JPS6236467A - Bacterial cellulose-containing molding material having high mechanical strength - Google Patents

Abstract

PURPOSE:To provide the titled molding material having excellent tensile strength, expansion resistance, elasticity, etc., containing bacterial cellulose composed of ribbon-form microfibrils. CONSTITUTION:A bacterial cellulose-producing strain of the microorganism of the Genns Acetobacter, Pseudomonas or Agrobacterium is cultured, and gel is isolated from the cultured medium contg. produced bacterial cellulose, purified and squeezed from the perpendicular direction under a pressure of 1-10kg/cm<2> to obtain bacterial cellulose wherein ribbon-form microfibrils are entangled. If desired, bacterial cellulose is macerated, stuck on a support such as glass sheet and dried to obtain a sheet of 1-500mu in thickness. The sheet is impregnated with a soln., an emulsion or dispersion of at lest one fixing immobilization support material selected from among hydrophilic and hydropho bic high-molecular materials, metal, inorg.materials, coupling agents, adhesives and antimicrobial agents to obtain the titled molding material having a bacterial cellulose content of 0.01-100%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding material with high elasticity and strength, which has excellent tensile strength and stretch resistance, and which is obtained by containing a specific cellulose produced by bacteria. It is something.

This molding material can be used in the form of paper and other various sheets, as well as in the form of threads or various three-dimensional molded products.

[Conventional technology]

Traditionally, cellulose produced by bacteria has been produced by Acetobacter xylinum (Acetobacter xylinum).
It is known that the sheet-like material produced by ATCC 23769 is used for medical purposes (Japanese Unexamined Patent Publication No. 120159/1983).

On the other hand, various conventional molding materials are known.
Regarding cellulose, there are fibers used in thread-like, sheet-like, and various three-dimensional molded products, as well as cellophane and celluloid, which are processed by dissolving cellulose derivatives. Various synthetic polymer materials have also been developed, some of which have molecular chains arranged in a certain direction to particularly increase the mechanical strength in that direction.

[Problem that the invention seeks to solve]

The mechanical strength of conventional cellulose and cellulose derivatives derived from various plants is not very high; for example, the elastic modulus of sheet-like celluloid or cellophane is at most 2 to 30 Pa.
It was about.

Also, among synthetic polymer materials, some of which have molecular chains arranged in a certain direction have an elastic modulus equivalent to that of metals or inorganic materials in one direction, but have a low elastic modulus in other directions, resulting in high elasticity. Its use as a strength material was inherently limited. For this reason, there is a need for structural materials that are strong and have no anisotropy in their molecular arrangement, but polymeric materials with randomly arranged molecules have low elastic modulus. High-performance molding materials made of synthetic polymers include polyester film, aramid sheet,
Although polyimide films and the like are known, their elastic modulus is about 4 to 70 Pa at most.

There is an example mentioned above that uses cellulose produced by bacteria, but its use is limited to medical pads, and it is not known at all that it is highly useful as a material in the field of high mechanical strength. Ta.

An object of the present invention is to provide a high-elasticity and high-strength molding material with excellent tensile strength and stretch resistance, which exceeds conventional molding materials.

Another object of the present invention is to provide a molding material that has not only high mechanical strength but also excellent hydrophilicity and no toxicity problems.

Yet another object of the present invention is to provide a high-strength molding material that can be used as a carrier for immobilizing enzymes, microorganisms, etc., and has functions of improving strength, preventing adhesion, and preventing leakage of microbial cells.

Still another object of the present invention is to provide excellent high mechanical strength materials in various fields of use by imparting electrical conductivity, magnetism, high insulation properties, thermal conductivity, weather resistance, chemical resistance, etc. in addition to high mechanical strength. Our goal is to provide the following.

[Means for Solving the Problems] In order to achieve these objectives, the present inventors conducted various studies and found that cellulose, which is composed of licon-like microfibrils produced by microorganisms, has extremely high mechanical strength such as tensile strength. It was discovered that the above object could be achieved by using a material containing this bacterial cellulose as a molding material, and based on this knowledge, the present invention was completed.

That is, the present invention relates to a high mechanical strength molding material containing bacterial cellulose consisting of ring-shaped microfibrils.

Bacterial cellulose has a width of lOO~500X and a thickness of lO~200X, as shown in the electron micrograph in Figure 1.
It is made up of X-sized redden-like microfibrils. It is generally obtained in the form of dal, and its moisture content is 95% (W
/ or more.

This cellulose is easily degraded by cellulase,
Produces glucose. That is, 0.0% of this cellulose.
Add cellulase (E C3,2,L) to a 1% (,/,) suspension.
, 4) (manufactured by Ohno Pharmaceutical) was dissolved to 0.5% (w/v) and incubated at 30°C in 0.1M acetate buffer.
The reaction was allowed to proceed for 4 hours. As a result, it was observed that a part of this substance was decomposed, and when the supernatant was developed by (-)1000 chromatography, multilobed cellobiose, cellotriose, and other cellooligosaccharides were detected in addition to glucose. Ta. In addition, small amounts of fructose, mannose, etc. were also detected.

That is, the bacterial cellulose of the present invention contains cellulose and a heteropolysaccharide with cellulose t[E chains, and contains glucan such as β-1,3, β-1,2, etc. In the case of heteropolysaccharides, components other than cellulose include mannose, fructose, galactose, xylose,
These include hexoses, pentoses, and organic acids such as arabic, north, rhamnose, and glucuronic acid. Note that these polysaccharides may be a single substance, or two or more types of polysaccharides may be mixed together due to hydrogen bonding or the like.

Any bacterial cellulose mentioned above can be used.

Microorganisms that produce such bacterial cellulose are not particularly limited, but include Acetobacter aceti subsp.
i aubsp-xyllnum) ATCC1082
1 or the same/'P stourian (A-pasteur)
ian), Aoraneens, Sarcinavsntrie
uli), Bacterium kyjiroides (Bacte
Bacterial cell a-
You can use anything that produces gas.

A method for culturing these microorganisms to produce and accumulate bacterial cellulose may be carried out in accordance with a general method for culturing bacteria. That is, microorganisms are inoculated into a normal nutrient medium containing a carbon source, a nitrogen source, inorganic salts, and other organic micronutrients such as amino acids and vitamins as necessary, and the culture medium is allowed to stand or is gently aerated and stirred. As a carbon source, glucose,
Sucrose, maltose, starch hydrolyzate, molasses, etc. are used, but ethanol, acetic acid, citric acid, etc. can also be used alone or in combination with the above sugars. Nitrogen sources include ammonium salts such as ammonium sulfate, ammonium chloride, ammonium phosphate, nitrates, urea,
Organic or inorganic nitrogen sources such as peptone are used.

As the inorganic salts, phosphates, magnesium salts, calcium salts, iron salts, manganese salts, etc. are used. As organic micronutrients, amino acids, vitamins, fatty acids, nucleic acids, peptones containing these nutrients, cabumino acids, yeast extracts, soybean protein hydrolysates, etc. are used, and auxotrophic mutations that require amino acids etc. for growth are used. When using strains, it is necessary to further supplement the required nutrients.

The culture conditions may be normal, with -5 to 9 and temperature 2.
If cultured for 30 days while controlling the temperature between 0 and 40°C, bacterial cellulose will accumulate in the form of glue on the surface layer.

The bacterial cellulose used in the present invention may be a purified product isolated from a culture of microorganisms, or may contain a certain amount of impurities depending on the intended use.

For example, there is no problem even if residual sugar, salts, yeast extract, etc. in the culture solution remain in the microbial cellulose.

Further, a certain amount of bacterial cells may be included.

Take out this glue and wash it with water if necessary.

Chemicals such as disinfectants and pretreatment agents can be added to this washing water depending on the purpose.

After washing with water, it is dried or mixed with other contaminants, etc., and then dried before use. Any drying method may be used, but it goes without saying that the drying must be carried out within a temperature range in which cellulose does not decompose. Furthermore, since the cellulosic material is composed of fine fibers having a large number of hydroxyl groups on the surface, the fibers may stick to each other during drying, resulting in the loss of the fibrous form. Therefore, when you want to prevent this and make use of the fine fibrous form,
It is preferable to use methods such as freeze drying or critical point drying.

Bacterial cellulose is preferably made into a structure in which microfibrils are entangled in order to increase its mechanical strength such as tensile strength.For this purpose, for example, by squeezing the glue taken out from the culture by applying pressure from the right angle, free water can be removed. An effective method is to remove most of the material and then dry it. Appropriate squeezing pressure is about 1-10 to 9/an. By this compression, the dried cellulose becomes oriented according to the direction of compression. Further, by performing an operation of stretching in one direction while applying pressure, that is, a rolling operation, the dried cellulose has orientation not only in the pressing direction but also in the rolling direction. The pressing device can be appropriately selected from commercially available models.

On the other hand, it is also effective to once disintegrate bacterial cellulose to increase its mechanical strength. The disintegration may be carried out using mechanical shearing force, and can be easily carried out using, for example, a rotary disintegrator or a mixer. It is also effective to perform the above-mentioned compression after disintegration.

The high mechanical strength molding material of the present invention can be molded into various shapes such as sheet, thread, cloth, and three-dimensional shapes.

When forming into a sheet, the bacterial cellulose may be disintegrated if necessary and then formed into a layer, which may be compressed and dried if necessary. In addition to obtaining a sheet with plane orientation by pressing, it is also possible to obtain a sheet with plane orientation and further uniaxial orientation by rolling.

It is desirable to dry the sheet after disintegration and/or compression by fixing it on a suitable support.

By fixing to this support, the degree of plane orientation is further increased, and a sheet with high mechanical strength can be obtained.

For example, a plate with a network structure, a glass plate, a metal plate, etc. can be used as the support. The drying temperature may be within a range in which cellulose is not decomposed, and freeze-drying can be used in addition to heat-drying.

The sheet thus obtained has a structure in which microfibrils are randomly entangled, as shown in FIG. According to the X-ray diffraction image, the pressed material has a planar orientation, and the rolled material has both a planar orientation and a uniaxial orientation. The elastic modulus of the sheet is usually 10-20G
It is about Pa.

The thickness of the sheet is determined depending on the application, but is usually 1 to 5.
It is about 00 μm.

Various additives can be added to the sheet.

For example, solutions of various polymeric materials (aqueous or non-aqueous),
By adding emulsions, dispersions, powders, melts, etc., properties such as strength, weather resistance, chemical resistance, water resistance, water repellency, and antistatic properties can be imparted depending on the characteristics of the additive. ◎ Electrical conductivity and thermal conductivity can be increased by adding metals such as aluminum, copper, iron, zinc, etc. or carzene in the form of powder or thread. Also,
Adding inorganic materials such as titanium oxide, iron oxide, calcium carbonate, kaolin, bentonite, zeolite, mica, alumina, etc. can improve heat resistance, insulation, etc., or add smoothness to the surface, depending on the type. can. Strength can be further increased by adding low-molecular organic substances or adhesives. It may be colored with pigments such as phthalocyanine, azo compounds, eyelids, and safflower. Various other paints, dyes, and pigments can be used for coloring. It can also be used as a medical sheet by adding medicines and disinfectants.

These contaminants and additives are added in an appropriate amount so that the desired physical properties can be obtained at 97% or less. The timing of these additions is not critical, and they may be added to the bacterial cellulose glue or its disintegrated product, after squeezing, or after drying. Furthermore, in some cases, it may be added to the culture medium or to the culture. The addition method may be by impregnation as well as mixing.

Such sheets can also be laminated with layers of other materials. The laminate is appropriately selected depending on the intended use of the sheet. It can also be selected from the kneaded materials or additives mentioned above, and for example, it can be coated with various polymeric materials to impart water resistance.

When used as paper, it is sufficient to disintegrate the bacterial cellulose glue, form it into paper, and dry it, which results in excellent tensile strength, stretch resistance, etc., as well as chemical stability, high water absorption, and high elasticity with excellent air permeability. and high strength paper can be obtained. In this case, usual additives, processing agents, etc. used in paper manufacturing can be used, and it is also possible to select and add from the above-mentioned contaminants and additives.

In recent years, the demand for electrically insulating paper, heat-resistant paper, flame-retardant paper, etc. has increased.
Synthetic paper, inorganic paper, etc. using non-cellulose fibers began to be made. When trying to make these by a wet method, polyethylene, polypropylene, polyacrylonitrile, polyethylene, polypropylene, polyacrylonitrile,
It is necessary to add cellulose pulp to papermaking, except in cases where pulped fibers such as aromatic polyamide fibers are obtained. In this case, it is required to reduce the amount of pulp as much as possible to improve insulation, heat resistance, and flammability. However, when making a mixture of wood and wood that is needed, the amount added reaches 20 to 50 inches, and the purpose cannot be achieved sufficiently. However, by using bacterial cellulose instead of wood/matrix, it was possible to reduce the cellulose ffl'r width, and it was possible to obtain paper with excellent insulation, heat resistance, and I+t AW properties. Therefore, the high mechanical strength molding material of the present invention is also effective for these.

Furthermore, photocrosslinkable polyvinyl alcohol is said to have a better affinity for living organisms than conventional photocrosslinkable resins, and it is thought that this will further improve the use of immobilizing agents for enzymes, microorganisms, etc. In addition, photoresists used when producing printing plates are made by coating a resin on a substrate, projecting a design, etc. to be printed onto it, causing photocrosslinking, and curing the resin. This photo-crosslinkable polyvinyl alcohol, which is water-soluble, has the advantage of being cheaper and easier to clean than conventional oil-soluble products, and is used in photoresists. is expected. However, in these cases, there was a problem in that the photocrosslinkable polyvinyl alcohol swelled with water and the crosslinked structure was destroyed. However, this swelling can be inhibited by adding bacterial cellulose.

To make yarn, for example, bacterial cellulose daruma is washed and dried, and then dissolved in a dimethylacetamide/lithium chloride solvent, etc., and the dissolved material is mixed with water, alcohols, ketones, dioxane, tetrahydrofradiate, etc. Spinning may be carried out using a coagulating liquid in which cellulose is insoluble and the cellulose solvent is soluble.

When making cloth, this thread may be woven in a conventional manner.

When making a three-dimensional object, the desired molded product is obtained by kneading bacterial cellulose with various types of plastics or by further laminating them. This can be used as an alternative to various FRP products or carbon fiber products, for example.

Conventionally, agar, carrageenan alginic acid, gelatin, colladan, polyamino acids, photocrosslinkable resins, polyacrylamide, various resins, etc. have been used as immobilization carriers.
IJ vinylidene chloride 1. T? IJ ester net, etc.
By mixing fibers as reinforcing materials with these carriers, efforts have been made to improve strength and prevent adhesion. However, in this immobilized product, the reinforcing material increases the size of the carrier and reduces the surface area per unit area, which may inhibit substrate diffusion within the carrier, or cause enzymes, biological substances, catalysts, etc. immobilized on the carrier to become larger. Other reactive substances (hereinafter “active ingredients”)
There has been a problem in that the concentration of the compound (referred to as ) is relatively reduced, resulting in a decrease in the reaction rate and reaction yield. In addition, there is a problem that the active ingredient leaks from the immobilization carrier, so if it is used for a long time or repeatedly, the activity gradually decreases. It was difficult to prevent leakage from the carrier. Among conventional immobilization carriers, very weak glues - for example, 6% of photocrosslinkable polyvinyl alcohol
When using a cross-linked aqueous solution as an immobilization carrier, there was a problem that the immobilization carrier was destroyed due to swelling caused by water ◎ Instead of the conventional immobilization carrier reinforcement material, bacteria By using cellulose as it is, disintegrating it, or exposing and drying these materials, the above-mentioned problems can be solved and an immobilization carrier with unprecedented high strength can be obtained.

There are the following methods for producing such an immobilization carrier. Basically, the bacterial cellulose and the immobilization carrier material described below may be mixed and then glued, polymerized, or molded. Further, if necessary, an active ingredient to be immobilized may be added at the time of this mixing to be immobilized, or the active ingredient may be immobilized after producing an immobilization carrier.

The carrier material is not particularly limited as long as it can be mixed with the bacterial cellulose, and for example, the following materials can be used. Agarose, dextran, cellulose, cellulose derivatives, alginic acid, alginate, chitin, chitosan, colladan, albumin, amino acid polymer, polystyrene, polyacrylamide, tannin, silicone rubber, casein, agar, carrageenan,
Polyurethane, poly-2-hydroxyethyl methacrylic acid, polyvinyl chloride, r-methylpolyglutamic acid, polyvinylpyrrolidone, polydimethylacrylamide, photocrosslinkable resin, polyethylene glycol derivative, polypropylene glycol derivative, polybutadiene derivative,
Collodion, nylon, polyurea, silicadal, silicone derivatives, phenylsiloxane, fibrin, Jl [
Cellulose, hydrocarbons, phospholipids, calcium phosphate glucose, phenoxyacetylated products, glucomannan, etc.

Regarding the manufacturing method of the immobilization carrier, when the bacterial cellulose is in the form of a glue produced by microorganisms, when it is a dried product obtained by drying this glue-like material, or when it is in the form of a delta. If the dried product obtained by disintegrating and drying does not maintain a pro-fibrotic morphology, the carrier material may be made into a solution with an appropriate solvent or molten to give it fluidity. An immobilized carrier can be obtained by impregnating the bacterial cellulose and gluing it.

Gluing methods vary widely depending on the carrier material, but
For example, in the case of sodium alginate, it may be added to a calcium solution after mixing, and in the case of agar, the temperature may be lowered.

When the bacterial cellulose is in a disaggregated state or in a dry state with a fibrous form obtained by a method such as freeze-drying or critical point drying, the bacterial cellulose and the carrier material are In contrast to the above-mentioned impregnation, an immobilized carrier can be obtained by mixing in a conventional manner and then gluing, polymerizing, or molding.

Concentration of the bacterial cellulose in the immobilization carrier 1-10
．． 011-99%, good it, <Ho, about 1-2% is good.

The shape of the immobilization carrier obtained by the above method can be freely selected according to the type and method of reaction. for example,
If it is packed in a column or placed in a stirring tank, it can be processed into a ball shape, or it can be shaped into a rod or film if necessary. When an immobilization carrier is produced by mixing the disintegrated bacterial cellulose with a carrier material and then gluing, polymerizing or molding the mixture, the immobilization carrier may be processed and molded in the same manner as conventional methods.

On the other hand, when directly producing an immobilized carrier from the glue-like form produced by microorganisms, the carrier material may be impregnated with glue-nucleating bacterial cellulose and then glued. In order to process it into a predetermined shape, it is possible to process the glutarous bacterial cellulose into the required shape and then impregnate it with the carrier material.On the other hand, it is also possible to manufacture the immobilization carrier and then process it into the required shape. good.

The active ingredients to be immobilized on the immobilization carrier of the present invention include enzymes, microorganisms, biological substances, catalysts, and other reactive substances, as long as they are commonly used. Examples of active ingredient enzymes include aspartase, L-aspartate β-
decalgexylase, L-leucine dehydrodanase,
Hydantoinase, DL-2-amino-Δ2-thiazoline-4-calgenic acid ice-melting enzyme, dihydropyrimidinase, acylase that acts on acylamino acids, trypto-7anase, tryptophan synthetase, tyrosinase,
fumarase, histidine ammonia lyase, L-amino acid oxidase, α-amylase, β-amylase,
Invertase, glucose isomerase, penicillin acylase, cephalosporin acylase, 5'-A
MP deaminase, adenylate kinase, aldolase, cysteine desulhydrase, methioninase, phosphogesterase, chymotrypsin, tridenine, i
4 i4 in, naringinase, lactase, glucoamylase, leucine aminoidetidase, pepsin,
Aminolactam hydrolase, amylolactam racemase, glutamate dehydrogenase, aspartate decarboxylase, zorlanase, hyaluronidase,
1.4-α-glucan phosphorylase, cyclodextrin lycosyltransferase, dextran sucrase, α-glucosidase, β-glucosidase,
Hexokinase, Δ1-hydrogenase, 111? -hydroxylase, 20β-dehydrogenase, 3β-dehydrogenase, Δ1-
Hydroxylase, steroid esterase, 5' phosphodiesterase, ATP deaminase, acetate kinase, adenylate kinase, adenosine kinase, carbamyl phosphokinase, pyruvate kinase, glycolytic enzyme chymosin, alkaline protease, rennin, pronase, protease, catalase , lysozyme, D-oxynidolase, alcohol dehydrogenase, glucose-6
- phosphate dehydronase, nitrate reductase, nitrite reductase, rhodanase, glutaminase, uricase, yl oxidase, dino-9-ase, cholesterol oxidase, benicillinase, alkaline phosphatase, acid phosphatase, acetylcholinesterase,
etc. Examples of microorganisms that are active ingredients include Brevibacterium ammoniagenes, Escherichia coli, Ervihervicola, Streptococcus faecalis, Pseudomonas putida, Serratia macerans, Bacillus spuptilus, Acetobacter aceti, Lactobacillus delbrettii, Pseudomonas fluorescens, Micrococcoccus 9 luteus, Bacillus
Examples include Megatherium, Penicillium chlorinum, Candida tropicalis, and Satucharomyces cerevisiae. In addition, animal cells, plant cells, etc. may be immobilized as necessary.

The immobilized product thus obtained can be used in the production of useful substances such as medicines and foods using microorganisms and enzymes. It can also be used as a bioreactor in analytical and industrial production processes.

Further, the catalyst and other reactive substances may be organic or inorganic substances that can coexist with the bacterial cellulose and are used in ordinary chemical reactions. These materials can be packed into a column and used as a reaction bed, and can also be used in various chromatographies. On the other hand, by selecting the particle diameter and size, the immobilized carrier can also be used to physically separate, select, or purify the target substance.

[Effect]

Bacterial cellulose is composed of ribbon-like microfibrils and has high mechanical strength such as tensile strength, stretch resistance, and elasticity. This mechanical strength is increased by the entanglement of each microfibril, and the strength in that direction is further increased by imparting orientation. Bacterial cellulose has the property of being easily oriented by pressing.

〔Example〕

Example 1 Sucrose 597d1. Yeast extract (Difeo) 0
．． 5Jii/dl, ammonium sulfate 0.511/di%KH2P
O40.3g/dt, MgSO4・7H200.05
1//dlcH5,o) 50 ml of medium with a composition of 20
The mixture was poured into a 0 at volume Erlenmeyer flask and steam sterilized at 120°C for 20 minutes. To this, yeast extract 0.517dl, peptone 0.311/dt, mannitol 2.5117di
One platinum loop of Acetobacter, Aceti, subspice, and Xylinum ATCC 10821 grown on a test tube slanted agar medium with a composition of (pH 6.0) (30°C, 3 days) was inoculated and cultured at 30°C. After 30 days, a dul-like film containing white bacterial cellulose polysaccharide was formed on the upper layer of the culture solution.

The Af membrane thus obtained was washed with water, spread to a thickness of about 1 cIrL, and pressed using a test press machine (Tester Sangyo ■) at a pressure of about 10 to 9/m to squeeze out the moisture. This was pasted on a glass plate and dried at 105° C. for 2 hours to obtain a sheet with a thickness of about 10 μm.

The X-ray diffraction pattern of the obtained sheet is shown in FIG.

This figure is a diffraction image taken by taking an X-ray incident perpendicularly to the rotation axis while rotating the sheet, with the rotation axis parallel to the sheet surface. As shown in the figure, (a) 1
All of the 01 plane, (b) lO1 plane, and (c) 002 plane were oriented, and this sheet had an extremely high degree of plane orientation.

The elastic modulus of this sheet, existing cellulosic sheets, and various two-dimensional polymeric materials were measured using a tensile tester, and the results are shown in the table below.

Sheet Elastic modulus Invention product 15.8GPa Cellophane 1.5 Celluloid 2・O Nomax *17.0 Lumirror $2, i9 *17f! IJ metaphenylene inphthalamide sheet *2 Biaxially stretched? Liethylene terephthalate sheet Example 2 The same glue-like bacterial cellulose used in Example 1 was compressed while being rolled in one direction using a roll press machine (Yoshida Kogyo ■). This material was also pasted on a glass plate and dried at 105° C. for 2 hours to obtain a sheet.

The X-ray diffraction pattern of the obtained sheet is shown in FIG.

This figure is a diffraction image taken with the sheet fixed and X-rays incident perpendicularly to the film surface.

In the figure, arrows indicate the rolling direction. As shown in the figure, orientation is found in all of the (a) 101 plane, (b) lO1 plane, and 002 plane, and -axis orientation is clear.

Furthermore, almost the same orientation as shown in FIG. 1 was observed regarding the plane orientation.

The elastic modulus of this sheet was measured in the same manner as in Example 1 and was found to be 20 GPa in the rolling direction.

Example 3 Bacterial cellulose was added to novoloid fiber (manufactured by Gunei Chemical Industry Co., Ltd., trade name Kynol Fiber KFO203, φ14 μm, 3 m length), and a sheet with a basis weight of 60 y/- was TA
Paper was made using the PPI method (TAPPI standard)
d T 205 m -58) Also, for comparison, highly beaten ordinary wood 9 Rude (N, U, SP) (
A mixed paper of C8F 245 rttt) and Kynol fiber was also produced.

The tearing length of these sheets was measured using a self-recording tensile tester. The results were as shown in the table below.

The use of bacterial cellulose has made it possible to make paper with a small amount of addition, and it has also become stronger.

In the case of normal use of the paper, it was impossible to make paper if less than 10 copies were used.

Example 4 Using various inorganic fibers, paper mixed with B and C was prepared and the tearing length was measured. The results are shown in the table below. In all cases, paper could be made with an addition of 5 to 10%.

Example 5 Glue-shaped bacterial cellulose was pressed and dried to obtain a sheet. The Young's modulus E measured by the vibration lead method was as follows.

E = 13.6 GPa This value is 5-10 times the normal Young's modulus of paper made only from wood pulp.

Example 6 Glue-like bacterial cellulose was disintegrated with a homogenizer and paper was made by the TAPP I method. Young's modulus EVi, E" 7-4 measured by the vibration reed method
GPa Furthermore, in order to improve r-aqueous properties and improve the yield of fine particles, 5 g (solid content ratio) of I-lyamide epichlorohydrin resin (Kaimen 557H, manufactured by Dick Vercules) was added and paper was made. The E of this paper was as follows.

E” 8.1 GPa In both cases, high-strength paper was obtained.

Example 7 Wood/4'A/P (N, U', KP) (C3F 54
0mA! ) versus bacterial cellulose (B, C,)
The properties of paper made by adding pan sulfate ±5% (solid content ratio) were as follows.

N, U, KP 100 parts Breaking length 3.69 kmN
, U, KP I O0 part E=1.38GPaB, C
, the paper strength was improved by adding .

Example 8 Glue-like bacterial cellulose obtained by a predetermined culture was disintegrated using a standard Norde disintegrator, and then passed through a 125 msgh sieve to obtain a hard star-like cellulose with a solid content of 8.8%. A disaggregated product was obtained. This was used in the following experiment to obtain F-O photo-linkable polyvinyl alcohol (PVA)-8bQ (G
H-17SbQ lo, 5wt* 1.2 mol f
y Toyo Gosei Kogyo ■), the above disintegrated product, and water were mixed in a dark room in the proportions shown in the table below.

(a) PVA-8bQ (GW 17 SbQ lO,
5 vrt% 1.2 mo1%) (b) Disaggregated bacterial cellulose (dry weight equivalent) (c) H2O The mixture in the table above was spread onto an acrylic plate using a glass rod to a thickness of about 0.5 mm.
7- was cast. After drying this in the evening, heat it at 40℃ for 30 minutes.
Air-dried for min. The operations up to this point were performed in a dark room. This was exposed to sunlight for 30 minutes and crosslinked to obtain a sheet.

The above material was cut into 3 x 1 cIrL IJ and yin shapes and placed in water for a 2 hr swelling test. The results are shown in the table below.

Sample length x width - length swelling rate weight x10~>Wl
3Xl 3.2X1. l 1.07 2.
46 4.87 1.982 3X1 3.3X1
．． 1 1.10 1.18 2,56 2.1
73 3Xl 3.3X1. l 1.10
1.43 3.34 2.36 By adding bacterial cellulose, swelling can be prevented.Next.

Next, this sheet was subjected to a tensile test.

1 1.612
1, 7.1 3 1.32 By adding bacterial cellulose, the elastic modulus is increased to 1.
．． It was possible to improve it by 3 to 1.6 times.

Example 9 A mixture having the composition shown in the table of Example 8 was sandwiched between two glass plates using a slide glass having a thickness of l+w as a spacer. This was directly exposed to sunlight for 30 minutes to cause crosslinking, thereby obtaining a wet konjac-like glue.

This was placed in distilled water and a swelling test was conducted in the same manner as in Example 8. The results are shown in the table below.

Sample weight (,9) Water absorption ratio 1 1.7
5 3.97 2 0.90 3.95 4.4*Sample 3.4 was destroyed due to swelling.

Incorporation of bacterial cellulose prevented the swelling and destruction of the glue.

Example 1O 100 parts of trimethylacetamide was added to 3.5 parts of dried bacterial cellulose, and the mixture was stirred under reflux for 60 minutes. Next, after cooling to 100° C. and gradually adding 10 parts of lithium chloride, the mixture was stirred at room temperature for one day to dissolve the bacterial cellulose. This spinning stock solution is converted into a tetrahydrofuran coagulation solution.
The yarn was spun at a spinning draft of 1.5 and a bath length of 8'0 crrL, and the yarn that came out of the spinning bath was stretched 50% in water at 50° C. and then dried. The properties of the obtained fibers are shown in the table below.

Also, for comparison, Mokuno J? The fibers (L, B, KP) were also spun in the same manner.

Example 11 Copper powder (φ10 μm manufactured by Fukuda Metal Foil and Powder Industries) and wood pulp (
Disintegrated bacterial cellulose was added to a mixture with N, U, KP) (C8F 540 Go), and paper was made by the TAPPI method. For comparison, a paper made from a mixture of copper powder and wood Noyalde was also prepared. The physical properties of these sheets were measured using an automatic recording tensile tester. The results are shown in the table below.

By using bacterial cellulose, there is no leakage of copper powder, and the strength has also been greatly improved. In the case of a normal T4 Rude, more than 60% of the copper powder leaked out.

Example 12 Wood pulp (N, U, KP) (C8F 540mj)
Disintegrated bacterial cellulose (BC) was added to the mixture, and paper was made by the TAPPI method. This paper was impregnated with phenol resin, air-dried, and hot-pressed to produce a phenol laminate.

For comparison, a phenolic laminate made of only wood pulp was also produced in the same manner. These phenol laminates were molded into a dumbbell type No. 1 (JIS K-7113), and their physical properties were measured using an automatic recording tensile tester. The results are shown in the table below.

The use of bacterial cellulose has greatly improved the strength of phenolic laminates.

Example 13 The same glue-like bacterial cellulose as used in ttrgfIIl was heated at 150°C for 5 kl? /cm2 for 5 minutes (Kichiichi Kogyo ■) to obtain a sheet. A polyethylene film treated with polyethyleneimine was laminated on the obtained sheet at 320°C to produce a laminate film. The physical properties of this laminated film were measured using an automatic recording tensile tester.

As a result, the elastic modulus was 16.2 GPa, which is normal cellophane.
Elastic modulus of polyethylene laminate film 1.7 GPa
A laminated film with improved width was obtained.

Example 14 Z? Bacterial cellulose BC) was added and paper was made by the TAPPI method. For comparison, the same procedure was also carried out for mixed papermaking with wood pulp (N, U, KP) and microfibril cellulose (MFC: manufactured by Daicel Chemical Industries, Ltd.). The physical properties of the obtained sheet were measured using an automatic recording type tensile tester. As a result, by using bacterial cellulose, there was no leakage of silicon nitride and silicon carbide, and the elastic modulus was greatly improved. In the case of normal pulp, more than 60 units of silicon nitride and silicon carbide leak and flow out, and in the case of MFC, most of it leaks and flows out.

Example 15 Fumaric acid 21/Idl, potassium dihydrogen phosphate 0.2j
! /di, manganese sulfate tetrahydrate 1m9/di, magnesium sulfate heptahydrate 1~/dt, calcium chloride 0.05E
/dt, yeast extract (Dlfco) 1.01/dl,
A liquid medium having a composition of 1.0, F/d/ was adjusted to pH 7.0 using ammonia.

50 al of this medium was dispensed into a 500ee Sakalo flask, and a loopful of E. coli ATCCl 1 775 was inoculated and cultured at 30° C. for 24 hours.

The bacterial cells were collected by centrifugation according to a conventional method. After washing twice with physiological saline, the sample was suspended in the same amount of physiological saline as the wet weight.

An attempt was made to immobilize these bacterial cells on a carrier made of gelatin Chigi cellulose by the following method. As the immobilization method, the transglutaminase-based immobilization method described in JP-A-59-66886 was used. Gelatin (Miyagi Kagaku) and the disintegrated bacterial cellulose were mixed in the composition shown in the table below. After further mixing bacterial cells to this mixture to a concentration of 3.5 cm, JP-A-59
According to the method described in Japanese Patent Application No. 66886, 0.1 unit of transglutaminase was added to 1 inch of gelatin, and the mixture was allowed to stand at 25°C for 1 hour in VC to undergo rutinization. This glue was cut into five square dice and added to the reaction solution to examine aspartase activity. The reaction solution was fumaric acid 2
01! /dl, ,1mM-MgSO4・7H20
A solution containing p) was adjusted to p) 18.5 using ammonia and used. Bacterial cell concentration is 0.5% based on the total amount of reaction solution.
Cell-immobilized gelatin glue was added to the reaction solution so that The reaction was carried out for 1 hour, and the reaction was repeated every 5 minutes.)J? The initial reaction rate was determined by colorimetrically determining the concentration of phosphoric acid using ninhydrin. The number of bacteria leaking into the reaction solution was determined by colony counting 30 minutes after the start of the reaction. The results are shown in the table below.

Gelatin concentration Reinforcement and additive concentration Number of leaked bacteria 12.5 0 1.2X1
0812.0 Bacterial cellulose 0.5
1. IXI 0712.5
9.8X10612.0 Polyester gauze 0.5 1.4 X I 0812.5
1.1X10
8 Enzyme activity was determined from the initial reaction rate. In addition, the enzyme activity was expressed as a relative value, with the first time when no bacterial cellulose was added as 100. Moreover, the reaction was repeated 10 times. The results are shown below.

Gelatin concentration Reinforcing agent and additive concentration Asparta pi m raw (chi) (chi)
1st 10th 12.5 0
100 3512.0 Bacterial cellulose 0.5 99 8012.5
1 102
8512.0 Polyester gauze 0.5
103 3712.5
97 38 Since leakage of bacterial cells was prevented by adding bacterial cellulose,
It is now possible to maintain activity even after repeated use.

In addition, the breaking strength of gelatin similar to that shown in the table above and gelatin to which a reinforcing material was added was measured. The measurement is
After gluing the gelatin solution described above in a cylindrical plastic container with a diameter of 22 crIL, a rheometer (
Fudo Kogyosha, NRM 2002J) and 5 cabinets φ
This was done by expressing the maximum load when the adapter was inserted directly into the glue as the breaking strength. The results are shown in the table below.

Gelatin concentration Reinforcement and additive concentration Breaking strength 12
．． 5 0 9012.5
Bacterial cellulose 0.5 14512
．． 5 1941
2.0 Polyester gauze 0.5 il
Bacterial cellulose was found to have a better reinforcing effect than conventional reinforcing materials.

Example 16 For immobilization on alginate glue, sodium alginate and bacterial cellulose were mixed according to the table below. Next, according to a conventional method, the mixture was added dropwise to an O, l M CaO12 solution to obtain a citrus bead-shaped glue.

Aspartase reaction was carried out under the same conditions as in Example 15. The number of leaked bacteria was determined by the number of colonies after 30 minutes without changing the reaction solution. The results are shown in the table below.

1.5 0 2.1X1081.0
Bacterial cellulose 0.5 5.3 X
I O'1.5 #
1.5XIO51,0 polyester gauze 0.5
1.9 X l 081.5
#2.0XLO8 The above reaction solution was replaced every 15 minutes, and the immobilization carrier reaction was repeated a total of 4 times. Enzyme activity was determined from the initial velocity by measuring the concentration of asno-4-lagic acid every 3 minutes. The results are shown in the table below. The aspartase activity was expressed as a relative value, with the first time when the cellulosic substance was not added being taken as 100.

1.5 0 100 85 32 20
1.0 Bacterial cellulose-'0.5 10
1 92 79 601.5
#97 90 87 851.0 Polyester gauze 0.5 101 80 29 191
．． 5 #98 89 39 25
As a result of adding bacterial cellulose as a reinforcing material, the leakage of bacterial cells was prevented, so that the high-strength immobilization carrier of the present invention could be used more repeatedly than conventional immobilization carriers.

Example 17 Invertase was immobilized on a photocrosslinkable resin by the method described below. 1 part invertase and phosphate buffer (pH 6)
, 0) and a photocrosslinkable resin solution (pH 6).
0) 20 parts were mixed. This mixed solution was cast onto a glass plate, air-dried for one day, and then irradiated with light for one hour to crosslink and cure. The reinforcing material was added to a final concentration of 5.

This immobilized membrane was cut into pieces with a size of 5×5+w, and
The decomposition rate of sucrose was determined by stirring reaction at 40° C. for 24 hours in a solution of Ii (50°C). The reaction was repeated 10 times.

In addition, the modulus of elasticity at break stress was also investigated. The results are shown in the table below.

0 25.1 0.95 Zoo 98 Bacterial Cellulose 5 32.0 1.53 10
0 99 Polyester gauze 5 28.3 1.20
The addition of Zoo 9B bacterial cellulose significantly improved the physical properties of the immobilized enzyme membrane, such as the membrane's breaking stress 1 modulus of elasticity, which is the strength of the immobilized enzyme membrane. Therefore, the operation for immobilizing the enzyme became easy, and the time required for the operation was shortened to 3/4 when the cellulosic substance was added compared to when the cellulosic substance was not added.

〔Effect of the invention〕

The high mechanical strength molding material of the present invention has excellent tensile strength, stretch resistance, elasticity, etc. In particular, the sheet obtained by drying after pressing has an extremely high modulus of elasticity. It was more than twice the elastic modulus of .

Therefore, this material can be used as a reinforcing material for composite plastics that require high strength, such as as a body material for ships, aircraft, and automobiles, as a wiring base, etc., as a high-quality paper such as recording paper, and as a diaphragm for percussion instruments. Can be used.

In addition, this material is a natural product, does not cause irritation to human skin, and has excellent breathability, making it an excellent Pan Ricoh base material.

In addition, it is excellent against destruction and deformation due to physical stress, and is also resistant to destruction and deformation caused by swelling V caused by solutions and the like. Therefore, when used as a constant loss carrier, it not only enables vigorous stirring and packing into very long columns, but also immobilizes carriers that were conventionally too weak to be used. It can now be used as a carrier. When producing this immobilization carrier, the aggregation of the active ingredient that often occurs during the manufacturing process of conventional immobilization carriers is avoided, and therefore the active ingredient can be uniformly dispersed within the immobilization carrier.

[Brief explanation of drawings]

FIG. 1 is an electron micrograph of a cellulosic substance produced by Acetobacter aceti subspice xylinum. FIG. 2 and FIG. 3 both show the X-ray diffraction pattern of the product of the present invention. Figure 2 Figure 3

Claims (18)

[Claims] (1) High mechanical strength molding material containing bacterial cellulose consisting of ribbon-like microfibrils (2) The high mechanical strength molding material according to claim 1, wherein the bacterial cellulose is produced by a microorganism belonging to the genus Acetobacter, Pseudomonas, or Agrobacterium. (3) The high mechanical strength molding material according to claim 1, wherein the content of bacterial cellulose is 0.01% to 100%. (4) One or more selected from the group consisting of hydrophilic polymer materials, hydrophobic polymer materials, metals, inorganic materials, coupling agents, adhesives, paints, dyes, pharmaceuticals, and antimicrobial agents. High mechanical strength molding material according to claim 1, which contains a substance. (5) Claim 1 containing a magnetic substance
High mechanical strength molding materials described in section (6) The high mechanical strength molding material according to claim 1, which contains a conductive substance. (7) The high mechanical strength molding material according to claim 1, which contains a substance having high thermal conductivity. (8) The high mechanical strength molding material according to claim 1, which contains a substance having high weather resistance. (9) The high mechanical strength molding material according to claim 1, which contains a substance having high chemical resistance. (10) The high mechanical strength molding material according to claim 1, which is made of disintegrated bacterial cellulose. (11) The high mechanical strength molding material according to claim 1, which is produced through an impregnation process. (12) The high mechanical strength molding material according to claim 1, which is produced through a coating process. (13) The high mechanical strength molding material according to claim 1, which is molded into a sheet. (14) The high mechanical strength molding material according to claim 13, wherein the sheet is paper. (15) The high mechanical strength molding material according to claim 1, which is formed into a thread shape. (16) The high mechanical strength molding material according to claim 17, which is molded into a cloth shape. (17) The high mechanical strength molding material according to claim 1, which is molded into a three-dimensional object. (18) The high mechanical strength molding material according to claim 1, which contains an immobilized carrier material.