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WO2012011577A1 - Composition de résine transparente armée de fibres, procédé de production correspondant, et feuille transparente - Google Patents

Composition de résine transparente armée de fibres, procédé de production correspondant, et feuille transparente Download PDF

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Publication number
WO2012011577A1
WO2012011577A1 PCT/JP2011/066736 JP2011066736W WO2012011577A1 WO 2012011577 A1 WO2012011577 A1 WO 2012011577A1 JP 2011066736 W JP2011066736 W JP 2011066736W WO 2012011577 A1 WO2012011577 A1 WO 2012011577A1
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Prior art keywords
fiber
transparent resin
meth
cellulose
resin composition
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English (en)
Japanese (ja)
Inventor
大村　雅也
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Daicel Corp
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Daicel Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/245—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using natural fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a fiber-reinforced transparent resin composition containing cellulose nanofibers, a method for producing the same, and a transparent sheet formed from the composition.
  • glass substrates with high transparency and dimensional stability have been used for the screens of display devices such as liquid crystal display devices (LCDs) and touch panels.
  • LCDs liquid crystal display devices
  • touch panels touch panels
  • transparent plastics is being considered in place of glass substrates that have low flexibility and are difficult to thin.
  • plastic since plastic has lower heat resistance and dimensional stability than glass, it contains nanometer-sized cellulose fibers as a reinforcing material to maintain heat resistance and dimensional stability while ensuring transparency.
  • a fiber reinforced resin composition has been proposed.
  • JP-A-2005-60680 contains fibers having an average fiber diameter of 4 to 200 nm and a matrix material, and has a light transmittance of 60% or more at a wavelength of 400 to 700 nm in terms of a thickness of 50 ⁇ m.
  • Fiber reinforced composite materials have been proposed. This document describes that as a fiber having an average fiber diameter of 4 to 200 nm, bacterial cellulose, particularly a bacterial cellulose structure having a three-dimensional cross structure that has not been disaggregated is preferable. Further, this document describes that the fiber content in the fiber-reinforced composite material is preferably 10% by weight or more, particularly 30% by weight or more, particularly 50% by weight or more, and the content in the examples is 70% by weight. is there. Furthermore, this document describes that the matrix material is preferably an amorphous synthetic polymer having a high glass transition temperature, and in the examples, phenol resin and acrylic resin are used.
  • Patent Document 2 discloses a fiber reinforced composite material including a fiber assembly and a matrix material impregnated in the fiber assembly, the scanning electron of the fiber assembly.
  • the line segment length of the bright region corresponding to the pore region of the fiber assembly obtained by statistical analysis of the one-way run length image prepared from the binary image obtained by binarizing the microscope image is L
  • a fiber reinforced composite material has been proposed in which the total length of the line segments of L ⁇ 4.5 ⁇ m is 30% or less of the total analysis length.
  • This document describes that as the fiber assembly, bacterial cellulose having an average fiber diameter of 4 to 200 nm is preferable.
  • these composite materials include a fiber assembly having a long fiber length and three-dimensional entanglement. Low transparency. Furthermore, the compatibility between the fiber and the matrix material is not sufficient, and the bacterial cellulose has a flat cross-sectional shape and a high degree of fiber branching. Sag and warp are likely to occur. In addition, bacterial cellulose requires a long time for culturing and has low productivity. In addition, Patent Document 2 describes that short fibers aggregate in a pill-like shape or a film shape when subjected to a dissociation treatment or a defibration treatment in order to make a fiber assembly composed of bacterial cellulose even thinner. .
  • Patent Document 3 JP-A-2006-241450 discloses a method for producing a fiber-reinforced composite material comprising a cellulose fiber aggregate and a matrix material, wherein water contained in the cellulose fiber aggregate is used as a hydrophilic organic solvent. A manufacturing method including a replacing step has been proposed. This document also describes cellulose obtained by treating cellulose with a high-pressure homogenizer in addition to bacterial cellulose as a cellulose fiber aggregate, and then repeatedly grinding with a grinder or the like. An ultraviolet curable acrylic resin composition containing 34% by weight of cellulose having a fiber diameter of 60 nm is described.
  • Patent Document 4 discloses a nanofiber non-woven fabric mainly composed of crystalline cellulose, and the lignin content in the nanofiber sheet is 10 ppm or more and 10 wt% or less.
  • a fiber resin composite material obtained by impregnating a sheet with tricyclodecane dimethacrylate, UV curing at 20 J / cm 2 , and heat-treating in vacuum at 160 ° C. for 2 hours, and containing a cured product of tricyclodecane dimethacrylate
  • a fiber-resin composite material having an amount of 60% by weight and a nanofiber content of 40% by weight has been proposed.
  • This document describes cellulose nanofibers obtained by passing wood powder through a lignin removing step and a grinder treatment step as nanofibers. Furthermore, in this document, cellulose derived from cotton and bacterial cellulose not containing lignin and hemicellulose are described as comparative examples.
  • Patent Document 5 proposes a cellulose fiber composite containing cellulose fibers, an oxetane resin as a matrix material, and a residue of a photocationic polymerization initiator in the same layer.
  • This document states that the average fiber diameter of cellulose fibers is preferably 4 to 400 nm, and the average fiber length is preferably 100 nm or more.
  • Patent Document 6 proposes a method for producing an optical film using a composition comprising acetylated cellulose containing cellulose nanofibers.
  • the average fiber diameter of cellulose nanofibers is preferably 4 to 200 nm and the fiber length is 100 nm or more.
  • softwood kraft pulp is pulverized with a high-pressure homogenizer and then treated with a grinder.
  • cellulose nanofibers having an average fiber diameter of 150 nm and an average fiber length of 450 nm are prepared.
  • the material using bacterial cellulose has the same problems as Patent Documents 1 and 2, and the material using pulp or wood powder is a fiber of cellulose nanofiber. Since the diameter is non-uniform and includes a large fiber diameter, transparency and optical properties are not sufficient. Furthermore, cellulose using pulp or wood powder has a short fiber length with respect to the fiber diameter, and therefore has insufficient mechanical properties.
  • JP 2005-60680 A (claims, paragraphs [0056] [0072] [0104], Examples) JP 2006-36926 (Claims, paragraph [0061]) JP 2006-241450 A (claims, paragraph [0077], Example 14) JP 2008-24788 A (Claims, Examples) JP 2009-155384 A (claims, paragraphs [0024] [0025]) JP 2008-209595 A (claims, paragraphs [0014] [0015], examples)
  • an object of the present invention is to provide a fiber-reinforced transparent resin composition having excellent transparency and high strength and dimensional stability, a method for producing the same, and a transparent sheet formed from the composition.
  • Another object of the present invention is to provide a fiber-reinforced transparent resin composition having excellent heat resistance, low haze and excellent optical properties, a method for producing the same, and a transparent sheet formed from the composition.
  • Still another object of the present invention is to form a fiber-reinforced transparent resin composition capable of suppressing warpage and undulation even when nanofibers are uniformly dispersed in a resin and molded into a sheet, and a method for producing the same, and the composition. Is to provide a transparent sheet.
  • the present inventor has obtained a fiber by combining a plant-derived cellulose fiber having a maximum fiber diameter of 100 nm or less and a relatively long fiber with a transparent resin. It was found that the strength and dimensional stability could be improved while ensuring the transparency of the reinforced resin composition, and the present invention was completed.
  • the fiber-reinforced transparent resin composition of the present invention is a fiber-reinforced transparent resin composition containing plant-derived cellulose fibers and a transparent resin, and the cellulose fibers have a maximum fiber diameter of 100 nm or less and an average.
  • the ratio of the average fiber length to the fiber diameter is 2000 or more.
  • the average fiber length of the cellulose fibers may be 100 to 500 ⁇ m.
  • the cellulose fiber may have an average fiber diameter of 15 to 80 nm and a standard deviation of fiber diameter distribution of 80 nm or less.
  • the cellulose fiber may have a maximum fiber diameter of 30 to 90 nm and a ratio of an average fiber length to an average fiber diameter of 3000 to 10,000.
  • the cellulose fibers may be cellulose fibers derived from never dry pulp formed of wood fibers and / or seed hair fibers, and the kappa number may be 30 or less.
  • the cross-sectional shape of the cellulose fiber may be a substantially isotropic shape.
  • the cellulose fiber is obtained by a production method including a dispersion preparation step of preparing a dispersion by dispersing raw cellulose fibers in a solvent, and a homogenization step of homogenizing the dispersion with a homogenizer equipped with a crushing type homovalve sheet. It may be a fiber.
  • the transparent resin may be at least one curable resin selected from the group consisting of a curable acrylic resin and an epoxy resin.
  • the transparent resin may be a photocurable polyfunctional acrylic resin having a hydroxyl group or an alicyclic epoxy resin.
  • the ratio of the cellulose fiber may be 1 to 50 parts by weight with respect to 100 parts by weight of the transparent resin.
  • the present invention includes a transparent sheet formed of the fiber-reinforced transparent resin composition.
  • the transparent sheet of the present invention may have a total light transmittance of 80% or more at a wavelength of 400 to 700 nm at a thickness of 60 ⁇ m.
  • the transparent sheet of the present invention may be a sheet that forms a display unit of a touch panel.
  • the present invention includes a method for producing the transparent sheet by impregnating a nonwoven fabric formed of cellulose fibers with a liquid composition for forming a transparent resin and curing it.
  • the fiber-reinforced resin composition is transparent by combining a plant-derived cellulose fiber having a maximum fiber diameter of 100 nm or less and a ratio of the average fiber length to the average fiber diameter of 2000 or more and a transparent resin. Strength and dimensional stability can be improved while securing the properties.
  • This fiber-reinforced transparent resin composition has excellent heat resistance, small haze, and excellent optical characteristics because the nanofiber fibers are thin and uniform. Further, since the nanofibers are uniformly dispersed in the resin, warping and undulation can be suppressed even when molded into a sheet.
  • FIG. 1 is a schematic cross-sectional view showing a process of homogenizing a dispersion containing fibers using a homogenizer.
  • FIG. 2 is an enlarged cross-sectional view of a facing portion between the crushing type homovalve seat and the homovalve.
  • FIG. 3 is a perspective view of a crushing type homo valve seat.
  • FIG. 4 is a perspective view of a non-crushing homo valve seat.
  • the fiber-reinforced transparent resin composition of the present invention is formed of plant-derived cellulose fibers and a transparent resin.
  • plant-derived cellulose fibers are used as cellulose fibers because they are highly transparent, light scattering can be suppressed, optical properties are excellent, and productivity is also excellent.
  • the cellulose fiber in the present invention is a nanometer-sized fiber having a maximum fiber diameter of 100 nm or less, but since natural plant-derived cellulose fibers are in the micron order, usually, the raw cellulose fibers are microfibrillated. can get.
  • the raw material cellulose fiber is not particularly limited as long as it is a polysaccharide having a ⁇ -1,4-glucan structure, and is derived from a higher plant-derived cellulose fiber [for example, wood fiber (wood pulp of conifers, hardwoods, etc.), bamboo, etc.
  • Natural cellulose fibers such as fiber, sugarcane fiber, seed hair fiber (cotton linter, Bombax cotton, kapok, etc.), gin leather fiber (eg, hemp, mulberry, mitsumata), leaf fiber (eg, Manila hemp, New Zealand hemp) (Pulp fibers, etc.), cellulose fibers chemically synthesized from higher plant-derived cellulose fibers [cellulose acetate (cellulose acetate), cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, etc.
  • Organic acid ester cellulose nitrate; Inorganic acid esters such as acid cellulose and cellulose phosphate; mixed acid esters such as cellulose nitrate acetate; hydroxyalkyl cellulose (eg, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, etc.); carboxyalkyl cellulose (carboxymethyl cellulose (CMC), carboxyethyl cellulose) And the like; alkyl cellulose (methyl cellulose, ethyl cellulose, etc.); cellulose derivatives such as regenerated cellulose (rayon, cellophane, etc.)] and the like.
  • HEC hydroxyethyl cellulose
  • CMC carboxymethyl cellulose
  • alkyl cellulose methyl cellulose, ethyl cellulose, etc.
  • cellulose derivatives such as regenerated cellulose (rayon, cellophane, etc.)] and the like.
  • the cellulose fiber is a high-purity cellulose having a high ⁇ -cellulose content, for example, an ⁇ -cellulose content of 70 to 100% by weight (eg, 95 to 100% by weight), preferably 98 to 100, depending on applications. It may be about wt%. Furthermore, in the present invention, by using high-purity cellulose having a low lignin or hemicellulose content, cellulose fibers having nanometer size and uniform fiber diameter can be prepared even when wood fibers or seed hair fibers are used.
  • Cellulose fibers having a low lignin or hemicellulose content are particularly cellulose having a kappa number ( ⁇ value) of 30 or less (eg, 0 to 30), preferably 0 to 20, more preferably 0 to 10 (particularly 0 to 5). It may be a fiber.
  • the kappa number can be measured by a method based on “Pulp-Kappa number test method” of JIS P8211. These raw material cellulose fibers may be used alone or in combination of two or more.
  • pulps such as wood fibers (wood pulp such as conifers and hardwoods) and seed hair fibers (such as cotton linter pulp) are widely used from the viewpoint of productivity, etc.
  • Pulp obtained by mechanical methods pulverized pulp, refiner ground pulp, thermomechanical pulp, semi-chemical pulp, chemiground pulp, etc.
  • pulp obtained by chemical methods craft pulp, sulfite pulp, etc.
  • beating fiber beating pulp or the like subjected to beating (preliminary beating) if necessary.
  • the raw material cellulose fiber may be a fiber subjected to a conventional refining treatment such as degreasing (for example, absorbent cotton).
  • never dry pulp that is, pulp having no drying history (dried) Pulp that retains its wet state without being
  • the never dry pulp is a pulp formed of wood fibers and / or seed hair fibers, and may be a pulp having a kappa number of 30 or less (particularly about 0 to 10).
  • Such pulp may be prepared by bleaching wood fibers and / or seed hair fibers with chlorine.
  • the cellulose fiber obtained by microfibrillation of such raw material fibers has a uniform nanometer size and does not substantially contain micron order size fibers. That is, the maximum fiber diameter of cellulose fibers is 100 nm or less, for example, about 20 to 100 nm, preferably 30 to 90 nm, and more preferably about 40 to 80 nm (particularly 50 to 70 nm). In the present invention, since the maximum fiber diameter is small, transparency is high, light scattering can be suppressed, and a transparent sheet having low haze can be prepared.
  • the average fiber diameter of the cellulose fibers is, for example, about 10 to 90 nm, preferably 15 to 80 nm, more preferably about 20 to 60 nm (particularly 25 to 50 nm). Further, the standard deviation of the fiber diameter distribution is, for example, about 80 nm or less (for example, 1 to 80 nm), preferably 3 to 50 nm, and more preferably 5 to 40 nm (particularly 10 to 30 nm).
  • the average fiber length of the cellulose fibers can be selected from a range of about 10 to 1000 ⁇ m. From the viewpoint of improving the mechanical properties of the fiber reinforced resin composition, for example, 100 to 500 ⁇ m, preferably 110 to 400 ⁇ m, more preferably 120 to It may be about 300 ⁇ m (particularly 130 to 200 ⁇ m). Further, the ratio of the average fiber length to the average fiber diameter (average fiber length / average fiber diameter) (average aspect ratio) is 2000 or more, for example, 2000 to 15000, preferably 3000 to 10,000, more preferably 4000 to 8000 ( In particular, it is about 5000 to 7000).
  • a resin composition and a sheet excellent in mechanical properties such as strength can be obtained.
  • the cross-sectional shape (cross-sectional shape perpendicular to the longitudinal direction of the fiber) of the cellulose fiber may be an anisotropic shape (flat shape) like bacterial cellulose, but from the viewpoint of optical properties such as transparency and low haze.
  • a substantially isotropic shape is preferred.
  • the substantially isotropic shape include a substantially circular shape such as a perfect circle shape, a regular polygonal shape, and the like.
  • the ratio of the major axis to the minor axis is, for example, 1 to 2, It is preferably about 1 to 1.5, more preferably about 1 to 1.3 (particularly 1 to 1.2).
  • the dehydration time of the cellulose fiber is, for example, 1000 seconds or more, preferably 1200 to 10000 seconds, when measured using a fiber slurry having a concentration of 0.5% by weight in accordance with a test method for dewatering amount of API standard. More preferably, it is about 1500 to 8000 seconds (especially 1800 to 7000 seconds). The longer the dehydration time, the higher the average fiber length / average fiber diameter ratio, and the higher the water retention, the better the mechanical properties.
  • Cellulose fibers are highly dispersible in water and can form a stable dispersion (or suspension).
  • the viscosity of a suspension obtained by suspending cellulose fibers in water to a concentration of 2% by weight is 3000 mPa ⁇ s or more, preferably 4000 to 15000 mPa ⁇ s, more preferably about 5000 to 10,000 mPa ⁇ s. is there.
  • the viscosity was measured using a B-type viscometer using a rotor No. 4 is a value measured as an apparent viscosity at 25 ° C. at a rotation speed of 60 rpm. If the degree of fibrillation is small or the fiber diameter is large, the dispersibility in water decreases, a uniform suspension cannot be obtained, and the viscosity cannot be measured.
  • the cellulose fiber is obtained by microfibrillation of the plant-derived raw fiber.
  • the dispersion preparation step of preparing a dispersion by dispersing the raw fiber in a solvent. It is obtained by a production method including a homogenization step of homogenizing the dispersion with a homogenizer equipped with a crushing type homovalve sheet.
  • cellulose fibers having the above-mentioned fine and uniform fiber diameter and an appropriate average aspect ratio can be prepared by microfibrillation of raw material cellulose fibers by the production method shown below.
  • the average fiber length of the raw fiber is, for example, about 0.01 to 5 mm, preferably about 0.03 to 4 mm, more preferably about 0.06 to 3 mm (particularly 0.1 to 2 mm), and usually 0.1 to 5 mm. It is about 5 mm.
  • the average fiber diameter of the raw fiber is about 0.01 to 500 ⁇ m, preferably about 0.05 to 400 ⁇ m, more preferably about 0.1 to 300 ⁇ m (particularly about 0.2 to 250 ⁇ m).
  • the solvent is not particularly limited as long as it does not cause chemical or physical damage to the raw fiber.
  • water organic solvents [alcohols (C 1-4 alkanol etc. such as methanol, ethanol, 1-propanol, isopropanol etc.), Ethers (diC 1-4 alkyl ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as tetrahydrofuran (cyclic C 4-6 ethers and the like)), esters (alkanoic esters such as ethyl acetate), ketones (acetone, DiC 1-5 alkyl ketones such as methyl ethyl ketone and methyl butyl ketone, C 4-10 cycloalkanones such as cyclohexanone), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (methyl chloride, fluoride) Methyl etc.), cellosolve
  • solvents may be used alone or in combination of two or more.
  • water is preferable from the viewpoint of productivity and cost.
  • a mixed solvent of water and an aqueous organic solvent (C 1-4 alkanol, acetone, etc.) may be used.
  • the raw material fiber to be subjected to the homogenization treatment may be in a state of coexisting at least in the solvent, and the raw material fiber may be dispersed (or suspended) in the solvent prior to the homogenization treatment.
  • Dispersion may be performed using, for example, a conventional disperser (such as an ultrasonic disperser, a homodisper, or a three-one motor).
  • the disperser may include mechanical stirring means (such as a stirring bar and a stirring bar).
  • the concentration of the raw fiber in the solvent is, for example, about 0.01 to 20% by weight, preferably about 0.05 to 10% by weight, more preferably about 0.1 to 5% by weight (particularly about 0.5 to 3% by weight). It may be.
  • FIG. 1 is a schematic view showing a process of homogenizing the dispersion with a homogenizer equipped with a crushing type homo-valve sheet
  • FIG. 2 is an enlarged cross-sectional view of a facing portion between the crushing type homo-valve sheet and the homo-valve
  • FIG. 3 is a perspective view of a crushing type homo-valve seat.
  • FIG. 4 is a perspective view of a non-crushing homo valve seat.
  • the homogenizer includes a hollow cylindrical impact ring 6, a hollow cylindrical convex portion 2 b of the homovalve seat 2 that is inserted and arranged on the upstream side of the impact ring 6, and a hollow cylinder on the downstream side of the impact ring 6.
  • a cylindrical homobulb 5 inserted opposite to the cylindrical convex portion 2b is provided, and the hollow cylindrical convex portion 2b and the columnar homobulb 5 have the same outer diameter.
  • the inner wall on the downstream side of the hollow cylindrical convex portion 2b has a tapered portion (inclined surface) 2d that expands in the downstream direction, and the downstream end of the hollow cylindrical convex portion 2b has an inner diameter d and a thickness t of the end surface.
  • a thin ring-shaped end face 2c having the shape is formed. Further, the ring-shaped end face 2c, the homo valve 5 and the impact ring 6 form a small diameter orifice (gap) 4.
  • the crushing type homo-valve seat 2 is a hollow member having a cylindrical flow path 3 therein, and extends in a downstream direction from a hollow disc-shaped main body portion 2a having an inflow port 3a and an inner wall of the disc-shaped main body portion 2a. And it is comprised with the hollow cylindrical convex part 2b which has the outflow port 3b. Furthermore, as described above, the crushing type homovalve seat 2 is formed with the tapered portion 2d having an enlarged inner diameter, so that compared to the general (normal) noncrushing type homovalve seat 12 shown in FIG. The ring-shaped end surface 2c that forms the outlet 3b is formed thin.
  • the dispersion liquid containing the raw fiber 1 flows into the flow path 3 in the homo valve seat from the inlet 3a of the crushing homo valve seat 2, and the flow path After passing through 3, it passes through the small-diameter orifice 4 and becomes a dispersion containing microfibers 7.
  • the raw material fiber 1 pumped through the homogenizer at high pressure collides with the wall surface of the small diameter orifice 4 (particularly, the wall surface of the impact ring 6) when passing through the small diameter orifice 4 which is a narrow gap.
  • the fiber is divided under shearing stress or cutting action to form uniform nanometer-sized microfibers 7.
  • the flow speed of the dispersion liquid increases rapidly.
  • the pumping pressure of the dispersion rapidly decreases in inverse proportion to the increase in. Therefore, the pressure difference of the dispersion liquid can be increased, the cavitation of the dispersion liquid that has passed through the gap becomes intense, and the uniform microfibril of the raw fiber 1 is increased due to the increase of the collision force with the wall surface in the small diameter orifice 4 and the collapse of the bubbles. It can be inferred that this has been realized.
  • the thickness of the end surface of the wall portion forming the outlet of the crushing type homovalve seat (the ring-shaped end surface at the downstream end of the hollow cylindrical convex portion).
  • the thickness of the end face of the wall portion forming the outlet can be selected according to the diameter of the outlet, but is usually 0.01 to 2 mm, preferably 0.05 to 1.5 mm, more preferably 0.1 to 1 mm. (Especially 0.2 to 0.8 mm).
  • the interval or clearance of the small diameter orifice (especially the interval between the end face of the convex portion of the homovalve seat and the homovalve) is, for example, about 5 to 50 ⁇ m, preferably 10 to 40 ⁇ m, more preferably 15 to 35 ⁇ m (particularly 20 to 30 ⁇ m). is there.
  • the pressure for passing through the small-diameter orifice can be selected from the range of about 30 to 200 MPa, preferably 35 to 150 MPa, More preferably, it may be about 40 to 140 MPa.
  • it can divide
  • the number of treatments (or the number of passes) for passing through the small-diameter orifice can be selected from the range of, for example, about 5 to 100 times, preferably 10 to 80 times, more preferably about 12 to 60 times.
  • the treatment pressure may be selected according to the number of treatments.
  • the treatment pressure is a high-pressure treatment (eg, about 60 to 200 MPa, preferably about 80 to 150 MPa, more preferably about 100 to 130 MPa)
  • the number of times is, for example, about 5 to 50 times, preferably about 10 to 40 times, more preferably about 12 to 30 times (particularly about 15 to 25 times).
  • the treatment pressure is a low-pressure treatment (for example, about 20 to 80 MPa, preferably about 30 to 70 MPa, more preferably about 40 to 60 MPa)
  • the number of treatments is, for example, 10 to 100 times, preferably 20 to 80 times. More preferably, it is about 30 to 70 times (particularly 40 to 60 times).
  • a homogenization process using a homogenizer equipped with a non-crushing type homo valve seat may be combined.
  • a homogenizing process may be performed using a homogenizer provided with a non-crushing type homogenizer.
  • pretreatment with a homogenizer provided with a non-crushing type homovalve sheet can improve the processing efficiency in the homogenizer provided with a crushing type homovalve sheet.
  • a tapered portion is usually formed on the inner wall of the hollow cylindrical convex portion 12 b extending from the hollow disc-shaped main body portion 12 a of the homo-valve seat 12.
  • the pressure for passing through the small-diameter orifice is, for example, 30 to 100 MPa, preferably 35 to 80 MPa, More preferably, it may be about 40 to 70 MPa.
  • the number of passes may be, for example, about 10 to 40 times, preferably about 12 to 30 times, and more preferably about 15 to 25 times.
  • the dispersion may be refined as a pre-process (preliminary process) of the homogenization process.
  • a disc refiner (single disc refiner, double disc refiner, etc.) can be used.
  • the disc refiner has a disc clearance of about 0.1 to 0.3 mm, preferably about 0.12 to 0.28 mm, more preferably about 0.13 to 0.25 mm (eg, 0.14 to 0.23 mm). May be.
  • the rotational speed of the disk is not particularly limited, and can be selected from a wide range of 1,000 to 10,000 rpm. For example, 1,000 to 8,000 rpm, preferably 1,300 to 6,000 rpm, more preferably 1,000 rpm. It may be about 600 to 4,000 rpm.
  • the number of processing (passing) may be 1 to 20 times, preferably 2 to 15 times, and more preferably 3 to 10 times (for example, 4 to 9 times).
  • the degree of raw fiber beating can be adjusted by the disc clearance and the number of refiner treatments. If the disk clearance is too narrow or the number of treatments is too high, the raw fiber will receive a large shearing force, fibrillation will proceed, twisting and roughening of the surface will occur, and the fibers will tend to get entangled. The dispersibility of the fibrillated fibers is reduced. On the other hand, if the disk clearance is too wide, the shearing force applied to the raw fiber becomes small, and an undivided portion remains.
  • the transparent resin is not particularly limited as long as it is transparent.
  • an olefin resin polypropylene, alicyclic polyolefin, etc.
  • an acrylic resin polymethyl methacrylate, etc.
  • a styrene resin polystyrene, etc.
  • a polyamide resin etc.
  • It may be a thermoplastic resin such as a resin (such as polyamide 6), a polyester resin (such as polyethylene terephthalate), or a polycarbonate resin (such as bisphenol A type polycarbonate), but it can impregnate relatively long cellulose fibers.
  • a curable resin is preferable.
  • the curable resin (or its precursor) is a compound having a functional group that reacts with, for example, heat or active energy rays (such as ultraviolet rays or electron beams), and is cured or cross-linked with heat or active energy rays.
  • heat or active energy rays such as ultraviolet rays or electron beams
  • Various curable compounds capable of forming (especially cured or crosslinked resins) can be used.
  • a photocurable resin such as an ultraviolet curable resin or an electron beam curable resin is preferable because of its high productivity and easy formation of a transparent sheet excellent in optical properties.
  • curable resin examples include curable acrylic resins, diallyl phthalates, unsaturated polyester resins, epoxy resins, melamine resins, phenol resins, silicone resins, polyimide resins, urethane resins, and the like. . Of these, acrylic resins and epoxy resins are particularly preferred because of their excellent transparency and mechanical properties.
  • the refractive index of the transparent resin may be, for example, 1.4 or more, preferably 1.4 to 1.6, and more preferably about 1.45 to 1.55.
  • the curable acrylic resin may be composed of, for example, an acrylic polymerizable composition containing a polymerizable acrylic component and a polymerization initiator.
  • the polymerizable acrylic component may be either a monomer or an oligomer (or a prepolymer), or may be used in combination of a monomer and an oligomer.
  • the acrylic monomer can be classified into, for example, a monofunctional acrylic monomer having one polymerizable group and a polyfunctional acrylic monomer having at least two polymerizable groups.
  • the polyfunctional acrylic monomer includes a polyfunctional acrylic monomer having about 2 to 8 polymerizable groups.
  • monofunctional acrylic monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, C 1-24 alkyl (meth) acrylates such as stearyl (meth) acrylate; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; dicyclopentyl (meth) acrylate,
  • aryl (meth) acrylates such as phenyl (meth) acrylate and nonylphenyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy C 2-10 alkyl (meth) acrylate or C 2-10 alkanediol mono (meth) acrylates such as hydroxybutyl (meth) acrylate; trifluoroethyl ( Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate; data) acrylate, tetrafluoropropyl (meth) acrylate, fluoroalkyl C 1-10 alkyl (meth) acrylates such as hexafluoroisopropyl (meth) acrylate and phenoxyethy
  • bifunctional acrylic monomer examples include allyl (meth) acrylate; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, and 1,4-butanediol.
  • Alkanediol di (meth) acrylates such as di (meth) acrylate, neopentylglycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; alkane polyol di (meth) such as glycerin di (meth) acrylate Acrylate: Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene Polyalkylene glycol di (meth) acrylates such as cold di (meth) acrylate and polyoxytetramethylene ether glycol di (meth) acrylate; 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2- C 2-4 alkylene of bisphenols (bisphenol A, S, etc.) such as bis (4- (meth) acryloxy
  • tri- or more functional acrylic monomer examples include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Alkane polyol poly (meth) acrylates such as acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; C 2-4 alkylene oxide addition of the alkane polyol Tri (meth) acrylate having a triazine ring such as poly (meth) acrylate; tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate A relation can be exemplified.
  • These tri- or higher functional acrylic monomers are usually tri- to 8-functional acrylic monomers, and may be, for example, 3- to 6-functional acrylic monomers (particularly tri- to 4-functional acrylic monomers). These trifunctional or higher functional acrylic monomers can be used alone or in combination of two or more.
  • acrylic oligomer examples include polyester (meth) acrylate [for example, aliphatic or aromatic polyester (meth) produced by reaction of polycarboxylic acid and polyol with (meth) acrylic acid and / or hydroxyalkyl (meth) acrylate.
  • polyester (meth) acrylate for example, aliphatic or aromatic polyester (meth) produced by reaction of polycarboxylic acid and polyol with (meth) acrylic acid and / or hydroxyalkyl (meth) acrylate.
  • epoxy (meth) acrylates for example, epoxy compounds having a plurality of epoxy groups (polyhydric alcohol type, polycarboxylic acid type, bisphenol types such as bisphenol A, F, S, novolac type, etc.) Epoxy (meth) acrylate with ring-opening addition of (meth) acrylic acid, etc.]; Urethane (meth) acrylate [for example, polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate, polycarbonate Urethane (meth) acrylate, etc.]; Silicone (meth) acrylate [for example, silicone di to hexa (meth) acrylate, etc.]; Polyacryl (meth) acrylate [for example, (meth) acrylic monomer and glycidyl (meth) acrylate A polyacrylic (meth) acrylate or the like obtained by ring-opening addition of (meth) acrylic acid, etc.]; Urethane (
  • the polymerizable acrylic component is preferably an acrylic component containing a polyfunctional acrylic monomer or oligomer (polyfunctional acrylic component) having at least two polymerizable groups from the viewpoint of curability.
  • the polyfunctional acrylic component can be selected depending on the application.
  • the polyfunctional acrylic component has a hydroxyl group in terms of improving compatibility and adhesion with cellulose fibers and improving optical properties and dimensional stability.
  • Acrylate may be used, and urethane (meth) acrylate may be used from the viewpoint of improving flexibility.
  • polyfunctional (meth) acrylate having a hydroxyl group examples include bifunctional (meth) acrylate [for example, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, glycerin di (meth) acrylate, penta Alkane polyol di (meth) acrylate such as erythritol di (meth) acrylate and dipentaerythritol di (meth) acrylate; di (meth) acrylate of C 2-4 alkylene oxide adduct of the alkane polyol] (Meth) acrylate [for example, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta Alkane polyol poly (meth) acrylate such
  • hydroxyl group-containing polyfunctional (meth) acrylates can be used alone or in combination of two or more.
  • 3 to 8 functions preferably 3 to 6 functions having a hydroxyl group such as pentaerythritol tri (meth) acrylate.
  • (Meth) acrylate is more preferable.
  • Urethane (meth) acrylate is not particularly limited.
  • polyisocyanate component or a prepolymer having a free isocyanate group formed by a reaction between a polyisocyanate component and a polyol component
  • Urethane (meth) acrylate obtained by reacting acrylate for example, hydroxyalkyl (meth) acrylate etc.
  • acrylate for example, hydroxyalkyl (meth) acrylate etc.
  • polyisocyanate component examples include aliphatic polyisocyanates [for example, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI); 1,6,11-undecane.
  • aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI); 1,6,11-undecane.
  • Aliphatic triisocyanates such as triisocyanate methyloctane and 1,3,6-hexamethylene triisocyanate
  • alicyclic polyisocyanates eg, cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate
  • Alicyclic diisocyanates such as hydrogenated bis (isocyanatophenyl) methane; alicyclic triisoses such as bicycloheptane triisocyanate Anate, etc.
  • aromatic polyisocyanates for example, phenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate (NDI), bis (isocyanatophenyl) methane (MDI), toluid
  • the polyol component is not particularly limited.
  • a low molecular weight polyol [aliphatic polyol (C 2-10 alkane diol such as ethylene glycol, propylene glycol, tetramethylene ether glycol, etc .; C such as glycerin, trimethylolpropane, pentaerythritol, etc.) 3-12 aliphatic polyols), cycloaliphatic polyols (cycloalkanediols such as 1,4-cyclohexanediol), hydrogenated bisphenols such as hydrogenated bisphenol A, or C 2-4 alkylene oxide adducts thereof ), Aromatic polyols (araliphatic diols such as xylylene glycol, bisphenols such as bisphenol A, S, and F, or their C 2-4 alkylene oxide adducts)], polymer polyols [example For example, polyether polyol (poly C 2-4 al
  • JP, 2008-74891, A etc. can refer to the manufacturing method of these urethane (meth) acrylates.
  • the weight average molecular weight of urethane (meth) acrylate may be about 500 to 10,000, preferably about 600 to 9000, and more preferably about 700 to 8,000 in terms of polystyrene in gel permeation chromatography (GPC).
  • the polyfunctional (meth) acrylate or urethane (meth) acrylate having a hydroxyl group may be combined with other polymerizable acrylic components from the viewpoints of hardness adjustment and workability.
  • Other polymerizable acrylic components may be alicyclic or aromatic (meth) acrylates from the viewpoint of improving dimensional stability and strength, while from the viewpoint of improving flexibility, (poly) Alkylene glycol (meth) acrylate may be sufficient.
  • Alicyclic or aromatic (meth) acrylates include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, bridged cyclic (meth) acrylates such as isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc.
  • An aryloxyalkyl (meth) acrylate may be used.
  • poly alkylene glycol (meth) acrylate As the (poly) alkylene glycol (meth) acrylate, (poly) C 2-6 alkylene glycol di (meth) acrylate and the like are widely used. From the viewpoint of flexibility, poly C 2-6 alkylene glycol di (meth) acrylate ( Particularly preferred are poly C 3-4 alkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate).
  • the average number of repeating oxy C 3-4 alkylene units can be selected from a range of about 1.2 to 30 mol per molecule, for example, 1.5 to 20 mol, preferably 2 to 10 mol, more preferably 2 It may be about 5 to 8 mol (particularly 3 to 5 mol).
  • polymerizable acrylic components may be monofunctional (meth) acrylates having hydroxyl groups, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, in order to improve the affinity with cellulose fibers. Hydroxy C 2-6 alkyl (meth) acrylate such as hydroxybutyl (meth) acrylate may be used. Also, other polymerizable vinyl components such as N-vinylpyrrolidone may be used together with other polymerizable acrylic components or instead of the other polymerizable acrylic components.
  • the former / the latter 90/10 to 3/97, preferably 70/30 to 5/95, more preferably 50/50 to 10/90 (particularly 30/70 to 15/85). Also good.
  • the polymerization initiator may be a thermal polymerization initiator (a thermal radical generator such as a peroxide such as benzoyl peroxide) or a photopolymerization initiator (photo radical generator). good.
  • a preferred polymerization initiator is a photopolymerization initiator.
  • photopolymerization initiator examples include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether), phenyl ketones [for example, acetophenones (for example, acetophenone, 2-hydroxy -2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc.), 2-hydroxy-2 -Alkyl phenyl ketones such as methylpropiophenone; cycloalkyl phenyl ketones such as 1-hydroxycyclohexyl phenyl ketone], aminoacetophenones ⁇ 2-methyl-1- [4- (methylthio) phene ] -2-morpholinoaminopropanone-1, 2-benzyl-2-dimethylaminoprop
  • the ratio of the polymerization initiator is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the polymerizable acrylic component. Degree.
  • the polymerization initiator does not need to contain substantially.
  • the photopolymerization initiator may be combined with a photosensitizer.
  • the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl.
  • Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenone such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone], triphenylphosphine, etc.
  • Phosphines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. It is done.
  • the photosensitizers may be used alone or in combination of two or more.
  • the amount of the photosensitizer used may be, for example, about 0.1 to 100 parts by weight, preferably about 0.5 to 80 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.
  • epoxy resin examples include conventional epoxy resins such as glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, glycidyl amine type epoxy resins, and long chain aliphatic epoxy resins.
  • glycidyl ether type epoxy resin examples include bisphenol type epoxy resins [for example, epoxy resins having a bis (hydroxyphenyl) C 1-10 alkane skeleton such as bisphenol A type, bisphenol F type, and bisphenol AD type epoxy resins, bisphenol S type epoxy.
  • bisphenol type epoxy resins for example, epoxy resins having a bis (hydroxyphenyl) C 1-10 alkane skeleton such as bisphenol A type, bisphenol F type, and bisphenol AD type epoxy resins, bisphenol S type epoxy.
  • novolac type epoxy resin eg phenol novolak type, cresol novolak type epoxy resin etc.
  • aliphatic type epoxy resin eg hydrogenated bisphenol A type epoxy resin, propylene glycol mono to diglycidyl ether, pentaerythritol mono To tetraglycidyl ether
  • monocyclic epoxy resin for example, resorcing ricidyl ether
  • heterocyclic epoxy resin for example, triglycidyl isocyanurate
  • hydantoin type epoxy resin tetrakis (glycidyloxyphenyl) ethane and the like.
  • glycidyl ester type epoxy resin examples include aliphatic carboxylic acid glycidyl esters (saturated C 2-24 aliphatic carboxylic acids such as glycidyl acetate, glycidyl butyrate, glycidyl laurate, glycidyl palmitate, and glycidyl stearate).
  • Glycidyl esters aliphatic dicarboxylic acid diglycidyl esters such as adipic acid diglycidyl ester, dodecanedioic acid diglycidyl ester), unsaturated carboxylic acid glycidyl ester [(meth) acrylic acid glycidyl ester, oleic acid glycidyl ester, linoleic acid and unsaturated C 2-24 aliphatic carboxylic acid glycidyl esters such as glycidyl esters, aromatic carboxylic acid glycidyl ester (glycidyl benzoate, lid Acid diglycidyl ester, terephthalic acid glycidyl ester), alicyclic carboxylic acid glycidyl ester (tetrahydrophthalic acid glycidyl esters, such as hexahydrophthalic acid glycidyl ester), and the like.
  • alicyclic epoxy resin examples include vinylcyclopentadiene dioxide, vinylcyclohexene mono-dioxide, dicyclopentadiene oxide, 3,4-epoxy-1- [8,9-epoxy-2,4-dioxaspiro [5.
  • Examples of the glycidylamine type epoxy resin include reaction products of amines (particularly polyamines) and epichlorohydrin, such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol, diglycidylaniline, diglycidyltoluidine, and the like.
  • Long chain aliphatic epoxy resins include, for example, epoxidized oils and fats (epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, etc.), epoxidized fatty acid alkyls (epoxidized methyl stearate, epoxidized butyl stearate, Epoxidized C 8-24 fatty acid C 1-12 alkyl such as epoxidized octyl stearate), epoxidized polybutadiene, long chain ⁇ -olefin oxide and the like.
  • oils and fats epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, etc.
  • epoxidized fatty acid alkyls epoxidized methyl stearate, epoxidized butyl stearate, Epoxidized C 8-24 fatty acid C 1-12 alkyl such as epoxidized octyl
  • epoxy resins can be used alone or in combination of two or more.
  • glycidyl ether type and glycidyl ester type may be used from the viewpoint of optical characteristics, but 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxy from the viewpoint of light resistance.
  • cyclohexanecarboxylate epoxy C 5-12 cycloalkyl C 1-3 alkyl-epoxy C 5-12 cycloalkane carboxylate such as cyclohexane carboxylate, 4,5-epoxycyclooctylmethyl-4 ′, 5′-epoxycyclooctanecarboxylate
  • An alicyclic epoxy resin is preferred.
  • curing agent examples include amine-based curing agents [for example, aliphatic polyamines (ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.), alicyclic polyamines (mensendiamine, isophorone).
  • amine-based curing agents for example, aliphatic polyamines (ethylenediamine, diethylenetriamine, triethylenediamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, etc.), alicyclic polyamines (mensendiamine, isophorone).
  • Aromatic carboxylic acid anhydrides (dodecenyl succinic anhydride, polyadipic acid anhydride, etc.), alicyclic carboxylic acid anhydrides (methyltetrahydrophthalic anhydride, methyl hymitic anhydride), aromatic carboxylic acid anhydrides (phthalic anhydride, anhydrous trimethyl Etc.
  • a cationic polymerization initiator for example, Bronsted acids (e.g., HBF 6, HPF 6, HAsF 6, HSbF onium salts (e.g., aromatic diazonium salts of 6, etc.), aromatic sulfonium salts, aromatic Group iodonium salts, etc.)] and the like.
  • Bronsted acids e.g., HBF 6, HPF 6, HAsF 6, HSbF onium salts (e.g., aromatic diazonium salts of 6, etc.), aromatic sulfonium salts, aromatic Group iodonium salts, etc.
  • These curing agents can be used alone or in combination of two or more.
  • amine-based curing agents such as the above-mentioned amine-based curing agents or modified products thereof (epoxy adducts, Mannich reaction products, Michael reaction products, thiourea reaction products, etc.), and cationic polymerization such as aromatic sulfonium salts Initiators are preferred.
  • the cationic polymerization initiator can be used as the photopolymerization initiator.
  • the proportion of the curing agent is, for example, about 1 to 30 parts by weight, preferably 2 to 20 parts by weight, more preferably 3 to 15 parts by weight (particularly 5 to 10 parts by weight) with respect to 100 parts by weight of the epoxy resin. .
  • the fiber-reinforced transparent resin composition of the present invention (when the transparent resin is a curable resin, the fiber-reinforced transparent resin composition after curing) has a high dimensional stability despite the relatively low content of cellulose fibers. Indicates mechanical strength.
  • the ratio of the cellulose fiber is, for example, about 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight (particularly 15 to 25 parts by weight) with respect to 100 parts by weight of the transparent resin. .
  • the fiber-reinforced transparent resin composition of the present invention a conventional additive, for example, a stabilizer such as an antioxidant or a heat stabilizer, a plasticizer, an antistatic agent, a flame retardant, and the like, as long as transparency is not impaired.
  • An ultraviolet absorber or the like may be contained.
  • the fiber-reinforced transparent resin composition before curing is an organic solvent such as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.).
  • Alicyclic hydrocarbons such as cyclohexane
  • aromatic hydrocarbons such as benzene
  • halogenated carbons such as dichloromethane and dichloroethane
  • esters such as methyl acetate and ethyl acetate
  • water alcohols
  • cellosolves methyl cellosolve, ethyl cellosolve, etc.
  • cellosolve acetates amides (dimethylformamide, dimethylacetamide, etc.) and the like may be contained.
  • the fiber-reinforced transparent resin composition (fiber-reinforced resin composition before curing) of the present invention may be solid at room temperature, but is preferably liquid from the viewpoint of productivity of the fiber-reinforced resin.
  • the viscosity (25 ° C.) of the liquid fiber-reinforced transparent resin composition (the curable resin precursor when the transparent resin is a curable resin) is, for example, 10 to 1000 mPa ⁇ s, preferably from the viewpoint of improving the impregnation efficiency. It is about 50 to 500 mPa ⁇ s, more preferably about 100 to 300 mPa ⁇ s (especially 150 to 250 mPa ⁇ s).
  • the fiber-reinforced transparent resin composition of the present invention (cured fiber-reinforced transparent resin composition) is also excellent in transparency, and has a total light transmittance of 400 to 700 nm (measured in accordance with JIS K7361-1)
  • the thickness (60 ⁇ m) may be 80% or more, for example, 80 to 100%, preferably 82 to 99%, more preferably 85 to 98% (especially 87 to 95%).
  • light scattering is also suppressed, and the haze (thickness 60 ⁇ m) measured according to JIS K7361-1 may be 30% or less, for example, 0.1 to 30%, preferably 0.5 to It is about 20%, more preferably about 1 to 15% (particularly 2 to 10%).
  • the fiber-reinforced transparent resin composition (fiber-reinforced transparent resin composition after curing) of the present invention is excellent in dimensional stability, and has a linear expansion coefficient of 50 ppm / K or less measured in accordance with JIS K7197.
  • it is about 1 to 40 ppm / K, preferably about 5 to 30 ppm / K, more preferably about 10 to 25 ppm / K (particularly about 15 to 20 ppm / K).
  • the transparent sheet of the present invention is formed of the fiber-reinforced transparent resin composition, and usually a liquid composition for forming a transparent resin after producing a nonwoven fabric previously formed of cellulose fibers in advance. It is obtained by impregnating a product and curing the liquid composition.
  • the method for producing the nonwoven fabric is not particularly limited, and can be produced by a conventional method, for example, papermaking such as wet papermaking or dry papermaking.
  • the wet papermaking can be performed by a conventional method, and for example, the papermaking may be performed using a wet papermaking machine equipped with a manual papermaking machine or a perforated plate.
  • Dry papermaking can also be made using conventional methods such as airlaid and card manufacturing.
  • the obtained non-woven fabric is, for example, about 1 to 100 ⁇ m, preferably 3 to 50 ⁇ m, more preferably 5 to 30 ⁇ m (particularly 10 to 25 ⁇ m).
  • a nonwoven fabric may be used by laminating a plurality of nonwoven fabrics according to the thickness of the intended transparent sheet.
  • the number of stacked layers may be selected from a range of about 2 to 30 sheets, for example, and may be about 3 to 20 sheets (particularly 5 to 15 sheets).
  • the nonwoven fabric may be laminated before or after impregnation with the liquid composition, but is usually laminated after impregnation in the liquid composition.
  • the basis weight of the nonwoven fabric may be, for example, about 0.1 to 50 g / m 2 , preferably about 1 to 30 g / m 2 , and more preferably about 3 to 20 g / m 2 .
  • the porosity of the nonwoven fabric may be 50% or more, preferably 50 to 90%, more preferably about 60 to 80%.
  • the air permeability of the nonwoven fabric is, for example, about 100 to 1200 seconds / ml, preferably 200 to 1000 seconds / ml, and more preferably about 300 to 800 seconds / ml.
  • the tensile strength of the nonwoven fabric is, for example, 5 N / 15 mm or more, preferably 5.5 to 15 N / 15 mm, more preferably 6 to 10 N / 15 mm (especially 6.5 to 8 N / 15 mm).
  • the impregnation method may be impregnated by coating or casting the liquid composition on the nonwoven fabric, but the nonwoven fabric is immersed in the liquid composition from the viewpoint that the transparent resin can be uniformly impregnated easily.
  • the conditions for the impregnation are usually immersed at a temperature of about room temperature (for example, 10 to 40 ° C., preferably 15 to 35 ° C.) and may be immersed under normal pressure.
  • the immersion may be performed under reduced pressure (for example, under reduced pressure of about 0.9 to 0.01 MPa, preferably about 0.8 to 0.1 MPa).
  • the immersion time is, for example, 1 to 36 hours, preferably 2 to 24 hours, and more preferably about 3 to 20 hours.
  • the curing method of the liquid composition can be selected according to the type of the liquid composition.
  • the liquid composition is a curable resin (polymerizable composition)
  • the polymerization initiator Although it may be cured by heating depending on the type, it can usually be cured by heating or irradiation with active energy rays.
  • active energy rays heat and / or light energy rays can be used, and it is particularly useful to use light energy rays.
  • light energy rays radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, electron beams (EB), etc. can be used, and usually ultraviolet rays and electron beams are often used.
  • EB electron beams
  • a Deep UV lamp for example, in the case of ultraviolet rays, a Deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. may be used. it can.
  • the illuminance of ultraviolet rays varies depending on the thickness of the coating film, but is, for example, about 10 to 500 W / cm 2 , preferably 50 to 300 W / cm 2 , and more preferably about 100 to 200 W / cm 2 .
  • the linear velocity of ultraviolet rays is, for example, about 1 to 20 m / min, preferably about 2 to 15 m / min, and more preferably about 3 to 10 m / min.
  • a method of irradiating an electron beam with an exposure source such as an electron beam irradiation apparatus can be used.
  • the irradiation amount (dose) varies depending on the thickness of the coating film, but is, for example, about 1 to 200 kGy (gray), preferably 5 to 150 kGy, more preferably 10 to 100 kGy (particularly 20 to 80 kGy).
  • the acceleration voltage is, for example, about 10 to 1000 kV, preferably about 50 to 500 kV, and more preferably about 100 to 300 kV.
  • inert gas for example, nitrogen gas, argon gas, helium gas, etc.
  • EB8402 Daicel Cytec Co., Ltd. “EBECRYL8402”, bifunctional urethane acrylate PETIA: Daicel Cytec Co., Ltd., trade name “PETIA”, trifunctional acrylic monomer having a hydroxyl group (pentaerythritol triacrylate) TPGDA: “TPGDA” manufactured by Daicel Cytec Co., Ltd., tripropylene glycol diacrylate, propylene oxide addition moles (about 3 moles)
  • EB110 “EBECRYL110” manufactured by Daicel Cytec Co., Ltd., phenoxyethyl acrylate CEL2021: “Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd.
  • CEL8000 “Celoxide 8000” manufactured by Daicel Chemical Industries, Ltd.
  • OXT-211 “OXT-211” manufactured by Toa Gosei Co., Ltd.
  • Oxtacene resin OXT-221 “OXT-221” manufactured by Toa Gosei Co., Ltd.
  • Oxacene resin YX-8000 “YX-8000” manufactured by JER Corporation
  • Photopolymerization initiator “Irgacure 184” manufactured by Ciba Japan Co., Ltd.
  • Photocationic polymerization initiator “SP170” manufactured by Adeka Co., Ltd.
  • Thermal cationic polymerization initiator “Sun-Aid SI-100L” manufactured by Sanshin Chemical Industry Co., Ltd., aromatic sulfonium salt.
  • Fiber length was measured using a fiber length measuring device (“FS-200” manufactured by Kajaani).
  • Total light transmittance and haze The obtained non-woven fabric and transparent sheet were measured according to JIS K7136 using a haze meter (trade name “NDH-5000W” manufactured by Nippon Denshoku Co., Ltd.).
  • Example 1 Using NBKP pulp (manufactured by Marusumi Paper Co., Ltd., solid content of about 50% by weight, copper number of about 0.3), 100 liters of a slurry liquid containing 1% by weight of pulp was prepared. Next, using a disk refiner (SUPERFIBRATER 400-TFS, manufactured by Hasegawa Tekko Co., Ltd.), a refiner-treated product was obtained by beating 10 times with a clearance of 0.15 mm and a disk rotation speed of 1750 rpm.
  • a disk refiner SUPERFIBRATER 400-TFS, manufactured by Hasegawa Tekko Co., Ltd.
  • the obtained fiber slurry was diluted to 0.2% by weight, and a paper machine equipped with a decompression device (“200 mm ⁇ 250 mm standard square machine” manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. Papermaking was performed using 5C filter paper as a filter cloth. As a blotting paper, no. Stacked 5C filter paper. Next, the paper body was immersed in isopropyl alcohol for 10 minutes with ultrasonic treatment to replace the solvent. Furthermore, the new No. Both sides were sandwiched with 5C filter paper. Then, it was attached to a drum dryer (manufactured by Kumagai Riki Kogyo Co., Ltd.) whose surface temperature was set to 100 ° C. and dried for 120 seconds. Table 1 shows the thickness, basis weight, porosity, tensile strength, total light transmittance, haze, and air permeability of the obtained nonwoven fabric.
  • urethane acrylate EB8402
  • TPGDA polypropylene glycol diacrylate
  • a photopolymerization initiator 1 part by weight
  • the nonwoven fabric was gently dipped in a metal vat filled with the mixed solution, and dipped for 12 hours at room temperature under reduced pressure (0.7 MPa).
  • the nonwoven fabric impregnated with the mixed solution was taken out from the metal vat and the excess impregnating solution was cut off, and then sandwiched between polyester films and irradiated with ultraviolet rays.
  • the ultraviolet irradiation conditions were an illuminance of 160 W / cm 2 , a linear velocity of 6 m / min, and an irradiation zone of 50 cm.
  • the polyester film was peeled off to obtain a transparent sheet formed of a cellulose fiber reinforced transparent resin composition.
  • Table 1 shows the fiber content, total light transmittance, haze, tensile strength, flexural modulus, and linear expansion coefficient of the obtained transparent sheet.
  • Example 2 A transparent sheet was obtained in the same manner as in Example 1 except that 21 parts by weight of pentaerythritol triacrylate (PETIA), 79 parts by weight of polypropylene glycol diacrylate (TPGDA), and 1 part by weight of a photopolymerization initiator were mixed as the resin for impregnation. It was. The evaluation results of the obtained transparent sheet are shown in Table 1.
  • PETIA pentaerythritol triacrylate
  • TPGDA polypropylene glycol diacrylate
  • photopolymerization initiator 1 part by weight
  • Example 3 A transparent sheet was obtained in the same manner as in Example 1 except that 20 parts by weight of urethane acrylate (EB8402), 80 parts by weight of phenoxyethyl acrylate (EB110), and 1 part by weight of a photopolymerization initiator were mixed as the impregnation resin.
  • the evaluation results of the obtained transparent sheet are shown in Table 1.
  • Example 4 A transparent sheet was obtained in the same manner as in Example 1 except that 17 parts by weight of pentaerythritol triacrylate (PETIA), 83 parts by weight of phenoxyethyl acrylate (EB110), and 1 part by weight of a photopolymerization initiator were mixed as the impregnation resin. .
  • PETIA pentaerythritol triacrylate
  • EB110 phenoxyethyl acrylate
  • photopolymerization initiator 1 part by weight
  • Example 5 In the same manner as in Example 1, a non-woven fabric impregnated with the mixed solution was prepared, and after the excess impregnating solution was cut, ten non-woven fabrics impregnated with the mixed solution were laminated and sandwiched between polyester films, alternately on the front and back surfaces. Ultraviolet rays were irradiated under the same irradiation conditions as in Example 1 except that the irradiation was performed 20 times in total. The evaluation results of the obtained transparent sheet are shown in Table 1.
  • Example 6 100 parts by weight of an alicyclic epoxy resin (“Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd.), a thermal cationic polymerization initiator (“Sun Aid SI-100L” manufactured by Sanshin Chemical Industries, Ltd.) 6 parts by weight were mixed, and 500 ml of the obtained mixed solution was filled in a metal vat. The viscosity of the mixed solution (cured resin precursor) was 15 mPa ⁇ s.
  • Example 1 The nonwoven fabric obtained in Example 1 was gently dipped in a metal vat filled with the mixed solution, and dipped for 12 hours under reduced pressure at normal temperature (0.7 MPa).
  • the nonwoven fabric impregnated with the mixed solution is taken out from the metal vat, and the excess impregnating solution is cut off, and then sandwiched between release-sprayed stainless steel plates, heated at 65 ° C. for 2 hours, and then at 150 ° C. under a pressure of 10 MPa. Heated for 1 hour. After the heat treatment, the stainless steel plate was peeled off to obtain a transparent sheet formed of a cellulose fiber reinforced transparent resin composition.
  • Table 1 The evaluation results of the obtained transparent sheet are shown in Table 1.
  • Example 7 As an impregnation resin, an alicyclic epoxy resin (“Celoxide 8000” manufactured by Daicel Chemical Industries, Ltd.) is used in place of an alicyclic epoxy resin (“Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd.). A transparent sheet was obtained in the same manner as in Example 6. The evaluation results of the obtained transparent sheet are shown in Table 1.
  • Comparative Example 1 A transparent sheet was obtained in the same manner as in Example 1 except that 0.2% by weight slurry of cellulose fiber (Daicel Chemical Industries, Ltd., serisch KY100G) was used as the fiber slurry before paper making. The evaluation results of the obtained transparent sheet are shown in Table 1.
  • Comparative Example 2 Cellulose fiber (Daicel Chemical Industries, Ltd., serish KY100G) was treated 20 times (20 passes) with a stone mill. Using this cellulose fiber, a 0.2 wt% slurry was prepared, and a nonwoven fabric and a transparent sheet were obtained in the same manner as in Example 1. The evaluation results of the obtained transparent sheet are shown in Table 1.
  • Comparative Example 3 Cellulose nanofibers were prepared according to Production Example 3 of JP-A-2005-60680. That is, 100 liters of a slurry liquid containing 1% by weight of pulp was prepared using NBKP pulp (manufactured by Marusumi Paper Co., Ltd., solid content of about 50% by weight, copper number of about 0.3). Next, using a disk refiner (SUPERFIBRATER 400-TFS, manufactured by Hasegawa Tekko Co., Ltd.), a refiner-treated product was obtained by beating 10 times with a clearance of 0.15 mm and a disk rotation speed of 1750 rpm.
  • NBKP pulp manufactured by Marusumi Paper Co., Ltd.
  • a refiner-treated product was obtained by beating 10 times with a clearance of 0.15 mm and a disk rotation speed of 1750 rpm.
  • the refiner-treated product is passed from the center to the outside through the disk rotating at 1200 rpm.
  • the operation was performed 30 times (30 passes).
  • the obtained fiber slurry was diluted to 0.2% by weight, and paper was produced in the same manner as in Example 1 to produce a nonwoven fabric, and then a resin was impregnated to obtain a transparent resin.
  • the evaluation results of the obtained transparent sheet are shown in Table 1.
  • Comparative Example 4 A transparent sheet was produced in accordance with Example 1 of JP2009-155384A. That is, rice pine wood flour (manufactured by Miyashita Wood Co., Ltd.) was degreased with a 2 wt% aqueous solution of sodium carbonate at 80 ° C for 6 hours. The wood flour was washed with demineralized water and then immersed in 0.66% by weight sodium chlorite and 0.14% by weight acetic acid aqueous solution at 80 ° C. for 5 hours to remove lignin.
  • rice pine wood flour manufactured by Miyashita Wood Co., Ltd.
  • the wood flour was washed with demineralized water and then immersed in 0.66% by weight sodium chlorite and 0.14% by weight acetic acid aqueous solution at 80 ° C. for 5 hours to remove lignin.
  • the obtained cellulose dispersion was diluted to 0.2% by weight with water, and 100 g was put into a 90 mm diameter filter using PTFE having a pore size of 1 ⁇ m.
  • 2-propanol was added. To replace water. Then, it press-dried at 120 degreeC and 0.15 MPa for 5 minutes, and obtained the cellulose nonwoven fabric.
  • the obtained cellulose nonwoven fabric was impregnated with 100 ml of acetic anhydride and heated at 100 ° C. for 7 hours. Thereafter, it was thoroughly washed with distilled water, and finally immersed in 2-propanol for 10 minutes, and then press-dried at 120 ° C. and 0.15 MPa for 5 minutes to obtain an acetylated cellulose nonwoven fabric having a thickness of 62 ⁇ m.
  • the transparent sheets of the examples have high total light transmittance, low haze, and high mechanical properties and dimensional stability despite low fiber content.
  • the transparent sheet of the comparative example cannot achieve both optical properties and mechanical properties.
  • the fiber-reinforced transparent resin composition and transparent sheet of the present invention are transparent and excellent in mechanical properties, they are electrical / electronic or precision equipment such as personal computers, televisions, mobile phones, gaming machines, mobile devices, watches, and calculators.
  • the transparent sheet of this invention is comprised with resin and has flexibility, it is useful as a sheet

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
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Abstract

La présente invention concerne une composition de résine transparente armée de fibres faisant preuve d'excellentes qualités de transparence, de résistance mécanique, et de stabilité des dimensions. Pour élaborer une telle composition de résine transparente armée de fibres, on combine une résine transparente à de la fibre de cellulose d'origine végétale, le diamètre maximal de la fibre n'excédant pas 100 nm, et le rapport longueur moyenne de la fibre sur diamètre moyen de la fibre étant d'au moins 2000. La longueur moyenne de la fibre de cellulose peut se situer entre 100 et 500 µm. Le diamètre moyen de la fibre de cellulose peut se situer entre 15 et 80 nm, l'écart type de la distribution des diamètres de fibres n'excédant pas 80 nm. La résine transparente peut être une résine polymérisable choisie dans le groupe comprenant les résines acryliques et les résines époxy. La feuille transparente obtenue à partir de la composition de résine transparente armée de fibres convient à la réalisation de la feuille constituant la partie affichage d'un écran tactile.
PCT/JP2011/066736 2010-07-22 2011-07-22 Composition de résine transparente armée de fibres, procédé de production correspondant, et feuille transparente Ceased WO2012011577A1 (fr)

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JP2015030829A (ja) * 2013-08-06 2015-02-16 Dic株式会社 セルロースナノファイバー含有エポキシ樹脂組成物の製造方法、強化マトリクス樹脂及び繊維強化樹脂複合体
JP2017082071A (ja) * 2015-10-27 2017-05-18 王子ホールディングス株式会社 シート及び成形体
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US12163287B2 (en) 2021-07-28 2024-12-10 Asahi Kasei Kabushiki Kaisha Fine cellulose fibers and production method therefor, nonwoven fabric, and fiber-reinforced resin and production method therefor

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