KR20180059594A - Synthetic method of Xylitol Sesquicaprylate - Google Patents

Abstract

The present invention relates to a method for synthesizing xylitol sesquicaprylate in a single step through dehydration condensation by adding a solid catalyst to xylitol and caprylic acid. Since the xylitol sesquicaprylate is synthesized via the single step using the solid catalyst, the process is easier and more economical than conventional multistage synthesis methods. In addition, the xylitol sesquicaprylate, according to the present invention, exhibits superior antibacterial activities by containing larger amounts of xylitol monocaprylate than existing products.

Description

Synthetic method of Xylitol sesquicaprylate < RTI ID = 0.0 >

The present invention relates to a method for synthesizing xylitol sesquiacrylate, and more particularly, to a method for synthesizing xylitol sesquiacrylate in a single step through dehydration condensation by adding a solid catalyst to xylitol and caprylic acid .

Many ingredients in cosmetics are emulsified products and contain nutrients of various bacteria such as animal, vegetable oil, mineral oil, fat, carbohydrate. Because of this, it is easily contaminated with microorganisms during long-term storage and use, and preservatives are used to prevent this. Conventional chemical preservatives commonly used in cosmetics include parabens, phenoxyethanol, and chlorphenesin. These chemical preservatives cause allergic and irritation such as sensitive skin and contact dermatitis.

In the meantime, according to a recent study published in the UK, it has been reported that the concentration of parabens in breast cancer cells is much higher than that of normal persons, and parabens can accumulate in the body tissue. In addition, estrogens, a type of female hormone, has been suspected as a substance that can disturb the endocrine system due to its action. In the cosmetics industry, there is an urgent need to study natural antimicrobial substances that can replace parabens.

On the other hand, xylitol sesqui-caprylate, which is known as a preservative, is obtained by dehydration condensation by the esterification reaction of xylitol and fatty acid. When xylitol is reacted with a fatty acid in the form of a polyhydric alcohol, a mixture of mono, di, and triesters is obtained. Previously known studies have shown that, in the synthesis of xylitol monocaprylate, four hydroxy groups of xylitol are protected with acetone and the remaining one hydroxyl group is subjected to dehydration condensation reaction with a fatty acid to obtain diacetonide monocaprylate, Thereby synthesizing xylitol monocaprylate. However, this method has a difficulty to be refined step by step in a multi-step process, and has a low yield.

In the case of currently commercialized xylitol sesquiacrylate, xylitol sesquiquesprylate mixed with mono, di and triesters and xylitol monocaprylate having double antiseptic effect is about 50% of the total It is very low.

Therefore, there is an urgent need to develop a method for synthesizing xylitol sesquiacrylate with a simple process while increasing the content of xylitol monocaprylate.

Korean Patent No. 10-0722673 (registered on May 22, 2007) discloses a cosmetic composition containing glyceryl caprylate and extract of Gossam ginseng as a preservative, wherein glyceryl caprylate and gossam extract Has excellent anti-buoyancy properties and has almost no skin irritation, and has excellent stability in formulation. Korean Patent No. 10-1517142 (registered on Apr. 27, 2015) discloses a cosmetic composition comprising caprylilyl glycol, glyceryl caprylate and propolis as a substitute for a preservative for cosmetics, 0.1 to 1.0% by weight of lysolecall; 0.1 to 1.0% by weight of glyceryl caprylate; And 0.01 to 2.0% by weight of propolis.

In the present invention, it is attempted to complement the disadvantages of existing xylitol sesquiacrylate having a complicated process and a low monocaprylate content by using a multistage synthesis method. However, in order to produce a high yield of xylitol monocaprylate And to provide a novel synthesis method of xylitol sesquiqualitate.

In the present invention, basic zeolite NaX, Basic Zeolite NaY and Amberlyst 15 acid resin are mixed as a solid catalyst after mixing xylitol and caprylic acid, And Nafion are added to the mixture to induce a dehydration condensation reaction. The present invention also provides a method for synthesizing xylitol sesquiqualitate. The production of xylitol sesqui-ka-caprate by the process of the present invention allows synthesis of xylitol sesqui-caprate in a single step, unlike the conventional multi-step synthesis process, to be.

In the present invention, Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin and Nafion are used as the solid catalysts. Respectively. Among them, Basic Zeolite NaX and Basic Zeolite NaY are X and Y type catalysts in which Na ions are exchanged in a zeolite known as crystalline aluminosilicate. Amberlyst 15 acid resin is an acidic metal catalyst. Nafion is a representative solid acid catalyst. 1 to 4, Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, and the like are used in the following description of the present invention. ), And Nafion were designated as Basic NaX, Basic NaY, and Amberlyst 15, respectively.

In the present invention, the xylitol and caprylic acid are preferably mixed at a molar ratio of 3: 1.

In the present invention, the solid catalyst is preferably added in an amount of 0.1 to 2% by weight based on the total weight of the solid catalyst. Preferably, the solid catalyst is Basic Zeolite NaX.

Further, in the present invention, the dehydration condensation reaction can be preferably an esterification reaction. At this time, the dehydration condensation reaction is preferably performed at a temperature of 150 to 230 ° C, more preferably 160 to 180 ° C, and most preferably 170 ° C .

In the present invention, the dehydration condensation reaction is preferably carried out for 6 to 10 hours.

Also, in the present invention, it is preferable that the dehydration condensation reaction is carried out by introducing a predetermined amount (30 cc / min) of nitrogen into the reaction vessel to block air contact.

On the other hand, in the present invention, after completion of the dehydration condensation reaction, the remaining solid catalyst is removed by filtration, and the unreacted xylitol and caprylic acid are removed by distillation under reduced pressure.

Since the present invention synthesizes xylitol sesquiacrylate in a single step using a solid catalyst, the process is easier and more economical than the conventional multistage synthesis method.

Further, the xylitol sesquiacrylate according to the present invention exhibits a superior antimicrobial activity effect because it contains xylitol monocaprylate which is significantly higher than that of the conventional product.

FIG. 1 is a graph showing the reaction time of xylitol sesquiaprylate according to the reaction times of each solid catalyst (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion and conventional acid base catalysts H ₂ SO ₄ and Na ₂ CO ₃ ) Monocaprylate < / RTI > production. (T = 170 DEG C, m _cat. 0.2 wt%).
FIG. 2 is a graph showing the relationship between the amount of xylitol sesquiacrylate monocarbons (basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion and conventional acid catalysts H ₂ SO ₄ and Na ₂ CO ₃ ) Lt; / RTI > (T = 170 DEG C, rxn time: 8 hr)
FIG. 3 is a graph showing the relationship between the reaction temperature of xylitol sesqui-caprylate and the mono-olefin content of each solid catalyst (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion and conventional acid catalysts H ₂ SO ₄ and Na ₂ CO ₃ ) Lt; RTI ID = 0.0 > caprylate < / RTI > production. _{(m cat:. 0.2wt%,} rxn time: 8hr)
4 is a graph (A: Existing product, B: MCA10) of xylitol sesquiacrylate (MCA10) B synthesized in the present invention and the components and content of a conventional product A measured by GC chromatography.

 In the present invention, a single step synthesis method using a solid catalyst has been developed in order to overcome the shortcomings of the conventional multistage synthesis method of xylitol monocaprylate which is known to have a preservative effect.

Synthesis of xylitol sesquiacrylate having a monocaprylate content remarkably increased by a single process by carrying out the reaction under the synthesis conditions in which the content of monocaprylate is maximized by setting an optimum amount of catalyst, reaction temperature and reaction time .

The monocaprylate content of the synthesized xylitol sesquiacrylate was confirmed by GC chromatogram analysis, and it was found that the xylitol sesquiqualpurylate produced by the method of the present invention, rather than the conventional C-type product (monocaprylate content of about 50%), In the case of the rate, it was confirmed that the content of monocaprylate (about 84%) was twice or more.

In addition, three gram-positive bacteria such as Propionibacterium acnes , ( Staphylococcus aureus ) , Bacillus subtilis ( Bacillus subtilis ) and two gram-negative bacteria ( Escherichia (disc diffusion assay, minimum inhibitory concentration (MIC) test, and challenge test) for E. coli and Pseudomonas aeruginosa were carried out. Xylitol sesquiacrylate showed excellent antimicrobial effect against phenoxyethanol and methylparaben which are used as conventional preservatives, and against Gram positive bacteria such as Propionibacterium acnes, Staphylococcus aureus and Bacillus subtilis, The antimicrobial effect of the two Gram-positive bacteria as well as the three Gram-positive bacteria was exhibited when they were prepared in combination with phenoxyethanol. It was also confirmed that the xylitol sesquiacrylate of the present invention is useful as a phenoxyethanol preservative synergist.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following embodiments, and includes modifications of equivalent technical ideas.

[ Example  One: Xylitol  Synthesis of sesquiqaprilate]

Xylitol sesqui caprate was synthesized by the esterification reaction of xylitol and caprylic acid. The amount of monocaprylate produced was analyzed by analyzing the amount of monocaprylate produced depending on the catalyst type, the amount of catalyst, and the synthesis temperature in order to find the optimum conditions for synthesizing xylitol sesquiacrylate Respectively.

First, xylitol (LG Chemical) and caprylic acid (Emery ^ⓡ 657), each three of mixing the equivalent of 1 molar ratio, corresponding to 0.1, 0.2, 0.5, 1, 2wt% of the total weight of the solid catalyst (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion, and SO ₄ , NA ₂ CO ₃ , which are conventional acid catalysts) were added and heat was applied to mix xylitol while dissolving it properly.

The mixed raw materials were subjected to dehydration condensation under various conditions (150, 170, 190, 210, 230 ℃) for various reaction times (2, 4, 6, 8 and 10 hours) under nitrogen condition. During the dehydration condensation reaction, the water produced through the esterification reaction was isolated through a cooling condenser and the reaction was maintained. After the reaction was carried out until the acid value became 7 or less, the solid catalyst was removed by filtration, and the free acid was removed by distillation under reduced pressure to lower the acid value to 1 or less.

After the completion of the reaction, the remaining solid catalyst was removed by filtration. The unreacted raw materials were washed with water and then distilled off under reduced pressure (80 ° C, 5 torr or less), followed by dehydration and deodorization. When the acid value was at least 1 mgKOH / g, the distillation under reduced pressure was terminated and decolorization and deodorization (at 80 DEG C, 1 torr or less) was carried out using activated carbon and diatomaceous earth to obtain xylitol sesquiacrylate.

(1) Determination of optimum reaction time

In order to confirm the optimum reaction time for the synthesis of xylitol sesquiacrylate, the reaction time was changed to 2, 4, 6, 8 and 10 hours at the same temperature (170 ° C) and the same catalyst amount (0.2 wt% Experiments were conducted in different ways.

In the case of using the conventional acid, base catalyst (H ₂ SO ₄ , Na ₂ CO ₃ ) and various solid catalysts (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion) . The results are shown in Table 1 and FIG. 1, respectively. ≪ tb >< TABLE >

Catalyst T (占 폚) ¹⁾ m _{cat .} Reaction time Acid value (wt%) ²⁾ 2 4 6 8 10 H ₂ SO ₄ 170 0.2 18.6 26.6 32.3 45.2 36.3 6.5 Na ₂ CO ₃ 170 0.2 19.1 30.9 38.8 45.6 38.7 5.6 Basic NaX 170 0.2 42.2 66.7 72.5 83.8 75.6 4.3 Basic NaY 170 0.2 39 54 66.6 71.6 67.8 3.2 Amberlyst 15 170 0.2 28.7 31.5 49.4 55.3 34 3.8 Nafion 170 0.2 32.2 34.4 37.1 49.7 32.1 5.1

1) T (占 폚): Reaction temperature

2) m _{cat .} (wt%): The amount of catalyst

As a result of comparing the content of monocaprylate by reaction time, it was confirmed that the content of monocaprylate was about 84% in the case of synthesis by using Basic NaX for 8 hours. Therefore, it was confirmed that the optimum reaction time of xylitol sesquiacrylate was 8 hours.

Figure 1 each of the solid catalyst by (Basic Zeolite NaX, Basic Zeolite NaY , Amberlyst 15 acid resin, Nafion and the conventional acid-base catalytic H ₂ SO ₄ and Na ₂ CO ₃₎ mono xylitol process kwika frill rate of the reaction time Lt; RTI ID = 0.0 > caprylate < / RTI > production. (T = 170 DEG C, m _{cat .} 0.2 wt%).

(2) Confirmation of optimum amount of solid catalyst input

To determine the optimum amount of catalyst for the synthesis of xylitol sesquiacrylate, the catalytic amounts were varied at 0.1, 0.2, 0.5, 1 and 2 wt% under the conditions of the same temperature (170 ° C) and the same reaction time (8 hours) Experiments were performed.

In the case of using the conventional acid, base catalyst (H ₂ SO ₄ , Na ₂ CO ₃ ) and various solid catalysts (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion) , And the amount of monocaprylate produced according to each catalyst amount was compared. The results are shown in Table 2 and FIG.

Catalyst T (占 폚) T (hr) m _{cat .} (wt%) 0.1 0.2 0.5 One 2 H ₂ SO ₄ 170 8 30.2 45.2 51.1 43.1 38.8 Na ₂ CO ₃ 170 8 36.9 45.6 41.1 36.2 32.6 Basic NaX 170 8 71.6 83.8 79.8 74.3 69 Basic NaY 170 8 59 71.6 67.4 61.3 56.1 Amberlyst 15 170 8 50.3 55.3 49.4 44.7 39.6 Nafion 170 8 35.6 49.7 46.5 42.7 33.3

As a result of comparing the amount of monocaprylate production by the amount of catalyst, the content of monocaprylate was the highest when 0.2 wt% of Basic NaX catalyst was used. From this, it was confirmed that 0.2 wt% was the most suitable catalyst amount for the synthesis of xylitol sesquiacrylate.

FIG. 2 is a graph showing the relationship between the amount of xylitol sesquiacrylate monocarbons (basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion and conventional acid catalysts H ₂ SO ₄ and Na ₂ CO ₃ ) Lt; / RTI > (T = 170 DEG C, rxn time: 8 hr)

(3) Determination of optimum synthesis temperature

To determine the optimal reaction temperature for the synthesis of xylitol sesquiacrylate, the reaction temperature was adjusted to 150, 170, 190, 210 and 230 ° C under the same catalytic amount (0.2 wt%) and the same reaction time (8 hours) Experiments were conducted in different ways.

In the case of using the conventional acid, base catalyst (H ₂ SO ₄ , Na ₂ CO ₃ ) and various solid catalysts (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion) , And the amounts of monocaprylate production according to the respective reaction temperatures were compared. The results are shown in Table 3 and FIG.

Catalyst m _{cat .} T (hr) Reaction temperature (캜) (wt%) 150 170 190 210 230 H ₂ SO ₄ 0.2 8 34 45.2 42.2 38.7 31.5 Na ₂ CO ₃ 0.2 8 40.4 45.6 47.7 34.4 29.7 Basic NaX 0.2 8 67.8 83.8 78.8 70.5 67.6 Basic NaY 0.2 8 64.9 71.6 68.8 63 59.6 Amberlyst 15 0.2 8 45.5 55.3 52.6 47.4 41.7 Nafion 0.2 8 32.1 49.7 44.4 39.3 33

The content of monocaprylate was the highest at reaction temperature of 170 ℃ using Basic NaX catalyst. From this, it was confirmed that 170 ° C was most suitable as the optimum reaction temperature for the synthesis of xylitol sesquiacrylate.

FIG. 3 is a graph showing the relationship between the reaction temperature of xylitol sesqui-caprylate and the mono-olefin content of each solid catalyst (Basic Zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion and conventional acid catalysts H ₂ SO ₄ and Na ₂ CO ₃ ) Lt; RTI ID = 0.0 > caprylate < / RTI > production. _{(m cat:. 0.2wt%,} rxn time: 8hr)

Xylitol sesquiacrylate (MCA10) was prepared using the basic NaX catalyst under the conditions of the optimum reaction temperature, reaction time and catalyst amount as described above, which was used in the following Examples 2 to 3.

[ Example  2: Synthesized Xylitol Sesquiacrylate  medium Monocaprylate  Confirm]

In this Example, the content of monocaprylate in the xylitol sesquiacrylate synthesized by the optimum conditions as described in Example 1 was examined.

The content of the monocaprylate of the existing C product (Existing product) and the xylitol sesquiacrylate product (MCA10) synthesized in Example 1 was confirmed by GC chromatography and the column was Agilent HP-5 25m x 0.2mm x 0.11 mu m, 19091J-002) was used. The oven was maintained at an initial temperature of 150 占 폚 for 5 minutes, then elevated to 280 占 폚 at a rate of 10 占 폚 / min and held at 280 占 폚 for 10 minutes. Then, the content of the compound was determined using the area percent method, and the results are shown in Table 4 and FIG. A in Table 4 is the existing product, and B is the MCA10 of the present invention.

Retention time Compound content(%) A ¹⁾ B ²⁾ 2.1 Caprylic acid 2.4 - 2.6 1,4- & 1,5-anhydroxylitol 2.6 0.6 10 - 12 XMC & AMC ^{3 )} 49.6 83.8 15 - 16 XDC & ADC ^{4 )} 39.3 13.9 20 XTC & ATC ^{5 )} 3.46 1.2

1) A: Existing product

2) B: MCA10 (T = 170, m _{cat .} 0.2 wt%, rxn time: 8 hr, Cat.

3) XMC: Xylitol monocaprylate, AMC: 1,4 & 1,5 anhydroxylitol monocaprylate

4) XDC: Xylitol dicaprylate, ADC: 1,4 & 1,5-anhydroxylitol dicaprylate

5) XTC: Xylitol tricaprylate, ATC: 1,4 & 1,5-anhydroxylitol tricaprylate

As a result of the experiment, peaks having retention times (RT) values of 5 or less were estimated as unreacted xylitol and caprylic acid, and respective peaks derived from RT10-12, RT16-17 and RT20-21 were found as xylitol mono, di, As a caprylate, it was confirmed that the content was dependent on the retention time (RT) value.

It was confirmed that the xylitol sesquiacrylate product (MCA10) of the present invention contains about 84% of xylitol monocaprylate, and when compared with the monocaprylate content of about 50% of the existing product of Company C, ≪ / RTI > product MCA10 contains a large amount of monocaprylate.

FIG. 4 is a graph (A: Existing product, B: MCA10) showing the components and contents of xylitol sesquiacrylate (MCA10) B synthesized in the present invention and the product A of the conventional C company.

[ Example  3: Buoyancy  Measure]

In this Example, the agar diffusion method, the minimum inhibitory concentration measurement, and the load measurement experiment were carried out to confirm the flushing force of the xylitol sesquiacrylate product (MCA10) produced in Example 1 above.

(1) Measurement of the buoyancy force by the disk diffusion method (DISC DIFFUSION ASSAY)

The antimicrobial activity of conventional C-products (including about 50% of monocaprylate) and MCA10 (including monocaprylate of 80%) of xylitol sesquiqualrylate of the present invention was measured on a total of five kinds of skin- Respectively. Three gram-positive bacteria, Propionibacterium acnes ) , Staphylococcus aureus ( Staphylococcus aureus ) and Bacillus ( Bacillus subtilis ) and Escherichia coli (two species of gram-negative bacteria) and Pseudomonas aeruginosa ) was used as a test strain and disc diffusion assay was used.

The cultured strains were adjusted to 10 ⁶ to 10 ⁷ CFU / ml, and then 100 μl of each strain cultured on a plate medium was sterilized by using a sterilizing cotton swab. The samples were 0.5 and 2.5 mg per disc, (Diameter 8 mm, Roshi kaisha. Ltd., Tokyo, Japan), followed by drying to volatilize the solvent.

The antimicrobial activity was measured by measuring the size of the clear zone (mm) produced around the disk after culturing the plate with the absorbed paper disks in close contact with each other on a plate-ground flat plate culture medium. Are shown in Table 5 below. The control group was measured by the same method using phenoxyethanol and methylparaben which is used as a conventional cosmetic preservative. A in Table 5 below is a conventional C company product, and B is an MCA10 product of the present invention.

Strains Zone diameter (mm) Gram positive bacteria Gram-negative bacteria S. aureus P. acnes B. subtillis E. coli P. aeruginosa A ¹⁾ 10 10 - - - B ²⁾ 13 13 - - - Phenoxyethanol 11 10 - 11 11 Methyl paraben 12 12 12 10 10

 1) A: Existing product

2) B: MCA10 (T = 170, m _{cat .} 0.2 wt%, rxn time: 8 hr, Cat.

As a result, the control group, phenoxyethanol, exhibited antimicrobial activity against Gram-positive bacteria such as Propionibacterium acnes , Staphylococcus aureus and Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa at a concentration of 2.5 mg / disc. , And antimicrobial activity in all strains except Bacillus subtilis.

In addition, the product of the existing C company and the xylitol sesquiacrylate product (MCA10) of the present invention showed antibacterial activity only in Gram-positive bacteria such as Propionibacterium acnes and Staphylococcus aureus. Particularly, the product xylitol sesquiacrylate (MCA10) showed the highest antimicrobial activity with a inhibition diameter of 13 mm as a result of the experiments on Propionibacterium acnes and Staphylococcus aureus.

Therefore, the xylitol sesquiacrylate product (MCA10) of the present invention is more effective than the control chemicals such as phenoxyethanol, methylparaben, and propionibacterium acnes, It was confirmed that the antimicrobial activity was remarkably high for Staphylococcus aureus.

(2) Determination of minimum inhibitory concentration (MIC)

The agar dilution method was used to measure the 'minimum inhibitory concentration (MIC)' of the xylitol sesquiacrylate product (MCA10) exhibiting antibacterial activity even at a low concentration (0.5 mg / disc) Respectively.

To increase the antimicrobial activity of the xylitol sesquiacrylate product (MCA10) of the present invention against Gram-negative bacteria, a composition (XcP) was prepared by combining xylitol sesquiacrylate product (MCA10) and phenoxyethanol in a ratio of 1: , The minimum inhibitory concentration was measured. At this time, it was compared with the minimum inhibitory concentration when xanthole sesquiacrylate (MCA10) alone without phenoxyethanol was added.

Each strain was adjusted to 10 ⁶ to 10 ⁷ CFU / ml and used in this experiment. In order to compare the minimum inhibitory concentration value of the composition (XcP) in which phenoxyethanol was used alone and the composition (XcP) in which xylitol sesquiacrylate and phenoxyethanol were combined, the minimum inhibitory concentration against the microorganism was measured and compared in the series dilution test .

The samples were used after diluting the concentration with dimethylsulfoxide (DMSO) using a twofold dilution method (sample concentrations: 10000 ppm, 5000 ppm, 2500 ppm, 1250 ppm, 1000 ppm, 625 ppm, 312 ppm, 156 ppm, 78 ppm, 39 ppm). Then, 20 ml of the medium containing 2 ml of each sample was injected into a Petri dish, and 100 μl of the test bacteria were plated on a flat plate culture. When cultured and visually observed, the concentration at which each microorganism was not proliferated was determined as the minimum inhibitory concentration. As a control, conventional C-products, phenoxyethanol, and methylparaben were used. The measurement was carried out in the same manner as described above, and the results are shown in Table 6 below. A in the following Table 6 is the product of the existing company C, and B is the product of MCA10 of the present invention.

Strains A ¹⁾ B ²⁾ XcP ^{3 )} Phenoxy
ethanol Methyl paraben S. aureus 0.5 0.125 0.1 0.5 0.25 P. acnes - 0.25 0.125 0.5 0.25 B. subtillis - - 0.125 0.25 0.25 E. coli - - 0.1 0.25 0.125 P. aeruginosa 0.5 - 0.25 0.5 0.25

 1) A: Existing product

2) B: MCA10 (T = 170, m _{cat .} 0.2 wt%, rxn time: 8 hr, Cat.

 3) XcP: Phenoxyethanol (50%) + MCA10 (50%)

As a result of the experiment, the composition (XcP) in which xylitol sesquiacrylate and phenoxyethanol were combined showed antimicrobial activity against both Gram-positive and Gram-negative bacteria. Experimental results on Gram-positive bacteria such as Propionibacterium acnes and Staphylococcus aureus Showed a minimum inhibitory concentration of 1000 ppm, which is 2.5 times and 5 times higher than the minimum inhibitory concentrations of methylparaben and phenoxyethanol, which are the control groups, 2500 ppm and 5000 ppm. On the other hand, when xylitol sesquiacrylate (MCA10) alone was applied, there was no antimicrobial activity effect, or the minimum inhibitory concentration was 5000 ppm and the antimicrobial activity effect was low.

On the other hand, the results of the minimum inhibitory concentration against Gram-negative bacteria Escherichia coli exhibited an antimicrobial activity effect of 2,500 ppm of phenoxyethanol, 1,250 ppm of methylparaben, and 1000 ppm of XcP, which was superior to phenoxyethanol by 2.5 times and methylparaben by 1.25 times .

Taken together, it has been confirmed that the antimicrobial effect against Gram-positive bacteria and Gram-negative bacteria is remarkably increased when xylitol sesquiacrylate synthesized in the present invention is used in combination with phenoxyethanol.

(3) Challenge test

Based on the results of the antimicrobial activity of the composition (XcP) comprising xylitol sesquiacrylate and phenoxyethanol combined as a result of the measurement of the minimum inhibitory ability, XcP was tested in a load test test). The experiments were performed according to CTFA (The Cosmetic, Toiletry, and Fragrance Association) standards.

For the experiment, lotion containing xylitol sesquiacrylate and phenoxyethanol composition (XcP) was prepared. To compare the flotation power, a conventional lotion containing 1% of phenoxyethanol and 0.3% of methylparaben, Containing lotion " and " no preservative added lotion ", respectively. The ingredient contents of each lotion thus prepared are shown in Table 7 below. (a is lotion with XcP added, b is lotion with methylparaben added, c is lotion with phenoxyethanol, d is lotion with no added)

Ingredient content of each lotion INCI Name content(%) a b c d Water qs 100 qs 100 qs 100 qs 100 Glycerin 3.0 3.0 3.0 3.0 Xanthan gum 0.2 0.2 0.2 0.2 Isostearyl isostearate 2.00 2.00 2.00 2.00 Cetearyl alcohol 0.5 0.5 0.5 0.5 pentylene glycol 3.0 3.0 3.0 3.0 Polyglyceryl-isostearate / Dimer dilinoleate copolymer 2.0 2.0 2.0 2.0 Polyglyceryl-10 stearate 1.5 1.5 1.5 1.5 Xylitol caprylate 0.5 - - - Phenoxyethanol 0.5 - 1.0 - Methyl paraben - 0.3 - -

The 5 kinds of bacteria were inoculated into the lotion by controlling the number of bacteria in the lotion at 7 × 10 ⁶ CFU / ml and stored at room temperature immediately after inoculation for 14 days. Respectively. The results of the measurement of the buoyancy of each lotion against five species of bacteria are shown in Tables 8 to 12 below.

Results of measurement of buoyancy of each lotion against Staphylococcus aureus Time T ₀ T ₁ T ₃ T ₃ T ₇ T ₁₄ XcP (CFU / g) 7.0 x 10 ⁶ 1.0x10 ³ 2.4x10 ND ND ND C (-) (CFU / g) 7.0 x 10 ⁶ 1.0x10 ⁴ 5.0x10 ² 7.6x10 ND ND C (+) (CFU / g) 7.0 x 10 ⁶ 1.0x10 ³ 1.2x10 ² 3.0x10 ND ND PFL 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶

T ₀ : Count immediately after inoculation

T ₁ , T ₃ , T ₅ , T ₇ , T ₁₄ : Count after 1,3,5,7 and 14 days

C (-): Negative control (Phenoxyethanol)

C (+): Positive control (Methyl paraben)

PFL: Preservative free lotion

Measurement results of buoyancy of each lotion against Propionibacterium acnes Time T ₀ T ₁ T ₃ T ₃ T ₇ T ₁₄ XcP (CFU / g) 7.0 x 10 ⁶ 5.0x10 ³ 2.0x10 ND ND ND C (-) (CFU / g) 7.0 x 10 ⁶ 2.5x10 ⁴ 2.0x10 ² 1.2x10 ND ND C (+) (CFU / g) 7.0 x 10 ⁶ 7x10 ³ 2.4x10 ² 2.0x10 ND ND PFL 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶

T ₀ : Count immediately after inoculation

T ₁ , T ₃ , T ₅ , T ₇ , T ₁₄ : Count after 1,3,5,7 and 14 days

C (-): Negative control (Phenoxyethanol)

C (+): Positive control (Methyl paraben)

PFL: Preservative free lotion

Results of measurement of buoyancy of each lotion against Bacillus subtilis Time T ₀ T ₁ T ₃ T ₃ T ₇ T ₁₄ XcP (CFU / g) 7.0 x 10 ⁶ 2.3x10 ⁴ 1.4x10 ² 9.3x10 ND ND C (-) (CFU / g) 7.0 x 10 ⁶ 4.5x10 ⁴ 1.4x10 ³ 3.5x10 ² 1.2x10 ND C (+) (CFU / g) 7.0 x 10 ⁶ 2.3x10 ⁴ 1.2x10 ³ 2.4x10 ND ND PFL 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶

T ₀ : Count immediately after inoculation

T ₁ , T ₃ , T ₅ , T ₇ , T ₁₄ : Count after 1,3,5,7 and 14 days

C (-): Negative control (Phenoxyethanol)

C (+): Positive control (Methyl paraben)

PFL: Preservative free lotion

Results of measurement of buoyancy of each lotion against E. coli Time T ₀ T ₁ T ₃ T ₃ T ₇ T ₁₄ Results (CFU / g) 7.0 x 10 ⁶ 2.3x10 ⁴ 2.4x10 ² 9.3x10 ND ND C (-) (CFU / g) 7.0 x 10 ⁶ 1.2x10 ⁴ 2.4x10 ² 1.0x10 ND ND C (+) (CFU / g) 7.0 x 10 ⁶ 2.3x10 ⁴ 1.4x10 ² 2.4x10 ND ND PFL 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶

T ₀ : Count immediately after inoculation

T ₁ , T ₃ , T ₅ , T ₇ , T ₁₄ : Count after 1,3,5,7 and 14 days

C (-): Negative control (Phenoxyethanol)

C (+): Positive control (Methyl paraben)

PFL: Preservative free lotion

Results of measurement of buoyancy of each lotion against P. aeruginosa Time T ₀ T ₁ T ₃ T ₃ T ₇ T ₁₄ XcP (CFU / g) 7.0 x 10 ⁶ 0.9x10 ⁴ 2.4x10 ³ 1.0x10 ² ND ND C (-) (CFU / g) 7.0 x 10 ⁶ 0.9x10 ⁵ 1.2x10 ³ 2.3x10 ² ND ND C (+) (CFU / g) 7.0 x 10 ⁶ 1.2x10 ⁴ 2.4x10 ³ 1.0x10 ² ND ND PFL 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶ 7.0 x 10 ⁶

T ₀ : Count immediately after inoculation

T ₁ , T ₃ , T ₅ , T ₇ , T ₁₄ : Count after 1,3,5,7 and 14 days

C (-): Negative control (Phenoxyethanol)

C (+): Positive control (Methyl paraben)

PFL: Preservative free lotion

As a result of the experiment, the lotion containing no preservative showed no difference in the number of bacteria even after about 14 days. In the case of the lotion containing the composition XcP in which the xylitol sesquiacrylate and phenoxyethanol of the present invention were combined, , The rate of bacterial death was faster than that of the lotion containing only phenoxyethanol, and it was confirmed that the antiseptic effect is superior to that of methylparaben in all bacteria.

Claims (10)

After mixing xylitol and caprylic acid, basic zeolite NaX, Basic Zeolite NaY, Amberlyst 15 acid resin, Nafion®, (Nafion) is added to the reaction mixture to induce a dehydration condensation reaction.
The method according to claim 1,
The xylitol and caprylic acid,
3: 1. ≪ RTI ID = 0.0 > 1. < / RTI >
The method according to claim 1,
The solid catalyst,
And 0.1 to 2% by weight based on the total weight of the xylitol sesquiquat;
The method according to claim 1,
The solid catalyst,
Wherein the basic zeolite NaX is basic zeolite NaX.
The method according to claim 1,
In the dehydration condensation reaction,
Wherein the esterification reaction is carried out in the presence of a base.
The method according to claim 1,
In the dehydration condensation reaction,
Characterized in that the reaction is carried out at a temperature of from 150 to 230 < RTI ID = 0.0 > C. ≪ / RTI >
The method according to claim 6,
In the dehydration condensation reaction,
Characterized in that the reaction is carried out at a temperature of from 160 to 180 < RTI ID = 0.0 > C. ≪ / RTI >
8. The method of claim 7,
In the dehydration condensation reaction,
Wherein the reaction is carried out for 6 to 10 hours.
The method according to claim 1,
In the dehydration condensation reaction,
(1-100 cc / min) of nitrogen is introduced into a reaction vessel to shut off air contact. The method of synthesizing xylitol sesquiqualitate according to claim 1,
The method according to claim 1,
The synthesis method of the xylitol sesqui-caprylate is,
After completion of the dehydration condensation reaction,
The remaining solid catalyst is removed by filtration, and the unreacted xylitol and caprylic acid are removed by distillation under reduced pressure to obtain xylitol sesquiqualrylate.

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