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WO2010073678A1 - Procédé de fabrication d'une feuille de cellulose microfibreuse et composite obtenu par imprégnation de la feuille de cellulose microfibreuse avec une résine - Google Patents

Procédé de fabrication d'une feuille de cellulose microfibreuse et composite obtenu par imprégnation de la feuille de cellulose microfibreuse avec une résine Download PDF

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Publication number
WO2010073678A1
WO2010073678A1 PCT/JP2009/007211 JP2009007211W WO2010073678A1 WO 2010073678 A1 WO2010073678 A1 WO 2010073678A1 JP 2009007211 W JP2009007211 W JP 2009007211W WO 2010073678 A1 WO2010073678 A1 WO 2010073678A1
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WIPO (PCT)
Prior art keywords
fine fibrous
fibrous cellulose
sheet
organic solvent
producing
Prior art date
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Ceased
Application number
PCT/JP2009/007211
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English (en)
Japanese (ja)
Inventor
野一色泰友
河向隆
角田充
浅山良行
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New Oji Paper Co Ltd
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Oji Paper Co Ltd
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Publication date
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Priority to JP2010543891A priority Critical patent/JP5664245B2/ja
Publication of WO2010073678A1 publication Critical patent/WO2010073678A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums

Definitions

  • the present invention relates to a method for producing a fine fibrous cellulose sheet that efficiently converts fine fibrous cellulose into a porous sheet, and a composite obtained by impregnating a resin into the fine fibrous cellulose sheet obtained by the production method.
  • the purpose is to provide.
  • cellulose fibers particularly wood-derived cellulose fibers (pulp) are widely used mainly as paper products. Most cellulose fibers used in paper have a width of 10 to 50 ⁇ m. Paper (sheet) obtained from such cellulose fibers is opaque and is widely used as printing paper because it is opaque.
  • a transparent paper (glassine paper) can be obtained by processing (beating, pulverizing) cellulose fibers with a refiner, kneader, sand grinder, etc., and then making the cellulose fibers fine (microfibril).
  • the transparency of the transparent paper is at a semi-transparent level, the light transmittance is lower than that of the polymer film, and the haze level (haze value) is large.
  • Cellulose fibers are aggregates of cellulose crystals having a high elastic modulus and a low coefficient of thermal expansion, and heat resistant dimensional stability is improved by combining cellulose fibers with a resin.
  • ordinary cellulose fibers are aggregates of crystals and have a limit in dimensional stability due to fibers having a cylindrical void.
  • the aqueous dispersion of fine fibrous cellulose having mechanically pulverized cellulose fibers and having a fiber width of 50 nm or less is transparent.
  • the fine fibrous cellulose sheet contains voids, it is diffusely reflected white and becomes highly opaque.
  • the fine fibrous cellulose sheet is impregnated with a resin, the voids are filled, so that a transparent sheet is obtained.
  • the fibers of the fine fibrous cellulose sheet are an aggregate of cellulose crystals, very stiff, and because the fiber width is small, the number of fibers is dramatically increased at the same mass compared to ordinary cellulose sheets (paper). To be more. Therefore, when combined with a resin, fine fibers are more uniformly and densely dispersed in the resin, and the heat-resistant dimensional stability is dramatically improved. Moreover, since the fibers are thin, the transparency is high.
  • the fine fibrous cellulose having such characteristics is expected to be highly expected as a flexible transparent substrate (a transparent substrate that can be bent or folded) for organic EL and liquid crystal displays by combining with a resin. Yes.
  • an aqueous dispersion of fine fibrous cellulose has a concentration of 1% by mass and a viscosity of about 500 to 10000 mPa ⁇ sec.
  • the drainage of the dispersion is extremely poor.
  • the papermaking speed is extremely slow, and industrial production by winding (continuous sheet) is difficult.
  • the reason why the production speed at the time of paper making is extremely slow is that the freeness (dehydration rate) of fine fibrous cellulose is very low.
  • Patent Documents 1 to 3 disclose techniques for making cellulose fibers into fine fibers. However, there are disclosures and suggestions about techniques for improving the drainage when making fine fibers into sheets. Absent.
  • Patent Documents 4 to 10 disclose a technique for improving physical properties such as mechanical strength by complexing fine fibrous cellulose with a polymer resin, but a technique (for example, cellulose) that facilitates complexation. However, there is almost no disclosure about a technique for making the resin easily impregnated.
  • Patent Documents 11 to 20 disclose a technique for forming a sheet of fine fibrous cellulose, but the industrial level of productivity has not been ensured, and the fine fibrous cellulose is made porous. Therefore, it is desired to provide a simple method for making the sheet.
  • the present invention has been made in view of the above circumstances, and is a method for producing a fine fibrous cellulose sheet that efficiently converts fine fibrous cellulose into a porous sheet, and a fine fibrous cellulose sheet obtained by the production method.
  • a composite obtained by impregnating a resin is provided.
  • the inventors In the dispersion step of dispersing fine fibrous cellulose in a mixed solvent composed of water and an organic solvent compatible with water, the inventors have a specific boiling point, surface tension, and molecular weight. And by drying the mixed solvent, it was found that fine voids were generated in the obtained fine fibrous cellulose sheet and the resin was easily impregnated, and the fine fibrous cellulose and organic solvent, water, interface By dispersing / mixing an emulsion of an organic solvent composed of an activator and forming the fine fibrous cellulose aqueous dispersion into a sheet, the resulting fine fibrous cellulose sheet has fine voids while ensuring process safety.
  • the resin is easily impregnated, and an aqueous suspension containing fine fibrous cellulose is filtered on a porous substrate.
  • the method for producing a fine fibrous cellulose sheet obtained by watering, forming a moisture-containing sheet, and heating and evaporating the moisture-containing sheet, the cellulose agglomerates into the aqueous suspension containing the fine fibrous cellulose.
  • the present invention was completed by finding a method for producing a fine fibrous cellulose sheet containing an agent.
  • the present invention includes the following inventions.
  • the organic solvent used in the dispersion process has a boiling point of 120 to 260 ° C., surface A method for producing a fine fibrous cellulose sheet having a tension of 20 to 45 N / m, a molecular weight of 100 to 200, and water-soluble.
  • a method for producing a fine fibrous cellulose sheet comprising: a papermaking step of dehydrating to form a sheet containing moisture, and a drying step of drying the sheet containing moisture.
  • the mixing process which mixes the emulsion which consists of the aqueous dispersion of a fine fibrous cellulose, an organic solvent, water, and a surfactant, The aqueous dispersion of the said fine fibrous cellulose,
  • the fine fiber according to (2) comprising: a papermaking step of dehydrating by filtration on a porous base material to form a sheet containing moisture; and a drying step of drying the moisture-containing sheet by heating.
  • the drying step includes a two-step drying step of evaporating water in the first drying step and then evaporating the organic solvent in the second drying step.
  • a method for producing a fine fibrous cellulose sheet according to claim 1. The method for producing a fine fibrous cellulose sheet according to any one of (2) to (4), wherein the organic solvent contained in the emulsion has a boiling point of 120 to 260 ° C. (6) The method for producing a fine fibrous cellulose sheet according to any one of (2) to (5), wherein the organic solvent contained in the emulsion has a hydrophilic functional group. (7) The fine fibrous cellulose sheet according to any one of (1) to (6), wherein a mixing ratio of water and the organic solvent in the mixed solvent is 100: 10 to 100: 500 Manufacturing method.
  • the fine fibrous cellulose according to any one of (1) to (14), wherein 0.5 to 200 parts by mass of a cellulose coagulant is blended with 100 parts by mass of the fine fibrous cellulose.
  • Sheet manufacturing method (16)
  • the cellulose coagulant is at least one selected from ammonium hydrogen carbonate, ammonium carbonate, aluminum sulfate, and a polyamide-based fine cationic resin, (1) to (15), Method for producing a fine fibrous cellulose sheet.
  • a fine fibrous cellulose composite obtained by impregnating a fine fibrous cellulose sheet obtained by the production method according to any one of (1) to (16) with a resin.
  • a production method capable of very efficiently producing a porous sheet of fine fibrous cellulose, and a composite having excellent physical properties obtained by impregnating a resin into the fine fibrous cellulose sheet obtained by the production method can be provided.
  • a porous sheet of fine fibrous cellulose is produced by impregnating wet paper with a hydrophilic organic solvent such as isopropyl alcohol or isobutyl alcohol, substituting water and the hydrophilic organic solvent, and then evaporating and drying the hydrophilic organic solvent. I got a sex sheet.
  • this method requires a large amount of hydrophilic organic solvent, and it takes a long time to replace water with the hydrophilic organic solvent, and industrial production is difficult.
  • the inventors have a specific boiling point, surface tension, and molecular weight of the organic solvent used in the dispersion step in which the fine fibrous cellulose is dispersed in water and a mixed solvent composed of an organic solvent compatible with water. It was assumed that by drying the mixed solvent, fine voids were generated in the obtained fine fibrous cellulose sheet, and the resin was easily impregnated.
  • the porous sheet can be made very efficient by emulsifying the organic solvent in water, adsorbing the emulsion to the surface of fine fibers to form a sheet, first evaporating the water, and then evaporating the emulsified organic solvent. We found that it can be manufactured well.
  • the present inventors added a cellulose coagulant to an aqueous suspension of fine fibrous cellulose, developed a gel, and developed it on a porous base material. On the contrary, it was found that it was easily dehydrated. According to the present invention, the range of selection of the organic solvent is widened, so that productivity is improved and control of the porosity is facilitated. In addition, since the amount of organic solvent used can be reduced, productivity and safety can be improved.
  • the fine fibrous cellulose in the present invention is a cellulose fiber or rod-like particle that is much narrower than the pulp fiber usually used for papermaking.
  • Fine fibrous cellulose is an aggregate of crystalline cellulose molecules, and its crystal structure is type I (parallel chain).
  • the width of the fine fibrous cellulose is preferably 2 nm to 1000 nm, more preferably 2 nm to 500 nm, still more preferably 4 nm to 100 nm when observed with a scanning or transmission electron microscope. When the width of the fiber is less than 2 nm, since the cellulose molecule is dissolved in water, the physical properties (strength, rigidity, dimensional stability) as the fine fiber are not expressed.
  • the fiber length (length-weighted average fiber length measured according to JAPAN TAPPI paper pulp test method No. 52: 2000) in the present invention is preferably 1 to 1000 ⁇ m, more preferably 10 to 600 ⁇ m, and 50 Particularly preferred is ⁇ 300 ⁇ m.
  • the aspect ratio which is a value obtained by dividing the fiber length by the fiber width, is preferably 100 to 30000, more preferably 500 to 15000, and particularly preferably 1000 to 10,000. If the fiber length is less than 1 ⁇ m, the strength for forming the sheet is remarkably low, and it becomes impossible to form a sheet. When the fiber length is 10 ⁇ m or more, the sheet can be formed reliably.
  • the fiber length is 50 ⁇ m or more
  • the sheet is further easily formed and the strength of the obtained sheet is improved.
  • the fiber length exceeds 1000 ⁇ m and the fiber diameter is 1 ⁇ m or less, it is necessary to reduce the fiber diameter so as not to cut the fiber as much as possible (so that the fiber length is not shortened). Needs to be machined for a long time with a weak shearing force, making industrial production difficult.
  • the aspect ratio is less than 100, when the fiber length is 50 ⁇ m or more, there is no significant difference in the physical properties of the sheet obtained compared to ordinary pulp fibers (with an aspect ratio of about 50), and the fiber diameter is reduced to the order of 10 nm. As a result, the fiber length becomes short, making it difficult to form a sheet, and the strength is significantly reduced.
  • the water compatibility is preferably 10% or more at 20 ° C., more preferably 30% or more, and even more preferably 50% or more.
  • glycol ethers such as dipropylene glycol methyl ether, ethylene glycol monobutyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and tetraethylene glycol dimethyl ether.
  • Glymes such as triethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dihydric alcohols such as 1,2-butanediol, 1,6 hexanediol, diethylene glycol monoethyl Ethereal Tate, ethylene glycol monomethyl ether acetate. Two or more of these organic solvents may be used in combination.
  • diethylene glycol dimethyl ether and diethylene glycol isopropyl methyl ether are particularly preferable because these organic solvents are excellent in water compatibility and have a good balance of boiling point, surface tension, and molecular weight.
  • the mixing ratio of water and the organic solvent of the mixed solvent used in the present invention is preferably 100: 10 to 100: 500, more preferably 100: 10 to 100: 200, still more preferably 100: 50 to 100: 200, and 100 : 20 to 100: 150 is particularly preferable, and 100: 25 to 100: 100 is most preferable.
  • the ratio of the organic solvent is less than 10, the porosity of the sheet may decrease.
  • the ratio of the organic solvent exceeds 500, the pulp concentration decreases too much and the papermaking efficiency decreases. If the ratio of the organic solvent exceeds 500 with the pulp concentration kept constant, the viscosity is too high or fine fibers aggregate. There is a risk of causing
  • an emulsion composed of the fine fibrous cellulose, an organic solvent, water, and a surfactant is dispersed in water and used.
  • the organic solvent include ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol-n-butyl ether, triethylene glycol-n-butyl ether, propylene glycol monoethyl.
  • Glycols such as ether, dipropylene glycol monomethyl ether, etc., diethylene glycol dibutyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, 1,6 hexanediol, 2-methyl-2,4- Dihydric alcohols such as pentanediol, n-butyl alcohol, s-butyl alcohol, iso Tyl alcohol, t-butyl alcohol, 2-methyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1 -Alcohols such as decanol, benzyl alcohol and phenol, ethers such as 1,4-dioxane, tetrahydrofuran and anisole
  • the organic solvent contained in the emulsion has a boiling point of 120 to 260 ° C. If the boiling point of the organic solvent is lower than 120 ° C., the amount of the organic solvent that evaporates when water is evaporated increases, which may cause a problem that a porous sheet cannot be obtained. On the other hand, when the boiling point exceeds 260 ° C., a high temperature is required to evaporate the organic solvent, which may cause a problem that the fine fibers turn yellow or the fiber strength decreases.
  • the organic solvent contained in the emulsion has a hydrophilic functional group.
  • organic solvents include glycol ethers such as ethylene glycol mono-t-butyl ether, glymes such as diethylene glycol isopropyl methyl ether, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, Examples thereof include alcohols such as 1-octanol, 1-nonanol, 1-decanol and 1,6 hexanediol, esters such as pentyl acetate, ethyl octoate and methyl benzoate, and terpenes such as terpineol.
  • surfactant used in the present invention examples include surfactants composed of anions (anions), cations (cations), amphoteric, nonions (nonions) and the like as described below.
  • anionic surfactant examples include fatty acid soap, N-acyl amino acid, N-acyl amino acid salt, polyoxyethylene alkyl ether carboxylate, carboxylate such as acylated peptide; alkyl sulfonate, alkyl benzene sulfonic acid Salt, alkylnaphthalene sulfonate, naphthalene sulfonic acid salt formalin polycondensate, melamine sulfonic acid salt formalin polycondensate, dialkyl sulfosuccinic acid ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkyl Sulfonates such as sulfoacetate, ⁇ -olefin sulfonate, N-acyl-N-methyl taurate, dimethyl-5-sulfoisophthalate sodium; sulfated oil, higher alcohol sulf
  • amphoteric surfactants include carboxybetaines, aminocarboxylates, imidazolinium betaines, lecithins, alkylamine oxides, and the like.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ether, single chain length polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene styrene ether, polyoxyethylene.
  • two or more kinds of surfactants described above can be used in combination as necessary.
  • at least one of an anionic surfactant and a cationic surfactant may be used in combination with at least one of an amphoteric surfactant and a nonionic surfactant.
  • the mixing ratio (parts by mass) of the fine fibrous cellulose used in the present invention and the organic solvent contained in the emulsion is preferably 100: 50 to 100: 500, more preferably 100: 50 to 100: 350, and 100: 60 to 100: 300 is more preferable. If the ratio of the organic solvent is less than 50, the porosity of the sheet may be lowered. Moreover, when the ratio of the organic solvent exceeds 500, the cellulose concentration decreases too much, and the papermaking efficiency decreases. When the ratio of the organic solvent exceeds 500 with the cellulose concentration kept constant, the viscosity is too high or fine fibers are May cause agglomeration.
  • the mixing ratio (parts by mass) of the organic solvent and the surfactant used in the present invention is preferably 100: 0.1 to 100: 30, more preferably 100: 0.5 to 100: 20, and 100: 1 to 100: 10 is more preferable. If the ratio of the surfactant is less than 0.1, the emulsion tends to be unstable. On the other hand, when the ratio of the surfactant exceeds 30, the effect of stabilizing the emulsion reaches its peak, which is uneconomical.
  • an emulsification method generally, a surfactant is added to water, an organic solvent is added thereto, and the mixture is stirred with a disperser or the like (hereinafter referred to as a direct emulsification method), and a surfactant is added to the organic solvent.
  • a direct emulsification method a disperser or the like
  • a surfactant is added to the organic solvent.
  • a transfer emulsification method in which this is introduced into a large amount of water.
  • an organic solvent is added to water while stirring, and then a surfactant is added.
  • the direct emulsification method is a method of pulverizing and emulsifying emulsion particles by applying a strong shearing force using a disperser, and an emulsion can be obtained relatively easily.
  • the shear force is not applied evenly to the emulsion particles, the particle size distribution becomes wide. Further, it is known that the stability with time is impaired as a stronger shearing force is applied in order to obtain particles having a small particle diameter.
  • the natural emulsification method emulsifies only by adding it to water, but it requires a high level of expertise in selecting a surfactant and cannot be applied to all substances.
  • the phase inversion emulsification method is a method in which water is gradually added to an organic solvent with a surfactant added thereto while stirring.
  • a W / O type emulsion is formed at first, the viscosity increases as the amount of water increases, and the phase is eventually changed to an O / W type emulsion.
  • the feature of the phase inversion emulsification method is that it passes through this phase inversion point. That is, an emulsion having a uniform small particle size with a very narrow particle size distribution can be obtained by sufficiently applying a shearing force and stirring at the phase inversion point where the particles and the continuous phase in which the particles are dispersed are interchanged.
  • the emulsion obtained by the phase inversion emulsification method is particularly excellent in stability.
  • the phase inversion emulsification method is generally performed manually using a beaker and a stirring bar, but various stirrers can be used to obtain a more uniform and small-sized emulsion.
  • stirrer used for emulsification is not particularly limited, but T.I. K. Robomix, T. K. Automixer, T.W. K. Stirring emulsifiers such as homomixers and T.W. K.
  • a high-speed stirrer such as Filmics or various ultrasonic treatment apparatuses can be used.
  • the ratio of water to the organic solvent is preferably 30:70 to 95: 5, more preferably 40:60 to 90:10, and even more preferably 50:50 to 85:15. If the ratio of water is less than 30, the stability of the emulsion is lowered. When the water ratio is 95% or more, the dispersion concentration of the fine fibrous cellulose is lowered, and the efficiency is lowered.
  • the fine fibrous cellulose aqueous dispersion used in the present invention is preferably added to the fine fibrous cellulose aqueous dispersion while stirring the emulsion of the organic solvent. Using an agitator, a homomixer, a pipeline mixer or the like as a stirring device, the mixture is uniformly mixed and dispersed.
  • the concentration of the fine fibrous cellulose dispersion in this case is preferably 0.1 to 1% by mass, more preferably 0.2 to 0.8% by mass. If the concentration of the dispersion is less than 0.1% by mass, the papermaking efficiency may be lowered. If it exceeds 1% by mass, the viscosity may be too high and handling may be difficult.
  • the viscosity of the dispersion is preferably about 100 to 5000 mPa ⁇ sec in B-type viscosity at 25 ° C. *
  • Examples of the cellulose coagulant that can be used in the present invention include water-soluble inorganic salts and water-soluble organic compounds containing a cationic functional group.
  • Water-soluble inorganic salts include sodium chloride, calcium chloride, potassium chloride, ammonium chloride, magnesium chloride, aluminum chloride, sodium sulfate, potassium sulfate, aluminum sulfate, magnesium sulfate, sodium nitrate, calcium nitrate, sodium carbonate, potassium carbonate, ammonium carbonate , Sodium phosphate, ammonium phosphate and the like.
  • water-soluble organic compound containing a cationic functional group examples include polyacrylamide, polyvinylamine, urea resin, melamine resin, melamine-formaldehyde resin, and a polymer obtained by polymerizing or copolymerizing a monomer containing a quaternary ammonium salt.
  • a weakly cationic compound a slightly cationic compound
  • compounds having weak cationic properties include ammonium carbonate compounds such as ammonium carbonate and ammonium hydrogen carbonate, and organic carboxylate ammonium compounds such as ammonium formate, ammonium acetate, and ammonium propionate.
  • ammonium carbonate and ammonium hydrogen carbonate which are decomposed and vaporized after heating and released from the sheet are preferable.
  • polyamide-based slightly cationic organic polymers such as polyamide compounds, polyamide polyurea compounds, polyamine polyurea compounds, polyamidoamine polyurea compounds, and polyamidoamine compounds can also be used.
  • the cellulose coagulant it is necessary to add the cellulose coagulant more than the amount that the aqueous suspension gels. Specifically, it is preferable to add 0.5 to 10 parts by mass of a cellulose coagulant with respect to 100 parts by mass of fine fibrous cellulose. Incidentally, when the addition amount of the cellulose coagulant is less than 0.5 parts by mass, the gelation of the aqueous suspension becomes insufficient, and there is a possibility that the effect of improving drainage may be poor. When the addition amount exceeds 10 parts by mass, gelation may proceed excessively and handling of the aqueous suspension may be difficult. More preferably, it is in the range of 1 to 8 parts by mass.
  • the gelation according to the present invention is a state change in which the viscosity of the aqueous suspension suddenly and greatly increases and loses fluidity.
  • the gel obtained here is jelly-like and easily broken by stirring. Judgment of gelation can be visually judged because it is in a state of rapidly losing fluidity.
  • a cellulose coagulant is blended in the dispersion of fine fibrous cellulose of the present invention, and the concentration is 0.5 mass% and the temperature is 25. Judged by the B-type viscosity (rotor No. 4, rotational speed 60 rpm) at ° C.
  • the viscosity is preferably 1000 mPa ⁇ second or more, more preferably 2000 mPa ⁇ second or more, and particularly preferably 3000 mPa ⁇ second or more.
  • the cellulose coagulant is preferably added in an amount of 10 to 200 parts by mass, more preferably 20 to 150 parts per 100 parts by mass of fine fibrous cellulose. It is in the range of 30 parts by weight, more preferably 30-100 parts by weight.
  • the addition amount of the weakly cationic cellulose coagulant is less than 10 parts by mass, the drainage may be deteriorated. On the contrary, when the addition amount exceeds 200 parts by mass, the transparency may be deteriorated.
  • the present invention it is not particularly limited as a method for forming a sheet of an aqueous suspension containing fine fibrous cellulose, and after dehydrating with a long net, a circular net, a slanted wire, etc., which are methods commonly used in papermaking, A method of dewatering with a roll press is preferred.
  • a drying method a method usually used in paper production is preferable, and examples thereof include a cylinder dryer, a Yankee dryer, hot air drying, and an infrared heater.
  • the drying is performed in two stages. That is, water is evaporated in the first drying step, and then an organic solvent having a boiling point higher than that of water is evaporated in the second drying step. Many fine voids are formed in the fine fibrous cellulose sheet obtained by this method, and it is extremely easy to impregnate the resin.
  • the air permeability measured according to JIS P 8117: 1998 is about 50 to 3000 seconds / 100 cc.
  • a wire used for general papermaking can be mentioned.
  • metal wires such as stainless steel and bronze
  • plastic wires such as polyester, polyamide, polypropylene, and polyvinylidene fluoride.
  • membrane filters such as a cellulose acetate base material, as a wire.
  • the opening of the wire is preferably 0.2 to 200 ⁇ m, more preferably 0.4 to 100 ⁇ m. If the mesh opening is less than 0.2 ⁇ m, the dehydration rate becomes extremely slow, which is not preferable. If it exceeds 200 ⁇ m, the yield of fine fibrous cellulose decreases, which is not preferable.
  • the basis weight of the fine fibrous cellulose sheet obtained in the present invention is preferably 0.1 ⁇ 1000g / m 2, more preferably 1 ⁇ 500g / m 2, particularly preferably 5 ⁇ 100g / m 2.
  • the basis weight is less than 0.1 g / m 2 , the sheet strength becomes extremely weak and continuous production cannot be performed. If it exceeds 1000 g / m 2 , dehydration takes a very long time and productivity is extremely lowered, which is not preferable.
  • the thickness of the fine fibrous cellulose sheet obtained in the present invention is preferably 0.1 to 1000 ⁇ m, more preferably 1 to 500 ⁇ m, and particularly preferably 5 to 100 ⁇ m.
  • the thickness is less than 0.1 ⁇ m, the sheet strength becomes extremely weak and continuous production cannot be performed. If it exceeds 1000 ⁇ m, dehydration takes a very long time, and productivity is extremely lowered, which is not preferable.
  • the density of fine fibrous cellulose sheet obtained in the present invention is preferably 0.10 ⁇ 1.5g / cm 3, more preferably 0.30 ⁇ 1.20g / cm 3, 0.40 ⁇ 0.80g / cm 3 Is particularly preferred.
  • the density is less than 0.10 g / cm 3 , the sheet strength becomes weak, which is not preferable. If it exceeds 1.5 g / cm 3 , there will be almost no voids, which is not preferable when combined with a resin or the like.
  • the density can be controlled by a dehydrating pressure during paper making, a pressing pressure, a calendar process after sheet formation, and the like.
  • the density of the present invention is a value obtained by dividing the basis weight by the thickness.
  • Examples of the resin that can be combined with the fine fibrous cellulose in the present invention include at least one resin selected from thermoplastic resins, thermosetting resins, photocurable resins, and resin cured products.
  • thermoplastic resins As thermoplastic resins, styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, aliphatic polyolefin resins, cyclic olefin resins, polyamides Resin, polyphenylene ether resin, thermoplastic polyimide resin, polyacetal resin, polysulfone resin, amorphous fluorine resin and the like.
  • Styrenic resin refers to homopolymers of vinyl aromatic monomers or copolymers with other monomers.
  • vinyl aromatic monomers include styrene, ⁇ -methylstyrene, paramethylstyrene, etc.
  • a homopolymer of styrene or a copolymer with other monomers is preferable.
  • a homopolymer it may be one having stereoregularity in the chain (isotactic, syndiotactic) or one having no stereoregularity (atactic).
  • Other monomers that can be copolymerized include acrylonitrile, methacrylonitrile, isoprene, butadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, acrylic monomers and styrene. It is possible to adjust the refractive index of a resin obtained by copolymerizing with a monomer, for example, acrylonitrile-styrene copolymer, styrene-methacrylic acid copolymer, etc., depending on the copolymerization ratio. This is preferable.
  • a resin having a refractive index of about 1.57 Is obtained.
  • the form of the copolymer there are a block copolymer, a random copolymer, and a graft copolymer.
  • Acrylic resins include methacrylic acid cyclohexyl, methacrylic acid-t-butylcyclohexyl, methacrylic acid alkyl esters such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isopropyl acrylate, and 2-ethylhexyl acrylate.
  • One or more monomers selected from acrylic acid alkyl esters such as are polymerized. Of these, a homopolymer of methyl methacrylate or a copolymer with other monomers is preferable.
  • Examples of monomers copolymerizable with methyl methacrylate include other alkyl methacrylates, alkyl acrylates, aromatic vinyl compounds such as styrene, vinyltoluene and ⁇ -methylstyrene, acrylonitrile and methacrylonitrile.
  • vinyl cyanides such as N-phenylmaleimide and N-cyclohexylmaleimide, unsaturated carboxylic acid anhydrides such as maleic anhydride, and unsaturated acids such as acrylic acid, methacrylic acid and maleic acid.
  • alicyclic acrylic resins such as tricyclodecyl methacrylate, are also mentioned.
  • the aromatic polycarbonate-based resin is an aromatic polycarbonate derived from an aromatic dihydroxy compound.
  • aromatic dihydroxy compound examples include 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2, Bis (hydroxyaryl) alkanes such as 2-bis (4-hydroxyphenyl) propane, bis (1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc.
  • Hydroxyaryl) cycloalkanes 4,4′-dihydroxydiphenyl ether, dihydroxyaryl ethers such as 4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4 ′ -Dihydroxy-3,3'-di Dihydroxyaryl sulfides such as tilphenyl sulfide, dihydroxyaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethylphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, Examples include dihydroxyaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethylphenylsulfone. Among these, 2,2-bis (4-hydroxyphenyl) propane (common name, bisphenol A) is particularly preferable. These aromatic dihydroxy compounds can be
  • the aromatic polyester resin is not particularly limited, but specific examples include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polyarylate, and the like.
  • the aliphatic polyester resin include a polymer mainly composed of aliphatic hydroxycarboxylic acid and a polymer mainly composed of aliphatic polycarboxylic acid and aliphatic polyhydric alcohol.
  • polymers having aliphatic hydroxycarboxylic acid as a main component include polyglycolic acid, polylactic acid, poly (3-hydroxybutyric acid), poly (4-hydroxybutyric acid), poly (4-hydroxyvalidic acid).
  • Polymers mainly composed of aliphatic polycarboxylic acid and aliphatic polyhydric alcohol include polyethylene adipate, polyethylene succinate, poly Examples include butylene adipate and polybutylene succinate.
  • Aliphatic polyolefin resins include polyethylene, polypropylene, ethylene-propylene copolymers, polymethylpentene, polybutene, ethylene-vinyl acetate copolymers, ionomer resins (ethylene-acrylic acid polymer salts and styrene-sulfonates). And the like, and copolymers thereof, modified products with maleic acid, and the like.
  • the cyclic olefin resin is a polymer containing a cyclic olefin skeleton in a polymer chain, such as norbornene or cyclohexadiene, or a copolymer containing these, and the production method thereof is not particularly limited.
  • cyclic olefin-based resin examples include norbornene-based resins composed of a repeating unit of a norbornene skeleton or a copolymer of a norbornene skeleton and a methylene skeleton.
  • Article manufactured by JSR, “ZEONEX” manufactured by Nippon Zeon Co., Ltd. And “Zeonoa”, “Appel” manufactured by Mitsui Chemicals, and “Topas” manufactured by Chicona.
  • the polyamide resin is not particularly limited as long as it is a known polyamide resin.
  • polycaprolactam polytetramethylene adipamide (nylon 4,6), polyhexamethylene adipamide (nylon 6,6), polyhexamethylene sebacamide (nylon 6,10), polyhexa Methylene dodecamide (nylon 6,12), polyundecamethylene adipamide (nylon 1,16), polyundecalactam (nylon 11), polydodecalactam (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMHT ), Polyhexamethylene isophthalamide (nylon 6I), polynonanemethylene terephthalamide (9T), polyhexamethylene terephthalamide (6T), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl) -Aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12
  • polyphenylene ether resin examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6).
  • polyphenylene ether resin examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl-6).
  • -Phenyl-1,4-phenylene ether poly (2,6-dichloro-1,4-phenylene ether) and the like, and copolymers of 2,6-dimethylphenol and other phenols (for example, And polyphenylene ether copolymers such as copolymers with 2,3,6-trimethylphenol and copolymers with 2-methyl-6-butylphenol as described in JP-B-52-17880.
  • polyphenylene ether copolymers such as copolymers with 2,3,6-trimethylphenol and copolymers
  • polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture.
  • the polyphenylene ether resin that can be used in the present invention may be a polyphenylene ether modified in whole or in part.
  • the modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl in the molecular structure.
  • the polyphenylene ether modified with at least one modifying compound having a group Since the polyphenylene ether resin has high heat resistance and excellent electrical characteristics, it can be suitably used for high heat resistance applications and electronic parts.
  • the monomer in the present invention refers to a monomer constituting these thermoplastic resins.
  • the number average molecular weight of these thermoplastic resins is generally 1000 or more, preferably 5000 or more and 5 million or less, and more preferably 10,000 or more and 1 million or less.
  • the compounding of the monomer that forms a cross-linked structure with another monomer such as divinylbenzene also improves the plasticity at high temperature. It is extremely effective in terms of suppression.
  • These thermoplastic resins can be used alone or in admixture of two or more. In the case of using a mixture of two or more thermoplastic resins, it is preferable because the refractive index of the resin can be adjusted by the mixing ratio.
  • a resin obtained by blending an acrylic resin and a styrene resin is preferable.
  • polymethyl methacrylate reffractive index: about 1.49
  • acrylonitrile-styrene copolymer acrylonitrile content: about 21%, refractive index: about 1) .57
  • thermosetting resin and the photocurable resin used in the present invention are relatively low molecular weight substances that are liquid, semi-solid or solid at room temperature and exhibit fluidity at room temperature or under heating. means. These can be an insoluble and infusible resin formed by forming a network-like three-dimensional structure while increasing the molecular weight by causing a curing reaction or a crosslinking reaction by the action of a curing agent, a catalyst, heat or light.
  • the cured resin in the present invention means a resin obtained by curing the thermosetting resin or the photocurable resin.
  • thermosetting resin used in the present invention is not particularly limited, but specific examples include epoxy resin, thermosetting modified polyphenylene ether resin, thermosetting polyimide resin, urea resin, allyl resin, Silicon resin, benzoxazine resin, phenol resin, unsaturated polyester resin, bismaleimide triazine resin, alkyd resin, furan resin, melamine resin, polyurethane resin, aniline resin, etc. Examples thereof include resins obtained by mixing seeds or more. Among these, an epoxy resin, an allyl resin, an unsaturated polyester resin, a vinyl ester resin, a thermosetting polyimide resin, and the like are suitable for use as an optical material because they have transparency.
  • the above epoxy resin refers to an organic compound having at least one epoxy group.
  • the number of epoxy groups in the epoxy resin is preferably 1 to 7 per molecule, more preferably 2 or more per molecule.
  • the number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy resin by the total number of molecules in the epoxy resin.
  • a conventionally well-known epoxy resin can be used, For example, the epoxy resin shown below etc. are mentioned. These epoxy resins may be used independently and may use 2 or more types together.
  • These epoxy resins are thermosetting resin precursor epoxy compounds, and by using a curing agent, a cured epoxy resin that is a cured product of the epoxy resin can be obtained.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac type epoxy resin, Aromatic epoxy resins such as trisphenol methane triglycidyl ether and hydrogenated products and brominated products thereof can be mentioned.
  • 1,4-butanediol diglycidyl ether 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether
  • Aliphatic epoxy resins such as glycidyl ethers, polyglycidyl ethers of long-chain polyols containing polyoxyalkylene glycols containing 2 to 9 (preferably 2 to 4) carbon atoms alkylene groups, polytetramethylene ether glycols, etc. It is done.
  • glycidyl ester type epoxy such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoic acid, glycidyl ether-glycidyl ester of salicylic acid, dimer acid glycidyl ester Examples thereof include resins and hydrogenated products thereof.
  • Examples thereof include glycidylamine type epoxy resins and hydrogenated products thereof.
  • the copolymer etc. of radical polymerizable monomers such as glycidyl (meth) acrylate, ethylene, vinyl acetate, (meth) acrylic-acid alkylester, etc. are mentioned.
  • (meth) acryl means acryl or methacryl.
  • the thing which epoxidized the double bond of the unsaturated carbon in the polymer mainly based on conjugated diene compounds, such as epoxidized polybutadiene, or the polymer of the partially hydrogenated thing is mentioned.
  • the copolymer include epoxidized unsaturated carbon double bonds of a conjugated diene compound.
  • urethane modified epoxy resins which have 1 or more, preferably 2 or more epoxy groups per molecule are mentioned.
  • urethane modified epoxy resins, polycaprolactone modified epoxy resins, etc. in which urethane bonds or polycaprolactone bonds are introduced into the structure of the epoxy resin, can be mentioned.
  • the modified epoxy resin include rubber modified epoxy resins in which the epoxy resin contains a rubber component such as NBR, CTBN, polybutadiene, and acrylic rubber.
  • a resin or oligomer having at least one oxirane ring may be added.
  • thermosetting resin and composition containing a fluorene group such as a fluorene containing epoxy resin, a fluorene containing acrylate resin, a fluorene containing epoxy acrylate resin, or its hardened
  • cured material is also mentioned.
  • fluorene-containing epoxy resins are suitably used because they contain a fluorene group in the molecule and thus have a high refractive index and high heat resistance.
  • curing agent for epoxy resins can be used, for example, compounds, such as an amine compound and the polyaminoamide compound synthesize
  • curing agents may be used independently and 2 or more types may be used together.
  • thermosetting resins or photocurable resins may be used alone or in combination of two or more.
  • the curing agent and curing catalyst used in combination with the thermosetting resin and the photocurable resin are not particularly limited as long as they are used for curing the thermosetting resin and the photocurable resin.
  • the curing agent include polyfunctional amines, polyamides, acid anhydrides, and phenol resins.
  • Specific examples of the curing catalyst include imidazole. These may be used alone or as a mixture of two or more. it can.
  • the polyimide resin in the present invention is not particularly limited, but is a resin containing an imide group in the main chain skeleton, and any of thermoplastic and thermosetting polyimide resins can be used. Specific examples include polyimide, polyamideimide, polyetherimide, polyesterimide, polysiloxaneimide, and the like.
  • Cured resins include acrylic resins, methacrylic resins, urethane resins, phenol resins, melamine resins, novolac resins, urea resins, guanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins. Examples thereof include resins, diallyl phthalate resins, silicone resins, furan resins, ketone resins, xylene resins, polyimide resins, styrylpyridine resins, and triazine resins.
  • An acrylic resin and a methacrylic resin are preferable in terms of transparency. These curable resins may be used alone or in combination of two or more.
  • the method of impregnating and polymerizing a monomer means that a monomer such as methyl methacrylate, which is a monomer constituting a thermoplastic resin, is impregnated into a fine fibrous cellulose sheet, and the monomer is then subjected to heat treatment or the like. It is a production method to obtain a composite consisting of a fine fibrous cellulose sheet and the above resin by polymerization, and starts polymerization of an organic peroxide such as peroxide or a polymerization catalyst generally used for polymerization of monomers. It can be used as an agent.
  • the polymerization catalyst impairs the performance of the composite as an impurity, impregnate a high-purity monomer that does not contain any polymerization inhibitor such as quinones, and heat without using a polymerization initiator. Polymerization is also effective.
  • a method of impregnating and curing a thermosetting resin precursor or a photocurable resin precursor is a method of curing a mixture of a thermosetting resin precursor such as an epoxy resin or a photocurable resin precursor and a curing agent with fine fibrous cellulose.
  • a thermosetting resin such as a fine fibrous cellulose sheet and the cured epoxy resin as the resin. It is a manufacturing method which obtains the composite_body
  • thermosetting resin precursor such as epoxy resin or the photocurable resin precursor
  • the precursor is heat-treated and melted in advance. It is also possible to impregnate a solution obtained by dissolving the precursor in a soluble solvent. In order to increase the smoothness of the surface, it is also effective to further advance the reaction by applying a heat press treatment when the curing reaction has progressed to some extent. It is also effective at the time of increasing the film thickness to stack and treat several composites that have undergone a certain degree of curing reaction during the heat treatment.
  • the method of drying after impregnating the solution of the resin is to dissolve the thermoplastic resin in a solvent that can be dissolved, impregnate the fine fibrous cellulose sheet, and dry the thermoplastic resin to the fine fibrous cellulose sheet. It is a manufacturing method to combine.
  • ⁇ Adjustment Example 1 Slurry A of fine fibrous cellulose> After adding 1150 parts by weight of water to 100 parts by weight of NBKP pulp (manufactured by Oji Paper Co., Ltd., 50% freeness 600 mLcsf) and defibrating with a disintegrator, the pulp concentration was adjusted to 2-3% and treated with a refiner. The freeness of the pulp treated with the refiner was 300 mLcsf. Add water to the pulp treated with the refiner so that the pulp concentration is between 0.5 and 0.7%, and use a mortar-type disperser ("Supermass colloider" manufactured by Masuko Sangyo Co., Ltd., mortar type G).
  • the slurry was processed 5 times to obtain a slurry A of fine fibrous cellulose.
  • the pulp concentration of the slurry was adjusted to 0.5%.
  • the width of the fine fibrous cellulose was observed and measured with a scanning electron microscope (SEM), the width of the fiber was in the range of 200 to 800 nm.
  • ⁇ Adjustment example 2 Slurry B of fine fibrous cellulose>
  • the fine fibrous cellulose A was treated 10 times with a high-pressure collision type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain a slurry B of fine fibrous cellulose.
  • a high-pressure collision type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain a slurry B of fine fibrous cellulose.
  • SEM scanning electron microscope
  • ⁇ Adjustment Example 4 Slurry D of fine fibrous cellulose> 150 parts by weight of water, 4 parts by weight of NBKP pulp (50% freeness 600 mL csf manufactured by Oji Paper Co., Ltd.), 0.025 parts by weight of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) and odor
  • a water dispersion prepared by sequentially adding 0.25 parts by mass of sodium chloride with stirring a 13% by mass aqueous solution of sodium hypochlorite was added to 1 g of absolute dry pulp so that the amount of sodium hypochlorite was 2 The reaction was started by adding 0.5 mmol.
  • a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10.5.
  • the pulp obtained by filtering and washing the reaction product was added with water so that the concentration became 1.5% to obtain a pulp dispersion.
  • the obtained pulp dispersion was defibrated with a disintegrator for about 5 minutes to obtain a slurry D of fine fibrous cellulose.
  • the concentration of the slurry was adjusted to 0.5%.
  • the width of the fine fibrous cellulose was observed and measured with a transmission electron microscope (TEM), the width of the fiber was in the range of 3 to 20 nm.
  • Emulsion A To 67 parts by mass of water, 3 parts by mass of cationic dodecylammonium chloride (trade name: “Kathiogen DDM”, manufactured by Daiichi Pharmaceutical Co., Ltd.) as a surfactant was added with stirring, followed by methyl benzoate as an organic solvent.
  • Emulsion A was prepared by adding 30 parts by mass (boiling point 199.6 ° C., manufactured by Wako Pure Chemical Industries, Ltd.). The average particle system of the emulsion was 2.8 ⁇ m.
  • the stirrer is a T.I. K homomixermark II type 2.5 was used. The number of revolutions was 6000 rpm, and the stirring time was 15 minutes after adding the organic solvent.
  • Emulsion E was prepared in the same manner as in Preparation Example 5, except that butyl acetate (boiling point: 125 ° C., Wako Pure Chemical Industries) was used as the organic solvent.
  • Emulsion F was prepared in the same manner as Preparation Example 5 except that terpineol (isomer mixture, boiling point: 214 to 224 ° C., Wako Pure Chemical Industries, Ltd.) was used as the organic solvent.
  • Emulsion G was prepared in the same manner as Preparation Example 5 except that (R)-(+)-limonene (boiling point 176 ° C., Wako Pure Chemical Industries) was used as the organic solvent.
  • ⁇ Adjustment Example 12 Slurry E of fine fibrous cellulose> After adding 1150 parts by weight of water to 100 parts by weight of NBKP pulp (manufactured by Oji Paper Co., Ltd., 50% freeness 600 mLcsf) and defibrating with a disintegrator, the pulp concentration was adjusted to 2-3% and treated with a refiner. The freeness of the pulp treated with the refiner was 300 mLcsf. Add water to the pulp treated with the refiner so that the pulp concentration is between 0.5 and 0.7%, and use a mortar-type disperser ("Supermass colloider" manufactured by Masuko Sangyo Co., Ltd., mortar type G).
  • the slurry was processed 5 times to obtain a slurry E of fine fibrous cellulose.
  • the pulp concentration of the slurry was adjusted to 0.5%.
  • the width of the fine fibrous cellulose was observed and measured with a scanning electron microscope (SEM), the width of the fiber was in the range of 200 to 800 nm.
  • ⁇ Adjustment Example 14 Slurry G of fine fibrous cellulose>
  • the fine fibrous cellulose E was treated 20 times with a high-pressure collision type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain a slurry G of fine fibrous cellulose.
  • a high-pressure collision type disperser (“Ultimizer” manufactured by Sugino Machine Co., Ltd.) to obtain a slurry G of fine fibrous cellulose.
  • SEM scanning electron microscope
  • ⁇ Adjustment Example 15 Slurry H of fine fibrous cellulose> 150 parts by weight of water, 4 parts by weight of NBKP pulp (50% freeness 600 mL csf manufactured by Oji Paper Co., Ltd.), 0.025 parts by weight of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) and odor
  • NBKP pulp 50% freeness 600 mL csf manufactured by Oji Paper Co., Ltd.
  • TEMPO 2,2,6,6-tetramethyl-1-piperidine-N-oxyl
  • odor To a water dispersion prepared by sequentially adding 0.25 parts by mass of sodium chloride with stirring, a 13% by mass aqueous solution of sodium hypochlorite was added to 1 g of absolute dry pulp so that the amount of sodium hypochlorite was 2 The reaction was started by adding 0.5 mmol.
  • a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10.5.
  • the pulp obtained by filtering and washing the reaction product was added with water so that the concentration became 1.5% to obtain a pulp dispersion.
  • the obtained pulp dispersion was defibrated for about 5 minutes with a disintegrator to obtain a slurry H of fine fibrous cellulose.
  • the concentration of the slurry was adjusted to 0.5%.
  • the width of the fine fibrous cellulose was observed and measured with a transmission electron microscope (TEM), the width of the fiber was in the range of 3 to 20 nm.
  • Example 1 While adding 10 parts of diethylene glycol dimethyl ether (DEGDME) (manufactured by Toho Chemical Co., Ltd., trade name: Hisolv MDM, molecular weight 134, boiling point 162 ° C., surface tension 28 N / m) to 100 parts of the fine fibrous cellulose slurry E of Preparation Example 12. The mixture was stirred to obtain a fine fibrous cellulose aqueous dispersion containing an organic solvent. A wet sheet was prepared while decompressing the dispersion on a 500 mesh polyester mesh. The wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying. The obtained sheet after the first drying was translucent and wet. The sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a 35 g / m 2 fine fibrous cellulose sheet.
  • DEGDME diethylene glycol dimethyl ether
  • Example 2 A fine fibrous cellulose sheet was obtained in the same manner as in Example 1 except that 20 parts of diethylene glycol dimethyl ether was added.
  • Example 3 A fine fibrous cellulose sheet was obtained in the same manner as in Example 1 except that 30 parts of diethylene glycol dimethyl ether was added.
  • Example 4 A fine fibrous cellulose sheet was obtained in the same manner as in Example 1 except that 50 parts of diethylene glycol dimethyl ether was added.
  • Example 5 A fine fibrous cellulose sheet was obtained in the same manner as in Example 1 except that 100 parts of diethylene glycol dimethyl ether was added.
  • Example 6 A fine fibrous cellulose sheet was obtained in the same manner as in Example 4 except that the fine fibrous cellulose slurry F of Preparation Example 13 was used.
  • Example 7 A fine fibrous cellulose sheet was obtained in the same manner as in Example 4 except that the fine fibrous cellulose slurry G of Preparation Example 14 was used.
  • Example 8 A fine fibrous cellulose sheet was obtained in the same manner as in Example 4 except that the fine fibrous cellulose slurry H of Preparation Example 15 was used.
  • Example 9 Fine fiber in the same manner as in Example 4 except that diethylene glycol isopropyl methyl ether (DEGIPME) (trade name: Hisolv IPDM, molecular weight 162, boiling point 179 ° C., surface tension 24 N / m) was used as the organic solvent. A cellulose sheet was obtained.
  • DEGIPME diethylene glycol isopropyl methyl ether
  • Example 10 Example 5 was used except that triethylene glycol monomethyl ether (TEGMME) (trade name: Hymor TM, molecular weight 164, boiling point 249 ° C., surface tension 36 N / m) was used as the organic solvent. A fine fibrous cellulose sheet was obtained.
  • TEGMME triethylene glycol monomethyl ether
  • Example 11 A fine fibrous state as in Example 5 except that diethylene glycol monomethyl ether (DEGMME) (trade name: Hisolv DM, molecular weight 120, boiling point 194 ° C., surface tension 34 N / m) was used as the organic solvent. Obtained cellulose sheet
  • Example 12 A fine fibrous cellulose sheet was obtained in the same manner as in Example 5 except that diethylene glycol (DEG) (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 106, boiling point 245 ° C., surface tension 45 N / m) was used as the organic solvent.
  • DEG diethylene glycol
  • Example 13 While adding 200 parts of diethylene glycol dimethyl ether (DEGDME) (manufactured by Toho Chemical Co., Ltd., trade name: Hisolv MDM, molecular weight 134, boiling point 162 ° C., surface tension 28 N / m) to 100 parts of the fine fibrous cellulose slurry E of Preparation Example 12. The mixture was stirred to obtain a fine fibrous cellulose aqueous dispersion containing an organic solvent. A wet sheet was prepared while decompressing the dispersion on a 500 mesh polyester mesh. The wet sheet was dried together with a 500 mesh polyester mesh at 130 ° C. for 5 minutes, and the sheet was peeled off from the polyester mesh to obtain a 35 g / m 2 fine fibrous cellulose sheet.
  • DEGDME diethylene glycol dimethyl ether
  • the fine fibrous cellulose sheets obtained in Examples 1 to 13 were impregnated with a thermosetting epoxy resin and cured by treatment at 130 ° C. for 3 minutes.
  • the cellulose sheet before impregnation was a white sheet, but the sheet after impregnation became transparent and the resin and the thermosetting epoxy resin could be combined.
  • a wet sheet was prepared while the fine fibrous cellulose slurry E of Preparation Example 12 was reduced in pressure on a 500 mesh polyester mesh.
  • the wet sheet was dried at 80 ° C. for 3 minutes together with a 500 mesh polyester mesh to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • a wet sheet was prepared while depressurizing the slurry F of fine fibrous cellulose of Preparation Example 13 on a 500 mesh polyester mesh.
  • the wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • a wet sheet was prepared while depressurizing the slurry G of fine fibrous cellulose of Preparation Example 14 on a 500 mesh polyester mesh.
  • the wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • a wet sheet was prepared while depressurizing the slurry H of fine fibrous cellulose of Preparation Example 15 on a 500 mesh polyester mesh.
  • the wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • IPA isopropyl alcohol
  • ⁇ Comparative Example 7> A fine fibrous cellulose sheet was obtained in the same manner as in Comparative Example 5, except that ethylene glycol (EG) (manufactured by Wako Pure Chemical Industries, molecular weight 62, boiling point 196 to 198 ° C., surface tension 48 N / m) was used as the organic solvent. It was.
  • EG ethylene glycol
  • ⁇ Comparative Example 10> A fine fibrous cellulose sheet was obtained in the same manner as in Example 5 except that ethylene glycol diethyl ether (EGDEE) (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 90, boiling point 136 ° C., surface tension 28 N / m) was used as the organic solvent. It was.
  • EGDEE ethylene glycol diethyl ether
  • thermosetting resin was impregnated into the fine fibrous cellulose sheet obtained in Comparative Examples 1 to 10, but the thermosetting resin was not impregnated into the fine fibrous cellulose sheet, and a composite sheet was not obtained.
  • Pore volume, pore diameter, pore surface area The pore volume, pore diameter, and pore surface area of fine fibrous cellulose were measured with a mercury porosimeter.
  • the sheet obtained by the method for producing a fine fibrous cellulose sheet of the present invention has a low air permeability, is a porous sheet, and is a resin composite that is excellent in transparency when impregnated with a resin.
  • the body is obtained.
  • Example 14 To 100 parts of the fine fibrous cellulose slurry E of Preparation Example 0.8, 0.83 part of Emulsion A of Preparation Example 5 was added and stirred to obtain a fine fibrous cellulose aqueous dispersion containing an organic solvent emulsion. A wet sheet was prepared while decompressing the dispersion on a 500 mesh polyester mesh. The wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying. The obtained sheet after the first drying was translucent and wet. The sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a 35 g / m 2 fine fibrous cellulose sheet.
  • Example 15 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 1.7 parts of Emulsion A of Preparation Example 5 was added.
  • Example 16 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 3.4 parts of Emulsion A of Preparation Example 5 was added.
  • Example 17 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of Emulsion A of Preparation Example 5 was added.
  • Example 18 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of Emulsion B of Preparation Example 6 was added.
  • Example 19 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of Emulsion C of Preparation Example 7 was added.
  • Example 20 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of Emulsion D of Preparation Example 8 was added.
  • Example 21 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of Emulsion E of Preparation Example 9 was added.
  • Example 22 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of Emulsion F of Preparation Example 10 was added.
  • Example 23 A fine fibrous cellulose sheet was obtained in the same manner as in Example 14 except that 6.7 parts of the emulsion G of Preparation Example 11 was added.
  • Example 24 A fine fibrous cellulose sheet was obtained in the same manner as in Example 17 except that the fine fibrous cellulose slurry F of Preparation Example 13 was used.
  • Example 25 A fine fibrous cellulose sheet was obtained in the same manner as in Example 417 except that the fine fibrous cellulose slurry G of Preparation Example 14 was used.
  • Example 26 A fine fibrous cellulose sheet was obtained in the same manner as in Example 17 except that the fine fibrous cellulose slurry H of Preparation Example 15 was used.
  • a wet sheet was prepared while the fine fibrous cellulose slurry E of Preparation Example 12 was reduced in pressure on a 500 mesh polyester mesh.
  • the wet sheet was dried at 80 ° C. for 3 minutes together with a 500 mesh polyester mesh to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • a wet sheet was prepared while depressurizing the slurry F of fine fibrous cellulose of Preparation Example 13 on a 500 mesh polyester mesh.
  • the wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • a wet sheet was prepared while depressurizing the slurry G of fine fibrous cellulose of Preparation Example 14 on a 500 mesh polyester mesh.
  • the wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • a wet sheet was prepared while depressurizing the slurry H of fine fibrous cellulose of Preparation Example 15 on a 500 mesh polyester mesh.
  • the wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and was in a dry state.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a fine fibrous cellulose sheet.
  • the sheet remained translucent.
  • Comparative Example 18 A fine fibrous cellulose sheet was obtained in the same manner as in Comparative Example 15 except that undecane was used. The obtained sheet was translucent and mixed with aggregates, and the surface was uneven.
  • Comparative Example 19 A fine fibrous cellulose sheet was obtained in the same manner as in Comparative Example 15 except that butyl acetate was used. The obtained sheet was translucent and mixed with aggregates, and the surface was uneven.
  • Comparative Example 20 A fine fibrous cellulose sheet was obtained in the same manner as in Comparative Example 15 except that terpineol was used. The obtained sheet was translucent and mixed with aggregates, and the surface was uneven.
  • thermosetting resin was impregnated with the fine fibrous cellulose sheet obtained in Comparative Examples 11 to 20, but the thermosetting resin was not impregnated with the fine fibrous cellulose sheet, and a composite sheet was not obtained.
  • Pore volume The pore volume of a 1 micrometer diameter or less of the fine fibrous cellulose sheet was measured with a mercury porosimeter. The larger the pore volume, the better the resin impregnation property.
  • the sheet obtained by the method for producing a fine fibrous cellulose sheet of the present invention has a low air permeability, is a porous sheet, and is a resin composite that is excellent in transparency by impregnating the resin.
  • the body is obtained.
  • Example 27 To 100 parts of an aqueous suspension prepared by adjusting the slurry A of fine fibrous cellulose to a pulp concentration of 0.5 mass%, aluminum sulfate (chemical formula: Al 2 (SO 4 ) 3 , solid content: 1.67 parts by mass) was added with stirring. The B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension (A) was 600 mPa ⁇ sec.
  • aluminum sulfate chemical formula: Al 2 (SO 4 ) 3 , solid content: 1.67 parts by mass
  • aqueous suspension 96.6 g was poured onto a cellulose acetate membrane filter (“Membrane filter” manufactured by Advantech) having a pore diameter of 0.45 ⁇ m, which was put on a Buchner funnel having a diameter of 142 mm, and suction filtration was performed. Filtration was completed in 1 minute.
  • the obtained fine fiber wet sheet was dried at 105 ° C. using a cylinder dryer to obtain a fine fibrous cellulose sheet.
  • the basis weight of the sheet was 30.0 g / m 2 , the thickness was 36 ⁇ m, and the density was 0.83 g / cm 3 .
  • Example 28 A fine fibrous cellulose sheet was obtained in the same manner as in Example 27 except that the fine fibrous cellulose slurry B was used.
  • the B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension (B) was 800 mPa ⁇ sec. Filtration was completed in 1 minute.
  • the basis weight of the sheet was 29.7 g / m 2 , the thickness was 30 ⁇ m, and the density was 0.99 g / cm 3 .
  • Example 29 A fine fibrous cellulose sheet was obtained in the same manner as in Example 27 except that the fine fibrous cellulose slurry C was used.
  • the B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension (C) was 1200 mPa ⁇ s. Filtration was completed in 2 minutes.
  • the obtained fine fiber wet sheet was dried at 105 ° C. using a cylinder dryer to obtain a fine fibrous cellulose sheet.
  • the basis weight of the sheet was 29.7 g / m 2 , the thickness was 30 ⁇ m, and the density was 0.99 g / cm 3 .
  • Example 30 A fine fibrous cellulose sheet was obtained in the same manner as in Example 27 except that the fine fibrous cellulose slurry D was used.
  • the B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension was 1900 mPa ⁇ sec. Filtration was completed in 2 minutes and 30 seconds.
  • the basis weight of the sheet was 29.7 g / m 2 , the thickness was 30 ⁇ m, and the density was 0.99 g / cm 3 .
  • the resulting aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 1200 mPa ⁇ sec, and filtration was completed in 2 minutes.
  • the basis weight of the sheet was 30.2 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.01 g / cm 3 .
  • Example 32 A fine fibrous cellulose sheet was obtained in the same manner as in Example 31, except that 15 parts of a cationic polymer unisense KHE1000L (Senka Co., Ltd.) aqueous solution diluted with water to 0.1% by mass as a cellulose coagulant was added.
  • the obtained aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 450 mPa ⁇ s, and filtration was completed in 2 minutes.
  • the basis weight of the sheet was 30.1 g / m 2 , the thickness was 29 ⁇ m, and the density was 1.04 g / cm 3 .
  • Example 33 A fine fibrous cellulose sheet was obtained in the same manner as in Example 31 except that 15 parts of a cationic polymer fixage-621 (Kurita Industrial Co., Ltd.) aqueous solution diluted with water to 0.1% by mass as a cellulose coagulant was added.
  • the resulting aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 1350 mPa ⁇ sec, and filtration was completed in 2 minutes.
  • the basis weight of the sheet was 30.4 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.01 g / cm 3 .
  • the basis weight of the sheet was 30.0 g / m 2 , the thickness was 60 ⁇ m, and the density was 0.50 g / cm 3 .
  • the obtained sheet was immersed in a phenolic resin (manufactured by Gunei Chemical Co., Ltd .: trade name “PL4414”, thermosetting type, solid content 40%, methanol solution) under reduced pressure (0.08 MPa) for 12 hours, and then the sheet was After taking out and air-drying for several hours, it was cured by hot pressing at 150 ° C. and 50 MPa for 10 minutes to obtain a phenol resin composite fine fiber sheet.
  • the obtained resin-composited fine fibrous sheet was significantly improved in transparency and flexible enough to bend by hand as compared with that before compositing.
  • Example 36 An aqueous suspension of ammonium hydrogen carbonate (Wako Pure Chemicals) as a cellulose coagulant (concentration: 10% by mass) in 100 parts of an aqueous suspension prepared by adjusting the fine fibrous cellulose C to a pulp concentration of 0.5% by mass. 5 parts were added with stirring. On the other hand, 109 g of the above aqueous suspension was poured onto a cellulose acetate membrane filter (Advantech, membrane filter) having a pore diameter of 0.45 ⁇ m, which was put on a Buchner funnel having a diameter of 142 mm, and suction filtration was performed to obtain a fine fibrous cellulose sheet.
  • a cellulose acetate membrane filter Advancedtech, membrane filter
  • the resulting aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 850 mPa ⁇ sec, and filtration was completed in 3 minutes.
  • the basis weight of the sheet was 31.0 g / m 2 , the thickness was 31 ⁇ m, and the density was 1.0 g / cm 3 .
  • Example 37 A fine fibrous cellulose sheet was obtained in the same manner as in Example 36 except that 5 parts of an aqueous solution (concentration: 10% by mass) of ammonium hydrogen carbonate (Wako Pure Chemical Industries) was added as a cellulose coagulant with stirring.
  • the obtained aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 1000 mPa ⁇ s, and filtration was completed in 2 minutes.
  • the basis weight of the sheet was 30.5 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.02 g / cm 3 .
  • Example 38 A fine fibrous cellulose sheet was obtained in the same manner as in Example 36, except that 10 parts of an aqueous solution (concentration: 10% by mass) of ammonium hydrogen carbonate (Wako Pure Chemical Industries) was added as a cellulose coagulant with stirring.
  • the resulting aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 1050 mPa ⁇ s, and filtration was completed in 2 minutes.
  • the basis weight of the sheet was 30.0 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.0 g / cm 3 .
  • Example 39 A fine cationic resin (trademark: SPI203, manufactured by Sumitomo Chemical Co., Ltd., solid content 50) as a cellulose coagulant was added to 100 parts of an aqueous suspension prepared by adjusting the slurry C of fine fibrous cellulose to a pulp concentration of 0.5% by mass. %, Polyamine polyamide resin) was added to 1 part of an aqueous solution diluted to 10% with stirring.
  • SPI203 fine cationic resin
  • solid content 50 solid content 50
  • aqueous suspension was poured onto a cellulose acetate membrane filter (Advantech, membrane filter) having a pore diameter of 0.45 ⁇ m, which was put on a Buchner funnel having a diameter of 142 mm, and suction filtration was performed to obtain a fine fibrous cellulose sheet.
  • the resulting aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 650 mPa ⁇ sec, and filtration was completed in 3 minutes.
  • the basis weight of the sheet was 30.9 g / m 2 , the thickness was 31 ⁇ m, and the density was 1.0 g / cm 3 .
  • Example 40 Example 39 except that 2.5 parts of an aqueous solution in which a slightly cationic resin (trademark: SPI203, solid content: 50%, polyamine polyamide resin) diluted to 10% was added as a cellulose coagulant while stirring was added. Similarly, a fine fibrous cellulose sheet was obtained.
  • the resulting aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 900 mPa ⁇ s, and filtration was completed in 2 minutes.
  • the basis weight of the sheet was 30.6 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.02 g / cm 3 .
  • Example 41 Except that 5 parts of an aqueous solution in which a slightly cationic resin (trademark: SPI203, solid content: 50%, polyamine polyamide resin) diluted to 10% was added as a cellulose coagulant with stirring was the same as in Example 39. Thus, a fine fibrous cellulose sheet was obtained.
  • the obtained aqueous suspension had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 1050 mPa ⁇ sec, and filtration was completed in 1 minute.
  • the basis weight of the sheet was 30.1 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.0 g / cm 3 .
  • ⁇ Comparative Example 22> A cellulose acetate membrane filter having a pore diameter of 0.45 ⁇ m obtained by grinding 95 g of an aqueous suspension prepared by adjusting slurry A of fine fibrous cellulose so as to have a pulp concentration of 0.5 mass% on a Buchner funnel having a diameter of 142 mm (manufactured by Advantech) The solution was poured onto a membrane filter ") and subjected to suction filtration. The obtained aqueous suspension (A) had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 80 mPa ⁇ s. Filtration was completed in 8 minutes. The obtained fine fiber wet sheet was dried at 105 ° C. using a cylinder dryer to obtain a fine fibrous cellulose sheet. The basis weight of the sheet was 30.2 g / m 2 , the thickness was 29 ⁇ m, and the density was 1.0 g / cm 3 .
  • a fine fibrous cellulose sheet was obtained in the same manner as in Comparative Example 22 except that the fine fibrous cellulose slurry B was used.
  • the B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension (B) was 150 mPa ⁇ sec. Filtration was completed in 9 minutes.
  • the obtained fine fiber wet sheet was dried at 105 ° C. using a cylinder dryer to obtain a fine fibrous cellulose sheet.
  • the basis weight of the sheet was 30.3 g / m 2 , the thickness was 30 ⁇ m, and the density was 1.0 g / cm 3 .
  • a fine fibrous cellulose sheet was obtained in the same manner as Comparative Example 22 except that the fine fibrous cellulose slurry D was used.
  • the B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension (D) was 430 mPa ⁇ sec. Filtration was completed in 11 minutes.
  • the obtained fine fiber wet sheet was dried at 105 ° C. using a cylinder dryer to obtain a fine fibrous cellulose sheet.
  • the basis weight of the sheet was 29.5 g / m 2 , the thickness was 19 ⁇ m, and the density was 1.55 g / cm 3 .
  • Example 42 While adding 50 parts of diethylene glycol dimethyl ether (DEGDME) (trade name: Hisolv MDM, molecular weight 134, boiling point 162 ° C., surface tension 28 N / m) manufactured by Toho Chemical Co. to 100 parts of the fine fibrous cellulose slurry A of Preparation Example 1. The mixture was stirred to obtain a fine fibrous cellulose aqueous dispersion containing an organic solvent. To 100 parts of the dispersion, 1.67 parts by mass of aluminum sulfate (chemical formula: Al 2 (SO 4 ) 3 , solid content: 0.3% by mass) as a cellulose coagulant was added with stirring.
  • DEGDME diethylene glycol dimethyl ether
  • the obtained aqueous suspension (A) had a B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of 530 mPa ⁇ s.
  • 150 g of the obtained aqueous suspension (A) was poured onto a cellulose acetate membrane filter having a pore diameter of 0.45 ⁇ m (“Membrane filter” manufactured by Advantech Co., Ltd.) drawn on a Buchner funnel having a diameter of 142 mm, and suction filtration was performed. . Filtration was completed in 1 minute.
  • the obtained wet sheet of fine fibers was dried at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and wet.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step) to obtain a fine fibrous cellulose sheet having a basis weight of 30 g / m 2 .
  • the resulting sheet was porous and opaque.
  • the thickness was 58 ⁇ m.
  • Example 43 A fine fibrous cellulose sheet was obtained in the same manner as in Example 42 except that the fine fibrous cellulose slurry C was used.
  • the B-type viscosity (25 ° C., 60 rpm, rotor No. 4) of the obtained aqueous suspension (C) was 1100 mPa ⁇ sec. Filtration was completed in 2 minutes.
  • the obtained wet sheet of fine fibers was dried at 80 ° C. for 3 minutes to obtain a sheet after the first drying.
  • the obtained sheet after the first drying was translucent and wet.
  • the sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step) to obtain a fine fibrous cellulose sheet having a basis weight of 30 g / m 2 .
  • Example 44 To 100 parts of the fine fibrous cellulose slurry A of Preparation Example 1, 0.83 part of Emulsion A of Preparation Example 5 and 2.5 parts of an aqueous solution of ammonium hydrogen carbonate (Wako Pure Chemical Industries) as a cellulose coagulant (concentration 10% by mass) The mixture was added and stirred to obtain a fine fibrous cellulose aqueous dispersion containing an organic solvent emulsion.
  • a wet sheet was prepared while decompressing the dispersion on a 500 mesh polyester mesh. The wet sheet was dried with a 500 mesh polyester mesh at 80 ° C. for 3 minutes to obtain a sheet after the first drying. The obtained sheet after the first drying was translucent and wet. The sheet after the first drying was dried at 130 ° C. for 3 minutes (second drying step), and the sheet was peeled off from the polyester mesh to obtain a 35 g / m 2 fine fibrous cellulose sheet.
  • the sheet obtained by the method for producing a fine fibrous cellulose sheet of the present invention has a low air permeability, is a porous sheet, and has excellent transparency by being impregnated with resin. A complex is obtained.
  • a porous sheet of fine fibrous cellulose can be produced simply and efficiently.
  • the composite base material useful for a flexible transparent substrate etc. can be obtained by impregnating resin to the obtained fine fibrous cellulose sheet.

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Abstract

L'invention concerne un procédé de fabrication d'une feuille de cellulose microfibreuse, selon lequel de la cellulose microfibreuse est efficacement mise sous la forme d'une feuille poreuse. L'invention concerne également un composite de cellulose microfibreuse qui est obtenu par imprégnation d'une feuille de cellulose microfibreuse, fabriquée par le procédé susmentionné, avec une résine. Le procédé de fabrication d'une feuille de cellulose microfibreuse est caractérisé en ce qu'il comprend : une étape de dispersion lors de laquelle une émulsion contenant de la cellulose microfibreuse et un solvant organique est dispersée dans de l'eau, ou une étape de dispersion lors de laquelle de la cellulose microfibreuse est dispersée dans un solvant mixte composé d'eau et d'un solvant organique compatible avec l'eau ; une étape de fabrication de papier lors de laquelle la dispersion aqueuse de cellulose microfibreuse est déshydratée par filtration sur une base poreuse, formant ainsi une feuille contenant de l'eau ; et une étape de séchage lors de laquelle la feuille contenant de l'eau est chauffée et séchée. Le composite de cellulose microfibreuse est obtenu en imprégnant une feuille de cellulose microfibreuse, obtenue par le procédé de fabrication, avec une résine.
PCT/JP2009/007211 2008-12-26 2009-12-24 Procédé de fabrication d'une feuille de cellulose microfibreuse et composite obtenu par imprégnation de la feuille de cellulose microfibreuse avec une résine Ceased WO2010073678A1 (fr)

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WO2012011559A1 (fr) * 2010-07-23 2012-01-26 王子製紙株式会社 Toile pour la fabrication d'une feuille de papier contenant de la cellulose microfibreuse et méthode de fabrication d'une feuille contenant de la cellulose microfibreuse
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