JPH046240B2 - - 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 hydrotropes and surfactants has extremely excellent cleaning power against oils and oil-polymerized stains. It is known as a cleaning agent with <Problems to be solved by the invention> However, this liquid detergent is effective in a homogeneous liquid state, and if it is separated into glycol ether and caustic alkaline aqueous solution, it can no longer exhibit excellent cleaning power. Can not. 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 agent is an alkaline aqueous solution, even if an antifoaming agent is added, it will not dissolve and will not 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 have conducted intensive research and found that a caustic alkali and a water-soluble alkanolamine, or a caustic alkali and a water-soluble alkanolamine and a water-soluble It has been discovered that the desired solid detergent can be obtained by mixing it in a mixed solvent with a glycol ether at a weight ratio of 15:1 to 1:5. When a solid caustic alkali and a liquid water-soluble alkanolamine or water-soluble alkanolamine or water-soluble glycol ether are mixed together, it may generate heat and become paste-like, but if left for a certain period of time, the caustic alkali and water-soluble alkanolamine or water-soluble glycol ether will mix. The water-soluble alkanolamine and the water-soluble glycol ether are present in powder, granular, small lump, large lump form, etc., and form a solid with a dry surface. In other words, even if left for a long time, it remains liquid or paste-like, or remains wet due to glycol ether adhering to the surface; The surface where these are united becomes a dry 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. Furthermore, water-soluble alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and the like. The proportion that becomes solid by mixing caustic alkali and water-soluble alkanolamine is the weight ratio of caustic alkali and water-soluble alkanolamine.
The ratio is 15:1 to 1:5, preferably 10:1 to 1:4. Furthermore, 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 thereto, but have both an ether bond and a hydroxyl group in the same molecule. Addition polymerization of ethylene oxide to monohydric alcohols includes diethylene glycol methyl ether, polyethylene glycol methyl ether (n = 3 to 5), monoethylene glycol ethyl ether, polyethylene glycol ethyl ether (n = 3 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 mixing weight ratio of water-soluble alkanolamine and water-soluble glycol ether is suitably in the range of 1:9 to 9:1, and the mixing ratio is varied within this range depending on the application. Furthermore, the proportion by which caustic alkali becomes solid by mixing it with a mixed solvent of water-soluble alkanolamine and water-soluble glycol ether varies depending on the type of mixed solvent, but the weight ratio of caustic alkali and mixed solvent varies depending on the type of mixed solvent. is 15:1 to 1:5, preferably 10:1 to 1:4. The form of the solid obtained by mixing a caustic alkali and a water-soluble alkanolamine or a mixed solvent of a water-soluble alkanolamine and a water-soluble glycol ether varies depending on the type and blending ratio of the water-soluble alkanolamine or mixed solvent. .
If the proportion of the water-soluble alkanolamine or mixed solvent is small, a product close to the original form of caustic alkali can be obtained, but as it grows, it becomes swollen granular or block-like. Once this happens, the mixed system becomes a slurry or paste, but if left undisturbed, 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 without changing its shape. In the third case, the product is made by leaving the slurry or paste in a container with a shape suitable for making it into a product, or by crushing a large lump and packing it into a packaging container to make the product. 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 the respective uses. can do. In this case, up to 90% by weight of the caustic alkali may be replaced by the 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 the caustic alkali to the water-soluble alkanolamine or the mixed solvent consisting of the water-soluble alkanolamine and the water-soluble glycol ether is 15:1 to 1:5 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. Hydroxycarboxylate; alkali metal glycolate, alkali metal gluconate, alkali metal citrate, alkali metal tartrate, etc. Carboxylate; alkali metal oxydiacetate;
Alkali metal carboxymethyloxysuccinates and the like. Aminocarboxylate; alkali metal ethylenediamine tetraacetate, alkali metal nitrilotriacetate, alkali metal hydroxyethylethylenediaminepentaacetate, alkali metal diethylenetriamine hexaacetate, alkali metal hydroxyimino2
These include acetic acid, alkali metal glycine, alkali metal dihydroxyethylglycine, and the like. 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 alkyl phosphate esters, fatty acids, higher alcohols and alkyl phenylnoethylene oxide propylene oxide addition polymers, higher alcohol ethylene oxide propylene oxide block copolymers, and the like. 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 sulfuric acid salts of higher alcohols 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. Further, 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 surfactants and amide surfactants that are hydrolyzed with caustic alkali are not included in the surfactant, 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 include higher alcohol ethoxylates, alkylphenyl ethoxylates, higher alcohol ethylene oxide propylene oxide adducts, alkylphenyl ethylene oxide propylene oxide adducts, ethylene oxide propylene oxide block polymers, and amine oxides. 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, etc. The blending ratio of surfactant is 0 to 10% by weight, and when used as a detergent for spray-type automatic washing machines, surfactants produce foam, which is rather harmful, but they are used for ultrasonic washing machines. In the case of immersion cleaning or immersion cleaning, the blending ratio of surfactant is effective. 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 of the present invention is a solid cleaning agent containing 100% active ingredients, which is a mixture of caustic alkali and water-soluble alkanolamine or water-soluble alkanolamine and water-soluble glycol ether. hand,
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 the present 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.
Additionally, 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. Furthermore, the water-soluble alkanolamine or the mixed solvent of water-soluble alkanolamine and water-soluble glycol ether in the present invention remains solid even when added in a larger amount to caustic alkali than in the case of water-soluble glycol ether alone. of cleaning agent is obtained. For example, if you add 30 parts of butyltetraethylene glycol ether to 10 parts of caustic soda, you will no longer obtain a solid detergent, but a paste, but an equivalent mixture of butyltetraethylene glycol ether and triethanolamine will result. A solid detergent is still obtained by mixing the parts, and a solid detergent is still obtained by adding 40 parts of triethanolamine. In this way, even if a large amount of a water-soluble alkanolamine or a mixed solvent of a water-soluble alkanolamine and a water-soluble glycol ether is blended, the solid state is maintained, so in the present invention, various characteristics are added to the cleaning ability of the cleaning agent. can be made to accumulate. Another advantageous feature of the present invention is that a surface-dry solid cleaning agent is obtained in which a caustic alkali and a water-soluble alkanolamine or a mixed solvent of a water-soluble alkanolamine and a water-soluble glycol ether are present together. It's about being able to do something. That is, a cleaning agent in which a water-soluble alkanolamine or a mixed solvent of a water-soluble alkanolamine and a water-soluble glycol ether is mixed in excess of the mixing ratio range of the present invention becomes a slurry or a paste. The condition is unstable, and when the temperature rises, the caustic alkali and water-soluble alkanolamine or the mixed solvent of water-soluble alkanolamine and water-soluble glycol ether separate, and the upper layer of water-soluble alkanolamine or water-soluble alkanolamine and water-soluble Sufficient cleaning power cannot be obtained even if either the glycol ether mixed solvent-rich portion or the caustic alkali-rich portion of the lower layer is collected. However, if the cleaning agent of the present invention is in a solid state in which a caustic alkali and a water-soluble alkanolamine or a mixed solvent of a water-soluble alkanolamine and a water-soluble glycol ether are combined together, when this is made into an aqueous solution during cleaning. Provides sufficient cleaning power. Furthermore, as mentioned above, if the cleaning agent exceeds the range of the mixing ratio of the present invention and becomes a slurry, it will solidify in the container and become difficult to take out when the temperature drops, which may be dangerous. Since the cleaning agent of the present invention can be in any form such as powder, granules, small lumps, or large lumps, it can be used in a wide variety of packaging containers and forms, and is easy to handle without causing any danger. do not have. Furthermore, if the mixing ratio of the cleaning agent exceeds the range of the present invention, the detergent becomes paste-like, and the water-soluble alkanolamine or the mixed solvent of water-soluble alkanolamine and water-soluble glycol ether adheres to the surface of the caustic alkali, resulting in a wet state. If it is placed in a bag made of polyethylene, for example, it will stick to the inside of the bag and be difficult to take out, and if you try to forcefully remove it by hitting it, it will scatter, creating a dangerous situation. On the other hand, since the cleaning agent of the present invention has a dry surface and is in a solid state, it can be easily taken out without adhering to the inside of a bag made of polyethylene or the like. 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 and 2 Pearlized caustic soda manufactured by Solvay (average particle size)
The following alkanolamine or a mixed solvent of alkanolamine and 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】

[Table] In Examples 1 to 8, 7 to 500 g of water-soluble alkanolamines were added to 100 g of Solvay's pearly caustic soda.
This is an example of a substance becoming a solid by adding . In addition, in Comparative Example 1, 600 g of triisopropanolamine was added, but this was a paste, whereas triisopropanolamine in Example 8
When 500g was added, it became a solid. In Examples 9 to 13, 10 to 400 g of a mixed solvent of a water-soluble alkanolamine and a water-soluble glycol ether were added to 100 g of pearly caustic soda manufactured by Solvay.
In contrast, in Control Example 2, 600 g of a mixed solvent of diisopropanolamine:3-methyl-3-methoxybutanol in a ratio of 1:9 was added, resulting in a paste. It became a state. Examples 14 and 15 In the same manner as in the above Examples, the compositions shown in Table 2 below were mixed and stirred to obtain a cleaning agent.

[Table] Example 14 was diluted with 3 times the amount of water and applied on a yakiniku griddle plate at 60 to 100°C, which is severely burnt, and after 1 to 2 minutes, it could be rubbed with a brush and washed off with water. When Example 15 was diluted 6 times with water and used to clean a cooking pot at a Chinese restaurant in the same manner as above, the stains could be easily washed off with water just by rubbing with a brush. Examples 16 to 20, Comparative Example 3 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] In the table, * Alkyl phosphate ester, petroleum oxide, higher alcohol ethyl
Mixture of Ren Oxide Adducts Example 16 was diluted 5 times with water, and was sprayed onto the inner wall of the A heavy oil tank using a foam spray washer, followed by water. Oil was removed from the wall after one cleaning. When Example 19 was diluted 5 times with water and sprayed on the inner wall surface of the A heavy oil tank using a foam spray washer to clean it, it was able to be washed off by repeated washing three times. This revealed that a high proportion of diisopropanolamine is effective in cleaning A-heavy oil, which is difficult to clean. Conventionally, disassembled machine parts were immersed in a solvent and scrubbed with a brush.At a pharmaceutical factory, the machine was disassembled after work, and 1 to 3 of Example 17 were applied to the machine parts.
When a % aqueous solution was sprayed at high pressure at 60°C, the grease could be easily washed off. Conventionally, plastic containers with heavy oil and exhaust gas stains are treated with a 5% aqueous solution of caustic soda.
After soaking it in 90% water, I pulled it out and scrubbed it with a nylon scrubber, but the dirt was not removed sufficiently. Further, even after washing with a 3% aqueous solution of Control Example 3 at 60° C. for 3 minutes in a high-pressure jet automatic washer, the stains did not come off. On the other hand, when the 2% aqueous solution of Example 18 was washed at 60° C. using a high-pressure jetting automatic washing machine for 1 minute under the same high-pressure conditions as above, it was possible to wash it off. When Example 19 was appropriately diluted with water and sprinkled on the floor of a machine tool factory and scrubbed with a brush, the dirt could be easily washed off. When Example 20 was diluted 10 times with water and sprayed onto polymerized and solidified oil stains in the kitchen, it was easily washed off.

Claims (1)

[Claims] 1. A solid detergent made by mixing a caustic alkali and a water-soluble alkanolamine in a weight ratio of 15:1 to 1:5. 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 alkanolamine in a weight ratio of 0 to 10:90, and having a weight ratio of 15:1 to 1:5. 3. Mixing caustic alkali with a mixed solvent consisting of water-soluble alkanolamine and water-soluble glycol ether
A solid cleaning agent mixed in a weight ratio of 15:1 to 1:5. 4 Caustic alkali and one or more of sequestrants, antifoaming agents, hydrotropes, and surfactants at 100:
A solid detergent, which is prepared by mixing the above-mentioned caustic alkali in a weight ratio of 0 to 10:90, and a mixed solvent consisting of a water-soluble alkanolamine and a water-soluble glycol ether in a weight ratio of 15:1 to 1:5.