WO2021079850A1 - Feuille stratifiée et stratifié - Google Patents

Feuille stratifiée et stratifié Download PDF

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Publication number
WO2021079850A1
WO2021079850A1 PCT/JP2020/039279 JP2020039279W WO2021079850A1 WO 2021079850 A1 WO2021079850 A1 WO 2021079850A1 JP 2020039279 W JP2020039279 W JP 2020039279W WO 2021079850 A1 WO2021079850 A1 WO 2021079850A1
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WIPO (PCT)
Prior art keywords
resin
laminated sheet
fiber
mass
fibrous cellulose
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PCT/JP2020/039279
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English (en)
Japanese (ja)
Inventor
速雄 伏見
利奈 宍戸
Original Assignee
王子ホールディングス株式会社
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Priority claimed from JP2020041997A external-priority patent/JP2021066171A/ja
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Publication of WO2021079850A1 publication Critical patent/WO2021079850A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • D06M17/00—Producing multi-layer textile fabrics

Definitions

  • the present invention relates to a laminated sheet and a laminated body.
  • fibrous cellulose having a fiber diameter of 10 ⁇ m or more and 50 ⁇ m or less has been widely used mainly as paper products.
  • fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is also known. Further, a sheet composed of such fine fibrous cellulose and a composite containing a fine fibrous cellulose-containing sheet and a resin layer have been developed. It is known that in sheets and composites containing fine fibrous cellulose, the contact points between fibers are remarkably increased, so that the tensile strength and the like are greatly improved. It is also known that the transparency is greatly improved by making the fiber width shorter than the wavelength of visible light.
  • Patent Document 1 discloses a laminate having a fiber layer containing fine fibrous cellulose and a resin layer in contact with one surface of the fiber layer.
  • an adhesion aid is blended in the resin layer in order to enhance the adhesion between the fiber layer and the resin layer.
  • Patent Document 2 discloses a laminate including a fiber layer formed of fine fibrous cellulose, a resin layer, and an adhesive layer provided between the fiber layers and the resin layer.
  • Patent Document 3 discloses a laminate in which a base material, an anchor layer, and a cellulose nanofiber layer are provided in this order. In References 2 and 3, it is studied to improve the adhesion between the fiber layer and the resin layer by providing an adhesive layer or an anchor layer between them.
  • a separation film for a secondary battery comprising a base material layer containing cellulosic nanofibers and polyethylene particles and a resin layer formed on one or both sides of the base material layer and made of a polyolefin resin.
  • polyethylene, polypropylene, polybutylene, and polypentene are mentioned as the polyolefin resin, but no specific example is disclosed in which the adhesion between the base material layer and the resin layer is evaluated.
  • a resin layer containing a polyolefin resin is used for various purposes because of its mechanical properties and excellent weather resistance.
  • the fiber layer and the resin layer are used. Adhesion was not sufficient, and improvement of interlayer adhesion was required. Further, the present inventors have found that even when a resin film is further laminated on a laminated sheet obtained by laminating a fiber layer on a resin layer containing a polyolefin resin, sufficient adhesion between the laminated sheet and the resin film cannot be obtained. It became clear by the examination of.
  • the present inventors have excellent interlayer adhesion between the resin layer containing the polyolefin resin and the fiber layer, and exhibit good adhesion to other resin films. We proceeded with the study for the purpose of providing a possible laminated sheet.
  • the present inventors have found in a laminated sheet having a fiber layer containing fine fibrous cellulose and a resin layer arranged on at least one surface of the fiber layer. , It has been found that by incorporating a modified polyolefin resin in the resin layer, a laminated sheet having excellent interlayer adhesion between the fiber layer and the resin layer and capable of exhibiting good adhesion to other resin films can be obtained. .. Specifically, the present invention has the following configuration.
  • the resin layer is a laminated sheet containing a modified polyolefin resin.
  • FIG. 1 is a cross-sectional view illustrating the configuration of the laminated sheet of the present invention.
  • FIG. 2 is a graph showing the relationship between the amount of NaOH added dropwise and the pH of a fibrous cellulose-containing slurry having a phosphoric acid group.
  • FIG. 3 is a graph showing the relationship between the amount of NaOH added dropwise to the fibrous cellulose-containing slurry having a carboxy group and the pH.
  • the present invention relates to a laminated sheet having a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less and a resin layer arranged on at least one surface of the fiber layer.
  • the resin layer contains a modified polyolefin resin.
  • fibrous cellulose having a fiber width of 1000 nm or less is also referred to as fine fibrous cellulose or CNF.
  • FIG. 1 is a cross-sectional view illustrating the configuration of the laminated sheet of the present invention.
  • the laminated sheet 10 of the present invention has a resin layer 2 and a fiber layer 6.
  • the resin layer 2 is directly laminated on the fiber layer 6, and the resin layer 2 and the fiber layer 6 are in contact with each other on one of the surfaces.
  • the laminated sheet of the present invention may have at least one resin layer 2 and one fiber layer 6, but may have two or more resin layers 2 and two or more fiber layers 6. It may be.
  • the laminated sheet may have a structure in which a fiber layer, a resin layer, and a fiber layer are laminated in this order, or a structure in which a resin layer, a fiber layer, and a resin layer are laminated in this order.
  • the laminated sheet of the present invention has a fiber layer and a resin layer, and the resin layer contains a modified polyolefin resin. Therefore, in the laminated sheet of the present invention, the interlayer adhesion between the fiber layer and the resin layer is excellent.
  • 100 1 mm 2 crosscuts are placed on the surface of the laminated sheet on the fiber layer side, and cellophane tape (manufactured by Nichiban Co., Ltd.) is attached onto it and pressed, and then 90.
  • cellophane tape manufactured by Nichiban Co., Ltd.
  • the number of peeled cells is more preferably 3 points or less, further preferably 1 point or less, and particularly preferably 0 points.
  • the laminated sheet of the present invention since the laminated sheet of the present invention has the above-mentioned structure, it can exhibit good adhesion to other resin films.
  • the other resin film is bonded to the resin layer in the laminated sheet.
  • the resin layer in the laminated sheet can function as an adhesive layer.
  • examples of other resin films to be adhered include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl acetate copolymer, cyclic olefin polymer, cyclic olefin copolymer and the like.
  • the adhesion between the laminated sheet and the other resin film can be evaluated by the following method.
  • a resin film is laminated on the surface of the laminated sheet on the resin layer side, and these are further sandwiched between two stainless steel plates. Then, a laminate is produced by hot-pressing the resin film above the glass transition temperature. Then, when the resin film is to be peeled off from the end portion of the laminated body, if the peeled area is 20% or less with respect to the area (bonded area) of the laminated body, it is determined that the adhesion is good. it can.
  • the peeled area is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less with respect to the total area (bonded area) of the laminated body.
  • the laminated sheet of the present invention has excellent interlayer adhesion between the fiber layer and the resin layer, and when bonded to another resin film, it is also excellent against other resin films. It can exhibit good adhesion.
  • the laminated sheet of the present invention is also excellent in transparency. Since the fiber layer contains fibrous cellulose having a fiber width of 1000 nm or less, it is excellent in transparency. In the laminated sheet having such a fiber layer, the transparency of the resin layer is maintained without being impaired.
  • the total light transmittance of the laminated sheet is preferably 60% or more, more preferably 65% or more, further preferably 70% or more, and particularly preferably 85% or more.
  • the total light transmittance is a value measured using a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) in accordance with JIS K 7361-1: 1997.
  • the haze of the laminated sheet is preferably less than 40%, preferably 30% or less, further preferably 20% or less, further preferably 15% or less, and 10% or less. Is even more preferable, and less than 5% is particularly preferable.
  • the haze is a value measured using a haze meter (manufactured by Murakami Color Technology Research Institute, HM-150) in accordance with JIS K 7136: 2000.
  • the laminated sheet of the present invention has a fiber layer and a resin layer, and the fiber layer can also function as a layer for reinforcing the resin layer. Therefore, the strength of the laminated sheet itself is increased. Further, even when the laminated sheet is attached to an adherend such as another resin film, the fiber layer functions as a layer for reinforcing the adherend. For example, when a polyolefin film is used as an adherend, the mechanical strength of the polyolefin film can be reinforced by laminating the laminated sheet of the present invention in order to increase the mechanical strength of the polyolefin film. As described above, the laminated sheet having the fiber layer also has an effect of reinforcing the adherend.
  • the reinforcing effect when the laminated sheet is attached to the adherend is 1.5 times or more the flexural modulus after the laminated sheet is attached to the adherend, compared with the flexural modulus of the adherend.
  • the flexural modulus after the laminated sheet is attached to the adherend is 2.0 times or more the flexural modulus of the adherend.
  • the total thickness of the laminated sheet is not particularly limited, but is preferably 30 ⁇ m or more, more preferably 40 ⁇ m or more, further preferably 50 ⁇ m or more, still more preferably 60 ⁇ m or more. , 70 ⁇ m or more is particularly preferable.
  • the total thickness of the laminated sheet is preferably 1000 ⁇ m or less.
  • the thickness of the laminated sheet can be appropriately adjusted according to the intended use, but from the viewpoint of exerting the effect of reinforcing the adherend, the total thickness of the laminated sheet is preferably 50 ⁇ m or more.
  • the ratio of the thickness of the resin layer to the thickness of the fiber layer is preferably 10 or less, more preferably 5 or less, and further preferably 1 or less. Further, for example, when the resin layer is a coating layer formed by coating, the ratio of the thickness of the resin layer to the thickness of the fiber layer (thickness of the resin layer / thickness of the fiber layer) is 0.5 or less. It may be 0.2 or less, 0.15 or less, or 0.1 or less.
  • the lower limit of the ratio of the thickness of the resin layer to the thickness of the fiber layer (thickness of the resin layer / thickness of the fiber layer) is not particularly limited, but is, for example, 0.01 or more. In the laminated sheet, when there are a plurality of fiber layers, the thickness of the fiber layers is the total thickness of the fiber layers, and when there are a plurality of resin layers, the thickness of the resin layers is the total thickness of the resin layers. is there.
  • the laminated sheet of the present invention has a good appearance. Specifically, when the laminated sheet is observed from the fiber layer side, no curl or wrinkles are observed, and the laminated sheet of the present invention has a flat shape. Such a laminated sheet is also excellent in design.
  • the laminated sheet of the present invention can also exhibit excellent mechanical strength.
  • the tensile elastic modulus of the laminated sheet at 23 ° C. and 50% relative humidity is preferably 2.5 GPa or more, more preferably 5.0 GPa or more, and even more preferably 10 GPa or more.
  • the tensile elastic modulus of the laminated sheet at 23 ° C. and 50% relative humidity is preferably 30 GPa or less, more preferably 25 GPa or less, and even more preferably 20 GPa or less.
  • the tensile elastic modulus of the laminated sheet is a value measured in accordance with JIS P 8113: 2006.
  • the laminated sheet has at least one resin layer.
  • the resin layer is preferably laminated directly on the fiber layer, and the resin layer and the fiber layer are in contact with each other on either surface.
  • the resin layer is preferably a resin layer (coated resin layer) formed by coating.
  • the resin layer is a layer containing a modified polyolefin resin, and is preferably a layer containing a modified polyolefin resin as a main component.
  • the main component refers to a component contained in an amount of 50% by mass or more with respect to the total mass of the resin layer.
  • the content of the modified polyolefin resin is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass, based on the total mass of the resin layer. It is particularly preferable that the content is% by mass or more.
  • the content of the modified polyolefin resin may be 100% by mass.
  • the modified polyolefin resin is obtained by modifying the polyolefin resin.
  • the method for modifying the polyolefin resin include acid modification, chlorination, and acrylic modification.
  • the modified polyolefin resin is preferably an acid-modified polyolefin resin.
  • the acid-modified component is preferably an unsaturated carboxylic acid component.
  • the unsaturated carboxylic acid component is a component derived from unsaturated carboxylic acid or its anhydride, and examples of the unsaturated carboxylic acid component include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. Acids, fumaric acid, crotonic acid and the like can be mentioned.
  • the unsaturated carboxylic acid component is preferably at least one selected from acrylic acid, methacrylic acid, maleic acid and maleic anhydride, and particularly preferably at least one selected from maleic acid and maleic anhydride. preferable.
  • the olefin component constituting the modified polyolefin resin examples include alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene.
  • the modified polyolefin resin may be a copolymer having two or more of the above olefin components. Further, the modified polyolefin resin may contain other copolymerization components such as vinyl acetate and norbornenes in addition to the above-mentioned olefin components.
  • the modified polyolefin resin is preferably a modified polypropylene resin, more preferably an acid-modified polypropylene resin, and even more preferably a maleine oxide polypropylene resin or anhydrous maleine oxide polypropylene resin.
  • the modified polyolefin resin is a chlorinated polyolefin resin.
  • the chlorine content is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total mass of the chlorinated polyolefin resin.
  • the chlorine content is preferably 50% by mass or less with respect to the total mass of the chlorinated polyolefin resin.
  • the modified polyolefin resin is particularly preferably an acid-modified chlorinated polyolefin resin.
  • the modified polyolefin resin is preferably maleic anhydride-chlorinated polyolefin resin or maleic anhydride-chlorinated polyolefin resin.
  • the main chain of the modified polyolefin resin preferably has a graft chain containing a carboxy group at the end.
  • a graft chain is a linking group that binds to the main chain of a modified polyolefin resin and a group that has a carboxy group at the end of the linking group.
  • the linking group constituting the graft chain is preferably an alkylene group having 1 to 10 carbon atoms. That is, in a preferred embodiment of the present invention, the modified polyolefin resin has a main chain skeleton of polyolefin, and a —R—COOH group (R represents an alkylene group having 1 to 10 carbon atoms) is grafted onto the main chain skeleton. It is a graft polymer.
  • the modified polyolefin resin may be an aqueous-based modified polyolefin resin, but is preferably an organic solvent-based modified polyolefin resin.
  • the resin composition forming the resin layer containing the modified polyolefin resin contains an organic solvent.
  • the organic solvent used in this case include an aliphatic organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, an ester-based organic solvent, an ether-based organic solvent, an aromatic organic solvent, and a cyclic alcan-based organic solvent. it can.
  • the organic solvent is preferably an aromatic organic solvent or a cyclic alkane-based organic solvent.
  • the aromatic organic solvent examples include benzene, toluene, xylene and the like.
  • the cyclic alkane-based organic solvent examples include cyclohexane, cyclopentane, cyclooctane, and methylcyclohexane.
  • the resin layer may contain an aromatic organic solvent or a cyclic alkane-based organic solvent.
  • modified polyolefin resin a commercially available product may be used.
  • examples of commercially available products include Hardlen TD-15B manufactured by Toyobo Co., Ltd., Hardlen F-2MB manufactured by Toyobo Co., Ltd., Arrow Base SB-1230N manufactured by Unitika Ltd., and the like.
  • the resin layer may further contain an adhesion aid in addition to the modified polyolefin resin.
  • the adhesion aid include a compound containing at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an oxazoline group, an amino group and a silanol group, and an organic silicon compound.
  • the adhesion aid is preferably at least one selected from a compound containing an isocyanate group (isocyanate compound) and an organosilicon compound, and more preferably an isocyanate compound. That is, in one embodiment of the present invention, the resin layer contains an isocyanate compound.
  • the organosilicon compound include a silane coupling agent condensate and a silane coupling agent.
  • the interlayer adhesion between the fiber layer and the resin layer can be enhanced, and when the resin layer is bonded to another resin film, the laminated sheet becomes the other resin film. On the other hand, excellent adhesion can be exhibited.
  • Examples of the isocyanate compound include polyfunctional isocyanates which are polyisocyanate compounds or more.
  • Specific examples of the polyisocyanate compound include aromatic polyisocyanates having 6 to 20 carbon atoms excluding carbon in the NCO group, aliphatic polyisocyanates having 2 to 18 carbon atoms, and 6 to 15 carbon atoms. Aliphatic polyisocyanates, aralkyl-type polyisocyanates having 8 or more and 15 or less carbon atoms, modified products of these polyisocyanates, and mixtures of two or more of these can be mentioned. Of these, alicyclic polyisocyanates having 6 to 15 carbon atoms, that is, isocyanurates are preferably used.
  • alicyclic polyisocyanate examples include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanatoethyl).
  • IPDI isophorone diisocyanate
  • MDI dicyclohexylmethane-4,4'-diisocyanate
  • cyclohexylene diisocyanate methylcyclohexylene diisocyanate
  • bis (2-isocyanatoethyl examples include -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornandiisocyanate, and 2,6-norbornandiisocyanate.
  • the organosilicon compound examples include a compound having a siloxane structure and a compound that forms a siloxane structure by condensation.
  • a silane coupling agent or a condensate of a silane coupling agent can be mentioned.
  • the silane coupling agent may have a functional group other than the alkoxysilyl group, or may have no other functional group.
  • the functional group other than the alkoxysilyl group include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group, a sulfide group and an isocyanate group.
  • the silane coupling agent used in the present invention is preferably a silane coupling agent containing a methacryloxy group.
  • the silane coupling agent having a methacryloxy group in the molecule include, for example, methacryloxypropylmethyldimethoxysilane, methaloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, and methacryloxypropyltriethoxysilane.
  • examples thereof include 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane.
  • at least one selected from methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane and 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane is preferably used.
  • the silane coupling agent preferably contains three or more alkoxysilyl groups.
  • silanol groups are generated after hydrolysis, and at least a part of silanol groups is present even after the fiber layers are laminated. Since the silanol group is a hydrophilic group, it is possible to improve the adhesion between the resin layer and the fiber layer by increasing the hydrophilicity of the surface of the resin layer on the fiber layer side.
  • the content of the adhesion aid is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the resin layer.
  • the content of the adhesion aid is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total mass of the resin layer.
  • the content of the isocyanate group contained in the resin layer is preferably 0.5 mmol / g or more, more preferably 0.6 mmol / g or more, and 0.8 mmol or more. It is more preferably / g or more, and particularly preferably 0.9 mmol / g or more.
  • the content of the isocyanate group contained in the resin layer is preferably 3.0 mmol / g or less, more preferably 2.5 mmol / g or less, and further preferably 2.0 mmol / g or less. It is preferably 1.5 mmol / g or less, and particularly preferably 1.5 mmol / g or less.
  • the surface of the resin layer on the fiber layer side may be surface-treated.
  • the surface treatment method include corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, flame treatment and the like.
  • the surface treatment is preferably at least one selected from the corona treatment and the plasma discharge treatment.
  • the plasma discharge treatment is preferably a vacuum plasma discharge treatment.
  • the surface of the resin layer on the fiber layer side may form a fine concavo-convex structure. Since the surface of the resin layer on the fiber layer side has a fine concavo-convex structure, the adhesion between the fiber layer and the resin layer can be more effectively enhanced.
  • a treatment step such as a blasting treatment, an embossing treatment, an etching treatment, a corona treatment, or a plasma discharge treatment. Is preferable.
  • a fine concavo-convex structure means a structure in which the number of recesses existing on one straight line having a length of 1 mm drawn at an arbitrary position is 10 or more.
  • the laminated sheet is immersed in ion-exchanged water for 24 hours, and then the fiber layer is peeled off from the resin layer. After that, the surface of the resin layer on the fiber layer side can be measured by scanning with a stylus type surface roughness meter (Surfcoder series manufactured by Kosaka Laboratory Co., Ltd.).
  • the pitch of the unevenness is extremely small on the submicron and nano-order, the number of unevenness can be measured from the observation image of the scanning probe microscope (AFM5000II and AFM5100N manufactured by Hitachi High-Tech Science Co., Ltd.).
  • the resin layer may contain any component other than the above-mentioned components.
  • the optional component include known components used in the field of resin films such as fillers, pigments, dyes, and ultraviolet absorbers.
  • the thickness of the resin layer of the laminated sheet is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 100 ⁇ m or more.
  • the thickness of the resin layer is preferably 5000 ⁇ m or less, more preferably 1000 ⁇ m or less, and even more preferably 500 ⁇ m or less.
  • the thickness of the resin layer may be 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more. Good.
  • the thickness of the resin layer is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 10 ⁇ m or less.
  • the thickness of the resin layer constituting the laminated sheet is measured by cutting out a cross section of the laminated sheet with Ultra Microtome UC-7 (manufactured by JEOL Ltd.) and observing the cross section with an electron microscope, a magnifying glass or visually. Value.
  • the laminated sheet contains a plurality of resin layers, the total thickness of the resin layers is preferably within the above range.
  • the fiber layer contains fibrous cellulose having a fiber width of 1000 nm or less.
  • the content of the fine fibrous cellulose contained in the fiber layer is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass or more, based on the total mass of the fiber layer. Is even more preferable.
  • the content of the fine fibrous cellulose contained in the fiber layer may be 50% by mass or more.
  • the fiber layer may contain fibrous cellulose having a fiber width of more than 1000 nm.
  • fibrous cellulose having a fiber width of more than 1000 nm is also referred to as coarse cellulose fiber.
  • the content of the coarse cellulose fibers in the fiber layer is preferably 80% by mass or less, more preferably 60% by mass or less, and 40% by mass or less, based on the total mass of the fiber layer. Is even more preferable.
  • the thickness of the fiber layer of the laminated sheet is preferably larger than 20 ⁇ m, more preferably 25 ⁇ m or more, further preferably 30 ⁇ m or more, further preferably 40 ⁇ m or more, still more preferably 50 ⁇ m or more. It is more preferably 60 ⁇ m or more, and particularly preferably 60 ⁇ m or more.
  • the upper limit of the thickness of the fiber layer is not particularly limited, but is preferably 2000 ⁇ m or less, for example.
  • the thickness of the fiber layer can be measured by a stylus type thickness system (Millitron 1202D manufactured by Marl Co., Ltd.).
  • the thickness of the fiber layer constituting the laminated sheet may be obtained by cutting out a cross section of the laminated sheet with Ultra Microtome UC-7 (manufactured by JEOL Ltd.) and observing the cross section with an electron microscope, a magnifying glass or visually.
  • the laminated sheet can further exert a reinforcing effect.
  • the strength of the adherend can be reinforced.
  • the density of the fiber layer is preferably 1.0 g / cm 3 or more, more preferably 1.2 g / cm 3 or more, and even more preferably 1.4 g / cm 3 or more.
  • the density of the fiber layer is preferably 1.7 g / cm 3 or less, more preferably 1.65 g / cm 3 or less, further preferably 1.6 g / cm 3 or less.
  • the density of each fiber layer is preferably within the above range.
  • the density of the fiber layer is calculated from the basis weight and thickness of the fiber layer in accordance with JIS P 8118: 1998.
  • the basis weight of the fiber layer can be calculated by cutting with Ultra Microtome UC-7 (manufactured by JEOL Ltd.) so that only the fiber layer of the laminated sheet remains, and in accordance with JIS P 8124: 2011.
  • the density of the fiber layer is a density containing an optional component other than the fine fibrous cellulose.
  • the fiber layer is preferably a non-porous layer.
  • the fact that the fiber layer is non-porous means that the density of the entire fiber layer is 1.0 g / cm 3 or more.
  • the density of the entire fiber layer is 1.0 g / cm 3 or more, it means that the porosity contained in the fiber layer is suppressed to a predetermined value or less, and it is distinguished from the porous sheet or layer. ..
  • the non-porous nature of the fiber layer is also characterized by a porosity of 15% by volume or less. The porosity of the fiber layer referred to here is simply calculated by the following formula (a).
  • Porosity (volume%) ⁇ 1-B / (M ⁇ A ⁇ t) ⁇ ⁇ 100
  • A is the area of the fiber layer (cm 2 )
  • t is the thickness of the fiber layer (cm)
  • B is the mass of the fiber layer (g)
  • M is the density of cellulose.
  • Fine fibrous cellulose is produced from a fiber raw material containing cellulose.
  • the fiber raw material containing cellulose is not particularly limited, but pulp is preferably used because it is easily available and inexpensive. Examples of pulp include wood pulp, non-wood pulp, and deinked pulp.
  • the wood pulp is not particularly limited, but is, for example, broadleaf kraft pulp (LBKP), coniferous kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), and unbleached kraft pulp (UKP).
  • the non-wood pulp is not particularly limited, and examples thereof include cotton pulp such as cotton linter and cotton lint, and non-wood pulp such as hemp, straw and bagasse.
  • the deinking pulp is not particularly limited, and examples thereof include deinking pulp made from recycled paper.
  • one of the above types may be used alone, or two or more types may be mixed and used.
  • wood pulp and deinked pulp are preferable from the viewpoint of availability.
  • wood pulp long fiber fine fibrous cellulose having a large cellulose ratio and a high yield of fine fibrous cellulose during defibration treatment and a large axial ratio with less decomposition of cellulose in the pulp can be obtained.
  • chemical pulp is more preferable, and kraft pulp and sulfite pulp are further preferable.
  • the fiber raw material containing cellulose for example, cellulose contained in ascidians and bacterial cellulose produced by acetobacter can be used. Further, instead of the fiber raw material containing cellulose, a fiber formed by a linear nitrogen-containing polysaccharide polymer such as chitin or chitosan can also be used.
  • the fiber layer contains fine fibrous cellulose having a fiber width of 1000 nm or less.
  • the fiber width of the fibrous cellulose is more preferably 100 nm or less, and further preferably 8 nm or less.
  • the fiber width of fibrous cellulose can be measured, for example, by observation with an electron microscope.
  • the average fiber width of the fibrous cellulose is, for example, 1000 nm or less.
  • the average fiber width of the fibrous cellulose is, for example, 2 nm or more and 1000 nm or less, more preferably 2 nm or more and 100 nm or less, further preferably 2 nm or more and 50 nm or less, and 2 nm or more and 10 nm or less. Especially preferable.
  • the fibrous cellulose is, for example, monofibrous cellulose.
  • the average fiber width of fibrous cellulose is measured as follows, for example, using an electron microscope. First, an aqueous suspension of fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and this suspension is cast on a hydrophilized carbon film-coated grid to prepare a sample for TEM observation. And. If it contains wide fibers, an SEM image of the surface cast on the glass may be observed. Next, observation is performed using an electron microscope image at a magnification of 1000 times, 5000 times, 10000 times, or 50,000 times depending on the width of the fiber to be observed. However, the sample, observation conditions and magnification should be adjusted so as to satisfy the following conditions.
  • a 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 that intersects the straight line perpendicularly is drawn in the same image, and 20 or more fibers intersect the straight line Y.
  • the fiber length of the fibrous cellulose is not particularly limited, but is preferably 0.1 ⁇ m or more and 1000 ⁇ m or less, more preferably 0.1 ⁇ m or more and 800 ⁇ m or less, and further preferably 0.1 ⁇ m or more and 600 ⁇ m or less. preferable.
  • the fiber length of the fibrous cellulose can be obtained by, for example, image analysis by TEM, SEM, or AFM.
  • the fibrous cellulose preferably has an I-type crystal structure.
  • the ratio of the type I crystal structure to the fine fibrous cellulose is, for example, preferably 30% or more, more preferably 40% or more, and further preferably 50% or more. As a result, even better performance can be expected in terms of heat resistance and low coefficient of linear thermal expansion.
  • the crystallinity is determined by a conventional method from the X-ray diffraction profile measured and the pattern (Seagal et al., Textile Research Journal, Vol. 29, p. 786, 1959).
  • the axial ratio (fiber length / fiber width) of the fibrous cellulose is not particularly limited, but is preferably 20 or more and 10000 or less, and more preferably 50 or more and 1000 or less.
  • the axial ratio is not particularly limited, but is preferably 20 or more and 10000 or less, and more preferably 50 or more and 1000 or less.
  • the fibrous cellulose in this embodiment has, for example, both a crystalline region and a non-crystalline region.
  • the fine fibrous cellulose having both a crystalline region and an amorphous region and having an axial ratio within the above range is realized by a method for producing fine fibrous cellulose described later.
  • the fibrous cellulose of the present invention preferably has an ionic substituent.
  • the ionic substituent can include, for example, either one or both of an anionic group and a cationic group. In this embodiment, it is particularly preferable to have an anionic group as the ionic substituent.
  • anionic group as an ionic substituent examples include a phosphate group or a substituent derived from a phosphorusoxo acid group (sometimes referred to simply as a phosphorusoxo acid group), a carboxy group or a substituent derived from a carboxy group (simply a carboxy group). It is preferably at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group), and at least one selected from a phosphorus oxo acid group and a carboxy group. It is more preferably one kind, and particularly preferably a phosphorusoxo acid group.
  • the phosphate group or the substituent derived from the phosphorus oxo acid group is, for example, a substituent represented by the following formula (1).
  • the phosphorus oxo acid group is, for example, a divalent functional group obtained by removing a hydroxy group from phosphoric acid. Specifically, it is a group represented by -PO 3 H 2.
  • Substituents derived from a phosphorus oxo acid group include substituents such as a salt of a phosphorus oxo acid group and a phosphorus oxo acid ester group.
  • the substituent derived from the phosphoric acid group may be contained in the fibrous cellulose as a group in which the phosphoric acid group is condensed (for example, a pyrophosphate group).
  • the phosphorous acid group may be, for example, a phosphorous acid group (phosphonic acid group), and the substituent derived from the phosphorous acid group is a salt of a phosphorous acid group, a phosphorous acid ester group, or the like. May be good.
  • R is a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched chain hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, and an unsaturated-branched chain hydrocarbon, respectively.
  • n is preferably 1.
  • Examples of the saturated-linear hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and the like, but are not particularly limited.
  • Examples of the saturated-branched chain hydrocarbon group include an i-propyl group and a t-butyl group, but are not particularly limited.
  • Examples of the saturated-cyclic hydrocarbon group include, but are not limited to, a cyclopentyl group, a cyclohexyl group and the like.
  • Examples of the unsaturated-linear hydrocarbon group include a vinyl group, an allyl group and the like, but are not particularly limited.
  • Examples of the unsaturated-branched chain hydrocarbon group include an i-propenyl group and a 3-butenyl group, but the group is not particularly limited.
  • Examples of the unsaturated-cyclic hydrocarbon group include, but are not limited to, a cyclopentenyl group, a cyclohexenyl group and the like.
  • Examples of the aromatic group include a phenyl group and a naphthyl group, but are not particularly limited.
  • the inducing group in R 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 or substituted with respect to the main chain or side chain of the above-mentioned various hydrocarbon groups.
  • the group is mentioned, but is not particularly limited.
  • the number of carbon atoms constituting the main chain of R is not particularly limited, but is preferably 20 or less, and more preferably 10 or less.
  • ⁇ b + is a monovalent or higher cation composed of an organic substance or an inorganic substance.
  • monovalent or higher cations composed of organic substances include aliphatic ammonium or aromatic ammonium
  • examples of monovalent or higher valent cations composed of inorganic substances include alkali metal ions such as sodium, potassium, and lithium.
  • examples thereof include cations of divalent metals such as calcium and magnesium, hydrogen ions, and the like, but the present invention is not particularly limited. These may be applied alone or in combination of two or more.
  • the monovalent or higher cation composed of an organic substance or an inorganic substance is preferably sodium or potassium ion which is hard to yellow when the fiber raw material containing ⁇ is heated and is easily industrially used, but is not particularly limited.
  • ⁇ b + may be an organic onium ion, and in this case, it is particularly preferable that it is an organic ammonium ion.
  • the amount of the ionic substituent introduced into the fibrous cellulose is, for example, 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, and 0.40 mmol / g per 1 g (mass) of the fibrous cellulose. It is more preferably / g or more, and particularly preferably 0.60 mmol / g or more.
  • the amount of the ionic substituent introduced into the fibrous cellulose is preferably 5.20 mmol / g or less, more preferably 3.65 mmol / g or less per 1 g (mass) of the fibrous cellulose, for example, 3 It is more preferably 0.00 mmol / g or less, further preferably 2.50 mmol / g or less, further preferably 2.00 mmol / g or less, and further preferably 1.50 mmol / g or less. It is more preferably 1.00 mmol / g or less, and particularly preferably 1.00 mmol / g or less.
  • the denominator in the unit mmol / g indicates the mass of fibrous cellulose when the counter ion of the ionic substituent is a hydrogen ion (H +).
  • the amount of the ionic substituent introduced into the fibrous cellulose can be measured by, for example, the neutralization titration method.
  • the introduction amount is measured by determining the change in pH while adding an alkali such as an aqueous sodium hydroxide solution to the obtained slurry containing fibrous cellulose.
  • FIG. 2 is a graph showing the relationship between the amount of NaOH added dropwise and the pH of a fibrous cellulose-containing slurry having a phosphoric acid group.
  • the amount of the phosphorus oxo acid group introduced into the fibrous cellulose is measured, for example, as follows. First, the slurry containing fibrous cellulose is treated with a strongly acidic ion exchange resin. If necessary, the defibration treatment similar to the defibration treatment step described later may be performed on the measurement target before the treatment with the strongly acidic ion exchange resin. Next, the change in pH is observed while adding an aqueous sodium hydroxide solution, and a titration curve as shown in the upper part of FIG. 2 is obtained.
  • the titration curve shown in the upper part of FIG. 2 plots the measured pH with respect to the amount of alkali added
  • the titration curve shown in the lower part of FIG. 2 plots the pH with respect to the amount of alkali added.
  • the increment (differential value) (1 / mmol) is plotted.
  • two points are confirmed in which the increment (differential value of pH with respect to the amount of alkali dropped) becomes maximum in the curve plotting the measured pH with respect to the amount of alkali added.
  • the maximum point of the increment obtained first when alkali is added is called the first end point
  • the maximum point of the increment obtained next is called the second end point.
  • the amount of alkali required from the start of titration to the first end point is equal to the amount of first dissociating acid of the fibrous cellulose contained in the slurry used for titration, and the amount of alkali required from the first end point to the second end point.
  • the amount is equal to the amount of the second dissociating acid of the fibrous cellulose contained in the slurry used for the titration, and the amount of alkali required from the start to the second end point of the titration is the fibrous cellulose contained in the slurry used for the titration. Is equal to the total amount of dissociated acid.
  • the value obtained by dividing the amount of alkali required from the start of titration to the first end point by the solid content (g) in the slurry to be titrated is the amount of phosphorus oxo acid group introduced (mmol / g).
  • the amount of phosphorus oxo acid group introduced (or the amount of phosphorus oxo acid group) simply means the amount of the first dissociated acid.
  • the region from the start of titration to the first end point is referred to as a first region, and the region from the first end point to the second end point is referred to as a second region.
  • the amount of weakly acidic groups in the phosphoric acid group is apparently It decreases, and the amount of alkali required for the second region is smaller than the amount of alkali required for the first region.
  • the amount of strongly acidic groups in the phosphorus oxo acid group is the same as the amount of phosphorus atoms regardless of the presence or absence of condensation.
  • the weakly acidic group does not exist in the phosphorous acid group, so that the amount of alkali required for the second region is reduced or the amount of alkali required for the second region is reduced. May be zero. In this case, there is only one point on the titration curve where the pH increment is maximized.
  • the denominator of the above-mentioned phosphorus oxo acid group introduction amount indicates the mass of the acid-type fibrous cellulose
  • the phosphorus oxo acid group amount of the acid-type fibrous cellulose (hereinafter referred to as the phosphorus oxo acid group amount). (Called (acid type))).
  • the denominator is converted to the mass of fibrous cellulose when the cation C is a counterion.
  • Phosphoric acid group amount (C type) Phosphoric acid group amount (acid type) / ⁇ 1+ (W-1) x A / 1000 ⁇ A [mmol / g]: Total amount of anion derived from phosphoric acid group of fibrous cellulose (total amount of dissociated acid of phosphoric acid group) W: Formulated amount of cation C per valence (for example, Na is 23, Al is 9)
  • FIG. 3 is a graph showing the relationship between the amount of NaOH added dropwise to the dispersion liquid containing fibrous cellulose having a carboxy group as an ionic substituent and the pH.
  • the amount of the carboxy group introduced into the fibrous cellulose is measured, for example, as follows. First, the dispersion liquid containing fibrous cellulose is treated with a strongly acidic ion exchange resin. If necessary, the defibration treatment similar to the defibration treatment step described later may be performed on the measurement target before the treatment with the strongly acidic ion exchange resin. Next, the change in pH is observed while adding an aqueous sodium hydroxide solution, and a titration curve as shown in the upper part of FIG. 3 is obtained.
  • the titration curve shown in the upper part of FIG. 3 plots the measured pH with respect to the amount of alkali added
  • the titration curve shown in the lower part of FIG. 3 plots the pH with respect to the amount of alkali added.
  • the increment (differential value) (1 / mmol) is plotted.
  • the increment (differential value of pH with respect to the amount of alkali dropped) became the maximum, and this maximum point was the first. Called one end point.
  • the region from the start of titration to the first end point in FIG. 3 is referred to as a first region.
  • the amount of alkali required in the first region is equal to the amount of carboxy groups in the dispersion used for titration. Then, the amount of alkali (mmol) required in the first region of the titration curve is divided by the solid content (g) in the dispersion liquid containing the fibrous cellulose to be titrated, so that the amount of carboxy group introduced (mmol). / G) is calculated.
  • the denominator of the above-mentioned carboxy group introduction amount (mmol / g) is the mass of the acid-type fibrous cellulose
  • the carboxy group amount of the acid-type fibrous cellulose (hereinafter, the carboxy group amount (acid type)). ) Is shown.
  • the counterion of the carboxy group is replaced with an arbitrary cation C so as to have a charge equivalent
  • the denominator is converted to the mass of fibrous cellulose when the cation C is a counterion.
  • the amount of carboxy groups (hereinafter, the amount of carboxy groups (C type)) possessed by the fibrous cellulose in which the cation C is a counter ion can be determined.
  • Carboxylic acid group amount (C type) Carboxylic acid group amount (acid type) / ⁇ 1+ (W-1) x (carboxyl group amount (acid type)) / 1000 ⁇ W: Formulated amount of cation C per valence (for example, Na is 23, Al is 9)
  • the amount of ionic substituents In the measurement of the amount of ionic substituents by the titration method, if the amount of one drop of sodium hydroxide aqueous solution is too large, or if the titration interval is too short, the amount of ionic substituents will be lower than it should be. It may not be obtained.
  • As an appropriate dropping amount and titration interval for example, it is desirable to titrate 10 to 50 ⁇ L of a 0.1 N sodium hydroxide aqueous solution every 5 to 30 seconds.
  • the process for producing fine fibrous cellulose preferably includes an ionic substituent introduction step, and examples of the ionic substituent introduction step include a phosphorus oxo acid group introduction step.
  • the phosphorus oxo acid group introduction step at least one compound (hereinafter, also referred to as “compound A”) selected from compounds capable of introducing a phosphorus oxo acid group by reacting with a hydroxyl group of a fiber raw material containing cellulose is introduced into cellulose. It is a step of acting on a fiber raw material containing. By this step, a phosphorus oxo acid group-introduced fiber can be obtained.
  • the reaction between the fiber raw material containing cellulose and Compound A is carried out in the presence of at least one selected from urea and its derivatives (hereinafter, also referred to as “Compound B”). You may.
  • the reaction of the fiber raw material containing cellulose with the compound A may be carried out in the absence of the compound B.
  • the method of allowing the compound A to act on the fiber raw material in the coexistence with the compound B there is a method of mixing the compound A and the compound B with the fiber raw material in a dry state, a wet state or a slurry state.
  • a fiber raw material in a dry state or a wet state since the reaction uniformity is high, it is preferable to use a fiber raw material in a dry state or a wet state, and it is particularly preferable to use a fiber raw material in a dry state.
  • the form of the fiber raw material is not particularly limited, but is preferably cotton-like or thin sheet-like, for example.
  • Examples of the compound A and the compound B include a method of adding the compound A and the compound B to the fiber raw material in the form of a powder or a solution dissolved in a solvent, or in a state of being heated to a melting point or higher and melted.
  • a method of adding the compound A and the compound B to the fiber raw material in the form of a powder or a solution dissolved in a solvent, or in a state of being heated to a melting point or higher and melted are examples of the compound A and the compound B.
  • the reaction is highly homogeneous, it is preferable to add the mixture in the form of a solution dissolved in a solvent, particularly in the form of an aqueous solution.
  • the compound A and the compound B may be added to the fiber raw material at the same time, may be added separately, or may be added as a mixture.
  • the method for adding the compound A and the compound B is not particularly limited, but when the compound A and the compound B are in the form of a solution, the fiber raw material may be immersed in the solution to absorb the liquid and then taken out, or the fiber raw material may be taken out. The solution may be dropped into the water. Further, the required amounts of compound A and compound B may be added to the fiber raw material, or after the excess amounts of compound A and compound B are added to the fiber raw material, respectively, the surplus compound A and compound B are added by pressing or filtering. It may be removed.
  • the compound A used in this embodiment may be a compound having a phosphorus atom and capable of forming an ester bond with cellulose, and may be phosphoric acid or a salt thereof, phosphoric acid or a salt thereof, dehydration condensed phosphoric acid or a salt thereof.
  • Examples thereof include salts and anhydrous phosphoric acid (diphosphorus pentoxide), but the present invention is not particularly limited.
  • the phosphoric acid those having various puritys can be used, and for example, 100% phosphoric acid (normal phosphoric acid) or 85% phosphoric acid can be used.
  • Examples of phosphorous acid include 99% phosphorous acid (phosphonic acid).
  • the dehydration-condensed phosphoric acid is one in which two or more molecules of phosphoric acid are condensed by a dehydration reaction, and examples thereof include pyrophosphoric acid and polyphosphoric acid.
  • Phosphates, phosphorous acids, dehydration-condensed phosphates include phosphoric acid, phosphorous acid or dehydration-condensed phosphoric acid lithium salts, sodium salts, potassium salts, ammonium salts, etc. It can be a sum.
  • sodium phosphate and sodium phosphate Salt potassium salt of phosphoric acid, ammonium or phosphite of phosphoric acid, sodium salt of phosphite, potassium salt of phosphite, ammonium salt of phosphite are preferred, phosphoric acid, sodium dihydrogen phosphate, Disodium hydrogen phosphate, ammonium dihydrogen phosphate, or phosphoric acid and sodium phosphite are more preferred.
  • the amount of compound A added to the fiber raw material is not particularly limited, but for example, when the amount of compound A added is converted to the phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5% by mass or more. It is preferably 100% by mass or less, more preferably 1% by mass or more and 50% by mass or less, and further preferably 2% by mass or more and 30% by mass or less.
  • the amount of phosphorus atoms added to the fiber raw material within the above range, the yield of fine fibrous cellulose can be further improved.
  • the addition amount of phosphorus atoms to the fiber raw material to be equal to or less than the above upper limit value, the effect of improving the yield and the cost can be balanced.
  • Compound B used in this embodiment is at least one selected from urea and its derivatives as described above.
  • Examples of compound B include urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like.
  • compound B is preferably used as an aqueous solution. Further, from the viewpoint of further improving the uniformity of the reaction, it is preferable to use an aqueous solution in which both compound A and compound B are dissolved.
  • the amount of compound B added to the fiber raw material is not particularly limited, but is preferably 1% by mass or more and 500% by mass or less, and more preferably 10% by mass or more and 400% by mass or less. It is more preferably 100% by mass or more and 350% by mass or less.
  • amides or amines may be contained in the reaction system in addition to compound B.
  • amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like.
  • amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine and the like.
  • triethylamine in particular is known to act as a good reaction catalyst.
  • the heat treatment temperature it is preferable to select a temperature at which a phosphorus oxo acid group can be efficiently introduced while suppressing the thermal decomposition and hydrolysis reaction of the fiber.
  • the heat treatment temperature is, for example, preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 130 ° C. or higher and 200 ° C. or lower.
  • equipment having various heat media can be used for the heat treatment, for example, a stirring drying device, a rotary drying device, a disk drying device, a roll type heating device, a plate type heating device, a fluidized layer drying device, and a band.
  • a mold drying device, a filtration drying device, a vibration flow drying device, an air flow drying device, a vacuum drying device, an infrared heating device, a far infrared heating device, a microwave heating device, and a high frequency drying device can be used.
  • compound A is added to a thin sheet-shaped fiber raw material by a method such as impregnation and then heated, or the fiber raw material and compound A are heated while kneading or stirring with a kneader or the like.
  • a method such as impregnation and then heated, or the fiber raw material and compound A are heated while kneading or stirring with a kneader or the like.
  • This makes it possible to suppress uneven concentration of the compound A in the fiber raw material and more uniformly introduce the phosphorus oxo acid group onto the surface of the cellulose fiber contained in the fiber raw material. This is because when the water molecules move to the surface of the fiber raw material due to drying, the dissolved compound A is attracted to the water molecules by the surface tension and also moves to the surface of the fiber raw material (that is, the concentration unevenness of the compound A is caused. It is considered that this is due to the fact that it can be suppressed.
  • the heating device used for the heat treatment always keeps the water content retained by the slurry and the water content generated by the dehydration condensation (phosphate esterification) reaction between the compound A and the hydroxyl group contained in the cellulose or the like in the fiber raw material. It is preferable that the device can be discharged to the outside of the device system. Examples of such a heating device include a ventilation type oven and the like. By constantly discharging the water in the apparatus system, it is possible to suppress the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the phosphate esterification, and also to suppress the acid hydrolysis of the sugar chain in the fiber. it can. Therefore, it is possible to obtain fine fibrous cellulose having a high axial ratio.
  • the heat treatment time is preferably 1 second or more and 300 minutes or less, more preferably 1 second or more and 1000 seconds or less, and 10 seconds or more and 800 seconds or less after the water is substantially removed from the fiber raw material. Is more preferable.
  • the amount of the phosphorus oxo acid group introduced can be within a preferable range by setting the heating temperature and the heating time within an appropriate range.
  • the phosphorus oxo acid group introduction step may be performed at least once, but may be repeated twice or more. By performing the phosphorus oxo acid group introduction step two or more times, many phosphorus oxo acid groups can be introduced into the fiber raw material.
  • the amount of the phosphorus oxo acid group introduced into the fiber raw material is, for example, 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, and 0.50 mmol / g / g per 1 g (mass) of fine fibrous cellulose. It is more preferably g or more, and particularly preferably 1.00 mmol / g or more.
  • the amount of the phosphorus oxo acid group introduced into the fiber raw material is preferably 5.20 mmol / g or less, more preferably 3.65 mmol / g or less per 1 g (mass) of fine fibrous cellulose, for example. It is more preferably 00 mmol / g or less.
  • the amount of the phosphorus oxo acid group introduced within the above range it is possible to facilitate the miniaturization of the fiber raw material and enhance the stability of the fine fibrous cellulose. Further, by setting the amount of the phosphorus oxo acid group introduced within the above range, a laminated sheet having excellent interlayer adhesion between the fiber layer and the resin layer and capable of exhibiting good adhesion to other resin films can be obtained. It will be easier. Further, by setting the amount of the phosphorus oxo acid group introduced within the above range, the transparency and appearance of the laminated sheet can be more effectively enhanced.
  • the process for producing fine fibrous cellulose may include, for example, a carboxy group introduction step as an ionic substituent introduction step.
  • the carboxy group introduction step has an oxidation treatment such as ozone oxidation, oxidation by the Fenton method, TEMPO oxidation treatment, a compound having a group derived from carboxylic acid or a derivative thereof, or a group derived from carboxylic acid with respect to the fiber raw material containing cellulose. This is done by treating with an acid anhydride of the compound or a derivative thereof.
  • the compound having a group derived from a carboxylic acid is not particularly limited, but for example, a dicarboxylic acid compound such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid, itaconic acid, citric acid, aconitic acid and the like.
  • Examples include tricarboxylic acid compounds.
  • the derivative of the compound having a group derived from a carboxylic acid is not particularly limited, and examples thereof include an imide of an acid anhydride of a compound having a carboxy group and a derivative of an acid anhydride of a compound having a carboxy group.
  • the imide of the acid anhydride of the compound having a carboxy group is not particularly limited, and examples thereof include an imide of a dicarboxylic acid compound such as maleimide, succinateimide, and phthalateimide.
  • the acid anhydride of the compound having a group derived from carboxylic acid is not particularly limited, but for example, a dicarboxylic acid compound such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. Acid anhydride can be mentioned.
  • the derivative of the acid anhydride of the compound having a group derived from carboxylic acid is not particularly limited, but for example, a compound having a carboxy group such as dimethylmaleic acid anhydride, diethylmaleic acid anhydride, diphenylmaleic acid anhydride and the like. Examples thereof include those in which at least a part of the hydrogen atom of the acid anhydride is substituted with a substituent such as an alkyl group or a phenyl group.
  • the aldehyde generated in the oxidation process can be efficiently oxidized to the carboxy group.
  • the TEMPO oxidation treatment may be carried out under the condition that the pH is 10 or more and 11 or less. Such a treatment is also referred to as an alkaline TEMPO oxidation treatment.
  • the alkaline TEMPO oxidation treatment can be carried out, for example, by adding a nitroxy radical such as TEMPO as a catalyst, sodium bromide as a co-catalyst, and sodium hypochlorite as an oxidizing agent to pulp as a fiber raw material. ..
  • the amount of carboxy group introduced into fibrous cellulose varies depending on the type of substituent, but for example, when a carboxy group is introduced by TEMPO oxidation, it may be 0.10 mmol / g or more per 1 g (mass) of fine fibrous cellulose. It is preferably 0.20 mmol / g or more, more preferably 0.40 mmol / g or more, and particularly preferably 0.60 mmol / g or more.
  • the amount of the carboxy group introduced into the fibrous cellulose is preferably 3.65 mmol / g or less, more preferably 3.00 mmol / g or less, and further preferably 2.50 mmol / g or less.
  • the substituent when it is a carboxymethyl group, it may be 5.8 mmol / g or less per 1 g (mass) of fine fibrous cellulose.
  • a washing step can be performed on the ionic substituent-introduced fiber, if necessary.
  • the washing step is performed by washing the ionic substituent-introduced fiber with, for example, water or an organic solvent. Further, the cleaning step may be performed after each step described later, and the number of cleanings performed in each cleaning step is not particularly limited.
  • an alkali treatment may be performed on the fiber raw material between the step of introducing an ionic substituent and the step of defibration treatment described later.
  • the alkaline treatment method is not particularly limited, and examples thereof include a method of immersing the ionic substituent-introduced fiber in an alkaline solution.
  • the alkaline compound contained in the alkaline solution is not particularly limited, and may be an inorganic alkaline compound or an organic alkaline compound.
  • sodium hydroxide or potassium hydroxide is preferably used as the alkaline compound because of its high versatility.
  • the solvent contained in the alkaline solution may be either water or an organic solvent.
  • the solvent contained in the alkaline solution is preferably a polar solvent containing water or a polar organic solvent exemplified by alcohol, and more preferably an aqueous solvent containing at least water.
  • an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is preferable because of its high versatility.
  • the temperature of the alkaline solution in the alkaline treatment step is not particularly limited, but is preferably 5 ° C. or higher and 80 ° C. or lower, and more preferably 10 ° C. or higher and 60 ° C. or lower.
  • the immersion time of the ionic substituent-introduced fiber in the alkaline solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or more and 30 minutes or less, and more preferably 10 minutes or more and 20 minutes or less.
  • the amount of the alkaline solution used in the alkaline treatment is not particularly limited, but is preferably 100% by mass or more and 100,000% by mass or less, and 1000% by mass or more and 10000% by mass or less, based on the absolute dry mass of the ionic substituent-introduced fiber. The following is more preferable.
  • the ionic substituent introduction fiber may be washed with water or an organic solvent after the ionic substituent introduction step and before the alkali treatment step. After the alkali treatment step and before the defibration treatment step, it is preferable to wash the alkali-treated ionic substituent-introduced fiber with water or an organic solvent from the viewpoint of improving handleability.
  • the fiber raw material may be subjected to acid treatment between the step of introducing an ionic substituent and the defibration treatment step described later.
  • the ionic substituent introduction step, the acid treatment, the alkali treatment, and the defibration treatment may be performed in this order.
  • the method of acid treatment is not particularly limited, and examples thereof include a method of immersing the fiber raw material in an acidic liquid containing an acid.
  • the concentration of the acidic liquid used is not particularly limited, but is preferably, for example, 10% by mass or less, and more preferably 5% by mass or less.
  • the pH of the acidic liquid used is not particularly limited, but is preferably 0 or more and 4 or less, and more preferably 1 or more and 3 or less.
  • an inorganic acid, a sulfonic acid, a carboxylic acid or the like can be used.
  • Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chloric acid, chloric acid, perchloric acid, phosphoric acid, boric acid and the like.
  • Examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like.
  • Examples of the carboxylic acid include formic acid, acetic acid, citric acid, gluconic acid, lactic acid, oxalic acid, tartaric acid and the like. Among these, it is particularly preferable to use hydrochloric acid or sulfuric acid.
  • the temperature of the acid solution in the acid treatment is not particularly limited, but is preferably 5 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower.
  • the immersion time in the acid solution in the acid treatment is not particularly limited, but is preferably 5 minutes or more and 120 minutes or less, and more preferably 10 minutes or more and 60 minutes or less.
  • the amount of the acid solution used in the acid treatment is not particularly limited, but is preferably 100% by mass or more and 100,000% by mass or less, and 1000% by mass or more and 10,000% by mass or less, for example, with respect to the absolute dry mass of the fiber raw material. Is more preferable.
  • Fine fibrous cellulose can be obtained by defibrating the ionic substituent-introduced fiber in the defibration treatment step.
  • a defibration treatment apparatus can be used.
  • the defibrating apparatus is not particularly limited, but for example, a high-speed defibrator, a grinder (stone mill type crusher), a high-pressure homogenizer or an ultra-high pressure homogenizer, a high-pressure collision type crusher, a ball mill, a bead mill, a disc type refiner, a conical refiner, and a biaxial A kneader, a vibration mill, a homomixer under high speed rotation, an ultrasonic disperser, or a beater can be used.
  • a high-speed defibrator a grinder (stone mill type crusher), a high-pressure homogenizer or an ultra-high pressure homogenizer, a high-pressure collision type crusher, a ball mill, a bead mill, a disc type refiner, a conical refiner, and a biaxial A kneader, a vibration mill, a homomixer under high speed rotation, an ultrasonic disperser, or a beater can be used
  • a high-speed defibrator a high-pressure homogenizer, and an ultra-high-pressure homogenizer, which are less affected by crushed media and have less risk of contamination.
  • the defibration treatment step for example, it is preferable to dilute the ionic substituent-introduced fiber with a dispersion medium to form a slurry.
  • a dispersion medium one or more selected from water and an organic solvent such as a polar organic solvent can be used.
  • the polar organic solvent is not particularly limited, but for example, alcohols, polyhydric alcohols, ketones, ethers, esters, aprotic polar solvents and the like are preferable.
  • alcohols include methanol, ethanol, isopropanol, n-butanol, isobutyl alcohol and the like.
  • polyhydric alcohols include ethylene glycol, propylene glycol, glycerin and the like.
  • ketones examples include acetone, methyl ethyl ketone (MEK) and the like.
  • ethers include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monon-butyl ether, propylene glycol monomethyl ether and the like.
  • esters include ethyl acetate, butyl acetate and the like.
  • the aprotic polar solvent examples include dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP) and the like.
  • the solid content concentration of fine fibrous cellulose during the defibration treatment can be set as appropriate.
  • the slurry obtained by dispersing the ionic substituent-introduced fiber in a dispersion medium may contain a solid content such as urea having a hydrogen bond property.
  • a fine fibrous cellulose dispersion (fine fibrous cellulose-containing slurry) can be obtained by the method described above. Such a dispersion may be diluted with water to the desired concentration. Moreover, you may mix arbitrary components as described later.
  • the fiber layer may contain an arbitrary component other than fine fibrous cellulose.
  • the optional component include a hydrophilic polymer, a hydrophilic low molecule, and an organic ion.
  • the hydrophilic polymer is preferably a hydrophilic oxygen-containing organic compound (however, the above-mentioned cellulose fibers are excluded).
  • the oxygen-containing organic compound is preferably non-fibrous, and such non-fibrous oxygen-containing organic compound does not include fine fibrous cellulose or thermoplastic resin fiber.
  • hydrophilic polymer examples include polyethylene glycol, polyethylene oxide, casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol (acetoacetylated polyvinyl alcohol, etc.), polyethylene oxide, polyvinylpyrrolidone, polyvinylmethyl ether, and poly.
  • examples thereof include acrylates, acrylic acid alkyl ester copolymers, urethane copolymers, and cellulose derivatives (hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose, etc.).
  • hydrophilic small molecule examples include glycerin, sorbitol, ethylene glycol and the like.
  • polyethylene glycol, polyethylene oxide, glycerin, and sorbitol are preferable from the viewpoint of improving the strength, density, chemical resistance, etc. of the fiber layer, and at least one selected from polyethylene glycol and polyethylene oxide is more preferable. It is preferably polyethylene glycol, more preferably polyethylene glycol.
  • the hydrophilic polymer is preferably an organic compound polymer having a weight average molecular weight of 50,000 or more and 8 million or less.
  • the hydrophilic small molecule may be a small molecule having a molecular weight of less than 1000.
  • the content of the hydrophilic polymer or the hydrophilic low molecule contained in the fiber layer is preferably 1% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass, based on the total mass of the fiber layer. It is more preferably mass% or more.
  • the content of the hydrophilic polymer or the hydrophilic low molecule contained in the fiber layer is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total mass of the fiber layer. ..
  • Examples of the organic ion include tetraalkylammonium ion and tetraalkylphosphonium ion.
  • Examples of the tetraalkylammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tributylmethylammonium ion, and lauryltrimethyl.
  • Examples thereof include ammonium ion, cetyltrimethylammonium ion, stearyltrimethylammonium ion, octyldimethylethylammonium ion, lauryldimethylethylammonium ion, didecyldimethylammonium ion, lauryldimethylbenzylammonium ion and tributylbenzylammonium ion.
  • Examples of the tetraalkylphosphonium ion include tetramethylphosphonium ion, tetraethylphosphonium ion, tetrapropylphosphonium ion, tetrabutylphosphonium ion, and lauryltrimethylphosphonium ion. Further, examples of the tetrapropyl onium ion and the tetrabutyl onium ion include tetra n-propyl onium ion and tetra n-butyl onium ion, respectively.
  • an antifoaming agent for example, phenoxyethanol
  • a lubricant for example, ethylene glycol
  • an ultraviolet absorber for example, ethylene glycol
  • a dye for example, ethylene glycol
  • a pigment for example, ethylene glycol
  • a stabilizer for example, ethylene glycol
  • a surfactant for example, phenoxyethanol
  • the method for producing a laminated sheet of the present invention includes a step of forming a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less and a step of applying a resin composition containing a modified polyolefin resin on the fiber layer. Is preferable. Further, the method for producing a laminated sheet of the present invention includes a step of applying a fine fibrous cellulose dispersion liquid containing fibrous cellulose having a fiber width of 1000 nm or less on a resin layer containing a modified polyolefin resin. You may.
  • a resin composition containing a modified polyolefin resin When applying a resin composition containing a modified polyolefin resin on a fiber layer or forming a modified polyolefin resin, a resin composition containing a modified polyolefin resin is applied, a coating film is formed, and then a drying step is performed. It is preferable to provide it. By providing such a drying step, heat is applied to the coating film containing the modified polyolefin resin, and the modified component of the modified polyolefin resin forms a crosslinked structure with the hydroxyl group and the like contained in the fine fibrous cellulose of the fiber layer. Conceivable.
  • the formation of the crosslinked structure of the modified component and the fine fibrous cellulose of the fiber layer may be, for example, a crosslinked structure via an adhesion aid.
  • a method for manufacturing a laminated sheet in addition to the method described above, a method in which a resin layer is placed on a fiber layer and heat-pressed can also be mentioned. Another method is to install a fiber layer in a mold for injection molding, inject a heated and melted resin into the mold, and bond the resin layer to the fiber layer.
  • the step of forming the fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less is a step of applying a fine fibrous cellulose dispersion liquid (fine fibrous cellulose-containing slurry) on a base material or a fine fibrous cellulose dispersion liquid. It is preferable to include a step of making paper. Further, when a fine fibrous cellulose dispersion liquid containing fibrous cellulose having a fiber width of 1000 nm or less is coated on the resin layer containing the modified polyolefin resin, the base material is changed to the resin layer and the coating method described later is performed. May be adopted.
  • the fine fibrous cellulose dispersion liquid fine fibrous cellulose-containing slurry
  • the fine fibrous cellulose dispersion liquid is applied on the base material, and this is applied.
  • This is a step of obtaining a sheet by peeling the fine fibrous cellulose-containing sheet formed by drying the material from the base material.
  • the concentration of the fine fibrous cellulose dispersion to be coated is not particularly limited, but is preferably 0.05% by mass or more and 5% by mass or less.
  • the quality of the base material used in the coating process is not particularly limited, but a material having higher wettability to the fine fibrous cellulose dispersion may suppress shrinkage of the sheet during drying, but is formed after drying. It is preferable to select a sheet that can be easily peeled off.
  • a resin plate or a metal plate is preferable, but it is not particularly limited.
  • resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates and polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates and iron plates, and those whose surfaces are oxidized, stainless steel.
  • a plate, brass plate, etc. can be used.
  • the viscosity of the fine fibrous cellulose dispersion when the viscosity of the fine fibrous cellulose dispersion is low and it develops on the base material, it is used for blocking on the base material in order to obtain a fine fibrous cellulose-containing sheet having a predetermined thickness and basis weight.
  • the frame may be fixed and used.
  • the quality of the dammed frame is not particularly limited, but it is preferable to select one in which the end portion of the sheet that adheres after drying can be easily peeled off. Of these, those obtained by molding a resin plate or a metal plate are preferable, but are not particularly limited.
  • resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates and polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates and iron plates, and those whose surfaces are oxidized, stainless steel.
  • a molded plate, brass plate, or the like can be used.
  • a coating machine for applying the fine fibrous cellulose dispersion for example, a bar coater, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used.
  • a bar coater, a die coater, a curtain coater, and a spray coater are preferable because the thickness can be made more uniform.
  • the coating temperature is not particularly limited, but is preferably 20 ° C. or higher and 45 ° C. or lower.
  • the coating temperature is at least the above lower limit value, the fine fibrous cellulose dispersion liquid can be easily coated, and when it is at least the above upper limit value, volatilization of the dispersion medium during coating can be suppressed.
  • the coating step it is preferable to coat the fine fibrous cellulose dispersion so that the finished basis weight of the sheet is 10 g / m 2 or more and 100 g / m 2 or less.
  • the basis weight is within the above range, a fiber layer having excellent strength can be obtained.
  • the manufacturing process of the fine fibrous cellulose-containing sheet preferably includes a step of drying the fine fibrous cellulose dispersion coated on the base material.
  • the drying method is not particularly limited, but may be a non-contact drying method or a method of drying while restraining the sheet, and these may be combined.
  • the non-contact drying method is not particularly limited, but a method of heating and drying with hot air, infrared rays, far infrared rays or near infrared rays (heat drying method) and a method of vacuum drying (vacuum drying method) are applied. Can be done.
  • the heat drying method and the vacuum drying method may be combined, but the heat drying method is usually applied. Drying with infrared rays, far infrared rays or near infrared rays can be performed using an infrared device, a far infrared device or a near infrared device, but is not particularly limited.
  • the heating temperature in the heat drying method is not particularly limited, but is preferably 20 ° C. or higher and 150 ° C.
  • the heating temperature is at least the above lower limit value, the dispersion medium can be rapidly volatilized, and when it is at least the above upper limit value, the cost required for heating can be suppressed and the discoloration of fine fibrous cellulose due to heat can be suppressed. ..
  • the obtained fine fibrous cellulose-containing sheet is peeled off from the base material.
  • the base material is a sheet
  • the fine fibrous cellulose-containing sheet and the base material are wound while being laminated to form fine fibers.
  • the fine fibrous cellulose-containing sheet may be peeled off from the process substrate immediately before the use of the cellulose-containing sheet. In this way, a fine fibrous cellulose-containing sheet to be a fiber layer can be obtained.
  • the resin composition containing the modified polyolefin resin is applied to the surface of the fine fibrous cellulose-containing sheet peeled off from the base material. It is preferable to do so. Thereby, the interlayer adhesion between the fiber layer and the resin layer can be further enhanced.
  • the step of manufacturing the fine fibrous cellulose-containing sheet to be the fiber layer may include a step of making a paper of the fine fibrous cellulose dispersion liquid.
  • Examples of the paper machine in the paper making process include continuous paper machines such as a long net type, a circular net type, and an inclined type, and a multi-layer paper making machine combining these.
  • known papermaking such as hand-making may be performed.
  • the fine fibrous cellulose dispersion is filtered on a wire and dehydrated to obtain a wet paper sheet, which is then pressed and dried to obtain the sheet.
  • concentration of the fine fibrous cellulose dispersion is not particularly limited, but is preferably 0.05% by mass or more and 5% by mass or less.
  • the filter cloth for filtration is not particularly limited, but it is important that the fine fibrous cellulose does not pass through and the filtration rate does not become too slow.
  • a filter cloth is not particularly limited, but a sheet made of an organic polymer, a woven fabric, or a porous membrane is preferable.
  • the organic polymer is not particularly limited, but non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, and polytetrafluoroethylene (PTFE) are preferable. Specific examples thereof include a porous membrane of polytetrafluoroethylene having a pore size of 0.1 ⁇ m or more and 20 ⁇ m or less, for example, 1 ⁇ m, polyethylene terephthalate having a pore diameter of 0.1 ⁇ m or more and 20 ⁇ m or less, for example, 1 ⁇ m, or a polyethylene woven fabric, but the present invention is not particularly limited.
  • non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, and polytetrafluoroethylene (PTFE) are preferable. Specific examples thereof include a porous membrane of polytetrafluoroethylene having a pore size of 0.1 ⁇ m or more and 20 ⁇ m or less, for example, 1 ⁇ m, poly
  • the method for producing a sheet from the fine fibrous cellulose dispersion is not particularly limited, and examples thereof include a method using the production apparatus described in WO2011 / 013567.
  • This manufacturing apparatus discharges the fine fibrous cellulose dispersion liquid onto the upper surface of the endless belt, and squeezes the dispersion medium from the discharged fine fibrous cellulose dispersion liquid to generate a web, and the web is dried. It has a drying section to produce a fiber sheet.
  • An endless belt is arranged from the watering section to the drying section, and the web generated in the watering section is conveyed to the drying section while being placed on the endless belt.
  • the dehydration method that can be used in the present invention is not particularly limited, and examples thereof include a dehydration method that is usually used in the production of paper.
  • the drying method is not particularly limited, and examples thereof include methods used in the production of paper.
  • a cylinder dryer, a yankee dryer, hot air drying, a near infrared heater, an infrared heater and the like are preferable.
  • the present invention may relate to a laminated body formed by laminating the above-mentioned laminated sheet and an adherend.
  • the adherend is arranged on the resin layer side of the laminated sheet, and in such a case, the resin layer in the laminated sheet may function as an adhesive layer.
  • the adherend include an organic film (hereinafter, also referred to as an organic layer) and an inorganic film (hereinafter, also referred to as an inorganic layer).
  • the laminated body of the present invention is preferably a laminated body formed by laminating the above-mentioned laminated sheet and an organic film.
  • the organic film include a resin film, a resin plate, and a resin molded product. That is, one embodiment of the present invention is a laminate obtained by laminating the above-mentioned laminated sheet and a resin film, and the resin film is arranged on the resin layer side of the laminated sheet.
  • a resin film, a resin plate, and a resin molded product are layers containing a natural resin or a synthetic resin as a main component.
  • the main component refers to a component contained in an amount of 50% by mass or more with respect to the total mass of the resin film.
  • the content of the resin component is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass, based on the total mass of the resin film. % Or more is particularly preferable.
  • the content of the resin component may be 100% by mass with respect to the total mass of the resin film.
  • Examples of the natural resin include rosin-based resins such as rosin, rosin ester, and hydrogenated rosin ester.
  • the synthetic resin examples include polyolefin resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyimide resin, polystyrene resin, acrylic resin and the like.
  • the synthetic resin is preferably a polyolefin resin, and preferably has at least one selected from a polyethylene resin and a polypropylene resin.
  • the polyolefin resin is preferably a resin having a cyclic olefin structure.
  • the resin having a cyclic olefin structure may be a cycloolefin resin (COP) or a cycloolefin copolymer. Therefore, in the laminate of the present embodiment, the resin film preferably contains a resin having a cyclic olefin structure.
  • the method for forming the organic layer is not particularly limited, and examples thereof include a coating method, an injection molding method, and a heating and pressurizing method.
  • a coating method it is preferable that the resin composition forming the organic layer is coated on the resin layer of the laminated sheet and then thermosetting or photocuring.
  • the heating and pressurizing method it is preferable to heat-press the resin film in a state of being laminated on the resin layer of the laminated sheet.
  • the heat pressing conditions at this time can be appropriately selected with reference to the glass transition temperature of the resin film and the like.
  • the substance constituting the inorganic layer is not particularly limited, and is, for example, aluminum, silicon, magnesium, zinc, tin, nickel, titanium; these oxides, carbides, nitrides, oxide carbides, oxide nitrides, or oxide carbides. Things; or mixtures thereof. From the viewpoint that high moisture resistance can be stably maintained, silicon oxide, silicon nitride, silicon oxide carbide, silicon nitride, silicon oxide, aluminum oxide, aluminum nitride, aluminum oxide, aluminum nitride, or any of these. The mixture is preferred.
  • the method for forming the inorganic layer is not particularly limited, and examples thereof include a chemical vapor deposition method (CVD) and a physical vapor deposition method (PVD).
  • CVD chemical vapor deposition method
  • PVD physical vapor deposition method
  • Specific examples of the CVD method include plasma CVD using plasma, catalytic chemical vapor deposition (Cat-CVD) in which a material gas is catalytically pyrolyzed using a heating catalyst, and the like.
  • Specific examples of the PVD method include vacuum deposition, ion plating, sputtering and the like.
  • an atomic layer deposition method (Atomic Layer Deposition, ALD) can also be adopted as a method for forming the inorganic layer.
  • ALD is a method of forming a thin film in atomic layer units by alternately supplying the raw material gas of each element constituting the film to be formed to the surface on which the layer is formed.
  • a preferred embodiment of the laminated sheet of the present invention is a laminated sheet that is transparent, has high mechanical strength, and has a small haze. From the viewpoint of utilizing excellent optical characteristics, it is suitable for applications of light-transmitting substrates such as various display devices and various solar cells. It is also suitable for applications such as substrates for electronic devices, parts for home appliances, window materials for various vehicles and buildings, interior materials, exterior materials, and packaging materials.
  • ⁇ Manufacturing example 1> Manufacturing of phosphorylated pulp
  • softwood kraft pulp made by Oji Paper solid content 93% by mass, basis weight 208 g / m 2 sheets, disintegrated and measured according to JIS P 811-2: 2012 Canadian standard drainage degree (CSF) ) Used 700 mL.
  • the raw material pulp was subjected to phosphorus oxo oxidation treatment as follows. First, a mixed aqueous solution of ammonium dihydrogen phosphate and urea is added to 100 parts by mass (absolute dry mass) of the raw material pulp to obtain 45 parts by mass of ammonium dihydrogen phosphate, 120 parts by mass of urea, and 150 parts by mass of water.
  • the obtained chemical-impregnated pulp was heated in a hot air dryer at 165 ° C. for 200 seconds to introduce a phosphoric acid group into the cellulose in the pulp to obtain a phosphorylated pulp.
  • the washing treatment is carried out by repeating the operation of pouring 10 L of ion-exchanged water into 100 g (absolute dry mass) of phosphorylated pulp, stirring the pulp dispersion liquid so that the pulp is uniformly dispersed, and then filtering and dehydrating the pulp. went.
  • the electrical conductivity of the filtrate became 100 ⁇ S / cm or less, the washing end point was set.
  • the phosphorylated pulp after washing was subjected to alkali treatment (neutralization treatment) as follows.
  • the washed phosphorylated pulp was diluted with 10 L of ion-exchanged water, and then a 1N aqueous sodium hydroxide solution was added little by little with stirring to obtain a phosphorylated pulp slurry having a pH of 12 or more and 13 or less. ..
  • the phosphorylated pulp slurry was dehydrated to obtain phosphorylated pulp subjected to alkali treatment (neutralization treatment).
  • the phosphorylated pulp after the neutralization treatment was subjected to the above-mentioned washing treatment.
  • the infrared absorption spectrum of the phosphorylated pulp thus obtained was measured using FT-IR.
  • this fine fibrous cellulose maintained the cellulose type I crystal. Moreover, when the fiber width of the fine fibrous cellulose was measured using a transmission electron microscope, it was 3 to 5 nm.
  • the amount of phosphoric acid group (first dissociated acid amount) measured by the method for measuring the amount of phosphoroxo acid group described later was 1.45 mmol / g.
  • the total amount of dissociated acid was 2.45 mmol / g.
  • the infrared absorption spectrum of the obtained subphosphorylated pulp was measured using FT-IR.
  • absorption based on P O of the phosphonic acid group, which is a tautomer of the phosphite group, was observed around 1210 cm -1, and the phosphorous acid group (phosphonic acid group) was added to the pulp.
  • P O of the phosphonic acid group
  • the phosphorous acid group phosphonic acid group
  • the amount of phosphite group (first dissociated acid amount) measured by the method for measuring the amount of phosphorous acid group described later was 1.51 mmol / g.
  • the total amount of dissociated acid was 1.54 mmol / g.
  • TEMPO oxidized pulp softwood kraft pulp (undried) made by Oji Paper was used. Alkaline TEMPO oxidation treatment was carried out on this raw material pulp as follows. First, the raw material pulp equivalent to 100 parts by mass of dry mass, 1.6 parts by mass of TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl), and 10 parts by mass of sodium bromide are added to 10000 parts by mass of water. It was dispersed in the parts. Then, a 13 mass% sodium hypochlorite aqueous solution was added to 1.0 g of pulp so as to be 3.8 mmol, and the reaction was started. During the reaction, a 0.5 M aqueous sodium hydroxide solution was added dropwise to keep the pH at 10 or more and 10.5 or less, and the reaction was considered to be completed when no change was observed in the pH.
  • the washing treatment is carried out by dehydrating the pulp slurry after TEMPO oxidation to obtain a dehydrated sheet, pouring 5000 parts by mass of ion-exchanged water, stirring and uniformly dispersing, and then repeating the operation of filtration and dehydration. It was. When the electrical conductivity of the filtrate became 100 ⁇ S / cm or less, the washing end point was set.
  • Example 1 (Dissolution of polyvinyl alcohol) Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval 105, degree of polymerization: 500, degree of saponification: 98 to 99 mol%) was added to ion-exchanged water so as to have a concentration of 20% by mass, and the mixture was stirred at 95 ° C. for 1 hour to dissolve it. .. An aqueous polyvinyl alcohol solution was obtained by the above procedure.
  • the fine fibrous cellulose dispersion (A) and the above polyvinyl alcohol aqueous solution were each diluted with ion-exchanged water so that the solid content concentration was 0.6% by mass. Then, the diluted polyvinyl alcohol aqueous solution was mixed with 30 parts by mass of the diluted fine fibrous cellulose dispersion liquid so as to be 70 parts by mass to obtain a mixed liquid. Further, the mixed solution was weighed so that the finished basis weight of the sheet was 100 g / m 2 , and developed on a commercially available acrylic plate. A frame for damming (inner dimensions 120 mm ⁇ 120 mm, height 5 cm) was arranged on the acrylic plate so as to have a predetermined basis weight. Then, it was dried in a dryer at 70 ° C. for 24 hours and peeled off from the acrylic plate to form a fiber layer. The thickness of the fiber layer was 75 ⁇ m.
  • Example 2 In Example 1 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified polypropylene resin solution. At this time, the polyisocyanate compound was made to have 10 parts by mass with respect to 90 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 1 to obtain an evaluation sheet (laminated sheet).
  • TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 3 In Example 1 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified polypropylene resin solution. At this time, the amount of the polyisocyanate compound was 25 parts by mass with respect to 75 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 1 to obtain an evaluation sheet (laminated sheet).
  • TPA-100 polyisocyanate compound manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 4 In Example 1 (formation of the fiber layer), 50 parts by mass of the diluted polyvinyl alcohol aqueous solution was mixed with 50 parts by mass of the diluted fine fibrous cellulose dispersion to obtain a mixed solution. Other procedures were the same as in Example 1 to obtain an evaluation sheet (laminated sheet).
  • Example 5 In Example 4 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified polypropylene resin solution. At this time, the polyisocyanate compound was made to have 10 parts by mass with respect to 90 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 4, and an evaluation sheet (laminated sheet) was obtained.
  • TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 6 In Example 4 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified polypropylene resin solution. At this time, the amount of the polyisocyanate compound was 25 parts by mass with respect to 75 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 4, and an evaluation sheet (laminated sheet) was obtained.
  • TPA-100 polyisocyanate compound manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 7 In Example 1 (formation of the fiber layer), 70 parts by mass of the diluted fine fibrous cellulose dispersion was mixed with 30 parts by mass of the diluted polyvinyl alcohol aqueous solution to obtain a mixed solution. Other procedures were the same as in Example 1 to obtain an evaluation sheet (laminated sheet).
  • Example 8 In Example 7 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified polypropylene resin solution. At this time, the polyisocyanate compound was made to have 10 parts by mass with respect to 90 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 7 to obtain an evaluation sheet (laminated sheet).
  • TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 9 In Example 7 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified polypropylene resin solution. At this time, the amount of the polyisocyanate compound was 25 parts by mass with respect to 75 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 7 to obtain an evaluation sheet (laminated sheet).
  • TPA-100 polyisocyanate compound manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 10 In Example 7 (formation of resin layer), instead of the maleic anhydride-modified polypropylene resin solution, a maleic anhydride-modified chlorinated polypropylene resin solution (manufactured by Toyobo Co., Ltd., Hardlen F-2MB: polypropylene resin component 20% by mass, methyl) Cyclohexane 55% by mass, butyl acetate 25% by mass) was used. Other procedures were the same as in Example 1 to obtain an evaluation sheet (laminated sheet).
  • a maleic anhydride-modified chlorinated polypropylene resin solution manufactured by Toyobo Co., Ltd., Hardlen F-2MB: polypropylene resin component 20% by mass, methyl
  • Example 11 In Example 10 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified chlorinated polypropylene resin solution. At this time, the polyisocyanate compound was made to have 10 parts by mass with respect to 90 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 10 to obtain an evaluation sheet (laminated sheet).
  • TPA-100 polyisocyanate compound manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 12 In Example 10 (formation of resin layer), a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the maleic anhydride-modified chlorinated polypropylene resin solution. At this time, the amount of the polyisocyanate compound was 25 parts by mass with respect to 75 parts by mass of the polypropylene resin component. Other procedures were the same as in Example 10 to obtain an evaluation sheet (laminated sheet).
  • TPA-100 polyisocyanate compound manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Example 13 In Example 11 (formation of the fiber layer), the fine fibrous cellulose dispersion (B) was used instead of the fine fibrous cellulose dispersion (A). Other procedures were the same as in Example 11 to obtain an evaluation sheet (laminated sheet).
  • Example 14 In Example 11 (formation of the fiber layer), the fine fibrous cellulose dispersion (C) was used instead of the fine fibrous cellulose dispersion (A). Other procedures were the same as in Example 11 to obtain an evaluation sheet (laminated sheet).
  • Example 15 In Example 11 (formation of the fiber layer), the fine fibrous cellulose dispersion (D) was used instead of the fine fibrous cellulose dispersion (A). Other procedures were the same as in Example 11 to obtain an evaluation sheet (laminated sheet).
  • Example 16 an evaluation sheet (laminated sheet) was obtained in the same manner as in Example 10 except that the procedure of (formation of the resin layer) was changed as follows.
  • (Formation of resin layer) An aqueous emulsion of carboxy-modified polyethylene (Arrow Base SB-1230N manufactured by Unitica: 26% by mass of polyethylene resin component, 58% by mass of water, 16% by mass of isopropyl alcohol) was applied to the surface of the fiber layer on the side peeled from the acrylic plate. After coating with a bar coater, a resin layer was formed by heating at 100 ° C. for 1 hour to cure. The thickness of the resin layer was 5 ⁇ m.
  • Example 17 In Example 11 (formation of the fiber layer), the mixed liquid was weighed so that the finished basis weight of the sheet was 30 g / m 2 , and developed on a commercially available acrylic plate. Other procedures were the same as in Example 11 to obtain an evaluation sheet (laminated sheet).
  • Example 10 formation of the resin layer was not performed, and the fiber layer alone was used as the evaluation sheet.
  • Example 10 an evaluation sheet (laminated sheet) was obtained in the same manner as in Example 10 except that the procedure of (formation of the resin layer) was changed as follows.
  • (Formation of resin layer) 15 parts by mass of a modified polycarbonate resin (Yupizeta 2136 manufactured by Mitsubishi Gas Chemical Company, Inc.), 57 parts by mass of toluene, and 28 parts by mass of methyl ethyl ketone were mixed.
  • a polyisocyanate compound (TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added. At this time, the amount of the polyisocyanate compound was 10 parts by mass with respect to 90 parts by mass of the polycarbonate resin component.
  • a resin layer was formed by applying these mixed solutions to the surface of the fiber layer on the side peeled from the acrylic plate with a bar coater and then heating at 100 ° C. for 1 hour to cure. The thickness of the resin layer was 5 ⁇ m.
  • Example 10 an evaluation sheet (laminated sheet) was obtained in the same manner as in Example 10 except that the procedure of (formation of the resin layer) was changed as follows.
  • a polyisocyanate compound (Asahi Kasei Chemicals, TPA-100) is added to a urethane acrylic resin solution (Acryt 8UA-347A, manufactured by Taisei Fine Chemicals, Inc .: urethane acrylic resin component 30% by mass, methyl ethyl ketone 65% by mass, isopropyl alcohol 5% by mass). Added.
  • the amount of the polyisocyanate compound was 10 parts by mass with respect to 90 parts by mass of the urethane acrylic resin component.
  • a resin layer was formed by applying these mixed solutions to the surface of the fiber layer on the side peeled from the acrylic plate with a bar coater and then heating at 100 ° C. for 1 hour to cure. The thickness of the resin layer was 5 ⁇ m.
  • Example 10 an evaluation sheet (laminated sheet) was obtained in the same manner as in Example 10 except that the procedure of (formation of the resin layer) was changed as follows.
  • a urethane polyol adhesive (Nipporan 2304 manufactured by Tosoh Co., Ltd .: urethane polyose component 35% by weight, methyl ethyl ketone 65% by mass) was applied to the surface of the fiber layer peeled from the acrylic plate with a bar coater, and then 100.
  • a resin layer was formed by heating at ° C. for 1 hour and curing. The thickness of the resin layer was 5 ⁇ m.
  • Example 10 an evaluation sheet (laminated sheet) was obtained in the same manner as in Example 10 except that the procedure of (formation of the resin layer) was changed as follows. (Formation of resin layer) A biaxially stretched polypropylene film (Toray Industries, Inc., Trefan # 50-2500H: thickness 50 ⁇ m) was superposed on the surface of the fiber layer on the side peeled from the acrylic plate. This was passed through a tabletop laminator, and the fiber layer and the biaxially stretched polypropylene film were laminated. An evaluation sheet (laminated sheet) was obtained by the above procedure.
  • a biaxially stretched polypropylene film Toray Industries, Inc., Trefan # 50-2500H: thickness 50 ⁇ m
  • ⁇ Measurement> (Measurement of phosphorus oxo acid group amount)
  • the amount of phosphorus oxo acid groups in the fine fibrous cellulose is adjusted by adding ion-exchanged water to the fine fibrous cellulose dispersion containing the target fine fibrous cellulose. It was adjusted to 0.2% by mass, treated with an ion exchange resin, and then titrated with an alkali to measure the weight.
  • a strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) having a volume of 1/10 was added to the fine fibrous cellulose-containing slurry, and the mixture was shaken for 1 hour. After that, it was poured on a mesh having a mesh size of 90 ⁇ m to separate the resin and the slurry.
  • titration using alkali changes the pH value indicated by the slurry while adding 10 ⁇ L of 0.1 N sodium hydroxide aqueous solution to the fine fibrous cellulose-containing slurry after treatment with an ion exchange resin every 5 seconds. It was done by measuring.
  • the titration was performed while blowing nitrogen gas into the slurry from 15 minutes before the start of the titration.
  • the increment (differential value of pH with respect to the amount of alkali dropped) becomes maximum in the curve plotting the measured pH with respect to the amount of alkali added.
  • the maximum point of the increment obtained first when alkali is added is called the first end point, and the maximum point of the increment obtained next is called the second end point (FIG. 2).
  • the amount of alkali required from the start of titration to the first end point is equal to the amount of first dissociated acid in the slurry used for titration.
  • the amount of alkali required from the start of titration to the second end point becomes equal to the total amount of dissociated acid in the slurry used for titration.
  • the amount of alkali (mmol) required from the start of titration to the first end point divided by the solid content (g) in the slurry to be titrated is the amount of phosphate groups (first dissociated acid amount) (mmol / g). ).
  • the value obtained by dividing the amount of alkali (mmol) required from the start of titration to the second end point by the solid content (g) in the slurry to be titrated was defined as the total amount of dissociated acid (mmol / g).
  • the carboxy group amount of the fine fibrous cellulose (equal to the carboxy group amount of the TEMPO oxide pulp) is set to 0 by adding ion-exchanged water to the fine fibrous cellulose dispersion containing the target fine fibrous cellulose. It was measured at 2% by mass, treated with an ion exchange resin, and then titrated with an alkali. The treatment with an ion exchange resin is carried out by adding a 1/10 volume of a strongly acidic ion exchange resin (Amberjet 1024; manufactured by Organo Corporation, conditioned) to a slurry containing 0.2% by mass of fine fibrous cellulose for 1 hour.
  • a strongly acidic ion exchange resin (Amberjet 1024; manufactured by Organo Corporation, conditioned)
  • the resin and the slurry were separated by pouring onto a mesh having a mesh size of 90 ⁇ m. Further, the titration using alkali was performed by measuring the change in the pH value indicated by the slurry while adding a 0.1 N sodium hydroxide aqueous solution to the fibrous cellulose-containing slurry treated with the ion exchange resin. .. By observing the change in pH while adding an aqueous sodium hydroxide solution, a titration curve as shown in FIG. 3 can be obtained. As shown in FIG.
  • the increment (differential value of pH with respect to the amount of alkaline drop) becomes maximum in the curve plotting the measured pH with respect to the amount of alkali added. Observed.
  • the maximum point of this increment is called the first end point.
  • the region from the start of titration to the first end point in FIG. 3 is referred to as a first region.
  • the amount of alkali required in the first region is equal to the amount of carboxy groups in the slurry used for titration.
  • the amount of alkali (mmol) required in the first region of the titration curve is divided by the solid content (g) in the fine fibrous cellulose-containing slurry to be titrated, so that the amount of carboxy group introduced (mmol / g). ) was calculated.
  • the above-mentioned amount of carboxy group introduced (mmol / g) is the amount of substituents per 1 g of mass of fibrous cellulose when the counterion of the carboxy group is hydrogen ion (H +) (hereinafter, the amount of carboxy group (acid). Type)) is shown.
  • the thickness of the fiber layer peeled from the acrylic plate was measured by a stylus type thickness system (Millitron 1202D manufactured by Marl Co., Ltd.).
  • a biaxially stretched polypropylene film (manufactured by Toray Industries, Inc., Trefan # 50-2500H: thickness 50 ⁇ m) was laminated on the surface of the evaluation sheet on the resin layer side. Next, these were sandwiched between two stainless steel plates having a thickness of 2 mm and a size of 200 mm square. Then, it was inserted into a mini test press (manufactured by Toyo Seiki Kogyo Co., Ltd., MP-WCH) set at room temperature, and the temperature was raised to 160 ° C. over 3 minutes under a press pressure of 1 MPa. After holding in this state for 30 seconds, it was cooled to 30 ° C. over 3 minutes.
  • a mini test press manufactured by Toyo Seiki Kogyo Co., Ltd., MP-WCH
  • B The polypropylene film is peeled from the laminate, but the polypropylene film is broken or cannot be peeled during the peeling process, and the peeled area is 5% or more and less than 20% of the whole.
  • C The polypropylene film is peeled from the laminate, but the polypropylene film is broken or cannot be peeled during the peeling process, and the peeled area is 20% or more and less than 100% of the whole.
  • D The polypropylene film is easily peeled off from the entire area of the laminate, and the peeled area is 100% of the whole area.
  • the haze of the evaluation sheet was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Research Institute) in accordance with JIS K 7136: 2000. From the measurement results, transparency was evaluated according to the following criteria.
  • a polypropylene plate having a size of 100 mm square and a thickness of 2 mm was sandwiched between two evaluation sheets trimmed to 100 mm square, and these were further sandwiched between two stainless steel plates having a size of 200 mm square.
  • the surface of the evaluation sheet on the resin layer side was arranged so as to be in contact with the polypropylene plate. Then, it was inserted into a mini test press (manufactured by Toyo Seiki Kogyo Co., Ltd., MP-WCH) set at room temperature, and the temperature was raised to 140 ° C. over 3 minutes under a press pressure of 0.2 MPa.
  • the flexural modulus of the laminate is 2.0 times or more that of the polypropylene plate
  • B: The flexural modulus of the laminate is 1.5 times or more and less than 2.0 times that of the polypropylene plate
  • C The flexural modulus of the laminate
  • D The flexural modulus of the laminate is less than 1.2 times that of polypropylene plate.
  • the interlayer adhesion between the fiber layer and the resin layer was good, and the adhesion with the polypropylene film was also good.
  • the interlayer adhesion between the fiber layer and the resin layer is excellent, and in the example where polyisocyanate is used as the adhesion aid and the example where chlorinated polypropylene is used, the adhesion with the polypropylene film is excellent.
  • the adhesion with the polypropylene film was insufficient.
  • the sheet obtained in the example using chlorinated polypropylene a sheet having excellent transparency was obtained. It was considered that this was because the crystallinity of polypropylene was reduced by chlorination. Further, the sheet obtained in the example had a good reinforcing effect of the resin material. In particular, the reinforcing effect was good in the case where the thickness of the fiber layer was large. On the other hand, in the sheet of the comparative example, which is inferior in adhesion to the polypropylene film, the adhesion to the polypropylene plate is also insufficient, and as a result, the reinforcing effect is also inferior. In addition, the sheet obtained in the examples had a good appearance. In particular, in the case where an organic solvent was used as the diluting material, the result was excellent in appearance.
  • B The cyclic olefin polymer film is peeled from the laminate, but the cyclic olefin polymer film is destroyed or cannot be peeled during the peeling process, and the peeled area is 5% or more and less than 20% of the whole.
  • C The cyclic olefin polymer film is peeled from the laminate, but the cyclic olefin polymer film is destroyed or cannot be peeled during the peeling process, and the peeled area is 20% or more and less than 100% of the whole.
  • D The cyclic olefin polymer film is easily peeled off from the entire area of the laminate, and the peeled area is 100% of the whole area.
  • Cyclic olefin polymer was injected between the cellulose-containing sheets). Further, the mold temperature was lowered to 60 ° C., and the cyclic olefin polymer was solidified to obtain a plate-shaped molded product. By the above procedure, a laminate of a cyclic olefin polymer plate and a laminated sheet was obtained.
  • A The flexural modulus of the laminate is 2.0 times or more that of the cyclic olefin polymer plate
  • C The laminated sheet is peeled from the cyclic olefin polymer plate, but the peeled area is 20% or more and less than 100% of the whole.
  • D The laminated sheet is peeled from the cyclic olefin polymer plate, and the peeled area is 100% of the whole.
  • the sheet having the resin layer containing the modified polyolefin resin obtained in the examples had good adhesion to the cyclic olefin polymer film.
  • the adhesion to the cyclic olefin polymer film was insufficient.
  • the sheet having the resin layer containing the modified polyolefin resin obtained in the examples had good adhesion to the cyclic olefin polymer plate and was excellent in the reinforcing effect.
  • the adhesion to the cyclic olefin polymer film was insufficient, and as a result, the reinforcing effect was also insufficient.
  • Example 101> (Lamination with cyclic olefin polymer film by coating) Maleic anhydride-modified polypropylene resin solution (manufactured by Toyobo Co., Ltd., Hardlen TD-15B: polypropylene resin component 15% by mass, methylcyclohexane 75% by mass, butyl acetate 10% by mass) and polyisocyanate compound (manufactured by Asahi Kasei Chemicals Co., Ltd., TPA-100) ) was added to obtain a coating liquid. At this time, the polyisocyanate compound was made to have 10 parts by mass with respect to 90 parts by mass of the polypropylene resin component.
  • Maleic anhydride-modified polypropylene resin solution manufactured by Toyobo Co., Ltd., Hardlen TD-15B: polypropylene resin component 15% by mass, methylcyclohexane 75% by mass, butyl acetate 10% by mass
  • polyisocyanate compound manufactured by As
  • this coating liquid was applied to a cyclic olefin polymer film (Zeon Corporation, Zeonoa film ZF14: thickness 23 ⁇ m) with a bar coater, and then heated at 80 ° C. for 10 minutes to form a resin layer. Further, the mixed solution obtained in Example 1 (formation of the fiber layer) was weighed so that the finished basis weight of the sheet was 100 g / m 2 , and the resin formed on the cyclic olefin polymer film. Expanded on the layer. A dammed frame (inner dimensions 120 mm ⁇ 120 mm, height 5 cm) was arranged on the acrylic plate so as to have a predetermined basis weight. Then, it was dried in a dryer at 70 ° C. for 24 hours to form a fiber layer. The thickness of the fiber layer was 75 ⁇ m. By the above procedure, a laminate of the cyclic olefin polymer film and the laminated sheet was obtained.
  • a cyclic olefin polymer film Zeon
  • Example 102 The following operation was performed on the evaluation sheet (laminated sheet) obtained in Example 17 to obtain a multilayer laminate with the cyclic olefin polymer film.
  • Maleic anhydride-modified chlorinated polypropylene resin solution manufactured by Toyobo Co., Ltd., Hardlen F-2MB: polypropylene resin component 20% by mass, methylcyclohexane 55% by mass, butyl acetate 25% by mass
  • polyisocyanate compound manufactured by Asahi Kasei Chemicals, TPA) -100
  • the mixed solution was applied to the surface of the evaluation sheet on the exposed side of the fiber layer with a bar coater, and then heated at 100 ° C. for 1 hour to be cured to form a resin layer.
  • a laminated sheet in which resin layers were formed on both sides of the fiber layer was obtained.
  • Five of these laminated sheets were laminated and sandwiched between two cyclic olefin polymer films (Zeon Corporation, Zeonoa film ZF14: thickness 50 ⁇ m). Next, these were sandwiched between two stainless steel plates having a thickness of 2 mm and a size of 200 mm square.
  • the state at this time was confirmed.
  • Each layer of the multilayer laminate did not peel off, the peeled area was less than 5% of the whole, and the adhesion was good.
  • the tensile elastic modulus of this multilayer laminate was measured in accordance with JIS P 8113: 2006, except that the distance between the two grips of the testing machine was set to 80 mm.
  • the tensile elastic modulus of the multilayer laminate was 7.6 GPa. Since the tensile elastic modulus of the cyclic olefin polymer film was 2.5 GPa, it was confirmed that the cyclic olefin polymer film could be reinforced by forming a multilayer laminate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'une feuille stratifiée dans laquelle une adhérence entre couches est excellente entre une couche de résine contenant une résine de polyoléfine et une couche de fibres, et qui peut présenter une bonne adhérence à d'autres films de résine. La présente invention concerne une feuille stratifiée ayant : une couche de fibres comprenant une cellulose fibreuse ayant une largeur de fibre d'au plus 1 000 nm ; et une couche de résine disposée sur au moins une surface de la couche de fibres, la couche de résine comprenant une résine de polyoléfine modifiée.
PCT/JP2020/039279 2019-10-21 2020-10-19 Feuille stratifiée et stratifié WO2021079850A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014079938A (ja) * 2012-10-16 2014-05-08 Toppan Printing Co Ltd 積層体およびその製造方法
WO2016072224A1 (fr) * 2014-11-04 2016-05-12 太陽ホールディングス株式会社 Matériau de carte de câblage, et carte de câblage mettant en œuvre celui-ci
WO2017047632A1 (fr) * 2015-09-18 2017-03-23 王子ホールディングス株式会社 Corps stratifié
WO2017126432A1 (fr) * 2016-01-20 2017-07-27 王子ホールディングス株式会社 Stratifié et son procédé de production
JP2018063925A (ja) * 2016-10-14 2018-04-19 王子ホールディングス株式会社 電池用セパレータ、電池及び電池用セパレータ塗液

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014079938A (ja) * 2012-10-16 2014-05-08 Toppan Printing Co Ltd 積層体およびその製造方法
WO2016072224A1 (fr) * 2014-11-04 2016-05-12 太陽ホールディングス株式会社 Matériau de carte de câblage, et carte de câblage mettant en œuvre celui-ci
WO2017047632A1 (fr) * 2015-09-18 2017-03-23 王子ホールディングス株式会社 Corps stratifié
WO2017126432A1 (fr) * 2016-01-20 2017-07-27 王子ホールディングス株式会社 Stratifié et son procédé de production
JP2018063925A (ja) * 2016-10-14 2018-04-19 王子ホールディングス株式会社 電池用セパレータ、電池及び電池用セパレータ塗液

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