JPH021158B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating crude sugar fatty acid esters. More specifically, the present invention relates to a method of treating a crude sugar fatty acid ester containing a specific fatty acid ester and a sugar fatty acid ester using a lipolytic enzyme.

Because sugar fatty acid esters have high biodegradability and safety, they have recently been used as additives in foods, cosmetics, pharmaceuticals, resins, etc. as surfactants that can fundamentally solve problems such as environmental pollution and toxicity to living organisms. ,
It is an extremely useful compound that is being developed for a wide range of uses, including laundry detergents, kitchen detergents, shampoos, and other detergents.

Various methods are known for producing sugar-fatty acid esters, among them sugar and fatty acid esters (usually glycerin fatty acid esters, fatty acid esters of aliphatic lower monohydric alcohols, fatty acid esters of aliphatic lower dihydric alcohols). ester, carbitol fatty acid ester, etc.) in the presence of a base catalyst is the most common method.

In addition to the target sugar fatty acid ester, the crude sugar fatty acid ester produced by this method usually contains unreacted sugars and soaps, and also contains unreacted fatty acid esters and alcohol. It generally also contains alcohols produced by lysis, and it is necessary to remove these impurities and purify the sugar fatty acid ester.

Among these impurities, sugars, soaps, and alcohols can be relatively easily and substantially lose sugar fatty acid esters due to differences in solubility in solvents and methods of conversion into other derivatives. It is possible to remove it almost completely.

On the other hand, unreacted fatty acid esters have chemical properties such as reactivity and physical properties such as solubility in solvents that are very similar to sugar fatty acid esters, especially sugar fatty acid polyesters having two or more ester bonds in one molecule. Therefore, if an attempt is made to remove unreacted fatty acid esters more completely, it has a major drawback in that it is inevitably impossible to avoid the loss of a considerable amount of sugar fatty acid esters.

The present inventors conducted various studies to overcome the deficiencies of conventional methods mainly based on chemical or physical methods, and as a result, we found that certain fatty acid esters, i.e., lower aliphatic A crude sugar fatty acid ester containing a sugar fatty acid ester and at least one type of fatty acid ester selected from the group consisting of fatty acid esters of alcohols, fatty acid esters of aliphatic lower dihydric alcohols, and carbitol fatty acid esters is lipolyzed. It has been discovered that by treatment with an enzyme, only impurity fatty acid esters can be selectively decomposed into easily separated corresponding fatty acids and alcohols without substantial loss of sugar fatty acid esters, and the present invention I was able to complete it.

Next, the present invention will be explained in detail.

Sugar fatty acid esters targeted by the method of the present invention include arabinose, xylose, ribose, glucose, mannose, galactose,
Fructose, maltose, cellobiose, trehalose, gentiobiose,
Isomaltose, lactose (milk sugar), sucrose (sucrose), raffinose, gentianose,
It is an ester of a monosaccharide, oligosaccharide, or polysaccharide such as maltotriose, stachyose, xylan, alaban, cellulose, or starch and a fatty acid having 6 to 24 carbon atoms, and there is one ester bond in the same molecule.
All sugar fatty acid esters present at least 1 are included. In particular, sucrose fatty acid ester is one of the sugar fatty acid esters most suitable for the method of the present invention in terms of ease of production and wide range of uses.

In addition, the impurity fatty acid esters include at least one fatty acid ester selected from the group consisting of fatty acid esters of aliphatic lower monohydric alcohols, fatty acid esters of aliphatic lower dihydric alcohols, and carbitol fatty acid esters. becomes.

Fatty acid esters of aliphatic lower monohydric alcohols refer to esters of methanol, ethanol, propanol, butanol, etc., and fatty acids having 6 to 24 carbon atoms.

Furthermore, the fatty acid ester of aliphatic lower dihydric alcohol refers to an ester of ethylene glycol, propylene glycol, butanediol, diethylene glycol, etc. and a fatty acid having 6 to 24 carbon atoms, and may be either a monoester or a diester.

In addition, carbitol fatty acid ester is carbitol, that is, diethylene glycol monolower alkyl ether, more specifically, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, etc., and carbitol having 6 to 24 carbon atoms. Refers to esters with fatty acids.

The crude sugar fatty acid ester to which the method of the present invention is applied contains, in addition to the above-mentioned fatty acid esters as impurities, soaps such as sodium soap, potassium soap, amine soap, and calcium soap, sugar,
It also targets crude sugar fatty acid esters containing fatty acids, aliphatic lower monohydric alcohols, aliphatic lower dihydric alcohols, alcohols such as carbitol, salts, etc., and includes at least the above-mentioned sugar fatty acid esters and fatty acid esters. The crude sugar fatty acid ester contained is a target for application of the method of the present invention, regardless of the manufacturing method, history, content of each component, etc.

Various methods can be employed when treating crude sugar fatty acid esters with a lipolytic enzyme in the presence of water, with or without a reducing agent. Usually, the crude sugar fatty acid ester is used as it is, or after some or all of the coexisting sugars, soaps, fatty acids, alcohols, salts, etc. have been removed by a known method, water is added to the water. Dissolved or suspended in an aqueous solution,
Alternatively, the most common method is to prepare an aqueous suspension and then add a lipolytic enzyme to decompose the fatty acid ester. Note that the reducing agent is generally added at the same time as the lipolytic enzyme is added.

The amount of water added is usually such that the concentration of the crude sugar fatty acid ester is 1 to 90% by weight, preferably 5 to 70% by weight, and more preferably 10 to 50% by weight. If the amount of water added is too large, a large amount of energy is required to remove the water afterwards, which is uneconomical, and if the amount of water added is too small, the viscosity of the aqueous solution or suspension increases. Both are unfavorable because the effects of the present invention cannot be fully exhibited.

Typical examples of lipolytic enzymes include acylglycerol lipase, including acylglycerol lipase derived from Rhizopus, acylglycerol lipase derived from Aspergillus, acylglycerol lipase derived from Mucoa, acylglycerol lipase derived from Pseudomonas, and acylglycerol lipase derived from Candida. , viscera-derived acylglycerol lipase, and the like.

Furthermore, the lipolytic enzyme does not necessarily have to be purified acylglycerol lipase;
Any substance can be used as long as it has lipolytic activity and does not decompose sugar fatty acid esters.

Further, although a reducing agent is not particularly required, the combined use of a reducing agent generally tends to promote the action of lipolytic enzymes.

As reducing agents, sodium dithionite, vitamin C, glutathione, 2-mercaptoethanol, sodium sulfite, sodium thiosulfate,
A typical example is hydroquinone.

These lipolytic enzymes and reducing agents are added to the above-mentioned aqueous solution or aqueous suspension of the crude sugar fatty acid ester, either as they are or after previously dissolved in water or the like.

The amount of lipolytic enzyme and reducing agent used varies depending on the content of fatty acid esters in the crude sugar fatty acid ester, but the amount of lipolytic enzyme (the amount used also depends on the potency of the lipolytic enzyme itself) , 0.0001 to 20% by weight, preferably 0.0005 to 10% by weight, more preferably 0.0005 to 10% by weight, based on the crude sugar fatty acid ester.
0.001 to 5% by weight, and as mentioned above, the reducing agent does not necessarily need to be used, but if used, it should be 2% by weight or less, preferably 1% by weight or less, based on the crude sugar fatty acid ester. More preferably
0.5% by weight or less is good. If the amount used is less than the above lower limit, it becomes difficult to fully exhibit the effects of the present invention, and if it is used in an amount greater than the upper limit, it becomes uneconomical, so both are not preferred.

Lipid-degrading enzymes (including when combined with reducing agents)
The pH and temperature conditions are most important when processing crude sugar fatty acid esters using The pH depends on the type and characteristics of the lipolytic enzyme used, but is usually 2 to 10, preferably 3 to 9.5, and more preferably 4.
It is best to adjust it to 5 to 9, most preferably 5 to 8.
PH regulators include formic acid, acetic acid, propionic acid,
Acids such as oxalic acid, succinic acid, glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide,
Bases such as calcium hydroxide, sodium carbonate, sodium hydrogen carbonate, calcium oxide, ammonia, methylamine, triethylamine, aniline, pyridine, morpholine, triethanolamine, and salts such as acid salts and basic salts are used.

Also, the temperature is usually 10 to 70℃, preferably 20 to 60℃.
It is preferable to maintain the temperature at 25 to 50°C. If the pH and temperature are outside the above ranges, the action of lipolytic enzymes will be suppressed, and especially under strongly acidic or basic conditions and at high temperatures, the acid bases of the sugar fatty acid esters themselves will be inhibited. This is not preferable because pure chemical hydrolysis reactions caused by catalysts tend to occur simultaneously.

The time required to treat crude sugar fatty acid esters using a lipolytic enzyme and decompose the fatty acid esters depends on the amount, type, potency, and characteristics of the lipolytic enzyme used, the type and content of fatty acid esters, and the time required to decompose the fatty acid esters. Although it varies depending on whether or not a reducing agent is used together,
The time is usually 30 minutes to 100 hours, preferably 1 to 70 hours, and more preferably about 3 to 50 hours.

By employing the treatment conditions using the above-described suitable lipolytic enzyme, most or almost all of the fatty acid esters in the crude sugar fatty acid ester are finally decomposed into fatty acids and alcohols.

The solution treated with the lipolytic enzyme thus obtained can be easily converted into a highly pure sugar fatty acid ester by appropriately combining known purification methods such as filtration, conversion to other derivatives of fatty acids, solvent extraction, and recrystallization. It is possible.

As detailed above, according to the method of the present invention, fatty acid esters in crude sugar fatty acid esters can be decomposed into easily separated fatty acids and alcohols,
Furthermore, it is possible to substantially prevent the loss of sugar fatty acid esters, which is extremely useful industrially.

The method of the present invention will be explained in more detail in the following examples.

Example 1 5.6 g of sucrose monostearate, 2.4 g of sucrose distearate, 2 g of methyl stearate and water
Add lipase AP4 to 90g of mixed solution (PH6.4) [Amano Pharmaceutical
Co., Ltd.] was added thereto, and the treatment was carried out for 20 hours with gentle stirring in a constant temperature bath at 35°C.
A portion of the treated solution was collected, and the produced stearic acid was quantitatively analyzed by neutralization titration (a separate blank test was conducted) using an alcohol standard solution of potassium hydroxide with phenolphthalein as an indicator. It was found that 95% of methyl stearate was decomposed into stearic acid.

Incidentally, as a result of quantitatively analyzing a portion of the separately collected treated liquid by gas chromatography, no decomposition of sucrose monostearate and sucrose distearate was observed.

Example 2 A mixed solution containing 15 g of sucrose coconut oil fatty acid ester (containing 65% by weight of monoester and 35% by weight of diester), 10g of potassium laurate, 5g of ethyl laurate and 70g of water was adjusted to pH 6 with acetic acid, and then treated with lipase. 0.03 g of P (manufactured by Amano Pharmaceutical Co., Ltd.) and 1 g of a 0.01% by weight aqueous solution of vitamin C were added, and the mixture was treated in a constant temperature bath at 37°C for 10 hours with gentle stirring. As a result of the analysis, 95% of ethyl laurate was decomposed into lauric acid, and virtually no decomposition of sucrose coconut oil fatty acid ester was observed.

Example 3 Sucrose hydrogenated beef tallow fatty acid ester (monoester
50% by weight, containing 50% by weight of diester) 10g, ethylene glycol monostearate 5g and water 85g
After adjusting the pH of the mixed solution containing potassium carbonate to 8, 0.01 g of pancreatin [manufactured by Amano Pharmaceutical Co., Ltd.] and 0.01 g of Lipase M AP-10 [manufactured by Amano Pharmaceutical Co., Ltd.] were added, and the mixture was kept at a constant temperature of 30°C. While stirring gently in the tank
The treatment was carried out for 20 hours.

As a result of the analysis, 90% of ethylene glycol monostearate was decomposed into stearic acid, and virtually no decomposition of sucrose hydrogenated beef tallow fatty acid ester was observed.

Example 4 Potassium carbonate and potassium hydroxide were used as catalysts,
Crude sucrose fatty acid ester obtained by alcoholysis of sucrose and propylene glycol dilaurate (23% by weight of sucrose monolaurate, 12% by weight of sucrose dilaurate, 10% by weight of propylene glycol dilaurate, propylene glycol monolaurate) 10% by weight, 45% by weight of sucrose, potassium laurate, propylene glycol, etc.)
PH a mixture containing 40g and 60g of water with citric acid.
After adjusting to 6.7, 0.1% by weight aqueous solution of glutathione 1
g and Lipase M AP-10 0.2g, 40
The treatment was carried out for 15 hours while continuing to stir slowly in a constant temperature bath at ℃. After the treatment was completed, a portion of the treated solution was collected, freeze-dried, and analyzed by gas chromatography. As a result, the content of propylene glycol monolaurate was 2% by weight, and no propylene glycol dilaurate was detected.
In addition, it was found that the sucrose fatty acid ester was not substantially decomposed.

Example 5 Sucrose palmitate ester (monoester 60
A mixed solution containing 10 g of stearic acid ester of diethylene glycol monoethyl ether and 80 g of water was adjusted to pH 5.8 with phosphoric acid and mixed with Lipase M AP-10 0.1.
g was added thereto, and the treatment was carried out for 24 hours with gentle stirring in a constant temperature bath at 37°C. Analysis revealed that 85% of diethylene glycol monoethyl ether stearate was decomposed into stearic acid. Incidentally, it was found that the sucrose palmitate ester was not substantially decomposed.

Example 6 Roughinose laurate (60% by weight monoester, 30% by weight diester, triester
Lipase M AP-10 in a mixed solution (PH6.2) of 35g (containing 10% by weight), 5g methyl laurate, and 60g water.
Add 0.1g of and stir in a constant temperature bath at 37℃.
The treatment was carried out for 30 hours. Analysis revealed that methyl laurate was completely decomposed into lauric acid.

In addition, it was found that the raffinose lauric acid ester was not substantially decomposed.

Claims (1)

[Scope of Claims] 1 Contains as an impurity at least one fatty acid ester selected from the group consisting of fatty acid esters of aliphatic lower monohydric alcohols, fatty acid esters of aliphatic lower dihydric alcohols, and carbitol fatty acid esters. 1. A method for treating crude sugar fatty acid esters, which comprises treating the crude sugar fatty acid esters with a lipolytic enzyme in the presence of water, with or without a reducing agent. 2. A patent claim in which the impurity is at least one compound selected from the group consisting of fatty acid esters, sugars, soaps, fatty acids, aliphatic lower monohydric alcohols, aliphatic lower dihydric alcohols, and carbitol. A method for treating a crude sugar fatty acid ester according to Scope 1. 3. The crude sugar fatty acid ester according to claim 1, wherein the crude sugar fatty acid ester is a reaction product obtained by alcoholysis of sugar and fatty acid ester in the presence of a base catalyst. Processing method. 4. The method for treating a crude sugar fatty acid ester according to claim 1 or 3, wherein the sugar fatty acid ester is a sucrose fatty acid ester. 5. Claim 1 uses as a reducing agent at least one compound selected from the group consisting of sodium dithionite, vitamin C, glutathione, 2-mercaptoethanol, sodium sulfite, sodium thiosulfate, and hydroquinone. A method for processing crude sugar fatty acid esters. 6. The method for treating crude sugar fatty acid esters according to claim 1, wherein the lipolytic enzyme is acylglycerol lipase.