JPH11209401A - Fine fibrous cellulose-containing mechanical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material having high elasticity and strength with excellent tensile strength and strain resistance, having an excellent hydrophilicity and no toxicity and providing an electric conductivity, magnetic properties, high insulating properties, a thermal conductivity, weatherability, chemical resistance or the like. SOLUTION: A fine fibrous cellulose is contained and the content thereof is 0.01-100%. It is preferable that the material contains one or more kinds of substances selected from the group consisting of a hydrophilic polymer material, a hydrophobic polymer material, an inorganic material, a coupling agent, an adhesive, a coating material, a dye, a pharmaceutical and an antibiotic.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high elasticity and high strength molding material having excellent tensile strength and stretch resistance obtained by incorporating fine fibrous cellulose. This molding material can be used as paper or other various sheets, and can also be used as a thread or various three-dimensional molded products. Further, the present invention relates to a method for producing a paper into which a filler is internally added, and more particularly to a method for producing a filler-inner paper having excellent opacity and strength.
The present invention also relates to a method for forming a cellulose coating comprising fine fibrous cellulose, a cellulose coating which can be produced by the method, and a substrate coated with the cellulose coating. The fine fibrous cellulose of the present invention is a parenchymal cell cellulose (Parenchymal Cell Cellulos).
e; hereinafter referred to as “PCC”).

[0002]

2. Description of the Related Art Various conventional molding materials are known. For cellulose, fibers are formed into a thread, a sheet, or the like.
In addition to those used for various three-dimensional molded products, there are cellophane, celluloid, and the like, which are prepared by dissolving a cellulose derivative once. In addition, various synthetic polymer materials have been developed, and some of them have molecular chains arranged in a certain direction to particularly increase the mechanical strength in that direction. Usually, fillers are added to paper used for printing or writing for the purpose of improving opacity, whiteness, smoothness, touch, writability, printability, and the like. As a method for producing such a paper internally containing a filler, a filler is added to pulp dispersed in water, and a paper furnish obtained by adding an internal additive usually used for papermaking to a fourdrinier paper. 2. Description of the Related Art A method of forming wet paper by a paper machine or a twin-wire paper machine and drying the wet paper has been conventionally known. Although these internal fillers prevent adhesion between the pulp fibers, increase the scattering specific surface area, or increase the scattering efficiency due to the difference in the refractive index, the opacity is improved,
In recent years, fillers have become more effective in reducing paper weight, saving pulp, and addressing increasing product quality requirements.
The importance of using more has increased. By including a large amount of filler, the opacity of the paper is improved,
At that time, since the strength of the paper is reduced, the filler content in the paper is limited. As a method of reducing the strength reduction of the paper due to the addition of filler, as described by AJ Hayes in Paper Technology and Industry, April 1985, after the filler is agglomerated with a chaotic polyelectrolyte,
Techniques for adding to stock are known. In addition,
No. 13680 discloses that a filler having a refractive index of 1.45 to 1.65 is aggregated to form a large number of internal voids having a pore diameter of 0.1 μm or more and as close to 0.1 μm as possible. JP-A-54-1164 discloses a method for producing paper having high opacity and whiteness and excellent filler yield by adding the aggregated particles thus obtained to a pulp slurry to form a paper.
No. 05 discloses a filled paper product in which particles having a diameter of 0.1 to 0.3 μm are aggregated and the aggregated particles are contained in an amount of 5 to 80% by weight based on the dry pulp. Furthermore, JP-A-60-119299 discloses a papermaking method in which heavy calcium carbonate is previously mixed with a cation-modified starch aqueous solution and then added to the stock to reduce wire abrasion.

[0003] However, the filler-filled paper obtained by dispersing the filler in the pulp slurry obtained by such a conventional method and adding an internal additive to the paper to form the filler has a problem in that the filler content is increased. However, although the opacity is improved accordingly, the fillers distributed between the fibers hinder the bonding between the fibers, resulting in a paper having a correspondingly lower strength. In addition, according to the technology of papermaking in which the filler is agglomerated in advance and then added to the stock, it is possible to reduce the degree of strength reduction of the paper due to the addition of the filler, but at that time, the purpose of adding the filler is The degree of improvement in the opacity of paper, which is one of the factors, also decreases. As described above, the opacity and the change in strength of the paper due to the filler are in conflict with each other, and it is very difficult to achieve both. Further, a cellulose coating formed from bacterial cellulose or microfibrous cellulose is disclosed in Japanese Patent Application No. 8-22944.
No. 5 describes it.

[0004] The parenchyma cells, especially the cell walls of the parenchyma cells found in sugar beet and citrus, have a unique morphology. Isolation of sugar beet pulp or other soft tissue cell sources from non-soft tissue cellulose and other structures is disclosed in any known method, for example, in Japanese Patent Publication No. 6-39482 and EPO Patent 102,829. Have been. Further, dispersions and suspensions of such cellulose components of parenchyma cells can be made, having unique rheological, chemical and physical behavior and properties useful in the practice of certain embodiments of the present invention. found.

[0005] Cellulose is known to consist of a linear array of beta 1-4 D-glucopyranose units.
The sequence of the beta 1-4 D-glucopyranose chains forming one aggregate consists of the secondary structure of cellulose.
In its native form of cellulose, this assemblage is called microfibrils. That is, the chains in the assembly may be arranged in a parallel, anti-parallel, or composite structure, and they may also be arranged randomly. It is at this stage of secondary structure that the basic cellulose type is recognized by those skilled in the art. Representative structures observed at this stage include cellulose I (more specifically, Iα, Iβ), II, III in the form of known crystalline cellulose.
And IV. The lower-order sequence, which is somewhat random depending on the type of cellulose, consists of amorphous cellulose. The native form of cellulose contains type I structural domains, whereas reconstituted cellulose such as rayon is primarily type II. The size of a native individual microfibril is primarily a function of the number of parallel chains generated by the biosynthetic organelle characteristic of the particular cell or tissue assembled.

[0006] Microfibrils consisting of the secondary structure of cellulose may then be arranged to form a tertiary structure. That is, various crystalline regions may disperse between themselves or between regions of amorphous cellulose in adjacent microfibrils to form strong microfibril associations that stabilize various tertiary structures. Thus, fibrils, bundles,
It can be seen that structures such as sheets comprise a tertiary structure. The cell wall of parenchyma cells is best described as a tertiary structure. In this regard, the sugar beet parenchyma cells are easily distinguished from, for example, stem fibrils or fibers also found in sugar beet. The quaternary structure of a cellulosic material is best understood as an arrangement or combination of tertiary structures. That is, a bundle of plant conduits, known as phloem, is distinguished from a similar bundle of conduits, xylem, as having a different quaternary structure, even though the tertiary structure is similar or even identical. Similarly, the parenchyma cell wall (tertiary structure) is structured somewhat differently, for example, to form parenchyma cells of sugar beet or certain fruits. The quaternary structure is also seen as consisting of macroscopic assemblies characteristic of a particular plant tissue. Such a structure would of course also comprise non-cellulosic materials.

[0007] In view of the foregoing, the structure represented by the isolated cell wall of parenchyma cells, such as those found in sugar beet and other flesh-like plant tissues, may be of a variety of other secondary and tertiary types known to those skilled in the art. It can be seen that the type is distinguished from the structure. In the present invention, it has been found that such cellulose obtained from the cell wall of parenchyma cells, hereinafter referred to as microfibrous cellulose or PCC, has unique physical, chemical and rheological properties. Further, dispersions of such parenchyma cell cellulose, especially in aqueous media, have other useful physical and rheological properties. The physicochemical and functional identity of PCC is believed to be related to its secondary and tertiary structure. The primary structure, the manner in which D-glucose molecules combine to form a linear polymer, is the same for all celluloses. The primary structural chains have an affinity for one another and naturally self-associate to form crystalline or other stages of structure that reflect their ordered assembly and spatial arrangement with one another.
Here, PCC begins to differ significantly from most other forms of cellulose. Micro fibrils (assembly)
Is formed by biosynthetic organelles controlled by the physiological mechanisms of the cell. Low angle X-ray crystallography shows that the PCC is composed of very small ordered regions with few reflective surfaces. P
The shape associated with the secondary structural element of CC appears to be a microfibril structure of currently very small dimensions, from high resolution, transmission electron microscopy. In summary, the PCC wall morphology reflects the tertiary structure arising from entangled layers of microfibrils.

Finally, the identification of the structure that forms the basis of functional plant tissue is based on the quaternary structure formed by combining tertiary structural elements with other high molecular weight substances such as hemicelluloses, lignins, proteins and the like. Done. The production of parenchyma cell cellulose primarily manipulates the structure in the quaternary and tertiary stages, but is also expected to have some effect on lower dimensional structures. In contrast, the production of other highly functional celluloses, such as microfibrillated cellulose and microcrystalline cellulose from high-purity alpha-cellulose wood pulp, reflects structural manipulation in the tertiary and quaternary stages, respectively. That is, each is distinguished from PCC.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high elasticity and high strength molding material having excellent tensile strength and elongation resistance over conventional molding materials. Another object of the present invention is to provide a molding material which is excellent in hydrophilicity and has no toxicity problem in addition to the high mechanical strength.
Still another object of the present invention is to provide a high-strength molding material that can be used as an immobilized carrier for enzymes, microorganisms, and the like having functions of improving strength, preventing adhesion, and preventing leakage of bacteria and the like. Still another object of the present invention is to provide a high mechanical strength material excellent in various application fields by imparting conductivity, magnetism, high insulation, thermal conductivity, weather resistance, chemical resistance, etc. in addition to high mechanical strength. Is to provide. It is a further object of the present invention to provide a filler composition which improves opacity without reducing the strength of the paper in a method for producing a paper internally containing a filler, and a production method using the composition. In addition, the present invention provides P
It is an object of the present invention to provide a method for forming CC as a coating on a substrate.

[0010]

Means for Solving the Problems The present inventors have conducted various studies to achieve these objects and found that the above objects can be achieved by using a material containing PCC as a molding material. Based on this finding, the present invention has been completed. That is, the present invention relates to a mechanical material containing fine fibrous cellulose (PCC). According to one embodiment, the PCC is about 4.
It can be isolated by acid hydrolysis of sugar beet pulp at a pH of less than 5, preferably less than about 4.0, more preferably 4.0 to 2.0. This strongly acidic condition is maintained at a temperature above room temperature and for a time substantially sufficient to release pectin and arabinogalactan from sugar beet pulp. Preferably, temperatures higher than about 125 ° C are used. According to one preferred method for PCC isolation, sugar beet pulp in an aqueous slurry is acidified with concentrated hydrochloric acid to a pH of about 2.5,
Hydrolyze at 60 ° C. for about 120 seconds. According to another approach, unlime-treated citrus pulp is treated with HCl for about 2.
Acidify to a pH of 2 and hydrolyze at about 165 ° C. for about 170 seconds. Also, as will be appreciated by those skilled in the art, the PC
A wide combination of pH, reaction time and temperature to obtain C is satisfactory.

The isolation of PCC from sugar beet pulp and other plant material containing parenchyma cells can also be achieved under strongly alkaline conditions. That is, a combination of high (strongly basic) pH, relatively high temperature, and relatively short reaction time is used for such isolation. This combination of high temperature, short time, strong alkaline pH allows for the co-production of hemicellulose components from such plant material without substantial degradation if desired. In some applications, co-isolation of PCC and hemicellulose may be desirable. In this regard, it is preferred that the hydrolysis employ a pH greater than about 8.0. More preferably, a pH of about 9.0 to about 13 is used, and even more preferably, a pH of about 10.5 to about 12.

The combination of pH, time and temperature may be varied by those skilled in the art without departing from the spirit of the present invention. Those skilled in the art will appreciate that such parameter changes may be used to modify the overall output of the hemicellulosic material produced according to the present invention, and thereby formulate various plant gums. In accordance with the practice of certain embodiments employing the alkaline hydrolysis of the present invention, conditions of time and temperature that are substantially sufficient to isolate the hemicellulose component without substantial degradation are used. In this regard, those skilled in the art will appreciate that the hemicellulose component present as pectin is rapidly hydrolyzed to a salt of pectic acid under basic conditions. Such pectic acid materials can comprise useful plant gums and other materials that lead to the desired combination with PCC.

The acidic or basic hydrolysis of sugar beet pulp or other soft tissue cell-containing material to isolate PCC or hemicellulose components is greatly facilitated by the use of physical shear in connection therewith. Preferably, the hydrolysis is performed with physical shear to maximize PCC fibrillation. In this regard, the application of physical stress or shearing aids in the destruction of the parenchymal intercellular tissue,
It appears to facilitate hemicellulose release. Various devices are used to perform such physical shearing.
That is, according to one embodiment, a tubular reactor is used in which a slurry of parenchyma cell-containing material is passed through one or more exit orifices at a desired pH at an elevated temperature and pressure. The slurry is then sprayed through the orifice into a lower pressure area. Other forms of mechanical shearing are also used immediately after isolation of the parenchyma cell cellulose or upon reactor discharge. For certain embodiments, the shearing causes substantial disruption between cell tissues and may be achieved by ultrasound, shock ejection or any other technique that helps to induce fibrillation of the wall.

It is most convenient to use physical shearing simultaneously with or shortly after the hydrolysis of sugar beet pulp and other plant material. That is, a stirring device such as a tubular reactor or an Oster blender having a "blow down" outlet orifice is preferred in view of convenience and cost. However, it is also possible to use hydrolysis and physical shear in separate steps. That is, the plant material is hydrolyzed under the pH, time and temperature conditions,
It may be stored under non-hydrolyzing conditions and then subjected to batch physical shear, for example in a high shear device. Other modifications of the hydrolysis / physical shear scheme will also be apparent to those skilled in the art. Hydrolysis combined with the physical shearing also serves to liberate parenchyma cell cellulose from parenchyma cell-containing plant material, especially sugar beet and citrus pulp. It is believed that the various forms of bonding between the parenchyma cell wall consisting of parenchyma cell cellulose and other forms of cellulose in spent sugar beet pulp and other materials are broken by a combination of hydrolysis and physical shear.
The material thus obtained has a solid and a liquid component. Further processing usually takes place after separation of solid and liquid substances. The solid material is found as crude parenchyma cell cellulose mixed with other cellulosic fragments such as bundles of fibers, fibers and the like. In addition, other solid components may be present. Preferably, the crude parenchyma cell cellulose is bleached by contact with a bleaching medium such as hypochlorite, peroxide or other material, or otherwise more suitable for dispersion. This bleaching step facilitates mechanical sorting and subsequent isolation of substantially pure parenchyma cell cellulose from non-parenchyma cell debris.

Parenchyma cell cellulose exhibits several unique properties. For example, a low solids slurry of about 0.5-2% by weight of PCC in water forms a stable homogeneous suspension after high shear homogenization. The high shear partially fibrillates the wall structure, causing the microfibrils to swell and dislocate from the surface, forming a collection of "expanded" or "hairy" membranes of the microfibrils. This suspension probably has more beneficial rheology due to the physical entanglement and interparticle association of the platelet-like morphology of the fibrillated PCC thus obtained. That is, the fibrillated PCC suspension has a high static viscosity and has thixotropic and pseudoplastic properties. P
The solution rheology of the CC dispersion is pseudoplastic and has the characteristics of a hydrocolloid suspension. It is believed that the expanded platelet structure of PCC is responsible for the unique solution rheology of the dispersed formulation. Highly hydrated platelets can be similar in density to water and can form a gravitationally stable suspension. Although the net shape of hydrated PCC is that of an elongated ellipsoid, there is considerable non-uniformity in shape. The average major dimension of the isolated membrane is 20-100 microns and the thickness is several hundred square meters. In the mid-shear range (10-100 s ^-1 ), the viscosity behavior of PCC can be approximated by the Bingham plastic model, a power law, commonly used to characterize colloidal dispersions. PCC
The mild thixotropy behavior, as indicated by, results from the relaxation of the time-dependent migration that forms a gel structure or hydrodynamic arrangement upon standing or upon mixing, respectively.
Platelet membranes are extremely shear resistant and are not affected by extreme temperatures, salts or pH. 2
At PCC concentrations above% w / w, the viscosity increases rapidly as particle-particle interactions begin to dominate the factors affecting solution rheology. At 4% w / w, PCC can form a gel.

[0016] Cellulose isolated from citrus pulp differs slightly from that obtained from sugar beet. Although the citrus PCC morphology is primarily on the membrane, there is considerable unevenness in size, and most particles cannot be sprayed through a 100 mesh screen. This is in contrast to PCC from sugar beet which has a relatively uniform particle size and can be easily rinsed through a 100 mesh screen apart from the fiber fraction. Citrus pulp cellulose is a film-former-like PCC and exhibits similar homogenate rheology. In the absence of water, membrane platelets associate strongly by hydrogen bonding. The transmembrane interaction is very effective during drying due to the high surface area to volume ratio of the fibrillated platelet structure. Depending on the amount and efficiency of hydrogen bonding interactions, dry PCC membranes can be extremely difficult to rehydrate. It has been found that the incorporation of certain cellulose ethers and the like is useful for preparing PCC that can be easily rehydrated.

Disintegration of such PCC once is also effective in increasing the mechanical strength. The defibration may be performed by using the mechanical shearing force described above. For example, the defibration can be easily performed after a rotary defibration or by a mixer or the like. The high mechanical strength molding material of the present invention can be formed into various shapes such as a sheet shape, a thread shape, a cloth shape, and a three-dimensional shape. In the case of forming a sheet, the PCC may be defibrated as required, then formed into a layer, and pressed and dried as necessary. In addition to pressing, a sheet having a plane orientation can be obtained, and a sheet having a plane orientation and a further uniaxial orientation can be obtained by applying rolling. It is desirable that drying of the sheet after defibration and / or squeezing be performed by fixing it to a suitable support. By fixing to a support, the degree of plane orientation is further increased, and a sheet having high mechanical strength can be obtained. As the support, for example, a plate having a network structure, a glass plate, a metal plate, or the like can be used. The drying temperature may be within a range in which cellulose is not decomposed, and a freeze-drying method can be used in addition to the heat-drying method. The sheet thus obtained has a structure in which fibrils are randomly entangled, as shown in FIG. According to the X-ray diffraction image, the squeezed product has a plane orientation, and the one subjected to rolling has a uniaxial orientation simultaneously with the plane orientation. The elastic modulus of the sheet is usually 10
About 20 GPa. The thickness of the sheet is determined according to the application, but is usually about 1 to 500 μm.

Various additives can be added to the sheet. For example, by adding solutions (aqueous or non-aqueous), emulsions, dispersions, powders, and deposits of various polymer materials, depending on the properties of the additives, strength, weather resistance, and chemical resistance , Water resistance, water repellency, antistatic properties and the like. Aluminum, copper,
If a metal such as iron or zinc or carbon is added in the form of powder or thread, conductivity and thermal conductivity can be increased.
In addition, if an inorganic material such as titanium oxide, iron oxide, calcium carbonate, kaolin, bentonite, zeolite, mica, and alumina is added, heat resistance, insulation, etc. are improved depending on the type, or surface smoothness is imparted. be able to. Strength can be further increased by adding low molecular weight organics or adhesives. It may be colored with a dye such as phthalocyanine, azo compound, eye, or reddish. For coloring, various paints, dyes and pigments can be used. It can also be used as a medical sheet by adding a medicine and a bactericide. Also,
Substances that absorb water, polar solvents, non-polar solvents, oils, etc.
It can also be added to the sheet. For example, a sheet can be formed by adding an oil-adsorbing substance such as a sodium acrylate-based water-absorbing polymer or urethane foam. A composite sheet may be formed by adding a plurality of the above components.
The amounts of these kneaded materials and additives are determined according to 99.
When the content is 9% or less, an appropriate amount for obtaining desired physical properties is added. The timing of these additions does not matter, and they may be added to the PCC disintegrated product or may be added after drying. In some cases, it may be added to the medium or to the culture. The addition method may be mixing or impregnation. Layers of other substances can be laminated on such a sheet.
The laminate is appropriately selected according to the purpose of use of the sheet. It can be selected from the above-mentioned kneaded materials or additives, and for example, various polymer materials can be coated to impart water resistance. When used as paper, the PCC may be paper-disintegrated after it is defibrated, and then dried, thereby providing excellent tensile strength, stretch resistance, etc., as well as high elasticity and high chemical stability, excellent water absorption and excellent air permeability. Strong paper can be obtained. Prior to papermaking, fine fibrous cellulose alone or a substance to be complexed with the fine fibrous cellulose is suspended in an appropriate liquid, for example, water, a polar solvent, a non-polar solvent, and the like, followed by a conventional method. Papermaking may be performed according to the following. Further, if necessary, the sheet thus formed can be coated with various substances by a method such as spraying or coating. Conversely, it is also possible to obtain a composite material by spraying or applying a suspension of fine fibrous cellulose to the surface of various sheets and molded products. In this case, the usual additives and processing agents used for papermaking can be used, and they can be added by selecting from the above-mentioned kneaded materials and additives.

In recent years, the demand for electric insulating paper, heat-resistant paper, flame-retardant paper, and the like has increased, and synthetic paper using non-cellulose fibers, non-papermaking, and the like have been produced. When these are to be produced by a wet method, non-cellulose fibers do not form hydrogen bonds, except when pulped fibers such as fibers of polyethylene, polypropylene, polyacrylonitrile, and aromatic polyamide are obtained. , It is necessary to add cellulose pulp to make paper. In this case, it is required to reduce the amount of pulp as much as possible to improve the insulation, heat resistance and flame retardancy. However, when a commonly used wood pulp is mixed, the addition amount is 20 to 5 times.
It reaches 0%, and the purpose is not fully achieved. However, by using bacterial cellulose instead of wood pulp, the amount of cellulose can be significantly reduced,
Paper with excellent heat resistance and flame retardancy was obtained. Therefore, the high mechanical strength molding material of the present invention is also effective for these.

It is said that photocrosslinkable polyvinyl alcohol has a higher affinity for living organisms than conventional photocrosslinkable resins, and it is thought that the use of immobilizing agents such as enzymes and microorganisms will be further improved. ing. Also, the photoresist used when making the original plate for printing is
A resin is coated on a substrate, and a pattern to be printed is projected on the substrate to cause photocrosslinking to cure the resin, and the uncured resin is washed away to produce a printing original plate. Photocrosslinkable polyvinyl alcohol also has the advantage of being cheaper and easier to wash than conventional oil-soluble photoresists, and is expected to be applied. But,
In these cases, there has been a problem that the photocrosslinkable polyvinyl alcohol swells with water and the crosslinked structure is destroyed. However, this swelling can be prevented by adding PCC. When the yarn is used, for example, PC
After washing and drying the dissociated product of C, it is dissolved in a dimethylacetamide / lithium chloride-based solution or the like, and the dissolved product is insoluble in water or cellulose such as alcohols, ketones, dioxane, and tetrahydrofuran, and the cellulose solvent is soluble. What is necessary is just to spin using a coagulation liquid. In the case of fabric, the yarn may be woven by a conventional method. In the case of forming a three-dimensional object, various plastics are kneaded with PCC or further laminated to obtain a desired molded product. This can be replaced with, for example, various FRP products or carbon fiber products.

Conventionally, agar, carrageenan alginic acid, gelatin, collagen, polyamino acid, photocrosslinkable resin, polyacrylamide and various resins have been used as the immobilizing carrier, and meshes and fibers such as polyvinylidene chloride and polyester are used as reinforcing materials. By mixing with these carriers, improvement in strength and prevention of sticking have been attempted. However, in this immobilized material, the support is enlarged by the reinforcing material, the surface area per unit area is reduced, substrate diffusion in the support is inhibited, or enzymes, biological substances, catalysts, and other substances immobilized on the support are immobilized. There has been a problem that the reaction rate and the reaction yield are reduced due to a relative decrease in the concentration of a reactive substance (hereinafter referred to as “active ingredient”). In addition, if the active ingredient is used for a long time or repeatedly to leak out from the immobilization carrier, there is a problem that the activity gradually decreases. It was difficult to prevent leakage from the carrier. 6% of photo-crosslinkable polyvinyl alcohol, which is an example of a very weak gel, among conventional immobilization carriers
In the case where a crosslinked aqueous solution is used as an immobilization carrier, there is also a problem that the immobilization carrier is destroyed due to swelling caused by water.

Instead of the conventional immobilized carrier reinforcing material, P
By using CC as it is, disintegrating it, or exposing these materials to dryness, the above-mentioned problems can be solved to obtain a high-strength immobilized carrier that has never been seen before. There are the following methods for producing such an immobilized carrier. Basically, with the bacterial cellulose,
The following immobilized carrier materials may be mixed, then gelled, polymerized or molded. If necessary, the active ingredient for the purpose of immobilization may be added together at the time of this mixing, or the active ingredient may be immobilized after the immobilization carrier is produced.
The carrier material is not particularly limited as long as it can be mixed with PCC. , Tannin, silicone rubber, casein, agar, carrageenan, polyurethane, poly-2-hydroxyethylmethacrylic acid, polyvinyl chloride, γ-methylpolyglutamic acid, polyvinylpyrrolidone, polydimethylacrylamide, photocrosslinkable resin, polyethylene glycol derivative, polypropylene glycol Derivatives, polybutadiene derivatives, collodion, nylon, polyurea, silica gel, silicon derivatives, phenylsiloxane, fibrin, cellulose nitrate, Hydrogen, phospholipid, calcium phosphate gel, phenoxyacetyl iodide, available glycolide mannan like.

The method for producing the immobilized carrier is described as follows.
The carrier material is made into a solution with an appropriate solvent, or is made to have fluidity by being in a molten state, and then PCC is added.
If this is gelled, an immobilized carrier can be obtained. Gelation methods vary widely depending on the carrier material, for example,
In the case of sodium alginate, it may be added to the calcium chloride solution after mixing, and in the case of agar, the temperature may be lowered. When the PCC is in a defibrated state or in a dry state while leaving a fibrous form obtained by a method such as freeze-drying or critical point drying, these PCC and the carrier material are mixed with each other as described above. In contrast to impregnation, the immobilized carrier is obtained by mixing, gelling, polymerizing or molding after mixing by a usual method. The concentration of PCC in the immobilized carrier is 0.01% to 99%, preferably about 0.1 to 2%.

The shape of the immobilized carrier obtained by the above method can be freely selected according to the type and method of the reaction. For example, when packed in a column or placed in a stirring tank, it may be processed into a ball shape, or may be formed into a rod shape or a film shape as needed. When the immobilized carrier is manufactured by mixing the disaggregated PCC with the carrier material and then gelling, polymerizing, or molding the same, the immobilized carrier may be processed and molded in the same manner as in the related art. The active ingredient immobilized on the immobilization carrier of the present invention is an enzyme, a microorganism, a biological substance, a catalyst, or another reactive substance, and may be any commonly used substance. In addition, animal cells, plant cells, and the like may be immobilized as necessary. The immobilized product thus obtained can be used for producing 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. The catalyst and other reactive substances may be any organic and inorganic substances that can coexist with PCC and are used for ordinary chemical reactions and the like. These can be packed in a column and used as a reaction bed, or can be used for various types of chromatography.
On the other hand, by selecting the particle size and size, the immobilized carrier can also be used for physically separating and selecting or purifying the target substance.

Further, the present inventors have conducted intensive studies in order to solve the above-mentioned various problems in producing paper into which a filler has been internally added. As a result, the filler and fine PCC have formed agglomerates in advance. It has been found that the opacity can be improved without lowering the strength by keeping the strength, and the present invention has been completed. That is, the present invention has an average particle size of 2.0 μm
A filler composition obtained by mixing and dispersing the following filler and PCC in water and coagulating in advance with a coagulant, and adding the filler composition to a paper stock, and forming a paper-filled paper characterized by being formed into a paper. It is a manufacturing method. As the filler of the present invention, talc, clay, titanium dioxide having an average particle size of 2.0 μm or less,
Use fillers that are commonly used for paper such as sedimentable calcium carbonate, heavy calcium carbonate, calcium sulfate, barium sulfate, aluminum hydroxide, activated clay, synthetic silicate, kaolin, calcined kaolin, and plastic pigment, alone or in combination. be able to. The average particle size is 2.
Fillers exceeding 0 μm do not provide sufficient opacity and strength. The average particle size in the present invention is determined by using a particle size distribution curve obtained by dispersing an aqueous dispersion of a filler with an ultrasonic disperser for 5 minutes and then applying a light transmission type particle size distribution analyzer (SKN type, manufactured by Seishin Enterprise Co., Ltd.). , The calculated cumulative weight percent is 50%
Is the diameter of the particle corresponding to

The PCC used in the present invention is preferably a PCC that has been subjected to a defibration treatment, and the defibration can be performed by a method described later. As the flocculant in the present invention, cationic polyacrylamide having a molecular weight of 100,000 or more, cationic starch, cationic guar gum and the like can be used among cationic polymer electrolytes. The amount of addition varies depending on the type of filler and PCC used.
Suitably, the weight percentage is not less than 10.0 weight percent. Further, an anionic polyelectrolyte such as forming an complex with these cationic polyelectrolytes to enhance aggregation, such as anionic polyacrylamide, or anionic inorganic fine particles, such as colloidal silica or bentonite aqueous dispersion, Further, or by using an amphoteric polymer electrolyte or an amphoteric inorganic fine particle aqueous dispersion in combination, it is also possible to form an aggregate of the filler and the bacterial cellulose disintegration product.

In the present invention, the content ratio (A / F) of the filler (A) having an average particle size of 2.0 μm or less and PCC (dry matter) (B) is used.
B) is preferably 0.5 to 20.0 by weight.
If (A / B) is less than 0.5, a sufficient opacity improving effect cannot be obtained for the required paper strength, and (A / B) is 2
If it exceeds 0.0, if the opacity is satisfied, the strength of the paper decreases. In the filler-filled paper of the present invention, additives usually used in papermaking, such as sizing agents, defoamers, slime control agents, dyes, coloring pigments, fluorescent agents, dry paper strength agents, wet paper strength agents, A water repellency improver, a retention improver, and the like can be included as needed. Further, starch, polyvinyl alcohol, various surface sizing agents and the like can be smeared on the surface of the filler-filled paper of the present invention.

The reason why a filler-filled paper having excellent opacity and strength can be produced by preliminarily aggregating the filler and PCC and then adding the paper to the paper material to form a paper is as follows. Although the interface effective for scattering is remarkably reduced, the refractive index is different from that of the filler, and fine PCC is coagulated together with the filler. In addition, since the filler is held between the fibers as agglomerates, it is considered that the amount of fine filler that inhibits the bonding between the fibers is small, and the decrease in strength is reduced.

Furthermore, the present invention relates to a method for forming a cellulose film, which comprises spraying a suspension containing PCC on a substrate. The spraying operation can be performed continuously or intermittently at appropriate times and intervals. The suspension can use water or an organic substance such as a polar solvent as a solvent. Drying after spraying can be carried out by a conventionally known suitable method, for example, natural drying such as air drying, hot pressing or a dryer using infrared rays, microwaves or the like. The present invention further relates to a cellulose coating that can be produced by the above method. The cellulose coating of the present invention imparts hydrophilicity or hydrophobicity to the substrate surface, prevents corrosion of the substrate surface, increases internal loss of the substrate, and further increases the Strength can be improved. Therefore, the present invention also relates to a method for forming a cellulose film, which is obtained by subjecting the film thus obtained to a secondary treatment such as chemical treatment or heat treatment for various purposes. By performing such secondary processing, the surface properties such as the strength of the coating are changed, for example,
Water resistance can also be imparted to the coating. About 1 heat treatment
The reaction is carried out at a temperature of 20 ° C. or higher, preferably about 130 ° C. to about 200 ° C., usually for about 5 minutes to about 60 minutes. The heat treatment may be performed using the same apparatus and method as the drying after spraying, by changing the temperature conditions and the like.

The present invention also relates to a coated substrate having at least one coating of the cellulose of the present invention. The substrate may further have a cellulose coating obtained by another method or a coating made of another substance, in addition to the coating of the present invention. As the substrate that can be coated by the method of the present invention, all kinds of substances can be considered. For example, various papers, cloths including nonwoven fabrics, wooden boards and plates such as plastic and metal, and plastics and the like can be used. Sheets and films,
Further, there may be mentioned composite substrates composed of these, as well as surfaces such as leaves and stems of plants or surfaces such as skin of animals and human bodies.

The spray operation itself can be performed using a conventional spray device. That is, as a specific method of spraying, for example, a method using a pressurized nozzle, a method using a two-fluid nozzle, and the like,
The particles are coarser than those of the two-fluid nozzle type.
The method of spraying can be appropriately selected according to the purpose. Also, there is no particular limitation on the average particle size during spraying,
Those having an average particle size of about 100 μm or less are preferably used. The thickness of the cellulose coating obtained in the present invention can be adjusted by the amount of spraying a predetermined area, and the range is usually from 0.02 μm to several cm or more. In the method of the present invention, in order to form a cellulose film by spraying, compared to a case where cellulose is applied to the substrate using a roll or a brush or the like, even on a substrate in any state such as a slope, A uniform coating layer can be easily formed.

In the method of the present invention, it is preferable that the PCC has been subjected to defibration. The disintegration phenomenon of PCC is
It is considered that the stress generated inside the cellulose due to a mechanical external force or the like is a phenomenon caused by deforming and breaking it. Therefore, the PCC disaggregation process can be performed by applying a mechanical external force to the PCC. Further, the disaggregation treatment can be carried out also by acid hydrolysis, enzymatic hydrolysis and bleach. Here, the mechanical external force is, for example, a pull,
Examples of the stress include bending, compression, torsion, impact, and shear stress, and generally, compression, impact, and shear stress are mainly contained. When actually applying these mechanical external forces to the PCC,
For example, this can be achieved by using an ultrasonic oscillator such as a mixer, a polytron or a self-excited ultrasonic pulverizer.

In the disaggregation process by the mixer, the mechanical external force is mainly an impact force due to collision of the stirring blade with the PCC and a shear force generated by a displacement phenomenon due to a difference in speed of the medium. In the disintegration process using Polytron, the mechanical external force is the compression force due to the PCC being sandwiched between the external teeth and the internal teeth, the impact force due to the collision of the PCC with the high-speed rotating teeth, and the high-speed rotation with the stationary external teeth. The shear stress generated in the medium existing in the gap between the internal teeth is mainly caused.
In the disintegration by the ultrasonic pulverizer, the mechanical external force is mainly cavitation (cavity phenomenon) continuously generated in the medium due to the oscillation of the ultrasonic oscillating unit, and significant shear stress locally generated. The disaggregation process of the present invention can be performed by any method other than the above-described specific examples as long as a constant load (mechanical external force) can be applied to the PCC. Other disaggregation treatment conditions can be appropriately selected by those skilled in the art. Furthermore, it can be sieved with a screen having a predetermined opening.

The suspension containing PCC is mixed with a third solvent other than water.
After adding the ingredients in advance, by spraying this,
Prevents hydrogen bonding between fine fibers formed during drying,
The porosity (such as voids) of the coating can be adjusted. Third
The components are selected by those skilled in the art according to the purpose of use of the cellulose coating of the present invention, in addition to adjusting the porosity of the coating. A solid component, a low-molecular soluble component, a high-molecular component and the like may be used in combination. For example, when preparing an inorganic powder sheet in the papermaking field, the binding characteristics of the inorganic powder of PCC and the function of the inorganic powder (for example, magnetic powder) can be efficiently expressed on the surface of the formed inorganic powder sheet. In order to make the film appear, the coating of the present invention, which is a raw material, comprises a PCC disintegration material, a magnetic inorganic powder, acrylamide (coagulant), and a cationized starch (paste), for example, of about 100: 15: 1: 3. What is necessary is just to mix and use by ratio. As another example,
When used as a gloss enhancer in the food field, xyloglucan, salt, sucrose and the like can be used, for example, by adding 10:
A combination of 5:50 may be used. In particular, when tasteless, odorless, colorless, and harmless substances are required for use in foods, the third component is preferably an edible soluble polymer. Further, in order to make the surface of the coating film hydrophobic, polystyrene latex or the like can be added as the third component, or various drug components can be added as the third component. The addition amount of these third components can be appropriately selected by those skilled in the art according to the type of the substance and the like, and is usually 2 to 1,000% by weight based on the weight of PCC. These third components can be separately applied to the substrate by other methods, in addition to being previously mixed in the suspension of the cellulose.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples. It will be clear to those skilled in the art that these examples do not limit the scope of the invention in any way. Example 1 PCC simply from sugar beet (beet pulp)
After washing 300 g of pomace of separated sugar beet (beet pulp) with a sufficient amount of water, 40 g in terms of dry weight
The equivalent was suspended in 1000 ml of 2% sodium hydroxide.
The suspension was divided into 500 ml portions, and crushed at the maximum speed for 10 minutes using an Oster blender. This was stirred at 80 ° C. for 2 hours. Thereafter, the suspension was added to 20
The solution was suction-filtered through a 0-mesh filter cloth and washed with a sufficient amount of water. Washing of the obtained wet product in a sodium hydroxide solution and washing with water were repeated again as described above. Equivalent to 8 g by dry weight of this wet product was put into 500 ml of water, and stirred and dispersed at 80 ° C. 3 g of sodium chlorite was added to the dispersion, and 0.6 ml of glacial acetic acid was further added, followed by bleaching at 80 ° C. for 1 hour. This bleaching step was repeated three times. After cooling to room temperature, the mixture was suction-filtered, and further washed with a sufficient amount of water on a Buchner funnel to obtain wet PCC. Purification and washing of the dried sugar beet pomace were performed in the same manner as described above to obtain wet PCC. A 0.5% suspension was prepared from these wet PCCs, and defibrated at a maximum speed of 250 ml using an Oster blender for a predetermined time. The obtained disintegrated product was used in each of the following examples.

Example 2 Example 1 against novoloid fiber (Kinoe fiber KF0203, φ14 μm, 3 mm length, manufactured by Gunei Chemical Industry Co., Ltd.)
The PCC prepared in the above (the same applies to Examples 2 and later) was added, and a sheet having a basis weight of 60 g / m ² was made by the TAPPI method. (TAPPI standard T205m-58) For comparison, a mixed paper made of highly beaten ordinary wood pulp (LBKP) (245 ml CSF) and kainol fiber was also prepared. The tear length of these sheets was measured with an automatic recording tensile tester. The results were as shown in the following table.
The mixing ratios (parts) shown in the following Tables 1 to 5 are parts by weight when each component is converted to dry matter.

[0037]

[Table 1]

By using PCC, papermaking became possible with a small amount of addition, and the strength was increased. In the case of using ordinary pulp, papermaking was not possible with less than 10 parts.

Example 3 Paper mixed with PCC was prepared using various inorganic fibers, and the breaking length was measured. The results were as shown in the following table.

[0040]

[Table 2]

In each case, papermaking was possible with the addition of 5 to 10%.

Example 4 PCC was made by the TAPPI method, and the Young's modulus of the PCC measured by a tensile test was 6.5 GPa. In addition, polyamide epichlorohydrin resin (Dick, Inc.) is used for the purpose of improving drainage and improving the yield of fine particles.
Hercules sponge 557H) 5% (solid content ratio)
Was added and papermaking was performed. The Young's modulus of this paper is 6.9 GPa
Met. In each case, high strength paper was obtained.

Example 5 Paper made by adding PCC to wood pulp (LBKP) (CSF 600 ml) and further adding 5% (solid content ratio) of aluminum sulfate was as follows.

[0044]

[Table 3]

Paper strength was improved by the addition of PCC.

Example 6 PCC disintegrated with wood pulp (LBKP) (CSF 600 ml)
Was added, and the paper was made by the TAPPI method. The paper was impregnated with a phenol resin, air-dried, and hot-pressed to produce a phenol laminate. The number of layers was five. For comparison, a phenol laminate made of only wood pulp was prepared in the same manner. These phenol laminates were molded into a dumbbell No. 1 type (JIS K-7113), and the physical properties were measured using an automatic recording type tensile tester. Table 4 shows the results.

[0047]

[Table 4] The strength is shown in units of kg / cm ² .

The strength of the phenol laminate was improved by using PCC.

Example 7 Gelatin (Miyagi Chemical Co., Ltd.) and PCC were disintegrated and mixed according to the composition shown in the following table. Add PCC to this mixture
Was mixed to a concentration of 0.5%, and then transglutaminase was added to gelatin in an amount of 0.1% according to the method described in JP-A-59-66886.
One unit was added and left at 25 ° C. for 1 hour to gel.
The breaking strength of gelatin and gelatin to which PCC was added as a reinforcing material was measured. The measurement was performed by gelling the above-mentioned gelatin solution in a cylindrical plastic container having a diameter of 22 cm, setting the rheometer (Fudo Industry Co., Ltd., NRM 2002J), and inserting a 5 mmφ adapter directly into the gel. This was done by expressing the maximum load as the breaking strength.
Table 5 shows the results.

[0050]

[Table 5] ゼ ラ チ ン Gelatin concentration PCC addition concentration Breaking strength (%) (%) (g) ─────── {12.5 080 12.5 0.5 136 12.5 1.0 190} ────────

Example 8 A hardwood kraft pulp slurry beaten with a beater to a standard Canadian freeness of 500 ml was prepared. Separately, the precipitated calcium carbonate (A) having a particle size of 1.0 μm and the PCC disintegrated product (B) prepared in Example 1 were weight ratio (A).
/ B) was dispersed and mixed in water at a solid content concentration of 10% at 10/1, and then heated and dissolved in advance, and the positive starch (Cato2, trade name, manufactured by Oji National Co., Ltd.) was added to the total weight of the precipitated calcium carbonate and the PCC disaggregated product. Add 1% equivalent of solid content, stir,
A slurry of the aggregate, which is the filler composition of the present invention, was obtained. Next, the previously prepared pulp slurry (10% pulp solid content)
(0 parts), 45 parts of the above-mentioned aggregate in solid content was added.
A paper having a basis weight of 60 g / m ² is hand-made from the slurry, water is applied to the wet paper by applying a pressure of 1.0 kg / cm ² ,
The sample was dried in a Hirasaka dryer at 80 ° C. for 10 minutes to obtain a sample of Example 8. The obtained sample was incinerated at 950 ° C. and the filler content was calculated. The filler content of this sample was 20%.

Comparative Example A The same positive starch as in Example 8 was added to an aqueous dispersion of precipitated calcium carbonate having an average particle size of 1.0 μm and having a solid concentration of 10% instead of the aggregate of Example 8, and the weight of calcium carbonate was changed. To obtain an aggregate. The same pulp slurry as used in Example 8 was used for 100 parts of pulp solid content.
41 parts of the aggregate was added as a solid content, and then 4 parts of the PCC deflocculate prepared in Example 1 were added. Next, the above-mentioned positive starch solution was added at 0.23% in solid content, and hand-made in the same manner as in Example 8 to obtain a sample. This sample is referred to as Comparative Example A.
The filler content of this sample was 20%.

Comparative Example B The same pulp slurry as in Example 8 (pulp solid content 100
Part), the same average particle diameter as 1.0 μm used in Example 8.
45 parts of precipitated calcium carbonate and P prepared in Example 1
4 parts of CC disintegration and 0.45 solids
Parts were separately added and mixed to obtain a stock. Next, a sample of Comparative Example B was obtained by hand-making in the same manner as in Example 1. The filler content of this sample was 20%.

Example 9 An aggregate was obtained in the same manner as in Example 8 except that the precipitated calcium carbonate used in Example 8 was changed to heavy calcium carbonate having an average particle diameter of 2.0 μm. Further, the same pulp slurry as prepared in Example 8 (pulp solid content: 100 parts)
In addition, 45 parts of the above-mentioned aggregates were added as a solid content, and 0.05 parts of an alkyl ketene dimer sizing agent was added as a solid content to obtain a stock. A paper having a basis weight of 60 g / m ² is hand-made from this stock, and after applying a pressure of 7.0 kg / m ^{2 to} the wet paper, water is extracted.
The sample was dried with a Hirasaka dryer at 95 ° C. for 3 minutes to obtain a sample of Example 9. The filler content of this sample was 20%.

Comparative Example C The heavy calcium carbonate used in Example 9 was prepared using an average particle size of 5.
Example 9 except that 0 μm heavy calcium carbonate was used.
A sample was obtained in the same manner as described above. The filler content of this sample was 2
It was 0%. This sample is referred to as Comparative Example C.

Examples 10 to 14 100 parts of the same pulp as in Example 8 were added with an average particle diameter of 0.3.
The mixing ratio (A / B) of the μm precipitated calcium carbonate (A) and the PCC disintegrated product (B) prepared in Example 1 was 0.2
5, 0.50, 1.0, 20.0, and 50.0, and 0.05% of a positive polyacrylamide (a product of Allied Colloid Co., Ltd.) based on the total weight of the filler and PCC disintegrated product of each mixture. Name Percoll 292)
Five kinds of agglomerates were produced, and five kinds of hand-made sheets were prepared in the same manner as in Example 8 so that the filler content in the sheet was 10% for each agglomerate. Fill these samples with filler and P
Example 1 was caused by the difference in the mixing ratio of the CC disintegration.
0, 11, 12, 13, and 14. The results are collectively shown in Tables 6 and 7.

[0057]

[Table 6]

[0058]

[Table 7]

In Tables 6 and 7, the opacity is a value measured according to JIS P-8138, and the internal bond strength in Table 6 is a value measured by an internal bond tester (manufactured by Kumagai Riki Co., Ltd.).

Example 15 The PCC disintegration material prepared in Example 1 (provided that the concentration of PCC was 0.4%) was sprayed on the surface of high-quality paper (copy paper made by Xerox) using a hand spray.
These papers were then dried under tension at 80 ° C. for 3 hours. It was found that a PCC coating was formed on the surface of the high quality paper. It was inferred from the change in basis weight that the thickness of the formed coating film was about 5 μm on average. The specific gravity of the film used for calculating the average thickness was 1.2 for convenience. In the following examples, this value was used for calculating the thickness unless otherwise specified.

Example 16 A PCC deflocculated product was sprayed on the surface of a commercially available newsprint using a two-fluid nozzle type spraying device. PC contained in disintegrated material
The concentration of C was 0.2%. 50 sprayed newspapers
Drying at <RTIgt; C </ RTI> formed a smooth, transparent coating on the newsprint surface. The coating formed did not come off the newsprint. The thickness of the coating averaged 15 μm. Example 17 A mixture obtained by adding a cationized starch to a PCC disintegration at a concentration of 0.05% was stirred at 100 ° C. for 30 minutes, and the added starch was gelatinized. This mixed solution was sprayed on the surface of newsprint using a hand spray, and then dried to form a transparent thin film on the surface. 20μm on average
Met.

Example 18 The PCC deflocculate prepared in Example 1 was applied by spraying on the surface of a thin nylon taffeta. This was dried in an air stream at 120 ° C. to obtain a nylon taffeta having four types of coatings formed on the surface. As a result of calculating the thickness of the coating from the difference between the weight of the nylon taffeta before application and the weight after application and drying, and the area of the applied portion, the thickness as shown in Table 8 was calculated. The specific gravity of all coatings is conveniently 1.0
And

[0063]

[Table 8] 種類 Type of disintegration material applied Average thickness of coating (μm) ──────── {(A) 15 (B) 61 (C) 63 (D) 70} ──────

In each case, the surface shape was smooth. Nylon taffeta itself, which is a substrate on which a coating is formed, has no hydrophilic property and has a water-repelling property, whereas when a coating is formed, all of them have hydrophilicity. Was observed.

Example 19 The nylon taffeta having the film formed thereon prepared in Example 18 was cut into a circular shape having a diameter of 45 mm. This has a diameter of 45
After the filter was mounted on a suction filtration device having a diameter of 1 mm, a vacuum filtration test was performed on 150 ml of n-propanol, and a filtration test was performed for a case where a film was formed and a case where a film was not formed.
When the coating was not formed, diethyl ether easily passed through gaps in the weave of the nylon taffeta. On the other hand, in each case where the four types of coatings were formed, almost no leakage of diethyl ether from the filtration surface was observed because the thin coating was formed on the surface of the nylon taffeta. In each case, wetting of the filtration surface was observed.

Example 20 A PCC deflocculate was heated to 150 ° C., having a thickness of 3 mm and a surface area of 6
One side of a 25 cm ² iron plate was sprayed using a two-fluid nozzle type spraying device. However, PC included in PCC disintegration
The concentration of C was 0.1%. Spraying was performed for 5 seconds every minute to prevent the temperature of the iron plate from lowering. As a result of measuring the thickness of the finally obtained coating with a caliper,
It was found to be 120 μm. The obtained iron plate with the coating was left in a large glass desiccator containing 10N hydrochloric acid at room temperature for 12 hours to conduct an exposure test with hydrogen chloride gas. After the exposure test, the coating on the side where the coating was formed was peeled off, and the surface of the iron plate was observed. As a result, almost no corrosion occurred on the iron plate surface.
On the other hand, the surface of the iron plate on which the film was not formed was corroded by hydrogen chloride gas. It is considered that the coating of PCC inhibits the permeation of hydrochloric acid, thereby reducing the corrosive action of the hydrogen chloride gas on the iron plate.

Example 21 Aluminum plate having a thickness of 150 μm (length 5 cm, width 5 mm)
Was autoclaved in water at 120 ° C. for 20 minutes to form an alumina layer on the surface. While heating the aluminum plate on which the alumina layer was formed to 80 ° C., the PCC disintegrated material prepared in Example 1 was intermittently sprayed at an interval of 2 seconds per minute using a hand spray. A coating was formed thereon. The coating was formed on both sides of the aluminum plate. The internal loss of this aluminum plate was measured using a vibration lead method. Table 9 shows the results.

[0068]

[Table 9] 内部 Sample internal loss (-) ─────────────────── ── Aluminum plate 0.0019 Alumina formed 0.0020 Aluminum plate Coated 0.013 Aluminum plate ─────────────────────

It was found that the formation of the film on the surface increased the internal loss of the aluminum plate. Greater internal loss means greater attenuation of sonic energy traveling through the material. Therefore, by forming such a coating on the surface of a metal plate having a small internal loss, it can be applied to a damping steel plate or the like.

Example 22 A PCC deflocculate was sprayed on a polyethylene sheet. Hand spray was used for spraying. However, the concentration of PCC contained in the defibrated material was 1.0%. By air-drying each spray-coated polyethylene sheet,
It was found that a film was formed on the polyethylene sheet.

Example 23 The PCC disaggregated product prepared in Example 1 was repeatedly suspended in ethanol and centrifuged to completely replace the water with ethanol. Next, this was repeatedly suspended in acetone and centrifuged to obtain an acetone-substituted product. This was suspended in ethyl acetate and centrifuged repeatedly to obtain a disintegration suspension containing 5% of PCC and 95% of ethyl acetate (hereinafter referred to as disintegration product E).
A). A mixture of 10 parts of the disintegrated product EA and 1 part of a butyl acetate solution of blocked isoisocyanate (Takenate B-830, manufactured by Takeda Pharmaceutical Co., Ltd.) was sprayed onto nylon taffeta to form a coating. This was left in an atmosphere of 170 ° C. for 3 minutes to remove the isocyanate protecting group,
Crosslinking was carried out by the reaction of hydroxyl groups of isocyanate and cellulose. As a control, a coating film was formed by spraying on nylon taffeta using the deflocculated product EA to which no blocked isocyanate was added. In the case of the control, peeling of the coating was observed by immersion in water for 1 hour, but no peeling of the coating occurred when the crosslinking treatment was performed. In addition, the touch of nylon taffeta has been improved from a cold and sticky feel to a warm and dry feel. Further, the nylon subjected to the cross-linking treatment was subjected to a washing test (picture display method 103 of JIS L0217). As a result, the coating of the PCC did not fall off due to washing, and no change was observed in the texture of the taffeta.

Example 24 Polyvinyl acetate latex suspension (commercial adhesive for woodworking)
And a PCC disintegrated product obtained by concentrating by centrifugation a PCC concentration of 3% and mixing them in equal amounts. Further, this mixture was diluted two-fold with water. This is sprayed onto the surface of the kraft paper using a hand spray, and then under tension.
Dry at 4 ° C. for 4 hours. The thickness of the film was measured with a caliper to be 105 μm.

Example 25 A suspension of polystyrene latex (average particle size: 0.3 μm, manufactured by Sigma) was mixed with a PCC disintegration product (PCC concentration: 0.2%). The concentration of latex in the mixture is about 0.
1%. This was sprayed on the surface of the cedar board using a two-fluid nozzle type spraying device. After spraying, the film was dried in an atmosphere of 70 ° C. to form a film. The coated plate was heated at 180 ° C. for 10 minutes using a tabletop heat press (manufactured by Tester Sangyo Co., Ltd.).
It was hot pressed at a gauge pressure of 10 atm. By hot pressing, the polystyrene latex contained in the coating fused with the cellulose fibers. The thickness of the coating was about 0.2 mm.
After cooling, water droplets were applied to the surface of the film, but the surface of the film was hydrophobic, and it was observed that the water droplets became beads. On the other hand, when no coating was applied, the surface of the plate was hydrophilic.

Example 26 The PCC disintegrated product prepared in Example 1 was heated to 90 ° C.
A coating was formed on a stainless steel plate of 0 cm, 10 cm in width and 5 mm in thickness while spraying intermittently. The spray interval was 10 seconds every 2 minutes. By adjusting the number of times of spraying, the thickness of the resulting film was adjusted. The thickness of the coating was measured with a caliper.
Finally, a film having a thickness of 5 mm was formed. The coating is PC
It was a plate-like material in which C fibrils were tightly bound. P
No in-plane anisotropy of CC fibrils was observed. After peeling the coating from the stainless steel plate, to prepare a strip-shaped test piece, using an Instron type tensile tester,
A tensile test was performed. The length of the test piece was 5 cm, the width was 1 cm, and the tensile speed was 1 cm per minute. As a result, the breaking strength was 120 MPa
It was found that a plate-like coating having a tensile modulus of 14 GPa was obtained.

Example 27 Using a centrifuge as in Example 23,
The water of the C disintegration was replaced with a solvent in which isopropanol, ethyl acetate and water were mixed at a ratio of 3: 2: 1. The content of PCC contained in the finally obtained mixed solvent was calculated as% by weight.
Was 0.7%. The PCC suspension was sprayed on a slide glass heated to 80 ° C. using a two-fluid nozzle type spraying device. In addition, as a comparative example, a 0.7% PCC concentration disintegration suspension obtained by centrifuging the PCC disintegrant was sprayed on a slide glass plate in the same manner. The thickness of each coating film obtained was 10 μm or less. When the coating formed by the engineering microscope was observed, the PCC coating obtained by the former method was porous,
The latter had a uniform and dense structure.

Example 28 PCC prepared in Example 1 with 2 g of polyvinylpyrrolidone
It was dissolved in the disaggregated product. This mixed solution was sprayed on nylon taffeta in the same manner as in Example 5 to form a film. As a result of the formation of the coating, it was found that the air permeability of the nylon taffeta was lost. Furthermore, this coated nylon taffeta was gently immersed in methanol and allowed to stand for 2 days. Further, after that, methanol was exchanged, and the mixture was allowed to stand again for 5 days. After the nylon taffeta was gently removed from methanol and air-dried, the air permeability was examined. As a result, it was found that the nylon taffeta had air permeability despite the formation of a film. As a comparative example, when a film was formed without adding polyvinylpyrrolidone, a breathable film was not obtained even when the same treatment was performed. It is considered that the reason why the air permeability was obtained when polyvinylpyrrolidone was added was that polyvinylpyrrolidone contained in the coating was dissolved and removed with methanol, and the coating became porous.

Example 29 2-Methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide
An emulsion containing 25% of an active ingredient (trade name: Salicion) was prepared by using PC prepared in Example 1 containing 0.2% of PCC.
It was diluted 80-fold with C disintegration (hereinafter referred to as drug solution (A)). This diluted solution was sprayed on lilies and roses in Kawasaki City, Kanagawa Prefecture. The spraying was performed three times using a hand spray. As a comparative example, a liquid diluted with water alone was used (hereinafter, chemical (B)). The weather was fine. After spraying the medicinal solution, the spreading state of the medicinal solution on the lily was visually examined. Table 10 shows the results.

[0078]

[Table 10] Spreading status of chemicals on lilies 種類 Kind of chemicals Degree of spreading on stems and leaves Chemical dripping ── ──────────────────────── Chemical solution (A) ◎-Chemical solution (B) ○ + ──────────────度 合 い Degree of spreading: ◎ Uniform spreading, ○ Spreading but non-uniform Chemical dripping: + dripping,-dripping at all

By spraying PCC in a chemical solution and spraying it, a film was formed on the stem and leaves of the lily, which helped to improve the degree of spreading of the chemical solution and to prevent dripping.

Similarly, a chemical solution was sprayed on roses. About 5 after spraying
After drying for an hour, a maximum rainfall of about 4 mm was observed per hour from the evening. After exposing roses for 3 hours in the rain,
The spreading degree of the chemical was visually examined. In the case of the chemical solution (A), the coating was maintained and the chemical solution was spread even after rainfall, whereas in the case of the chemical solution (B), the chemical solution was not spread. Example 30 Allesulin against larvae of Chad deer moth on sasanqua
At the same time as spraying an insecticide / bactericide containing tetrachloroisophthalnitrile (Kadan D, manufactured by Fumakiller), the disintegrated product having a PCC concentration of 0.2% prepared in Example 1 was sprayed for about 5 seconds using a hand spray. . The spray amounts of both spray liquids were almost the same. As a comparative example, a spray of insecticide / bactericide and water were simultaneously sprayed. The state of Chadokuga after spraying was visually observed. As a result, when the disintegrated material was used, a bacterial cellulose film was formed on the body surface of Chad's moth after spraying.As a result, the insecticide and fungicide adhered well to the Chad's moth. Was. On the other hand, in the case of the comparative example, the movement did not stop, and it was not confirmed whether the larva of the chadokuga escaped to the back side of the leaf and died.

Example 31 A defibrated material having a PCC concentration of 0.2% was intermittently sprayed on a cedar board (7 cm wide, 35 cm long, 5 mm thick) at 70 ° C. using a two-fluid nozzle type spray. While drying, the coating was formed evenly on all surfaces of the cedar board. After the formation of the coating, the thickness of the coating was measured with a vernier caliper and found to be 0.2 to 0.5 mm. The modulus of the coated plate was measured by a tensile test. Table 11 shows the results.

[0082]

[Table 11] ─────────────────────────────── Measurement direction Fiber radiation tangent ──────────杉 Cedar board with coated film 8.5 2.2 2.0 Cedar board without coated film 6.9 0. 5 0.2 ─────────────────────────────── All numbers are GPa. The measured value is the average of three points.

As a result of the formation of the PCC coating, it was found that the board was significantly reinforced as compared with the case where no coating was formed.

Example 32 The PCC disintegration was centrifuged to give a PCC concentration of 2.4.
%. This concentrate and a commercial poster color were mixed at a ratio of 1: 1. This mixed solution was sprayed on a plywood surface set up at right angles using a hand spray. As a result, the spray liquid spread well on the plywood surface, and there was no dripping. The coating containing the paint formed after drying,
It was uniform without unevenness. On the other hand, when the poster color and water were mixed at a ratio of 1: 1 and sprayed, poor spreadability and dripping occurred, and unevenness was observed on the dried painted surface. Example 33 PCC deflocculate was sprayed on the back of the hand using a hand spray. After standing for several tens of minutes, a dry film was formed on the skin. And by peeling off this film,
The pores on the back of the hand have been cleaned. Also, by spraying thinly on the back of the hand, a film that adheres to the skin is formed,
It was found that the feel improved and the wrinkles grew.

Example 34 The PCC disaggregated product was repeatedly suspended in ethanol and centrifuged repeatedly to completely replace water with ethanol. Next, this was repeatedly suspended in acetone and centrifuged to obtain an acetone-substituted product. The suspension was suspended in ethyl acetate and centrifuged repeatedly to obtain a disintegration suspension containing 5% of PCC and 95% of ethyl acetate (hereinafter, this is referred to as disintegration EA). The disintegrated product (B) prepared in Example 1 was sprayed on nylon taffeta and dried to form a film. A mixture of one part of a butyl acetate solution of blocked isoisocyanate (Takenate B-830, manufactured by Takeda Pharmaceutical) and 10 parts of ethyl acetate was sprayed on nylon taffeta. This was left in a closed container for 30 minutes and dried. And 170 ° C
The protective group of the isocyanate was removed by leaving it for 3 minutes in an atmosphere, and crosslinking was performed by the reaction between the isocyanate and the hydroxyl group of cellulose. As a control, an experiment without crosslinking was also performed. In the case of the control, peeling of the coating was observed by immersing in water and stirring the liquid, but when the crosslinking treatment was performed, the coating did not peel. Further, the nylon subjected to the crosslinking treatment was subjected to a washing test (JISL0217) in the same manner as in Example 10.
When the method 103) was carried out, the coating of the PCC did not fall off due to washing, and no change was observed in the texture of the taffeta.

Example 35 A skin moisturizer was tested using a PCC deflocculated product. As a test method, the same lotion after face wash
I applied makeup in the order of foundation cream, foundation and tongue. After makeup, the left half of the face was sprayed twice with a 0.2% PCC aqueous suspension by hand spraying, and the right half was sprayed with water only twice by hand spraying. Five minutes later, actual use evaluation was performed for each item shown in Table 6. In addition, in the case of the disintegrated material, the evaluation of each panel was described, but regarding the evaluation of the water spray as a comparative example, since all the panelists had the same evaluation for each item, the results were collectively described.

[0087]

[Table 12] Evaluation symbol ◎: extremely good, ○: good, Δ: normal, ×: poor,-: not evaluated

Example 36 A similar panel was sprayed twice with a 0.2% PCC water suspension on the left half of the face by hand spraying, and the right half was sprayed with water only. Sprayed twice with hand spray. Next, makeup was applied in the order of the same lotion, foundation cream, foundation, and tongue.
Five minutes later, each item shown in Table 7 was evaluated for actual use.
In the case of a disintegrated product, the evaluation of each panel was described, but regarding the evaluation of the water spray as a comparative example, since all the panelists had the same evaluation for each item, the results were collectively described.

[0089]

[Table 13] Evaluation symbol ◎: extremely good, ○: good, Δ: normal, ×: poor,-: not evaluated

By spraying the defibrated material onto the skin to form a film, the occurrence of wrinkles due to evaporation and drying of water from the skin, the moist feeling and suppleness of the skin are maintained, Can be made shallower. Further, by applying a BC water suspension by spraying or the like before or after normal make-up, it is possible to prevent the skin from drying without disturbing the make-up.

Example 37 A soil area of 50 cm × 50 cm was placed on a roof with a slope of 40%.
A cultivation bed having the following characteristics was installed and filled with Kanuma soil so as to be parallel to the slope of the roof. 3 g (dry weight) of PCC subjected to defibration treatment by a rotary mixer, alfalfa seeds 5
00 particles were suspended in 1 L of water to prepare a composition of the present invention. This composition was sprayed on the soil surface to form a coating layer. The germination rate was inspected two weeks later, and the growth was measured one month later. Simply add 500 alfalfa seeds to water 1
The germination rate and growth rate were measured in the same manner using the suspension in L as a blank. However, these two cultivation beds are arranged side by side so as to be in contact with each other, and there is no difference in conditions such as sunshine hours and rainfall. Table 14 shows the results.

[0092]

[Table 14] 芽 Germination rate Growth rate (average plant height) ─────────栽培 Cultivation system using the composition of the present invention at 85% 9.0 cm─────────────── ────────────── Control 43% 5.5cm ─────────────────────────────

From the results shown in Table 14, it was found that the composition of the present invention stably retained seeds and germinated them even on sloping land. In addition, the support after germination was excellent, and good growth was obtained.

Example 38 A sample prepared by diluting the PCC disintegrated product prepared in Example 1 to 0.05% with water was sprayed on a slide glass heated to 85 ° C., dried and pipetted on a slide glass at room temperature. Each sample dried at 85 ° C. after dropping was observed with a dark-field optical microscope. The sprayed PCC was uniformly dispersed and dried on the slide glass to form a coating, whereas the dropped PCC was unevenly dried to form an aggregate and did not form a coating.

Example 39 PCC disintegrated material was sprayed on cut flowers (impatiens) three times by hand spraying, and the cut flowers that had been cut were sprayed with water and allowed to stand indoors under the same conditions. As a result, three hours after the cutting, the cut flowers sprayed only with water began to wither with the petals and leaves. On the other hand, the cut flowers obtained by spraying the disaggregated material were not wilted as they were immediately after cutting, because the coating was formed on the surface of the petals and leaves. In addition, the formed film was transparent. After 5 hours, each part of the cut flower sprayed with water alone was completely wilted, but the sprayed material of the disintegrated material did not keep its shape immediately after cutting. It was 8 hours after cutting when some of the petals of the cut flowers sprayed with the disintegrated material began to wilted.

Example 40 A carboxymethylcellulose (hereinafter, CMC, manufactured by Nacalai Chemical) and xanthan gum (manufactured by Dainippon Pharmaceutical Co., Ltd.) were dissolved in a 0.1% concentration PCC disintegration product to prepare a mixed solution. The respective concentrations were 0.05% and 0.1%. This mixed solution is filtered using a hand spray filter (Advantech Toyo N
o.2) and plain weave mesh of fluororesin fiber (30
(0 mesh) by spraying onto the surface, followed by drying at 80 ° C. to form a film on the surface.
The coating is applied at 105 ° C. for 10 minutes or at 132 ° C.
After drying under the condition of 60 minutes, it was heat-treated. After the heat treatment, the coating was immersed in water while being kept on the substrate (filter paper and mesh). The immersion treatment was carried out for 1 day while stirring at 200 rpm in a 300 ml Erlenmeyer flask with a baffle. The peeling state of the immersion-treated film was visually observed. Table 15 shows the results when the additive concentration is 0.05%, and Table 16 shows the results when the additive concentration is 0.1%.

[0097]

[Table 15] 加熱 Heat drying conditions Base material Additives Peelability after immersion treatment １０５ 105 ℃ Filter paper CMC Xanthan gum with peeling off 片 Mesh CMC 〃 Xanthan gum １３２ 132 ℃ Filter paper CMC Almost no peeling Xanthan gum メ ッ シ ュ Mesh CMC キ サ ン Xanthan gum 〃

[0098]

[Table 16] ────────────────────────────────── Heat drying conditions Base material Additives Peeling after immersion treatment Properties １０５ 105 ° C Filter paper CMC Almost the coating peels off and the coating and filter paper break. Xanthan gum Same as above. Mesh CMC Same as above. Xanthan gum Same as above. Xanthan gum Same as above Xanthan gum Same as above. ─────────────────────────────

It was found that both the CMC and the xanthan gum dried at 105 ° C. partially peeled off the film when shaken in water. In particular, in the case of filter paper, the filter paper itself was broken and became fibrous. On the other hand, the 132 ° C. treated product formed a stable film without any change.

0.1% concentration of PCC disintegration, 0.1%
A CMC solution, a 0.1% xanthan gum solution, and water were used to form a coating on the filter paper in the same manner as described above.
After the formation of the film, 105 ° C. or 13
Heat treated at 2 ° C. After the filter paper was dipped in the same manner as in Example 36, the state of peeling of the coating and the state of breakage of the filter paper were visually observed. As a result, with the dried product at 105 ° C., all of the film was peeled off and the filter paper was broken. In contrast, when treated at 132 ° C., water and
For the one coated with 0.1% PCC, the filter paper was broken, but for the one coated with 0.1% CMC or xanthan gum, no peeling of the coating film and no breakage of the filter paper were observed.

Example 41 A mixed solution was prepared by adding and dissolving CMC and xanthan gum to a disintegration of PCC having a concentration of 0.1%. The concentrations of the additives were 20% and 50%, respectively, relative to PCC.
And The mixed solution was dried on a polypropylene plate kept at 80 ° C. while spraying using a hand spray to form a film. The thickness of this coating was about 100 μm. This film was peeled and collected using a razor, and then subjected to heat treatment under various conditions as shown in Table 14,
After standing in water for 2 minutes, the mixture was stirred with a magnetic stirrer at 1000 rpm for 30 minutes to prepare a resuspension. The concentration of PCC in this suspension was adjusted to be 0.1%, which is the same as the concentration of the disintegrated product before drying. The centrifugal sedimentation degree of the obtained suspension was measured according to the following method. Method for measuring the degree of centrifugal sedimentation 10 ml of a 0.2% PCC suspension was mixed with 15 ml of Falcon
After centrifugation at 3,000 rpm for 15 minutes, the volume of the sedimented portion was represented by the ratio to the total volume. The larger the value of the degree of sedimentation, the harder the sedimentation, and the more dispersed the particles. The value of the sedimentation degree recovery ratio (the sedimentation degree of the disaggregated matter after drying and condensate / the sedimentation degree of the disaggregated matter before drying) was used. Table 17 shows the results.

[0102]

[Table 17] All% figures are centrifugal sedimentation values.

[0103]

According to the present invention, the present invention has high tensile strength and high elasticity and high strength excellent in elongation resistance exceeding conventional molding materials, and further has excellent hydrophilicity and has no toxicity problem, and Enhancement, prevention of adhesion, enzymes having a function of preventing leakage of cells, etc., can be used as an immobilized carrier for microorganisms,
A high mechanical strength material containing fine fibrous cellulose capable of imparting conductivity, magnetism, high insulation, heat conductivity, weather resistance, chemical resistance, and the like can be provided.

Claims (32)

[Claims] 1. A high mechanical strength molding material containing fine fibrous cellulose. 2. The fine fibrous cellulose content of 0.0
The high mechanical strength molding material according to claim 1, wherein the amount is 1% to 100%. 3. A hydrophilic polymer material, a hydrophobic polymer material,
2. The high dynamics according to claim 1, comprising one or more substances selected from the group consisting of metals, inorganic materials, coupling agents, adhesives, paints, dyes, pharmaceuticals and antimicrobial agents. Strength molding material. 4. The high mechanical strength molding material according to claim 1, which contains a substance having magnetism. 5. The high mechanical strength molding material according to claim 1, comprising a substance having conductivity. 6. The high mechanical strength molding material according to claim 1, which contains a substance having high thermal conductivity. 7. The high mechanical strength molding material according to claim 1, comprising a substance having high weather resistance. 8. The high mechanical strength molding material according to claim 1, which contains a substance having high chemical resistance. 9. The high mechanical strength molding material according to claim 1, wherein the fine fibrous cellulose is pulverized. 10. The high mechanical strength molding material according to claim 1, which is manufactured through an impregnation step. 11. The high mechanical strength molding material according to claim 1, which is produced through a coating step. 12. The high mechanical strength molding material according to claim 1, which is formed into a sheet. 13. The method according to claim 1, wherein the sheet is paper.
3. The high mechanical strength molding material according to item 2. 14. The high mechanical strength molding material according to claim 1, which is formed into a thread. 15. The high mechanical strength molding material according to claim 1, which is formed in a cloth shape. 16. The high mechanical strength molding material according to claim 1, which is formed into a three-dimensional object. 17. The high mechanical strength molding material according to claim 1, further comprising an immobilized carrier material. 18. A filler composition obtained by mixing and dispersing a filler having an average particle diameter of 2.0 μm or less and fine fibrous cellulose in water, and coagulating the mixture with a coagulant in advance. 19. The content ratio by weight (A / B) of the filler (A) having an average particle diameter of 2.0 μm or less to the fine fibrous cellulose (B) is 0.5 or more and 20.0 or less. Item 19. A filler composition according to Item 18. 20. The filler composition according to claim 18, wherein the flocculant is a cationic polyelectrolyte. 21. A process for producing a filler-filled paper, which comprises adding the filler composition according to any one of claims 18 to 20 to a stock to form a paper. 22. A method for forming a cellulose coating, comprising spraying a suspension containing fine fibrous cellulose on a substrate. 23. The method according to claim 22, wherein the solvent of the suspension is water. 24. The method according to claim 22, wherein the solvent of the suspension is an organic substance. 25. The method according to claim 22, wherein the substrate is paper, cloth, sheet, film or plate. 26. The method according to any one of claims 22 to 25, wherein the fine fibrous cellulose has been subjected to a defibration treatment. 27. The method according to claim 26, wherein the method of the disaggregation treatment is a method using mechanical shearing force, ultrasonic wave, high pressure treatment, acid hydrolysis, enzymatic hydrolysis or a bleaching agent, or a combination thereof. 28. The suspension according to claim 22, wherein a third component other than cellulose and a solvent is added to the suspension.
The method according to any one of the preceding claims. 29. A method for forming a cellulose film, wherein the cellulose film obtained by the method according to claim 22 is further subjected to secondary processing. 30. The method according to claim 29, wherein the secondary processing is a heat treatment performed at about 120 ° C. or higher. 31. A cellulose coating that can be produced by the method according to any one of claims 1 to 30. 32. A coated substrate having at least one cellulose coating according to claim 31.