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WO2023100924A1 - Procédé de production d'un produit en couches contenant des nanofibres de cellulose - Google Patents

Procédé de production d'un produit en couches contenant des nanofibres de cellulose Download PDF

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Publication number
WO2023100924A1
WO2023100924A1 PCT/JP2022/044126 JP2022044126W WO2023100924A1 WO 2023100924 A1 WO2023100924 A1 WO 2023100924A1 JP 2022044126 W JP2022044126 W JP 2022044126W WO 2023100924 A1 WO2023100924 A1 WO 2023100924A1
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Prior art keywords
coating
cellulose nanofibers
coating method
cellulose
cnf
Prior art date
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PCT/JP2022/044126
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English (en)
Japanese (ja)
Inventor
昌浩 森田
丈史 中谷
武史 堀田
駿生 濱谷
丈博 吉松
清 畠山
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Priority claimed from JP2021197013A external-priority patent/JP2023082962A/ja
Priority claimed from JP2021197015A external-priority patent/JP2023082963A/ja
Priority claimed from JP2022182544A external-priority patent/JP2023083222A/ja
Application filed by Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Publication of WO2023100924A1 publication Critical patent/WO2023100924A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B23/20—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 esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
    • C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
    • C08B5/14—Cellulose sulfate

Definitions

  • the present invention relates to a method for manufacturing a laminate containing cellulose nanofibers.
  • Cellulose nanofibers obtained by introducing anionic or cationic groups into cellulose and defibrating using the charge repulsion of these introduced groups have a very fine fiber diameter and are generally It has been extensively studied because of its characteristics such as high homogeneity, various functionalities based on the introduced groups, and high strength.
  • an anion-modified cellulose nanofiber obtained by introducing an anionic group into cellulose and defibrating it some of the hydroxyl groups of cellulose are oxidized to carboxyl groups using the surface oxidation reaction of cellulose by an N-oxyl compound.
  • oxidized cellulose nanofibers obtained by fibrillating and carboxymethylated cellulose nanofibers having a degree of carboxymethyl substitution of 0.01 to 0.30 and an average fiber diameter of 3 to 500 nm have been reported (patent References 1 and 2).
  • cellulose nanofibers exhibit unique properties in various applications due to the effects of nanostructures.
  • cellulose nanofibers are commercially available in the form of aqueous dispersions or powdery solids, and for industrial use, it is necessary to perform secondary processing. In particular, it is expected to form a coating film of cellulose nanofibers on a substrate and use it as a functional layer.
  • an object of the present invention is to provide a method of manufacturing a laminate having an optimal functional layer for application to such various industrial uses.
  • [1] including a lamination step of forming a functional layer containing anion-modified cellulose nanofibers on a supporting substrate by a coating method or a transfer coating method; A method for manufacturing a laminate.
  • [2] The production method according to [1], wherein a coating liquid containing anion-modified cellulose nanofibers is used in the lamination step, and the coating liquid has a viscosity of 50 to 1000 mPa ⁇ s at 60 rpm.
  • [3] The manufacturing method according to [1] or [2], wherein the film thickness of the functional layer is 30 ⁇ m or less.
  • the supporting substrate has a receptive layer, and in step 2, the receptive layer and the coating surface are laminated, and in step 3, the functional layer is formed on the supporting substrate via the receptive layer; A method for manufacturing the described laminate.
  • the transfer substrate has a release layer on the surface on which the coating film is provided, and in step 1, the coating film is formed on the transfer substrate via the release layer, [9] or [10] ].
  • [1-1] A step of applying a coating solution containing anion-modified cellulose nanofibers onto a supporting substrate by a pre-weigh coating method to form a functional layer,
  • the viscosity of the coating liquid at 60 rpm is 50 to 1000 mPa s,
  • the film thickness of the functional layer is 30 ⁇ m or less,
  • a method for manufacturing a laminate [1-2] The production method according to [1-1], wherein the anion-modified cellulose nanofibers are oxidized cellulose nanofibers having carboxyl groups and/or carboxylate groups.
  • [1-3] The production method according to [1-1], wherein the anion-modified cellulose nanofibers are carboxyalkylated cellulose nanofibers.
  • [1-4] The production method according to [1-1], wherein the anion-modified cellulose nanofibers are phosphorylated cellulose nanofibers.
  • [1-5] The production method according to [1-1], wherein the anion-modified cellulose nanofibers are sulfate-esterified cellulose nanofibers.
  • [1-6] The production method according to any one of [1-1] to [1-5], wherein the pre-metering coating method is a die coating method.
  • [1-7] The production method according to any one of [1-1] to [1-5], wherein the pre-metering coating method is a curtain coating method.
  • [2-1] A step of applying a coating solution containing anion-modified cellulose nanofibers onto a supporting substrate by a post-metering coating method to form a functional layer, The film thickness of the functional layer is 30 ⁇ m or less, A method for manufacturing a laminate.
  • [2-2] The production method according to [2-1], wherein the anionic cellulose nanofibers are oxidized cellulose nanofibers having carboxyl groups and/or carboxylate groups.
  • [2-3] The production method according to [2-1], wherein the anionic cellulose nanofibers are carboxyalkylated cellulose nanofibers.
  • [2-4] The production method according to [2-1], wherein the anionic cellulose nanofibers are phosphorylated cellulose nanofibers.
  • [2-5] The production method according to [2-1], wherein the anionic cellulose nanofibers are sulfate-esterified cellulose nanofibers.
  • [2-6] The production method according to any one of [2-1] to [2-5], wherein the post-metering coating method is a bar coating method.
  • [2-7] The production method according to any one of [2-1] to [2-5], wherein the post-metering coating method is a knife coating method.
  • [2-8] The production method according to any one of [2-1] to [2-5], wherein the post-metering coating method is a blade coating method.
  • [2-9] A laminate obtained by the manufacturing method according to any one of [2-1] to [2-8].
  • the transfer substrate has a release layer on the surface on which the coating film is provided, and the coating film is formed on the transfer substrate via the release layer, [3-1] or [3 -2].
  • Laminate> The laminate comprises a functional layer containing anion-modified cellulose nanofibers on a supporting substrate.
  • the functional layer of the laminate contains anionically modified cellulose nanofibers.
  • nanofibers refer to nanofibers having an average fiber diameter of less than 1 ⁇ m.
  • the average fiber diameter is preferably about 3 nm to 500 nm, more preferably about 3 nm to 150 nm, still more preferably about 3 nm to 20 nm.
  • the aspect ratio is usually 30 or more or 35 or more, preferably 40 or more, more preferably 50 or more, and still more preferably 100 or more. Although the upper limit of the aspect ratio is not limited, it is about 500 or less.
  • anion-modified cellulose nanofibers (hereinafter also referred to as anion-modified CNF) are used in the present invention.
  • anion-modified CNF is NF in which an anion group is introduced into the molecular chain of cellulose.
  • Anion-modified CNF can be obtained by defibrating anion-modified cellulose obtained by introducing an anion group into the pyranose ring of cellulose so as to have an average fiber diameter of less than 1 ⁇ m.
  • Anion-modified CNF maintains at least part of its fibrous shape even when dispersed in water, and does not completely dissolve in water.
  • a fibrous substance can be observed by observing the aqueous dispersion of anion-modified CNF with an electron microscope.
  • the functional layer containing anion-modified CNF can exhibit good physical strength because the fibrous shape of the anion-modified CNF is maintained within the layer.
  • cellulose used as a raw material for anion-modified cellulose is not particularly limited.
  • bleached or unbleached mechanical pulp e.g., thermomechanical pulp (TMP), groundwood pulp
  • chemical pulp e.g., sulfite pulp
  • softwood hardwood, cotton, straw, bamboo, hemp, jute, kenaf, etc.
  • kraft pulp e.g., sulfite pulp
  • dissolving pulp e.g., regenerated cellulose, fine cellulose, microcrystalline cellulose excluding non-crystalline regions, and the like, and any of these can be used as the cellulose raw material.
  • Anion-modified cellulose can be produced by introducing an anion group into such a cellulose raw material.
  • the method for introducing the anionic group is not particularly limited, but examples include a method of directly oxidizing the hydroxyl group of the pyranose ring of cellulose to a carboxyl group, and a method of introducing an anionic group by an esterification reaction at the hydroxyl group portion of the pyranose ring.
  • Anion-modified CNF can be obtained by defibrating the anion-modified cellulose obtained by introducing an anion group so that the average fiber diameter is less than 1 ⁇ m.
  • the defibration method is not particularly limited, and examples thereof include a method using a known defibration device such as a high-speed rotation type, colloid mill type, high pressure type, roll mill type, and ultrasonic type. Among them, a method using a wet high-pressure or ultrahigh-pressure homogenizer is preferable.
  • anion-modified CNF- (oxidized CNF)
  • An example of anion-modified CNF is oxidized CNF having a carboxyl group and/or a carboxylate group.
  • a carboxyl group refers to -COOH (acid form) and -COOM (metal salt form) (wherein M is a metal ion), and a carboxylate group refers to -COO - .
  • Oxidized CNF having a carboxyl group and/or a carboxylate group is obtained by obtaining oxidized cellulose using a known method of oxidizing the hydroxyl group of the pyranose ring of cellulose to a carboxyl group. and then fibrillating.
  • oxidized cellulose for example, oxidation is performed in the presence of an N-oxyl compound such as 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) and bromide and/or iodide.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxy radical
  • Examples include a method of oxidizing cellulose in water using an agent, and a method of oxidizing cellulose by bringing it into contact with a cellulose raw material using an ozone-containing gas as an oxidizing agent.
  • the total amount of carboxyl groups and carboxylate groups in the oxidized CNF is preferably 0.4 to 3.0 mmol/g, more preferably 0.6 to 2.0 mmol/g, relative to the absolute dry mass of the oxidized CNF. 0 to 2.0 mmol/g, more preferably 1.1 to 2.0 mmol/g.
  • the amount of carboxyl groups and carboxylate groups in oxidized CNF can be adjusted by controlling reaction conditions such as the amount of oxidizing agent added and reaction time.
  • Carboxyalkylated CNF An example of anion-modified CNF is carboxyalkylated CNF having a carboxyalkyl group.
  • a carboxyalkyl group refers to -RCOOH (acid form) and -RCOOM (metal salt form).
  • R is an alkylene group such as a methylene group and an ethylene group
  • M is a metal ion (e.g., alkali metals such as Li, Na, and K; alkaline earth metals such as Mg and Ca; Fe; preferably Li, Na, or Ca, more preferably Na) (the same shall apply hereinafter).
  • carboxyalkylated CNF having a carboxyalkyl group carboxymethylated CNF having a carboxymethyl group in which R is a methylene group is most preferred (hereinafter "carboxymethyl” is referred to as "CM").
  • Carboxyalkylated CNF is obtained by obtaining carboxyalkylated cellulose using a known method of treating a cellulose raw material with a mercerizing agent and then treating it with a carboxyalkylating agent to introduce a carboxyalkyl group, and then defibrating it. Obtainable.
  • CM-cellulose which is a raw material for CM-CNF, maintains at least a part of its fibrous shape even when dispersed in water, and is distinguished from carboxymethyl cellulose, which is an example of a water-soluble polymer described later. be done.
  • carboxymethyl cellulose which is an example of a water-soluble polymer described later.
  • the degree of carboxyalkyl substitution per anhydroglucose unit of the carboxyalkylated CNF is preferably less than 0.40. Moreover, the lower limit of the degree of carboxyalkyl substitution is preferably 0.01 or more. Considering the workability, the degree of substitution is preferably 0.02 or more and 0.35 or less, more preferably 0.10 or more and 0.35 or less, and 0.15 or more and 0.35 or less. It is more preferably 0.15 or more and 0.30 or less.
  • the anhydroglucose unit means an individual anhydroglucose (glucose residue) constituting cellulose, and the degree of carboxyalkyl substitution refers to the hydroxyl group (—OH) in the glucose residue constituting cellulose.
  • the ratio of those substituted by groups (-ORCOOH or -ORCOOM) (the number of carboxyalkyl groups per glucose residue) is shown.
  • the degree of carboxyalkyl substitution can be adjusted by controlling reaction conditions such as the amount of mercerizing agent and reaction time.
  • the degree of CM substitution per glucose unit can be measured by the following method: About 2.0 g of CM-modified CNF (absolute dry) is precisely weighed and placed in a 300 mL conical flask with a common stopper. Add 100 mL of a liquid obtained by adding 100 mL of special grade concentrated nitric acid to 900 mL of methanol and shake for 3 hours to convert the salt-type CM-CNF to the hydrogen-type CM-CNF.
  • CM-CNF hydrogen-type CM-CNF (absolute dry) is accurately weighed and placed in a 300 mL conical flask equipped with a common stopper. Hydrogen-type CM-CNF is wetted with 15 mL of 80 mass % methanol, 100 mL of 0.1N NaOH is added, and shaken at room temperature for 3 hours. Excess NaOH is back-titrated with 0.1 N H 2 SO 4 using phenolphthalein as an indicator.
  • the degree of substitution of carboxyalkyl groups other than CM groups can also be measured in the same manner as above.
  • the crystallinity of cellulose type I in CM-CNF is preferably 50% or more, more preferably 60% or more.
  • the crystallinity of cellulose type I in CM-CNF can be controlled by the concentration of the mercerizing agent during the production of CM-cellulose as a raw material, the temperature during treatment, and the degree of carboxymethylation. Since a high concentration of alkali is used in mercerization and carboxymethylation, type I crystals of cellulose are easily converted to type II. Desired crystallinity can be maintained by adjusting the degree.
  • the upper limit of the crystallinity of cellulose type I is not particularly limited. Realistically, it is considered that the upper limit is about 90%.
  • the crystallinity of cellulose type I in CM-modified cellulose and the crystallinity of cellulose type I in CM-CNF obtained by fibrillating CM-modified cellulose are generally the same.
  • Phosphate esterified CNF An example of anion-modified CNF is phosphorylated CNF.
  • Phosphate-esterified CNF can be obtained by mixing the above-mentioned cellulose raw material with a phosphoric acid compound powder or aqueous solution, or by adding an aqueous solution of a phosphoric acid compound to a slurry of the cellulose raw material. It can be obtained by introducing an acid-based group into cellulose to obtain phosphate-esterified cellulose and defibrating it.
  • Phosphoric acid compounds include phosphoric acid, polyphosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, polyphosphonic acid, and esters or salts thereof.
  • phosphoric acid sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium phosphite, potassium phosphite, sodium hypophosphite, Potassium phosphite, sodium pyrophosphate, sodium metaphosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, potassium metaphosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, ammonium metaphosphate and the like.
  • a phosphoric acid group derived from a phosphoric acid compound can be introduced into cellulose by using one or more of these in combination.
  • the phosphoric acid group derived from a phosphoric acid compound includes a phosphoric acid group, a phosphorous acid group, a hypophosphorous acid group, a pyrophosphate group, a metaphosphoric acid group, a polyphosphoric acid group, a phosphonic acid group, and polyphosphonic acid groups.
  • Phosphate-esterified cellulose and phosphate-esterified CNF include those in which one or more of these phosphoric acid groups are introduced into the molecular chain of cellulose.
  • the pH is preferably pH 3-7.
  • a nitrogen-containing compound such as urea may also be added.
  • the amount of the compound having a phosphate group added to the cellulose raw material is preferably 0.1 to 500 parts by mass, more preferably 1 to 400 parts by mass, in terms of phosphorus element, with respect to 100 parts by mass of the solid content of the cellulose raw material. 2 to 200 parts by mass is more preferable. As a result, a yield corresponding to the amount of the compound having a phosphate group can be efficiently obtained.
  • the reaction temperature is preferably 0 to 95°C, more preferably 30 to 90°C.
  • the reaction time is not particularly limited, it is usually about 1 to 600 minutes, preferably 30 to 480 minutes. If the conditions for the esterification reaction are within any of these ranges, excessive esterification of cellulose and its susceptibility to dissolution can be suppressed, and the yield of phosphate esterified cellulose can be improved.
  • a basic compound e.g., urea, methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine, etc.
  • the heating temperature is preferably 100 to 170 ° C., and while water is contained during the heat treatment, heat at 130 ° C. or lower (preferably 110 ° C.
  • washing treatment such as washing with cold water and/or neutralization treatment. Thereby, defibration can be performed efficiently. Washing may be performed by adding water and dehydrating (for example, filtering), and may be repeated twice or more. Washing is preferably carried out until the electric conductivity of the filtrate decreases. For example, it can be carried out until the electric conductivity is preferably 200 or less, more preferably 150 or less, and still more preferably 120 or less. Moreover, after washing, neutralization treatment may be performed as necessary. Neutralization treatment can be carried out, for example, by addition of alkali (eg, sodium hydroxide). Washing may be performed again after neutralization.
  • alkali eg, sodium hydroxide
  • the lower limit of the degree of substitution of a phosphate group per glucose unit in the phosphorylated CNF is preferably 0.001 or more.
  • the upper limit is preferably 3.0 or less, more preferably less than 0.40.
  • the degree of phosphate group substitution per glucose unit can be measured by the following method: A slurry of phosphorylated CNF having a solids content of 0.2% by weight is prepared. To the slurry, 1/10 by volume of a strongly acidic ion exchange resin (Amberjet 1024; manufactured by Organo, conditioned) was added, shaken for 1 hour, and then poured onto a mesh with an opening of 90 ⁇ m to pour the resin.
  • a second example of a method for producing esterified cellulose fibers includes phosphite esterified cellulose fibers.
  • Phosphite cellulose fibers usually have a structure in which at least one of the carbon atoms constituting the cellulose molecular chain (for example, the carbon atom having a primary hydroxyl group at the C6 position constituting the glucopyranose unit) is phosphorylated. .
  • the degree of phosphite group substitution per glucose unit in the phosphite-esterified cellulose fiber is preferably 0.001 to 0.60. This facilitates electrical repulsion between cellulose particles, facilitating nano-fibrillation.
  • the degree of phosphite group substitution can be measured by the same method as the method for measuring the degree of phosphate group substitution.
  • the degree of phosphite group substitution can be adjusted by controlling reaction conditions such as the amount of phosphorous acid or a salt thereof added, the amount of an alkali metal ion-containing substance used as necessary, and the amount of urea or a derivative thereof added.
  • an unmodified cellulose fiber is reacted with phosphorous acid or a metal salt thereof (preferably sodium hydrogen phosphite) to introduce an ester group of phosphorous acid. method.
  • Examples of phosphorous acid and metal salts thereof include phosphorous acid, sodium hydrogen phosphite, ammonium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, sodium phosphite, and lithium phosphite. , potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, phosphorous acid compounds such as pyrophosphite, and combinations of two or more selected from these.
  • Sodium hydride is preferred. Thereby, alkali metal ions can also be introduced into the cellulose fibers.
  • the amount of phosphorous acid or its metal salt to be added is preferably 1 to 10,000 g, more preferably 100 to 5,000 g, still more preferably 300 to 1,500 g, per 1 kg of unmodified cellulose fibers.
  • alkali metal ion-containing substances e.g., hydroxides, metal sulfates, metal nitrates, metal chlorides, metal phosphates, metal carbonates
  • urea or a derivative thereof may be further added to the reaction system. This can also introduce carbamate groups into the cellulose fibers.
  • Urea and urea derivatives include, for example, urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, and combinations of two or more selected from these, with urea being preferred.
  • the amount of urea and urea derivatives to be added is preferably 0.01 to 100 mol, more preferably 0.2 to 20 mol, still more preferably 0.5 to 10 mol, per 1 mol of phosphorous acid or its metal salt.
  • the reaction temperature is preferably 100-200°C, more preferably 100-180°C, even more preferably 100-170°C. It is more preferable to heat at 130° C. or less (preferably 110° C. or less) while water is contained in the heat treatment, and after removing the water, heat-treat at 100 to 170° C.
  • the reaction time is usually about 10 to 180 minutes, more preferably 30 to 120 minutes.
  • the phosphite-esterified cellulose fibers are preferably washed prior to defibration.
  • the degree of substitution of the phosphite group per glucose unit is preferably 0.01 or more and less than 0.23.
  • Sulfated CNF can be obtained by reacting the above-described cellulose raw material with a sulfuric acid-based compound to introduce a sulfuric acid-based group derived from the sulfuric acid-based compound into cellulose to obtain sulfated cellulose, which is defibrated. can be done.
  • sulfuric acid compounds include sulfuric acid, sulfamic acid, chlorosulfonic acid, sulfur trioxide, and esters or salts thereof. Among these, sulfamic acid is preferably used because cellulose has low solubility and low acidity.
  • the amount of sulfamic acid used can be appropriately adjusted in consideration of the amount of anionic groups to be introduced into the cellulose chain. For example, it can be used in an amount of preferably 0.01 to 50 mol, more preferably 0.1 to 3.0 mol, per 1 mol of glucose units in the cellulose molecule.
  • the amount of sulfate-based groups per glucose unit in the sulfated CNF is preferably 0.1 to 3.0 mmol/g.
  • the amount of sulfate groups per glucose unit can be measured by the following method: The aqueous dispersion of sulfated CNF is subjected to solvent substitution in the order of ethanol and t-butanol, and then freeze-dried. 15 ml of ethanol and 5 ml of water are added to 200 mg of the obtained sample, and the mixture is stirred for 30 minutes. After that, 10 ml of 0.5N sodium hydroxide aqueous solution is added, and the mixture is stirred at 70° C.
  • the functional layer is a layer containing anion-modified CNF.
  • the functional layer preferably contains anion-modified CNF as a main component, and the content of anion-modified CNF is usually more than 50%, 60% or more, 70% or more, 80% or more, or 90% or more, It may consist only of anion-modified CNF (content 100%).
  • a functional layer can exhibit functions, such as a dielectric property and an insulating property, by including anion-modified CNF.
  • the film thickness (after drying) of the functional layer is usually 30 ⁇ m or less, preferably 25 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
  • the lower limit is not particularly limited, it is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 1 ⁇ m or more, and 1.3 ⁇ m or more so that the functional layer can easily exert an appropriate effect in various applications. , 1.5 ⁇ m or more or 2 ⁇ m or more are particularly preferred. It is preferable that the film thickness is substantially uniform. Thereby, a homogeneous functional layer can be obtained in which the distribution of anionic CNF is not biased.
  • the surface layer of the functional layer preferably has uniform smoothness. As a result, localization of the effect of the functional layer can be suppressed.
  • having uniform smoothness means that the functional layer does not have irregularities at the visual level.
  • the functional layer only needs to contain anion-modified CNF, and may contain other optional components.
  • Optional components include, for example, optional components of the subsequent coating liquid.
  • any base material can be used without particular limitation as long as it is composed of a material capable of forming a substantially uniform functional layer on its surface.
  • supporting substrates include resin substrates, paper substrates, and metal substrates. Among them, metal species having desired properties can be selected according to various uses. is preferred.
  • metals constituting the metal substrate include metals such as aluminum, copper, iron, zinc, titanium, nickel, lead, silver, platinum, tungsten, bismuth, stainless steel, brass, chromium, and alloys thereof.
  • Aluminum or copper is preferred because of its high versatility.
  • the shape and size of the supporting substrate are not particularly limited. Examples thereof include sheet-like and film-like substrates.
  • the laminate may have other layers.
  • Other layers include, for example, a primer layer, a receiving layer, and a release layer (peeling layer).
  • the primer layer and receiving layer are sandwiched between the supporting substrate and the functional layer, and the release layer is provided on the surface of the functional layer (generally peeled off at the end but may remain).
  • the primer layer By providing the primer layer, the coatability of the functional layer (coating liquid) in the pre-metering coating method and the post-metering coating method can be improved.
  • the primer that constitutes the primer layer include polyaniline.
  • the receiving layer can also improve the coatability of the functional layer in each coating method. Also, by providing a release layer, the workability of peeling in the transfer coating method can be enhanced. The receiving layer and release layer will be described later in the section of the transfer coating method.
  • Laminate manufacturing method The laminate described above can be produced by a method including a step of forming a functional layer containing anion-modified CNF on a support substrate.
  • a coating liquid containing anion-modified CNF can be used to form the functional layer, for example, by a coating method (coating method, for example, pre-metering coating method, post-metering coating method) or transfer coating method.
  • the pre-metering coating method means a coating method in which the wet film thickness is determined by specifying the flow rate per unit coating width and the substrate speed in the wet coating technology in which continuous wet coating is performed.
  • Pre-metering coating methods include, for example, die coating, curtain coating, gravure coating, forward roll coating, reverse coating, doctor coating, kiss coating, and applying tension to the base material on the die.
  • a tension web coating method that adjusts the coating amount can be used.
  • the die coating method and the curtain coating method are preferable because the flow rate can be stably controlled in continuous coating.
  • the die coating method can be by slot die coating.
  • Slot die coating is a method of coating a substrate while extruding a coating liquid from a die head.
  • An example of the coating method by slot die coating is as follows. A coating liquid is supplied into the die cavity that constitutes the slot die coater. While adjusting the coating speed so that the liquid (coating liquid) can be stably coated at a uniform flow rate in the width direction from the tip of the die (discharge hole) through the slit channel by pump, pressurization, etc. ( For example, coating speed: 0.1 to 1.0 m/min, coating width 0.1 to 1.0 m) Extrusion.
  • the size (slit width) of the die coater and the position (clearance) with respect to the substrate may be appropriately adjusted (for example, slit width 50 to 500 ⁇ m, clearance 100 to 1000 ⁇ m).
  • the slot die is of fixed type, the base material is run on a backup roll and continuously supplied to the vicinity of the tip of the die. It is possible to apply so as to obtain a predetermined wet film thickness while forming a so-called liquid pool.
  • the slot die is of a movable type, the slot die moves along the substrate (fixed) surface while discharging the coating agent, forming a uniform coating film on the surface of the substrate.
  • the pressure on the upstream side of the die tip may be reduced. Thereby, the pressure in the coating gap between the substrate and the die tip can be adjusted, and the bead on the substrate can be stabilized.
  • the degree of pressure reduction is preferably in the range of 0.05 kPa to 1.00 kPa from the atmospheric pressure, but may be appropriately adjusted depending on the speed of the base material and the properties of the coating liquid.
  • the pressure can be adjusted by installing a vacuum chamber.
  • the curtain coating method is a method in which a coating solution is dropped in a band (curtain) and the substrate is passed through the curtain to apply the coating solution.
  • Curtain coating methods are classified according to the method of forming a curtain, and examples thereof include overflow type, orifice type, die feed type, and slide hopper type.
  • the overflow type is a method in which the coating liquid overflows from the edge of the container in which the coating liquid is stored.
  • the overflow type is a system in which the coating liquid flows out from an orifice in the lower part of the coating liquid reservoir.
  • the large feed type pushes the coating liquid from the bottom of the die to form a curtain.
  • the slide hopper type forms a curtain by letting the coating liquid flow down from the slide surface.
  • Orifice type, die feed type and slide hopper type are preferable as the curtain coating method.
  • a constant flow pressure can be continuously applied, and the change in liquid property due to thixotropy caused by the action of the anion-modified CNF in the coating liquid containing the anion-modified CNF can be suppressed.
  • the amount of coating liquid supplied onto the substrate in the pre-metering coating method is usually 400 mL/min or less, preferably 300 mL/min or less, or more. It is preferably 250 mL/min or less, more preferably 200 mL/min or less. Although the lower limit is not particularly limited, it is usually 1 mL/min or more, preferably 50 mL/min or more, more preferably 80 mL/min or more. In the case of die coating, the above speed can be adjusted by the moving speed of the die or the moving speed of the substrate (the moving speed of the belt that moves the substrate).
  • the post-metering coating method means a coating method in which an external force is applied to a liquid film to remove excess liquid to obtain a predetermined coating film thickness in the wet coating technique of performing continuous wet coating.
  • Examples of post-metering coating methods include bar coating, blade coating, (air) knife coating, dip coating, and tension web coating, in which tension is applied to the substrate to adjust the coating amount on a roll. can be mentioned.
  • the bar coating method, the blade coating method, and the knife coating method are preferable because the clearance with the substrate can be easily adjusted, and as a result, the generation of scratches due to contact with the supporting substrate can be suppressed in continuous coating.
  • Bar coating method In the bar coating method, after the coating liquid is brought into contact with the supporting substrate, the bar is placed near the contacted coating liquid, and the bar or the supporting substrate is moved so as to scrape off the coating liquid. Coated by As such a bar, it is possible to use either a wire-wrapped wire bar or a wireless bar integrally formed with grooves, but the wireless bar is used from the viewpoint of suppressing scratches on the metal substrate during coating. is preferred.
  • the amount of coating liquid to be applied can be adjusted by the moving speed of the bar, the structure of the surface of the bar, and other factors.
  • the size of the grooves of the wireless bar is not particularly limited, but for example, it is preferable that the pitch is 0.05 to 0.5 mm and/or the depth is 5 to 15 ⁇ m.
  • Blade coating method In the blade coating method, after the coating liquid is brought into contact with the supporting substrate, a blade is placed in the vicinity of the contacted coating liquid, and the edge of the blade is pressed against the substrate surface to scrape off the coating liquid. Apply by moving the blade as shown.
  • the material of the blade is usually metal, but other materials such as ceramics may also be used.
  • the blade coating method is easy to control the coating amount and has a high affinity with a coating liquid having a high viscosity liquidity, so the highly viscous anion-modified CNF aqueous dispersion is applied to a predetermined film thickness. suitable for the purpose.
  • the coating amount of the coating liquid (film thickness of the functional layer) can be adjusted by the blade angle, clearance setting (clearance between the blade and the base material), moving speed, etc.
  • a smaller blade angle (for example, 80° or less, 70° or less, 60° or less, or 50° or less with respect to the substrate) is preferable.
  • a highly viscous coating liquid for example, aqueous dispersion liquid of anion-modified CNF.
  • Clearance settings are typically 800 ⁇ m or less, preferably 700 ⁇ m or less, more preferably 600 ⁇ m or less. In the case of the blade coating method, one set of coating and subsequent drying (described later) may be repeated multiple times.
  • the knife coating method is a coating method that uses a non-rotating knife roll with a knife-like edge and a backup roll that supplies a substrate so as to be in contact with the knife roll. That is, the coating liquid is supplied onto the base material, and a smooth coating film is formed by the effect of the shearing force in the gap between the knife roll and the base material.
  • the knife coating method is suitable when using a highly viscous anion-modified CNF water dispersion as a coating liquid.
  • the air knife coating method can also be used.
  • the air knife coating method is a coating method that uses an applicator roll that supplies a coating liquid in contact with the substrate and an air knife that blows air onto the surface of the substrate. That is, the base material contacted with the coating liquid by the applicator roll is adjusted to a predetermined coating amount by the air jetted from the air knife. It is preferable to adjust the viscosity of the coating liquid because it facilitates adjustment of the coating amount.
  • the coating liquid contains anion-modified CNF and is usually liquid.
  • the coating liquid preferably has moderate viscosity. Thereby, coatability becomes favorable.
  • the 60 rpm viscosity of the coating liquid is usually 30 mPa ⁇ s or more, or 50 mPa ⁇ s or more, preferably 52 mPa ⁇ s or more, more preferably 54 mPa ⁇ s or more, and still more preferably 55 mPa ⁇ s or more.
  • the upper limit is usually 1000 mPa s or less, 900 mPa s or less, 800 mPa s or less, preferably 700 mPa s or less, 600 mPa s or less, or 500 mPa s or less, more preferably 450 mPa s or less, or 400 mPa s or less. be.
  • the 6 rpm viscosity is usually 60 mPa ⁇ s or more or 65 mPa ⁇ s or more, preferably 70 mPa ⁇ s or more, more preferably 75 mPa ⁇ s or more.
  • the upper limit is usually 6000 mPa ⁇ s or less or 5000 mPa ⁇ s or less, preferably 4000 mPa ⁇ s or less, more preferably 3000 mPa ⁇ s or less, or 2500 mPa ⁇ s or less.
  • the 6 rpm viscosity and 60 rpm viscosity vary depending on conditions such as the type of anionic group, the average fiber diameter of CNF, the average fiber length, the aspect ratio, and the concentration of anion-modified CNF in the coating solution.
  • the 6 rpm viscosity and the 60 rpm viscosity can be measured using a Brookfield viscometer at 25° C. under the conditions of 6 rpm and 60 rpm, respectively.
  • the solid content of the anion-modified CNF contained in the coating liquid is preferably less than 5%, more preferably 4% or less, even more preferably 3% or less, and particularly preferably 2% or less. This can suppress an increase in the viscosity of the coating liquid and excessive expression of thixotropic properties.
  • the lower limit is preferably 0.1% or more, more preferably 0.2% or more, and even more preferably 0.3% or more.
  • the dispersion medium for the coating liquid examples include water and solvents (for example, hydrophilic solvents such as alcohol), which can be selected as appropriate.
  • the aqueous dispersion (for example, after fibrillation) at the time of production of anion-modified CNF can be used as a coating liquid as it is.
  • the viscosity and volatility of the coating liquid can be adjusted according to the coating conditions by using a solvent as the dispersion medium (substituting the solvent for water) or by mixing the solvent with water.
  • the coating liquid can be used in combination with other additives within a range that does not impair the effects of the present invention.
  • additives include leveling agents, antifoaming agents, dispersion stabilizers such as water-soluble polymers, preservatives, binders, and rheology control agents.
  • water-soluble polymers include cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose), xanthan gum, xyloglucan, dextrin, dextran, carrageenan, locust bean gum, alginic acid, alginate, pullulan, starch, potato starch, Kudzu flour, processed starch (cationized starch, phosphorylated starch, phosphoric acid cross-linked starch, phosphate monoesterified phosphoric acid cross-linked starch, hydroxypropyl starch, hydroxypropylated phosphate cross-linked starch, acetylated adipic acid cross-linked starch, acetylated phosphate cross-linked starch, Acetylated oxidized starch, sodium octenyl succinate, starch acetate, oxidized starch), cornstarch, gum arabic, gellan gum, polydextrose, pectin, chitin,
  • the coating liquid may be applied directly to the surface of the supporting substrate, but when an arbitrary primer layer is provided between the supporting substrate and the functional layer, the coating liquid for the primer layer is applied and dried before applying. be able to.
  • a drying process is a process of drying the coating film formed in the coating process.
  • a known drying method such as air drying, reduced pressure, infrared rays, or the like can be used, and a dryer such as an explosion-proof dryer can be used. Drying is preferably carried out under heating conditions.
  • the drying temperature is preferably 75 to 150°C, more preferably 75 to 130°C, still more preferably 80 to 120°C.
  • the drying time is usually 5 seconds or longer, preferably 10 seconds or longer, more preferably 30 seconds or longer, and still more preferably 45 seconds or longer.
  • the upper limit is preferably 10 minutes or less, more preferably 9 minutes or less, still more preferably 8 minutes or less. It is preferably 10 seconds to 10 minutes, more preferably 10 seconds to 9 minutes, more preferably 10 seconds to 8 minutes, even more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.
  • the solvent drying rate is preferably 0.1 wt%/sec or more, more preferably 0.2 wt%/sec or more, and still more preferably 0.22 wt%/sec or more.
  • the upper limit is preferably 5.0 wt%/sec or less, more preferably 4.0 wt%/sec or less or 3.0 wt%/sec or less, still more preferably 2.0 wt%/sec or less, 1.5 weight %/sec or less, or 1.07 weight %/sec or less. Therefore, 0.1 to 5.0% by weight/sec is preferable, and 0.22 to 1.07% by weight/sec is more preferable.
  • the drying speed of the solvent can be calculated by dividing the ratio (% by weight) of the solvent in the entire coated sample by the time (sec) required for the solvent to volatilize and the coating film to dry. The drying speed can be adjusted by drying temperature and wind speed.
  • the wind speed during drying is preferably 100 m/min or less, 90 m/min or less, 80 m/min or less, 70 m/min or less, 60 m/min or less, 50 m/min or less, 40 m/min or less, Or 30 m/min or less is more preferable. Thereby, the influence on the coating film surface can be suppressed.
  • the lower limit is preferably 1 m/min or more, more preferably 5 m/min or more or 10 m/min or more. This can prevent insufficient drying.
  • Step 1 A step of forming a coating film containing anion-modified CNF on a substrate for transfer.
  • Step 2 A step of laminating a supporting substrate to the surface of the coating film.
  • Step 3 A step of peeling the transfer base material from the coating film and forming a functional layer on the support base material.
  • a known coating method can be selected as a method for forming a coating film containing anion-modified CNF on the substrate for transfer.
  • coating methods include bar coating, blade coating, (air) knife coating, dip coating, tension web coating, die coating, curtain coating, and the like.
  • a construction method is preferred, and a blade coating method is more preferred.
  • a coating solution containing anion-modified CNF can be used to form the coating film.
  • the coating method, examples of the coating liquid, and preferred conditions are as described in the description of the coating method in the preceding paragraph.
  • the coating film after coating is usually subjected to drying treatment. Drying can be carried out by a known drying method.
  • the drying temperature is preferably 80 to 150°C, more preferably 100 to 150°C, still more preferably 120 to 150°C.
  • the drying time is preferably 5 to 180 seconds, more preferably 10 to 120 seconds.
  • the drying time is preferably 5-180 seconds, more preferably 10-120 seconds.
  • the drying speed and air speed in the case of air drying are the same as the preferred conditions described above.
  • the coating surface is preferably uniform.
  • the substrate for transfer may be any known polymer film, such as polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polycarbonate, polyvinyl chloride, polyacetylcellulose, polyether, polyacryl, (meth)acrylonitrile, and the like.
  • a polymeric film is mentioned.
  • polyethylene terephthalate film is preferable because it is excellent in mechanical strength, thermal stability and economic efficiency.
  • the transfer substrate may have a release layer (peeling layer).
  • peeling layer By having the release layer, transfer (peeling of the coating film from the substrate for transfer) can be easily performed.
  • the release layer is usually provided on the surface of the transfer substrate on which the coating film is formed (usually on one surface).
  • a coating film containing anion-modified CNF is formed on the surface of the release layer.
  • the release layer examples include, but are not limited to, silicone-based resins, acrylic resins, cellulose-based resins, melamine-based resins, phenol-based resins, urethane-based resins, isocyanate-based resins, urea-based resins, epoxy-based resins, unsaturated Polyester-based resins, etc., can be used, but silicone-based resins with low surface tension can be used so that the surface tension can be designed to be lower than that of the transfer base material, and the functional layer can be peeled off at the interface between the release layer and the functional layer for transfer. Resins, acrylic resins, cellulose resins, and the like are preferred.
  • the film thickness of the release layer is preferably 0.1 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m.
  • an unevenness imparting agent may be added.
  • the presence of the unevenness-imparting agent makes it easier to separate the functional layer from the release layer, while imparting an appropriate degree of roughness to the surface of the functional layer, which is suitable for increasing the surface area of the functional layer.
  • the average particle size of the roughening agent is preferably about 0.1 to 10 ⁇ m.
  • the release layer may also contain a release agent.
  • release agents include solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder, fluorine-based and phosphate ester-based surfactants, silicone resins, and silicone oils.
  • the method for forming the release layer is not particularly limited, and examples thereof include bar coating, blade coating, (air) knife coating, dip coating, tension web coating, die coating, and curtain coating. It can be appropriately selected from among these.
  • the release layer is preferably a uniform coating film.
  • Step 2 a support substrate is attached to the surface of the coating film formed on the transfer substrate.
  • the lamination method a known method can be used and is not particularly limited. , or 55 ° C. or higher, the upper limit is usually 80 ° C. or lower) and / or pressurization (e.g., 0.2 MPa or higher, 0.3 MPa or higher, 0.4 MPa or higher, the upper limit is usually 1.0 MPa or lower) method (e.g. , lamination method).
  • the support substrate and the coating film can be brought into closer contact with each other, and stronger adhesive force can be obtained than the interface between the functional layer and the transfer substrate or the release layer.
  • Lamination is performed continuously (for example, 0.1 m/min or more, 0.2 m/min or more, 0.3 m/min or more, 0.4 m/min or more, 0.5 m/min or more, and the upper limit is usually 1.0 m/min or less) may be performed.
  • Lamination may be performed using a device such as a laminator.
  • the coating film formed on the transfer base material in step 1 may be subjected to the bonding treatment in step 2 in a state in which it contains a small amount of a dispersion medium without being completely dried. As a result, the support substrate and the coating film can be brought into closer contact with each other, and stronger adhesive force than the interface between the functional layer and the transfer substrate or the release layer can be obtained.
  • the supporting substrate and the coating film may be directly laminated or may be laminated via the receiving layer.
  • the receiving layer include acrylic resins, cellulose resins, melamine resins, phenol resins, urethane resins, isocyanate resins, urea resins, epoxy resins, vinyl chloride resins, polypropylene, and the like.
  • Polyolefin resin halogenated resin such as polyvinyl chloride or polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer or vinyl resin such as polyacrylate, polyethylene
  • halogenated resin such as polyvinyl chloride or polyvinylidene chloride
  • polyvinyl acetate vinyl chloride-vinyl acetate copolymer
  • ethylene-vinyl acetate copolymer or vinyl resin such as polyacrylate
  • polyethylene examples include polyester resins such as terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene or propylene and other vinyl polymers, and polycarbonates.
  • the receiving layer in the transfer coating method is not particularly limited as long as it has a higher surface tension than the interface between the coating film serving as the functional layer and the substrate for transfer or the release layer, and improves the transferability of the functional layer.
  • the receiving layer may be formed on the surface of the supporting substrate, and is usually formed before step 2 in the case of the transfer coating method.
  • the method for forming the receptive layer can be selected appropriately according to the usual technique and conditions (for example, the same method as exemplified as the method for forming the release layer).
  • the receiving layer may be provided in advance on either the supporting substrate or the coating before lamination.
  • Step 3 the transfer substrate is peeled off to form a functional layer.
  • Existing methods such as roll peeling can be used as the peeling method.
  • the release layer and the coating film may be separated at the interface to form the functional layer, or the transfer base material and the release layer may be separated at the interface.
  • a release layer and a functional layer may be formed on the supporting substrate by peeling, but the former is preferred.
  • Applications of Laminate include, for example, substrates for various display devices, substrates for electronic devices, members for home appliances, back surface protective sheets for solar cell modules, sealing of organic EL elements, packaging materials for electronic parts, batteries and Electrodes for power storage devices, electronic members such as flexible printed wiring boards; Interior members, exterior members, door side panels, bonnets, roofs, lithium ion battery (LIB) spacers, battery cases, LED headlamps and other automotive members; Examples include packaging materials for pharmaceuticals and foods, but are not particularly limited to these exemplified uses.
  • substrates for various display devices substrates for electronic devices, members for home appliances, back surface protective sheets for solar cell modules, sealing of organic EL elements, packaging materials for electronic parts, batteries and Electrodes for power storage devices, electronic members such as flexible printed wiring boards; Interior members, exterior members, door side panels, bonnets, roofs, lithium ion battery (LIB) spacers, battery cases, LED headlamps and other automotive members;
  • LIB lithium ion battery
  • the laminate of the present invention is wetted, the anion-modified CNF in the wetted portion causes an electrical adsorption phenomenon due to redispersion, so it has self-regenerative properties without causing defects in the functional layer. It is expected. Therefore, the laminate is preferably used as an electronic member.
  • the reaction was terminated when the sodium hypochlorite was consumed and the pH in the system stopped changing.
  • the mixture after the reaction was filtered through a glass filter to separate the pulp, and the pulp was sufficiently washed with water to obtain an oxidized pulp.
  • the pulp yield at this time was 90%, and the time required for the oxidation reaction was 90 minutes.
  • the oxidized pulp obtained in the above steps was adjusted with water to each concentration shown in Table 1, and defibrated five times with an ultrahigh pressure homogenizer (20 ° C., 150 MPa) to obtain oxidized CNF dispersions A1 to A3. Obtained.
  • the resulting oxidized CNF had a carboxyl group content of 1.42 mmol/g, an average fiber diameter of 3.4 nm, and an average fiber length of 528 nm (Table 1).
  • CM-modified pulp obtained in the above steps was adjusted with water to each concentration shown in Table 1, and defibrated three times with an ultrahigh-pressure homogenizer (20°C, 150 MPa) to obtain CM-CNF dispersions B1 and B2. got The CM-CNF had an average fiber diameter of 3.7 nm and an average fiber length of 425 nm (Table 1).
  • the phosphate esterified pulp obtained in the above step is adjusted to 0.4% (w / v) with water, and defibrated three times with an ultrahigh pressure homogenizer (20 ° C., 150 MPa) to phosphate ester.
  • a dispersion C of CNF was obtained.
  • the phosphorylated CNF had a phosphate group substitution degree of 0.89 mmol/g, an average fiber diameter of 3.4 nm, and an average fiber length of 625 nm (Table 1).
  • the sulfated pulp obtained in the above step was adjusted to 0.4% (w / v) with water, and defibration was performed three times with an ultrahigh pressure homogenizer (20 ° C., 150 MPa) to produce sulfated CNF.
  • a dispersion D was obtained.
  • the sulfated CNF had a sulfate group content of 0.92 mmol/g, an average fiber diameter of 4.2, and an average fiber length of 354 (Table 1).
  • a reagent A was prepared by mixing 130 g of sodium hydrogen phosphite pentahydrate, 108 g of urea, and 762 g of water. 1000 g of prepared reagent A and 100 g of softwood pulp (manufactured by Nippon Paper Industries Co., Ltd., NBKP) were mixed and dried at 105°C. The dried pulp was reacted at 130° C. for 2 hours, washed with water and filtered twice to obtain a phosphite esterified pulp.
  • the phosphite esterified pulp obtained in the above process was adjusted to 0.4% (w/v) with water, and defibrated three times with an ultra-high pressure homogenizer (20°C, 150 MPa). A dispersion F of esterified CNF was obtained.
  • the phosphite-esterified CNF had a phosphite group substitution degree of 2.11 mmol/g, an average fiber diameter of 3.9 nm, and an average fiber length of 471 nm (Table 1).
  • the pH in the system decreased during the reaction, but was adjusted to pH 10 by successively adding 0.5N sodium hydroxide aqueous solution. After reacting for 2 hours, the mixture was filtered through a glass filter and thoroughly washed with water to obtain carboxylated cellulose.
  • Carboxylated cellulose slurries G1 and G2 were prepared by adding water to each concentration shown in Table 1, to which hydrogen peroxide was added at 2% (w/w) relative to the carboxylated cellulose, and 3M sodium hydroxide was added. to adjust the pH to 11.3. This slurry was left at a temperature of 80° C. for 2 hours for hydrolysis.
  • TEMPO-oxidized CNF dispersions G3, G1, G2, G4 and G5.
  • the resulting TEMPO-oxidized CNF had a carboxyl group content of 1.7 mmol/g, an average fiber diameter of 5.7 nm, and an average fiber length of 230 nm (Table 1).
  • sliding angle A liquid drop was dropped on a plate and the angle at which the liquid dropped when lifted was measured. That is, 0.2 g of CNF slurry is dropped on an aluminum plate at a temperature of 25 ° C. After standing for 1 minute, one side of the aluminum plate is lifted. values were measured.
  • the sliding angle is usually 70° or less, especially 60° or less, it can be evaluated that the coating uniformity is good.
  • the lower limit is usually 5° or more, preferably 10° or more.
  • B type viscosity Using a TV-10 type viscometer (Toki Sangyo Co., Ltd.), the B-type viscosity of each dispersion was measured under the conditions of 25° C. and 6 rpm or 60 rpm.
  • contact angle The contact angle between CNF slurry and aluminum foil was measured under the following conditions.
  • Contact angle measurement conditions Apparatus: Dynamic contact angle tester 1100DAT, manufactured by Fibro System AB Discharge amount: 5 ⁇ l Time until droplets drop after ejection: 40 seconds
  • Substrate Aluminum foil A contact angle of usually 70° or less, especially 65° or less can be evaluated as good wettability. The lower limit is usually 50° or more.
  • Ti value is the ratio of 6 rpm viscosity to 60 rpm viscosity and is proportional to thixotropy. In general, if the thixotropic properties are too high, the coating liquid will turn into a jelly, making it difficult to feed the liquid.
  • the Ti value is preferably 7.0 or less, more preferably 6.8 or less.
  • the lower limit is preferably 1.0 or more, more preferably 1.2 or more.
  • dispersions A3, B2, G3 to G5 Compared with dispersions A3, B2, G3 to G5, dispersions A1, A2, B1, C, D, F and G1 and G2 exhibit moderate sliding angles, contact angles, uniformity during coating, The wettability was evaluated as good. In addition, the fluidity and dripping properties were also evaluated as good.
  • Examples 1-1 to 1-5 Using a die coater and a lab coater equipped with a belt for transporting the substrate to the die coater, coating was performed under the following conditions.
  • the slit width of the die coater was set to 130 ⁇ m and the clearance was set to 500 ⁇ m.
  • the aqueous dispersion of each anion-modified CNF listed in Table 2 is used as a coating liquid so that it can be stably coated. It was spread evenly over the base material while adjusting the amount in minutes.
  • the coated sample was extracted from the lab coater, dried at 100° C. for 10 minutes in an explosion-proof dryer, and then cooled at room temperature to obtain a laminate produced by the die coating method (Table 2). .
  • Example 1 A laminate was obtained in the same manner as in Example 1, except that instead of using a die, the aluminum substrate was sprayed (spray coated) so that the film thickness after drying was about 6 ⁇ m (Table 2).
  • Example 1-6 to 1-17 and Comparative Examples 1-2 to 1-6 Using a lab coater equipped with a slot die for applying the coating liquid to the substrate, a dryer for drying the coating film after application, a slot die, and a belt and rolls for supplying the substrate in the order of the dryer, shown in Table 3
  • the coating and drying were performed continuously under the conditions, each dispersion shown in Table 3 was used as the coating liquid as an aqueous dispersion of anion-modified CNF, and the discharge amount was 130 to 200 mL so that stable coating could be performed.
  • a laminate produced by the die coating method in the same manner as in Example 1 was obtained (Table 3), except that the clearance was adjusted to 100 to 500 ⁇ m.
  • the drying temperature indicates the temperature of each sample.
  • the drying temperature in the drying device was set to 100°C.
  • Example 6 die coating was performed at a set temperature of the drying device of 100 ° C. and a sheet temperature of 85/83/84/85/86/81 ° C., and the drying conditions were a wind speed of 20 m / min and the conditions shown in Table 4. was performed in the same manner to confirm the degree of drying ( ⁇ : sufficiently dried; ⁇ : locally insufficient drying; ⁇ : insufficient drying (Table 4).
  • the laminate could be dried regardless of the drying conditions, but as is clear from the results of Examples 18 to 22, the drying time was 1 minute 30 seconds to 7 minutes 30 seconds and the coater speed was 1 to 5 m/min. Thus, sufficient drying was achieved (Table 4).
  • Example 5 After contacting one side of an aluminum substrate as a supporting substrate with an aqueous dispersion containing anion-modified CNF as shown in Table 5 as a coating liquid, a wireless bar (pitch 0.1 mm, depth 12 ⁇ m). was used to evenly spread the coating liquid on the substrate (Table 5).
  • Examples 3-1 to 3-5 A polyethylene terephthalate (PET) film having a film thickness of 100 ⁇ m was used as a transfer substrate, and an aluminum substrate was used as a support substrate.
  • PET polyethylene terephthalate

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  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un procédé de production d'un produit en couches comportant une couche fonctionnelle qui est idéale pour une utilisation dans diverses applications industrielles. La présente invention concerne un procédé de production d'un produit en couches, le procédé comprenant une étape de stratification consistant à former une couche fonctionnelle contenant des nanofibres de cellulose modifiée par voie anionique sur un substrat de support à l'aide d'un procédé d'application de revêtement tel qu'un procédé d'application de revêtement pré-dosage, un procédé d'application de revêtement post-dosage, ou un procédé d'application de revêtement par transfert. Les nanofibres de cellulose modifiée par voie anionique sont des nanofibres de cellulose oxydée comportant un groupe carboxyle et/ou un groupe carboxylate, et sont de préférence des nanofibres de cellulose carboxyalkylée, des nanofibres de cellulose estérifiée par de l'acide phosphorique, ou des nanofibres de cellulose estérifiée par de l'acide sulfurique.
PCT/JP2022/044126 2021-12-03 2022-11-30 Procédé de production d'un produit en couches contenant des nanofibres de cellulose Ceased WO2023100924A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2021-197013 2021-12-03
JP2021197013A JP2023082962A (ja) 2021-12-03 2021-12-03 セルロースナノファイバーを含む積層体の製造方法、及びその積層体。
JP2021-197014 2021-12-03
JP2021197015A JP2023082963A (ja) 2021-12-03 2021-12-03 セルロースナノファイバーを含む積層体の製造方法、及びその積層体。
JP2021-197015 2021-12-03
JP2021197014 2021-12-03
JP2022182544A JP2023083222A (ja) 2021-12-03 2022-11-15 セルロースナノファイバーを含む積層体の製造方法、及びその積層体
JP2022-182544 2022-11-15

Publications (1)

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WO2023100924A1 true WO2023100924A1 (fr) 2023-06-08

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040547A1 (fr) * 2009-09-30 2011-04-07 日本製紙株式会社 Matériau barrière en papier
JP2011202010A (ja) * 2010-03-25 2011-10-13 Toppan Printing Co Ltd 膜形成用材料およびその製造方法ならびにシート
JP2012076231A (ja) * 2010-09-30 2012-04-19 Nippon Paper Industries Co Ltd 紙製ガスバリア材料
WO2017111112A1 (fr) * 2015-12-25 2017-06-29 関西ペイント株式会社 Procédé de formation de film de revêtement multicouche
WO2017175468A1 (fr) * 2016-04-04 2017-10-12 関西ペイント株式会社 Dispersion de pigment brillant et procédé de formation d'un film de revêtement multicouche
WO2018012014A1 (fr) * 2016-07-13 2018-01-18 関西ペイント株式会社 Dispersion de pigment brillant
WO2018168736A1 (fr) * 2017-03-13 2018-09-20 富士フイルム株式会社 Film de transfert et procédé de formation d'image
JP2019202434A (ja) * 2018-05-22 2019-11-28 第一工業製薬株式会社 積層体
JP2021137983A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 紙バリア積層体および紙バリア容器
JP2021137982A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 両面ラミネート紙および紙カップ

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040547A1 (fr) * 2009-09-30 2011-04-07 日本製紙株式会社 Matériau barrière en papier
JP2011202010A (ja) * 2010-03-25 2011-10-13 Toppan Printing Co Ltd 膜形成用材料およびその製造方法ならびにシート
JP2012076231A (ja) * 2010-09-30 2012-04-19 Nippon Paper Industries Co Ltd 紙製ガスバリア材料
WO2017111112A1 (fr) * 2015-12-25 2017-06-29 関西ペイント株式会社 Procédé de formation de film de revêtement multicouche
WO2017175468A1 (fr) * 2016-04-04 2017-10-12 関西ペイント株式会社 Dispersion de pigment brillant et procédé de formation d'un film de revêtement multicouche
WO2018012014A1 (fr) * 2016-07-13 2018-01-18 関西ペイント株式会社 Dispersion de pigment brillant
WO2018168736A1 (fr) * 2017-03-13 2018-09-20 富士フイルム株式会社 Film de transfert et procédé de formation d'image
JP2019202434A (ja) * 2018-05-22 2019-11-28 第一工業製薬株式会社 積層体
JP2021137983A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 紙バリア積層体および紙バリア容器
JP2021137982A (ja) * 2020-03-02 2021-09-16 凸版印刷株式会社 両面ラミネート紙および紙カップ

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