KR20190069016A - Manufacturing method of fatty acid ester - Google Patents

Abstract

Fatty acid esters manufactured by a method according to the present invention use readily available sugars and vegetable fats as raw materials, do not use a toxic organic solvent such as DMSO, thereby preventing an increase in manufacturing costs due to solvent removal, and at the same time are nontoxic by using a human-friendly eutectic solvent. In addition, the sugar-based fatty acid esters have antiseptic properties, and thus do not need to add a preservative harmful to the human body. Fatty acid esters according to the present invention, due to the properties, can be widely provided as non-toxic products in the field of cleaners, which are in frequent contact with humans, such as cosmetics, human body cleaners, baby bottle cleaners, vegetable-fruit wash, dishwashing detergents and the like.

Description

{Manufacturing method of fatty acid ester}

The present invention relates to a process for producing a sugar fatty acid ester, and more particularly, to a process for producing a fatty acid ester of a fatty acid ester, which comprises synthesizing a saccharide as a natural substance and a fatty acid extracted from a vegetable oil fat but synthesizing it under a Deep Eutectic Solvent And a manufacturing method thereof.

Sugar fatty acid esters obtained by esterifying fatty acids in saccharides are kinds of surfactants having a wide range of HLB (hydrophile-lipophile balance) values of 2 to 16, and they are used as emulsifiers, foaming agents, detergents, (Yamada et al., Yakagaku, 29, 543, 1980; Lauridesen. J. Am. Oil. Chem., 5c. 53, 400, 1976) because they are not toxic and are widely used in the fields of foodstuffs, cosmetics and pharmaceuticals.

The sugar-fatty acid ester has excellent emulsifying, foaming, washing and dissolving properties, has no irritating properties to the eyes and skin, has excellent biodegradability and does not cause environmental pollution, and is a tasteless, odorless and non-toxic surfactant. Cosmetics and so on.

Such sugar-fatty acid esters have been produced mainly by chemical synthesis using a metal catalyst. However, since the miscibility of the two reactants is poor, a solvent such as dimethylformamide or pyridine, which is harmful to the human body, , And since there are several alcohol groups (-OH) in the sugar residue, one or more of the fatty acids may optionally be bonded to form a mixture of various mono-, di-, tri- and higher esters, Physical properties are not constant. That is, this chemical synthesis leads to the formation of undesired by-products, and it is necessary to purify the desired sugar-fatty acid ester after synthesis.

Also, since a toxic organic solvent such as dimethyl formamide (DMF) or dimethyl sulphoxide (DMSO) should be used, the process of dispersion, washing, and filtration may be performed to remove the toxic organic solvent Since it must be repeated many times, it involves high manufacturing cost.

Korean Patent No. 10-0369117 discloses a technique related to the sugar-fatty acid ester as described above, and is characterized in that it is synthesized by using water instead of a toxic solvent such as DMSO. However, a process of emulsifying the reaction starting material into soap is added There is a technical problem that the remaining soap must be removed after synthesis and the final reaction yield is as low as 30%.

Korean Registered Patent No. 10-0369117 (Jan. 09, 2003)

Disclosure of the Invention The present invention has been conceived in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method of synthesizing a natural substance saccharide and a fatty acid extracted from a vegetable oil fat to produce a food additive which is harmless to the human body, such as choline chloride and a hydrogen bond donor such as betaine, It is an object of the present invention to provide a method for producing a sugar-fatty acid ester which is produced by using an eutectic solvent in which hydrogen-bonding receptors are bonded through hydrogen bonding.

The present invention relates to a process for preparing fatty acid esters.

One aspect of the present invention relates to a process for producing a fatty acid ester obtained by reacting a fatty acid having a carboxylic acid group in a molecule with a sugar, wherein the fatty acid ester is reacted in a eutectic solvent during the reaction.

In the present invention, the solvent includes monosaccharides, disaccharides, Hydrogen-binding substances between saccharides, for example, sucrose / fructose / glucose 1/1/1 mixture in the presence of a small amount of water, including one or a plurality of saccharides selected from polysaccharides and choline chloride, Wherein the fatty acid is selected from the group consisting of capric acid, lauric acid, myristic acid, palauric acid, palmitic acid, stearic acid, oleic acid, maleic acid, , Linolenic acid and arachidonic acid, and the sugar is any one or a plurality selected from glucose, fructose, galactose, maltose, sucrose and lactose.

Also, the method of the present invention is characterized in that 100 to 300 parts by weight, 100 to 200 parts by weight of the solvent and 0.01 to 10 parts by weight of the catalyst are reacted with respect to 100 parts by weight of the fatty acid.

Another aspect of the present invention is a composition prepared from the above process, wherein the composition has any one of the formulations selected from the personal care and home care product groups.

Fatty acid esters prepared by the method according to the present invention can be easily obtained by using saccharides and vegetable fats as raw materials and do not use a toxic organic solvent such as DMSO to prevent an increase in manufacturing cost due to solvent removal, It is non-toxic using phosphorus eutectic solvents.

In addition, the fatty acid ester has an anti-buoyancy property and has an advantage that it is not necessary to add a preservative harmful to the human body.

The fatty acid ester according to the present invention can be widely provided as a non-toxic product in the cleaning agent field frequently contacted with humans such as bottle cleaner, vegetable-fruit cleaner, kitchen detergent, etc. due to the above-mentioned characteristics.

FIG. 1 is a graph showing the results of a test for antibacterial activity of a test piece prepared in Example 2. FIG.
FIG. 2 is a graph showing the results of the test for the antibacterial activity of the test piece prepared in Example 6. FIG.

Hereinafter, a method for producing a fatty acid ester according to the present invention will be described in detail with reference to specific examples. The following specific embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention.

Therefore, the present invention is not limited to the embodiments shown below, but may be embodied in other forms. The embodiments shown below are only for clarifying the spirit of the present invention, and the present invention is not limited thereto.

Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

The present invention is characterized in that it is obtained by reacting a sugar with a fatty acid having a carboxylic acid group in a molecule.

In the present invention, the fatty acid may be a saturated fatty acid or an unsaturated fatty acid having 10 to 30 carbon atoms, more preferably 10 to 24 carbon atoms. Examples thereof include capric acid, lauric acid, myristic acid, , Stearic acid, oleic acid, linolenic acid and arachidonic acid.

The fatty acids may be derived from liquid oils derived from plants, marine or animal, including but not limited to, olive oil, corn oil, soybean oil, canola oil, cottonseed oil, palm oil, palm kernel oil, coconut oil, Sesame oil, sunflower oil, borage seed oil, Syzigium aromaticum oil, hempseed oil, herring oil, cod-liver oil, salmon oil, , Flaxseed oil, wheat germ oil, evening primrose oil, and the like.

In the present invention, the sugar is a kind of carbohydrate, and may include a monosaccharide and a disaccharide. Examples of the sugar include glucose, fructose, galactose, maltose, sucrose, and lactose, and the like. , And the use of sucrose or lactose is advantageous in terms of securing the cleansing power and early bubbling power.

Particularly, in the case of using sucrose in the above sugar chain, when the content of sugar (mixture of glucose and fructose) is high in the phosgene, the product may be colored and unnecessary substances may be produced in the esterification reaction. desirable.

In the present invention, the sugar is preferably added in an amount of 100 to 300 parts by weight based on 100 parts by weight of the fatty acid. If it is added in an amount of less than 100 parts by weight, a fatty acid may remain in the composition, and if it is added in an amount of more than 300 parts by weight, an excessive amount of sugar may remain to deteriorate the performance as a surfactant.

In the present invention, the eutectic solvent may be used as the solvent. In general, organic solvents have been used in the extraction and synthesis processes. The organic solvents have advantages such as low cost and high extraction, reaction efficiency and emulsification degree. However, they are mostly toxic, have low stability due to high volatility, There is a disadvantage that it can be caused.

The eutectic solvent according to the present invention is an ionic liquid, which is composed of ionic bonds of cations and anions. The eutectic solvent exists in a liquid state at a temperature of 100 ° C or lower and has a vapor pressure close to zero. . It is also possible to dissolve a variety of inorganic substances, organic substances, and polymeric substances, and easily change the physico-chemical properties such as hydrophobicity, solubility, viscosity and density.

The Deep Eutectic Solvent (DES) is a mixture of two or more solid or liquid materials, which is liquefied at room temperature due to mixing of two compounds having a high melting point to form hydrogen bonds between the molecules, It is an environmentally friendly solvent based on natural materials such as alcohol and organic acid. It is easy to manufacture and does not require a separate purification process, and thus has a low production cost, non-toxicity, non-inflammability and nonvolatility, , Can be regenerated and is easily recovered as a biodegradable solvent. In addition, since it has the physicochemical properties of the constituent materials, it can be used for various purposes by controlling the composition and the ratio.

In the present invention, the eutectic solvent acts as a kind of hydrogen bond acceptor, which can easily dissolve a fatty acid or a saccharide which is a hydrogen bond donor.

In the present invention, the eutectic solvent may be a mixture of a saccharide and choline chloride, a betaine, a mixture thereof, or a hydrogen bond material between saccharides such as sucrose / fructose / glucose in the presence of a small amount of water in a 1/1/1 volume ratio It is preferable to use a mixed eutectic solvent in which a mixed eutectic solvent and a sucrose / malic acid are mixed in a 1/1 volume ratio. It is preferable to prepare an eutectic solvent before synthesis without specifying the mixing ratio, And may include all reactions that perform the reaction.

Choline chloride acts as a hydrogen bond acceptor of saccharides and is a dietary component characteristic of the ingredient itself. It is present in an independent form in food or in an esterified form such as phosphocholine, glycerophosphocholine, sphingomyelin and the like exist. The choline chloride functions as a precursor of acetylcholine, phospholipid, and betaine as a methyl donor and plays an important role in metabolism such as structural stability of the cell membrane, transport of lipids and cholesterol, and signal transduction.

The betaine is an amino acid extracted from sugar beet and acts as a hydrogen bond acceptor for various fatty acids. Betaine also has excellent moisturizing effect to prevent moisture loss of the skin and to protect skin tissue from harmful substances such as ultraviolet ray, infrared ray, and dust. It also has anti-inflammatory and whitening effect, which is a non-toxic substance used in acne treatment, anti-aging and whitening products.

In the present invention, the eutectic solvent is preferably a mixture of choline chloride and betaine. At this time, the mixing ratio of the composition is preferably 30 to 70% by weight of choline chloride and 10 to 30% by weight of betaine.

In the present invention, the eutectic solvent is preferably mixed with 100 to 200 parts by weight based on 100 parts by weight of the fatty acid. When the amount is less than 100 parts by weight, the solubility is poor and the stirring may be difficult. When the amount is more than 200 parts by weight, reaction yield may be affected.

Also, the preparation method according to the present invention may use a solid-phase sugar and a sugar as a eutectic solvent. In this case, a separate additional eutectic solvent may not be required. In this case, it is preferable to add 100 to 500 parts by weight of sugar relative to 100 parts by weight of the fatty acid.

In the present invention, a catalyst may be further added to the composition to promote the reaction in the production of the fatty acid ester. The catalyst is not limited to the alkali catalysts conventionally used in the art, and examples thereof include alkali metal hydrides, alkali metal hydroxides, alkali metal salts and the like. For example, sodium hydroxide, sodium carbonate, , Sodium acetate, potassium hydroxide, potassium carbonate, potassium acetate, zinc acetate, calcium carbonate, and the like, . At this time, it is preferable that 0.01 to 10 parts by weight of the catalyst is added to 100 parts by weight of the total composition to improve the reaction rate and facilitate purification.

The present invention also provides a process for preparing a fatty acid ester comprising the steps described above.

a) forming a reaction mixture comprising a sugar, a fatty acid, a eutectic solvent and a catalyst;

b) esterifying the reaction mixture under temperature, pressure and stirring conditions; And

c) separating the fatty acid ester from the reaction mixture after the reaction;

The reaction mixture can be prepared by first suspending a sugar and a fatty acid in a eutectic solvent, and then adding a mixture of the catalyst, the catalyst and the co-catalyst.

Also, the reaction temperature in step b) may be 70-150 ° C, and more preferably 90-120 ° C. However, it may be heated at a temperature higher than the above temperature to accelerate the completion of the reaction after dropping the entire reaction raw material.

It is preferable to adjust the addition amount of the catalyst so that the pH is maintained weakly alkaline during the reaction. Particularly under strong alkaline conditions, side reactions of hydrolysis become significant, so it is advisable to adjust the pH to not exceed 11.

The reaction time is not particularly limited as long as the reaction between the sugar and the fatty acid is sufficiently completed, and it is preferable to conduct the reaction within about 12 hours depending on the starting compound and various conditions.

 The present invention can include a composition having any one of the formulations selected from personal care, fatty acid ester as a surfactant, home care product line and vegetable fruit detergent, bottle cleaning agent. The detergent may further contain additives such as a foam adjuvant, a gelling agent, an active ingredient, and an antioxidant, if necessary.

In the present invention, the personal care refers to a general skin contact product that can be used by individuals such as basic cosmetics, color cosmetics, sunscreen, shampoo, detergent, toothpaste, and the like, which are used in daily life by consumers around the world. Is a concept used for the human body to maintain or enhance the health of skin or hair, and specifically includes all products covered by the Cosmetic Act enacted by the Ministry of Health and Welfare ( http: // terms.naver.com/entry.nhn?docId=1155234&cid=40942&categoryId=32161).

The home care is a liquid type product used for a kitchen or clothes, and includes a kitchen cleaner, a household cleaner, a clothes cleaner, a fabric softener, a vegetable fruit cleaner, a bottle cleaner, and the like.

Such foam adjuvants include fatty alcohols having at least 15 carbons in the carbon chain, such as cetyl alcohol and stearyl alcohol (or mixtures thereof). Examples of other fatty alcohols include arachidyl alcohol (C20), behenyl alcohol (C22), 1-triacontanol (C30), and longer carbon chains (maximum C50) And the like. The concentration of fatty alcohols required to maintain the foam system is inversely proportional to the length of the carbon chain. Fat alcohols derived from beeswax, in which the carbon chain of most alcohols comprise an alcohol mixture having at least 20 carbons, are particularly suitable as foam adjuvants.

Other classes of foam adjuvants include fatty acids with 16 or more carbons in the carbon chain, such as hexadecanoic acid (C16), stearic acid (C18), arachidic acid (C20) , Behenic acid (C22), octacosanoic acid (C28), fatty acids having a longer carbon chain (maximum C50), and mixtures thereof.

If necessary, the carbon atom chain of the fatty alcohol or fatty acid may have at least one double bond. Another class of foam adjuvants includes long chain fatty alcohols or fatty acids with branches in the carbon atom chain. In another class of foam adjuvants, the carbon chain of the fatty acid can be replaced by a hydroxy group (-OH), for example, 12-hydroxy stearic acid.

Examples of the gelling agent include locust bean gum, sodium alginate, sodium carinate, egg albumin, gelatin agar, caragein guanosine alginate, xanthan gum, corn seed extract, tragacanth gum, starch, Modified starch and the like, and compositions made by cellulose ethers (e.g., hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropylmethyl cellulose), microcrystalline cellulose and FMC (Avicel types) , And semisynthetic polymeric materials such as polyvinyl pyrrolidone, polyvinyl alcohol, guar gum, hydroxypropyl guar gum, water-soluble starch, cationic cellulose, cationic guar, and the like, and carboxyvinyl polymer, polyvinylpyrrolidone, polyvinyl alcohol poly Acrylic acid polymers, polymethacrylic acid polymers, polyvinyl acetate polymers, polybasic There can be a chloride polymers, polyvinylidene chloride polymers, such as synthetic polymeric materials, but are not limited to these, it is also possible to use mixtures of the above-mentioned compounds, if necessary.

The active ingredient is intended for the frequent contact of the skin to the skin during use of the detergent, such as, for example, cleansing the skin such as alpha-or beta-hydroxy acid; Wrinkle inhibitors such as hyaluronic acid and phytic acid; Skin whitening agents such as hydroquinone and azelaic acid; A skin peel agent, and the like.

The antioxidant is used for protecting the skin and imparting vitality to the skin. Examples of the antioxidant include ascorbic acid (vitamin C) and salts thereof, ascorbyl esters of fatty acids, ascorbic acid derivatives (e.g., magnesium ascorbyl phosphate, sodium ascorbate Tocopherol (vitamin E), tocopherol sorbate, tocopherol acetate, esters of other tocopherols, butylated hydroxybenzoic acid and its salts, 6-hydroxy-2,5,7,8 -Tetramethylchroman-2-carboxylic acid (trade name Trolox), alkyl esters with gallic acid, in particular propyl gallate, uric acid and its salts and alkyl esters, sorbic acid and its salts, For example, N, N-diethylhydroxylamine, amino-guanidine, sulfhydryl compounds such as glutathione, dihydroxyfumaric acid and its salts, ricin pydolate, arginine pilolate, Draw nine Ayia Platte mountain, you can use the bioflavonoids, connectors are Min (curcumin), lysine, methionine, proline, superoxide dismutase, silymarin, tea extracts, grape skin / seed extracts, melanin, and rosemary extracts.

Other additives such as an abrasive, an absorbent, a perfume, a pigment, a pigment, a buffer, a thickener, a chelating agent, a pH adjusting agent, a reducing agent and the like may be further added. The amount of the additive to be added is not limited, and the amount of the additive can be appropriately controlled within the range not impairing the object of the present invention.

The fatty acid ester according to the present invention can be easily obtained by using saccharides and vegetable fats which are easily available, and it is possible to prevent an increase in manufacturing cost due to the removal of solvent by using no toxic organic solvent such as DMSO and at the same time, It is non-toxic using.

In addition, the fatty acid ester has an anti-buoyancy property and has an advantage that it is not necessary to add a preservative harmful to the human body.

The fatty acid ester according to the present invention can be widely provided as a non-toxic product in the cleaning agent field frequently contacted with humans such as bottle cleaner, vegetable-fruit cleaner, kitchen detergent, etc. due to the above-mentioned characteristics.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The physical properties of the specimens prepared through the following examples and comparative examples were measured as follows.

(Bubble force)

500 g of a 1% concentration sample solution was prepared using 5 g of the sample and 495 g of water. Next, the sample solution was measured using a SITA R-2000 bubble analyzer. The stirring speed and time were 800 rpm and 1 minute. The volume of bubbles was measured immediately after the rotation of the rotor stopped.

(Washing power)

Soybean oil, lard oil, woji, and starch were mixed at a ratio of 1/1/1/1. The contaminated liquid was spread on a standard plate in 3 g portions and dried at 25 ° C for 24 hours. Test 3 g of the surfactant 0.1 g of diluted solution was bubbled using 1 m droppings, the prepared dish was washed with a wringer, and the number of washed dishes was evaluated by counting the number of washed dishes as an end point.

(Antibacterial activity)

In order to evaluate the microbial resistance, the bactericidal effect against four kinds of microorganisms was examined. The target microorganisms are Staphylococcus aureus , Pseudomonas aeruginosa , Escherichia coli , and Saccaromyces cerevisiae . One loop of each strain is inoculated into the optimal medium for each strain, And cultured under optimal culture conditions to prepare an inoculated cell suspension.

The specimens were then placed in a test tube and diluted with sterile water. At this time, dilution magnification was 0% (specimen-free), 0.5%, 1%, 1.5%, 2%, and 2.5%, respectively. Separately, the medium was prepared for each strain and steam sterilized in a test tube. 10 ml of the diluted solution of the above specimen and 0.1 ml of the suspension were added thereto, and the suspension was set on a BioPhoto recorder (manufactured by Advantoy Toyoda) and incubated for 24 hours at 30 캜 with shaking culture (30 rpm).

The lowest inhibition concentration (MIC) of the diluted series in which no turbidity due to the growth of microorganisms did not occur within the incubation time was designated as MIC. The results are shown in FIGS. 1 and 2.

(Example 1)

200 g of sugar, 100 g of capric acid (10 carbon atoms) and 10 g of potassium carbonate were added to a reactor in 100 L eutectic solvent (choline chloride: betaine = 7: 3 by volume). The reactor was reacted for 8 hours at a temperature of 90 캜, a pressure of 200 Torr, and a stirring speed of 50 rpm to obtain a sugar-capric acid polymer.

(Examples 2 to 6)

A sample was prepared in the same manner as in Example 1, except that the sugar was replaced with capric acid, which is a fatty acid, as shown in Table 1.

(Comparative Examples 1 to 5)

For comparison with the sugar-fatty acid esters, commercially available surfactants and detergents were prepared as shown in Table 1.

[Table 1]

As shown in Table 1, the sugar-fatty acid esters prepared according to the present invention exhibit cleaning power and initial foaming power similar to those of general surfactants and commercial kitchen detergents. In particular, Example 6 using lauric acid (carbon number 12) and sugar as the fatty acid and saccharide respectively, and Example 6 using lauric acid (carbon number 12) and sucrose as the fatty acid and saccharide, respectively, And it has been confirmed that it has the quality of commercial surfactant level.

FIG. 1 and FIG. 2 were obtained by measuring the antibacterial activity of each of Example 2 and Example 6, and it was confirmed that the minimum inhibitory concentration of the microorganisms was 1.5 to 2% in both specimens. When the microbial minimum inhibitory concentration of a typical commercial detergent is expressed when 5% by weight or more of a surfactant is added, the sugar-fatty acid ester of the Example itself seems to be enough to control the microorganism itself, and the preservative It does not need to be added.

 From the above description, it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. In this regard, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention without departing from the scope of the present invention as defined by the appended claims.

Claims (8)

Wherein the fatty acid ester is reacted in a eutectic solvent during the reaction, wherein the fatty acid ester is obtained by reacting a fatty acid having a carboxylic acid group in a molecule with a sugar.
The method according to claim 1,
Wherein the eutectic solvent is a hydrogen bond of a saccharide, choline chloride, betaine, a mixture thereof, or a saccharide.
The method according to claim 1,
Wherein the fatty acid is at least one selected from capric acid, lauric acid, myristic acid, pervylic acid, palmitic acid, stearic acid, oleic acid, linolenic acid and arachidonic acid.
The method according to claim 1,
The sugars are monosaccharides, disaccharides. A polysaccharide, a polysaccharide, and a polysaccharide.
The method according to claim 1,
Wherein the production method comprises reacting 100 to 300 parts by weight of the fatty acid, 100 to 200 parts by weight of the eutectic solvent and 0.01 to 10 parts by weight of the catalyst with respect to 100 parts by weight of the fatty acid.
The method according to claim 1,
Wherein the method comprises reacting 100 to 500 parts by weight of the fatty acid with 100 parts by weight of the fatty acid and 0.01 to 10 parts by weight of the catalyst.
A composition comprising a saccharide fatty acid ester prepared by a process according to any one of claims 1 to 5.
The method according to claim 6,
Wherein the composition has one of the formulations selected from the personal care and home care product groups.

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