JPH046239B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a solid detergent that can easily clean strong oily stains adhering to, for example, hard surfaces. <Prior art> A liquid detergent made by dissolving glycol ethers and caustic alkalis in water and adding a hydrotrope and a surfactant to the solution is extremely effective against oils and stains made of polymerized oils. It is known as a cleaning agent with cleaning power. <Problems to be solved by the invention> However, this liquid detergent is effective in a uniform liquid state, and if it is separated into glycol ether and caustic alkaline aqueous solution, it can no longer exhibit excellent cleaning power. I can't. However, glycol ether and caustic aqueous solution are inherently difficult to be compatible with each other, and various hydrotropes are added to make them a homogeneous aqueous solution. However, even if a hydrotrope is added as mentioned above, it will not become a homogeneous aqueous solution unless the water content is maintained at about 70% or more. There will be a large amount of water that does not have a cleaning effect on the cleaning ingredients. In addition, since the above-mentioned cleaning agents are alkaline aqueous solutions, they do not dissolve even if an antifoaming agent is added and cannot function as an antifoaming agent. This requires a complicated operation in which an antifoaming agent must be added. On the other hand, plastic containers contaminated with oil, exhaust carbon, and dust can be cleaned using a liquid cleaning agent containing an aqueous solution of glycol ether surfactant, caustic soda, and hydrotrope, or by immersion in a high-temperature, high-concentration caustic soda aqueous solution for a long period of time, followed by manual labor. They had to be scrubbed with water, and could not be cleaned automatically using the spray pressure of an automatic washer. In view of the above circumstances, the present invention aims to provide a solid detergent consisting of 100% active ingredients. A further object of the present invention is to provide a cleaning agent that can easily wash off strong oily stains adhering to hard surfaces such as plastic containers. <Means for Solving the Problems> In order to solve the above problems, the inventors of the present application, as a result of intensive research, developed a method for mixing caustic alkali and water-soluble glycol ether in a weight ratio of 10:1 to 1:2. It has been discovered that the desired solid detergent can be obtained by mixing. When solid caustic alkali and liquid water-soluble glycol ether are mixed, they generate heat and become paste-like; however, if left for a certain period of time, for example, the caustic alkali and water-soluble glycol ether are combined into a powder form. It is a solid with granular, small lump, large lump shapes, etc., and a dry surface. In other words, even if left for a long time, it remains liquid or paste-like, or the surface is not wet due to adhesion of water-soluble glycol ether, but the surface where the caustic alkali and water-soluble glycol ether are combined becomes dry. It becomes a solid. Here, the caustic alkali includes lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Among these, the most used is sodium hydroxide. The caustic alkali may be in any form such as powder, beads, flakes, etc. Water-soluble glycol ethers are those obtained by addition polymerizing alkylene oxide to a monohydric alcohol, and those which do not have alkylene oxide added, but have both an ether bond and a hydroxyl group in the same molecule. Addition polymerization of ethylene oxide to monohydric alcohol includes diethylene glycol methyl ether, polyethylene glycol methyl ether (n=3 to 5), monoethylene glycol ethyl ether, polyethylene glycol ethyl ether (n=2 to 5), and monoethylene glycol. Propyl ether, polyethylene glycol propyl ether (n = 2-5), monoethylene glycol butyl ether, polyethylene glycol butyl ether (n = 2-5), monoethylene glycol amyl ether, polyethylene glycol amyl ether (n = 2-5), polyethylene Glycolhexyl ether (n=2-5) and the like can be mentioned. Addition polymerization of propylene oxide to monohydric alcohol includes monopropylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, tetrapropylene glycol methyl ether, monopropylene glycol ethyl ether, dipropylene glycol ethyl ether, Tripropylene glycol ethyl ether, tetrapropylene glycol ethyl ether, monopropylene glycol propyl ether, dipropylene glycol propyl ether, tripropylene glycol propyl ether, monopropylene glycol butyl ether, dipropylene glycol butyl ether, monobutylene glycol methyl ether, monobutylene glycol ethyl Examples include ether, monobutylene glycol propyl ether, monoamylene glycol methyl ether, monoamylene glycol ethyl ether, monoamylene glycol propyl ether, etc., and the most commonly used ones are monoethylene glycol butyl ether, diethylene glycol butyl ether, and These include amylene glycol methyl ether and 3-methyl-3-methoxybutanol. The ratio at which caustic alkali and water-soluble glycol ether can be mixed to maintain a solid state varies depending on the type of water-soluble glycol ether, but the weight ratio of caustic alkali and water-soluble glycol ether is 10:1 to 10:1. 1:2, preferably 5:1~
The ratio is 1:1. The form of the solid depends on the blending ratio of water-soluble glycol ether; if the blending ratio of water-soluble glycol ether is small, a product close to the original form of caustic alkali can be obtained, but as it becomes larger, it expands. When the mixture becomes larger, it becomes a slurry or paste, but if left as it is, it becomes a large lump with the same shape as a hard plastic mixing container. In the first and second cases above, the product can be packaged in a packaging container in its original shape and made into a product. In the third case, the product is made by leaving the slurry or paste state in a container with a shape suitable for making it into a product, or it is made into a product by crushing a large lump and packing it into a packaging container. I can do it. In addition, the solid detergent of the present invention has a wide range of uses, and may contain one or more other substances such as sequestering agents, hydrotropes, antifoaming agents, and surfactants depending on each use. can do. Up to 90% by weight of the caustic alkali may be replaced by other substances mentioned above. That is, the weight ratio of caustic alkali to other substances is 100:0 to 10:90. The weight ratio of caustic alkali and water-soluble glycol ether is 10:1 to 1:2 as described above. Here, the following can be mentioned as the metal ion sequestering agent. Condensed phosphates: alkali metal pyrophosphates, alkali metal tripolyphosphates, alkali metal hexametaphosphates, alkali metal polyphosphates, and the like. Hydroxycarboxylic acid salts; alkali metal glycolates, alkali metal gluconates, alkali metal citrates, alkali metal tartrates, and the like. Carboxylate; alkali metal oxydiacetate;
Alkali metal carboxymethyloxysuccinates and the like. Aminocarboxylic acid salts; alkali metal ethylenediamine tetraacetate, alkali metal nitrilotriacetate, alkali metal hydroxyethylethylenediamine pentaacetate, alkali metal diethylenetriamine hexaacetate, alkali metal hydroxyiminodiacetic acid, alkali metal glycine, alkali metal dihydroxyethyl Glycine etc. Water-soluble synthetic resins; carboxymethyl cellulose, polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and vinyl compounds, copolymers of maleic anhydride and vinyl compounds, copolymers of maleic anhydride and ethylene , alkali metal salts such as maleic acid polymers. In addition, sodium imidobis sulfate and the like can also be used. Although up to 90% by weight of the caustic alkali can be replaced by the sequestering agent, it is better to limit the substitution to 75% by weight in order to obtain good detergency. In addition, the antifoaming agents mentioned above include silicone oil and its emulsifier, paraffin, petroleum oxide,
These include ethylene oxide propylene oxide addition polymers of alkyl phosphate esters, fatty acids, higher alcohols and alkylphenyls, and higher alcohol ethylene oxide propylene oxide block copolymers. The blending ratio of the antifoaming agent is 0 to 5% by weight. This antifoaming agent is an absolutely necessary component when used as a detergent for spray-type automatic washing machines, but it is not necessary to add it when washing by immersion. Examples of hydrotropes include xylene sulfonate, toluene sulfonate, lignin sulfonic acid, and higher alcohol sulfate salt having 6 to 12 carbon atoms. The blending ratio of the hydrotrope is 0 to 15% by weight, and is unnecessary when the solid detergent is diluted 50 times or more with water. Also, if it is blended in an amount of 15% by weight or more, the blending ratio of components necessary for cleaning becomes low, which is not preferable. Furthermore, carboxylic acid ester-based and amide-based surfactants that can be hydrolyzed with caustic alkali are excluded from the scope of the present invention, and the following surfactants can be used here. Anionic surfactant; alkylbenzene sulfonate, naphthalene sulfonate, alkylnaphthalene sulfonate, petroleum sulfonate, naphthalene formalin condensate sulfonate, higher alcohol sulfate, higher alcohol ethoxysulfate These include phonate salts, alkylphenyl ethoxylate sulfates, alkyl phosphate ester salts, and soaps. Nonionic surfactants: higher alcohol ethoxylates, alkylphenyl ethoxylates, higher alcohol ethylene oxide propylene oxide adducts, alkylphenyl ethylene oxide propylene oxide adducts, ethylene oxide propylene oxide block polymers, amine oxides, and the like. Cationic surfactants: alkyl quaternary ammonium compounds, alkylpyridinium compounds, alkylbenzylammonium compounds, alkylamine compounds, alkylpolyoxyethyleneamine compounds, amine oxide compounds, etc. Ampholytic surfactants; alkali betaine compounds, sulfobetaine compounds, alkylimidazolinium compounds, alkylaminopropionic acid compounds,
Alkyliminopropionic acid compounds and the like. The blending ratio of surfactant is 0 to 10% by weight, and when used as a detergent for spray-type automatic washing machines, surfactants create foam, which is rather harmful, but when used for ultrasonic washing machines. , or in the case of immersion cleaning, it is effective to incorporate a surfactant. In addition to the above ingredients, optional ingredients such as alkali metal silicates, alkali metal hydrochlorides, alkali metal sulfates, alkali metal carbonates, alkali metal phosphates, and other substances commonly included in detergents may be added. It can also be blended. <Effects of the Invention> As described above, the cleaning agent according to the present invention is a solid cleaning agent consisting of 100% active ingredients made by mixing caustic alkali and water-soluble glycol ether, and
Extremely good cleaning power. For example, if a plastic container is so contaminated with oil, exhaust carbon, dust, etc. that it cannot be cleaned without scrubbing with other cleaning agents, it can be scrubbed by hand using the aqueous solution of the cleaning agent of this invention. It can be easily washed off with the jet pressure of an automatic washing machine. Furthermore, to illustrate the excellent cleaning power of the cleaning agent of the present invention, in food factories, pharmaceutical factories, etc., machines are disassembled and immersed in a solvent after the end of the day's work.
Furthermore, the lubricating oil, grease, etc. had to be scrubbed off with a brush before reassembly, which posed a safety problem. Such stains can be easily washed off by using an aqueous cleaning solution according to the present invention with an automatic jet washing machine, and the washing time can be significantly shortened. Another advantageous feature of the present invention is that it provides a surface-dry solid detergent in which caustic alkali and water-soluble glycol ether are present together. That is, when an excess amount of water-soluble glycol ether is added to caustic alkali beyond the mixing ratio range of the present invention, it becomes slurry-like or paste-like, but these states are unstable and the temperature increases. As it rises, the caustic alkali and water-soluble glycol ether separate, and the upper layer of glycol-rich portion,
No matter which portion of the lower layer rich in caustic alkali is collected, sufficient cleaning power cannot be obtained. However, if the detergent of the present invention is in a solid state in which caustic alkali and water-soluble glycol ether are integrated, this aqueous solution will have sufficient detergency. In addition, if the cleaning agent that exceeds the mixing ratio range of the present invention becomes slurry or paste and solidifies in the container due to a drop in temperature, it will be difficult and dangerous to remove it from the container. As with the invention, if the solid is powder, granule, small lump, or large lump from the beginning, the shape can be selected according to the application.
It does not cause any particular difficulty in handling and does not pose any danger. On the other hand, if the solid caustic alkali and the water-soluble glycol ether are not integrated and the water-soluble glycol ether simply adheres to the surface of the caustic alkali and it is wet, when placed in a bag made of polyethylene, etc. It sticks to the inside of the bag and is difficult to remove. Also, if you try to forcefully remove it by hitting it, it will scatter and cause a dangerous situation. On the other hand, the cleaning agent of the present invention has a dry surface and is in a solid state, so it can be easily taken out without adhering to the inside of the bag. In addition, since the cleaning agent of the present invention is composed only of active ingredients for cleaning, the amount used is small.
It does not take up much space during transportation or storage. <Examples> Examples of the present invention will be shown below. Examples 1 to 12, Control Examples 1 to 4 Pearlized caustic soda manufactured by Solvay (average particle size)
The following glycol ether was added to 100 g of 0.4 mm) and mixed with stirring to obtain a cleaning agent as shown in Table 1 below.

[Table] Examples 1 to 12 are examples in which solids were obtained. The monoethylene glycol methyl ethers of Control Examples 1 to 3 did not become solid whether the amount added was small or large. Alternatively, in Control Example 4, when the ratio of tetraethylene glycol methyl ether and Solvay's pearly caustic soda was 1:3, it was paste-like, but in Example 11, when the ratio was 1:2, it became solid. . Examples 13 to 16, Comparative Example 5 A cleaning agent was obtained by mixing and stirring the composition shown in Table 2 below in the same manner as in the above example.

【table】

[Table] Comparative Example 5 has extremely excellent properties as an immersion cleaning agent for heating grease filters, but when Example 13 is diluted 6 times with water, it has the same composition as Comparative Example 5, and has a lower cleaning power. Since they are the same, they are suitable for export. Furthermore, when the cleaning agents of Examples 14, 15, and 16 were diluted with water and used to wash the floor of a machine tool factory, extremely excellent cleaning effects were obtained. Examples 17 to 19, Comparative Example 6 Cleaning agents were obtained by mixing and stirring the formulations shown in Table 3 below in the same manner as in the above examples.

[Table] *2 Alkyl phosphate ester, petroleum oxide, higher alcohol ethylene
Mixture of oxide adducts Example 17-2 was applied to a plastic container that was previously immersed in a 5% concentration caustic soda aqueous solution at 80 to 90°C, then pulled up and scrubbed with a nylon scrubber, but the stains could not be removed sufficiently. % aqueous solution,
When washed using a high-pressure automatic washer with water at a temperature of 60°C, it was possible to completely clean it in 45 seconds. On the other hand, the cleaning agent of Comparative Example 6 was used for cleaning under the same conditions, but the stains were not removed. Good results were obtained by using Example 18 as a cleaning agent for disassembling machines in a pharmaceutical factory and Example 19 in a food factory to remove grease adhering to parts. That is, in the past, disassembled machine parts were dipped in a solvent and scrubbed with a brush, but Example 18
The grease could be easily washed off by spraying a 1-3% aqueous solution of No. 1 and No. 19 at high pressure at a water temperature of 60°C.

Claims (1)

[Claims] 1. A solid detergent prepared by mixing caustic alkali and water-soluble glycol ether in a weight ratio of 10:1 to 1:2. 2 Caustic alkali and one or more of sequestering agents, antifoaming agents, hydrotropes, and surfactants at 100:
A solid detergent obtained by mixing the above caustic alkali and water-soluble glycol ether in a weight ratio of 0 to 10:90, and having a weight ratio of 10:1 to 1:2.