JP2003247000A - Solid detergent for automatic washer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid detergent for automatic washers that is suitable for washing hard surfaces of tableware, cans for food, bottles, containers or trays. <P>SOLUTION: The solid detergent for the automatic washers comprises (a) an alkali metal silicate, (b) an ion-sealing agent, (c) a carbonate salt and (d) water. These components are fused and powdery or granular alkali metal silicate is added to the fused mixture at a temperature of ≤70°C and the mixture is solidified by cooling. The detergent can be easily produced and the whole part can be solidified stably and can be stored without deformation for a long time. In addition, the erosion of glass or aluminum can be inhibited and the washings of all kinds can be directly washed without selection. <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to tableware, food cans,
The present invention relates to a solid detergent for an automatic washing machine which is suitable for cleaning hard surfaces such as bottles, containers, trays, etc., and which can be easily produced in a solid detergent, and can be solidified in a short time. 2. Description of the Related Art Conventionally, automatic dishwashers have been used in hotels, restaurants, catering and the like in order to wash a large amount of used dishes and cans. In addition, automatic washing machines are used in various manufacturing factories and distribution systems to wash utensils, containers, containers, and the like. [0003] As the detergent used in these washing machines, powder and liquid types containing a large amount of a strong alkaline agent have been mainly used, but in recent years, solid type detergents have become popular due to safety and ease of use. Have been. As a solid type cleaning agent, for example, Japanese Patent Publication No. 59-4480 discloses a solid obtained by mixing a sequestering agent with a hot-dissolved aqueous caustic solution, pouring the mixture into a container, and solidifying by cooling. A casting detergent and the like are disclosed. According to this cleaning agent, the cleaning components constituting the cleaning agent are uniform, and a strong solid cleaning agent can be obtained. [0004] However, such a high-alkaline cleaning agent has a problem in that the pattern of gold-colored tableware is lost or glass or aluminum products are eroded. It is known that the problem of erosion of glass and aluminum can be avoided by using an alkali metal silicate as a main component. However, if a large amount of an alkali metal silicate is added to a heated melt, it does not solidify for a long time even when cooled. There is a problem. In order to solve such a problem, Japanese Patent Application Laid-Open No. 64-51498 discloses a method in which a crystalline alkali metal silicate is mixed with an alkali metal condensed phosphate having water of hydration or added water. A solidified casting composition that cools and solidifies after melting is known, and Japanese Patent Application Laid-Open No. 2000-144196, which is a prior application of the applicant of the present invention, discloses a method in which an alkali metal silicate or water is blended and melted, and then the container is melted. It discloses that particles of alkali metal metasilicate are added to a storage container when the mixture is cooled and solidified to increase the solidification rate. However, the former JP-A-64-5
No. 1498 has a problem that the added water needs to be deionized, and that a large amount of alkali metal condensed phosphate having water of hydration must be mixed. The latter JP-A-2000-14
No. 4196 has an excellent effect,
The alkali metal metasilicate particles must be newly added to the storage container, and the addition of added water causes a change in the hydration state of the alkali metal silicate. When the solidified container swells, or when the solid material that has been die-cut is placed in a plastic bag or the like, there is also a problem that the solid material tends to crack or swell. On the other hand, JP-A-09-217100,
In JP-A-11-349997, a solid detergent that is allowed to solidify spontaneously under non-heating and non-pressurization without adding water at all, or a detergent mixture at 32 ° C. or more without adding water at all. There is known a solid detergent which is kept at a temperature lower than the melting temperature of a hydrate for a predetermined time and then cooled at a temperature lower than 30 ° C. for a predetermined time. However, in the technology disclosed in these publications, it takes time to solidify, and even if it becomes a solid product, the substantial bulk specific gravity is equivalent to that of powder, and there is a problem that compactness cannot be obtained. is the current situation. Further, Japanese Patent Application Laid-Open No. 2000-80400 discloses that a solid material is produced by an extrusion molding machine with a small amount of added water. However, in this technique, after extrusion molding, the solid is once put in a mold and solidified. There is a problem that the manufacturing process is complicated because the mold is taken out of the mold, cut into a required size, and further packaged. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems and the current state of the prior art, and has been made to solve the problem. The present invention relates to tableware, cans, bottles, containers, and the like. Solid cleaning agents used in automatic washing machines for cleaning hard surfaces such as trays, without the use of alkali metal hydroxides, are easy to manufacture, can be completely solidified in a short time, and can be used for a long time. It is an object of the present invention to provide a solid cleaning agent for an automatic washing machine which does not change the shape of solids even upon storage, can suppress erosion of glass and aluminum products, etc., and can wash without selecting sorted items. I do. The present invention has been made as a result of intensive studies on the above-mentioned conventional problems and the like. As a result, (a) an alkali metal silicate, (b) a sequestering agent, (c) a carbonate and (c) d) containing water and adding a specific shape of alkali metal silicate to a melt obtained by melting them at a specific temperature or lower and solidifying by cooling, whereby the above-mentioned solid cleaning agent for an automatic cleaning machine is obtained. They found what they could do, and completed the invention. That is, the solid detergent for an automatic washing machine of the present invention contains (a) an alkali metal silicate, (b) a sequestering agent, (c) a carbonate, and (d) water,
A powder or particulate alkali metal silicate is added at a temperature of 70 ° C. or less to a melt obtained by melting these, and the mixture is cooled and solidified. Embodiments of the present invention will be described below in detail. The solid detergent for an automatic washing machine of the present invention (hereinafter simply referred to as “detergent”) contains (a) an alkali metal silicate, (b) a sequestering agent, (c) a carbonate, and (d) water. A powder or particulate alkali metal silicate is added at a temperature of 70 ° C. or lower to a molten material obtained by melting them, and the mixture is cooled and solidified. In the detergent of the present invention, an alkali metal silicate is used as the component (a), and any of these anhydrides and hydrates can be used. Examples of the alkali metal silicate that can be used include sodium metasilicate anhydride, sodium metasilicate / pentahydrate, sodium metasilicate / nine hydrate, potassium metasilicate, No. 1 sodium silicate, No. 2 sodium silicate, No. sodium silicate, potassium C silicate, potassium B silicate and potassium A silicate. These alkali metal silicates can be used alone or in a mixture of two or more. Preferably, in terms of prevention of aluminum erosion and detergency, S
Sodium silicate having a molar ratio of iO ₂ / Na ₂ O of 0.5 to about 3 is more preferable, and more preferably a molar ratio of SiO ₂ / Na ₂ O of about 1 to 2 is preferable. The content of these alkali metal silicates is preferably 10 to 50% by mass (hereinafter simply referred to as "%"), more preferably 20 to 40%, based on the total amount of the detergent in terms of anhydride. It is desirable. In the detergent of the present invention, a sequestering agent is used as the component (b), and any of these anhydrides and hydrates can be used. Examples of sequestering agents that can be used include, for example, aminocarboxylic acid or a salt thereof, hydroxycarboxylic acid or a salt thereof, condensed phosphoric acid or a salt thereof, polyacrylic acid or a salt thereof,
Examples thereof include polymaleic acid or a salt thereof, a copolymer with acrylic acid or a salt thereof, and a copolymer with maleic anhydride or a salt thereof. These sequestering agents can be used alone or in a mixture of two or more. The salt is an alkali metal such as sodium or potassium, and may be partially or entirely neutralized. Specifically, nitrilotriacetic acid or trisodium salt, tripotassium salt, ethylenediaminetetraacetic acid or tetrasodium salt, four potassium salt, diethylenetriaminepentaacetic acid or five sodium salt, five potassium salt, hydroxyethylethylenediaminetriacetic acid or three sodium salt, 3 potassium salt, triethylenetetraamine hexaacetic acid or 6 sodium salt, 6 potassium salt, citric acid or 3 sodium salt, 3 potassium salt, malic acid or disodium salt, 2 potassium salt, sodium, potassium pyrophosphate,
Examples include sodium tripolyphosphate, potassium polyphosphate, polyacrylic acid or sodium salt, polymaleic acid or sodium salt, acrylic acid / maleic anhydride copolymer or sodium salt, olefin / maleic anhydride copolymer or sodium salt, and the like. it can. Preferably, aminocarboxylic acid or a salt thereof, olefin / maleic anhydride copolymer or a salt thereof, polyacrylic acid or a salt thereof, polymaleic acid or a salt thereof, acrylic acid / Maleic anhydride copolymer or a salt thereof is desirable. The content of these sequestering agents is preferably 10 to 50%, more preferably 20 to 40%, based on the total amount of the detergent in terms of anhydride. In the cleaning agent of the present invention, the component (c) comprises:
It is included to reduce the viscosity of the melt during production and to prevent the solid from swelling. As the component (c),
Carbonate is used, and any of these anhydrides and hydrates can be used. Examples of the carbonate that can be used include sodium carbonate or potassium carbonate, sodium sesquicarbonate, sodium bicarbonate, and the like, and these are used alone or in a mixture of two or more. Preferably, sodium carbonate or potassium carbonate is used from the viewpoint of further reducing the viscosity of the melt during the production and preventing swelling of the solid. The content of these carbonates is preferably from 1 to 10%, more preferably from the total amount of the detergent.
It is desirable to set it to 1 to 7%. If the content of this carbonate is less than 1%, the viscosity of the melt at the time of production becomes high, and it becomes difficult to stir with a stirrer, and swelling of a solid may occur, which is not preferable. 10%
If the content exceeds the above range, the aluminum product is eroded, which is not preferable. In the cleaning agent of the present invention, water is used as the component (d). The water used is a hydrate of an alkali metal silicate, a hydrate of a sequestering agent, a hydrate of a carbonate, or added water (purified water, ion-exchanged water, pure water, tap water, etc.).
Is used, and preferably 10 to 10
It is desirable to be 40%, more preferably 15 to 30%. When the content of water is less than 10%, the viscosity of the melt becomes high, and it becomes difficult to stir with a stirrer. Problems such as inability to solidify, cracking or swelling of the solid even after solidification, and swelling of the container when placed in a container will occur. Further, in the cleaning agent of the present invention, optional components can be added as needed within a range that does not impair the quality and the productivity. As optional components that can be used, for example, a surfactant, an oxidizing agent, an enzyme, sodium sulfate, a dye, a fragrance, and the like can be used. Surfactants are used to improve detergency, but those having low foaming properties are desirable. Examples of such a surfactant include polyoxyethylene polyoxypropylene condensate, polyoxypropylene polyoxyethylene condensate of ethylenediamine, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl phenyl ether and the like. Is mentioned. In the present invention, the temperature of the molten metal powder or particulate alkali metal silicate is reduced with respect to the molten metal containing the alkali metal silicate, sequestering agent, carbonate and water. By adding below 70 ° C,
The melt can be solidified in a short time. The addition amount of the powdery or particulate alkali metal silicate is desirably 0.1 to 10%, preferably 0.1 to 5%, based on the total amount of the detergent in terms of anhydride. If the amount is less than 0.1%, the melt may not be able to be solidified, or the time required for solidification may be long.
Even if added in excess of 10%, the effect is not changed, but a distribution occurs in the components in the system. The alkali metal silicate to be added is in the form of powder or particles, for example, sodium metasilicate anhydride, sodium metasilicate.
Examples thereof include pentahydrate, sodium metasilicate / 9-hydrate, and these can be used alone or in a mixture of two or more. The average particle size of the alkali metal silicate particles to be added is 0.05 to 5 mm, preferably 0. 5 mm, from the viewpoint of uniformly dispersing and solidifying in a short time.
It is desirable that it is 1 mm to 3 mm. If the temperature of the melt exceeds 70 ° C. and the powder or particulate alkali metal silicate is added, the melt cannot be solidified in a short time, which is not preferable. As a specific example, water [(d)
Component] and a carbonate [component (c)] to dissolve or disperse the carbonate, and then an alkali metal silicate [component (a)] is added, and a temperature of 75 ° C. or higher, which is a preferable melting temperature, is added. Dissolve or disperse the alkali metal silicate with stirring. Next, a sequestering agent [component (b)] and optional components are added to prepare a uniform melt. Then
When cooled and the temperature of the melt drops below 70 ° C., a powder or particulate alkali metal silicate is added. Preferably,
The temperature of the melt is preferably from 40 to 70 ° C., more preferably from 50 to 65, from the viewpoint that the melt is solidified well in a shorter time.
When the temperature reaches ° C, it is desirable to add an alkali metal silicate. The cleaning agent of the present invention thus constituted is
The low viscosity of the melt makes it easy to manufacture, solidifies the melt in a short time, does not change the shape of the solid even after long-term storage, and corrodes glass and aluminum products. Can be suppressed, and the object can be washed without sorting. Specifically, the alkali metal silicate, sequestering agent, carbonate, water, and a molten material containing an optional component and the like are melted, and the powder or particulate alkali metal silicate is heated to 70 ° C. By adding below, the viscosity of the melt is kept low and the melt can be stably solidified in a short time, and the hydration state of the alkali metal silicate does not change due to the inclusion of carbonate, The shape of the solid does not change even after storage for a long period of time, and the solid does not crack or swell even when the molded solid is placed in a plastic bag or the like. Further, since the cleaning agent of the present invention does not use an alkali metal hydroxide, erosion of glass, aluminum products, and the like can be suppressed, and a solid cleaning agent for an automatic cleaning machine that can be washed without selecting an object to be washed can be obtained. It will be. Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. [Examples 1 to 9 and Comparative Examples 1 to 5] Detergents having the composition shown in Tables 1 and 2 below were produced by the following method, and the viscosity and solidification of the melt were evaluated by the following evaluation methods. , Swelling of the container and erosion of aluminum were evaluated. The results are shown in Tables 1 and 2 below. [Manufacturing Method] (1) Examples 1 to 6 Water and potassium carbonate were placed in a 1 L stainless steel container and heated at 85 ° C. in a water bath so that the total amount was 1000 g according to the composition shown in Table 1 below. Then, stirring was performed using a three-one motor. After the potassium carbonate was uniformly dissolved, when the liquid temperature reached 80 ° C., sodium metasilicate / anhydrous salt or sodium metasilicate / pentahydrate was added to uniformly dissolve or disperse. With the liquid temperature maintained at 80 ° C., nitrilotriacetic acid trisodium monohydrate or sodium tripolyphosphate, ACUSOL 460N
D and sodium sulfate were added sequentially to prepare a uniform melt. Next, the temperature of the water bath was adjusted to 65 ° C., and when the temperature of the melt reached 65 ° C., sodium metasilicate / anhydrous salt or sodium metasilicate · 5
Add water salt to disperse uniformly, and maintain
After stirring for 60 minutes, the mixture was cooled to 60 ° C., and 500 g of the melt was poured into an opening having a diameter of 80 mm and a height of 120 mm.
mm polyethylene container and allowed to cool to room temperature (25
(C, the same applies hereinafter)) and the plate was left covered. (2) Example 7 Water was placed in a 1 L stainless steel container, heated in a water bath at 80 ° C., and stirred using a three-one motor so that the total amount was 1000 g according to the composition shown in Table 2 below. went. When the liquid temperature reached 75 ° C., sodium metasilicate pentahydrate was added to uniformly dissolve and disperse. While maintaining the liquid temperature at 75 ° C., potassium carbonate, trisodium nitrilotriacetic acid, and sodium sulfate were sequentially added to prepare a uniform melt. Then, the temperature of the water bath was adjusted to 55 ° C., and when the temperature of the melt reached 55 ° C., particles of sodium metasilicate / anhydrous salt were added as additional particles to uniformly disperse the particles. After stirring for 500 minutes, 500 g of the molten material is 80 m in diameter with an open port.
m, and stored in a polyethylene container having a height of 120 mm and allowed to cool. When the temperature reached room temperature, the container was covered and left to stand. (3) Example 8 Water was placed in a 1 L stainless steel container, heated in a water bath at 80 ° C., and stirred using a three-one motor so that the total amount was 1000 g according to the composition shown in Table 2 below. went. When the liquid temperature reached 75 ° C., sodium metasilicate pentahydrate was added to uniformly dissolve and disperse. While maintaining the liquid temperature at 75 ° C., sodium carbonate, trisodium nitrilotriacetate, Quinflow 750, and sodium sulfate were sequentially added to prepare a uniform melt. Next, the temperature of the water bath was adjusted to 60 ° C., and when the temperature of the melt reached 60 ° C., sodium metasilicate / anhydrous salt was added as additional particles to uniformly disperse the mixture, and the mixture was maintained at 60 ° C. and stirred for 30 minutes. The melt was placed in a polyethylene container having an opening and having a diameter of 80 mm and a height of 120 mm, and was allowed to cool. When the temperature reached room temperature, the lid was left standing. (4) Example 9 Water was placed in a 1 L stainless steel container, heated in a water bath at 80 ° C., and stirred using a three-one motor so that the total amount was 1000 g according to the composition shown in Table 2 below. went. When the liquid temperature reached 75 ° C., sodium metasilicate / anhydrous salt was added to uniformly dissolve and disperse. While maintaining the liquid temperature at 75 ° C., potassium carbonate, trisodium nitrilotriacetate, and sodium sulfate were sequentially added to prepare a uniform melt. Next, the temperature of the water bath was adjusted to 68 ° C., and when the temperature of the melt reached 68 ° C., sodium metasilicate / anhydrous salt was added as additional particles to uniformly disperse the mixture. The mixture was maintained at 68 ° C. and stirred for 30 minutes. The mixture was cooled to 60 ° C., and 500 g of the melt was placed in a polyethylene container having an opening and having a diameter of 80 mm and a height of 120 mm, and was allowed to cool. (5) Comparative Example 1 The procedure of Example 1 was repeated, except that potassium carbonate was not used in accordance with the composition shown in Table 1 below. (6) Comparative Example 2 According to the composition shown in Table 1 below, the same procedure was performed as in Example 2 except that sodium metasilicate / anhydrous salt was not used as the added particles in Example 2. (7) Comparative Example 3 According to the composition shown in Table 1 below, sodium hydroxide was used in place of sodium metasilicate / anhydrous salt in Example 6,
Example 6 was carried out in the same manner as in Example 6 except that sodium metasilicate / anhydrous salt of the added particles was not used. (8) Comparative Example 4 In the same manner as in Example 8 except that the addition temperature of the added particles was changed to 75 ° C. in accordance with the composition shown in Table 2 below. (9) Comparative Example 5 According to the composition shown in Table 2 below, the same procedures as in Example 8 were carried out except that sodium carbonate was used instead of sodium metasilicate / anhydrous salt of the added particles in Example 8. Each composition in each of the Examples and Comparative Examples obtained in each of the above Production Examples was evaluated according to the following evaluation methods and the like. (1) Viscosity of melt The viscosity of the melt (25
° C) using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). A melt viscosity in a range of 1000 to 7000 mPa · s is a preferable range in terms of uniform dispersion and easy stirring by a stirrer. (2) The solidified melt was placed in a polyethylene container and allowed to cool at room temperature for 2 hours.
The following evaluation criteria were used to determine whether the glass rod would not enter the interior. Evaluation criteria: ：: Glass rod does not penetrate ×: Glass rod penetrates (3) Swelling of container The polyethylene container containing the molten material was left at room temperature for one day, and the circumference of the container was measured. Was stored in a constant temperature bath for one month, allowed to stand at room temperature for one day, returned to room temperature, and the circumference of the container was measured to calculate the difference between the two. (4) Erosiveness of aluminum The aluminum plate (25 mm × 75 mm) which had been washed and rinsed with a neutral detergent in advance and dried was placed in a 100 ml volume containing 50 ml of a 0.15% detergent solution (65 ° C.). Was immersed for about half in a glass bottle and left for 1 hour while maintaining at 65 ° C. in a water bath. After standing, the aluminum plate was taken out of the beaker, rinsed thoroughly with running water, and dried. The state of the dried aluminum plate was evaluated according to the following evaluation criteria. Evaluation criteria: ：: No change in the same state as before immersion X: Gas is generated during immersion, and the aluminum plate becomes black and discolored or loses luster [Table 1] [Table 2] As is evident from the results of Tables 1 and 2, Examples 1 to 9, which are within the scope of the present invention, have a higher viscosity of the melt than Comparative Examples 1 to 5, which are outside the scope of the present invention. It was found that the solidification was good, the container did not swell, and there was no erosion of aluminum. Looking at the comparative examples individually,
Comparative Example 1 without using potassium carbonate [component (c)]
Comparative Example 2 in which sodium metasilicate / anhydrous salt was not used as additive particles
Then, it was found that it could not be solidified in a short time.
In Comparative Example 3 in which sodium hydroxide was used instead of sodium metasilicate / anhydrous salt, erosion of aluminum occurred, and Comparative Example 4, in which the addition temperature of the added particles exceeded 70 ° C. and was 75 ° C., In addition, in Comparative Example 5 using sodium carbonate instead of sodium metasilicate / anhydrous salt of the added particles, it was found that solidification could not be performed in a short time. Therefore, the alkali metal silicate in the scope of the present invention, a sequestering agent, carbonate, water, and a melt containing the optional components and the like, and melted, powder or particulate alkali metal silicate. For the first time, by adding a detergent at 70 ° C or less, the melt can be solidified stably in a short time, and the shape of the solid does not change even after long-term storage. It has been found that erosion such as the above can be suppressed, and that the object can be washed without sorting. According to the present invention, the production is easy, the whole can be solidified stably in a short time, the shape does not change even after long-term storage, and the erosion of glass and aluminum is prevented. Provided is a solid detergent for an automatic washing machine, which can be suppressed and can be washed without sorting an object to be washed.

Claims (1)

Claims: 1. A melt containing (a) an alkali metal silicate, (b) a sequestering agent, (c) a carbonate and (d) water, and A powdery or particulate alkali metal silicate at a temperature of 70 ° C. or lower and solidification by cooling.