formula (hereinafter referred to as potadine), and the following formula (3)

[0014]

Embedded image And diglycine hydroperiodide. These are well-known chemical substances that have been conventionally used as a disinfectant for drinking water in the field (INDUSTRIAL AND ENGINEERING CHEMISTRY).
Vol. 45 No. 5 1013 to 1015), and its production method is described in, for example, J. Am. Chem. 74, 1346 (1952).

As the organic acid used in the anti-seize agent molded product of the present invention, those which are solid at room temperature are used.
For example, benzoic acid, p-hydroxybenzoic acid, salicylic acid, adipic acid, succinic acid, phthalic acid, terephthalic acid,
Examples thereof include isophthalic acid, citric acid, fumaric acid, malic acid, and tartaric acid, and a mixture of one or more selected from this group can be used.

As the moisture-absorbing component to be incorporated into the molded article of the present invention, a wide range of moisture-absorbing and powdery or solid components is useful. However, in view of the characteristics of the form of use, more preferable examples include the following inorganic hygroscopic agents and hygroscopic polymers.

Examples of the inorganic moisture absorbent include silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon. And when these are included in the molded article of the present invention, the above-mentioned object is achieved, and in addition, on the actual use, effects such as a further sustained release of iodine and a slow solubility of the molded article are obtained. An anti-slime agent molded article which is added and almost always generates extremely quantitative free iodine is provided.

Further, specific examples of the hygroscopic polymer include:
Examples include polyvinylpyrrolidone, polyamino acids, sodium polyamino acids, polyvinylacetamide, carboxymethylcellulose, and the like. And when these are contained in the molded article of the present invention, the above-mentioned object is achieved, of course, the tableting property is further improved, and the hygroscopic polymer is used as a binder for the iodoglycine complex. Since it plays a role, the moldability is further improved, and it is extremely hard to collapse during actual use, resulting in an extremely stable molded product.

In the molded article of the present invention, not only one kind but also two or more kinds of the above-mentioned inorganic moisture-absorbing agents and polymers contained as the moisture-absorbing component may be used. It is also possible to use both of the hygroscopic polymers at the same time to obtain a molded article having the above-mentioned effects. In the present invention, the proportion of the moisture absorbent component contained therein is usually in the range of 0.05 to 5% by weight, more preferably 0.2 to 2% by weight in the molded product.

In the molded article of the present invention, there is no particular limitation on the mixing ratio of the iodoglycine complex and the organic acid, and the mixing ratio can be arbitrarily selected so that a desired dissolution rate can be obtained at the time of use. . Usually, the organic acid is frequently used in the range of about 1 to 50 parts by weight per 1 part by weight of the iodoglycine complex, but more preferably 2 to 20 parts by weight.
It is in the range of parts by weight.

If the dissolution inhibitor in the present invention is desired to have a slower dissolution rate in water, the effect can be obtained by adding stearic acid, silicone oil, polypropylene glycol or beeswax. Can be When added, usually 0.1 to 5% by weight in the molded product
Range.

Furthermore, in the molded article of the present invention,
Depending on the purpose or need, inorganic corrosion inhibitors such as nitrite, silicate, polyphosphate, etc., organic corrosion inhibitors such as carboxylic acid, metal soap, sulfonic acid, amine, ester, phosphate ester, EDTA By adding a corrosion inhibitor such as a chelating compound such as gluconic acid and nitrilotriacetic acid salt, the corrosion resistance of the metal can be improved.

In the case of pressure molding, if necessary, a lubricant such as calcium stearate, magnesium stearate, sodium stearate, sodium benzoate, orthoboric acid, etc. may be added to the iodoglycine complex and the organic acid. By adding 0.5 to 5% by weight based on the weight of the mixture of the above, pressure molding can be made easier.

The anti-seize agent molded product of the present invention can be formed into various shapes, and the shape and size are not limited at all.
A molded article having an arbitrary shape such as a square shape, a granular shape, a spherical shape, a cylindrical shape, a perforated disk shape and the like can be selected.

In producing the anti-seize agent molded product of the present invention, the moisture absorbent, iodoglycine complex and organic acid may be in any form such as powder or granule. After mixing, it can be molded by a known method such as tablet molding. The pressure during molding is usually in the range of 0.2 to 3 ton / cm ² , and more preferably 0.5 to 2 ton / cm ² .

[0026]

The molded articles of the present invention will be described in detail with reference to production examples and examples and comparative examples. However, the invention is not limited to these examples in any way. In the following, all parts and percentages are by weight. Also, the iodoglycine complex used below is
Each was manufactured as follows.

Production of Globulin To 950 ml of pure water, 75.1 g (1.0 mol) of glycine and 114.0 g (0.5 mol) of a 56% strength aqueous hydrogen iodide solution are added and dissolved. Then, at 60 ° C., 225 g (3.0 mol) of glycine and 80 g (0.32 mol) of iodine are added with increasing temperature. The temperature is raised to 70 ° C., aged at this temperature for 1 hour, and then gently cooled to 5 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure. 170.9 g of blackish brown needle-like crystals having a metallic luster were obtained. As a result of elemental analysis, it was confirmed that the obtained product was (NH ₂ CH ₂ COOH) ₄ .HI.5 / ₄ I ₂ .

Production of Potadine 75.1 g (1.0 mol) of glycine and 83.1 g (0.5 mol) of potassium iodide are added to 950 ml of pure water and dissolved. Then, at 60 ° C. while heating, 225 g (3.0 mol) of glycine and iodine
127 g (0.5 mol) are added. The temperature is raised to 70 ° C., aged at this temperature for 1 hour, and then gently cooled to 5 ° C. The precipitated crystals were separated by filtration and dried under reduced pressure. 318.2 g of blackish brown needle-like crystals having a metallic luster were obtained. As a result of elemental analysis, it was confirmed that the obtained product was (NH ₂ CH ₂ COOH) ₄ .KI ₃ .

Manufacture of anti-slip agent molded article Manufacture example 1 Using a mortar, put 5 parts of globulin, 93 parts of fumaric acid, 1 part of silicone oil and 1 part of zeolite,
These were mixed well while grinding. Next, 15 g of this mixture was press-formed at a pressing pressure of 500 kg / cm ² to obtain a columnar shaped product having a diameter of 30 mm and a height of 13 mm.

Production Examples 2 to 10 The iodoglycine complex, fumaric acid, hygroscopic agent, and silicone oil were mixed well in a mortar in the proportions shown in Table 1 in the types and amounts shown below, and the operation was carried out in the same manner as described in Production Example 1 above. A molded product was obtained.

Comparative Production Example 1 Using a mortar, 5 parts of globulin, 94 parts of fumaric acid, and 1 part of silicone oil were added thereto, and these were mixed well with grinding. This was prepared in the following Production Example 1
A molded product was obtained in the same manner as described.

Production Examples 1 to 10 and Comparative Production Example 1
Table 1 shows the component types of the molded articles and their composition ratios.

[0033]

[Table 1]

Test Example 1 (Storage stability test) 100 parts by weight of fumaric acid was put in a mortar, 1 part by weight of water was sprayed, mixed and forcedly absorbed, and dried under reduced pressure at room temperature with an evaporator. Then, fumaric acid having a water content of 2000 ppm is prepared while measuring the water content with a Karl Fischer moisture meter. Using the fumaric acid that has been forcibly absorbed, preparations of anti-sedimentation agents are respectively prepared in the manner shown in Production Examples 1, 4, 6 to 10 and Comparative Production Example 1. After placing each molded product in a polyethylene bag and heat-sealing it, putting it in a bag made of filter paper and sealing it, it is further put in a polyethylene bag and heat-sealed to obtain a specimen.
This is left in a room at a temperature of 15 to 25 ° C and a relative humidity of 30 to 70% for 30 days. Every 10 days, the colored state of the molded product, the inner bag (filter paper bag)
Observe the colored state of. After 30 days, the effective iodine concentration in the anti-sedimentation agent molded article is measured to calculate the iodine residual rate. Table 2 shows the obtained results.

[0035]

[Table 2]

The numerical values described in Table 2 are as shown in Table 3 below.
1 shows the colored state described in FIG.

[Table 3]

From the results shown in Table 2, the molded article of the present invention obtained by adding a hygroscopic agent to the anti-slippery composition containing an iodoglycine complex as an active ingredient and then molding the composition is derived from raw materials and the like. Even if the molded product absorbs moisture, the decomposition of the iodoglycine complex is suppressed by the effect of the hygroscopic agent, so that free iodine is not generated during storage, and therefore, the phenomenon such as discoloration of the molded product itself and coloring of the packaging material is prevented. It can be seen that generation can be remarkably suppressed and that the iodine content as an active ingredient can be stored very stably for a long time without loss.

Test Example 2 (Solubility / Effect Persistence Test) Each of the molded products obtained in Production Examples 1 to 6 and Comparative Production Example 1 was placed in a plastic container having a large number of small holes, and these were each 2 liters. Hang in an Erlenmeyer flask. The plastic container containing the molded product is set at a position about 20 mm from the bottom. Into this, 2 liters of ion-exchanged water is added and stirred with a stirrer to dissolve the molded product. After dissolving in this state for 10 hours, the effective iodine concentration in water is measured to calculate the iodine elution rate. Also, the weight of the molded product after dissolution is measured to calculate the dissolution rate of the molded product. Further, the molded product after the dissolution treatment is placed in a 1-liter screw-bottle bottle, capped and allowed to stand for 2 hours, and then the concentration of iodine volatilized in the bottle is measured using a Kitagawa type detection tube. After these measurements are completed, new ion-exchanged water is put into an Erlenmeyer flask, the molded product is returned to the container and suspended again in the Erlenmeyer flask, and the same operation as above is performed. This series of operations is repeated until the molded product is completely dissolved. Table 4 shows the obtained results.

[0039]

[Table 4]

From the results shown in Table 4, the present invention is obtained by adding an inorganic hygroscopic agent such as zeolite among the hygroscopic agents to the anti-slippery composition containing an iodoglycine complex as an active ingredient, and molding. Compared to those containing no hygroscopic agent, the elution of iodine in the initial stage of dissolution and the dissolution of the molded product are suppressed, so the effect of improving the sustained release of iodine and the slow solubility of the molded product In addition, since the amount of volatile iodine, which is a direct factor in preventing slimming, is equivalent to that containing no hygroscopic agent, it can be seen that there is no reduction in the slimming effect even in actual use. .

[0041]

As described above, the molded product obtained by further adding a hygroscopic agent to the anti-slime agent composition containing an iodoglycine complex as an active ingredient in the present invention, and molding is as follows.
The dissolution tendency of the molded product, the tendency to generate free iodine, and the effect of preventing slimming have no adverse effect, and the occurrence of phenomena such as discoloration of itself or coloring of the packaging material can be significantly suppressed, It can be stored very stably for a long time.

Further, when a specific inorganic hygroscopic agent is blended as a hygroscopic component, it also has a feature that a constant amount of free iodine is constantly generated during the entire use period during actual use. Things.

 ──────────────────────────────────────────────────の Continued on the front page (72) Ryoichi Seki 1900 Togo, Mobara-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Hideyuki Yamaguchi 1579-206 Mobara, Mobara-shi, Chiba

Claims (5)

[Claims] 1. A molded article of anti-seize agent comprising an iodoglycine complex and a moisture absorbent component. 2. An iodoglycine complex, a hygroscopic component and, in addition thereto, benzoic acid, p-hydroxybenzoic acid, salicylic acid, adipic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, citric acid, fumaric acid, A molded article of anti-slimming agent comprising at least one organic acid selected from the group consisting of malic acid and tartaric acid, and formed by pressure molding. 3. The anti-sedimentation agent molded article according to claim 1, wherein the hygroscopic component is one or more selected from the group consisting of silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon. . 4. The method according to claim 1, wherein the hygroscopic component is polyvinylpyrrolidone,
2. One or more selected from the group consisting of polyamino acids, sodium polyamino acids, polyvinyl acetamide, and carboxymethyl cellulose.
Or a molded article of the anti-slip agent according to 2. 5. The anti-slimming agent according to claim 1, wherein the iodoglycine complex is tetraglycine hydroperiodide, potassium tetraglycine triiodide or diglycine hydroperiodide.