Fatty acid ester quaternary ammonium salt prepared using recycled oil

Abstract

The present invention relates to a fatty acid ester quaternary ammonium salt surfactant obtained by performing an amine esterification reaction and a quaternization reaction of fatty acids, which are obtained through one or more steps selected from the group consisting of decolorization, degumming, partial hydrogenation, fatty acid decomposition, and fatty acid purification of coffee oil extracted from coffee grounds, wherein a structure in which fatty acid residues derived from the coffee grounds are esterified accounts for 45 wt% or greater of 100 wt % of the total cationic surfactant. In addition, the fatty acid ester quaternary ammonium salt comprises 40 wt% or greater of diesterquat and 20 wt% or less of triesterquat, and thus has the advantages of high flexibility, good absorption, and excellent long-term storage stability.

Description

Quaternary ammonium salt of fatty acid ester manufactured using recycled oil

[0001] The present invention relates to the production of a quaternary ammonium salt of fatty acid ester as a cationic surfactant using recycled oil.

[0002]

[0003] Currently, most fatty acid ester quaternary ammonium salts are manufactured from palm oil and are mainly used as fabric softeners and hair conditioners.

[0004] Demand for palm oil is increasing every year, and the destruction of tropical rainforests due to palm oil cultivation is causing steadily increasing damage, such as causing habitat loss and climate problems, and the serious problem of carbon emissions is also emerging as a social issue.

[0005] Meanwhile, with population growth and rising demand for food and beverages, bio-byproducts, including coffee grounds, are increasing. Various developments utilizing bio-byproducts are attracting attention as significant developments, as they are also linked to reduced carbon emissions. Due to the growing demand for coffee, over 10 million tons of coffee grounds are generated globally each year, and the disposal of these grounds generates approximately 3.4 million tons of CO2 annually.

[0006]

[0007] In the present invention, we attempted to develop a cationic surfactant by recycling discarded coffee grounds as a substitute for palm oil.

[0008]

[0009] The purpose of the present invention is to provide a cationic surfactant using oil extracted from discarded coffee grounds.

[0010] Another object of the present invention is to provide a fabric softener composition comprising the cationic surfactant.

[0011]

[0012] The present invention is a surfactant manufactured using a fatty acid having a purity of 90% or more obtained by subjecting coffee oil extracted from coffee grounds to decolorization, degumming, partial hydrogenation, fatty acid decomposition or fatty acid purification steps, wherein the proportion of diester quat is 40 wt% or more and the proportion of triester quat is 20 wt% or less among the total synthesized quaternized surfactants, and has the advantages of high flexibility, good absorbency and excellent long-term storage stability.

[0013]

[0014] Figure 1 relates to a hydrolysis and distillation device used for fatty acid hydrolysis and separation and purification of coffee oil derived from coffee grounds.

[0015]

[0016] As one embodiment for achieving the above object, the present invention provides a cationic surfactant represented by chemical formula 1, which is manufactured by carrying out an esterification reaction and a quaternization reaction of a fatty acid with an amine.

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1,

[0020] R1 is selected from the group consisting of CH3, CH2CH2OH and CH2CH2COOR,

[0021] R2 is OH or COOR,

[0022] M is selected from the group consisting of Cl, CH3SO4 and CH3CH2SO4,

[0023] The above fatty acid is obtained by subjecting coffee oil extracted from coffee grounds to one or more steps selected from the group consisting of decolorization, degumming, partial hydrogenation, fatty acid decomposition, and fatty acid purification.

[0024] R is a fatty acid residue obtained by performing an amine esterification reaction and a quaternization reaction on the fatty acid obtained above,

[0025] The above cationic surfactant has a structure in which R is esterified, which accounts for at least 45 wt% of the total 100 wt%.

[0026] In the present invention, coffee oil extracted from coffee grounds is subjected to one or more steps selected from the group consisting of decolorization, degumming, partial hydrogenation, fatty acid decomposition, and fatty acid purification, and fatty acids are obtained by subjecting the resulting fatty acid to an amine esterification reaction and a quaternization reaction, thereby producing a cationic surfactant represented by chemical formula 1.

[0027] In addition, R of the cationic surfactant represented by the above chemical formula 1 corresponds to a fatty acid residue obtained by subjecting coffee oil extracted from coffee grounds to one or more steps selected from the group consisting of decolorization, degumming, partial hydrogenation, fatty acid decomposition, and fatty acid purification, and subjecting the fatty acid to an amine esterification reaction and a quaternization reaction, and the obtained fatty acid may include one or more selected from the group consisting of oleic acid, palmitic acid, stearic acid, linoleic acid, and linolenic acid.

[0028] In the above cationic surfactant, the diester structure in which two Rs are esterified is at least 45 wt% of the total 100 wt% of the cationic surfactant.

[0029]

[0030] The specific process for manufacturing the cationic surfactant of the present invention is described below.

[0031]

[0032] Extraction of coffee oil from coffee grounds

[0033] Methods for extracting oil from coffee grounds include pressing, organic solvent extraction, supercritical / subcritical extraction, and enzyme extraction. Pressing, supercritical / subcritical processes, and enzyme extraction are environmentally friendly, but are not suitable for mass production and economic feasibility.

[0034] In the present invention, an organic solvent extraction method based on the circular reuse of an extraction solvent is the most economical and efficient method for extracting oil from coffee grounds.

[0035] For oil extraction from the above coffee grounds, C1~C3 alcohols and solvents such as hexane and acetone can be used. According to the test results of the inventors of the present invention, the extraction efficiency of coffee oil was highest under mixed conditions of hexane and isopropyl alcohol.

[0036] When extracted with hexane alone, approximately 15% oil was obtained from dried coffee grounds containing less than 5% moisture, whereas when extracted with a hexane / isopropyl alcohol mixed solvent, up to 17-20% was extracted depending on the mixing ratio. This is because polar structures such as monoglycerides as well as triglycerides in the oil are extracted and included in isopropyl alcohol.

[0037]

[0038] Primary decolorization of coffee oil

[0039] When coffee oil is mixed with an extraction solvent for decolorization and deodorization, the fluidity is reduced, which has the advantage of facilitating the removal (filtration) of the decolorant (activated carbon or clay). Decolorization can be performed using activated carbon, acid clay, or activated clay, but in the present invention, decolorization can be performed using acid clay. When coffee oil is contacted with acid clay, the acidic portion of the clay donates protons to the pigment molecules, forming positively charged organic cations, and the pigment molecules are fixed to the clay surface by electrostatic bonding.

[0040] First, activated carbon or clay is activated by heating to 100-120℃. At this time, the activated adsorbent increases its surface area and improves its ability to adsorb impurities. After raising the temperature of the mixture containing coffee oil / hexane / isopropyl alcohol to 30-50℃, or more specifically, around 40℃, the activated carbon or clay is added, stirred for 30-60 minutes, and then filtered.

[0041] The color of the coffee oil extracted in the above extraction step was a color of Gardner 40 or higher, but through the decolorization process described above, the color can be improved to around Gardner 32 to 34, 33.

[0042]

[0043] Degumming

[0044] Coffee ground oil contains trace amounts of various components such as free fatty acids, pigments, diterpene alcohols, sterols, phospholipids, metal ions, proteins, and salts in addition to the main component, triglycerides. Although the refining process selection varies depending on the condition of the oil, the degumming process can remove sterols, tocopherols, and phospholipids, which are called gums. After the degumming process using water and acid, the gum and moisture are removed through centrifugation, and then the residual moisture is removed through heating, and activated carbon, acid clay, or activated clay can be injected to perform the secondary decolorization process described below.

[0045] First, the coffee oil, which has undergone a decolorization process, is heated to 80-90°C, and 0.1-0.5 wt% of water is added. This water binds with impurities and helps form insoluble precipitates. Next, 0.05-0.2 wt% of an acid (phosphoric acid, sulfuric acid, etc.) is added. This acid also binds with impurities, promoting precipitate formation and adjusting the pH to create a stable separation environment.

[0046] Stir for 30 to 60 minutes to ensure that the water and acid are thoroughly mixed with the coffee oil that has undergone the bleaching process. The stirring process helps promote sediment formation and keeps the sediment size small.

[0047] Afterwards, centrifuge at 4,000–6,000 rpm for 30–60 minutes to remove sediment. While increasing the amount of water increases the efficiency of removing impurities, it also increases the loss of coffee oil. Furthermore, increasing the amount of acid also increases the impurity removal rate, but this can affect subsequent processes. Therefore, the degumming process can be performed while maintaining the above content.

[0048] Degumming plays an important role in increasing the efficiency of subsequent processes and improving the quality of the final fatty acids, and it also affects the stability of coffee oil and the storage stability of the manufactured cationic surfactant.

[0049]

[0050] Secondary decolorization of coffee oil

[0051] First, activated carbon, clay, or silica gel is heated to 100 to 120°C to activate it. At this time, the activated adsorbent has an increased surface area and an improved ability to adsorb impurities.

[0052] Coffee oil, which has undergone the primary bleaching and degumming process, is heated, activated carbon, clay, or silica gel is added, and the color is decolorized by stirring for 30 to 60 minutes. The remaining color is then filtered out. This process has been shown to improve color to Gardner 10 to 20, depending on variables such as the type of adsorbent, the amount of adsorbent added, and the adsorption time.

[0053] Although the larger the amount and time of the adsorbent, the design takes into account energy consumption and coffee oil loss, and the appropriate amount to use is 0.5 to 1 wt% of activated carbon, 1 to 3 wt% of white clay, and 2 to 5 wt% of silica gel.

[0054]

[0055] Partial hydrogenation reaction

[0056] Partial hydrogenation is a critical process due to the unique carbon distribution of coffee ground oil. While palm oil has a high content of oleic acid, which has a single intramolecular unsaturated bond, of over 35% by weight, coffee ground oil has a high content of linoleic acid, which has two or more intramolecular double bonds, of over 45% by weight. This structure is detrimental to the properties and long-term stability of the cationic surfactant produced in the present invention.

[0057] Specifically, the fatty acid of the coffee ground oil of the present invention includes 32 to 40 wt% of palmityl group (C16:0), 5 to 8 wt% of stearyl group (C18:0), 7 to 10 wt% of oleyl group (C18:1), and 45 to 50 wt% of linoleyl group (C18:2) and linolenyl group (C18:3) having 18 carbon atoms and two or more double bonds (≥C18:2). In addition, it may include a very small amount of saturated or fluorinated fatty acid having C20.

[0058] Surfactants made with fatty acids with two or more double bonds are prone to oxidation, resulting in poor storage stability and an unpleasant odor. Therefore, a hydrogenation reaction is necessary to convert the linoleyl (C18:2) and linolenyl (C18:3) groups in the fatty acids of coffee ground oil to oleyl (C18:1) or stearyl (C18:0) groups. However, if full hydrogenation is performed to increase only the stearyl group content, this can have the side effect of reducing emulsification stability and sweat absorbency. Therefore, a technology is required to evenly increase the ratio of stearic acid and oleic acid by carefully selecting the degree of hydrogenation.

[0059] (In Table 1 below, C18:1 indicates that the total number of carbons in the fatty acid is 18 and the number of double bonds in the fatty acid is 1, and ≥C18:2 indicates that the total number of carbons in the fatty acid is 18 and the number of double bonds in the fatty acid is 2 or more.)

[0060] Comparison of alkyl groups of fatty acids in coffee ground oil and palm oil (weight%) Unit (weight%) C16:0 C18:0 C18:1≥C18:2 Coffee oil 32~40 5~87~10 45~50 Palm oil 40~45 3~5 38~44 8~13

[0061] The cationic surfactant of the present invention is a quaternary ammonium salt of a fatty acid ester represented by Chemical Formula 1, and is used as a fabric softener for clothing or as a softener product in the textile industry. The softener product must have both softness and absorbency. However, softness and absorbency have opposing characteristics, such that when there is a lot of unsaturated fatty acids, absorbency improves but softness decreases, and when there is a lot of saturated fatty acids, softness improves but absorbency decreases. Among saturated fatty acids, the stearyl group (C18:0) has a characteristic that is advantageous in softness compared to the palmityl group (C16:0).

[0062] Meanwhile, among saturated fatty acids, if the proportion of stearyl group (C18:0) is increased too much just for the sake of improving softness, the stability of the emulsified phase of the cationic surfactant will decrease, so an appropriate mixing composition is important.

[0063] Therefore, it is important to maintain the content of palmityl group (C16:0) while converting some of the double bonds of linoleyl group (C18:2) and linolenyl group (C18:3) into stearyl group (C18:0) and some into oleyl group (C18:1) through hydrogenation reaction to create a ratio that allows for both softness and absorbency.

[0064] The above partial hydrogenation reaction can be carried out by mixing coffee oil and water that have undergone primary decolorization, degumming, and secondary decolorization under conditions of 10 to 25 wt% of NiO / Al2O3 catalyst having a ratio of 1:6 to 1:9, at a ratio of 1:0.5 to 1:3, and then carrying out the hydrogenation reaction under conditions of a pressure of 30 to 70 bar for 1 to 5 hours after reaching 250 to 270°C.

[0065] In the present invention, the term "hydrogenation" reaction generally refers to a reaction of adding hydrogen to an unsaturated bond and is a type of reduction.

[0066] In one embodiment of the present invention, the hydrogenation reaction was performed in a 300 mL stainless steel batch reactor, the reaction was performed at a maximum pressure of 30 to 70 bar, and the reaction mixture was composed of 100 g of coffee oil that had undergone primary decolorization, degumming, and secondary decolorization, and 100 g of water, so that the coffee oil / water raw material ratio was 1, and the stirring speed was maintained at 250 rpm.

[0067] At a NiO / Al2O3 ratio of 1:6 to 1:9, specifically, at 10 to 25 wt% of NiO / Al2O3 catalyst of 11.47 / 88.47, the reaction was carried out at 250 to 270°C for 1 to 3 hours, and the hydrolysis state was observed to analyze the degree of hydrogenated alkyl groups according to the reaction time and reaction temperature. As a result, in order to obtain the desired degree of hydrogenation under the above catalytic conditions, 25 wt% of the catalyst and a reaction time of about 3 hours were required, and it was confirmed that at a reaction temperature of 250°C and under reaction conditions of 3 hours, more than 90 wt% of the polyunsaturated bonds (≥C18:2) were converted to oleyl groups (C18:1), and at a reaction temperature of 270°C and under reaction conditions of 3 hours, more than 90 wt% of the polyunsaturated bonds (≥C18:2) were converted to monounsaturated bonds or saturated bonds, and among these, more than 30 wt% were confirmed to be converted to saturated bonds, i.e., stearyl groups (C18:0).

[0068] The above coffee oil has a ratio of two or more unsaturated bonds per fatty acid molecule of 45 wt% or more, and through partial hydrogenation of the coffee oil having a ratio of two or more unsaturated bonds (≥C18:2) of 45 wt% or more, the ratio of two or more unsaturated bonds per fatty acid molecule is lowered to within 11 wt%, thereby increasing the total single unsaturated bond to 30 wt% or more.

[0069] The distribution of fatty acids of coffee oil that has undergone the above partial hydrogenation is characterized by 30 to 50 wt% of palmityl group (C16:0), 10 to 30 wt% of stearyl group (C18:0), and 30 to 50 wt% of oleyl group (C18:1), and includes 10 wt% or less of linoleyl group (C18:2) and 1 wt% or less of linolenyl group (C18:3).

[0070] Specifically, the distribution of the partially hydrogenated coffee oil fatty acids includes 30 to 50 wt% of palmityl group (C16:0), 10 to 30 wt% of stearyl group (C18:0), 30 to 50 wt% of oleyl group (C18:1), and 10 wt% or less, preferably 0.1 to 10 wt%, of linoleyl group (C18:2). In addition, the linolenyl group (C18:3) includes 1 wt% or less, preferably 0 to 1 wt%.

[0071] The above hydrogenation reaction is an example, and the desired ratio can be obtained under various catalyst conditions and reaction conditions.

[0072]

[0073] Coffee waste oil splitting and refining

[0074] Chemical and physical refining are used to refine coffee oil. Chemical refining, which involves hydrolyzing coffee oil with methanol or converting it to fatty acid soaps with a strong alkali, then chemically reducing it to fatty acids, has the advantage of successfully reducing levels of free fatty acids (FFAs), phospholipids, waxes, aldehydes, and ketones. However, the use of chemicals makes it unfriendly and generates a large amount of waste byproducts.

[0075] Physical refining is preferred because it reduces the loss of triglycerides (neutral fat), minimizes the use of chemicals and water, and allows the recovery of high-quality free fatty acids. In the present invention, considering the impact on the environment, it is preferable to purify through a physical route as shown in Fig. 1.

[0076] The reaction of decomposing coffee oil into fatty acids through the above partial hydrogenation reaction can utilize the traditional Colgate-Emery process, which is widely used, and fatty acid decomposition was carried out at a ratio of coffee oil neutral lipid:water = 1:1 at a temperature of 220 to 250°C, 50 to 70 bar, 300 to 400 rpm, specifically, 60 bar and 350 rpm, without a catalyst. In this case, it was confirmed in Examples 1 to 7 that more than 95 wt% of the neutral lipid of the coffee oil was converted into fatty acids. This method enables a high level of hydrolysis without a catalyst due to the high temperature and countercurrent flow, and the residual energy of the splitter discharge stream is used to evaporate moisture in the stream, which has the advantage of reducing energy consumption in subsequent processing.

[0077] In addition, the purification (separation) of the decomposed fatty acids utilizes a distillation method. In the present invention, a small-scale distillation column was manufactured, and the inside of the column was set to 5 to 15 torr, the top to 250 to 300°C, and the bottom to 180 to 200°C, specifically 10 torr, the top to 280°C, and the bottom to 190°C, and then fatty acids and glycerin were separated.

[0078] The coffee oil fatty acid obtained through the above distillation step had a Gardner color of 2 to 5 at a temperature of 70°C or higher, and a fatty acid content of 90% or higher.

[0079] The above decomposition and purification steps are examples, and the desired ratio can be obtained under various temperatures, pressures, and reaction conditions.

[0080] The fatty acid obtained by going through one or more steps selected from the group consisting of decolorization, degumming, partial hydrogenation, fatty acid decomposition and fatty acid purification may include one or more selected from the group consisting of oleic acid, palmitic acid, stearic acid, linoleic acid and linolenic acid.

[0081] The coffee oil fatty acid that has undergone the above partial hydrogenation process contains 30 to 50 wt% of palmitic acid (C16:0), 10 to 30 wt% of stearic acid (C18:0), 30 to 50 wt% of oleic acid (C18:1), and 10 wt% or less, preferably 0.1 to 10 wt%, of linoleic acid (C18:2), and 1 wt% or less, preferably 0 to 1 wt%, of linolenic acid (C18:3).

[0082]

[0083] Synthesis of quaternary ammonium salts of fatty acid esters

[0084] The coffee oil fatty acid used in the synthesis of the cationic surfactant is characterized by having a conversion rate of 90% or higher, i.e., a purity of the fatty acid of 90% or higher.

[0085] Specifically, the coffee oil fatty acid used in the synthesis of the above cationic surfactant is a fatty acid obtained by subjecting coffee oil extracted from coffee grounds to a pretreatment process such as primary decolorization, degumming, secondary decolorization, partial hydrogenation, fatty acid decomposition or purification (separation), and has a fatty acid purity of 90% or higher.

[0086] A fatty acid derived from coffee grounds obtained through the above pretreatment process is used to produce a quaternary ammonium salt of fatty acid ester through esterification and quaternization.

[0087] In addition, the fatty acid used in the present quaternary surfactant uses a fatty acid derived from coffee extract oil, and in order to improve the characteristic that the coffee extract oil has a ratio of two or more unsaturated bonds (≥C18:2) that adversely affects storage stability of 45 wt% or more, while the C18:0 ratio that has a good effect on softness is low at 10 wt% or less, a selective hydrogenation reaction using a catalyst is used to increase C18:0 stearic acid to 10 to 30 wt%, increase oleic acid, which is a C18:1 monounsaturated fatty acid, to 30 to 50 wt%, and lower the ratio of two or more unsaturated bonds (≥C18:2) to 11 wt%, specifically, 5 wt% or less.

[0088] The first step of esterification is a synthetic method in which coffee-derived fatty acids and tertiary alkanolamines that have undergone the above-mentioned pretreatment process are combined under high-temperature vacuum conditions, and the second step is a synthetic method in which a quaternary ammonium salt is converted using a quaternary agent.

[0089] Step 1

[0090]

[0091] Step 2

[0092]

[0093] In the specific first step of synthesis, the reactor temperature is raised to 90°C and coffee fatty acids are added. The temperature is maintained at 80-90°C, an alkanolamine such as triethanolamine is added, and then the temperature is raised to 120-190°C. An esterification reaction is performed under vacuum conditions for 2-6 hours to produce an amine ester. This reaction is performed under nitrogen atmosphere and a reduced pressure of 10-20 torr.

[0094] In the above step 1 esterification reaction, the molar ratio of fatty acid and amine is characterized by being 1.4:1 to 1.9:1. If the fatty acid molar ratio is less than 1.4, a large amount of monoester is generated, reducing softness, and if the fatty acid molar ratio exceeds 1.9, the generation of unreacted fatty acid increases, or the triester content increases, lowering flexibility, absorbency, etc., and may even lower the storage stability of the product.

[0095] The above fatty acid may be a fatty acid obtained by pretreatment through one or more steps selected from the group consisting of the above-mentioned decolorization, degumming, partial hydrogenation, fatty acid decomposition, and fatty acid purification.

[0096] Meanwhile, as the diester ratio increases, it is advantageous to deliver water-insoluble active ingredients, including fragrances, of consumer products. This is because the final fatty acid ester quaternary ammonium salt can easily form vesicles to contain active ingredients and deliver them to fibers or clothing.

[0097] In the above 2nd step, for the quaternization reaction, a reaction solvent such as ethanol, isopropyl alcohol or glycol was mixed with the amine ester obtained in the 1st step process, and then a quaternization agent such as dimethyl sulfate was added dropwise at 50 to 60°C, specifically 55°C, to cause a reaction. At this time, heat was generated, so it was controlled with cooling water, and care was taken not to exceed 60°C. After the dropwise addition of dimethyl sulfate was completed, the mixture was stirred for 1 to 5 hours, specifically 3 hours, while maintaining the temperature at 60°C, and the final pH was maintained at 3.3 to 4.0.

[0098] The amine used in the above-mentioned first step synthetic process is not limited to triethanolamine, and various tertiary amines such as dimethylethanolamine and methyldiethanolamine can be used, and the quaternizing agent is also not limited to dimethyl sulfate, and various quaternizing agents such as methyl chloride and diethyl sulfate can be used.

[0099] In the above 2nd step, when producing a cationic surfactant, the molar ratio of the amine ester produced in the esterification reaction of the 1st step and the quaternizing agent used in the quaternizing reaction may be 0.9:1 to 1:0.9. If the amine ester molar ratio is less than 0.9, the yield of the fatty acid ester quaternary ammonium salt produced is reduced, and the quaternizing agent, which is a hazardous substance, remains as an unreacted product. If the amine ester molar ratio exceeds 1.0, the adsorption power to the fiber is reduced, and the water-insoluble amine ester increases, which may lower flexibility and absorbency as well as the storage stability of the product.

[0100] The quaternary ammonium surfactant manufactured through the esterification reaction of the first step and the quaternization reaction of the second step is characterized in that the diester structure in which two Rs are esterified is 45 wt% or more out of 100 wt% of the total cationic surfactant, and the proportion of the triester structure in which three Rs are esterified is 20 wt% or less.

[0101] In addition, when the ratio of diesterquat in the cationic surfactant represented by chemical formula 1 is 40 wt% or more, it has the advantage of improving flexibility, and when the ratio of triesterquat is 20 wt% or less, it has the advantage of improving oxidation stability and storage stability, and when the total unsaturated bonds of the coffee oil fatty acid that has gone through the pretreatment step used in the production of the quaternized surfactant are 30 to 60 wt%, it has the advantage of not significantly damaging flexibility, improving absorbency, and improving emulsification stability.

[0102] Specifically, among the entire quaternized surfactant, the proportion of diester quat is 40 to 90 wt%, the proportion of monoester quat is 10 to 45 wt%, and the proportion of triester quat is 0 to 20 wt%. In addition, in the present invention, the total unsaturated bonds of the coffee oil fatty acids that have gone through the pretreatment step used in the production of the quaternized surfactant are 30 to 60 wt%, more specifically, the monounsaturated bonds are 30 to 50 wt%, and the total unsaturated bonds are 30 to 60 wt%, which is the best when the aforementioned flexibility, oxidation stability, storage stability, absorption capacity, etc.

[0103]

[0104] In another aspect, the present invention provides a fabric softener composition comprising the cationic surfactant.

[0105] The term "cationic surfactant" in the present invention is as described above, and can be manufactured by the synthetic process as described above.

[0106] The above fabric softener or industrial fabric softener composition may contain 0.1 to 40 wt% of the cationic surfactant, and specifically 3.0 to 25 wt%.

[0107] The above fabric softener composition may be a household fabric softener or an industrial fabric softener composition.

[0108] The cationic surfactant of the present invention is characterized by using coffee oil as a starting material, and the cationic surfactant manufactured in this way can be very usefully used in product groups that come into direct contact with the human body by being absorbed into hair or clothing, such as hair conditioners and household fabric softeners, and can also be utilized as a softener in the clothing industry that provides softness to clothing in particular.

[0109]

[0110] In another aspect, the present invention provides a method for producing a cationic surfactant represented by chemical formula 1, comprising the steps of: a first step of producing an amine ester by esterifying a fatty acid with an amine; and a second step of performing a quaternization reaction on the produced amine ester with a quaternizing agent.

[0111] In the present invention, the terms “cationic surfactant” and “method for producing the same” are as described above.

[0112] The matters mentioned in the cationic surfactant of the present invention are equally applicable to the method for producing the cationic surfactant, unless they are contradictory.

[0113]

[0114] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0115]

[0116] <Synthetic Example> Preparation of quaternary ammonium salt of fatty acid ester

[0117] Example 1.

[0118] Partial hydrogenation of coffee oil after extraction and decolorization was performed. The hydrogenation reaction was performed in a 300 mL stainless steel batch reactor, and the maximum pressure was 30 to 70 bar. The reaction mixture consisted of 100 g of coffee oil and 100 g of water so that the oil / water raw material ratio was 1, and the stirring speed was maintained at 250 rpm. 25% of a NiO / Al2O3 catalyst with a NiO / Al2O3 ratio of 11.47 / 88.47 was added, and the reaction was performed for 3 hours after reaching 270°C.

[0119] The obtained partially hydrogenated fatty acid triglycerides were decomposed using a tubular high-pressure reactor using the Colgate-Emery process without a catalyst, at a temperature of 220-250℃, and 60 bar, by adding coffee oil neutral lipids:water = 1:1 ratio, and the result was that more than 95% of the neutral lipids were converted into a fatty acid mixture. The obtained fatty acid mixture was separated from fatty acids, glycerin, and other byproducts in a small-scale distillation column by setting the inside pressure of the column to 10 torr, the top to 280℃, and the bottom to 190℃, and fatty acids with a fatty acid content of 94% were obtained.

[0120] 57.5 g of the obtained fatty acid was placed in a reactor, the temperature was set to 90°C, and dissolved. After nitrogen replacement for 20 minutes, the reactor temperature was maintained at 90°C, 18.4 g of triethanolamine was placed, mixed well, and the reactor temperature was increased to 190°C. Then, sodium methoxide was used as a catalyst and reacted for 4 hours to produce an amine ester.

[0121] 15 g of isopropyl alcohol for fluidity was added to the manufactured amine ester, mixed well, and 14.2 g of dimethyl sulfate was added to manufacture a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0122]

[0123] Example 2.

[0124] Fatty acids were obtained by synthesis under the same conditions as in Example 1, and 54.8 g of the obtained fatty acids were charged into a reactor, the temperature was set to 90°C, and dissolved. After nitrogen replacement for 20 minutes, the reactor temperature was maintained at 90°C, 18.4 g of triethanolamine was charged, mixed well, and the reactor temperature was increased to 190°C. Then, sodium methoxide was used as a catalyst and the reaction was carried out for 4 hours to produce an amine ester.

[0125] 15 g of isopropyl alcohol for fluidity was added to the manufactured amine ester, mixed well, and 14.2 g of dimethyl sulfate was added to manufacture a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0126]

[0127] Example 3.

[0128] Synthesis was performed under the same conditions as Example 1, except that the hydrogenation temperature was lowered from 270°C to 250°C to perform the hydrogenation reaction, and the remaining reactions were performed in the same manner to produce a quaternary ammonium salt of fatty acid ester with an active content of 85%.

[0129]

[0130] Example 4.

[0131] Synthesis was performed under the same conditions as Example 2, except that the hydrogenation temperature was lowered from 270°C to 250°C to perform the hydrogenation reaction, and the remaining reactions were performed in the same manner to produce a quaternary ammonium salt of fatty acid ester with an active content of 85%.

[0132]

[0133] Example 5.

[0134] Fatty acids were obtained by synthesis under the same conditions as in Example 1, and 60.9 g of the obtained fatty acids were charged into a reactor, set at 90°C, and dissolved. After nitrogen replacement for 20 minutes, the reactor temperature was maintained at 90°C, 14.7 g of methyldiethanolamine was charged, mixed well, and the reactor temperature was increased to 190°C. Then, sodium methoxide was used to react for 4 hours to produce an amine ester.

[0135] 15 g of isopropyl alcohol for fluidity was added to the manufactured amine ester, mixed well, and 14.2 g of dimethyl sulfate was added to manufacture a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0136]

[0137] Example 6.

[0138] Synthesis was performed under the same conditions as Example 5, except that the hydrogenation temperature was lowered from 270°C to 250°C to perform the hydrogenation reaction, and the remaining reactions were carried out in the same manner to produce a quaternary ammonium salt of fatty acid ester with an active content of 85%.

[0139]

[0140] Example 7.

[0141] The amine ester reaction was carried out under the same conditions as Example 1.

[0142] Afterwards, 15 g of isopropyl alcohol was added to the amine ester for fluidity and mixed well, and 15.9 g of diethyl sulfate was added to produce a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0143]

[0144] Comparative Example 1.

[0145] Fatty acids were obtained by synthesis under the same conditions as in Example 1, and 45.7 g of the obtained fatty acids were introduced into a reactor, the temperature was set to 90°C, and dissolved. After nitrogen replacement for 20 minutes, the reactor temperature was maintained at 90°C, 18.4 g of triethanolamine was introduced, mixed well, and the reactor temperature was raised to 190°C. Then, sodium methoxide was used to react for 4 hours to produce an amine ester.

[0146] 15 g of isopropyl alcohol for fluidity was added to the manufactured amine ester, mixed well, and 14.2 g of dimethyl sulfate was added to manufacture a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0147]

[0148] Comparative Example 2.

[0149] Fatty acids were obtained by synthesis under the same conditions as in Example 1, and 66.0 g of the obtained fatty acids were charged into a reactor, set to 90°C, and dissolved. After nitrogen replacement for 20 minutes, the reactor temperature was maintained at 90°C, 18.4 g of triethanolamine was charged, mixed well, and the reactor temperature was increased to 190°C. Then, sodium methoxide was used to react for 4 hours to produce an amine ester.

[0150] 15 g of isopropyl alcohol for fluidity was added to the manufactured amine ester, mixed well, and 14.2 g of dimethyl sulfate was added to manufacture a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0151]

[0152] Comparative Example 3.

[0153] Comparative Example 3 is a product manufactured by adding the same ratio of currently commercialized palm stearic fatty acid and palm oleic acid. 28.5 g of palm stearic fatty acid and 29.0 g of palm oleic acid were added to a reactor, and the temperature was set to 90°C before dissolving. After nitrogen purging for 20 minutes, the reactor temperature was maintained at 90°C, 18.4 g of triethanolamine was added, and the mixture was mixed well. The reactor temperature was then raised to 190°C. Then, sodium methoxide was used and the mixture was reacted for 4 hours to manufacture an amine ester.

[0154] 15 g of isopropyl alcohol for fluidity was added to the manufactured amine ester, mixed well, and 14.2 g of dimethyl sulfate was added to manufacture a quaternary ammonium salt of fatty acid ester with an active ingredient of 85%.

[0155]

[0156] Comparative Example 4.

[0157] Coffee oil was extracted, and 60.9 g of coffee oil and 16.3 g of triethanolamine were reacted at 180°C under a nitrogen atmosphere in a reactor at a pressure reduced to 20 torr, and the reaction was carried out for 6 hours while removing the generated water. Sodium methoxide was used as a catalyst. After the reaction was completed, the acid value was 2 or less. After cooling, 13 g of isopropyl alcohol was added thereto, and 12.8 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature below 55°C. After the addition was completed, the reaction was carried out at 55°C for 5 hours and then terminated.

[0158]

[0159] [Example] Physical property evaluation

[0160] The properties of the above examples and comparative examples were evaluated based on the following criteria.

[0161]

[0162] [Example 1] Flexibility Assessment

[0163] Fabric softener samples were prepared by adding 7.1 wt% of the cationic surfactants of the examples and comparative examples to purified water at 70°C and then strongly dispersing them.

[0164] Using the standard dosage of general detergent, commercially available 100% cotton towels were washed 5 times in a washing machine, 5 per sample, and then dehydrated. After setting the washing machine to the rinse cycle, the manufactured fabric softener composition was dissolved in the standard dosage (6.7 ml / 10 liters of wash water), and the dehydrated cotton towels were placed in each rinse water to soften them and then dehydrated. The dehydrated cotton towels were dried under conditions of 20°C and 65% relative humidity for 24 hours.

[0165] Next, the fabric softener compositions manufactured using the cationic surfactants of Examples 1 to 7 and Comparative Examples 1 to 4 were subjected to a sensory evaluation to evaluate the degree of touch, thereby evaluating flexibility, using experienced test subjects.

[0166] Flexibility was assessed by giving a flexibility score from 1 to 5 points for the degree of tactile sensitivity, and the evaluation score was calculated as follows.

[0167] Evaluation score = Sum of 10 evaluation scores / 10 Evaluation score 5 points 4 points 3 points 2 points 1 point Evaluation criteria Very good Good Average Somewhat low Very low

[0168]

[0169] [Test Example 2] Absorbency Evaluation

[0170] The absorbency of the fabric softener manufactured in Test Example 1 was measured.

[0171] A standard cotton cloth was cut into 2 cm x 15 cm pieces, separated into weft and warp yarns, and then subjected to a softening treatment in the same manner as in the flexibility evaluation test described above, followed by dehydration and drying for 24 hours under conditions of 20°C and 65% relative humidity. The treated cotton cloth was hung vertically using a clamp and a weight, and the ends of the cotton cloth were simultaneously immersed in an aqueous solution of a water-soluble blue dye diluted to 0.1%. 20 minutes after immersing the cotton cloth, the height of the blue dye rise was measured, and the above process was repeated three or more times, and the absorbency was evaluated as the average value.

[0172] Absorption height (mm) 100 or more 70~100 40~70 40 or less Evaluation criteria Very good Excellent Average Poor

[0173]

[0174] [Example 3] Quantitative analysis of mono-, di-, and triesters

[0175] Reverse phase high performance liquid chromatography (RP-HPLC) on a CN column was used for separation and analysis of the reaction mixture, and the mobile phase was 10 parts of tetraphenyl phosphonium bromide dissolved in water and isopropanol at a ratio of 70:30. -3 It was composed of M solution and a flow rate of 1 ml / min. Before use, the solvents were mixed and filtered through a purifier system, and the column effluent was monitored by UV absorption measurement at 254 nm, and the analysis process was performed at 50°C.

[0176] Mono-, di-, and triesteramines that were not quaternized were detected at 4.0, 5.2, and 5.6 minutes, respectively, and mono-, di-, and triesterquats that were quaternized were detected at 17.2, 20.5, and 22.3 minutes, respectively, and quantitative analysis was calculated using peak area ratios.

[0177]

[0178] [Evaluation Results]

[0179] The carbon distribution of fatty acids of coffee oil used in the above examples and comparative examples is shown. In addition, the results of evaluating the flexibility and absorbency of fabric softeners manufactured using these examples and comparative examples and the alkyl group ratio of the manufactured quaternary surfactants are shown in Table 4.

[0180] The distribution of fatty acids that went through the pretreatment step for obtaining the above fatty acids was confirmed to be, as shown in Table 4, 30 to 50% palmityl group (C16), 10 to 30% stearyl group (C18), 30 to 50% oleyl group (C18:1), 10% or less linoleyl group (C18:2), and 1% or less lenolenyl group (C18:3).

[0181] Examples 1, 2, 5, and 7 and Comparative Examples 1 and 2 used the same fatty acids with increased saturated fatty acid distribution during the hydrogenation process, and Examples 3, 4, and 6 used fatty acids with increased oleic acid content during the hydrogenation process. In this way, by partially hydrogenating coffee oil having a ratio of two or more unsaturated bonds per fatty acid molecule of 45% or more, the ratio of two or more unsaturated bonds per fatty acid molecule was reduced to less than 11%, thereby increasing the total monounsaturated bonds to 30% or more.

[0182] In the total fatty acid ester quaternary ammonium salts of Examples 1 to 7 synthesized using fatty acids that had undergone a pretreatment step having the fatty acid carbon distribution as described above, the proportion of diester quats was 40% or more, the proportion of monoester quats was 45% or less, and the proportion of triester quats was 20% or less. Specifically, among the total quaternized surfactants, the proportion of diester quats was 40 to 90%, the proportion of monoester quats was 10 to 45%, the proportion of triester quats was 0 to 20%, and the proportion of unsaturated bonds in the fatty acids that had undergone the pretreatment step used in the production of the quaternary fatty acid ester quaternary ammonium salts was 30 to 60%.

[0183] In addition, the fatty acid ester quaternary ammonium salts manufactured in Examples 1 to 7 had similar absorbency to the comparative examples, but had good flexibility and had the advantage of excellent long-term storage stability due to a low ratio of triesterquat.

[0184] Carbon distribution of fatty acids (weight %) * Quaternary surfactant (esterquat) ratio (weight %) * C16C18C18:1≥C18:2MonoditriExample 14.810338.228.432.11.338.950.110.2Example 24.610338.228.432.11.341.548.28Example 34.610838.221.737.92.234.654.29Example 44.510838.221.737.92.240.349.17.8Example 5510138.228.432.11. 320.977.60Example 6510138.221.737.92.219.878.80Example 74.810238.228.432.11.337.652.58.8Comparative Example 13.511138.228.432.11.362.432.22.6Comparative Example 23.48838.228.432.11.332.545.321.8Comparative Example 34106302247.50.438.846.912.3Comparative Example 4 ** 3.211239.28.98.743.234.638.28.8

[0185] *This is the result of GC and HPLC analysis. The total sum may not be 100% based on peak area.

[0186] ** Comparative Example 4 was analyzed to have an unreacted glycerin fatty acid ester content of 8-12% and a glycerin content of 5-6%.

[0187]

[0188] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims also fall within the scope of the present invention.

Claims

1. A cationic surfactant represented by chemical formula 1, manufactured by carrying out an esterification reaction and a quaternization reaction of a fatty acid with an amine: [Chemical Formula 1] In the above chemical formula 1, R1 is selected from the group consisting of CH3, CH2CH2OH and CH2CH2COOR, R2 is OH or COOR, M is selected from the group consisting of Cl, CH3SO4 and CH3CH2SO4, The above fatty acid is obtained by subjecting coffee oil extracted from coffee grounds to one or more steps selected from the group consisting of decolorization, degumming, partial hydrogenation, fatty acid decomposition, and fatty acid purification. The above R is a fatty acid residue obtained by performing an amine esterification reaction and a quaternization reaction on the obtained fatty acid, The above cationic surfactant has a structure in which R is esterified in an amount of at least 45 wt% out of the total 100 wt%.

2. In paragraph 1, The above coffee oil has a ratio of two or more unsaturated bonds per fatty acid molecule of 45% by weight or more, A cationic surfactant in which the proportion of two or more unsaturated bonds per fatty acid molecule is lowered to 11 wt% or less through partial hydrogenation of the coffee oil, thereby increasing the total single unsaturated bond to 30 wt% or more.

3. In paragraph 1, A cationic surfactant, wherein the distribution of the fatty acids of the coffee oil that has undergone the above partial hydrogenation is 30 to 50 wt% of palmityl group (C16:0), 10 to 30 wt% of stearyl group (C18:0), 30 to 50 wt% of oleyl group (C18:1), and 10 wt% or less of linoleyl group (C18:2).

4. In paragraph 1, The above cationic surfactant is a cationic surfactant having a diester structure in which two Rs are esterified, which accounts for 45 wt% or more of the total 100 wt% of the cationic surfactant.

5. In paragraph 1, A cationic surfactant, wherein the molar ratio of fatty acid and amine in the above esterification reaction is 1.4:1 to 1.9:

1.

6. In paragraph 1, A cationic surfactant, wherein the molar ratio of the amine ester produced in the above esterification reaction and the quaternizing agent used in the quaternizing reaction is 0.9:1 to 1:0.

9.

7. A fabric softener composition comprising the cationic surfactant of paragraph 1.

Images