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WO2013073652A1 - Procédé de production de cellulose microfibreuse, procédé de production d'un tissu non tissé, cellulose microfibreuse, suspension contenant de la cellulose microfibreuse, tissu non tissé et complexe - Google Patents

Procédé de production de cellulose microfibreuse, procédé de production d'un tissu non tissé, cellulose microfibreuse, suspension contenant de la cellulose microfibreuse, tissu non tissé et complexe Download PDF

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Publication number
WO2013073652A1
WO2013073652A1 PCT/JP2012/079743 JP2012079743W WO2013073652A1 WO 2013073652 A1 WO2013073652 A1 WO 2013073652A1 JP 2012079743 W JP2012079743 W JP 2012079743W WO 2013073652 A1 WO2013073652 A1 WO 2013073652A1
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Prior art keywords
cellulose
fine fibrous
group
fibrous cellulose
nonwoven fabric
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Japanese (ja)
Inventor
裕一 野口
岸田　隆之
泰友 野一色
日出子 赤井
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Oji Holdings Corp
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Oji Holdings Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
    • 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
    • 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
    • D21H11/20—Chemically or biochemically modified fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Definitions

  • the present invention relates to a method for producing fine fibrous cellulose, a method for producing a non-woven fabric, fine fibrous cellulose, a fine fibrous cellulose-containing slurry, a non-woven fabric, and a composite.
  • This application claims priority based on Japanese Patent Application No. 2011-252649 filed in Japan on November 18, 2011 and Japanese Patent Application No. 2012-024458 filed in Japan on February 7, 2012, The contents are incorporated here.
  • cellulose fibers having a fiber diameter of 10 to 50 ⁇ m, particularly cellulose fibers (pulp) derived from wood have been widely used mainly as paper products so far.
  • fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is also known as the cellulose fiber, and the sheet containing the fine fibrous cellulose has advantages such as high mechanical strength, and can be used for various applications.
  • Application has been studied (Patent Document 1). For example, it is known that fine fibrous cellulose is made into a non-woven fabric and used as a high-strength sheet.
  • Patent Document 2 discloses a method of treating lignocellulose in an aqueous solvent containing a nitroxyl radical derivative, an alkali bromide and an oxidizing agent.
  • Patent Document 3 discloses a method in which a polybasic acid anhydride is half-esterified into a part of a hydroxy group of cellulose to introduce a carboxy group, and then fibrillated and refined.
  • Patent Document 2 requires the use of a special catalyst, which increases the cost.
  • the fiber raw material is insufficiently refined. Since the yield was low and the stability of the dispersion was insufficient, there were problems such as low production efficiency from the fiber raw material, high cost, and high environmental load.
  • An object of this invention is to provide the manufacturing method of the fine fibrous cellulose which solved the said problem, the manufacturing method of a nonwoven fabric, a fine fibrous cellulose, a fine fibrous cellulose containing slurry, a nonwoven fabric, and a composite_body
  • the present invention relates to the following.
  • [1] (a) A fiber raw material containing cellulose is treated with at least one compound selected from the group consisting of phosphorus oxoacids and salts of phosphorus oxoacids, and phosphorus oxoacids are introduced into the cellulose. And (b) a step of defibrating the cellulose into which the phosphorus oxoacid is introduced in the step (a), and a method for producing fine fibrous cellulose, [2] The method for producing fine fibrous cellulose according to [1], wherein the fiber raw material is a chemical pulp obtained from wood.
  • a fine fibrous cellulose having a fiber width of 1 to 1000 nm and a cellulose in which a part of hydroxy groups of cellulose constituting the fiber is substituted with a functional group represented by the following structural formula (1): (In the structural formula (1), a, b, m and n are natural numbers (where a b ⁇ m).
  • ⁇ 1 , ⁇ 2 ,..., ⁇ n and ⁇ ′ at least one O - a and the remainder is either R, and oR .R are each a hydrogen atom, a saturated - linear hydrocarbon radical, saturated - branched chain hydrocarbon group, a saturated - cyclic Any one of a hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group, an aromatic group, and a derivative group thereof, ⁇ is a monovalent or higher valent compound composed of an organic substance or an inorganic substance.
  • a fine fibrous cellulose-containing slurry in which the fine fibrous cellulose according to [5] is dispersed in a dispersion medium [7] A nonwoven fabric containing the fine fibrous cellulose according to [5], [8] A composite containing the fine fibrous cellulose described in [5] and a matrix material, and a composite containing the nonwoven fabric described in [9] [7] and a matrix material.
  • the method for producing fine fibrous cellulose of the present invention since the fiber raw material can be sufficiently refined and the yield of fine fibrous cellulose is high, the production efficiency of fine fibrous cellulose from the fiber raw material is high. Moreover, the manufacturing method of the fine fibrous cellulose of this invention is low cost, and its environmental impact is small. According to the method for producing a nonwoven fabric of the present invention, the production efficiency of the nonwoven fabric with respect to the fiber raw material can be improved. Since the fine fibrous cellulose of the present invention has a small fiber width and a large axial ratio (fiber length / fiber width), the slurry stability of the fine fibrous cellulose is high, and the resulting nonwoven fabric has a high strength. The composite of the fine fibrous cellulose and the matrix resin of the present invention has high strength and a low linear thermal expansion coefficient.
  • FIG. 2 is a transmission electron micrograph of cellulose contained in the defibrated pulp slurry obtained in Example 1.
  • FIG. 4 is a transmission electron micrograph of cellulose contained in the defibrated pulp slurry obtained in Example 3.
  • FIG. It is a schematic block diagram of one Embodiment of the manufacturing apparatus used with the manufacturing method of the nonwoven fabric of this invention.
  • ⁇ Fine fibrous cellulose> a part of the hydroxy group (—OH group) is substituted with a functional group represented by the following structural formula (1).
  • the fine fibrous cellulose of the present invention is a cellulose fiber or cellulose rod-like particles that are much thinner than pulp fibers that are usually used in papermaking applications.
  • R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group, respectively.
  • the saturated-linear hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
  • Examples of the saturated-branched hydrocarbon group include i-propyl group and t-butyl group.
  • Examples of the saturated-cyclic hydrocarbon group include a cyclopentane group and a cyclohexane group.
  • Examples of the unsaturated-linear hydrocarbon group include a vinyl group and an allyl group.
  • Examples of the unsaturated-branched hydrocarbon group include i-propenyl group and 3-butenyl group.
  • Examples of the saturated-cyclic hydrocarbon group aromatic group include a phenyl group and a naphthalene group.
  • the derivative in R is a functional group in which at least one of functional groups such as a carboxy group, a hydroxy group, or an amino group is added to or substituted for the main chain or side chain of the various hydrocarbon groups. Groups.
  • the number of carbon atoms constituting the main chain of R is preferably 20 or less, and more preferably 10 or less.
  • ⁇ is a monovalent or higher cation composed of an organic substance or an inorganic substance.
  • the monovalent or higher cation made of an organic substance include aliphatic ammonium or aromatic ammonium.
  • examples of the monovalent or higher cation made of an inorganic substance include ions of alkali metals such as sodium, potassium, or lithium, Examples thereof include a cation of a divalent metal such as calcium or magnesium, or a hydrogen ion. These may be applied alone or in combination of two or more.
  • sodium or potassium ions that are less likely to yellow when heated to a fiber raw material containing ⁇ and are industrially useful are preferable.
  • Structural Formula (1) is preferably a monoester that does not contain a cellulose molecular chain in ⁇ and ⁇ ′.
  • ⁇ and ⁇ ′ contain cellulose molecular chains
  • the cellulose molecular chains are cross-linked with each other, so that there is a possibility of inhibiting the miniaturization.
  • the cellulose fiber width is preferably 1 nm to 1000 nm, more preferably 2 nm to 500 nm, and still more preferably 4 nm to 100 nm, as observed with an electron microscope.
  • the fiber width of the fine fibrous cellulose is less than 1 nm, the physical properties (strength, rigidity, or dimensional stability) as the fine fibrous cellulose are not expressed because cellulose molecules are dissolved in water.
  • the fiber width is preferably 2 nm to 30 nm, more preferably 2 to 20 nm, because it tends to occur and the transparency tends to decrease.
  • a composite obtained from fine fibrous cellulose as described above generally has a high strength because it becomes a dense structure, and in addition to obtaining a high elastic modulus derived from cellulose crystals, it also scatters visible light. Since there are few, high transparency is also obtained.
  • the fine fibrous cellulose of the present invention is an aggregate of cellulose molecules and has a crystal structure.
  • the crystal structure is type I (parallel chain).
  • the measurement of the fiber width by electron microscope observation of fine fibrous cellulose is performed as follows.
  • a slurry containing fine fibrous cellulose having a concentration of 0.05 to 0.1% by mass is prepared, and the slurry is cast on a carbon film-coated grid subjected to a hydrophilic treatment to prepare a sample for TEM observation.
  • an SEM image of the surface cast on glass may be observed.
  • Observation by an electron microscope image is performed at any magnification of 1000 times, 5000 times, 10000 times, 20000 times, 40000 times, or 50000 times depending on the width of the fibers constituting the fibers.
  • the sample, observation conditions, and magnification are adjusted to satisfy the following conditions (1) and (2).
  • (1) One straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers intersect the straight line X.
  • a straight line Y perpendicularly intersecting the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.
  • the fine fiber width in the present invention is an average value of the fiber widths read in this way.
  • the fiber length is preferably 0.1 ⁇ m or more.
  • the fiber length can be determined by TEM, SEM, or AFM image analysis.
  • the said fiber length is a fiber length of the cellulose which occupies 30 mass% or more of fine fibrous cellulose.
  • the range of the fiber length of the fine fibrous cellulose of the present invention is preferably from 0.1 to 50 ⁇ m, more preferably from 0.3 to 30 ⁇ m, still more preferably from 0.5 to 10 ⁇ m.
  • the axial ratio (fiber length / fiber width) of the fine fibrous cellulose according to the present invention is calculated and calculated as follows. In the measurement of the fiber width by the electron microscope observation of the fine fibrous cellulose, the fiber length of each fiber whose fiber width is determined is also read visually. After calculating the axial ratio (fiber length / fiber width) for each fiber, the average of the observed number of fibers is taken as the axial ratio of fine fibrous cellulose.
  • the axial ratio of fine fibrous cellulose is preferably in the range of 100 to 10,000. If the axial ratio is less than 100, it may be difficult to form a fine fibrous cellulose-containing nonwoven fabric. When the axial ratio exceeds 10,000, the slurry viscosity becomes high, which is not preferable.
  • the ratio of the crystal part contained in the fine fibrous cellulose of the present invention is a cellulose fiber having a crystallinity obtained by X-ray diffraction of 60% or more, but the crystallinity is preferably 65% or more, more When it is preferably 70% or more, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion.
  • the degree of crystallinity was determined by measuring an X-ray diffraction profile and using a conventional method (Segal et al., Textile Research Journal, 29, 786, 1959).
  • the range of the crystallinity is preferably 60 to 100%, more preferably 65 to 100%, and further preferably 70 to 100%.
  • oxo acid having a hydroxy group and an oxo group bonded to a phosphorus atom (hereinafter referred to as “phosphoroxo acid”) Is introduced). It is presumed that the electrical repulsion between the cellulose fibers is strengthened by the phosphorus oxoacid. Moreover, it is excellent in the dispersion stability when it is made into a slurry.
  • the introduction amount of the phosphorus oxo acid group in the hydroxy group (—OH group) of the cellulose of the fiber raw material is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol per 1 g (mass) of fine fibrous cellulose. . If the introduction amount of the phosphorus oxo acid group is less than 0.1 mmol, it is difficult to refine the fiber raw material, and the stability of the fine fibrous cellulose is poor. If the introduction amount of the phosphorus oxo acid group exceeds 2.0 mmol, the fine fibrous cellulose may be dissolved.
  • the calculation is performed according to TAPPI T237 cm-08 (2008) except that the difference between the calculated values is a substantial substituent introduction amount.
  • the calculation method for introducing an acidic group is basically a method for calculating the introduction amount of a monovalent acidic group (carboxy group)
  • the calculation of the introduction amount of a phosphorus oxo acid group which is a polyvalent acidic group is performed.
  • the value obtained by dividing the introduction amount of the substituent obtained as the introduction amount of the monovalent acidic group by the acid number of the phosphorus oxo acid group was taken as the introduction amount of the group of phosphorus oxo acid.
  • the fiber raw material containing cellulose is at least one compound selected from the group consisting of phosphorus oxoacids and phosphorus oxoacid salts (hereinafter referred to as “compound A”).
  • compound A phosphorus oxoacid salts
  • [Phosphooxo group introduction step (a)] As a method of treating the fiber raw material with the compound A, a method of mixing the powder or aqueous solution of the compound A with a dry or wet fiber raw material, a method of adding the powder or aqueous solution of the compound A to the fiber raw material slurry, etc. Is mentioned. Among these, since the uniformity of the reaction is high, a method of adding an aqueous solution of compound A to a dry fiber material (pulp), or a powder or aqueous solution of compound A to a wet fiber material (pulp) The method is preferred.
  • Examples of the fiber raw material containing cellulose include paper pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as hemp, straw or bagasse; or cellulose isolated from squirts or seaweed .
  • paper pulp is preferable in terms of availability.
  • Paper pulp includes hardwood kraft pulp (bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), oxygen bleached kraft pulp (LOKP), etc.), softwood kraft pulp (bleached kraft pulp (NBKP), unbleached kraft pulp) (NUKKP, oxygen bleached kraft pulp (NOKP), etc.), sulfite pulp (SP), soda pulp (AP) and other chemical pulp; semi-chemical pulp (SCP), semi-chemical pulp (CGP), etc. Chemical pulp; mechanical pulp such as groundwood pulp (GP) or thermomechanical pulp (TMP, BCTMP); non-wood pulp made from cocoon, sardine, hemp, kenaf, etc .; or deinked pulp made from waste paper Can be mentioned.
  • a fiber raw material may be used individually by 1 type, and may be used in mixture of 2 or more types.
  • wood pulp or deinked pulp is preferable in terms of availability.
  • chemical pulp has a high cellulose ratio, so the yield of fine fibrous cellulose is high, and the cellulose in the pulp is small, resulting in long fiber fine fibrous cellulose with a large axial ratio.
  • chemical pulps kraft pulp or sulfite pulp is most preferably selected.
  • Pulp for papermaking may be beaten with a double disc refiner, a single disc refiner, or a beater, etc., but pulp with less beating (Canadian Standard Freeness (CSF) is preferably 400 ml or more, more preferably 500 ml or more Is preferably used.
  • CSF Canadian Standard Freeness
  • the dewatering and washing properties when the pulp is washed with water or an organic solvent before and after the alkali treatment described later are improved.
  • Examples of the compound A used in the present invention include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, polyphosphonic acid, and salts or esters thereof.
  • a compound having a phosphoric acid group is preferable because it is low-cost, easy to handle, and can further improve the fibrillation efficiency by introducing a phosphoric acid group into the hydroxy group of cellulose.
  • Examples of the compound having a phosphate group include phosphoric acid; lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, or lithium polyphosphate which are lithium salts of phosphoric acid; and sodium phosphate Sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, or sodium polyphosphate; and potassium diphosphate potassium phosphate, dipotassium hydrogen phosphate, phosphorus Examples include tripotassium acid, potassium pyrophosphate, and potassium polyphosphate.
  • phosphoric acid sodium salt of phosphoric acid
  • a potassium salt of phosphoric acid is preferred, and sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferred.
  • the compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introduction of the phosphorus oxo acid group is increased.
  • the pH of the aqueous solution of Compound A is preferably 7 or less because of the high efficiency of introduction of the phosphorus oxoacid group, but is preferably 3 to 7 from the viewpoint of suppressing the hydrolysis of the pulp fibers.
  • the pH may be adjusted by, for example, using a phosphoric acid group-containing compound in combination with an acidic one and an alkalinity, and changing the amount ratio thereof. You may adjust by adding an inorganic alkali or an organic alkali to what shows.
  • the mass ratio of Compound A with respect to the fiber raw material is preferably 0.2 to 500 parts by mass, more preferably 1 to 400 parts by mass, and more preferably 2 to 200 parts by mass with respect to 100 parts by mass of the fiber raw material. Is most preferred. If the ratio of the compound A is 0.2 mass part or more, the yield of fine fibrous cellulose can be improved more. However, even if the proportion of Compound A exceeds 500 parts by mass, the effect of improving the yield reaches a peak, and only Compound A is used in vain.
  • heat treatment is preferably performed.
  • the heat treatment temperature a temperature at which a phosphorus oxo acid group can be efficiently introduced while suppressing thermal decomposition or hydrolysis reaction of cellulose is selected.
  • the temperature is preferably 50 to 250 ° C., more preferably 100 to 170 ° C.
  • the slurry is preferably heated to 50 to 130 ° C., more preferably 70 to 110 ° C.
  • heat treatment is preferably performed at 100 to 170 ° C.
  • the concentration of the compound A in the fiber raw material may be uneven, and the introduction of the phosphorus oxo acid group to the cellulose surface may not proceed uniformly.
  • a very thin sheet-like fiber material is used, or heat drying while kneading the fiber material and compound A with a kneader or the like.
  • a method of drying under reduced pressure may be employed.
  • a heating device used for the heat treatment moisture retained by the slurry and moisture generated by addition reaction to cellulose hydroxyl groups such as a phosphoroxo acid group can always be discharged out of the apparatus system, and an air blowing oven or the like is preferable. If water in the apparatus system is always discharged, in addition to suppressing the hydrolysis reaction of the phosphorus oxo acid ester bond, which is the reverse reaction of the phosphorus oxo acid esterification, the acid hydrolysis of the cellulose sugar chain can also be suppressed. A fine fibrous cellulose having a high ratio can be obtained.
  • the heat treatment time is after the fiber raw material slurry to which compound A has been added is heat-treated, and the water content of the slurry is 30% by mass or less, preferably 0 to 20% by mass with respect to the total mass of the slurry. It is preferably 15 to 180 minutes, and more preferably 30 to 90 minutes.
  • Defibration processing step (b) In the defibrating treatment step (b), usually, the phosphooxo acid-introduced cellulose is defibrated using a defibrating device to obtain a fine fibrous cellulose-containing slurry.
  • Defibration treatment equipment includes high-speed defibrator, grinder (stone mortar grinder), high-pressure homogenizer and ultra-high pressure homogenizer, high-pressure collision grinder, ball mill, bead mill, disk refiner, conical refiner, twin-screw kneader, vibration mill
  • An apparatus for wet pulverization such as a homomixer under high-speed rotation, an ultrasonic disperser, or a beater, can be used as appropriate.
  • Favorable defibrating treatment methods include a high-speed defibrator, a high-pressure homogenizer, and an ultra-high pressure homogenizer that are less affected by the grinding media and less susceptible to contamination.
  • the defibrating treatment it is preferable to dilute the phosphorus oxoacid-introduced cellulose into a slurry by diluting water and an organic solvent alone or in combination.
  • the solid content concentration of the diluted phosphoroic acid-introduced cellulose is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass. If the solid content concentration of the diluted phosphorus oxoacid-introduced cellulose is 0.1% by mass or more, the efficiency of the defibrating treatment is improved, and if the solid content concentration is 20% by mass or less, in the defibrating apparatus. Can be blocked.
  • step (a) it is preferable to have an alkali treatment step between step (a) and step (b) because the yield of fine fibrous cellulose is improved.
  • a cation can be supplied to the phosphorus oxoacid group introduced into the cellulose to easily form a salt.
  • the alkali compound contained in the alkali solution may be an inorganic alkali compound or an organic alkali compound.
  • Inorganic alkali compounds include alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal carbonates or alkaline earth metal carbonates, alkali metal phosphates or alkaline earth metal phosphates Salt.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and examples of the alkaline earth metal hydroxide include calcium hydroxide.
  • Examples of the alkali metal carbonate include lithium carbonate, lithium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, and sodium hydrogen carbonate.
  • Examples of the alkaline earth metal carbonate include calcium carbonate.
  • Examples of the alkali metal phosphate include lithium phosphate, potassium phosphate, trisodium phosphate, and disodium hydrogen phosphate.
  • Examples of alkaline earth metal phosphates include calcium phosphate and calcium hydrogen phosphate.
  • Examples of the organic alkali compounds include ammonia, aliphatic amines, aromatic amines, aliphatic ammoniums, aromatic ammoniums, heterocyclic compounds and their hydroxides, carbonates, and phosphates.
  • the organic alkali compound contained in the alkali solution of the present invention includes, for example, ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane.
  • Diaminopentane diaminohexane, cyclohexylamine, aniline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, pyridine, N, N-dimethyl-4 -Aminopyridine, ammonium carbonate, ammonium hydrogen carbonate, diammonium hydrogen phosphate and the like.
  • the solvent in the alkaline solution may be either water or an organic solvent, but a polar solvent (polar organic solvent such as water or alcohol) is preferred, and an aqueous solvent containing at least water is more preferred.
  • a polar solvent polar organic solvent such as water or alcohol
  • an aqueous solvent containing at least water is more preferred.
  • a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is particularly preferred because of its high versatility.
  • the pH at 25 ° C. of the alkaline solution soaked with the phosphooxo group-introduced cellulose is preferably 9 to 14, more preferably 10 to 14, and still more preferably 11 to 14. If the pH of the alkaline solution is 9 or more, the yield of fine fibrous cellulose will be higher. However, when pH exceeds 14, the handleability of an alkaline solution will fall.
  • “the pH at 25 ° C. of the alkaline solution in which the cellulose containing phosphorus oxoacid groups is immersed is 9 to 14” refers to the alkaline solution in which the cellulose having phosphorus oxyacid groups introduced is immersed, based on a temperature of 25 ° C. Means that the pH is within the above range. That is, when the alkaline solution is prepared at a temperature other than 25 ° C., the pH range is corrected according to the temperature. It is also included in the scope of the present invention to prepare the alkaline solution in the pH range thus corrected.
  • the temperature of the alkali solution in the alkali treatment step is preferably 5 to 80 ° C, more preferably 10 to 60 ° C.
  • the immersion time in the alkali alkali solution in the alkali treatment step is preferably 5 to 30 minutes, and more preferably 10 to 20 minutes.
  • the amount of the alkali solution used in the alkali treatment is preferably from 100 to 100,000% by mass, more preferably from 1000 to 10,000% by mass, based on the absolute dry mass of the phosphorus oxoacid-introduced cellulose.
  • the phosphorus oxo acid group-introduced cellulose may be washed with water or an organic solvent before the alkali treatment step.
  • a fiber raw material can fully be refined
  • the reason for this is that the pulp treated with Compound A is introduced with a phosphoroxo acid group and the like in the cellulose, the electrostatic repulsion between the cellulose fibers is increased, and the osmotic pressure of water between the celluloses is improved, so that the fibrillation property is improved. Is estimated to be high.
  • the manufacturing method of the said fine fibrous cellulose does not need to use a nitroxy radical derivative, an alkali bromide, and an oxidizing agent, cost is low and environmental impact is also small.
  • the fine fibrous cellulose-containing slurry of the present invention is obtained by dispersing fine fibrous cellulose in a dispersion medium.
  • a polar organic solvent can be used in addition to water.
  • Preferred polar organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, or tbutyl alcohol, Examples thereof include ketones such as acetone or methyl ethyl ketone (MEK), ethers such as diethyl ether or tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), or dimethylacetamide (DMAc). These may be one type or two or more types.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, or tbutyl alcohol
  • ketones such as acetone or methyl ethyl ketone (MEK)
  • ethers such as diethyl ether or tetrahydrofuran (THF)
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • a nonpolar organic solvent can be used.
  • the content of the fine fibrous cellulose in the fine fibrous cellulose-containing slurry is preferably 0.05 to 20% by mass, and preferably 0.1 to 10% by mass with respect to the total mass of the fine fibrous cellulose and the solvent. Is more preferable. If the content of fine fibrous cellulose is 0.05% by mass or more, it is excellent in production efficiency when producing a non-woven fabric or a composite described later, and if the content of fine fibrous cellulose is 20% by mass or less. Excellent dispersion stability of the slurry.
  • a method for producing the fine fibrous cellulose-containing slurry a method of dispersing in a dispersion medium before the defibrating process and performing the defibrating process as it is, or after removing the solvent with a membrane filter or the like after the defibrating process, Examples of the method include substitution with a solvent and redispersion.
  • Nonwoven fabric contains the fine fibrous cellulose.
  • the thickness of the nonwoven fabric of the present invention is not particularly limited, but is preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, particularly preferably 50 ⁇ m or more, preferably 10 cm or less, more preferably 1 cm or less, more preferably 1 mm. Hereinafter, it is particularly preferably 250 ⁇ m or less.
  • the thickness range of the nonwoven fabric is preferably 10 ⁇ m to 1 mm, more preferably 20 to 500 ⁇ m, further preferably 30 to 250 ⁇ m, and particularly preferably 50 ⁇ m to 150 ⁇ m.
  • the thickness of the nonwoven fabric is preferably 10 ⁇ m or more from the viewpoint of production stability and strength, and is preferably 10 cm or less from the viewpoint of productivity, uniformity or resin impregnation.
  • the porosity of the nonwoven fabric of the present invention is preferably 20 vol% or more, more preferably 35 vol% or more and 60 vol% or less.
  • the porosity of the nonwoven fabric is small, the reaction is difficult to proceed when the above chemical modification is applied, or the matrix material such as resin is difficult to impregnate, and the unimpregnated portion remains when the composite is formed. Scattering occurs and haze increases.
  • the non-woven fabric has a high porosity, when it is made into a composite, a sufficient reinforcing effect by cellulose fibers cannot be obtained, and the linear thermal expansion coefficient becomes large, which is not preferable.
  • the porosity here refers to the volume ratio of the voids in the nonwoven fabric, and the porosity can be determined from the area, thickness, and mass of the nonwoven fabric according to the following formula.
  • Porosity (vol%) ⁇ 1-B / (M ⁇ A ⁇ t) ⁇ ⁇ 100
  • A is the area (cm 2 ) of the nonwoven fabric
  • t (cm) is the thickness
  • B is the mass (g) of the nonwoven fabric
  • M 1.5 g / cm 3 is assumed in the present invention.
  • the film thickness of the nonwoven fabric is measured at 10 points at various positions of the nonwoven fabric using a film thickness meter (PDN-20 manufactured by PEACOK), and the average value is adopted.
  • the porosity when obtaining the porosity of the nonwoven fabric in the composite, the porosity can also be obtained by performing image analysis of spectroscopic analysis or SEM observation of the cross section of the composite.
  • Air permeability of the nonwoven fabric of the present invention is not particularly limited since it depends on the basis weight, for example, when a basis weight of the sheet 50 g / m 2 is preferably 100 to 20,000 sec / 100 cc.
  • the manufacturing apparatus 1 of this embodiment includes a dewatering section 20, a drying section 40 provided on the downstream side of the dewatering section 20, and a winding section 60 provided on the downstream side of the drying section.
  • the dewatering section 20 is a section for dewatering the fine fibrous cellulose-containing slurry 3a using the papermaking wire 10 to obtain the water-containing web 3b.
  • the papermaking wire woven or non-woven fabric such as plastic wire or metal wire, or paper can be used, and among these, non-woven fabric and paper are preferable.
  • the dewatering section 20 is provided with a feed reel 21 for feeding out the papermaking wire 10, a discharge unit 20a for the fine fibrous cellulose-containing slurry 3a, and a dehydrating unit 30 for the dispersion medium.
  • Two or more die heads 22 for discharging the fine fibrous cellulose-containing slurry 3a to the running paper-making wire 10 fed from the delivery reel 21 and disposed downstream of each die head 22 are discharged to the discharge unit 20a.
  • a plate 24 for leveling the upper surface of the fine fibrous cellulose-containing slurry 3a.
  • the discharge unit 20a and the dehydrating unit 30 are provided with suction devices 26 and 32 for forcibly dehydrating the dispersion medium from the fine fibrous cellulose-containing slurry 3a.
  • the suction devices 26 and 32 are disposed below the paper making wire 10, and a plurality of suction holes (not shown) connected to a vacuum pump (not shown) are formed on the upper surface thereof.
  • the suction hole is not formed on the upstream side of the suction device 26 and is a non-suction hole that is not connected to the vacuum pump. If the suction hole is formed on the upstream side, the surface of the coating film of the fine fibrous cellulose-containing slurry 3a may become rough. Further, since the amount of dewatering is reduced on the downstream side, the suction device 32 in the dewatering unit 30 may not have a hole formed on the downstream side.
  • the drying section 40 is a section that obtains the nonwoven fabric 3c by drying the hydrous web 3b using a dryer.
  • the drying section 40 is provided with a first dryer 42 and a second dryer 52 configured by a cylinder dryer, and a felt cloth 44 disposed along the outer periphery of the first dryer 42 in a hood 49.
  • the first dryer 42 is disposed on the upstream side of the second dryer 52. Further, the felt cloth 44 is endless and is circulated by a guide roll 46.
  • the water-containing web 3 b is transferred by the guide roll 48.
  • the surface A (hereinafter referred to as “application surface A”) of the water-containing web 3b on which the fine fibrous cellulose-containing slurry 3a is applied is in contact with the outer peripheral surface of the first dryer 42, and the water-containing web 3b.
  • the surface B on which the fine fibrous cellulose-containing slurry 3a has not been applied (hereinafter referred to as “non-application surface B”) is transferred so as to be in contact with the felt cloth 44, and then the application surface A is the outer peripheral surface of the second dryer 52. To come in contact with.
  • the winding section 60 is a section that separates the nonwoven fabric 3c from the papermaking wire 10 and winds it.
  • a pair of separation rollers 62a and 62b for separating the nonwoven fabric 3c from the papermaking wire 10 a winding reel 64 for winding the nonwoven fabric 3c, and a used papermaking wire 10 are wound and collected.
  • a collection reel 66 is provided.
  • the separation roller 62b is disposed on the papermaking wire 10 side, and the separation roller 62a is disposed on the nonwoven fabric 3c side.
  • the method for producing a nonwoven fabric according to this embodiment includes a dehydration step of dehydrating a slurry containing fine fibrous cellulose produced by the method for producing fine fibrous cellulose on a filter medium to obtain wet paper, and drying the wet paper It has a drying process for obtaining a nonwoven fabric and a winding process for winding the nonwoven fabric.
  • the papermaking wire 10 is fed out from the delivery reel 21, the fine fibrous cellulose-containing slurry 3a is discharged from the die head 22 to the papermaking wire 10, and the upper surface of the fine fibrous cellulose-containing slurry 3a of the papermaking wire 10 is plated. Level by 24.
  • the suction medium 26 and 32 sucks the dispersion medium contained in the fine fibrous cellulose-containing slurry 3a on the papermaking wire 10 and dehydrates it to obtain the water-containing web 3b.
  • the papermaking wire 10 may be broken. Therefore, a wire used for normal papermaking is placed under the papermaking wire 10 for papermaking.
  • the wire 10 may be supported.
  • the papermaking wire 10 Before supplying the fine fibrous cellulose-containing slurry 3a to the papermaking wire 10, the papermaking wire 10 may be preliminarily impregnated with water to be in a wet state. When the fine fibrous cellulose-containing slurry 3a is discharged onto the papermaking wire 10, the wrinkle may be generated due to water absorption of the wire. However, if it is made wet in advance, the generation of the wrinkle can be prevented.
  • Examples of means for bringing the papermaking wire 10 into a wet state include a water tank in which the papermaking wire 10 is immersed in water, or a water coating apparatus.
  • a blade coater As the water coating apparatus, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, a curtain coater, a die coater, or the like can be used.
  • the fine fibrous cellulose-containing slurry 3a supplied to the papermaking wire 10 in the dehydration step is a liquid containing fine fibrous cellulose and water.
  • the fine fibrous cellulose-containing slurry 3a may contain a resin emulsion.
  • the resin emulsion is an emulsion in which particles of natural resin or synthetic resin having a particle size of 0.001 to 10 ⁇ m are emulsified in water.
  • the particulate resin contained in the resin emulsion is not particularly limited, but polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, poly (meth) acrylic acid alkyl ester polymer, ( (Meth) acrylic acid alkyl ester copolymer, poly (meth) acrylonitrile, polyester, polyurethane, polyamide, epoxy resin, oxetane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin, diallyl phthalate resin, etc.
  • Precursors, and resin emulsions such as monomers and oligomers constituting them; natural rubber, styrene-butadiene copolymer, or —SH, —CSSH, —SO 3 H, — (COO) x M, - (SO 3) x M, and Modified with at least one functional group selected from the group of CO—R (wherein M is a cation, x is an integer of 1 to 3 depending on the valence of M, and R is an alkyl group)
  • Modified styrene-butadiene copolymer such as acid-modified, amine-modified, amide-modified, or acrylic-modified; (meth) acrylonitrile-butadiene copolymer; polyisoprene; polychloroprene; styrene-butadiene- Examples include methyl methacrylate copolymer; styrene- (meth) acrylic acid alkyl
  • polyethylene, polypropylene, polyurethane, ethylene-vinyl acetate copolymer or the like may be emulsified by a post-emulsification method. Two or more kinds of these resin emulsions can be contained.
  • the slurry when dehydrated and dried, it can be obtained in a state in which fine fiber cellulose and a matrix material are contained in the nonwoven fabric 3c. You can also. In this case, two or more sheets may be laminated and cured.
  • the fine fibrous cellulose-containing slurry 3a can contain a cellulose coagulant.
  • the cellulose coagulant include a water-soluble inorganic compound and a water-soluble organic compound 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 Examples thereof include sodium phosphate and ammonium phosphate.
  • water-soluble organic compound containing a cationic functional group examples include polyacrylamide, polyvinylamine, urea resin, melamine resin, melamine-formaldehyde resin, or a polymer obtained by polymerizing or copolymerizing a monomer containing a quaternary ammonium salt. .
  • the fine fibrous cellulose-containing slurry 3a can contain one or more materials such as a water-soluble organic polymer, an inorganic polymer, or a hybrid polymer of an organic polymer and an inorganic polymer.
  • the water-soluble polymer includes polyvinyl alcohol, a vinyl alcohol / ethylene copolymer, and a copolymer structure of vinyl alcohol and other monomers such as butyral; polyethylene oxide or an alkyl-modified end thereof
  • Nonionic water-soluble polymers such as polypropylene oxide or polybutyral resin (water-soluble grade); poly (meth) acrylic acid and poly (meth) acrylate; organic amino of poly (meth) acrylic acid Derivative ester; Polyethyleneimine and its derivatives; Polyamine; Polyacrylamide; Acrylamide / sodium acrylate copolymer; Starch; Cationized starch; Phosphorylated starch; Carboxymethylcellulose; Alginic acid and Alginate.
  • the inorganic polymer include ceramics
  • the mass ratio of water to the organic solvent is preferably 100: 10 to 10: 100, more preferably 100: 30 to 30: 100, : 50 to 50: 100 is more preferable. If the mixing amount of the organic solvent is not less than the lower limit, the porosity of the nonwoven fabric 3c can be sufficiently improved, and if it is not more than the upper limit, the increase in viscosity of the fine fibrous cellulose-containing slurry 3a can be suppressed. .
  • the mixing amount of the organic solvent is 10 parts by mass or more with respect to 100 parts by mass of water, the porosity of the nonwoven fabric 3c can be sufficiently improved, and it should be 100 parts by mass or less with respect to 100 parts by mass of water. If it is, the increase in viscosity of the fine fibrous cellulose-containing slurry 3a can be suppressed.
  • the wet paper prepared to have a solid content of 5% by mass to 30% by mass after dehydrating the fine fibrous cellulose-containing slurry 3a is combined with an organic solvent or water.
  • the nonwoven fabric of the present invention can be obtained by impregnating or applying a mixed solution to an organic solvent mixed solution, treating it by suction dehydration, and drying.
  • Examples of the organic solvent include alcohols, ketones, ethers, esters, aromatic compounds, hydrocarbons, cyclic hydrocarbons, and cyclic hydrocarbon derivatives.
  • Alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, 2-ethyl-1-hexanol, benzyl alcohol, or phenol Monohydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, tri Dihydric alcohols such as ethylene glycol, 1,2-hexanediol, or 1,2-octanediol; dipropylene glyco
  • ethers include diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, or glymes such as diethylene glycol isopropyl methyl ether, 1,4-dioxane, Tetrahydrofuran, anisole, etc. are mentioned.
  • ketones As ketones, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, t-butyl methyl ketone, diisopropyl ketone, butyl isopropyl ketone, isobutyl isopropyl ketone, diisobutyl ketone, 3-methyl-2-pentanone, 4-methyl-2- Examples include pentanone, 3-methyl-2-hexanone, 5-methyl-3-heptanone, 2-decanone, 3-decanone, 4-decanone, and 5-decanone.
  • Esters include methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl acetoacetate, amyl acetate, amyl acetoacetate, hexyl acetate, hexyl acetoacetate, heptyl acetate, aceto Heptyl acetate, octyl acetate, octyl acetoacetate, methyl propionate, ethyl propionate, ethyl 2-hydroxypropionate, methyl butyrate, ethyl butyrate, methyl valerate, ethyl valerate, methyl hexanoate, ethyl hexanoate, methyl heptanoate , Ethyl heptanoate, methyl octanoate, e
  • Examples of the aromatic compound include benzene, toluene, xylene, and ethylbenzene.
  • Examples of the hydrocarbon include n-hexane, n-heptane, and n-octane.
  • Examples of the cyclic hydrocarbon include cyclopentane, cyclohexane, and terpene.
  • Examples of the cyclic hydrocarbon derivative include cyclopentanol, cyclopentanone, cyclopentyl methyl ether, cyclohexanol, cyclohexanone, cyclohexanone dimethyl acetal, terpinolene, and terpineol.
  • the above organic solvents can be used in combination of two or more. Moreover, when mixing and using it, the ratio of the organic solvent which occupies in a mixed solution becomes like this. Preferably it is 40 mass% or more, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more. The upper limit of the ratio of the organic solvent is not particularly limited. Two or more kinds of organic solvents can be used in the mixed solution. Furthermore, the organic solvent is preferably dissolved in water, but an organic solvent that does not dissolve in water can be emulsified and used as an emulsion.
  • the solid content concentration of the fine fibrous cellulose-containing slurry 3a is preferably 0.05 to 1.5% by mass, and more preferably 0.1 to 0.8% by mass. If the concentration of the fine fibrous cellulose-containing slurry 3a is 0.05% by mass or more, sufficient production efficiency can be ensured in the dehydration step, and if it is 1.5% by mass or less, increase in viscosity is prevented, and handling is easy. Can be improved.
  • the fine fibrous cellulose-containing slurry 3a is supplied so that the basis weight of the obtained nonwoven fabric 3c is preferably 10 to 900 g / m 2 , more preferably 20 to 300 g / m 2 .
  • the basis weight is 10 g / m 2 or more, the obtained non-woven fabric 3c can be easily peeled from the papermaking wire 10 and is suitable for continuous production.
  • the basis weight is 900 g / m 2 or less, the dehydration time can be further shortened, and the productivity can be further increased.
  • the coated surface A is in contact with the outer peripheral surface of the first dryer 42, with the water-containing web 3b placed on the upper surface of the paper making wire 10 being approximately half the outer periphery of the heated first dryer 42. It winds and the dispersion medium which remained in the water-containing web 3b is evaporated. The evaporated dispersion medium evaporates from the felt cloth 44 through the pores of the papermaking wire 10.
  • the water-containing web 3b is wound around about 3/4 of the outer peripheral surface of the heated second dryer 52 so that the coating surface A is in contact with the outer peripheral surface of the second dryer 52, and remains on the water-containing web 3b. Evaporate the dispersion medium. In this way, the water-containing web 3b is dried to obtain the nonwoven fabric 3c.
  • Winding process In the winding process, the papermaking wire 10 and the nonwoven fabric 3c are sandwiched between a pair of separation rollers 62a and 62b, whereby the nonwoven fabric 3c is separated from the papermaking wire 10 and transferred to the surface of one separation roller 62a. Thereafter, the nonwoven fabric 3 c is pulled away from the surface of the separation roller 62 a and is taken up by the take-up reel 64. At the same time, the used paper making wire 10 is taken up by the collection reel 66.
  • the said manufacturing apparatus 1 does not need to be used.
  • the papermaking wire 10 may be transported on an endless or endless belt.
  • the paper machine used when manufacturing a general paper can be applied easily.
  • a continuous paper machine such as a long-mesh type, a circular net type, or an inclined type, a multi-layered paper machine combining these can be applied.
  • the method for producing the nonwoven fabric is a method for producing a nonwoven fabric by dehydrating the fine fibrous cellulose-containing slurry 3a produced by the production method above and drying it to improve the yield of the nonwoven fabric relative to the fiber raw material. Can do.
  • the nonwoven fabric obtained by the said nonwoven fabric manufacturing method has a moderate space
  • complex with a matrix material is favorable.
  • the nonwoven fabric of this invention can also be used alone. For example, it can be suitably used for filter members, battery separators, and the like by taking advantage of the fine structure unique to fine fibers.
  • chemical modification treatment may be applied to cellulose.
  • the chemical modification is to add a functional group including the structure of the chemical modifier by reacting the hydroxyl group in cellulose with the chemical modifier.
  • the chemical modification treatment may be performed at any point in the production of the fine fibrous cellulose, may be performed on the fiber raw material, may be performed on the phosphorus oxo acid group-introduced cellulose, or may be performed on the alkali-treated cellulose. It may be applied to the nonwoven fabric. Further, the chemical modification treatment may be performed simultaneously with the phosphorus oxo acid group introduction step.
  • acetyl group As functional groups to be introduced into cellulose by chemical modification, acetyl group, acryloyl group, methacryloyl group, propionyl group, propioyl group, butyryl group, 2-butyryl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, Decanoyl group, undecanoyl group, dodecanoyl group, myristoyl group, palmitoyl group, stearoyl group, pivaloyl group, benzoyl group, naphthoyl group, nicotinoyl group, isonicotinoyl group, furoyl group, cinnamoyl group and other acyl groups, 2-methacryloyloxyethyl isocyanate Isocyanate group such as noyl group, methyl group, ethyl group, propyl
  • an acyl group having 2 to 12 carbon atoms such as an acetyl group, an acryloyl group, a methacryloyl group, a benzoyl group, or a naphthoyl group, or an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, or a propyl group.
  • an acyl group having 2 to 12 carbon atoms such as an acetyl group, an acryloyl group, a methacryloyl group, a benzoyl group, or a naphthoyl group, or an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, or a propyl group.
  • Groups are preferred.
  • the modification method is not particularly limited, and there is a method of reacting cellulose fibers with the following chemical modifiers. Although there are no particular limitations on the reaction conditions, a solvent, a catalyst, or the like can be used, or heating, decompression, or the like can be performed as desired.
  • the chemical modifier may be one or more substances selected from the group consisting of cyclic ethers such as acids, acid anhydrides, alcohols, halogenating reagents, isocyanates, alkoxysilanes, and oxiranes (epoxies). Can be mentioned.
  • cyclic ethers such as acids, acid anhydrides, alcohols, halogenating reagents, isocyanates, alkoxysilanes, and oxiranes (epoxies).
  • Examples of the acid include acetic acid, acrylic acid, methacrylic acid, propanoic acid, butanoic acid, 2-butanoic acid, and pentanoic acid.
  • Examples of the acid anhydride include acetic anhydride, acrylic anhydride, methacrylic anhydride, propanoic anhydride, butanoic anhydride, 2-butanoic anhydride, and pentanoic anhydride.
  • halogenating reagent examples include acetyl halide, acryloyl halide, methacryloyl halide, propanoyl halide, butanoyl halide, 2-butanoyl halide, pentanoyl halide, benzoyl halide, or naphthoyl halide.
  • the alcohol examples include methanol, ethanol, propanol, and 2-propanol.
  • isocyanate examples include methyl isocyanate, ethyl isocyanate, and propyl isocyanate.
  • alkoxysilane examples include methoxysilane and ethoxysilane.
  • cyclic ether such as oxirane (epoxy) include ethyl oxirane or ethyl oxetane.
  • acetic anhydride, acrylic anhydride, methacrylic anhydride, benzoyl halide, or naphthoyl halide is particularly preferable.
  • These chemical modifiers may be used alone or in combination of two or more.
  • the catalyst it is preferable to use a basic catalyst such as pyridine, triethylamine, sodium hydroxide, or sodium acetate, or an acidic catalyst such as acetic acid, sulfuric acid, or perchloric acid.
  • a basic catalyst such as pyridine, triethylamine, sodium hydroxide, or sodium acetate
  • an acidic catalyst such as acetic acid, sulfuric acid, or perchloric acid.
  • the reaction time depends on the chemical modifier and the chemical modification rate, it is usually from several minutes to several tens of hours.
  • the chemical modification rate of cellulose is usually 65 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less, based on the total hydroxy groups of cellulose.
  • the chemical modification rate By performing chemical modification, the decomposition temperature of cellulose increases and the heat resistance increases, but if the chemical modification rate is too high, the cellulose structure is destroyed and the crystallinity is lowered. The thermal expansion coefficient tends to increase, which is not preferable.
  • the chemical modification rate as used herein refers to the proportion of all hydroxy groups in cellulose that have been chemically modified.
  • the chemical modification rate can be determined by IR, NMR, titration method or the like.
  • the chemical modification rate of a cellulose ester with a monovalent acid can be measured by the following titration method.
  • 0.05 g of dry cellulose is precisely weighed, and 1.5 ml of ethanol and 0.5 ml of distilled water are added thereto. This is allowed to stand in a hot water bath at 60 to 70 ° C. for 30 minutes, and then 2 ml of 0.5N aqueous sodium hydroxide solution is added. This is left to stand in a hot water bath at 60 to 70 ° C. for 3 hours, and then shaken with an ultrasonic cleaner for 30 minutes. This is titrated with 0.2N hydrochloric acid standard solution using phenolphthalein as an indicator.
  • the number of moles Q of the substituent introduced by chemical modification is obtained by the following formula.
  • Q (mol) 0.5 (N) ⁇ 2 (ml) /1000 ⁇ 0.2 (N) ⁇ Z (ml) / 1000
  • the introduction amount of the carboxy group before chemical modification is A mmol / g, a mol%
  • the molecular weight of the substituent is S
  • the introduction amount of the chemical modification group is B mmol / g, b mol%, the substituent.
  • the molecular weight of T is A
  • Ammol / g is calculated by the above method
  • a mol% is calculated from Ammol / g by the following formula (I).
  • Bmmol / g is calculated from Q and A by the following formula (II).
  • B (mmol / g) (Q ⁇ 1000) / sample amount ⁇ 2A (II)
  • Bmmol / g and b mol% are in the relationship of the following formula (III).
  • b mol% is represented by the following formula (IV).
  • the composite of the present invention contains fine fibrous cellulose and a matrix material.
  • the matrix material is a material that fills voids between fine fibrous celluloses or, when fine fibrous cellulose forms a nonwoven fabric, preferably a polymer material.
  • Polymer materials suitable as the matrix material include thermoplastic resins, thermosetting resins (cured products obtained by polymerization and curing of thermosetting resin precursors by heating), or photocurable resins (precursors of photocurable resins). Is a cured product obtained by polymerization and curing upon irradiation with radiation (such as ultraviolet rays or electron beams). These may be one kind or two or more kinds.
  • thermoplastic resin Styrenic resin, acrylic resin, aromatic polycarbonate resin, aliphatic polycarbonate resin, aromatic polyester resin, aliphatic polyester resin, aliphatic polyolefin Resin, cyclic olefin resin, polyamide resin, polyphenylene ether resin, thermoplastic polyimide resin, polyacetal resin, polysulfone resin, or amorphous fluorine resin.
  • thermosetting resin is not particularly limited, but epoxy resin, acrylic resin, oxetane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin, polyurethane resin, diallyl phthalate resin, etc. Is mentioned.
  • the photocurable resin is not particularly limited, and examples thereof include the epoxy resin, acrylic resin, or oxetane resin exemplified as the above-described thermosetting resin.
  • thermoplastic resin thermosetting resin
  • photocurable resin examples include those described in JP-A-2009-299043.
  • the matrix material is preferably an amorphous synthetic polymer having a high glass transition temperature (Tg) from the viewpoint of obtaining a composite having excellent transparency and high durability.
  • Tg glass transition temperature
  • the degree of amorphousness is preferably 10% or less in crystallinity, and particularly preferably 5% or less.
  • Tg is preferably 110 ° C. or higher, particularly 120 ° C. or higher, particularly 130 ° C. or higher. If Tg is low, there is a risk of deformation when touched with hot water or the like, which causes a practical problem.
  • the Tg of the matrix material is determined by measurement by the DSC method, and the crystallinity can be calculated from the density of the amorphous part and the crystalline part.
  • the matrix material preferably has few hydrophilic functional groups such as a hydroxy group, a carboxy group, or an amino group.
  • the content of the fine fibrous cellulose in the composite of the present invention is 1% by mass to 99% by mass with respect to the total mass of the fine fibrous cellulose and the matrix material, and the content of the matrix material is the fine fibrous cellulose. And 1% by mass or more and 99% by mass or less with respect to the total mass of the matrix material.
  • the content of fine fibrous cellulose is 1% by mass or more with respect to the total mass of fine fibrous cellulose and matrix material, and the content of matrix material is fine fibrous cellulose and matrix material.
  • the content of fine fibrous cellulose is 99% by mass or less based on the total mass of the fine fibrous cellulose and the matrix material.
  • the content of the matrix material is preferably 1% by mass or more based on the total mass of the fine fibrous cellulose and the matrix material.
  • a more preferable range is that the content of fine fibrous cellulose is 2% by mass to 90% by mass with respect to the total mass of the fine fibrous cellulose and the matrix material, and the matrix material is the total mass of the fine fibrous cellulose and the matrix material.
  • the content of fine fibrous cellulose is 5% by mass to 80% by mass, and the content of the matrix material is 20% by mass to 95% by mass. % Or less.
  • the content of the fine fibrous cellulose is 70% by mass or less with respect to the total mass of the fine fibrous cellulose and the matrix material
  • the content of the matrix material is the total of the fine fibrous cellulose and the matrix material. It is preferable that the content of the fine fibrous cellulose is 60% by mass or less and the content of the matrix material is 40% by mass or more with respect to the mass by 30% by mass or more. Further, the content of the fine fibrous cellulose is 10% by mass or more and the content of the matrix material is 90% by mass or less. Furthermore, the content of the fine fibrous cellulose is 15% by mass or more and the content of the matrix material is 85% by mass.
  • the content of the fine fibrous cellulose fiber is 20% by mass or more and the content of the matrix material is 80% by mass or less.
  • the contents of the fine fibrous cellulose and the matrix material in the composite can be determined, for example, from the mass of the nonwoven fabric before the composite and the mass of the composite.
  • the composite can be immersed in a solvent in which the matrix material is soluble to remove only the matrix material, and can be determined from the mass of the remaining fibers.
  • the functional group derived from a matrix material or a cellulose fiber can also be quantified and determined by using a specific gravity of the matrix material, NMR, or IR.
  • the composite of the present invention may be a flat film (film) or a flat plate, a film having a curved surface or a plate, or other three-dimensional shape. .
  • the thickness is preferably 10 ⁇ m or more and 10 cm or less. Strength can be maintained by using a composite having such a thickness.
  • the thickness of the composite is more preferably 50 ⁇ m or more and 1 cm or less, and further preferably 80 ⁇ m or more and 250 ⁇ m or less. Further, the thickness is not necessarily uniform, and may be partially different.
  • the composite of the present invention when the composite of the present invention is in the form of a film or a plate, two or more sheets may be stacked to form a laminate. Moreover, you may laminate
  • a thick film can be formed by applying a heat press treatment to the laminate.
  • the thick film composite can be suitably used as a glazing or structural material.
  • the composite of the present invention may be laminated with an inorganic film on the surface according to the application.
  • the inorganic material constituting the inorganic film include metals such as platinum, silver, aluminum, gold, and copper, silicon, ITO, SiO 2 , SiN, SiOxNy, ZnO, and the like, or TFT. These combinations and film thicknesses can be designed arbitrarily.
  • A A method in which a nonwoven fabric is impregnated with a plastic resin precursor and polymerized.
  • B A method in which a non-woven fabric is impregnated with a thermosetting resin precursor or a photocurable resin precursor and polymerized and cured.
  • C After impregnating a nonwoven fabric with a resin solution (a solution containing one or more solutes selected from a thermoplastic resin, a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor) and drying , A method of adhering with a heating press or the like and polymerizing and curing as desired.
  • thermoplastic resin precursor a thermosetting resin precursor, or a photocurable resin precursor is applied to one side or both sides of a non-woven fabric and polymerized and cured.
  • a resin solution (a solution containing one or more solutes selected from a thermoplastic resin, a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor) to one side or both sides of a nonwoven fabric Then, after removing the solvent, a method of polymerizing and curing as desired.
  • a fine fibrous cellulose-containing slurry and a monomer solution or dispersion (a solution containing one or more solutes or dispersoids selected from a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor, or (Dispersion liquid) and then solvent removal and polymerization curing.
  • the nonwoven fabric is impregnated with a liquid thermoplastic resin precursor and polymerized.
  • the nonwoven fabric is impregnated with a polymerizable monomer or oligomer, and the monomer is polymerized by heat treatment or the like to obtain a cellulose fiber composite.
  • a method is mentioned.
  • a polymerization catalyst used for polymerization of monomers can be used as a polymerization initiator.
  • thermosetting resin precursor such as an epoxy resin monomer, or a photocurable resin such as an acrylic resin monomer.
  • thermosetting resin precursor such as an epoxy resin monomer
  • photocurable resin such as an acrylic resin monomer.
  • a resin solution a solution containing one or more solutes selected from a thermoplastic resin, a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor
  • a resin solution a solution containing one or more solutes selected from a thermoplastic resin, a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor
  • the method of causing the resin to adhere by heating press or the like and polymerizing and curing as desired include a method in which the resin is dissolved in a solvent in which the resin is dissolved, the nonwoven fabric is impregnated with the solution, and dried to obtain a cellulose fiber composite. .
  • a photo-curing resin polymerization curing by radiation or the like is further performed as desired.
  • the solvent for dissolving the resin may be selected according to the solubility of the resin
  • thermoplastic resin As a method of impregnating a nonwoven fabric with a melt of a thermoplastic resin and closely adhering with a heating press or the like, the thermoplastic resin is dissolved by heat treatment at a glass transition temperature or higher or a melting point or higher, and impregnated into the nonwoven fabric.
  • the method of obtaining a cellulose fiber composite by sticking with a heating press etc. is mentioned.
  • the heat treatment is preferably performed under pressure, and the use of equipment having a vacuum heating press function is effective.
  • thermoplastic resin sheet and the nonwoven fabric As a method of alternately arranging the thermoplastic resin sheet and the nonwoven fabric and closely adhering them with a heating press or the like, placing a thermoplastic resin film or sheet on one side or both sides of the nonwoven fabric, and heating or pressing as desired And a method of laminating a thermoplastic resin and a nonwoven fabric.
  • an adhesive or a primer may be applied to the surface of the nonwoven fabric and bonded together.
  • a method of passing between two pressurized rolls or a method of pressing in a vacuum state can be used so that bubbles are not embraced at the time of bonding.
  • thermosetting resin precursor As a method of applying and curing a liquid thermoplastic resin precursor, a thermosetting resin precursor or a photocurable resin precursor on one side or both sides of the nonwoven fabric, a thermal polymerization initiator is applied to one side or both sides of the nonwoven fabric.
  • a thermosetting resin precursor formulated with a photocuring resin precursor formulated with a photopolymerization initiator After applying a thermosetting resin precursor formulated with a photocuring resin precursor formulated with a photopolymerization initiator on one side or both sides of a nonwoven fabric, by curing by heating and curing both And a method of curing by irradiating with radiation such as ultraviolet rays.
  • the nonwoven fabric may be further laminated and then cured.
  • a resin solution (a solution containing one or more solutes selected from a thermoplastic resin, a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor) is applied to one side or both sides of the nonwoven fabric. Then, after removing the solvent, as a method of compounding by polymerizing and curing as desired, a resin solution in which a resin soluble in the solvent is dissolved is prepared, applied to one or both sides of the nonwoven fabric, and the solvent is removed by heating. The method of removing is mentioned. In the case of a photo-curing resin, polymerization curing by radiation or the like is further performed as desired. A solvent for dissolving the resin may be selected according to the solubility of the resin.
  • a fine fibrous cellulose-containing slurry and a monomer solution or dispersion a solution containing one or more solutes or dispersoids selected from a thermoplastic resin precursor, a thermosetting resin precursor, and a photocurable resin precursor, or As a method of compounding by mixing the dispersion liquid) and then passing through the steps of solvent removal and polymerization and curing, a solution in which a monomer soluble in the solvent or a dispersion liquid is prepared, and fine fibrous cellulose is prepared. Mix the slurry.
  • the cellulose fibers are preferably defibrated by using an organic solvent in advance as a dispersion medium (solvent), or when defibrated in water, the water is preferably replaced with an organic solvent.
  • a cellulose fiber composite can be obtained by polymerizing and curing the monomer in this mixed solution or polymerizing and curing the monomer after removing the solvent.
  • the solvent is removed to form a composite.
  • a dispersion is prepared and mixed with the fine fibrous cellulose slurry.
  • the cellulose fibers are preferably defibrated by using an organic solvent in advance as a dispersion medium (solvent), or when defibrated in water, the water is preferably replaced with an organic solvent.
  • a cellulose fiber composite can be obtained by removing the solvent of the mixed solution.
  • thermoplastic resin precursor thermosetting resin precursor, and photocurable resin precursor
  • a chain transfer agent an ultraviolet absorber, a filler other than cellulose, or a silane coupling agent is appropriately blended.
  • curable composition a composition (hereinafter referred to as “curable composition”).
  • the reaction can proceed uniformly.
  • a chain transfer agent for example, a polyfunctional mercaptan compound having two or more thiol groups in the molecule can be used.
  • a polyfunctional mercaptan compound By using a polyfunctional mercaptan compound, moderate toughness can be imparted to the cured product.
  • mercaptan compounds include pentaerythritol tetrakis ( ⁇ -thiopropionate), trimethylolpropane tris ( ⁇ -thiopropionate), or tris [2- ( ⁇ -thiopropionyloxyethoxy) ethyl] triisocyanurate. It is preferable to use 1 type (s) or 2 or more types.
  • the chain transfer agent is usually contained in a proportion of 30% by mass or less with respect to the total of radically polymerizable compounds in the curable composition.
  • the curable composition contains an ultraviolet absorber
  • coloring can be prevented.
  • an ultraviolet absorber it selects from a benzophenone series ultraviolet absorber and a benzotriazole type ultraviolet absorber, for example,
  • the ultraviolet absorber may use 1 type and may use 2 or more types together.
  • the ultraviolet absorber is usually contained at a ratio of 0.01 to 1 part by mass with respect to a total of 100 parts by mass of radically polymerizable compounds in the curable composition. .
  • the filler examples include inorganic particles and organic polymers.
  • inorganic particles such as silica particles, titania particles, or alumina particles, transparent cycloolefin polymer particles such as Zeonex (Nippon Zeon) and Arton (JSR), or general-purpose such as polycarbonate and polymethyl methacrylate
  • thermoplastic polymer particles include thermoplastic polymer particles.
  • use of nano-sized silica particles is preferable because transparency can be maintained.
  • the polymer particles having a structure similar to that of the ultraviolet curable monomer are used as the filler, the polymer can be dissolved to a high concentration, which is preferable.
  • silane coupling agent examples include ⁇ -((meth) acryloxypropyl) trimethoxysilane, ⁇ -((meth) acryloxypropyl) methyldimethoxysilane, and ⁇ -((meth) acryloxypropyl) methyldiethoxy.
  • examples include silane, ⁇ -((meth) acryloxypropyl) triethoxysilane, and ⁇ - (acryloxypropyl) trimethoxysilane. These have a (meth) acryl group in the molecule and are preferable because they can be copolymerized with other monomers.
  • the silane coupling agent is usually 0.1 to 50% by mass, preferably 1 to 20%, based on the total of radically polymerizable compounds in the curable composition. It is made to contain so that it may become mass%. If the blending amount is too small, the effect of containing it is not sufficiently obtained, and if it is too large, optical properties such as transparency of the cured product may be impaired.
  • the curable composition can be polymerized and cured by a known curing method to obtain a cured product.
  • the curing method include thermal curing and radiation curing, and radiation curing is preferable.
  • the radiation include infrared rays, visible rays, ultraviolet rays, electron beams, and the like, but light that is an electromagnetic wave having a wavelength of 1 to 1000 nm is preferable. More preferred is an electromagnetic wave having a wavelength of about 200 nm to 450 nm, and still more preferred is an ultraviolet ray having a wavelength of 300 to 400 nm.
  • thermo polymerization a method in which a thermal polymerization initiator that generates radicals and acids by heating is added to the curable composition in advance and polymerized by heating
  • a photopolymerization initiator that generates radicals and acids by radiation such as ultraviolet rays is added to the curable composition in advance and polymerized by irradiation with radiation (preferably light) (hereinafter referred to as “light”).
  • light preferably light
  • polymerization a method in which both a thermal polymerization initiator and a photopolymerization initiator are added in advance and polymerized by a combination of heat and light.
  • UV of 300 to 450 nm is preferably in the range of 0.1 to 200 J / cm 2 , more preferably in the range of 1 to 20 J / cm 2 . Irradiate with. Further, it is more preferable to irradiate the radiation in two or more times.
  • the lamp used for radiation irradiation include a metal halide lamp, a high pressure mercury lamp lamp, an ultraviolet LED lamp, and an electrodeless mercury lamp.
  • Photopolymerization and thermal polymerization may be performed at the same time in order to quickly complete the polymerization and curing.
  • the curable composition is heated at a temperature in the range of 30 to 300 ° C. at the same time as the irradiation with radiation to be cured.
  • a thermal polymerization initiator may be added to the curable composition in order to complete the polymerization, but when added in a large amount, the birefringence of the cured product is increased and the hue is deteriorated. Therefore, the addition amount of the thermal polymerization initiator is preferably 0.1 to 2% by mass, and more preferably 0.3 to 1% by mass with respect to the total of the curable monomer components.
  • thermal polymerization initiator used for thermal polymerization examples include hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxycarbonate, peroxyketal, and ketone peroxide.
  • hydroperoxide dialkyl peroxide, peroxyester, diacyl peroxide, peroxycarbonate, peroxyketal, and ketone peroxide.
  • the thermal polymerization initiator may be used alone or in combination of two or more.
  • the thermal polymerization initiator preferably has a 1 minute half-life temperature of 120 ° C. or higher and 300 ° C. or lower.
  • photopolymerization initiator used for photopolymerization a photoradical generator or a photocationic polymerization initiator is usually used.
  • a photoinitiator may be used independently or may use 2 or more types together.
  • photoradical generator known compounds that can be used for this purpose can be used.
  • examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide. .
  • benzophenone or 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferable.
  • the photocationic polymerization initiator is a compound that initiates cationic polymerization by irradiation with radiation such as ultraviolet rays or electron beams, and includes the following.
  • aromatic sulfonium salts include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfone).
  • Nio) phenyl] sulfide bishexafluoroborate bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoro, diphenyl-4- (phenylthio) ) Phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenyl Rufonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium te
  • Aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecyl) Phenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexaflu
  • aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and the like.
  • Aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2- Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2- Examples thereof include cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
  • (2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron.
  • UVI6990 UVI6979 manufactured by Union Carbide
  • SP-150 SP-170
  • SP-172 manufactured by ADEKA
  • Irgacure 261 manufactured by Ciba Geigy
  • Irgacure 250 Rhodia SILPI PI2074, JMF-2456 manufactured by Rhodia
  • Sun Aid SI-60L SI-80L
  • SI-100L SI-110L
  • SI-180L SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.
  • a curing agent for curing the cationic polymerizable monomer may be added.
  • the curing agent include amine compounds, compounds such as polyaminoamide compounds synthesized from amine compounds, tertiary amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenolic compounds, thermal latent cationic polymerization catalysts. Or dicyanamide and derivatives thereof. These hardening
  • curing agents may be used independently and 2 or more types may be used together.
  • Adeka Opton® CP-66 or CP-77 manufactured by ADEKA Corporation
  • Sun Aid® SI-15 SI-20, SI-25, SI-40, SI -45, SI-47, SI-60, SI-80, SI-100, SI-100L, SI-110L, SI-145, SI-150, SI-160, or SI-180L (Sanshin Chemical Industry Co., Ltd. )).
  • a photosensitizer can be added.
  • Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin.
  • Examples of commercially available photosensitizers include Adekapitomer SP-100 (manufactured by ADEKA Corporation).
  • the component amount of the photopolymerization initiator is preferably 0.001 part by mass or more and 0.01 part by mass or more when the total amount of polymerizable compounds in the curable composition is 100 parts by mass. Is more preferably 0.05 parts by mass or more.
  • the amount of the photopolymerization initiator component is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and further preferably 0.1 parts by mass or less. That is, the range of the component amount of the photopolymerization initiator is preferably 0.001 to 5 parts by mass, and 0.01 to 2 parts when the total amount of polymerizable compounds in the curable composition is 100 parts by mass. Part by mass is more preferable, and 0.05 to 0.1 part by mass is even more preferable.
  • the photopolymerization initiator when it is a photocationic polymerization initiator, it is 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably, with respect to 100 parts by mass of the total amount of the cationic polymerizable monomer. 0.5 parts by mass or more, usually 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less. That is, when the photopolymerization initiator is a photocationic polymerization initiator, the component amount of the photopolymerization initiator ranges from 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the cationic polymerizable monomer.
  • the polymerization proceeds rapidly, not only increasing the birefringence of the resulting cured product but also deteriorating the hue.
  • the concentration of the photopolymerization initiator is 5 parts by mass, absorption of the photopolymerization initiator causes light to not reach the side opposite to the irradiation of ultraviolet rays, resulting in an uncured part. Further, it is colored yellow and the hue is markedly deteriorated.
  • the amount is too small, the polymerization may not proceed sufficiently even if ultraviolet irradiation is performed.
  • the nonwoven fabric of the present invention and the matrix material are composited, it is preferable to perform the above-described chemical modification treatment on the nonwoven fabric before the composite of the matrix material.
  • the nonwoven fabric may be substituted with an organic solvent such as alcohol and dried, and then the chemical modification may be performed, or the chemical modification may be performed without drying. Since the reaction rate of chemical modification becomes faster after drying, it is preferable. Drying may be air drying, vacuum drying, or pressure drying. It can also be heated.
  • the nonwoven fabric When the nonwoven fabric is chemically modified, it is preferable to thoroughly wash after the chemical modification in order to terminate the reaction. If the unreacted chemical modifier remains, it is not preferable because it causes coloring later or becomes a problem when it is combined with the resin. In addition, after washing sufficiently, it is preferable to further replace with an organic solvent such as alcohol. In this case, the nonwoven fabric can be easily replaced by immersing it in an organic solvent such as alcohol.
  • the nonwoven fabric when chemically modifying a nonwoven fabric, is normally dried after chemical modification. This drying may be air drying, vacuum drying, pressure drying, or heat drying.
  • This drying may be air drying, vacuum drying, pressure drying, or heat drying.
  • the temperature is preferably 50 ° C or higher, more preferably 80 ° C or higher, 250 ° C or lower is more preferable, and 150 ° C or lower is more preferable. That is, the temperature range when heating during drying is preferably 50 to 250 ° C, more preferably 80 to 150 ° C. If the heating temperature is too low, drying may take time or drying may be insufficient. If the heating temperature is too high, the nonwoven fabric may be colored or decomposed.
  • the pressure is preferably 0.01 MPa or more, more preferably 0.1 MPa or more, and preferably 5 MPa or less, more preferably 1 MPa or less. That is, the pressure (gauge pressure) in the case of pressurization is preferably 0.01 to 5 MPa, more preferably 0.1 to 1 MPa. If the pressure is too low, drying may be insufficient, and if the pressure is too high, the nonwoven fabric may be crushed or decomposed.
  • the composite of the present invention is a fiber composite having a thickness of 100 ⁇ m, heated at 190 ° C. with an oxygen partial pressure of 0.006 MPa or less for 1 hour, and then the yellowness (YI value) measured according to JIS standard K7105 is 30 or less. It is preferable that The yellowness is more preferably 25 or less.
  • the yellowness of the composite can be measured, for example, using a color computer manufactured by Suga Test Instruments.
  • the yellowness of the composite can be reduced by chemically modifying the cellulose fibers or using a highly transparent matrix material.
  • the composite of the present invention fibers having a fiber diameter thinner than the wavelength of visible light are used. Therefore, if a highly transparent material is used for the matrix material, a composite having high transparency, that is, having a low haze is obtained. Can do.
  • the haze value of the composite is preferably from 0 to 5, more preferably from 0 to 3, more preferably from 0 to 2, and particularly preferably from 0 to 1, as measured according to JIS standard K7136 for a composite having a thickness of 100 ⁇ m.
  • the haze of the composite can be measured, for example, with a haze meter manufactured by Suga Test Instruments, and the value of C light is used.
  • the composite of the present invention has a low water absorption, but in a 100 ⁇ m thickness, the water absorption measured in accordance with JIS standard K7209 (D method) is preferably 1% or less, 0.8 % Or less is more preferable, 0.5% or less is further preferable, and 0.3% or less is particularly preferable.
  • the water absorption rate exceeds 1%, the composite dehydrated in the processing process is undesirably stretched by absorbing moisture in the air and causing dimensional deformation when left in the air.
  • the composite of the present invention has a thickness of 100 ⁇ m, and the total light transmittance measured in accordance with JIS standard K7105 in the thickness direction is preferably 60% or more, more preferably 70% or more, more preferably 80%. More preferably, it is 82% or more, more preferably 84% or more, still more preferably 86% or more, particularly preferably 88% or more, and particularly preferably 90% or more. If this total light transmittance is less than 60%, it becomes translucent or opaque, and it may be difficult to use it in applications requiring transparency.
  • the total light transmittance can be measured, for example, using a Suga Test Instruments haze meter, and the value of C light is used.
  • the parallel light transmittance measured in accordance with JIS standard K7105 in the thickness direction is 57% or more, further 70% or more, particularly 80% or more, especially 89%. The above is preferable. If the parallel light transmittance is less than 57%, the amount of scattered light is increased and haze is increased. For example, in an organic EL device application, the pixel becomes unclear and the color is blurred or blurred.
  • the parallel light transmittance can be measured, for example, using a Suga Test Instruments haze meter, and the value of C light is used.
  • the composite of the present invention can easily have a low coefficient of linear thermal expansion, but preferably has a coefficient of linear thermal expansion of 1 to 50 ppm / K.
  • the linear thermal expansion coefficient of the composite of the present invention is more preferably 30 ppm / K or less, and particularly preferably 20 ppm / K or less. Further, the linear thermal expansion coefficient is preferably 1 ppm / K or more, and more preferably 5 ppm / K or more. That is, the range of the composite linear thermal expansion coefficient is preferably 1 to 50 ppm / K, more preferably 5 to 30 ppm / K, and still more preferably 5 to 20 ppm / K.
  • linear thermal expansion coefficient of an inorganic thin film transistor is about 15 ppm / K
  • the linear thermal expansion coefficient of the composite exceeds 50 ppm / K
  • two layers are combined in an inorganic film.
  • the difference in coefficient of linear thermal expansion between layers becomes large, and cracks and the like are generated.
  • the linear thermal expansion coefficient is measured by the method described in the section of Examples described later.
  • the matrix material is filled in the gaps between the fine fibrous celluloses, but when the nonwoven fabric is used, the matrix material is filled in the gaps in the nonwoven fabric. Therefore, the volume ratio of the matrix material filling portion is substantially equal to the porosity of the nonwoven fabric.
  • the tensile strength of the composite of the present invention is preferably 40 MPa or more, more preferably 100 MPa or more. If the tensile strength is lower than 40 MPa, sufficient strength cannot be obtained, which may affect the use of a structural material or the like to which a force is applied.
  • the composite of the present invention has a tensile modulus of preferably 0.2 to 100 GPa, more preferably 1 to 100 GPa.
  • a tensile modulus of preferably 0.2 to 100 GPa, more preferably 1 to 100 GPa.
  • the tensile elastic modulus is lower than 0.2 GPa, sufficient strength cannot be obtained, which may affect the use in applications where force is applied such as structural materials.
  • there is a suitable range for the tensile elastic modulus of the substrate If the tensile elastic modulus of the substrate is low, the substrate is bent by its own weight, and it becomes difficult to form a smooth surface. For this reason, transistors and other elements cannot be formed with high accuracy.
  • the tensile elastic modulus is too high, it becomes hard and brittle, causing problems such as cracking of the substrate itself.
  • the composite of the present invention has a low linear thermal expansion coefficient, high elasticity, and high strength.
  • the composite of the present invention can be used as a structural material.
  • it is suitably used as automobile materials such as glazing, interior materials, outer plates, or bumpers, personal computer casings, home appliance parts, packaging materials, building materials, civil engineering materials, marine products, or other industrial materials.
  • those having high transparency, high strength, low water absorption and small haze are excellent in optical properties, so that they are liquid crystal displays, plasma displays, organic EL displays, field emission displays, or rear projections. It is suitable for a display such as a television, a substrate, and a panel.
  • substrates for solar cells such as silicon-based solar cells or dye-sensitized solar cells.
  • substrates for solar cells such as silicon-based solar cells or dye-sensitized solar cells.
  • it may be laminated with a barrier film, ITO, TFT or the like.
  • window materials for automobiles window materials for railway vehicles, window materials for houses, window materials for offices, factories and the like.
  • a fluorine film, a film such as a hard coat film, or a shock-resistant or light-resistant material may be laminated as desired.
  • the method for producing fine fibrous cellulose includes: (A) phosphoric acid; lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate that are lithium salts of phosphoric acid; and diphosphoric acid phosphate that is a sodium salt of phosphoric acid Sodium hydrogen, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate; and potassium phosphate dibasic potassium phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, pyrophosphate Treating kraft pulp or sulfite pulp with at least one compound selected from the group consisting of potassium and potassium polyphosphate; (B) It is preferable to have a step of defibrating the cellulose treated in the step (a).
  • the method for producing fine fibrous cellulose according to another aspect of the present invention is as follows.
  • the method for producing fine fibrous cellulose according to another aspect of the present invention is as follows.
  • Example 1 10.14 g of sodium dihydrogen phosphate dihydrate and 1.79 g of disodium hydrogen phosphate are dissolved in 19.27 g of water, and an aqueous solution of a phosphate compound (hereinafter referred to as “phosphorylation reagent A”). Got. The pH of this phosphorylating reagent A was 4.73 at 25 ° C. Softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., water 50%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121) is added with water to a concentration of 4%, and an irregularity is made with a double disc refiner.
  • CSF Canadian standard freeness
  • Beating CSF (plain mesh 80 mesh, according to JIS P8121 except that the amount of pulp collected was 0.3 g) was beaten to 250 ml and the length average fiber length was 0.68 mm to obtain a pulp slurry.
  • 3 g of the obtained pulp slurry was collected at an absolutely dry mass, diluted to 0.3% with ion-exchanged water, and then dehydrated by a papermaking method to obtain a pulp sheet.
  • the obtained pulp sheet had a moisture content of 90% and a thickness of 200 ⁇ m.
  • This pulp sheet was immersed in 31.2 g of the phosphorylating reagent A (80.2 parts by mass as phosphorus element amount with respect to 100 parts by mass of dried pulp), and 2 hours by a 170 ° C.
  • blower dryer (Yamato Scientific Co., Ltd. DKM400) Half-heat treatment was performed to introduce a phosphorus oxoacid group into cellulose. Subsequently, 500 ml of ion-exchanged water was added to the cellulose into which the phosphorus oxo acid group had been introduced, and after stirring and washing, filtration and dehydration were performed to obtain a dehydrated sheet. The obtained dehydrated sheet was diluted with 300 ml of ion-exchanged water, and 5 ml of 1N sodium hydroxide aqueous solution was added little by little with stirring to obtain a pulp slurry having a pH of 12 to 13.
  • this pulp slurry was dehydrated and washed by adding 500 ml of ion exchange water. This dehydration washing was further repeated twice to obtain a dehydrated sheet of cellulose containing phosphooxo acid. Ion exchange water was added to the dehydrated sheet of phosphooxoacid-introduced cellulose obtained after washing and dehydration, and the mixture was stirred to make a slurry of 0.5% by mass. This slurry was defibrated for 30 minutes using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.) at 21500 rpm, to obtain a defibrated pulp slurry.
  • a defibrating apparatus Cleamix-2.2S, manufactured by MTechnic Co., Ltd.
  • the defibrated pulp slurry is centrifuged according to the method described below (centrifugation in the supernatant yield after centrifugation), and the supernatant is purified according to the method described below (observation with a transmission electron microscope). And observed. Thereby, it was confirmed that it became the fine fibrous cellulose about 4 nm wide (FIG. 1). Further, by X-ray diffraction, the cellulose maintained the cellulose type I crystal, and the absorption based on the phosphate group was observed at 1230 to 1290 cm ⁇ 1 by measurement of the infrared absorption spectrum by FT-IR. The addition was confirmed. Therefore, the obtained phosphoric acid oxoacid-introduced cellulose was one in which a part of the hydroxy group of the cellulose was substituted with the functional group of the following structural formula (2).
  • Example 2 In Example 1, a defibrated pulp slurry was obtained in the same manner as in Example 1 except that the pH of the phosphorylating reagent A at 25 ° C. was adjusted to pH 6.0 with a 1N sodium hydroxide aqueous solution. The defibrated pulp slurry was centrifuged as in Example 1, and the supernatant was observed and measured with a transmission electron microscope. It was confirmed to be a fine fibrous cellulose having a width of about 4 nm (not shown).
  • the cellulose maintained the cellulose type I crystal, and the absorption based on the phosphate group was observed at 1230 to 1290 cm ⁇ 1 by measurement of the infrared absorption spectrum by FT-IR. The addition was confirmed.
  • Example 3 the pulp sheet was defibrated in the same manner as in Example 2 except that the pulp sheet was heat-treated at 105 ° C. for 1 hour and then at 150 ° C. for 1 hour with a blow dryer (Yamato Scientific Co., Ltd. DKM400). Got. The defibrated pulp slurry was centrifuged as in Example 1, and the supernatant was observed and measured with a transmission electron microscope. It was confirmed to be a fine fibrous cellulose having a width of about 4 nm (FIG. 2).
  • the cellulose maintained the cellulose type I crystal, and the absorption based on the phosphate group was observed at 1230 to 1290 cm ⁇ 1 by measurement of the infrared absorption spectrum by FT-IR. The addition was confirmed.
  • Example 4 In Example 3, 0.51 g of sodium dihydrogen phosphate dihydrate and 0.09 g of disodium hydrogen phosphate were dissolved in 30.6 g of water, and an aqueous solution of a phosphate compound (hereinafter referred to as “phosphorylation reagent”). B "). A defibrated pulp slurry was obtained in the same manner as in Example 3 except that this phosphorylating reagent B was used to introduce a phosphorus oxoacid group into cellulose. The defibrated pulp slurry was centrifuged as in Example 1, and the supernatant was observed and measured with a transmission electron microscope.
  • phosphorylation reagent a phosphate compound
  • Example 5 A defibrated pulp slurry was obtained in the same manner as in Example 3 except that the alkali treatment step was omitted.
  • Example 6 6.75 g of sodium dihydrogen phosphate dihydrate and 4.83 g of disodium hydrogen phosphate are dissolved in 19.62 g of water, and an aqueous solution of a phosphoric acid compound (hereinafter referred to as “phosphorylation reagent C”). Got. The pH of this phosphorylating reagent C was 6.0 at 25 ° C. Conifer unbleached kraft pulp (manufactured by Oji Paper Co., Ltd., water 50%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121) is added with water to a concentration of 4%, and double disc refiner is used.
  • CSF Canadian standard freeness
  • Beating irregular CSF (plain mesh 80 mesh, according to JIS P8121 except that the amount of pulp collected was 0.3 g) was beaten to 200 ml and length average fiber length was 0.66 mm to obtain pulp slurry.
  • 3 g of the obtained pulp slurry was collected at an absolutely dry mass, diluted to 0.3% with ion-exchanged water, and then dehydrated by a papermaking method to obtain a pulp sheet.
  • the obtained pulp sheet had a moisture content of 90% and a thickness of 200 ⁇ m.
  • This pulp sheet was immersed in 31.2 g of the phosphorylating reagent C (80.2 parts by mass as the amount of phosphorus element with respect to 100 parts by mass of dry pulp), and 1 hour in a fan dryer at 105 ° C.
  • this pulp slurry was dehydrated and washed by adding 500 ml of ion exchange water. This dehydration washing was further repeated twice to obtain a dehydrated sheet of cellulose containing phosphooxo acid. Ion exchange water was added to the dehydrated sheet of phosphooxoacid-introduced cellulose obtained after washing and dehydration, and the mixture was stirred to make a slurry of 0.5% by mass. This slurry was defibrated for 30 minutes using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.) at 21500 rpm, to obtain a defibrated pulp slurry.
  • a defibrating apparatus Cleamix-2.2S, manufactured by MTechnic Co., Ltd.
  • the defibrated pulp slurry is centrifuged according to the method described below (centrifugation in the supernatant yield after centrifugation), and the supernatant is purified according to the method described below (observation with a transmission electron microscope). And observed. Thereby, it was confirmed that it was a fine fibrous cellulose having a width of about 4 nm (not shown). Further, by X-ray diffraction, the cellulose maintained the cellulose type I crystal, and the absorption based on the phosphate group was observed at 1230 to 1290 cm ⁇ 1 by measurement of the infrared absorption spectrum by FT-IR. The addition was confirmed.
  • Example 7 Softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., water 50%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121) is added with water to a concentration of 4%, and an irregularity is made with a double disc refiner.
  • a pulp slurry was obtained by beating CSF (plain mesh 80 mesh, according to JIS P8121 except that the amount of collected pulp was 0.3 g) until the average fiber length was 0.66 mm. The obtained pulp slurry was concentrated to 13% solid content with a centrifugal dehydrator.
  • Ion exchange water was added to the dehydrated sheet of phosphooxoacid-introduced cellulose obtained after washing and dehydration, and the mixture was stirred to make a slurry of 0.5% by mass.
  • This slurry was defibrated for 30 minutes using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.) at 21500 rpm, to obtain a defibrated pulp slurry.
  • the defibrated pulp slurry is centrifuged according to the method described below (centrifugation in the supernatant yield after centrifugation), and the supernatant is purified according to the method described below (observation with a transmission electron microscope). And observed.
  • Example 8 1.69 g of sodium dihydrogen phosphate dihydrate and 1.21 g of disodium hydrogen phosphate are dissolved in 3.39 g of water, and an aqueous solution of a phosphoric acid compound (hereinafter referred to as “phosphorylation reagent D”). Got.
  • the pH of this phosphorylating reagent D was 6.0 at 25 ° C.
  • Softwood bleached kraft pulp manufactured by Oji Paper Co., Ltd., moisture 50%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121
  • CSF Canadian standard freeness
  • This pulp slurry was defibrated for 30 minutes at 21500 rpm using a defibrating apparatus (Cleamix-2.2S, manufactured by MTechnic Co., Ltd.) to obtain a defibrated pulp slurry.
  • the defibrated pulp slurry is centrifuged according to the method described below (centrifugation in the supernatant yield after centrifugation), and the supernatant is purified according to the method described below (observation with a transmission electron microscope). And observed. Thereby, it was confirmed that it was a fine fibrous cellulose having a width of about 4 nm (not shown).
  • the cellulose maintained the cellulose type I crystal, and the absorption based on the phosphate group was observed at 1230 to 1290 cm ⁇ 1 by measurement of the infrared absorption spectrum by FT-IR. The addition was confirmed.
  • Example 1 a defibrated pulp slurry was obtained in the same manner as in Example 1 except that heating was performed without adding the phosphorylating reagent A, alkali treatment was performed, and then defibration treatment was performed.
  • Example 2 a defibrated pulp slurry was obtained in the same manner as in Example 2 except that heating was performed without adding the phosphorylating reagent A and alkali treatment was omitted.
  • Example 6 (Comparative Example 3) In Example 6, a defibrated pulp slurry was obtained in the same manner as in Example 6 except that heating was performed without adding the phosphorylating reagent C, alkali treatment followed by defibrating treatment.
  • Example 9 The fine fibrous cellulose-containing slurry obtained in Example 3 was diluted with water so that the cellulose concentration became 0.127% by mass, adjusted to 150 ml, and 30 ml of isopropyl alcohol (IPA) was gently added from above the liquid. In addition, vacuum filtration was performed. As a filter, KG-90 made by Advantech was used, and a PTFE membrane filter made by Advantech having a pore size of 1.0 ⁇ m was placed on the glass filter. The effective filtration area was 48 cm 2 .
  • IPA isopropyl alcohol
  • Example 10 A nonwoven fabric was obtained in the same manner as in Example 9 except that the supernatant after centrifugation of the fine fibrous cellulose-containing slurry obtained in Example 3 was used.
  • Porosity of nonwoven fabric It calculated
  • Porosity (vol%) ⁇ 1-B / (M ⁇ A ⁇ t) ⁇ ⁇ 100
  • A is the area (cm 2 ) of the nonwoven fabric
  • t (cm) is the thickness
  • B is the mass (g) of the nonwoven fabric
  • M is the density of cellulose
  • M 1.5 g / cm 3 is assumed in the present invention. did.
  • the film thickness of the nonwoven fabric was measured at 10 points at various positions of the nonwoven fabric using a film thickness meter (IP65 manufactured by Mitutoyo Co., Ltd.), and the average value was adopted.
  • Example 11 ⁇ Composite with resin matrix material> 100 parts by mass of 1,10-decanediol diacrylate, 0.02 parts by mass of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO” manufactured by BASF), and the nonwoven fabric obtained in Example 9
  • the mixed solution of 0.01 parts by mass of benzophenone was impregnated and left under reduced pressure overnight.
  • the obtained cellulose fiber aggregate impregnated with the resin solution was sandwiched between two glass plates, and was cured with an ultraviolet ray using an electrodeless mercury lamp lamp (“D bulb” manufactured by Fusion UV Systems).
  • irradiation intensity 400 mW / cm 2 at a wavelength 365 nm is semi-cured through the front and back twice in total to the line speed 7m / min, then the irradiation intensity at a wavelength of 365nm 1900mW / cm 2, line speed 2m /
  • the test was carried out under the condition of complete curing by passing through the front and back twice each time (total 4 times). After the ultraviolet irradiation, the glass plate was removed and heated in a vacuum oven at 190 ° C. for 1 hour to obtain a cellulose fiber composite having a thickness of 51 ⁇ m.
  • the ultraviolet irradiance was measured with an ultraviolet illuminance meter “UV-M02” manufactured by Oak Seisakusho using an attachment “UV-35”, and the illuminance of ultraviolet rays of 320 to 390 nm was measured at 23 ° C.
  • Example 12 A cellulose fiber composite having a thickness of 84 ⁇ m was obtained in the same manner as in Example 11 except that the nonwoven fabric obtained in Example 10 was used.
  • Example 4 ⁇ Hardened material composed only of resin>
  • a non-woven fabric was not used, and only the photocurable resin was cured under the same conditions to produce a cured product of a resin having a thickness of 83 ⁇ m.
  • [Tensile modulus of composite] The obtained composite was cut into a length of 10 mm ⁇ 40 mm with a laser cutter. Using a DMS6100 manufactured by SII, the chuck was 20 mm in chuck mode, the frequency was 10 Hz, and 2 ° C./min. The tensile elastic modulus was determined from the storage elastic modulus E ′ (unit: GPa) at 23 ° C. from ⁇ 100 ° C. to 250 ° C.
  • Total light transmittance of composite or cured resin Based on JIS standard K7105, the total light transmittance by C light was measured using the haze meter by Suga Test Instruments.
  • the composites of Examples 11 to 12 had high transparency, high strength, and low linear thermal expansion coefficient.
  • the fiber raw material can be sufficiently refined, and the yield of fine fibrous cellulose is high, so that the production efficiency of fine fibrous cellulose from the fiber raw material is high.
  • the manufacturing method of the fine fibrous cellulose of this invention is low cost, and its environmental impact is small.
  • the manufacturing efficiency of the nonwoven fabric with respect to a fiber raw material can be improved.
  • the fine fibrous cellulose of the present invention has a small fiber width and a large axial ratio (fiber length / fiber width), the slurry stability of the fine fibrous cellulose is high, and the resulting nonwoven fabric has high strength.
  • the composite of the fine fibrous cellulose and the matrix resin of the present invention has high strength and a low coefficient of linear thermal expansion, it has industrial applicability.

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Abstract

La présente invention concerne un procédé de production d'une cellulose microfibreuse, comprenant les étapes de : (a) traitement d'un matériau de fibre brut contenant une cellulose par au moins un composé sélectionné dans le groupe constitué par un oxoacide de phosphore et un sel d'un oxoacide de phosphore ; et (b) le défibrage de la cellulose qui a été traitée dans l'étape (a). Ledit au moins un composé sélectionné dans le groupe constitué d'un oxoacide de phosphore et d'un sel d'oxoacide de phosphore est de préférence un composé présentant un groupe acide phosphorique. Selon la présente invention, un procédé de production d'une cellulose microfibreuse, qui permet la production de la cellulose microfibreuse à partir de matériau de pulpe brut contenant une cellulose de manière hautement efficace, est obtenu à faible coût et est écologique.
PCT/JP2012/079743 2011-11-18 2012-11-16 Procédé de production de cellulose microfibreuse, procédé de production d'un tissu non tissé, cellulose microfibreuse, suspension contenant de la cellulose microfibreuse, tissu non tissé et complexe Ceased WO2013073652A1 (fr)

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