JPH08281003A - Draining agent and draining method - Google Patents

Abstract

PURPOSE: To provide a draining agent which has an excellent draining effect of the washing water sticking to a solid surface and has high safety to the human body and a draining method for the washing water sticking to the solid surface which uses finish washing water contg. the draining agent. CONSTITUTION: This draining agent consists of a mixture composed of a monocaprylic ester and/or a monocapric ester of at least one kind of polyhydric alcohols selected from among 1,5-sorbitan, 1,4-sorbitan and isosorbite and a dicaprylic ester and/or a dicapric ester of at least one kind of polyhydric alcohols selected from among 1,5-sorbitan, 1,4-sorbitan and isosorbid. The draining agent does not substantially contain a tricaprylic ester and/or a tricapric ester of a polyhydric alcohols or the content thereof is <=5wt.% and the weight ratio of the monoester and the diester is in a range of 3/7 to 9/1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a draining agent and a method for draining washing water adhering to a solid surface.

[0002]

2. Description of the Related Art Conventionally, after washing a solid surface with washing water, the washing water adhering to the solid surface is drained (removed).
In order to do so, the final washing water containing the draining agent (rinsing water) is sprayed onto the solid surface, or the solid surface is dipped in the finishing washing water containing the draining agent, etc. It is common practice to replace water with drainage containing finish water. For example, the washing of dishes and crates with an automatic dishwasher or a crate washer is performed by a washing process of spraying an aqueous alkaline detergent solution,
It is carried out by a draining process and a drying process by spraying finish washing water containing a draining agent heated to 80 to 90 ° C. The main requirements that the draining agent used in such a method should have are as follows. Do not leave water spots or stains on the tableware or crate surface after drying. It should have a performance as a so-called drying accelerator, in which water droplets adhering to the surface of dishes and crates after the draining process are quickly dried and disappear. Even if a small amount of draining agent remains on the surface of tableware or crate, it should have high safety without affecting the human body. Conventionally, as a draining agent, pluronic, sucrose fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester,
It is known to use nonionic surfactants such as polyglycerin fatty acid ester, but there are still problems that water spots and stains remain on the tableware after drying, water drops remain forever and it takes time to dry. The current situation is that it has not been resolved. Glass cups made of glass are especially transparent, which makes water spots and stains conspicuous and spoils the aesthetics.In busy restaurants such as family restaurants, it is necessary to quickly organize the dishes after they have been washed in the cupboard. Therefore, they have to be stored in a wet state that is not completely dried, and there is a concern about hygiene. On the other hand, in the crate cleaning, a huge amount of heat energy is consumed, for example, hot air is blown for rapid drying. Further, as a material that covers these drawbacks, a draining agent composed of polyoxyethylene sorbitan fatty acid ester has been proposed (Patent Publication 6).
-47680), this was not a food additive, so there was a problem in terms of safety.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a cleaning agent which is excellent in draining the cleaning water adhering to the solid surface and which is highly safe for the human body, and a cleaning solution which adheres to the solid surface using finish cleaning water containing the same. It is an object to provide a method for draining water.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a monocaprylic acid ester and / or a monocapric acid ester of at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide;
A mixture of at least one polyhydric alcohol selected from 5-sorbitan, 1,4-sorbitan, and isosorbide with a dicaprylic acid ester and / or a dicapric acid ester, and a tricaprylic acid ester and / or tricaprin of the polyhydric alcohol. Substantially free of acid ester or its content is 5% by weight or less,
And the weight ratio of the monoester and the diester is 3/7.
There is provided a draining agent characterized by being in the range of ˜9 / 1. Moreover, according to the present invention, 1,5-sorbitan,
1,4-sorbitan and isosorbide consisting of a mixture of at least one polyhydric alcohol monocapric acid ester and dicapric acid ester, which is substantially free of the trihydric alcohol tricapric acid ester or its The content is 5% by weight or less, and the weight ratio of the monoester and the diester is 3/7 to 9
A draining agent is provided which is in the range of / 1. Further, according to the present invention, in the method of removing the washing water adhering to the solid surface after the washing treatment by bringing the solid surface into contact with the finishing washing water, the finishing washing water is any one of the above-mentioned drainers. A method for draining washing water adhering to a solid surface is provided, which is characterized by containing an agent.

The polyhydric alcohol used as a raw material for synthesizing the draining agent of the present invention is selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide. These polyhydric alcohols can be used alone or as a mixture thereof. As the polyhydric alcohol, it is preferable to use one containing 50% by weight or more of 1,4-sorbitan. The structural formulas of 1,5-sorbitan, 1,4-sorbitan and isosorbide described above are as follows. (1,5-sorbitan) (1,4-sorbitan) (Isosorbide)

The polyhydric alcohol can be obtained by intramolecular dehydration condensation of sorbitol.
The sorbitol dehydration condensation product thus obtained contains the above-mentioned 1,5-sorbitan, 1,4-sorbitan, isosorbide and unreacted sorbitol.
In the case of the present invention, 1,5 is obtained from the dehydrated condensate of sorbitol.
-Sorbitan, 1,4-sorbitan, and isosorbide can be separated from each other, and a single product or a mixed product thereof can be used as a raw material for the draining agent. Further, in the case of the present invention, the sorbitol dehydration condensate can be advantageously used as it is as a raw material for the draining agent.

The composition of the sorbitol dehydration condensate which is preferably used for the synthesis of the draining agent of the present invention is as follows: sorbitol: 0 to 10% by weight, preferably 0 to 5% by weight,
Sorbitan (total amount of 1,5-sorbitan and 1,4-sorbitan): 10 to 100% by weight, preferably 10 to
97% by weight, particularly preferably 50-80% by weight, isosorbide: 0-90% by weight, preferably 3-50% by weight
Is. The component composition of the sorbitol dehydration condensate can be changed according to the dehydration reaction conditions of sorbitol, the reaction method, the catalyst, and the like. It can also be prepared by mixing the individual products. The smaller the amount of sorbitol in the sorbitol dehydration condensate, the more preferable. However, if the content of sorbitol is 10% by weight or less, there is no particular adverse effect on the performance of the draining agent obtained.

As the other raw material of the draining agent of the present invention,
Caprylic acid [CH ₃ (CH ₂ ) ₆ COOH] or capric acid [CH ₃ (CH ₂ ) ₈ COOH] or their lower alcohol esters are used. Examples of the lower alcohol ester include alcohol esters having 1 to 4 carbon atoms such as methyl ester, ethyl ester, propyl ester and butyl ester.

To produce the draining agent of the present invention, first,
The above-mentioned polyhydric alcohol or a mixture thereof (including sorbitol dehydration condensate itself) and caprylic acid or a lower alkyl ester thereof or capric acid or a lower alkyl ester thereof are subjected to an esterification reaction by a conventionally known method. In the esterification reaction in the presence of a chemical catalyst such as an acid or a base, a considerable amount of triester is produced in the obtained reaction product. It is necessary to separate and remove from the product, and the method using such a chemical catalyst is still unsatisfactory from the viewpoint of process economy. According to the study of the present inventors, when the esterification reaction is carried out in an organic solvent using a neutral thermostable lipase without using a chemical catalyst, by-production of triester is prevented and the monoester is prevented. It has been found that a mixture of and diester can be obtained efficiently.

When the esterification reaction is carried out in the presence of neutral thermostable lipase, the reaction temperature is 40 to 95 ° C, preferably 60 to 90 ° C. As the neutral thermostable lipase, 50 mg of the lipase powder is dissolved in 0.4 ml of phosphate buffer (0.1 M, pH 7) and the residual activity after heating at 70 ° C. for 30 minutes is 40% or more, preferably 80%.
% Or more, more preferably 95% or more,
Any one can be used as long as it has the maximum hydrolysis activity in the range of pH 5.0 to 10.0, more preferably pH 5.5 to 9.5. Examples of such neutral thermostable lipase include porcine pancreatic lipase, yeast lipase derived from yeast of the genus Candida, mold lipases such as those of the genus Alpengillus and genus Mucor, and bacterial lipases such as the genus Cydomonas. Further, those obtained by modifying the above lipase by genetic engineering etc. are also included. As the preferable neutral thermostable lipase used in the present invention, a neutral thermostable lipase derived from Candida antarctica (sp-382, sp-435, manufactured by NOVO Co., maximum activity pH 7.5), Mucor miehe
i) Neutral thermostable lipase derived from Lipozyme, N
OVO Co., Ltd., maximum active pH 6.0) and the like can be used, but the invention is not limited thereto.

The lipase may be a purified enzyme or a crude enzyme, but is preferably immobilized. The immobilization method may be any of the carrier binding method, the cross-linking method and the entrapping method, but the carrier binding method is particularly preferable from the viewpoint of activity expression and the like. As the immobilization carrier, activated carbon, porous glass, acid clay, bleaching clay, kaolinite, alumina, silica gel, bentonite, hydroxyapatite, calcium phosphate, inorganic substances such as metal oxides, starch, natural polymers such as gluten, polyethylene , Polypropylene, phenol formaldehyde resin, acrylic resin, anion exchange resin, cation exchange resin, and other synthetic polymers. In the present invention, it is preferable to use a porous polymer, for example, porous polyethylene, porous polypropylene, porous phenol formaldehyde resin or the like. The amount of lipase used during the reaction can be appropriately selected and is not limited, but it may be 0.1% to 100 parts by weight of the polyhydric alcohol.
It may be in the range of 1 to 10000 parts by weight, preferably 1 to 2000 parts by weight.

Examples of the organic solvent include aliphatic hydrocarbons such as n-heptane, n-hexane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclobutane; benzene, toluene, xylene and phenol. Aromatic hydrocarbons; ketones such as acetone and methyl isobutyl ketone; acetonitrile, morpholine, N-methylmorpholine, N-ethylmorpholine, 2-nitropropane, pyridine, 2-
Ethylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, pyrrole, N-methylpyrrole, piperidine, N-methylpiperidine, N-ethylpiperidine, piperazine, N-methylpiperazine, 1,4-dimethylpiperazine, pyrrolidine, 1-methylpyrrolidine, quinoline, butylamine, tributylamine, N, N, N ',
N'-tetramethyl-1,6-hexanediamine, N,
Nitrogen-containing solvents such as N, N ′, N′-pentamethyl-diethylene-triamine and dimethylformamide; ethers such as dimethyl ether, diethyl ether and dioxane; γ-butyrolactone, α-acetyl-γ-butyrolactone, diethyl carbonate, Esters such as ethylene carbonate and propylene carbonate; carbon tetrachloride, chloroform,
Halogenated hydrocarbons such as methylene chloride; Sulfoxide solvents such as dimethylsulfoxide; Secondary alcohols such as 2,4-dimethyl-3-pentanol 1,6-dimethyl-4-heptanol; Tertiary-butyl alcohol , Tertiary-amyl alcohol, diacetone alcohol, 2,4-dimethyl-3-pentanol, 2,6-dimethyl-4-heptanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol , 3-propyl-
3-pentanol, 2-methyl-2-hexanol, 2
Examples thereof include tertiary alcohols such as ethyl-2-hexanol.

Of these, the nitrogen-containing solvents which are particularly preferred when used alone are pyridine, 2-ethylpyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine and 2,4-dimethyl. Pyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, N
-Methylpyrrole, N-methylpiperidine, N-ethylpiperidine, 1,4-dimethylpiperazine, 1-methylpyrrolidine, and isooctane, γ-butyrolactone, α-acetyl-γ-butyrolactone, diacetone alcohol and the like can also be used. , But not limited to these. Other organic solvents may be used alone, but are preferably used in combination, for example, N-methylmorpholine and N-methylpiperidine;
It is possible to use a mixture of two or more kinds of organic solvents such as tertiary butyl alcohol and N, N'-dimethylformamide; tertiary amyl alcohol and N, N'-dimethylformamide, among them, tertiary alcohol And a polyhydric alcohol-soluble solvent are preferable, and the solvent mixing ratio in such a case can be appropriately selected.
It can range from 9 to 99: 1. The amount of the organic solvent used is preferably such that the polyhydric alcohol or lipase moves in the reaction vessel to promote the reaction, and is not particularly limited, but for example, 1 to 99% (W of the reaction system). /
W), preferably about 10 to 95% (W / W), may be added and reacted. Further, these organic solvents may be gradually added as the reaction progresses.

Regarding the water content in the reaction system, the water content does not necessarily have to be 0%, but the lower the water content, the better in order to prevent the stability of the enzyme and the re-decomposition of the ester. A system without addition is preferred.

The reaction system for producing caprylic acid or capric acid ester of polyhydric alcohol is, for example, a packed column system in which immobilized lipase is packed in a column and a substrate solution is supplied to react with the enzyme, and an enzyme is mixed in a stirring tank. There are a batch system in which a substrate is reacted and a continuous stirring tank system in which the reaction is continued in the stirring tank, but the reaction can be carried out by adopting any system. Further, water or lower alcohol is produced as a by-product in this enzymatic reaction, but it is necessary to remove this by-product in order to proceed the reaction efficiently. As a method of removing these by-products, for example, a method of adsorbing and removing with zeolite, molecular sieves, sodium sulfate, etc., a method of aeration with dry air or an inert gas in the reaction tank, and a method of evaporating and removing into the gas, or a reaction Although there is a method of reducing the pressure in the inside to evaporate it and discharging it from the reaction system, any method can be used in combination with the enzyme reaction. After completion of the reaction, the desired ester can be separated and collected from the reaction product by a known method. In the method for producing a draining agent using the neutral thermostable lipase, the one containing a monoester and a diester is obtained, the weight ratio thereof is the ratio of the polyhydric alcohol and the fatty acid component, the reaction temperature, the reaction rate, etc. Can be adjusted by.

The draining agent of the present invention can be added to the final washing water as it is or in the form of an aqueous solution, but it is preferably added in the form of an aqueous solution. The draining agent of the present invention is 10 to 80% by weight, preferably 30 to 70% by weight.
It is advantageously used in the form of a wt% aqueous solution. When such a water-removing agent aqueous solution is added to the finish-wash water to dilute it, the water-removing agent rapidly and uniformly dissolves in the finish-wash water. The dilution temperature in this case is normal temperature or 40 to 9
The heating can be 5 ° C.

If desired, various auxiliary components can be added to the draining agent of the present invention or its aqueous solution. For example, for the draining agent of the present invention or an aqueous solution thereof, sucrose fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, nonionic surfactants such as polyglycerin fatty acid ester, sodium citrate, sodium gluconate, Chelating agents such as sodium malate and sodium ethylenediaminetetraacetic acid can be added, and as a solubilizer that is highly safe and keeps the draining agent aqueous solution stable for a long time, glycerin, sorbit, mannitol, xylit, etc. It is also possible to add the sugar alcohols mentioned above, and it is also possible to add commonly used alcohols such as ethanol.

Next, the method of using the draining agent of the present invention will be described in detail. The draining agent of the present invention is used for draining washing water attached to the solid surface after washing the solid surface with washing water. The washing treatment of the solid surface with washing water can be carried out by a conventionally known method. For example,
A method of spraying washing water on the solid surface, a method of bringing the washing water into contact with flowing washing water, or the like can be adopted. Examples of the washing water include various conventionally known ones, such as alkaline washing water, acidic washing water, and washing water containing a surfactant.

The draining agent of the present invention is used by adding it to the finishing wash water when finishing washing (rinsing) the solid surface after the washing treatment with the washing water. In order to finish-wash the solid surface after the washing treatment with the final wash water containing the draining agent of the present invention, the final washing water containing the draining agent of the present invention may be brought into contact with the solid surface after washing. . Examples of the contact method in this case include a method of spraying finishing water on the solid surface, a method of immersing the solid surface in the finishing water, a method of contacting the solid surface with flowing finishing water, and the like. As the contact conditions, room temperature or heating conditions are applied. The heating condition is 50 to 9
A temperature condition of 5 °, preferably 80 to 90 ° is adopted. In addition, after the finish washing, a drying step can be adopted if necessary. In this drying step, cold air drying, hot air drying, drying in a thermostatic chamber, etc. are adopted.

The concentration of the draining agent in the finish wash water is 0.0
001 to 10% by weight, preferably 0.001 to 1% by weight
Is.

The solid surface includes various solid surfaces such as glass, plastic, metal, ceramics and wood. Examples of products having these solid surfaces include tableware, crates, containers, bottles filled with drinking water (bin beer, etc.), cans (canned beer, canned products, etc.), and the like.

When the solid surface is highly hydrophilic glass or the like,
The weight ratio of the monoester and diester constituting the draining agent applied thereto is particularly preferably set in the range of 5: 5 to 9: 1, preferably 6: 4 to 8: 2. When the solid surface has low hydrophilicity such as polypropylene, melamine resin, and polyethylene and is relatively rich in lipophilicity, the weight ratio of the monoester and diester constituting the draining agent is 3: 7-5. : 5, preferably 3: 7-
It is preferable to specify it in the range of 4: 6.

[0023]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

EXAMPLE Using an automatic dishwashing machine (IHI-JWD6 type), the dish was heated at a temperature of 0.2% by weight of alkaline washing water (detergent: Washmate S, manufactured by ADEKA CLEAN AID) : 8 including a draining agent after washing at 40 ° C
Finished wash with 0 ° water. In this case, as the final washing water, water (water-drainage agent concentration: 0.001% by weight) obtained by diluting an aqueous solution of the composition shown in Table 2 containing the water-drainage agent shown in Table 1 at a concentration of 20% by weight 20,000 times. Using. Next, the time until the tableware after the finish washing treatment was completely dried, the number of water spots, and the number of stains were examined, and the results are shown in Table 3. The measured values shown in Table 3 are average values for 8 glass cups and 8 melamine dishes.

[0025]

[Table 1] * A product obtained by esterification in an organic solvent using neutral thermostable lipase.

[0026]

[Table 2] A to F show the present invention, and G to K show comparative examples.

[0027]

[Table 3] A to F show the present invention, and G to K show comparative examples.

[0028]

The draining agent of the present invention exhibits an excellent draining effect. By contacting the solid surface on which the washing water after the washing treatment is adhered with the finishing wash water containing the draining agent of the present invention, the solid surface is washed. The washing water that adheres can be effectively drained.

Claims (5)

[Claims] 1. A monocaprylic acid ester and / or monocapric acid ester of at least one polyhydric alcohol selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, and 1,5-sorbitan, 1. ，
A mixture of at least one polyhydric alcohol selected from 4-sorbitan and isosorbide with a dicaprylic acid ester and / or a dicapric acid ester,
The tricaprylic acid ester and / or tricapric acid ester of the polyhydric alcohol is not substantially contained or the content thereof is 5% by weight or less, and the weight ratio of the monoester and the diester is 3/7 to 9 /. A drainage agent characterized by being in the range of 1. 2. A mixture of at least one polyhydric alcohol monocaprate ester and dicaprate ester selected from 1,5-sorbitan, 1,4-sorbitan and isosorbide, wherein said polyhydric alcohol tricaprin is used. A draining agent which is substantially free of acid ester or its content is 5% by weight or less, and the weight ratio of the monoester and diester is in the range of 3/7 to 9/1. . 3. The draining agent according to claim 1, which is an aqueous solution. 4. A method of draining the washing water adhering to the solid surface after the washing treatment by bringing the solid surface into contact with finishing washing water, wherein the finishing washing water is any one of claims 1 to 3. A method of draining washing water attached to a solid surface, which comprises a drainer. 5. The method according to claim 4, wherein the temperature of the finish wash water is 50 to 95 ° C.