JP2003252981A - Fatty acid ester of polyol polymer and fatty acid ester of meso-erythritol polymer, and method for manufacturing these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fatty acid ester of a polyol polymer bearing more hydroxy groups. <P>SOLUTION: The fatty acid ester of a polyol polymer is mainly composed of a polymer which comprises as a constituent monomer a polyol containing meso-erythritol and is obtained by polymerizing 2-16 molecules of the constituent monomer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fatty acid ester of a polyol polymer and a method for producing the same.

[0002]

2. Description of the Related Art Polyglycerin is known as a polyol polymer having a large number of hydroxyl groups. This polyglycerin is used as a raw material for surfactants and the like.

However, the obtained fatty acid ester surfactant may have insufficient hydrophilicity depending on the application. In order to improve hydrophilicity, addition of alkylene oxide or introduction of hydrophilic functional group such as sulfonic acid group has been attempted, but the former must use highly toxic alkylene oxide such as ethylene oxide as a raw material, and the latter. Irritation to the skin can be a problem.

Therefore, the object of the present invention is to provide a fatty acid ester of a polyol polymer having more hydroxyl groups.

[0005]

According to the present invention, a polyol containing a meso-erythritol is used as a constituent monomer, and a fatty acid ester of a polyol polymer containing a polymer obtained by polymerizing 2 to 16 molecules of the constituent monomer as a main component is used. By doing so, the above problems have been solved.

Since meso-erythritol has one more hydroxyl group than glycerin, the resulting polyol polymer is
It has more hydroxyl groups and is more hydrophilic than polyglycerin. Therefore, even if the fatty acid ester of this polymer is used as a surfactant or a raw material thereof, the hydrophilicity of the obtained surfactant is further improved.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The fatty acid ester of the polyol polymer according to the present invention is obtained by esterifying a polyol polymer having a polyol containing meso-erythritol as a constituent monomer and a polymer obtained by polymerizing 2 to 16 molecules of the constituent monomer as a main component. is there.

The above-mentioned polyol is a compound having two or more hydroxyl groups, and examples thereof include ethylene glycol, glycerin, erythritol, threitol, lyxitol, ribitol, xylitol and sorbitol.

Among these, erythritol, especially meso-
Erythritol is the main component, that is, 5 of the constituent monomers
It is preferable that 0 mol% or more is meso-erythritol. Thereby, the obtained polyol polymer can contain more hydroxyl groups. Particularly, when only meso-erythritol is used as the polyol, the obtained polyol polymer becomes a meso-erythritol polymer.

The polyols and meso-erythritol used as raw materials are sterilized, decolorized, desalted, after synthesis or fermentation.
Not only high-purity products that have been processed by resin purification and / or recrystallization, but also raw materials before purification can be used as they are depending on the application and purpose. For example, when meso-erythritol, which has been subjected to only sterilization treatment after fermentation, contains several% of other polyols, when these are polymerized, a polyol polymer having a meso-erythritol unit content of 90 to 99% is obtained.

In the following, "meso-erythritol" and "meso-erythritol polymer" are simply referred to as "erythritol" and "polyerythritol", respectively.
Enter.

The degree of polymerization of the main component of the polyol polymer in the above polymer is preferably 2 to 16, preferably 2 to 14, more preferably 2 to 8, and most preferably 3 to 6. This is because one constituent monomer does not serve as a polymer. On the other hand, polymerization with 17 or more constituent monomers requires harsh reaction conditions, and gelation of by-products and coloring is remarkable. Therefore, it is not easy.

The polyol polymer according to the present invention can be manufactured by the following method. That is, it can be produced by polymerizing a polyol containing erythritol in the presence of a catalyst at a predetermined temperature and pressure. Since the polyol is liquid at the reaction temperature, it can be reacted without a solvent. As the catalyst, alkali metal compounds having basicity such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate are preferable. Among these, if a sodium compound showing basicity is used,
It has a higher catalytic activity and can accelerate the polymerization reaction.

The amount of the catalyst used is 0.005 to the total weight of the polyol containing erythritol as a raw material for polymerization.
10% by weight is preferable, and 0.0 from the viewpoint of reaction rate and economics.
5 to 3% by weight is preferable.

The above reaction temperature is selected according to the type of constituent monomer used. When erythritol and one or more other polyols are used in combination as constituent monomers, the temperature is preferably 200 to 280 ° C.
When only erythritol is used as a constituent monomer, 200 to 270 ° C. is preferable and 210 to 2
40 ° C is more preferable. This is because if the temperature is too high, coloring and the formation of by-products are extremely unfavorable, while if the temperature is too low, the polymerization reaction is remarkably slowed.

Further, the reaction pressure is selected depending on the type of constituent monomer used. When erythritol and one or more kinds of other polyols are used in combination as the constituent monomer, 2 to 760 mmHg is preferable. When only erythritol is used as the constituent monomer, 10 to 760 mmHg is preferable. Also,
When the polymerization rate is important and the reaction is desired to be completed in a short time, 10 to 400 mmHg is preferable and 15 to 60 mmH.
g is preferred. Furthermore, when it is desired to obtain a polymer in high yield by suppressing the production of by-products and the vaporization of monomers, 400
˜760 mmHg is preferable, and 600 to 760 mmHg is preferable. Regarding the vaporization of the monomer, it is possible to use a condenser, a distillation column or the like to reflux or recover the monomer.

The polyol polymer thus obtained can be used as it is, depending on the intended use.
It is obtained as a pale yellow or colorless liquid after decolorization using activated carbon or the like. Deionization may be carried out by passage through an ion exchange resin if further purification is required. Also,
If necessary, after the reaction or in a series of treatment steps,
Deodorization by passing gas such as steam and nitrogen at high temperature, distilling off unreacted polyol monomer and low-molecular substances at high temperature and high vacuum, fractionation by chromatography, unreacted polyol monomer such as alcohol and ketone, and The low molecular weight substance may be distilled off, or extracted and purified using an organic solvent such as alcohol.

The polyol polymer thus obtained is, in addition to a linear polymer chain, a polymer chain having a cyclic structure, a polymer chain having a branched structure, and a polymer having both a cyclic structure and a branched structure. Including chains and the like.

By esterifying the obtained polyol polymer, a fatty acid ester of the polyol polymer is obtained. In particular, when erythritol alone is used as the polyol, a fatty acid ester of polyerythritol is obtained. As the above-mentioned polyol polymer, in addition to a purified product obtained by decolorization, ion exchange, etc., it may be used in an unpurified form depending on the purpose and application, or esterification may be carried out after the polymerization reaction.

Examples of the esterification method include a method of esterifying the above polyol polymer with a fatty acid in the presence of a catalyst, a method of transesterifying with a fatty acid ester, a method of esterifying with a fatty acid halide, and the like. The fatty acid ester of the polyol polymer is produced by these methods.

The type of the above-mentioned fatty acid is not particularly limited, and linear or branched saturated or unsaturated fatty acid having 6 to 24 carbon atoms, further hydroxyl group-substituted fatty acid and its condensate are used. This fatty acid may be used alone or in combination of two or more depending on the purpose.

Examples of such fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid. , Nonadecyl acid, arachidic acid, behenic acid, lignoceric acid, 2-ethylhexanoic acid, 4-propylpentanoic acid, 4-ethylpentanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 5-propyloctanoic acid, 3-methyl Hendecanoic acid, 6-propylnonanoic acid,
2-methyldodecanoic acid, 2-methyltridecanoic acid, 2-
Methyl tetradecanoic acid, 2-ethyl tetradecanoic acid, 1
5-methylhexadecanoic acid, 2-ethylhexadecanoic acid, 2-butyltetradecanoic acid, 2-methyloctadecanoic acid, 3-methyloctadecanoic acid, 3-methylnonadecanoic acid, 2-ethyloctadecanoic acid, 2-methylicosanoic acid, 2-propyloctadecane Acid, 2-butyloctadecanoic acid, 2-methyldocosanoic acid, 2-methyltricosanoic acid, 3-methyltricosanoic acid, 2-hexyloctadecanoic acid, 2-butyl-5-methylpentanoic acid, 2,3-dimethylnonanoic acid 4,4-dimethyldecanoic acid, 2-ethyl-3-methylnonanoic acid, 2,2-dimethyl-4-ethyloctanoic acid, 2,3-dimethyldodecanoic acid, 3,7,
11-trimethyldodecanoic acid, 2,2-dimethyltetradecanoic acid, 3,3-dimethyltetradecanoic acid, 2,2-
Dimethylhexadecanoic acid, 2-octyl-3-methylnonanoic acid, 2,4-dimethyloctadecanoic acid, 3,3-dimethyloctadecanoic acid, obtsylic acid, caproic acid, undecylenic acid, 2-lauroleic acid, 5-lauroleic acid, 11- Lauroleic acid, linderic acid, tsuzuic acid, fizeteric acid, myristoleic acid, 5-myristoleic acid, 2-palmitoleic acid, 7-palmitoleic acid, zomarinic acid, petroselinic acid, petroceredic acid, oleic acid, elaidic acid, Asclepic acid, parsenic acid, codonic acid, gondonic acid, erucic acid, brassic acid, ceracoleic acid, 2-methyl-2-heptenoic acid, 3-methyl-2-nonenoic acid, 5-methyl-2-hendecenoic acid, 2- Methyl-2-dodecenoic acid, 5-methyl-
2-tridecenoic acid, 2-methyl-9-octadecenoic acid,
2-Ethyl-9-octadecenoic acid, 2-propyl-9-
Octadecenoic acid, 2-methyl-2-icosenoic acid, 5,9
-Dimethyl-2-decaenoic acid, 2,5-dimethyl-2-
Heptadecaenoic acid, 2,2-dimethyl-11-icosaenoic acid, 2-octynoic acid, 2-nononic acid, 2-decynic acid,
2-undecic acid, 6-dodecic acid, 8-tridecic acid, 7-hexadecic acid, 2-heptadecic acid, 5-octadecic acid, 6-octadecic acid, 9-nonadecic acid, 13-docosic acid, 11,16-docosadiyne acid,
21-tricosic acid, linoleic acid, linolenic acid, ricinoleic acid, condensed ricinoleic acid, hydroxystearic acid and the like can be mentioned. Furthermore, beef tallow oil, corn oil, soybean oil, palm oil, olive oil, cottonseed oil, peanut oil, castor oil, Flaxseed oil, cacao butter, white mustard oil, sesame oil, rice bran oil, safflower oil, tea seed oil, camellia oil, rapeseed oil, sunflower oil, coconut oil, wax, etc. Fatty acids and the like containing a large amount of 24 components can be mentioned.

Examples of the fatty acid ester include methyl, ethyl and glycerin esters of the above fatty acid. Examples of the above fatty acid halide include acid halides such as chlorine and bromine of the above fatty acids.

The molar ratio of the polyol polymer to the fatty acid raw material such as the fatty acid, the fatty acid ester or the fatty acid halide in the esterification reaction can be appropriately selected according to the desired degree of esterification. For example, when the target degree of esterification is n, the polyol polymer: fatty acid raw material (molar ratio) is usually 1: 0.5n.
˜1: 1.5n is preferable, and in consideration of economical reasons such as unreacted raw materials, 1: 0.8n to 1: 1.1n is preferable. The upper limit of n is the number of hydroxyl groups in the polyol polymer. For example, when polyerythritol having an average degree of polymerization of 4 is used, n is 10. Further, particularly when a high content of 1 mol adduct is required, 1: 1 to 10: 1,
It is preferable to carry out in the range of 1.2: 1 to 5: 1.

The esterification reaction using the above fatty acid is preferably a reaction without a solvent, and the reaction temperature is 120 to
250 ° C is preferable, and 150 to 240 ° C is preferable. Also,
The reaction for esterification by transesterification with the above fatty acid ester is preferably a reaction without a solvent, and the reaction temperature is 12
0-270 degreeC is good and 130-200 degreeC is preferable. When the reaction is carried out using a solvent, the reaction temperature is 100
~ 240 ° C is preferable, and 130 to 230 ° C is preferable. Further, the esterification reaction using the above fatty acid halide is preferably carried out using a solvent, and the reaction temperature is preferably room temperature to 180 ° C, preferably 40 to 130 ° C.

The reaction temperature may be in the above range, and the heating method can be carried out without limitation depending on the purpose such as reaction time, yield, quality and the like. For example, there may be mentioned a method of maintaining a constant temperature from the start of the reaction, a method of performing a low temperature when a large amount of a fatty acid raw material is present, and a method of raising the temperature in the latter half of the reaction.

In order to facilitate the compatibility and accelerate the reaction, sorbitan fatty acid ester, propylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene adducts thereof and the like may be added, if necessary. A surfactant may be added.

The reaction pressure is not particularly limited, and either a reduced pressure system or a normal pressure system can be used.
Further, the reaction time varies depending on the reaction method, the reaction reagent and the synthetic scale, but is preferably 1 to 24 hours, and preferably 1 to 16 hours.

When a reaction solvent is used in the esterification reaction, the reaction solvent dissolves the polyol polymer,
A solvent inert to the above reaction is preferable. For example, N, N
-Dimethylformamide, dimethylsulfoxide, N,
N-dimethylacetamide, N-methylpyrrolidone, N
-Acetylmorpholine, N-methylsuccinimide, pyridine, N, N-dimethylbenzylamine, N-formylpyrrolidine and the like can be mentioned. The amount of the reaction solvent used is appropriately 1 to 10 in weight ratio with respect to the polyol polymer.

As the catalyst for the esterification reaction, an acid, a base or the like which is known as an esterification reaction catalyst can be used, but a basic compound is preferable from the viewpoint of side reactions. Examples thereof include tertiary amines such as N, N-dimethylbenzylamine, sodium methylate, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydride, calcium hydroxide, oxidation. Examples thereof include calcium, trimethylbenzylammonium hydroxide, fatty acid sodium and fatty acid potassium.

The amount of the above catalyst used is 0.001 of the total weight.
-20% by weight is preferable, and 0.05-10% by weight is preferable. When the above fatty acid halide is used for the reaction, a catalyst such as triethylamine, 4-dimethylaminopyridine, sodium hydroxide is added in an amount of 0.1 to 3 equivalents based on the fatty acid halide, although it can be carried out without a catalyst. It is preferable to add 1 to 1.5 equivalents.

When an unpurified polyol polymer is used, or when esterification is carried out subsequent to the polymerization reaction, the catalyst used for the polymerization can be utilized, so that the amount of the above catalyst used can be reduced or a further catalyst can be added. It is possible to do without.

In the above-mentioned polymerization reaction of erythritol and polyol, and esterification reaction of polyol polymer,
As a method for charging the raw materials, the catalyst and the like, all of them may be charged all at once in the initial stage of the reaction, or after the reaction is started, both the raw material monomer and the catalyst, or either of them may be added in a divided or continuous manner. Good. These are selected in consideration of operability and productivity.

In the above-mentioned polymerization reaction of erythritol or polyol and esterification reaction of the polyol polymer, the system is replaced with a gas which does not affect the reaction containing an inert gas,
Alternatively, it is preferably performed under an air stream. In particular, in the reaction from a weak decompression degree to normal pressure, it is preferable to carry out the reaction under an air stream in order to efficiently discharge the produced water out of the system. Examples of the gas that does not affect such a reaction include inert gases such as nitrogen and helium, carbon dioxide, and hydrogen. When a gas that does not affect this reaction is not used, for example, the reaction proceeds even in an air atmosphere, but when the temperature is high, the monomer or the reaction product is easily oxidized or colored.

In the present invention, the name of the polyol polymer fatty acid ester is determined by the reaction molar ratio of the polyol polymer and the fatty acid raw material. For example, a reaction product of 1 mol of polyerythritol and 1 mol of lauric acid is referred to as polyerythritol monolaurate ester. However, the polyol polymer fatty acid ester is usually not a single degree of substitution, but unreacted polyol polymer, monoester,
It is a mixture of polysubstituted compounds such as diesters and triesters. Further, depending on the reaction conditions, unreacted fatty acids and fatty acid salts obtained by neutralization with bases are also included. Although such a mixture can be used as it is, it is also possible to use a mixture which has been subjected to purification / fractionation such as decolorization with activated carbon or the like, solvent extraction, or chromatographic treatment with a resin, depending on the purpose.

In the solvent extraction method as the above-mentioned purification method, the polyol polymer fatty acid ester is soluble and the polyol polymer and / or fatty acid (or its salt) is soluble in the reaction product or in its aqueous solution or suspension. Hardly soluble solvents, for example, alcohols such as 2-propanol, t-butanol, n-butanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, hydrocarbons such as toluene and hexane, ethers such as isopropyl ether, tetrahydrofuran and dioxane, chloroform. Halogenated hydrocarbons such as, ethyl acetate, etc., acetonitrile, etc. are added, the polyol polymer fatty acid ester is extracted into the organic layer, and then the solvent is distilled off to obtain a high purity polyol polymer fatty acid ester. be able to.

Furthermore, when the above reaction product is in the state of an aqueous solution or suspension, depending on the hydrophilicity of the target product, the fatty acid chain of the ester and the type of solvent, the substitution degree, etc. It may contain an organic salt.

When the purification method is an adsorption column method, the reaction product is treated with an alcohol such as methanol, ethanol or 2-propanol, a ketone such as methyl ethyl ketone or acetone, an ether such as tetrahydrofuran or dioxane, and an organic solvent such as acetonitrile. To obtain a high-purity polyol polymer fatty acid ester by dissolving it in a mixed solvent of water, passing it through a column of a reverse phase resin adsorbent, adsorbing the polyol polymer fatty acid ester, and then eluting it with an eluent. You can As the adsorbent, any reverse phase resin can be used, but styrene type (including copolymer with divinylbenzene), acrylic type (including copolymer with divinylbenzene), phenol type synthesis Adsorbents are preferred.

As an example of such a resin, Diaion HP series (HP20, HP21, HP2MG, H
P20SS; manufactured by Mitsubishi Chemical Corporation, SepaBeads SP series (SP825, SP850, SP206, SP2)
07, SP20SS; manufactured by Mitsubishi Chemical Corporation, Amberlite XAD series (XAD2, XAD4, XAD7
HP, XAD761, XAD16, XAD1600, X
AD1180, XAD2000; made by Organo, Amber Chrome CG series (CG-161, CG-30)
0, CG-1000, etc .; manufactured by Rohm and Haas Company, Dowex L series (L-323, L-28
5, L-493; manufactured by Dow Chemical Co., Duolite S series (S-862, S-861, S866, etc.);
Sumitomo Chemical Co., Ltd.), sperite DAX series DAX-8 etc .; made by Superco), HW-40 (Tosoh Corp.), Muromac SAP series (SAP-9)
510, SAP-9610; manufactured by Muromachi Technos Co., Ltd.) and the like.

By the method as described above, the unreacted polyol polymer such as polyerythritol can be reduced to 5% by weight or less, and particularly when the adsorption column is used, the unreacted polyol polymer is completely removed (that is, It is also possible that the amount of unreacted polyol polymer is 0% by weight). Such a high-purity polyol polymer fatty acid ester improves various physical properties such as emulsification performance, surface activity, and coating on a film.

The content of the unreacted polyol polymer is determined by dissolving the purified product of the reaction product in water-alcohol and passing it through Diaion HP20 (manufactured by Mitsubishi Chemical Co., Ltd.) with a water-alcohol eluent. It can be measured by the weight of the eluted components. The composition of the water-alcohol eluent at this time is usually
A 5 to 50% by volume methanol aqueous solution (or ethanol aqueous solution) is used, but the solvent is selected under the following HPLC conditions under which the polyol component is not contained in the adsorbing component at all, depending on the type of the polyol polymer fatty acid ester. be able to.

<HPLC conditions> Column: TSK-gel ODS-80Ts Eluent: methanol or ethanol Flow rate: 0.2 ml / min Temperature: 40 ° C Detector: Differential refractometer

As an example of the above-mentioned fractionation, in the method using a solvent, the polyol polymer fatty acid ester is dissolved in at least two solvents having different polarities, and the high-polarity solvent layer and the low-polarity solvent layer, which are separated into layers, are respectively separated. By separating and distilling off the solvent, it is possible to separate into a high polarity component and a low polarity component of the polyol polymer fatty acid ester. The solvent can be used without limitation as long as it is a combination that dissolves the polyol polymer fatty acid ester and then separates the layers, and examples thereof include water, methanol, ethanol, 2-propanol, and n-.
Alcohols such as butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and isopropyl ether, hydrocarbons such as hexane and toluene, halogenated hydrocarbons such as chloroform, esters such as ethyl acetate, dimethyl. A combination of at least two kinds of solvents having different polarities from formamide, dimethyl sulfoxide, acetonitrile and the like can be mentioned, and particularly as a highly polar solvent, water and hydrophilicity such as water-methanol, water-ethanol, water-2-propanol, water-acetone and the like. It is preferable to use a mixed solvent of organic solvents.

Further, as an example of the above-mentioned fractionation, in the method using an adsorption column, fractionation is performed in the step of eluting the adsorbed polyol polymer fatty acid ester with an eluent in the purification using the above-mentioned reversed phase adsorption column. Can be carried out by adjusting the composition ratio of water-organic solvent in the eluent or by applying a gradient.

By the method as described above, it is possible to fractionate the polyol polymer fatty acid ester having different hydrophilicity.
For example, in the ionic strength in the chart obtained by a liquid chromatograph time-of-flight mass spectrometer (LC-TOFF-MS) under the following conditions, that is, in the amount of ions present, the meso-erythritol polymer or this meso-erythritol polymer is The content ratio of the mono-substituted ester of the polyol polymer containing as a main component to the meso-erythritol polymer or the di-substituted ester of the polyol polymer containing the meso-erythritol polymer as a main component is
It is possible to obtain a fraction having a di-substituted ester of 7 to 1000. Such fractions are excellent in emulsification performance in salt resistance and acid resistance, and have improved physical properties as various surfactants.

If the above content ratio is less than 7, a large amount of the polysubstituted ester, which is a hydrophobic component, is included, so that the water solubility of the polyol polymer fatty acid ester becomes insufficient or the physical properties such as surface activity are deteriorated. There is. On the other hand, it is possible to obtain a component having a content ratio of more than 1000 by making the fractionated fraction fine, repeating solvent extraction, or devising the mixing ratio of the solvent, but the recovery rate is low, and it becomes complicated. Is inefficient.

<LC-TOFF-MS conditions> ・ Ionization method: ESI ・ Measurement ion: Positive ion -Mobile phase flow rate: 0.1 mL / min (methanol) ・ Spray voltage: 3000V ・ Cone voltage: 30V ・ Desolvation gas: Nitrogen (700 L / h) ・ Ion source temperature: 80 ℃ ・ Desolvation temperature: 120 ℃ ・ Scanning range: m / z 50-1500

The fatty acid ester of the polyol polymer according to the present invention is required to have high water solubility (water affinity) of the compound and high acid resistance and salt resistance of the aqueous solution in the field of surfactants, especially emulsifiers for food. There are cases where In the case of application to those fields, such properties are also desired for the fatty acid ester of the polyol polymer according to the present invention.
In such a case, the higher the water solubility, the better. For example, the transmittance (at 650 nm) of an aqueous solution of 1% by weight of polyerythritol fatty acid ester (water suspension) at 35 ° C is 100%. Good, 60-100%
Are more preferred.

Further, the acid resistance of the aqueous solution is preferably high. For example, when the pH of the 0.1% by weight polyerythritol fatty acid ester aqueous solution is set to pH 2, the transmittance at 650C (650
(in nm) is preferably 20 to 100%, 35
-100% is more preferable.

Further, it is preferable that the aqueous solution has excellent salt resistance. For example, when 1% by weight of sodium chloride is added to 0.1% by weight of polyerythritol fatty acid ester aqueous solution, the transmittance (at 650 nm) at 25 ° C. is 20. -100% is preferable, and 30-100% is more preferable.

When the water solubility, acid resistance, and salt resistance of the fatty acid ester of the above-mentioned polyol polymer are below the ranges under the above-mentioned conditions, a large amount of precipitates are formed or aggregated in water, which is not preferable for practical use. Since the concentration inside becomes low, the ability of emulsification, foaming, dispersion, solubilization, etc. also decreases.

It is preferable that the fatty acid ester of the polyol polymer according to the present invention has high emulsification performance. Further, as described above, the aqueous solution of the fatty acid ester of the polyol polymer has high acid resistance and salt resistance, and has a function of imparting those functions even to emulsification. For example, while stirring 100 parts by weight of a 5% by weight polyerythritol fatty acid ester aqueous solution (water suspension) with a homomixer, 150 parts by weight of soybean oil was added dropwise to prepare an emulsion, which was allowed to stand for 7 days. Since the emulsion does not separate into two layers and stably exists as an emulsion, and shows stable emulsion performance even when used in a state of high salt concentration (containing 5% by weight of salt). preferable.

The fatty acid ester of the polyol polymer according to the present invention has antibacterial properties. For example, in the case of polyerythritol fatty acid ester, a mono-substituted product is preferable, and among them, those having a fatty chain length of about C6 to C24 are preferable, and those having C6 to C18 are more excellent in antibacterial properties.

Further, the polyol polymer and the fatty acid ester thereof according to the present invention are excellent in heat resistance. For example, when polyerythritol and its fatty acid ester are subjected to thermobalance analysis in the atmosphere at a heating rate of 10 ° C./min, the weight loss at 200 ° C. is preferably 20% or less, more preferably 10% or less. .

The foaming power of the fatty acid ester of the polyol polymer according to the present invention is desired to be high depending on the application. For example, a polyol polymer fatty acid ester of 0.
Los Miles method (JIS K
When the foaming force is measured according to 3362), the height of bubbles is preferably 50 mm or more, more preferably 80 mm or more. If the height of the bubbles is less than 50 mm, the bubbles may be insufficient when blended in a detergent, for example.

In some cases, particularly high ability of the fatty acid ester of the polyol polymer according to the present invention to reduce the surface tension is desired. In such a case, for example, a Wilhelmy method (automatic surface tension meter CBVP-
When the surface tension is measured according to A3 type; manufactured by Kyowa Interface Science Co., Ltd., the surface tension is preferably 44 dyne / cm or less, 42d
It is more preferably yne / cm or less. 44 dyne
If it exceeds / cm, the ability as a surfactant may be insufficient. However, when other functions such as safety, compatibility, W / O emulsifying property, and the like are also important, stearic acid esters, oleic acid esters, and the like exceeding the upper limit may be used.

The fatty acid ester of the polyol polymer according to the present invention is a surfactant, various kinds (for food, cosmetics,
(Industrial) Emulsifiers, cosmetics, detergents, defoamers, dispersants, solubilizers, preservatives, oil / fat crystal regulators, foaming agents, dyeing aids, inks (printing inks, [ballpoint pen] aqueous inks) , Ink additives, ink jet recording liquids, W / O type inks for stencil printing, fiber softeners, plasticizers (for cellulose acetate, polyolefin, photographic film, phenol resin, rubber, PVC, Polymer concrete, etc., Antistatic agent (for polyolefin, P
VC, styrene resin, polyester, etc.), antifogging agent (for polyolefin, styrene, PVC, etc.), moisturizer, moisture regulator, lubricant, emulsification aid, fiber modifier, sizing agent, surface treatment Agent, binder, viscosity modifier, flame retardant, adhesive, antibacterial agent, polymer raw material (polyurethane, epoxy resin, polyester, etc.), polymer stabilizer (for polyurethane, PVC, acetal resin, paraformaldehyde) Etc.), sugar crystal sizing agent, coloring preparation, fragrance enhancer, flavoring preparation, transparent soap, silicone rubber additive, polyether copolymer additive, polyolefin toughening agent, bonding agent,
Antifreeze, paint additive, developing toner, mold release agent, sterilization aid, crayon release agent, ore flotation recovery improver, cement crack preventive agent, cement strengthener, nicotine remover, green leaf preservative, soil It can be used as a stabilizer, a thickening gelling agent, a sludge accumulation preventing agent, a fiber wrinkle finishing agent, a petroleum wax removing agent, a synthetic oil and the like, or their constituents or raw materials.

Furthermore, since the polyol polymer fatty acid ester has a high heat resistance, it is used for applications requiring heat resistance, for example, kneaded molded products for plastic materials (polyethylene, polypropylene, EVA, polystyrene, PVC, etc.). it can.

[0059]

EXAMPLES The present invention will be described in more detail below with reference to examples. First, HPLC conditions and LC-TOFF-
The MS conditions are shown. [HPLC conditions] Column: TSK-gel ODS-80Ts Eluent: Methanol or ethanol Flow rate: 0.2 ml / min Temperature: 40 ° C Detector: Differential refractometer

[LC-TOFF-MS conditions] ・ Ionization method: ESI ・ Measurement ion: Positive ion -Mobile phase flow rate: 0.1 mL / min (methanol) ・ Spray voltage: 3000V ・ Cone voltage: 30V ・ Desolvation gas: Nitrogen (700 L / h) ・ Ion source temperature: 80 ℃ ・ Desolvation temperature: 120 ℃ ・ Scanning range: m / z 50-1500

[Production Example 1] (Synthesis of polyerythritol) To 150 g of erythritol was added 1.5 g of sodium hydroxide, and the mixture was reacted at 240 ° C., 40 mmHg for 2 hours. After the reaction was completed, it was cooled to 100 ° C. or lower, dissolved in 200 ml of distilled water, and neutralized with dilute hydrochloric acid. The aqueous solution was decolorized with activated carbon, desalted, and concentrated under reduced pressure to obtain 100 g of a colorless viscous liquid (water content 5%). The average degree of polymerization of the obtained polyerythritol was 4. If moisture-free is required, it can be vacuum dried at 120 ° C.

[Production Example 2] The reaction pressure was atmospheric pressure (760 mm).
Hg), and the reaction was carried out in the same manner as in Production Example 1 except that the reaction was carried out in a nitrogen stream for 6 hours to obtain 126 g of a colorless viscous liquid (water content 1%). The average degree of polymerization of the obtained erythritol polymer was 3.

[Production Example 3] (Synthesis of erythritol-glycerin copolymer) 0.3 g of sodium hydroxide was added to 27 g of erythritol and 3 g of glycerin, and 240 g at 240 ° C. and 220 mmHg.
Reacted for hours. After completion of the reaction, the same treatment as in Production Example 1 was carried out to obtain 20.3 g of a colorless viscous liquid (water content 5%).
The average degree of polymerization of the obtained copolymer was 3. If moisture-free is required, it can be vacuum dried at 120 ° C.

Example 1 (Polyerythritol monolaurate) 24.2 g of polyerythritol produced in Production Example 1
To (0.053 mol, water content 5%), 11.3 g (0.053 mol) of methyl laurate and 0.113 g of sodium carbonate were added, and the pressure was reduced to 150 mmH.
It was reacted at 180 ° C. for 5 hours. After completion of the reaction, the crude product was extracted 3 times with 50 ml of methyl ethyl ketone. The extract was dried under reduced pressure to obtain a white paste-like target product 26.
0 g was obtained.

When the IR spectrum (KBr) of the product was measured, in addition to absorption derived from polyerythritol such as 3350 cm ^-1 (-OH stretching vibration), 2922 cm ^-1 and 2853 cm ^-1 (increase due to the introduction of a fatty chain). -CH ₂
-Stretching vibration), 1739 cm ^-1 (C derived from ester bond
= O stretching vibration), absorption of 1077 cm ^-1 (C-O-C stretching vibration) was observed. On the other hand, also in the ¹³ C-NMR spectrum (CDCl ₃ ), in addition to the peak of 60-80 ppm derived from polyerythritol, 171-175 p
Ester carbon was observed at pm and carbon in the fatty chain at 14-35 ppm.

(Example 2) (Polyerythritol monolaurate) 28.3 g of polyerythritol synthesized in Production Example 2
Lauric acid 17.1 g (0.085 mol) and sodium hydroxide 0.2 g were added to (0.085 mol, water content 1%), and atmospheric pressure, under nitrogen stream, 190 ° C., 3
Reacted for hours. After the reaction was completed, ethanol was added and decolorized with activated carbon, and ethanol was distilled off from the filtrate to obtain 40.8 g of the target product in the form of a pale yellow paste.

In the IR spectrum (KBr) of the product, 3400 cm ^-1 (-OH stretching vibration), 2925 cm
^{-1, 2855cm -1} (-CH ₂ - stretching vibration), 1738
cm ^{- 1} (C = O stretching vibration), 1079 cm- ¹ (C-O-
C stretching vibration), 6 in ¹³ C-NMR (CDCl ₃ )
0-80 ppm (polyerythritol carbon), 171-
175 ppm (ester carbon) and 14-35 ppm (fatty chain carbon) were observed.

(Example 3) (Polyerythritol monolaurate) The reaction temperature was 230 ° C, and the addition amount of sodium hydroxide was 0.
The same procedure as in Example 2 was carried out except that the amount of the reaction product was set to 05 g and the reaction time was set to 2 hours to obtain 41.2 g of the target product in the form of a pale yellow paste. The obtained target product was analyzed by HPLC. The chart of the result is shown in FIG. The peak at 10 minutes in FIG. 1 is the peak of polyerythritol. When the target product was analyzed by LC-TOFF-MS, the ionic strength ratio (mono-substituted ester of polyerythritol / di-substituted ester of polyerythritol polymer) was found to be 6.8.
Met.

In the IR spectrum (KBr) of the product, 3400 cm ^-1 (-OH stretching vibration), 2926 cm
^{-1, 2855cm -1} (-CH ₂ - stretching vibration), 1738
cm ^{- 1} (C = O stretching vibration), 1112 cm- ¹ , 1082
cm ^-1 (C-O-C stretching vibration), ¹³ C-NMR spectrum (CDCl ₃ ) 61-80 ppm (polyerythritol carbon), 173-175 ppm (ester carbon), 14-35 ppm (fatty chain carbon) observed Was done.

(Example 4) (Polyerythritol monolauric acid ester) The same reaction as in Example 3 was carried out, the reaction product was dissolved in 180 ml of a 30% ethanol aqueous solution to decolorize the activated carbon, and then the synthetic adsorbent Diaion HP20 (manufactured by Mitsubishi Kagaku Co., Ltd.) was used. ) Was poured into a glass column having a diameter of 5 cm, and then unadsorbed components such as polyerythritol were eluted with a 30% ethanol aqueous solution, and then the adsorbed components were eluted with 100% ethanol. The 100% ethanol eluate was dried under reduced pressure to obtain 33.5 g of the desired product in the form of a pale yellow paste. When analyzed by HPLC, polyerythritol was not detected at all in the target product. The HPLC chart is shown in FIG.

(Example 5) (Polyerythritol monolaurate) After the same reaction as in Example 3, 200 ml of 2-propanol was added.
And then washed with 50 ml of 10% saline solution to remove unreacted easily water-soluble substances such as polyerythritol.
The 2-propanol layer is decolorized with activated carbon, and then 2-propanol is distilled off from the filtrate to obtain a pale yellow paste-like target product 3
0.1 g was obtained. This target product was passed through a synthetic adsorbent in the same manner as in Example 4, and the eluate portion of 30% ethanol was evaporated to dryness under reduced pressure. The eluted component was 1.1 g, and the content of unreacted polyerythritol was 3.2. %Met.

(Example 6) (Polyerythritol monolaurate) A reaction was carried out in the same manner as in Example 3. In the post-treatment, 150 ml of n-butanol and 10% saline were added, the n-butanol layer was decolorized with activated carbon, and then n-butanol was distilled off to obtain 33.8 of the target product in the form of a pale yellow paste. The unreacted polyerythritol content was 1.9%.

(Example 7) (Polyerythritol monolaurate) After the same reaction as in Example 3, 90% aqueous methanol solution 10 was added.
It was dissolved in 0 ml and 80 ml of hexane, decolorized with activated carbon, separated into layers, and dried under reduced pressure. A pale yellow paste (31.3 g) was obtained from the methanol layer, and a white paste (9.2 g) was obtained from the hexane layer. LC-T was added to the aqueous methanol extract.
When analyzed by OFF-MS, the ionic strength ratio (mono-substituted ester of polyerythritol / di-substituted ester of polyerythritol) was 15.2.

(Example 8) (Polyerythritol monolaurate) 20.0 g of polyerythritol monolaurate obtained in Example 4 was mixed with 95% 2-propanol aqueous solution 1
It was dissolved in 00 ml and 100 ml of hexane, and after separating the layers, they were dried under reduced pressure. A pale-yellow paste (14.1 g) was obtained from the 2-propanol aqueous solution layer, and a white paste (5.9 g) was obtained from the hexane layer. 2-Propanol extract component LC-
When analyzed by TOFF-MS, the ionic strength ratio (mono-substituted ester of polyerythritol / di-substituted ester of polyerythritol) was 12.8.

(Example 9) (Polyerythritol monolaurate) After the reaction was carried out in the same manner as in Example 3, the reaction product was dissolved in 150 ml of a 20% ethanol aqueous solution to decolorize the activated carbon, and then the synthetic adsorbent Diaion HP20 (manufactured by Mitsubishi Chemical). ) Was poured into a glass column having a diameter of 5 cm, and then adsorbed components such as polyerythritol were eluted with a 20% aqueous ethanol solution. Subsequently, the adsorbed component was eluted with 70% ethanol, and only the elution part of 150 ml from the start of elution of polyerythritol monolaurate was dried under reduced pressure to obtain 12.2 g of the target product in the form of a pale yellow paste. LC-TOFF-
When analyzed by MS, the ionic strength ratio (mono-substituted ester of polyerythritol / di-substituted ester of polyerythritol) was 19.8.

(Example 10) (Polyerythritol dilaurate) 34.2 g of lauric acid which is 2 equivalents of polyerythritol
The same procedure as in Example 3 was carried out except that (0.17 mol) was added to obtain 52.1 g of the target product in the form of a pale yellow paste.

The IR spectrum (KBr) of the product
3422 cm^-1(-OH stretching vibration), 2924 cm
^-1, 2855cm^-1(-CH2-stretching vibration), 1742
cm ^-1(C = O stretching vibration), 1172 cm^-1, 111
3 cm^-1(C-O-C stretching vibration),¹³C-NMR spectrum
Toll (CDCl₃) At 61-80 ppm (polyether
Lithritol carbon), 171-176 ppm (ester
Carbon), 14-35 ppm (fatty chain carbon) was observed
It was

(Example 11) (Polyerythritol monostearate) 24.9 g of polyerythritol produced in Production Example 2
21.2 g (0.075 mol) of stearic acid and 0.4 g of sodium hydroxide were added to (0.075 mol: water content 1%), and atmospheric pressure (760 mmHg), under nitrogen stream, 230 ° C., 2 hours. It was made to react. After the completion of the reaction, the same treatment as in Example 2 was carried out to cool the residue in the kettle to obtain 42.8 g of the desired product in the form of white flakes.

(Example 12) (Polyerythritol monostearate) After the same reaction as in Example 11, an 80% ethanol aqueous solution 2 was added.
It was dissolved in 00 ml and 160 ml of hexane, decolorized with activated carbon, separated into layers, and dried under reduced pressure. White flakes (32.4 g) were obtained from the ethanol layer, and white flakes (10.8 g) were obtained from the hexane layer. LC of the aqueous ethanol extract
When analyzed by -TOFF-MS, the ionic strength ratio (mono-substituted ester of polyerythritol / di-substituted ester of polyerythritol) was 20.5.

(Example 13) (Polyerythritol monostearate) Reaction was carried out in the same manner as in Example 11. In the post-treatment, 100 ml of n-butanol and 10% saline were added, the n-butanol layer was decolorized with activated carbon, and then n-butanol was distilled off to obtain 35.8 white flakes of the target product. The unreacted polyerythritol content was 1.6%.

(Example 14) (Polyerythritol monostearate) After the same reaction as in Example 11, a 30% aqueous ethanol solution 1 was added.
After dissolving in 20 ml and decolorizing with activated carbon, it was poured into a glass column with a diameter of 5 cm filled with Amberlite XAD4 (manufactured by Organo) as a synthetic adsorbent, and then unadsorbed components such as polyerythritol were eluted with a 30% aqueous ethanol solution. The adsorbed component was eluted with 100% ethanol. Concentrate the 100% ethanol eluate to 120 mL (30% solids), water 30 mL, hexane 100 mL.
After adding and separating layers, each was dried under reduced pressure. White flakes (26.0 g) were obtained from the ethanol aqueous layer, and white flakes (8.5 g) were obtained from the hexane layer. When the ethanol aqueous solution extract component was analyzed by LC-TOFF-MS, the ionic strength ratio (mono-substituted ester of polyerythritol / di-substituted ester of polyerythritol) was 35.5.

Example 15 Polyerythritol Tristearate Erythritol 17.7 g produced in Production Example 1
To (0.039 mol: water content 5%), 33.3 g (0.117 mol) of stearic acid and 0.5 g of sodium hydroxide were added, and the pressure was reduced to 20 mmHg under a pressure of 2 mm.
The reaction was carried out at 00 ° C for 6 hours. After completion of the reaction, toluene was added to the crude product and the mixture was heated and dissolved at 60 ° C. When the hot toluene solution was poured into methanol, crystals were precipitated.
The crystals were filtered and dried to obtain 43.9 g of the desired product as white powder.

In IR spectrum (KBr) of the product, 3391 cm ^-1 (-OH stretching vibration), 2914 cm
^{-1, 2848cm -1} (-CH ₂ - stretching vibration), 1739
cm ^{- 1} (C = O stretching vibration), 1104 cm- ¹ (C-O-
C stretching vibration), 6 in ¹³ C-NMR (CDCl ₃ )
0-80 ppm (polyerythritol carbon), 171-
175 ppm (ester carbon) and 14-35 ppm (fatty chain carbon) were observed.

(Example 16) (Polyerythritol monooleate) Instead of stearic acid, 21.2 g (0.
The same procedure as in Example 11 was carried out except that 075 mol) was used to obtain 41.0 g of the desired product as a yellow viscous liquid.

IR spectrum (KBr) of the product
3436 cm^-1(-OH stretching vibration), 2925 cm
^-1, 2855cm^-1(-CH2-stretching vibration), 1741
cm ^-1(C = O stretching vibration), 1093 cm^-1(C-O-
C stretching vibration),¹³C-NMR spectrum (CDCl₃)
At 61-80 ppm (polyerythritol charcoal
Elementary), 171-176 ppm (ester carbon), 14-
35ppm (Fat chain carbon), 130ppm (Fat chain fatigue)
(Japanese carbon) was observed.

(Example 17) (Polyerythritol trioleate) Instead of stearic acid, 63.6 g (0.
(225 mol) was carried out in the same manner as in Example 11 to obtain 78.0 g of the desired product as a yellow viscous liquid.

In IR spectrum (KBr) of the product, 3435 cm ^-1 (-OH stretching vibration), 2925 cm
^{-1, 2854cm -1} (-CH ₂ - stretching vibration), 1741
cm ^{- 1} (C = O stretching vibration), 1118 cm- ¹ (C-O-
C stretching vibration), ¹³ C-NMR spectrum (CDCl ₃ ).
At 61-80 ppm (polyerythritol carbon), 170-176 ppm (ester carbon), 14-
35 ppm (fatty chain carbon) and 130 ppm (fatty chain unsaturated carbon) were observed.

(Example 18) (Polyerythritol monocaprylic acid ester) 33.7 g of polyerythritol synthesized in Production Example 2
(0.101 mol), 15.6 g of caprylic acid
(0.108 mol), and sodium hydroxide 0.05
g, and under normal pressure and nitrogen flow at 200 ° C. for 2 hours, 2
React at 40 ° C for 2 hours to obtain the target product 4 which is a pale yellow viscous liquid.
6.7 g was obtained.

In IR spectrum (KBr) of the product, 3398 cm ^-1 (-OH stretching vibration), 2919 cm
^{-1, 2853cm -1} (-CH ₂ - stretching vibration), 1738
cm ^{- 1} (C = O stretching vibration), 1076cm- ¹ (C-O-
C stretching vibration), ¹³ C-NMR spectrum (CDCl ₃ ).
At 61-80 ppm (polyerythritol carbon), 171-176 ppm (ester carbon), 14-
35 ppm (fatty chain carbon) was observed.

(Example 19) (Polyerythritol monocaprylic acid ester) The same reaction as in Example 18 was carried out. In the post-treatment, the reaction product was extracted with 100 mL of methyl ethyl ketone, the methyl ethyl ketone solution was decolorized with activated carbon, and then the methyl ethyl ketone was distilled off to obtain 38.1 g of the target product as a colorless viscous liquid. The unreacted polyerythritol content was 3.6%.

(Example 20) (Polyerythritol tricaprylic acid ester) 22.0 g of polyerythritol synthesized in Production Example 2
20.0 g of caprylic acid to (0.066 mol)
(0.201 mol), and sodium hydroxide 0.06
g, and under normal pressure and nitrogen flow at 200 ° C. for 2 hours, 2
The reaction was carried out at 20 ° C for 2 hours and at 240 ° C for 1 hour. After the completion of the reaction, the same treatment as in Example 2 was carried out to obtain 45.0 g of the desired product as a pale yellow viscous liquid.

In the IR spectrum (KBr) of the product, 3412 cm ^-1 (-OH stretching vibration), 2924 cm
^{-1, 2856cm -1} (-CH ₂ - stretching vibration), 1745
cm ^{- 1} (C = O stretching vibration), 1111cm ^-1 (C-O-
C stretching vibration), ¹³ C-NMR spectrum (CDCl ₃ ).
At 61-80 ppm (polyerythritol carbon), 171-176 ppm (ester carbon), 14-
35 ppm (fatty chain carbon) was observed.

(Example 21) (Polyerythritol monocapric acid ester) 33.7 g of polyerythritol synthesized in Production Example 2
(0.101 mol), 14.6 g of capric acid
(0.101 mol) was charged, the temperature was raised, and 0.05 g of sodium hydroxide was added at 200 ° C.
The reaction was carried out at 220 ° C. for 2 hours and at 240 ° C. for 2 hours to obtain 44.1 g of the desired product as a pale yellow viscous liquid.

In IR spectrum (KBr) of the product, 3360 cm ^-1 (-OH stretching vibration), 2916 cm
^{-1, 2851cm -1} (-CH ₂ - stretching vibration), 173
9 cm ^-1 (C = O stretching vibration), 1076 cm ^-1 (C-O
-C stretching vibration), ¹³ C-NMR spectrum (CDC
61-80ppm in l ³⁾ (poly erythritol carbon), 171-176Ppm (ester carbon), 14
-35 ppm (fatty chain carbon) was observed.

(Example 22) (Polyerythritol monocaprylic acid / monooleic acid ester) 38.4 g of polyerythritol synthesized in Production Example 2
(0.115 mol), 16.9 g of caprylic acid
(0.117 mol), 32.6 g of oleic acid (0.1
15 mol) and 0.44 g of sodium hydroxide were added, and the mixture was reacted at 200 ° C. for 3 hours and 240 ° C. for 2 hours under a normal pressure and a nitrogen stream to obtain 79.8 g of the desired product as a brown viscous liquid.

In IR spectrum (KBr) of the product, 3410 cm ^-1 (-OH stretching vibration), 2922 cm
^{-1, 2856cm -1} (-CH ₂ - stretching vibration), 1735
cm ^{- 1} (C = O stretching vibration), 1098 cm- ¹ (C-O-
C stretching vibration), ¹³ C-NMR spectrum (CDCl ₃ ).
At 61-80 ppm (polyerythritol carbon), 171-176 ppm (ester carbon), 14-
35 ppm (fatty chain carbon) and 130 ppm (fatty chain unsaturated carbon) were observed.

(Example 23) (Erythritol-glycerin copolymer monostearate) 11.0 g (0.034 mol) of the erythritol-glycerin copolymer prepared in Preparation Example 3 was added to 50 ml of N, N-dimethylformamide and nitrogen. It was made to melt | dissolve at 60 degreeC under air flow. 10.4 g of stearic acid chloride was added to the solution.
20 ml of an N, N-dimethylformamide solution containing (0.034 mol) was added dropwise over 30 minutes, and the temperature was 80 ° C. and 2.
The reaction was carried out for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a crude product, which was extracted with methyl ethyl ketone. The extract is dried under reduced pressure to give 12.5 g of the desired product as a white paste.
Got

The IR spectrum (KBr) of the product was measured. As a result, in addition to absorption derived from the polyol polymer such as 3385 cm ^-1 (-OH stretching vibration), 2918 cm ^-1 and 2850 cm ^-1 (-due to the introduction of a fatty chain). CH ₂ - stretching vibration), 1735cm ^-1 (C = O stretching vibration derived from an ester bond), the absorption of 1101cm ^-1 (C-O-C stretching vibration) was observed. ¹³ C-NMR spectrum (CDCl ₃ )
Also, the polyol polymer-derived 60-80 ppm
In addition to the peak of 1, the ester carbon was observed at 171-175 ppm and the carbon of the fatty chain was observed at 14-35 ppm.

[Various Performance Tests] (Evaluation Test 1) [Water Solubility (Water Affinity) Test] The polyerythritol monostearate obtained in Example 11 and Example 12 above was used at a concentration of 0.1% by weight, Distilled water to be 0.5% by weight and 1.0% by weight 2
It was suspended or dissolved in 0 ml at 50 ° C, and left standing at 20 ° C for 24 hours. The obtained suspension or solution was transferred to a cuvette, and the transmittance (%) at 650 nm was measured with a spectrophotometer. For comparison, the same measurement was performed using tetraglycerin monostearate and hexaglycerin monostearate. The results are shown in Table 1.

[0100]

[Table 1]

<Results> Compared with tetraglycerin monostearate and hexaglycerin monostearate, polyerythritol monostearate, particularly polyerythritol monostearate with a hydrophilic part fractionated, has a high transmittance and is soluble in water. It was found that the property is better, that is, the water affinity is higher.

(Evaluation Test 2) [Acid Resistance Test of Aqueous Solution] A 0.1% by weight aqueous solution of polyerythritol monostearate obtained in Example 11 and Example 12 was replaced with an aqueous sodium hydroxide solution or an aqueous hydrochloric acid solution. Was adjusted to a predetermined pH shown in Table 2 at 25 ° C. This was left still at 25 ° C. for 24 hours. The obtained suspension or solution was transferred to a cuvette, and the transmittance (%) at 650 nm was measured with a spectrophotometer. For comparison, the same measurement was performed using tetraglycerin monostearate and sucrose monostearate. The results are shown in Table 2.
Shown in.

[0103]

[Table 2]

<Results> Compared with tetraglycerin monostearate and sucrose monostearate,
It was found that the polyerythritol monostearate, particularly the polyerythritol monostearate with the hydrophilic part fractionated, has a high transmittance in the acidic region and good acid resistance.

(Evaluation Test 3) [Salt Resistance Test of Aqueous Solution] The concentration shown in Table 3 was obtained in a 0.1% by weight aqueous solution of polyerythritol monostearate obtained in Examples 11 and 12 above. The salt was dissolved in. This was left still at 25 ° C. for 24 hours. The obtained suspension or solution was transferred to a cuvette, and the transmittance (%) at 650 nm was measured with a spectrophotometer. For comparison, the same measurement was performed using tetraglycerin monostearate and sucrose monostearate. The results are shown in Table 3.

[0106]

[Table 3]

<Results> Compared with tetraglycerin monostearate and sucrose monostearate,
It was found that polyerythritol monostearate, particularly polyerythritol monostearate having a hydrophilic portion fractionated, had a high transmittance and a good salt resistance.

(Evaluation Test 4) [Emulsification Performance Test] To the saline solutions having the concentrations shown in Table 4, the polyerythritol monostearate obtained in Example 5 and Example 14 was added and the content was 5.0% by weight. A water suspension (aqueous solution) of was prepared. While stirring 12 parts by weight of this aqueous suspension (aqueous solution) at 5000 rpm with a homomixer, 18 parts by weight of soybean oil was added dropwise, and further mixed at 8000 rpm for 2 minutes to prepare an emulsion. This emulsion was allowed to stand at room temperature for 1 to 7 days, and the stability of the emulsion was visually observed. The results were evaluated according to the following criteria. ○: Not divided into two layers. Δ: Divided into two layers. X: Divided into two layers. As a comparison, the same measurement was performed using tetraglycerin monostearate. The results are shown in Table 4.

[0109]

[Table 4]

<Results> The tetraglycerin monostearate ester has a salt concentration of 0.5% by weight or more,
All two-layer separation occurred, but in the case of polyerythritol monostearate, no two-layer separation occurred.

(Evaluation test 5) [Antibacterial test] Nutrient agar (manufactured by Difco) was adjusted so that the polyerythritol monolaurate ester synthesized in Example 1 had the concentration shown in Table 5. It was prepared and sterilized. Then, 10 ml of the above-prepared medium was poured into a sterile petri dish, allowed to cool and solidified, and then Nutrient broth.
Staphylococcus aureus IFO1273 cultured at 37 ° C. for 24 hours in (manufactured by Difco)
Inoculate the agar suspension with the bacterial suspension from 2) with a platinum loop and incubate at 37 ° C for 2
Cultured for 4 hours. The degree of inhibition of the growth of the bacteria was visually determined. As a comparison, the same measurement was performed using tetraglycerin monostearate. The results are shown in Table 5. In Table 5, ◯ means that the growth of the bacterium was not visible, Δ means that the bacterium slightly grew, and x means that the bacterium grew.

[0112]

[Table 5]

<Results> Tetraglycerin monostearate did not show antibacterial properties, but polyerythritol monolaurate showed antibacterial properties.

(Evaluation Test 6) [Thermal Stability Test] The polyerythritol monostearate ester synthesized in Example 11 was thermobalanced (manufactured by Rigaku Denki KK; TAS-2).
The residual rate of weight (the residual rate of weight when the charged amount was 100%) was measured at a temperature of 10 ° C./min in the atmosphere.

[0115]

[Table 6]

<Results> The polyerythritol monostearate ester remained at 96.7% at 200 ° C.,
It was found that these have excellent thermal stability.

(Evaluation Test 7) [Foaming Power Performance Test] The polyerythritol monolaurate obtained in Example 3 and Example 9 was dissolved in distilled water to give 0.3.
Adjusted to% by weight, loss miles method (JIS K336
According to 2), the foaming power and the stability of the foam after 5 minutes were measured at 30 ° C. For comparison, the same measurement was performed using tetraglycerin monolaurate. The results are shown in Table 7.

[0118]

[Table 7]

<Results> Polyerythritol monolaurate showed excellent foaming power.

(Evaluation Test 8) [Measurement of Surface Tension] The polyerythritol monolaurate obtained in Example 3 and Example 4 and the polyerythritol monocaprylate obtained in Example 19 were dissolved in distilled water. The amount was adjusted to 0.005% by weight, and measured according to the Wilhelmi method using an automatic surface tensiometer (CBVP-A3 type; manufactured by Kyowa Interface Science Co., Ltd.) under the condition of 25 ° C. Also,
As a comparison, the same measurement was performed using tetraglycerin monolaurate. The results are shown in Table 8.

[0121]

[Table 8]

<Results> It was found that the polyerythritol fatty acid ester is excellent in the surface tension lowering ability.

[0123]

According to the present invention, erythritol is
Since there is one more hydroxyl group than glycerin, the resulting polyol polymer has more hydroxyl groups than polyglycerin. Therefore, when the fatty acid ester of this polymer is used as a surfactant or the like or a raw material thereof, the hydrophilicity of the obtained surfactant or the like is further improved.

Further, the fatty acid ester of the obtained polyol polymer can improve the acid resistance and salt resistance of the aqueous solution, as compared with the fatty acid ester of polyglycerol.
The emulsifying power can also be improved.

[Brief description of drawings]

FIG. 1 is an HPLC chart in Example 3.

FIG. 2 HPLC chart in Example 4

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hirokuni Tajima             1-8-10 Jiyugaoka, Kanazu-cho, Sakai-gun, Fukui Prefecture             No. Rengo Co., Ltd. Fukui Research Center F-term (reference) 4J005 AA21 BD02

Claims (9)

[Claims] 1. A fatty acid ester of a polyol polymer, which comprises a polyol containing meso-erythritol as a constituent monomer, and a polyol polymer obtained by polymerizing 2 to 16 molecules of the constituent monomer as a main component. 2. A fatty acid ester of a meso-erythritol polymer, which comprises meso-erythritol as a constituent monomer and a meso-erythritol polymer obtained by polymerizing 2 to 16 molecules of meso-erythritol as a main component. 3. A fatty acid ester of a polyol polymer or a meso-erythritol polymer, wherein a polyol polymer containing meso-erythritol as a main component or a meso-erythritol polymer is transesterified with a fatty acid ester in the presence of a catalyst. Manufacturing method. 4. A fatty acid ester of a polyol polymer or a fatty acid of a meso-erythritol polymer, wherein a polyol polymer containing meso-erythritol as a main component or a meso-erythritol polymer is esterified with a fatty acid in the presence of a catalyst. Method for producing ester. 5. A fatty acid ester of a polyol polymer or meso-erythritol polymer, which comprises esterifying a polyol polymer containing meso-erythritol as a main component or a meso-erythritol polymer with a fatty acid halide in the presence of a catalyst. The method for producing the fatty acid ester of. 6. The content of unreacted polyol polymer is 5
The fatty acid ester of the polyol polymer according to claim 1, which is contained in an amount of not more than wt%. 7. The fatty acid ester of a meso-erythritol polymer according to claim 2, wherein the unreacted meso-erythritol polymer content is 5% by weight or less. 8. The content ratio of the mono-substituted ester of the polyol polymer containing meso-erythritol as a main component and the di-substituted ester of the polyol polymer is such that the mono-substituted ester of the polyol polymer / the di-substituted ester of the polyol polymer = 7.
The fatty acid ester of the polyol polymer according to claim 1, which is ˜1000. 9. The content ratio of the mono-substituted ester of the meso-erythritol polymer and the di-substituted ester of the meso-erythritol polymer is such that the mono-substituted ester of the meso-erythritol polymer / the di-substituted ester of the meso-erythritol polymer = 7. The fatty acid ester of the meso-erythritol polymer according to claim 2, which is ˜1000.