[go: up one dir, main page]

WO2018038055A1 - Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne - Google Patents

Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne Download PDF

Info

Publication number
WO2018038055A1
WO2018038055A1 PCT/JP2017/029798 JP2017029798W WO2018038055A1 WO 2018038055 A1 WO2018038055 A1 WO 2018038055A1 JP 2017029798 W JP2017029798 W JP 2017029798W WO 2018038055 A1 WO2018038055 A1 WO 2018038055A1
Authority
WO
WIPO (PCT)
Prior art keywords
bacterial cellulose
dispersion
producing
organic solvent
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/029798
Other languages
English (en)
Japanese (ja)
Inventor
松島　得雄
健次 田島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kusano Sakko Inc
Original Assignee
Kusano Sakko Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kusano Sakko Inc filed Critical Kusano Sakko Inc
Priority to JP2018535665A priority Critical patent/JPWO2018038055A1/ja
Publication of WO2018038055A1 publication Critical patent/WO2018038055A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds

Definitions

  • the present invention relates to a technique for producing highly dispersible bacterial cellulose, and in particular, a method for producing a dispersible bacterial cellulose dried product having a high dispersibility in a liquid and a bacterial cellulose dispersion in which bacterial cellulose is dispersed almost uniformly in a liquid. Regarding the method.
  • Bacterial cellulose is cellulose produced by bacteria such as acetic acid bacteria, and has high mechanical strength, biocompatibility, biodegradability, etc., and can be used in various industrial fields including cosmetics and pharmaceuticals. It is attracting attention as a material.
  • bacterial cellulose is obtained as a bacterial cellulose dispersion in a state of being dispersed in water by culturing bacterial cellulose-producing bacteria by aeration and stirring.
  • this bacterial cellulose dispersion contains a large amount of water, there is a problem that it is expensive to distribute.
  • Patent Document 2 discloses a powdered bacterial cellulose preparation (FIG. 9), in addition to bacterial cellulose dispersion.
  • a method for producing a fibrous bacterial cellulose preparation by adding an organic solvent to the liquid, followed by pressure filtration and ventilation drying (paragraph [0137]) is disclosed.
  • bacterial cellulose when used as a product material, it is often used in the form of a sol or gel by adding a liquid, so that the dried bacterial cellulose has the property of being uniformly dispersed in the liquid. It is preferable.
  • the bacterial cellulose dried product described in Patent Document 1 has not been studied for dispersibility in liquids, and development of a dispersible bacterial cellulose dried product having such properties has been demanded.
  • the present invention has been made to solve such problems, and is a method for producing a dried bacterial cellulose product having high dispersibility in a liquid, and the bacterial cellulose is dispersed almost uniformly in the liquid.
  • An object is to provide a method for producing a bacterial cellulose dispersion.
  • the inventors of the present invention produced a dried bacterial cellulose product having high dispersibility in a liquid by adding an organic solvent to the bacterial cellulose dispersion, and subsequently removing the water and the organic solvent and drying them. I found out that I can do it. Further, after adding a dispersant to the bacterial cellulose dispersion and stirring while heating, an organic solvent is added, and then water and the organic solvent are removed and dried, so that the dispersibility is remarkably high, and The present inventors have found that a dried bacterial cellulose product that does not generate agglomerates upon application can be produced.
  • the bacterial cellulose dispersion can be produced in which the bacterial cellulose is uniformly dispersed and no agglomerates are generated during coating. Moreover, it discovered that the dispersibility in an organic solvent became remarkably high by combining hydroxypropyl cellulose with the fiber surface of bacterial cellulose. Furthermore, bacterial cellulose formed by binding hydroxypropyl cellulose by replacing the dispersion medium of the bacterial cellulose dispersion with water from an organic solvent and subsequently removing the dispersion medium and drying the liquid has high dispersibility in the liquid. It has been found that dried bacterial cellulose can be produced. Accordingly, the following inventions have been completed based on these findings.
  • a first aspect of the method for producing a dried dispersible bacterial cellulose product according to the present invention includes an organic solvent addition step A in which an organic solvent is added to a bacterial cellulose dispersion obtained by dispersing bacterial cellulose in water, A drying step B in which water and the organic solvent are removed from the bacterial cellulose dispersion added with the organic solvent to dry the bacterial cellulose.
  • the bacterial cellulose dispersion to which a dispersant has been added is stirred while being heated to a temperature of more than 45 ° C. before the organic solvent addition step A. It is preferable to have a heating and stirring step A ′.
  • the heating and stirring step A ′ is carried out by subjecting the bacterial cellulose dispersion to which the dispersant has been added to a temperature exceeding 45 ° C. for a time exceeding 15 minutes.
  • the step of stirring is preferable.
  • the bacterial cellulose dispersion to which the dispersant used in the heating and stirring step A ′ is added is 9 (w / W)
  • a bacterial cellulose dispersion added so as to have a concentration exceeding% is preferable.
  • the dispersant is one or more selected from the group consisting of carboxymethyl cellulose, hydroxypropyl cellulose, and hydroxyethyl cellulose. It is preferable that
  • a dried bacterial cellulose obtained by removing water and an organic solvent and drying is dispersed in water containing a dispersant.
  • the regenerating warming stirring step Y is a step of stirring the regenerated bacterial cellulose dispersion at a temperature of more than 45 ° C. for a period of more than 15 minutes. It is preferable.
  • the dispersant is one or more selected from the group consisting of carboxymethyl cellulose, hydroxypropyl cellulose, and hydroxyethyl cellulose. It is preferable.
  • the second aspect of the method for producing a bacterial cellulose dispersion according to the present invention includes an organic solvent dispersion step Z in which bacterial cellulose formed by binding hydroxypropyl cellulose is dispersed in an organic solvent.
  • a second aspect of the method for producing a dried dispersible bacterial cellulose product according to the present invention is a dispersion medium replacement in which a dispersion medium of a bacterial cellulose dispersion obtained by dispersing bacterial cellulose in water is replaced with water from an organic solvent.
  • a dry product of bacterial cellulose can be easily produced, which can contribute to a reduction in the distribution cost of bacterial cellulose.
  • the dispersible bacterial cellulose dried product produced according to the present invention has high dispersibility in a liquid and is excellent in moldability and miscibility with other substances, so that it can be used as a useful material in various industrial fields. Can do.
  • the dispersible bacterial cellulose dried product produced according to the present invention has a property that does not generate agglomerates when applied to the skin or the like in the dispersion, in addition to paints, cosmetics and pharmaceuticals It can be particularly suitably used as the material.
  • a bacterial cellulose dispersion in which bacterial cellulose is dispersed almost uniformly in the liquid can be produced.
  • the bacterial cellulose dispersion produced by the present invention is excellent in moldability and miscibility with other substances, and can be used in various industrial fields.
  • the bacterial cellulose dispersion produced by the present invention also has a property that does not generate agglomerates when applied to the skin or the like, it is particularly suitable as a material for cosmetics and pharmaceuticals in addition to paints. Can be used.
  • FIG. 1 is a table showing the state of dispersion of dried bacterial cellulose (BC dried product) produced by changing the final concentration of carboxymethyl cellulose (CMC) and the presence or absence of agglomerates during skin application.
  • II of FIG. 1 is a photograph showing a state of dispersion of a dried BC product produced by changing the final concentration of CMC at a restoration time of 60 minutes.
  • I in FIG. 2 is a table showing the state of dispersion of the dried BC product produced by changing the stirring temperature and stirring time, and the presence or absence of the generation of agglomerates during skin application.
  • II of FIG. 2 is a photograph showing a state of dispersion of a dried BC product produced by changing the stirring temperature and stirring time.
  • 3I is a table showing the filterability, dispersion state, and presence / absence of agglomerates during skin application of the dried BC product produced by changing the amount of ethanol added.
  • II in FIG. 3 is a photograph showing a state of dispersion of a dried BC product produced by changing the amount of ethanol added.
  • I in FIG. 4 is a table showing the state of dispersion of the dried BC product produced by changing the drying temperature.
  • II of FIG. 4 is a photograph showing a state of dispersion of a dried BC product produced by changing the drying temperature at a restoration time of 90 minutes. It is a graph which shows the ratio of the various dispersing agent couple
  • FIG. 8I is a table showing the state of dispersion in various dispersion media for BC to which various dispersants are bonded. II of FIG. 8 is the photograph which observed the said BC in various dispersion media with the polarizing microscope. It is a photograph which shows the mode of dispersion
  • FIG. 10I shows the state of BC dispersion in a BC dispersion liquid (comparative control) to which hydroxypropyl cellulose (HPC) is bound, and a dispersion liquid (restored BC dispersion liquid) in which the dry product of BC is dispersed. It is a photograph shown. II in FIG. 10 is a graph showing the light transmittance at a wavelength of 500 nm.
  • bacterial cellulose dried product refers to bacterial cellulose that has been subjected to a treatment for removing liquid components such as water and organic solvents. That is, as a result of the removal process of the liquid component, the bacterial cellulose in which the liquid component remains to some extent is also included in the “bacterial cellulose dried product”.
  • the “dispersed bacterial cellulose dried product” refers to a dried bacterial cellulose product having a high dispersibility in a liquid.
  • bacterial cellulose dispersion refers to a liquid containing bacterial cellulose and present in a state where bacterial cellulose is dispersed in the liquid.
  • “dispersing” bacterial cellulose in a liquid means that the bacterial cellulose is suspended or suspended in the liquid.
  • “High dispersibility” means that the particle size and fiber width in the liquid (dispersion medium) of bacterial cellulose as a dispersoid are relatively small, or the bacterial cellulose as a dispersoid is in the liquid (dispersion medium). It means that it is suspended or suspended relatively uniformly.
  • “low dispersibility” means that the particle size and fiber width in the liquid (dispersion medium) of bacterial cellulose as a dispersoid is relatively large, or the bacterial cellulose as a dispersoid is in the liquid (dispersion medium). It means that it is relatively non-uniformly suspended or suspended, and that bacterial cellulose is unevenly distributed, precipitated, aggregated, etc. in the liquid (dispersion medium).
  • the first aspect of the method for producing a dispersible bacterial cellulose dry product according to the present invention includes: Organic solvent addition step A; adding an organic solvent to a bacterial cellulose dispersion obtained by dispersing bacterial cellulose in water; Drying step B; a step of drying bacterial cellulose by removing water and organic solvent from the bacterial cellulose dispersion to which the organic solvent has been added; The above steps A and B are included.
  • the “bacterial cellulose dispersion in which bacterial cellulose is dispersed in water” is, for example, bacterial cellulosic bacteria produced by stirring culture or aeration culture, and removing bacterial cell components from the obtained culture liquid. Can be obtained by purification.
  • bacterial cellulose-producing bacteria known bacteria capable of producing bacterial cellulose can be used, and specifically, for example, Gluconacetobacterlxylinus ATCC53582 strain, Gluconacetobacter hansenii ATCC23769 strain, and GluconacetobacterPRBlAT8C7lin8 strain7PR7 , Gluconacetobacter swingsii BPR3001E strain, Acetobacter xylinum JCM10150 strain, Enterobacter sp. CJF-002 strain, Gluconacetobacterium intermediaus SIID9587 strain (Accession number NITE BP-01495) and the like can be used.
  • the culture conditions for bacterial cellulose-producing bacteria can be known culture conditions used for culturing the above-mentioned bacteria.
  • the aeration rate is 1 to 10 L / min
  • the rotation speed is 100 to 800 rpm
  • the temperature is 20 to 40 ° C.
  • Examples include culture conditions for a period of 1 to 7 days.
  • the medium a known medium used for culturing the above-mentioned bacteria such as a Hestrin-Schram standard medium can be used.
  • the concentration of bacterial cellulose is not particularly limited, but as shown in Example 4 to be described later, In the dispersion, the concentration is preferably less than 1.0 (w / w)% from the viewpoint of suppressing the generation of agglomerates during coating.
  • Organic solvent refers to an organic compound that is liquid at normal temperature and pressure. In general, organic solvents are roughly classified into those having low polarity and those having medium / high polarity, and any of these may be used, but those having medium / high polarity are more preferable. Specific examples of the medium / high polarity organic solvent include ethanol, methanol, isopropyl alcohol, acetone, ethyl acetate, tetrahydrofuran, N, N-dimethylformamide (DMF), acetonitrile, tert-butyl alcohol, dimethyl sulfoxide ( DMSO), dichloromethane, diethyl ether and the like.
  • medium / high polarity organic solvent include ethanol, methanol, isopropyl alcohol, acetone, ethyl acetate, tetrahydrofuran, N, N-dimethylformamide (DMF), acetonitrile, tert-butyl alcohol, dimethyl
  • the addition amount of the organic solvent in the organic solvent addition step A is not particularly limited, but as shown in Example 5 described later, the effect of facilitating the production of the dried bacterial cellulose and the liquid of the produced dried bacterial cellulose
  • the amount is preferably more than 0.5 times the amount of the bacterial cellulose dispersion, and more than 1.0 times the amount of the bacterial cellulose dispersion. More preferred.
  • the dispersibility of the produced bacterial cellulose dried product in a liquid is increased and applied. It is preferable to have the following heating and stirring step A ′ before the organic solvent addition step A in terms of the effect of suppressing the generation of agglomerates. Heating and stirring step A ′; a step of stirring the bacterial cellulose dispersion added with the dispersant while heating to a temperature of more than 45 ° C.
  • the heating and stirring step A ′ is a step of stirring while heating until the bacterial cellulose is almost uniformly dispersed in the liquid.
  • the temperature over 45 degreeC can be mentioned, for example, 50 degreeC or more is more preferable.
  • time to stir at the said temperature 5 minutes or more can be mentioned, for example, 15 minutes or more are preferable and 30 minutes or more are more preferable.
  • the dispersing agent binds to the bacterial cellulose, promotes the dispersion of the bacterial cellulose in the liquid, and can suppress the generation of agglomerates during application.
  • the concentration of the dispersant is not particularly limited. However, in terms of the effect of increasing the dispersibility of the produced dried bacterial cellulose in the liquid, 2 It is preferable that it is (w / w)% or more. In addition, the concentration of the dispersant is more than 9 (w / w)% in terms of the effect of improving the dispersibility of the dried bacterial cellulose product in the liquid and suppressing the generation of agglomerates during coating. It is preferable that the concentration is 14% or more.
  • the concentration of the dispersant refers to the concentration of all the dispersants contained in the bacterial cellulose dispersion regardless of whether or not it is bound to the bacterial cellulose.
  • “dispersant” refers to a substance that binds to bacterial cellulose and improves the dispersibility of bacterial cellulose in a liquid. Specifically, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxy Examples thereof include propylcellulose (HPC) and carboxymethyl chitin. As shown in Example 8 to be described later, in terms of the effect of improving the dispersibility of bacterial cellulose in water, a dispersant of cellulose derivatives such as CMC, HEC, and HPC is preferable, and the effect of improving the dispersibility in an organic solvent. Of these, HPC is preferred among these.
  • the bacterial cellulose dispersion added with the organic solvent is subjected to filtration and filtered.
  • the filtration method include natural filtration, vacuum filtration, pressure filtration, squeeze filtration, and centrifugal filtration.
  • the drying method include heat drying, ventilation drying, freeze drying, and spray drying.
  • the drying method may be a method in which the bacterial cellulose dispersion added with the organic solvent is subjected to heat drying, ventilation drying, freeze drying, spray drying, or the like without performing the above-described filtration.
  • the temperature for heating and drying the bacterial cellulose is 105 ° C. in terms of the effect of increasing the dispersibility of the produced dried bacterial cellulose in the liquid, as shown in Example 6 described later. Drying at a lower temperature is preferable, and drying at a temperature of 80 ° C. or lower is more preferable.
  • the second aspect of the method for producing a dried dispersible bacterial cellulose product according to the present invention includes: Dispersion medium replacement step C; a step of replacing the dispersion medium of the bacterial cellulose dispersion obtained by dispersing bacterial cellulose in water with an organic solvent, A drying step D; a step of removing the dispersion medium from the bacterial cellulose dispersion in which the dispersion medium has been substituted and drying the bacterial cellulose; It has the process of C and D above.
  • the description of the same or corresponding configuration as the first aspect described above is omitted.
  • the bacterial cellulose dispersion is subjected to centrifugation and the supernatant is removed.
  • an equivalent amount of an organic solvent is added and suspended, and then subjected to centrifugation again to remove the supernatant several times.
  • the bacterial cellulose dispersion in which the dispersion medium is replaced may be that most of the dispersion medium is an organic solvent, and a small amount of water may remain.
  • the method for producing a dried bacterial cellulose according to the present invention may further include other steps as long as the characteristics of the present invention are not impaired. Examples of such steps include a step for culturing bacterial cellulose-producing bacteria, Examples include a purification process of bacterial cellulose, a preparation process of a bacterial cellulose dispersion, and a pulverization process of a dried bacterial cellulose.
  • a first aspect of the method for producing a bacterial cellulose dispersion according to the present invention is a method for producing a bacterial cellulose dispersion using water as a dispersion medium
  • Recovery water dispersion step X A step of preparing a restored bacterial cellulose dispersion by dispersing a dried bacterial cellulose obtained by removing water and an organic solvent and drying in water containing a dispersant
  • Heating and stirring step for restoration Y Step of stirring the restored bacterial cellulose dispersion while heating to a temperature of more than 45 ° C., It has the process of X and Y above.
  • the “bacterial cellulose dried product obtained by removing water and organic solvent and drying” in the water dispersion step X for restoration refers to removing a dispersion medium from a bacterial cellulose dispersion containing water and / or an organic solvent as a dispersion medium.
  • Such dried bacterial cellulose can be obtained by the same method as in the drying step B described above.
  • water containing a dispersant refers to water to which a dispersant has been added to a predetermined concentration.
  • the concentration of the dispersant in the water is not particularly limited, but is preferably 4 (w / w)% or more in terms of the effect of enhancing the dispersibility of the bacterial cellulose.
  • the concentration of the dispersant is preferably more than 9 (w / w)%, and 14% More preferable is the above concentration.
  • a method of dispersing the dried bacterial cellulose in water containing a dispersant in the water dispersion step X for restoration for example, after adding water containing a dispersant to the dried bacterial cellulose and allowing it to stand for a predetermined time
  • a method of mixing or suspending by a conventional method such as pipetting, vortexing, or shaking can be used.
  • the amount of water containing the dispersant can be set according to the desired bacterial cellulose concentration in the bacterial cellulose dispersion, for example, the bacterial cellulose concentration is 0.5 to 2.0 (w / w)%. Or the like.
  • the standing time after adding the water containing the dispersant can be appropriately set according to the concentration of the dispersant, the concentration of bacterial cellulose, etc., for example, 30 minutes to 24 hours. it can.
  • the regenerating warming stirring step Y is a step of stirring while heating until the bacterial cellulose in the reconstituted bacterial cellulose dispersion is almost uniformly dispersed in the liquid.
  • the temperature over 45 degreeC can be mentioned, for example, 50 degreeC or more is more preferable.
  • time to stir at the said temperature 5 minutes or more can be mentioned, for example, 15 minutes or more are preferable and 30 minutes or more are more preferable.
  • the dispersing agent binds to the bacterial cellulose, promotes the dispersion of the bacterial cellulose in the liquid, and can suppress the generation of agglomerates during application.
  • a second aspect of the method for producing a bacterial cellulose dispersion according to the present invention is a method for producing a bacterial cellulose dispersion using an organic solvent as a dispersion medium,
  • Organic solvent dispersion step Z a step of dispersing bacterial cellulose formed by binding hydroxypropylcellulose in an organic solvent.
  • the second aspect of the method for producing a bacterial cellulose dispersion according to the present invention is the same as or corresponding to the first aspect of the method for producing a dried dispersible bacterial cellulose and the method for producing a bacterial cellulose dispersion described above. As for, the repeated explanation is omitted.
  • bacterial cellulose formed by binding hydroxypropyl cellulose may be in the form of a dispersion in which HPC-bonded BC is dispersed in water, or in a dry product state.
  • HPC-bound BC in a dispersion state is obtained by stirring and aeration culture of bacterial cellulose-producing bacteria under the above-described culture conditions using a medium supplemented with HPC, and removing cell components from the obtained culture liquid. It can be obtained by purifying bacterial cellulose.
  • the HPC concentration in the medium may be, for example, 0.2 to 2.0 (w / w)%.
  • the HPC-bound BC in a dried state can be obtained by drying the dispersion of the HPC-bound BC obtained as described above by a method such as heat drying, ventilation drying, freeze drying, or spray drying.
  • the solvent replacement method described above for the dispersion medium replacement step C (the organic solvent is changed).
  • an operation of suspending and removing the supernatant by centrifugation is repeated several times.
  • a method of adding or dissolving an organic solvent and mixing or suspending by a conventional method such as pipetting, vortexing or shaking can be mentioned.
  • the addition amount of the organic solvent can be set according to the desired bacterial cellulose concentration in the bacterial cellulose dispersion, for example, an amount that gives a bacterial cellulose concentration of 0.5 to 2.0 (w / w)%, etc. can do.
  • the method for producing a bacterial cellulose dispersion according to the present invention may have other steps as long as the characteristics of the present invention are not impaired. Examples of such steps include a step for culturing bacterial cellulose-producing bacteria, Examples include bacterial cellulose purification steps.
  • the production of bacterial cellulose includes Hestrin-Schramm standard medium (HS medium, composition; bacto pepton 0.5 (w / v)%, yeast extract 0.5 ( w / v)%, Na 2 HPO 4 0.27 (w / v)%, citric acid 0.115 (w / v)%, glucose 2 (w / v)%).
  • the BC concentration in the liquid was measured by a 105 ° C. drying method. That is, first, a certain amount of sample (bacterial cellulose dispersion) is taken, and the mass is measured. Subsequently, the sample is put in a drier and heated and dried at 105 ° C. for 4 hours or more. After allowing to cool, the mass of the dried product was measured, and the concentration by mass was calculated based on these measured values.
  • Example 1 Production of dried BC (1) Production of BC 400 ⁇ L of a suspension of Gluconacetobacter xylinus ATCC 53582, a bacterial cellulose-producing bacterium, was added to 10 mL of HS medium and left to stand at 30 ° C. for 3 days. This was used as a culture medium in advance. Next, 1 mL of the previous culture solution was added to 10 mL of a new HS standard medium, and static culture was performed at 30 ° C. for 3 days, which was used as a preculture solution. 2.0 g of carboxymethylcellulose (CMC; Wako Pure Chemical Industries, Ltd.) was added to 100 mL of a new HS standard medium.
  • CMC carboxymethylcellulose
  • Bacterial cellulose is obtained by adding 5 mL of the preculture solution and performing aeration and agitation culture for 3 days under the conditions of an aeration rate of 7 to 10 L / min, a rotation speed of 150 rpm, and a temperature of 30 ° C. (main culture). Produced.
  • the culture solution after the main culture was centrifuged (8000 rpm, 15 minutes), and the precipitate was collected.
  • 1 (w / v)% NaOH aqueous solution was added 5 times the volume of the precipitate, and the cells were dissolved by shaking at 70 ° C. and 100 rpm for 2 hours. Thereafter, this was subjected to centrifugation under the same conditions, and the supernatant was removed to collect the precipitate, thereby removing water-soluble bacterial cell components.
  • the ultrapure water was added to the solution and centrifuged under the same conditions, the supernatant was removed and repeated until the pH of the precipitate was 7 or less in a wet state to purify BC.
  • a liquid containing BC was used as a BC dispersion.
  • sample b a dry BC product was produced by the steps (ii) and (iii) without performing the step (i).
  • sample c BC dried material was manufactured by making it dry for 60 minutes at 80 degrees C or less.
  • the dried BC (sample c) obtained by drying the BC dispersion was not dispersed in water. Moreover, since the sample c did not disperse
  • Example 2 Production of dried BC; Examination of final concentration of dispersant Using the BC dispersion liquid of Example 1 (1), steps (i) to (iii) described in Example 1 (2) BC dry product was produced. However, the final concentration of CMC in step (i) is 4 (w / w)%, 9 (w / w)%, 14 (w / w)%, 19 (w / w)% and 24 (w / w). )%. Thereafter, the dried BC product was dispersed in water by the method described in Example 1 (3) to obtain a restored BC dispersion.
  • the standing time (restoration time) after adding water to the BC dried product was changed to 0 minutes, 10 minutes, 60 minutes, and 24 hours instead of 60 minutes, and the dispersion of BC in the restored BC dispersion liquid at each time. The state of was observed. Moreover, the presence or absence of agglomeration at the time of skin application was observed with respect to a restoration time of 24 hours. The results are shown in I and II of FIG.
  • the final concentrations of CMC were 4 (w / w)%, 9 (w / w)%, 14 (w / w)%, 19 (w / w)% and 24 (
  • the BC dried product produced as w / w)% was highly dispersible in water when the restoration time was 60 minutes or more.
  • the dried BC product produced with a final CMC concentration of 14 (w / w)%, 19 (w / w)%, and 24 (w / w)% has a remarkably high dispersibility and is applied to the skin. Almost no agglomerates were generated.
  • Example 3 Production of dried BC; Examination of temperature and stirring time during stirring Steps (i) to (iii) described in Example 1 (2) using the BC dispersion liquid of Example 1 (1) ) Produced BC dry product.
  • the final concentration of CMC in step (i) is 19 (w / w)%
  • the temperature during stirring (stirring temperature) is 25 ° C, 45 ° C, 55 ° C, 65 ° C and 80 ° C instead of 55 ° C. It was.
  • the stirring time (stirring time) in the step (i) was set to 0 minutes, 15 minutes, 30 minutes, and 60 minutes instead of 30 minutes.
  • Example 1 Thereafter, the dried BC product was dispersed in water by the method described in Example 1 (3), and the state of BC dispersion in the restored BC dispersion was observed. Moreover, about the dry BC product which made stirring time 60 minutes, the presence or absence of the lump generation
  • the dried BC product with a stirring temperature of 25 ° C. or 45 ° C. did not disperse in water, and agglomerates were generated when the skin was applied. Moreover, the BC dried product with a stirring time of 0 or 15 minutes had low dispersibility in water. On the other hand, a dry BC product having a stirring temperature of 55 ° C., 65 ° C. or 80 ° C. and a stirring time of 30 minutes or 60 minutes has high dispersibility in water and has no lump when applied to the skin. Did not occur.
  • a BC dispersion containing a dispersant is stirred at a temperature of more than 45 ° C. to produce a dry BC product that has a remarkably high dispersibility in the liquid and does not generate agglomerates during coating. It became clear that we could do it. This is because the dispersion of the BC dried product is promoted by binding the BC to the BC by stirring the BC dispersion containing the dispersant in a temperature zone heated to a predetermined temperature or higher. The present inventors believe that this is the case.
  • Example 4 Manufacture of dried BC; Examination of BC concentration in BC dispersion Steps (i) to (iii) described in Example 1 (2) using the BC dispersion of Example 1 (1) A BC dry product was produced by the above method. However, the BC concentration of the BC dispersion in step (i) is 0.5 (w / w)%, 0.7 (w / w)% and 1.0 instead of 0.7 (w / w)%. (W / w)%. Thereafter, a restored BC dispersion was obtained by the method described in Example 1 (3), and the state of BC dispersion and the presence or absence of agglomerates during skin application were observed. The results are shown in Table 2.
  • the BC dried product produced with the BC concentration in the BC dispersion as 0.5 (w / w)%, 0.7 (w / w)% and 1.0 (w / w)% Both were highly dispersible in water.
  • the BC dried product produced with a BC concentration of 0.5 (w / w)% and 0.7 (w / w)% no lump was generated when the skin was applied.
  • Example 5 Production of dried BC; Examination of addition amount of organic solvent Using the BC dispersion liquid of Example 1 (1), the steps (i) to (iii) described in Example 1 (2) A BC dry product was produced. However, the stirring temperature in the step (i) was set to 65 ° C. instead of 55 ° C. The amount of ethanol added in step (ii) is 0.5 times, 1 time and 1.5 times the amount of BC dispersion instead of 1.5 times the amount of BC dispersion, and step (iii) Filterability (easy removal of water and ethanol by suction filtration) was confirmed. Thereafter, a restored BC dispersion was obtained by the method described in Example 1 (3), and the state of BC dispersion and the presence or absence of agglomerates during skin application were observed. The results are shown in I and II of FIG.
  • the amount of ethanol added was 0.5 times the amount of the BC dispersion, filterability was poor and it was difficult to remove moisture and ethanol by suction filtration.
  • the amount of ethanol added was 1.0 and 1.5 times that of the BC dispersion, the filterability was good and water and ethanol could be easily removed by suction filtration.
  • the BC dried product produced by adding 0.5% of the amount of ethanol added to the BC dispersion does not disperse in water, and agglomerates are generated when applied to the skin.
  • the dried BC product produced by adding ethanol in an amount 1.0 and 1.5 times that of the BC dispersion is highly dispersible in water, and is agglomerated when applied to the skin. Did not occur.
  • Example 6 Production of BC dried product; Examination of drying temperature BC dried product according to steps (i) to (iii) described in Example 1 (2) using the BC dispersion liquid of Example 1 (1) Manufactured.
  • the BC concentration of the BC dispersion in step (i) was 0.67 (w / w)%, and the stirring temperature was 65 ° C. instead of 55 ° C.
  • the temperature (drying temperature) for drying the filtrate in step (iii) was set to 65 ° C., 80 ° C. and 105 ° C. instead of 60 ° C. Thereafter, a restored BC dispersion was obtained by the method described in Example 1 (3).
  • the BC dried product with a drying temperature of 105 ° C. did not disperse in water during any restoration time.
  • the BC dried product having a drying temperature of 65 ° C. and 80 ° C. was remarkably high in dispersibility in water at the restoration times of 30, 60 and 90 minutes. From these results, it became clear that a BC dried product having remarkably high dispersibility in a liquid can be produced by setting the temperature for drying BC to 80 ° C. or lower.
  • Example 7 Production of BC Dispersion CMC was added to the restored BC dispersion of sample b of Example 1 (3) to a final concentration of 20 (w / w)%, and then at 55 ° C. for 30 minutes. Stirring was performed, and the obtained restored BC dispersion was designated as sample b ′. With respect to the restored BC dispersion of sample b and sample b ′, the state of BC dispersion and the presence or absence of agglomerates during skin application were observed. The results are shown in Table 3.
  • the reconstituted BC dispersion of sample b ′ had higher BC dispersibility than the reconstituted BC dispersion of sample b, and no agglomerates were generated during skin application. From this result, the BC dried product is dispersed in water containing a dispersant and then stirred while warming, whereby BC is dispersed almost uniformly in water and no agglomerates are generated during coating. It became clear that a BC dispersion could be produced.
  • Example 8 Examination of Dispersant (1) Production of BC As a dispersant, 2 types of CMC (CMC-1 and CMC-2) and 3 types of HEC (HEC-1, HEC-2, HEC) -3) and 3 types of HPC (referred to as HPC-1, HPC-2, and HPC-3), BC was produced by the method described in Example 1 (1). Obtained. Table 4 shows the dispersant used. However, the bacterial cellulose-producing bacterium is Gluconacetobacter intermedius SIID9587 strain (Accession number NITE BP-01495; As a comparative control, BC was produced in the same manner without using a dispersant to obtain a BC dispersion.
  • This aqueous solution contains a dispersant bonded to BC.
  • the aqueous solution was subjected to vacuum filtration to collect the residue, dried at 70 ° C. for 1 hour, and then weighed. Based on the measurement result, the ratio ((w / w)%) of the weight of the dispersant to the weight of the dried BC was calculated. The result is shown in FIG.
  • the weight ratio of CMC-1, CMC-2, HEC-1, HEC-2, HEC-3, HPC-1, HPC-2 and HPC-3 in the dried BC is Was 10 (w / w)% or more. From this result, it became clear that all of the dispersants of CMC, HEC and HPC are bound to BC in a considerable amount.
  • the width (average value) of cellulose fibers was 28.55 nm for BC produced using CMC-2, 34.76 nm for BC produced using HEC-3, and HPC-3 was used.
  • the BC produced was 47.18 nm, and was significantly smaller than the 63.74 nm BC produced without using a dispersant. From this result, it became clear that the fibers of BC can be thinned by combining a dispersant such as CMC, HEC, and HPC.
  • BC bonded with CMC-2 was highly dispersible in water and methanol, and relatively high in N, N-dimethylformamide.
  • BC bound with HEC-3 was highly dispersible in water, methanol and N, N-dimethylformamide, and was relatively dispersible in tetrahydrofuran.
  • BC bound with HPC-3 was highly dispersible in all of water, methanol, isopropyl alcohol, acetone, ethyl acetate, tetrahydrofuran, N, N-dimethylformamide and acetonitrile. From this result, it has been clarified that BC formed by combining HPC has significantly increased dispersibility in not only water but also an organic solvent.
  • Example 9 Manufacture of a dried product of BC bonded with HPC (1)
  • a dried product of BC Among the BC dispersion liquid of Example 8 (1), a product produced using HPC-3 was prepared, and water was prepared. Was added to adjust the BC concentration to 0.1 (w / w)%. Some of these were set aside as “comparison controls”. The remaining BC dispersion was divided into two equal parts, which were designated as sample p and sample q.
  • the dispersion medium of sample p was substituted from water to tert-butyl alcohol by the method described in Example 8 (5). In sample q, the dispersion medium was left as water. These were freeze-dried to obtain a dried BC product.
  • Example 9 Restoration of BC dispersion Water was added to the dried BC product (samples p and q) of Example 9 (1) so that the BC concentration was 0.1 (w / w)%, and vortex mixer was used. The BC was dispersed by stirring to obtain a restored BC dispersion.
  • the transmittance of the comparative control (BC dispersion before drying) was 79.5%, whereas the transmittance of the restored BC dispersion (sample p) was 64.0%. It was an equivalent value. That is, the dispersion in which the dried product of BC bound with HPC-3 was dispersed showed the same high dispersibility as before drying. From this result, it is clarified that, by replacing the dispersion medium of the BC dispersion liquid with water and then drying, a BC dry product having high dispersibility in the liquid can be produced for BC combined with HPC. It was.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Cosmetics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention a pour but de fournir : un procédé de fabrication d'un produit sec d'une cellulose bactérienne dispersible qui est extrêmement dispersible dans un liquide; un procédé de production d'une dispersion de cellulose bactérienne. Pour atteindre ce but, la présente invention concerne un procédé de fabrication d'un produit sec d'une cellulose bactérienne dispersible, ledit procédé comprenant les étapes suivantes : l'ajout de solvant organique (A) à une dispersion de cellulose bactérienne, une cellulose bactérienne étant dispersée dans de l'eau; le séchage (B) qui permet d'éliminer l'eau et le solvant organique de la dispersion de cellulose bactérienne contenant le solvant organique ajouté à celle-ci et qui sèchent ainsi la cellulose bactérienne.
PCT/JP2017/029798 2016-08-23 2017-08-21 Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne Ceased WO2018038055A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018535665A JPWO2018038055A1 (ja) 2016-08-23 2017-08-21 分散性バクテリアセルロース乾燥物の製造方法およびバクテリアセルロース分散液の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-162693 2016-08-23
JP2016162693 2016-08-23

Publications (1)

Publication Number Publication Date
WO2018038055A1 true WO2018038055A1 (fr) 2018-03-01

Family

ID=61246062

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/029798 Ceased WO2018038055A1 (fr) 2016-08-23 2017-08-21 Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne

Country Status (2)

Country Link
JP (1) JPWO2018038055A1 (fr)
WO (1) WO2018038055A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020136629A1 (fr) * 2018-12-28 2020-07-02 Universidade Do Minho Formulations de cellulose bactérienne, procédés et utilisations associés
JP2021126054A (ja) * 2020-02-12 2021-09-02 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法
KR20210148721A (ko) * 2020-06-01 2021-12-08 주식회사 엘지화학 셀룰로오스 분산액 및 이의 제조 방법
JP2022017280A (ja) * 2019-02-01 2022-01-25 嬌朋生技股▲分▼有限公司 生物繊維組成物
JP2022064229A (ja) * 2020-10-13 2022-04-25 堀川化成株式会社 セルロース繊維有機系分散液の製造方法
WO2024171889A1 (fr) * 2023-02-15 2024-08-22 楠本化成株式会社 Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06233691A (ja) * 1993-02-09 1994-08-23 Kohjin Co Ltd バクテリアセルロースのキセロゲルの製法及びそれにより 製造された誘導体
WO2001005838A1 (fr) * 1999-07-15 2001-01-25 Pharmacia Corporation Sechage de cellulose bacterienne reticulee sans co-agents
JP2002262898A (ja) * 2001-03-07 2002-09-17 Canon Inc 水溶性セルロースエーテルを用いたセルロース生産菌のスクリーニング方法、バクテリアセルロース、及びバクテリアセルロースの製造方法
JP2012167273A (ja) * 2011-01-28 2012-09-06 Sanei Gen Ffi Inc 多糖類の精製方法
JP2014118498A (ja) * 2012-12-17 2014-06-30 Chiba Flour Milling Co Ltd 発酵セルロース又は発酵セルロース製剤の精製方法、及び、精製発酵セルロース又は精製発酵セルロース製剤、並びに化粧料、医薬品、医薬部外品

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06233691A (ja) * 1993-02-09 1994-08-23 Kohjin Co Ltd バクテリアセルロースのキセロゲルの製法及びそれにより 製造された誘導体
WO2001005838A1 (fr) * 1999-07-15 2001-01-25 Pharmacia Corporation Sechage de cellulose bacterienne reticulee sans co-agents
JP2002262898A (ja) * 2001-03-07 2002-09-17 Canon Inc 水溶性セルロースエーテルを用いたセルロース生産菌のスクリーニング方法、バクテリアセルロース、及びバクテリアセルロースの製造方法
JP2012167273A (ja) * 2011-01-28 2012-09-06 Sanei Gen Ffi Inc 多糖類の精製方法
JP2014118498A (ja) * 2012-12-17 2014-06-30 Chiba Flour Milling Co Ltd 発酵セルロース又は発酵セルロース製剤の精製方法、及び、精製発酵セルロース又は精製発酵セルロース製剤、並びに化粧料、医薬品、医薬部外品

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022517739A (ja) * 2018-12-28 2022-03-10 ユニベルズィダード ドゥ ミンホ バクテリアセルロースの配合物、方法および使用法
CN113272377A (zh) * 2018-12-28 2021-08-17 米尼翁大学 细菌纤维素配制品、方法及其用途
CN113272377B (zh) * 2018-12-28 2023-08-11 米尼翁大学 细菌纤维素配制品、方法及其用途
WO2020136629A1 (fr) * 2018-12-28 2020-07-02 Universidade Do Minho Formulations de cellulose bactérienne, procédés et utilisations associés
US20220106459A1 (en) * 2018-12-28 2022-04-07 Universidade Do Minho Bacterial cellulose formulations, methods and uses thereof
JP7272696B2 (ja) 2019-02-01 2023-05-12 嬌朋生技股▲分▼有限公司 生物繊維組成物
JP2022017280A (ja) * 2019-02-01 2022-01-25 嬌朋生技股▲分▼有限公司 生物繊維組成物
JP2021126054A (ja) * 2020-02-12 2021-09-02 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法
JP2024051046A (ja) * 2020-02-12 2024-04-10 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法
JP7489656B2 (ja) 2020-02-12 2024-05-24 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法
JP7663210B2 (ja) 2020-02-12 2025-04-16 伊那食品工業株式会社 バクテリアセルロース複合化粉末およびその製造方法
KR20210148721A (ko) * 2020-06-01 2021-12-08 주식회사 엘지화학 셀룰로오스 분산액 및 이의 제조 방법
KR102686420B1 (ko) 2020-06-01 2024-07-17 주식회사 엘지화학 셀룰로오스 분산액 및 이의 제조 방법
JP2022064229A (ja) * 2020-10-13 2022-04-25 堀川化成株式会社 セルロース繊維有機系分散液の製造方法
JP7643704B2 (ja) 2020-10-13 2025-03-11 堀川化成株式会社 セルロース繊維有機系分散液の製造方法
WO2024171889A1 (fr) * 2023-02-15 2024-08-22 楠本化成株式会社 Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau

Also Published As

Publication number Publication date
JPWO2018038055A1 (ja) 2019-06-20

Similar Documents

Publication Publication Date Title
WO2018038055A1 (fr) Procédé de fabrication d'un produit sec de cellulose bactérienne dispersible et procédé de production d'une dispersion de cellulose bactérienne
JP6872396B2 (ja) セルロースナノファイバーの分散液およびその製造方法
JP3042892B2 (ja) ミクロフィブリル化セルロース及び一次壁植物パルプ、特にビートパルプからのその製造方法
JP5752332B2 (ja) バクテリアセルロースおよびこれを生産する細菌
EP3351562A1 (fr) Produit contenant de la cellulose microfibreuse
JP2018529013A (ja) 水溶性ポリマーの脱水方法
EP3902870B1 (fr) Formulations de cellulose bactérienne, procédés et utilisations de celles-ci
JP6484585B2 (ja) 自己結合性顔料粒子懸濁液の調製方法
WO2010007483A1 (fr) Formulations contenant de la cellulose bactérienne ne comportant pas un composant de carboxyméthylcellulose
CN103459429B (zh) 降低水溶性纤维素衍生物中水不溶性纤维的量的方法
WO2013016982A1 (fr) Procédé de préparation de microsphères d'acétate de cellulose et produit ainsi obtenu
Martins et al. Dry Bacterial Cellulose and Carboxymethyl Cellulose formulations with interfacial-active performance: processing conditions and redispersion
JP7663210B2 (ja) バクテリアセルロース複合化粉末およびその製造方法
CN113892490B (zh) 羧甲基壳聚糖包覆纳米氧化锌抗菌胶体及其制备方法
WO2001005838A1 (fr) Sechage de cellulose bacterienne reticulee sans co-agents
EP1265931A1 (fr) Production de complexes de cyclodextrine
JP2018505269A (ja) 水不溶性粒子の含有量を減少させた水溶性セルロース誘導体を生成するための方法
WO2022071463A1 (fr) Composition visqueuse
JP2020002504A (ja) バクテリアセルロースと樹脂との複合糸およびその製造方法
CN113892491A (zh) L-半胱氨酸接枝纳米氧化锌水性抗菌胶体及其制备方法
JP6698286B2 (ja) サイリウムシードガムの製造方法及びサイリウムシードガム
CA1212573A (fr) Procede pour separer des farines contenant des polyosides en fractions riches et pauvres en proteines
Castro-Guerrero et al. Purification of cellulose from rice husk for the synthesis of nanocellulose
CN112190498B (zh) 一种具有水溶性的茶碱和环糊精包合物及其制备方法
WO2024171889A1 (fr) Composition de poudre et son procédé de production, et agent de contrôle de rhéologie pour revêtement à base d'eau

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17843535

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018535665

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17843535

Country of ref document: EP

Kind code of ref document: A1