WO2011040547A1 - Paper barrier material - Google Patents

Paper barrier material Download PDF

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Publication number
WO2011040547A1
WO2011040547A1 PCT/JP2010/067118 JP2010067118W WO2011040547A1 WO 2011040547 A1 WO2011040547 A1 WO 2011040547A1 JP 2010067118 W JP2010067118 W JP 2010067118W WO 2011040547 A1 WO2011040547 A1 WO 2011040547A1
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WO
WIPO (PCT)
Prior art keywords
gas barrier
paper
water
resin
barrier material
Prior art date
Application number
PCT/JP2010/067118
Other languages
French (fr)
Japanese (ja)
Inventor
民治郎 兼行
武史 中山
瑛司 草野
正一 宮脇
志穂 勝川
裕 阿部
夕子 飯嶋
Original Assignee
日本製紙株式会社
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Publication date
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2011534321A priority Critical patent/JPWO2011040547A1/en
Publication of WO2011040547A1 publication Critical patent/WO2011040547A1/en

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Classifications

    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B23/06—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 paper or cardboard
    • 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
    • B32B23/14—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 characterised by containing special compounding ingredients
    • 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
    • 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
    • B32B23/22—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 ethers
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7166—Water-soluble, water-dispersible
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier

Definitions

  • the present invention relates to a barrier material made of gas barrier property paper.
  • gas barriers especially oxygen barriers
  • oxygen barriers are well known in paper, cardboard and cardboard.
  • an oxygen barrier layer is provided on paper, cardboard base paper, and cardboard to provide oxygen barrier properties.
  • a metal foil or metal vapor deposition film made of a metal such as aluminum, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, etc.
  • a method of extruding and laminating or pasting resin films, films coated with these resins, ceramic vapor deposited films deposited with inorganic oxides such as silicon oxide and aluminum oxide, etc. onto paper substrates has been mainly used. It was.
  • Patent Document 1 proposes a method of providing polyvinyl alcohol and an inorganic layered compound on a paper substrate.
  • Patent Document 2 proposes, similarly to Patent Document 1, a laminated paper for packaging provided with a paper layer and a resin composition layer having an inorganic layer compound on the paper layer.
  • Patent Document 3 proposes a paper composite having a resin composition layer containing 0.01 to 200 parts by weight of a layered inorganic compound with respect to 100 parts by weight of a water-soluble polymer compound on at least one surface of paper. Yes.
  • Patent Document 4 discloses a saponified ethylene-vinyl ester copolymer (A) having an ethylene content of 1 to 15 mol%, a saponified ethylene-vinyl ester copolymer (B) having an ethylene content of 15 to 70 mol%, and A resin composition comprising an inorganic layered compound (C) has been proposed.
  • Patent Document 5 in a laminate comprising a coating layer 1, a barrier layer 2, and a paper base material 3, the barrier layer 2 is a paper or biaxially stretched film base material B and vinyl having an ethylene content of 0 to 15 mol%.
  • a laminate comprising a layer A of an alcohol polymer has been proposed.
  • Patent Document 6 discloses a gas barrier laminate in which a first gas barrier layer and a second gas barrier layer containing a water-soluble polymer and an inorganic layered compound are provided in this order on a paper support.
  • the mass ratio of the water-soluble polymer to the inorganic layered compound is 75/25 to 50/50, and the mass ratio of the water-soluble polymer to the inorganic layered compound in the second gas barrier layer is 95/5 to 75 /
  • a gas barrier laminate of 25 is proposed.
  • Patent Document 7 in a gas barrier laminate in which a gas barrier layer containing a water-soluble polymer, an inorganic layered compound, and a synthetic resin is provided on a paper support, the inorganic layered compound is used with respect to 100 parts by mass of the water-soluble polymer.
  • a gas barrier laminate in which 10 to 150 parts by mass and 5 to 100 parts by mass of a synthetic resin has been proposed.
  • Patent Document 8 discloses a gas barrier layer and a heat seal layer in which a first gas barrier layer containing an ethylene-modified polyvinyl alcohol resin and an inorganic layered compound and a second gas barrier layer made of ethylene-modified polyvinyl alcohol are sequentially provided on a paper support. A gas barrier laminate having good adhesion is proposed.
  • the present invention can be inspected by a metal detector by applying a water-soluble paint and providing a coating layer having a gas barrier property on a paper base material.
  • An object of the present invention is to provide a paper barrier material that can be heat sealed and produced at low cost.
  • the present inventors apply an aqueous solution containing cellulose nanofibers (hereinafter sometimes referred to as “CNF”) and a water-soluble gas barrier resin to paper to provide a gas barrier layer, thereby providing a gas barrier layer.
  • CNF cellulose nanofibers
  • the present inventors have found that a paper barrier material having a barrier property can be obtained, and have achieved the present invention.
  • the present invention provides a paper barrier material in which a gas barrier layer containing cellulose nanofibers and a water-soluble gas barrier resin is provided on at least one surface of a paper substrate, and the cellulose nanofibers in the gas barrier layer Is a paper barrier material in which the weight ratio of the water-soluble gas barrier resin to the water-soluble gas barrier resin is 0.1 to 43 parts by mass with respect to 100 parts by mass of the water-soluble gas barrier resin.
  • the water-soluble gas barrier resin is carboxymethylcellulose, methylcellulose, carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, chitosan, polyacrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, and ethylene-vinyl alcohol. It is preferably at least one of a polymer, polymethacrylic acid, polyamine, polyvinylpyridine, salts of these compounds, and a mixture of any of these materials. Furthermore, gas barrier properties can be improved by subjecting CNF to ultraviolet (UV) treatment.
  • UV ultraviolet
  • a metal detector by applying a small amount of a coating liquid containing cellulose nanofibers and a water-soluble gas barrier resin as a water-soluble paint on a paper substrate, and providing a gas barrier layer, a metal detector is used. It is possible to obtain a paper barrier material that can be inspected, can be treated as a combustible material after use, does not emit harmful substances during combustion, can be heat-sealed, and can be produced at low cost.
  • the cellulose nanofibers are nanofibers using natural cellulose microfibrils, and are superior in strength and heat resistance compared to conventional cellulose materials.
  • the cellulose nanofiber is not limited to a single unit and is usually used in a bundle of a plurality of pieces, but a more preferable form is a single microfibril.
  • the preferred size of the cellulose nanofibers is 0.5 to 800 nm in width (the dimension in the direction perpendicular to the length direction, corresponding to the diameter in the case of a single bundle and the diameter of the bundle in the case of a bundle of plural fibers). (Including the width when plural bundles are formed), more preferably 2 to 5 nm in width and about 1 to 5 ⁇ m in length.
  • the cellulose nanofiber dispersion of the present invention has a B-type viscosity (60 rpm, 20 ° C.) at a concentration of 1.0% by mass (w / v) of 1000 mPa ⁇ s or less, preferably 800 mPa ⁇ s or less, more preferably 500 mPa ⁇ s.
  • the light transmittance (660 nm) at a concentration of 0.1% by mass (w / v) is 90% or more, preferably 95% or more.
  • the cellulose nanofibers used in the present invention are excellent in fluidity and transparency, and further excellent in gas barrier properties and heat resistance, and thus can be used in various applications such as packaging materials.
  • the B-type viscosity of the cellulose nanofiber dispersion can be measured using a normal B-type viscometer commonly used by those skilled in the art, for example, TV-10 type viscosity of Toki Sangyo Co., Ltd. Using a meter, it can be measured at 20 ° C. and 60 rpm.
  • the amount of carboxyl groups of the cellulose nanofiber of the present invention is preferably 0.5 mmol / g or more, more preferably 1.0 mmol / g to 3.0 mmol / g, based on the absolute dry mass of the cellulose-based raw material.
  • the amount of carboxyl groups can be adjusted by adjusting the oxidation reaction time, adjusting the oxidation reaction temperature, adjusting the pH during the oxidation reaction, adjusting the amount of N-oxyl compound, bromide, iodide, and oxidizing agent added. It can be the amount of carboxyl groups.
  • the concentration of the oxidized cellulose raw material is 0.1% by mass or more. This is preferable because the flowability of the cellulosic raw material is good and the reaction efficiency is increased. Therefore, when irradiating with ultraviolet rays, the concentration of the oxidized cellulose-based raw material is preferably 0.1 to 12% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 5% by mass. It is.
  • the temperature of the cellulosic raw material when irradiating with ultraviolet rays is preferably 20 ° C. or higher because the efficiency of the photooxidation reaction is increased.
  • the temperature of the cellulosic raw material when irradiated with ultraviolet rays is preferably 20 to 95 ° C., more preferably 20 to 80 ° C., and still more preferably 20 to 50 ° C.
  • the pH at the time of irradiation with ultraviolet rays is not particularly limited, but it is preferable from the viewpoint of simplification of the process to carry out the treatment in a neutral region, for example, about pH 6.0 to 8.0.
  • the wavelength of the ultraviolet light is preferably 100 to 400 nm, more preferably 100 to 300 nm. Among these, ultraviolet rays having a wavelength of 135 to 260 nm are preferable from the viewpoint of reducing the viscosity.
  • ultraviolet rays contained in sunlight ultraviolet rays having a wavelength of 200 nm or less are absorbed by oxygen molecules and nitrogen molecules, and ultraviolet rays having a wavelength of 200 to 280 nm are usually prevented from being present on the ground surface because they are prevented by the ozone layer. Further, the ultraviolet irradiation treatment can be repeated a plurality of times. The number of repetitions can be appropriately set according to the target quality of the oxidized cellulosic raw material and the relationship with post-treatment such as bleaching.
  • ultraviolet rays of 100 to 400 nm, preferably 135 to 260 nm are applied 1 to 10 times, preferably about 2 to 5 times, 0.5 to 10 hours per time, preferably 0.5 to 3 times. It can be irradiated for as long as an hour.
  • the mechanism is unclear by irradiating the cellulosic raw material oxidized with the N-oxyl compound with ultraviolet rays, followed by defibration / dispersion treatment.
  • Cellulose nanofibers that are excellent in transparency and that exhibit high gas barrier properties can be obtained.
  • cellulose nano-materials excellent in fluidity and transparency even at a high concentration are obtained by irradiating ultraviolet rays to cellulose-based raw materials oxidized using an N-oxyl compound, and then performing defibration and dispersion treatment.
  • a fiber dispersion can be obtained with low power consumption. The reason is guessed as follows. A carboxyl group is localized on the surface of the cellulosic raw material oxidized with the N-oxyl compound, and a hydrated layer is formed. Therefore, it is considered that there is a microscopic gap between the raw materials which is not found in ordinary pulp due to the action of the charge repulsion between carboxyl groups.
  • the raw material When the raw material is irradiated with ultraviolet rays, active oxygen species having excellent oxidizing power such as ozone are generated from oxygen dissolved in the hydration layer on the surface of the raw material or pore water of the raw material, and this product is oxidized.
  • active oxygen species having excellent oxidizing power such as ozone are generated from oxygen dissolved in the hydration layer on the surface of the raw material or pore water of the raw material, and this product is oxidized.
  • cellulose nanofibers when cellulose nanofibers are added to other water-soluble gas barrier resins and coated on paper, further improvement in gas barrier properties can be expected. This is considered to have both the gas barrier properties of cellulose nanofibers and the prevention of penetration into paper due to the thickening action of the coating liquid.
  • the water-soluble gas barrier resin and the cellulose nanofibers can be mixed and applied rather than separately, thereby obtaining a synergistic effect as a gas barrier material. Although it is not clear about this effect
  • the ultraviolet irradiation treatment described above can be mentioned, and the gas barrier property can be improved by subjecting the cellulose nanofibers to ultraviolet treatment.
  • the gas barrier layer can be made thin. The improvement is about 50%, and the layer thickness can be halved.
  • the viscosity of the paint is increased, which may cause poor stirring and impair the coating suitability.
  • the flexibility of the barrier material is impaired, it does not have the folding processability required when used as a packaging material.
  • the preferable compounding quantity of the said cellulose nanofiber shall be 0.1 to 43 mass parts with respect to 100 mass parts of water-soluble gas barrier resin, More preferably, it is 25 mass parts or less.
  • the preferable compounding quantity of the said cellulose nanofiber shall be 0.1 to 43 mass parts with respect to 100 mass parts of water-soluble gas barrier resin, More preferably, it is 25 mass parts or less.
  • Water-soluble gas barrier resin is carboxymethylcellulose, methylcellulose, carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, chitosan, polyacrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, ethylene-vinyl alcohol copolymer
  • the polymer, polymethacrylic acid, polyamine, polyvinyl pyridine, and salts of these compounds, and any of these materials are used.
  • a gas barrier resin having a hydroxyl group has high binding properties to cellulose nanofibers. Therefore, it is more preferable.
  • a barrier material having high gas barrier properties can be obtained by using an ethylene-vinyl alcohol copolymer or polyvinyl alcohol.
  • the ethylene-vinyl alcohol copolymer resin (EVOH) is obtained by hydrolysis of ethylene and vinyl acetate copolymer.
  • Polyvinyl alcohol has high gas barrier properties, oil resistance, and transparency, and also has properties such as moisture resistance and melt extrusion processability of ethylene components.
  • it is possible to modify the water-soluble gas barrier resin by adding a small amount of cellulose nanofibers to the above-mentioned water-soluble gas barrier resin, thereby improving the gas barrier characteristics of the paper gas barrier material. Can be improved.
  • the gas barrier property in the present invention has an oxygen transfer rate (OTR) of less than 10 cc / m 2 / day when measured at 0% relative humidity (% RH) at standard temperature and pressure (STP). More preferably, it is less than 3 cc / m 2 / day.
  • OTR oxygen transfer rate
  • a water-soluble gas barrier resin such as polyvinyl alcohol requires a large amount of material per 1 m 2 in order to achieve the above-mentioned effects. However, when cellulose nanofiber is mixed with this, the required amount can be reduced. it can.
  • the paper base is an aggregate in which pulp fibers are intertwined mainly composed of cellulose, and includes wrapping paper, paperboard, cardboard base paper, laminated paper and the like. It is also effective to provide a sealing layer between the paper substrate and the gas barrier layer in order to give the barrier material a high gas barrier property.
  • the sealing layer include a coating layer containing a pigment such as clay and a binder resin, and a coating layer made of a resin having a film property.
  • providing a moisture barrier layer that provides a barrier to liquids and water vapor between the paper substrate and the oxygen barrier layer, or the exposed surface of the oxygen barrier layer, or both suppresses the deterioration of barrier properties under high humidity. It is effective for.
  • a layer of heat sealable material may be applied to the exposed surface of the gas barrier layer.
  • the paper barrier material of the present invention can be formed and processed into food packaging materials, containers, cups and the like.
  • the gas barrier layer is provided by applying a water-based coating liquid containing cellulose nanofibers and a water-soluble gas barrier resin to the surface of the paper substrate and then drying it.
  • a coating solution containing cellulose nanofibers a two-roll size press coater, a gate roll coater, a blade metering coater, a rod metering coater, a blade coater, an air knife coater, a roll coater, a brush coater, and a kiss coater.
  • a known coating machine such as a squeeze coater, a curtain coater, a die coater, a bar coater, a gravure coater, or a dip coater can be used.
  • a well-known dryer can be used for drying.
  • chemicals such as a sizing agent, water-proofing agent, water repellent, and dye can be mixed and used in the gas barrier layer as needed without impairing the effects of the present invention.
  • the auxiliary agent is not blended.
  • Example 1 One part of cellulose nanofiber (solid content concentration 1%) was mixed with 100 parts of polyvinyl alcohol-based resin (trade name EXEVAL, Kuraray Co., Ltd., solid content concentration 20%) to prepare a coating solution. Using a Mayer bar, this coating solution is applied to the coated surface of coated paper (trade name: Aurora Coat, 157 g / m 2 , manufactured by Nippon Paper Industries Co., Ltd.) at a solid content of 1.0 g / m 2. The gas barrier layer was applied and dried at a drying temperature of 105 ° C. using a blow dryer to obtain a paper barrier material.
  • coated paper trade name: Aurora Coat, 157 g / m 2 , manufactured by Nippon Paper Industries Co., Ltd.
  • the gas barrier layer was applied and dried at a drying temperature of 105 ° C. using a blow dryer to obtain a paper barrier material.
  • Examples 2 to 9, Comparative Examples 1 to 7 As shown in Tables 1 and 2, with respect to the composition of the gas barrier layer, the same as in Example 1, except that the addition ratio of cellulose nanofiber, polyvinyl alcohol resin, mica, and the coating amount of the gas barrier layer was changed. A barrier material was obtained.
  • oxidized powdered cellulose was separated by centrifugal operation (6000 rpm, 30 minutes, 20 ° C.) and sufficiently washed with water to obtain oxidized powdered cellulose.
  • a 2% (w / v) slurry of oxidized powdered cellulose was treated with a mixer at 12,000 rpm for 15 minutes, and the powdered cellulose slurry was further treated with an ultra-high pressure homogenizer five times at a shipping pressure of 140 MPa to obtain a transparent gel A dispersion was obtained.
  • the obtained 2% (w / v) cellulose nanofiber dispersion was further diluted to obtain a cellulose nanofiber dispersion having a solid concentration of 1% (w / v).
  • the B type viscosity of the obtained cellulose nanofiber was 890 (mPa ⁇ s).
  • the maximum fiber diameter of the cellulose nanofibers was 10 nm, and the number average fiber diameter was 6 nm.
  • ⁇ Bending aptitude evaluation method> A film having a thickness of 30 ⁇ m was prepared from each oxygen barrier layer coating solution, and it was observed whether or not the film was broken when it was bent 180 degrees. Evaluation criteria ⁇ : The film does not crack. X: The film is cracked. Or the film is torn.
  • ⁇ Laminate adhesion> A polyethylene layer having a thickness of 20 ⁇ m was extruded and laminated on the oxygen barrier layer, and an adhesive tape peeling test was performed on each sample after lamination to observe the peeling state.
  • As a pressure-sensitive adhesive tape a 15 mm wide transparent tape manufactured by Nichiban Co., Ltd. was used. The pressure-sensitive adhesive tape was attached on the oxygen barrier layer and rubbed several times by hand, and then the pressure-sensitive adhesive tape was peeled off. Evaluation criteria A: Adhesion between the gas barrier layer and the polyethylene is good, and the paper substrate is destroyed on the entire surface of the adhesive tape. ⁇ : The paper base material is partially destroyed. X: Peeling has occurred between the gas barrier layer and the polyethylene.
  • the paper barrier materials obtained in the examples corresponding to the present invention were excellent in oxygen barrier properties, bendability and laminate adhesion even when the coating amount of the gas barrier layer was small.
  • the oxygen permeability was 8.1 and 4.2 at polyvinyl alcohol coating amounts of 10 g / m 2 and 15 g / m 2 , respectively. Therefore, in order to satisfy the oxygen permeability of 3.0, at least the coating amount of polyvinyl alcohol needs to be 15 g / m 2 or more.
  • Example 1 From Examples 1 to 9, it can be seen that by adding 1 to 43 parts of cellulose nanofiber to 100 parts of polyvinyl alcohol resin, the amount of oxygen permeation is reduced.
  • Example 4 having a coating amount of 5.0 g / m 2 is compared with Comparative Example 2, the oxygen permeability is 0.14: 13.2, which is about 100 times different.
  • Example 1 and Comparative Example 1 having a coating amount of 1.0 g / m 2 have an oxygen permeability of 2.8: 32, which is about 10 times.
  • the present invention exhibits an improvement of about 10 times the dependency of CNF on the layer thickness.
  • the lamination adhesiveness improved by adding a cellulose nanofiber to polyvinyl alcohol-type resin.
  • the folding characteristic is an index that affects the performance of a container or the like accompanied by a bending process. This indicator is not necessary when the influence of bending such as heat sealing can be ignored.
  • gas barrier properties could be further improved by adding a small amount of a flat pigment such as layered silicic acid represented by mica.
  • Example 10 10 parts of cellulose nanofiber (solid content concentration 1%) is mixed with 100 parts of polyvinyl alcohol resin (trade name EXEVAL, Kuraray Co., Ltd., solid content concentration 10%), and 11 parts of isopropyl alcohol is mixed with this mixed solution.
  • the coating liquid was adjusted by adding at a ratio.
  • This coating solution is applied on a laminated surface of polyethylene single-sided laminated paper (paper basis weight: 200 g / m 2 , polyethylene thickness: 20 ⁇ m) using a Meyer bar so that the solid content is 0.5 g / m 2. And dried using a blow dryer at a drying temperature of 80 ° C. to obtain a paper barrier material.
  • Example 11 After obtaining powdered cellulose oxidized in the same manner as in Examples 1 to 10, it was treated with a 20 W low-pressure mercury lamp that irradiates 254 nm ultraviolet light for 0.5 hour. Ultraviolet-treated oxidized pulp slurry was treated 10 times with an ultra-high pressure homogenizer (treatment pressure 140 MPa), and a transparent gel-like cellulose nanofiber dispersion was obtained. Type B at 1% (w / v) of the dispersion The viscosity (60 rpm, 20 ° C.) was 700 mPa ⁇ s. A paper barrier material was obtained in the same manner as in Example 10 except that this cellulose nanofiber dispersion was used.
  • Example 12 From observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofiber was 10 nm, and the number average fiber diameter was 6 nm.
  • a paper barrier material was obtained in the same manner as in Example 11 except that the wavelength of the ultraviolet light was changed to 380 nm. From observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofibers is 10 nm, the number average fiber diameter is 6 nm, and the B-type viscosity (60 rpm, 20 ° C.) at 1% (w / v) of the dispersion. ) was 800 mPa ⁇ s.
  • Example 13 A paper barrier material was obtained in the same manner as in Example 11 except that the ultraviolet irradiation time was changed to 6 hours. From observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofibers is 10 nm, the number average fiber diameter is 6 nm, and the B-type viscosity (60 rpm, 20 ° C.) at 1% (w / v) of the dispersion. ) was 320 mPa ⁇ s.
  • AFM atomic force microscope
  • Example 8 Based on Example 10, a paper barrier material coated with PVA and CNF separately was prepared and tested.
  • the coating liquid (B) was adjusted at a ratio of 1 part of isopropyl alcohol to 10 parts of cellulose nanofiber (solid content concentration 1%). Then, the coating liquid (A) containing the polyvinyl alcohol-type resin which made solid content 0.45g / m ⁇ 2 > was prepared.
  • a coating liquid (B) containing cellulose nanofibers having a solid content of 0.05 g / m 2 was prepared. (A) It coated separately in the order of (B).
  • Example 10 and Comparative Example 8 From Example 10 and Comparative Example 8, the cellulose nanofiber and the water-soluble gas barrier resin exhibited a high gas barrier property by applying them by mixing rather than applying them separately. Further, in Examples 11 and 13 in which ultraviolet ray irradiation was added to the production process of cellulose nanofiber, the gas barrier property was further improved as the irradiation time became longer. In addition, as for the ultraviolet wavelength, the treatment at 254 nm in Example 11 was more effective than the treatment at 380 nm in Example 12. When Example 13 and Example 3 are compared, the oxygen permeability is comparable. This indicates that the UV-treated Example 11 has about half the amount of CNF compared to Example 3, so that the gas barrier property can be improved by twice or more by the UV treatment.

Abstract

A paper barrier material provided, on at least one surface of a paper base, with a gas-barrier layer comprising cellulose nanofibers and a water-soluble oxygen-barrier resin, wherein said gas-barrier layer contains, in terms of the weight ratio of the cellulose nanofibers to a water-soluble gas-barrier resin, 0.1 to 43 parts by mass inclusive of the cellulose nanofibers per 100 parts by mass of the water-soluble gas-barrier resin. The paper barrier material thus provided is applicable to search with a metal detector, can be discarded as flammable garbage after using, generates no harmful substance during combustion, can be heat-sealed and can be produced at a low cost.

Description

紙製バリア材料Paper barrier material
　本発明は、ガスバリア特性紙製バリア材料に関する。 The present invention relates to a barrier material made of gas barrier property paper.
　紙、段ボール原紙および厚紙において、ガスバリア（特に、酸素バリア）に対する必要性はよく知られている。
　酸素が製品に接触すると、製品の貯蔵寿命は低減されてしまう。このため、酸素バリア層が、紙、段ボール原紙および厚紙上に設けられ酸素バリア特性が付与される。 The need for gas barriers (especially oxygen barriers) is well known in paper, cardboard and cardboard.
When oxygen comes into contact with the product, the shelf life of the product is reduced. For this reason, an oxygen barrier layer is provided on paper, cardboard base paper, and cardboard to provide oxygen barrier properties.
　従来、紙基材へのガスバリア性の付与には、ガスバリア層として、アルミニウム等の金属からなる金属箔や金属蒸着フィルム、ポリビニルアルコールやエチレン－ビニルアルコール共重合体、ポリ塩化ビニリデン、ポリアクリロニトリル等の樹脂フィルム、あるいはこれらの樹脂をコーティングしたフィルム、さらに酸化珪素や酸化アルミニウム等の無機酸化物を蒸着したセラミック蒸着フィルム等を紙基材に押し出しラミネート、または、貼合する方法が主に用いられてきた。 Conventionally, for providing a gas barrier property to a paper substrate, as a gas barrier layer, a metal foil or metal vapor deposition film made of a metal such as aluminum, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, etc. A method of extruding and laminating or pasting resin films, films coated with these resins, ceramic vapor deposited films deposited with inorganic oxides such as silicon oxide and aluminum oxide, etc. onto paper substrates has been mainly used. It was.
　また、近年でも紙基材表面にガスバリア層を形成する技術が多数提案されている。特許文献１にはポリビニルアルコールと無機層状化合物を紙基材上に設ける方法が提案されている。特許文献２には、特許文献１と同様に、紙状物層と、上記紙状物層上に無機層状化合物を有する樹脂組成物層とを備えている包装用積層紙が提案されている。特許文献３には、紙の少なくとも一面に、水溶性高分子化合物１００重量部に対し、層状無機化合物を０．０１～２００重量部含有する樹脂組成物の層を有する紙複合体が提案されている。特許文献４には、エチレン含有量１～１５モル％のエチレン－ビニルエステル共重合体ケン化物（Ａ）、エチレン含有量１５～７０モル％のエチレン－ビニルエステル共重合体ケン化物（Ｂ）および無機層状化合物（Ｃ）からなる樹脂組成物が提案されている。 In recent years, many techniques for forming a gas barrier layer on the surface of a paper substrate have been proposed. Patent Document 1 proposes a method of providing polyvinyl alcohol and an inorganic layered compound on a paper substrate. Patent Document 2 proposes, similarly to Patent Document 1, a laminated paper for packaging provided with a paper layer and a resin composition layer having an inorganic layer compound on the paper layer. Patent Document 3 proposes a paper composite having a resin composition layer containing 0.01 to 200 parts by weight of a layered inorganic compound with respect to 100 parts by weight of a water-soluble polymer compound on at least one surface of paper. Yes. Patent Document 4 discloses a saponified ethylene-vinyl ester copolymer (A) having an ethylene content of 1 to 15 mol%, a saponified ethylene-vinyl ester copolymer (B) having an ethylene content of 15 to 70 mol%, and A resin composition comprising an inorganic layered compound (C) has been proposed.
　特許文献５には、被覆層１、バリア層２および紙基材３からなる積層体において、バリア層２が、紙または二軸延伸フィルムの基材Ｂおよびエチレン含有率０～１５モル％のビニルアルコール系重合体の層Ａからなる積層体が提案されている。特許文献６には、紙支持体上に水溶性高分子および無機層状化合物を含む第１ガスバリア層と第２ガスバリア層とを、この順で設けたガスバリア性積層体において、第１ガスバリア層中の水溶性高分子と無機層状化合物との質量比が７５／２５～５０／５０であり、かつ、第２ガスバリア層中の水溶性高分子と無機層状化合物との質量比が９５／５～７５／２５であるガスバリア性積層体が提案されている。特許文献７には、紙支持体上に水溶性高分子と無機層状化合物と合成樹脂とを含むガスバリア層を設けたガスバリア性積層体において、水溶性高分子１００質量部に対して、無機層状化合物が１０～１５０質量部、合成樹脂が５～１００質量部であるガスバリア性積層体が提案されている。特許文献８には、紙支持体上にエチレン変性ポリビニルアルコール樹脂と無機層状化合物を含む第１のガスバリア層と、エチレン変性ポリビニルアルコールからなる第２のガスバリア層を順次設けたガスバリア層とヒートシール層の接着が良好なガスバリア性積層体が提案されている。 In Patent Document 5, in a laminate comprising a coating layer 1, a barrier layer 2, and a paper base material 3, the barrier layer 2 is a paper or biaxially stretched film base material B and vinyl having an ethylene content of 0 to 15 mol%. A laminate comprising a layer A of an alcohol polymer has been proposed. Patent Document 6 discloses a gas barrier laminate in which a first gas barrier layer and a second gas barrier layer containing a water-soluble polymer and an inorganic layered compound are provided in this order on a paper support. The mass ratio of the water-soluble polymer to the inorganic layered compound is 75/25 to 50/50, and the mass ratio of the water-soluble polymer to the inorganic layered compound in the second gas barrier layer is 95/5 to 75 / A gas barrier laminate of 25 is proposed. In Patent Document 7, in a gas barrier laminate in which a gas barrier layer containing a water-soluble polymer, an inorganic layered compound, and a synthetic resin is provided on a paper support, the inorganic layered compound is used with respect to 100 parts by mass of the water-soluble polymer. A gas barrier laminate in which 10 to 150 parts by mass and 5 to 100 parts by mass of a synthetic resin has been proposed. Patent Document 8 discloses a gas barrier layer and a heat seal layer in which a first gas barrier layer containing an ethylene-modified polyvinyl alcohol resin and an inorganic layered compound and a second gas barrier layer made of ethylene-modified polyvinyl alcohol are sequentially provided on a paper support. A gas barrier laminate having good adhesion is proposed.
特開平１１－１２９３８１号公報JP-A-11-129381 特開平１１－３０９８１７号公報Japanese Patent Laid-Open No. 11-309817 特開平１３－２１４３９６号公報Japanese Patent Laid-Open No. 13-214396 特開平１４－０６９２５５号公報Japanese Patent Application Laid-Open No. 14-069255 特開平１５－０９４５７４号公報Japanese Patent Laid-Open No. 15-094574 特開２００７－２１６５９２号公報JP 2007-216592 A 特開２００７－２１６５９３号公報JP 2007-216593 A 特開２００９－１８４１３８号公報JP 2009-184138 A
　ガスバリア性を有する合成樹脂層だけでは、食品の包装材としては十分なガスバリア性が得られずに、先行文献に示したような工夫が提案され、実用されている。しかし、金属箔を使用すると、ガスバリア性に優れるが、検査の際金属探知器が使用できないこと、リサイクル時にセルロース繊維との分離が難しく再利用ができないこと等の問題がある。また、ポリアクリロニトリル等は廃棄・焼却の際に有害物質の原料となりうる可能性がある等の問題がある。また、紙にポリビニルアルコールやエチレン－ビニルアルコール共重合体を押し出しラミネートする場合でも、水溶性塗料として紙に塗工するよりコスト高となる。また、セラミック蒸着フィルム等は、蒸着層がセラミック故に可撓性に欠け加工適性に十分注意しなければならない、加工機が高価な為コストが高くなる等の問題がある。 Only a synthetic resin layer having a gas barrier property cannot provide a gas barrier property sufficient as a packaging material for food, and a device as shown in the prior art has been proposed and put into practical use. However, when a metal foil is used, the gas barrier property is excellent, but there are problems that a metal detector cannot be used for inspection and that it cannot be reused because it is difficult to separate from cellulose fibers during recycling. In addition, polyacrylonitrile and the like have a problem that they can become a raw material for harmful substances during disposal and incineration. Even when polyvinyl alcohol or ethylene-vinyl alcohol copolymer is extruded and laminated on paper, the cost is higher than when it is applied to paper as a water-soluble paint. In addition, the ceramic vapor-deposited film has a problem that since the vapor-deposited layer is ceramic, it is inflexible and sufficient attention must be paid to processing suitability, and the processing machine is expensive, resulting in high costs.
　したがって、本発明は、水溶性塗料を塗工して、ガスバリア性を有する塗工層を紙基材上に設けることにより、金属探知器による検査が可能で、リサイクル性に優れ、燃焼時に有害物質が出ず、ヒートシール可能で、かつ、低コストで生産可能な紙製バリア材料を提供することを目的とする。 Therefore, the present invention can be inspected by a metal detector by applying a water-soluble paint and providing a coating layer having a gas barrier property on a paper base material. An object of the present invention is to provide a paper barrier material that can be heat sealed and produced at low cost.
　本発明者らは、セルロースナノファイバー（以下「ＣＮＦ」と称することがある）と水溶性のガスバリア性樹脂を含有する水溶液を紙に塗工してガスバリア層を設けることにより、酸素等のガスの遮断性を有する紙製バリア材料が得られることを見出し、本発明を成すに至った。したがって、本発明は、紙基材の少なくとも一方の表面に、セルロースナノファイバーと水溶性ガスバリア性樹脂とを含有するガスバリア層を設けた紙製バリア材料であって、前記ガスバリア層中のセルロースナノファイバーと水溶性ガスバリア性樹脂の含有重量比が水溶性ガスバリア性樹脂１００質量部に対し、セルロースナノファイバー０．１質量部以上４３質量部以下である、紙製バリア材料である。
　また、前記水溶性ガスバリア性樹脂が、カルボキシメチルセルロース、メチルセルロース、カルボキシアルキルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、キトサン、ポリアクリルアミド、ポリアクリル酸、ポリエチレンオキシド、ポリビニルアルコール、エチレン－ビニルアルコール共重合体、ポリメタクリル酸、ポリアミン、ポリビニルピリジン、およびこれらの化合物の塩、ならびにこれらの材料のいずれかの混合物のうち少なくとも１種であることが好ましい。
　さらに、ＣＮＦに紫外線（ＵＶ）処理を施すことにより、ガスバリア性を向上させることができる。 The present inventors apply an aqueous solution containing cellulose nanofibers (hereinafter sometimes referred to as “CNF”) and a water-soluble gas barrier resin to paper to provide a gas barrier layer, thereby providing a gas barrier layer. The present inventors have found that a paper barrier material having a barrier property can be obtained, and have achieved the present invention. Accordingly, the present invention provides a paper barrier material in which a gas barrier layer containing cellulose nanofibers and a water-soluble gas barrier resin is provided on at least one surface of a paper substrate, and the cellulose nanofibers in the gas barrier layer Is a paper barrier material in which the weight ratio of the water-soluble gas barrier resin to the water-soluble gas barrier resin is 0.1 to 43 parts by mass with respect to 100 parts by mass of the water-soluble gas barrier resin.
In addition, the water-soluble gas barrier resin is carboxymethylcellulose, methylcellulose, carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, chitosan, polyacrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, and ethylene-vinyl alcohol. It is preferably at least one of a polymer, polymethacrylic acid, polyamine, polyvinylpyridine, salts of these compounds, and a mixture of any of these materials.
Furthermore, gas barrier properties can be improved by subjecting CNF to ultraviolet (UV) treatment.
　本発明によれば、水溶性の塗料としてセルロースナノファイバーと水溶性ガスバリア性樹脂とを含有する塗工液を紙基材上に少量塗工して、ガスバリア層を設けることにより、金属探知器による検査が可能で、使用後に可燃物として処理でき、燃焼時に有害物質が出ず、ヒートシール可能で、かつ、低コストで生産可能な紙製バリア材料を得ることが可能となる。 According to the present invention, by applying a small amount of a coating liquid containing cellulose nanofibers and a water-soluble gas barrier resin as a water-soluble paint on a paper substrate, and providing a gas barrier layer, a metal detector is used. It is possible to obtain a paper barrier material that can be inspected, can be treated as a combustible material after use, does not emit harmful substances during combustion, can be heat-sealed, and can be produced at low cost.
　本発明において、セルロースナノファイバーとは、天然セルロースのミクロフィブリルを利用したナノファイバーであり、従来のセルロース材料に比べて高強度、耐熱性に優れている。本発明において、セルロースナノファイバーは、１本単位のものに限らず通常は、複数本の束で使用されるが、より好ましい形態はシングルミクロフィブリルである。
　セルロースナノファイバーの好ましい大きさは、幅（長さ方向と直交する方向の寸法であり、１本の場合には直径、複数本束の場合には束の径に相当）は０．５～８００ｎｍ（複数本束にされた場合の幅を含む）であり、より好ましくは幅２～５ｎｍであり、長さは１～５μｍ程度である。

　本発明のセルロースナノファイバー分散液は、１．０質量％濃度（ｗ／ｖ）におけるＢ型粘度（６０ｒｐｍ、２０℃）が１０００ｍＰａ・ｓ以下、好ましくは８００ｍＰａ・ｓ以下、さらに好ましくは５００ｍＰａ・ｓ以下であり、かつ、０．１質量％濃度（ｗ／ｖ）における光透過率（６６０ｎｍ）が９０％以上、好ましくは９５％以上であることが好ましい。本発明で使用されるセルロースナノファイバーは、流動性と透明性に優れ、さらに、ガスバリア性および耐熱性にも優れるので、包装材料等の様々な用途に使用することが可能である。
　なお、本発明において、セルロースナノファイバー分散液のＢ型粘度は、当業者に慣用される通常のＢ型粘度計を用いて測定することができ、例えば、東機産業社のＴＶ－１０型粘度計を用いて、２０℃および６０ｒｐｍの条件で測定することができる。
　本発明のセルロースナノファイバーのカルボキシル基量は、セルロース系原料の絶乾質量に対して、０．５ｍｍｏｌ／ｇ以上となることが好ましく、より好ましくは１．０ｍｍｏｌ／ｇ～３．０ｍｍｏｌ／ｇ、さらに好ましくは１．４ｍｍｏｌ／ｇ～３．０ｍｍｏｌ／ｇ、とりわけ好ましくは２．０ｍｍｏｌ／ｇ～２．５ｍｍｏｌ／ｇである。カルボキシル基量は、酸化反応時間の調整、酸化反応温度の調整、酸化反応時のｐＨの調整、Ｎ－オキシル化合物や臭化物、ヨウ化物、酸化剤の添加量の調整等を行うことにより、所望のカルボキシル基量とすることができる。
　本発明において、酸化されたセルロース系原料に紫外線を照射することは、セルロースナノファイバーの分散液の粘度を低下させることができるため好ましい。酸化されたセルロース系原料に紫外線を照射する場合、酸化されたセルロース系原料の濃度を０．１質量％以上にすることはエネルギー効率の点から好ましく、１２質量％以下にすることで紫外線照射時のセルロース系原料の流動性が良好となり、反応効率が高まるため好ましい。したがって、紫外線を照射する場合、酸化されたセルロース系原料の濃度を、０．１～１２質量％にすることが好ましく、より好ましくは０．５～５質量％、さらに望ましくは１～５質量％である。
　また、紫外線を照射する際のセルロース系原料の温度は、２０℃以上であれば光酸化反応の効率が高まるため好ましく、一方、９５℃以下であればセルロース系原料の品質の悪化等の悪影響を及ぼさないため好ましい。したがって、紫外線を照射する際のセルロース系原料の温度は、２０～９５℃にすることが好ましく、より好ましくは、２０～８０℃、さらに好ましくは、２０～５０℃である。
　また、紫外線を照射する際のｐＨは特に限定はないが、中性領域、例えばｐＨ６．０～８．０程度で処理することがプロセスの簡素化の点から好ましい。
　紫外線の波長は、好ましくは１００～４００ｎｍであり、より好ましくは１００～３００ｎｍである。このうち、波長１３５～２６０ｎｍの紫外線は、低粘度化の点から好ましい。なお、太陽光に含まれる紫外線のうち、２００ｎｍ以下の紫外線は酸素分子や窒素分子によって吸収され、２００～２８０ｎｍの紫外線はオゾン層により防がれるため、通常はほとんど地表に存在しない。
　また、紫外線照射処理は、複数回繰り返すことができる。繰り返しの回数は目標とする酸化されたセルロース系原料の品質や、漂白等の後処理等との関係に応じて適宜設定できる。例えば、特に制限されないが、１００～４００ｎｍ、好ましくは１３５～２６０ｎｍの紫外線を、１～１０回、好ましくは２～５回程度、１回あたり０．５～１０時間、好ましくは０．５～３時間くらいの長さで、照射することができる。
　本発明において、Ｎ－オキシル化合物を用いて酸化されたセルロース系原料に紫外線を照射し、次いで解繊・分散処理することで、そのメカニズムは不明であるが、高濃度であっても流動性と透明性に優れ、且つ高度なガスバリア性を発現するセルロースナノファイバーを得ることができる。
　本発明では、Ｎ－オキシル化合物を用いて酸化されたセルロース系原料に紫外線を照射し、次いで解繊・分散処理することで、高濃度であっても流動性と透明性に優れているセルロースナノファイバー分散液を低い消費電力量で得ることができる。その理由は、以下のように推察される。Ｎ－オキシル化合物を用いて酸化されたセルロース系原料の表面にはカルボキシル基が局在しており、水和層が形成されている。そのため、該原料同士の間には、カルボキシル基同士の電荷反発力の作用で、通常のパルプでは見られない微視的隙間が存在すると考えられる。そして、該原料に紫外線を照射すると、該原料の表面の水和層または該原料の間隙水に溶存している酸素からオゾン等の酸化力に優れる活性酸素種が生成し、この生成物が酸化されたセルロース系原料を改質することで、次工程での解繊・分散処理における分散液のＢ型粘度が顕著に低下し、分散液の流動性が向上すると考えられる。また、紫外線照射処理により、透明性に優れたセルロースナノファイバー分散液が得られるとともに、水中での分散性が高まり、塗工後に形成されるガスバリア層がより均一になり、高度なガスバリア性が発現すると考えられる。 In the present invention, the cellulose nanofibers are nanofibers using natural cellulose microfibrils, and are superior in strength and heat resistance compared to conventional cellulose materials. In the present invention, the cellulose nanofiber is not limited to a single unit and is usually used in a bundle of a plurality of pieces, but a more preferable form is a single microfibril.
The preferred size of the cellulose nanofibers is 0.5 to 800 nm in width (the dimension in the direction perpendicular to the length direction, corresponding to the diameter in the case of a single bundle and the diameter of the bundle in the case of a bundle of plural fibers). (Including the width when plural bundles are formed), more preferably 2 to 5 nm in width and about 1 to 5 μm in length.

The cellulose nanofiber dispersion of the present invention has a B-type viscosity (60 rpm, 20 ° C.) at a concentration of 1.0% by mass (w / v) of 1000 mPa · s or less, preferably 800 mPa · s or less, more preferably 500 mPa · s. The light transmittance (660 nm) at a concentration of 0.1% by mass (w / v) is 90% or more, preferably 95% or more. The cellulose nanofibers used in the present invention are excellent in fluidity and transparency, and further excellent in gas barrier properties and heat resistance, and thus can be used in various applications such as packaging materials.
In the present invention, the B-type viscosity of the cellulose nanofiber dispersion can be measured using a normal B-type viscometer commonly used by those skilled in the art, for example, TV-10 type viscosity of Toki Sangyo Co., Ltd. Using a meter, it can be measured at 20 ° C. and 60 rpm.
The amount of carboxyl groups of the cellulose nanofiber of the present invention is preferably 0.5 mmol / g or more, more preferably 1.0 mmol / g to 3.0 mmol / g, based on the absolute dry mass of the cellulose-based raw material. More preferably, it is 1.4 mmol / g to 3.0 mmol / g, and particularly preferably 2.0 mmol / g to 2.5 mmol / g. The amount of carboxyl groups can be adjusted by adjusting the oxidation reaction time, adjusting the oxidation reaction temperature, adjusting the pH during the oxidation reaction, adjusting the amount of N-oxyl compound, bromide, iodide, and oxidizing agent added. It can be the amount of carboxyl groups.
In the present invention, it is preferable to irradiate the oxidized cellulose raw material with ultraviolet rays because the viscosity of the dispersion of cellulose nanofibers can be reduced. When irradiating ultraviolet rays on the oxidized cellulose raw material, it is preferable from the viewpoint of energy efficiency that the concentration of the oxidized cellulose raw material is 0.1% by mass or more. This is preferable because the flowability of the cellulosic raw material is good and the reaction efficiency is increased. Therefore, when irradiating with ultraviolet rays, the concentration of the oxidized cellulose-based raw material is preferably 0.1 to 12% by mass, more preferably 0.5 to 5% by mass, and still more preferably 1 to 5% by mass. It is.
The temperature of the cellulosic raw material when irradiating with ultraviolet rays is preferably 20 ° C. or higher because the efficiency of the photooxidation reaction is increased. It is preferable because it does not reach. Therefore, the temperature of the cellulosic raw material when irradiated with ultraviolet rays is preferably 20 to 95 ° C., more preferably 20 to 80 ° C., and still more preferably 20 to 50 ° C.
Further, the pH at the time of irradiation with ultraviolet rays is not particularly limited, but it is preferable from the viewpoint of simplification of the process to carry out the treatment in a neutral region, for example, about pH 6.0 to 8.0.
The wavelength of the ultraviolet light is preferably 100 to 400 nm, more preferably 100 to 300 nm. Among these, ultraviolet rays having a wavelength of 135 to 260 nm are preferable from the viewpoint of reducing the viscosity. Of the ultraviolet rays contained in sunlight, ultraviolet rays having a wavelength of 200 nm or less are absorbed by oxygen molecules and nitrogen molecules, and ultraviolet rays having a wavelength of 200 to 280 nm are usually prevented from being present on the ground surface because they are prevented by the ozone layer.
Further, the ultraviolet irradiation treatment can be repeated a plurality of times. The number of repetitions can be appropriately set according to the target quality of the oxidized cellulosic raw material and the relationship with post-treatment such as bleaching. For example, although not particularly limited, ultraviolet rays of 100 to 400 nm, preferably 135 to 260 nm, are applied 1 to 10 times, preferably about 2 to 5 times, 0.5 to 10 hours per time, preferably 0.5 to 3 times. It can be irradiated for as long as an hour.
In the present invention, the mechanism is unclear by irradiating the cellulosic raw material oxidized with the N-oxyl compound with ultraviolet rays, followed by defibration / dispersion treatment. Cellulose nanofibers that are excellent in transparency and that exhibit high gas barrier properties can be obtained.
In the present invention, cellulose nano-materials excellent in fluidity and transparency even at a high concentration are obtained by irradiating ultraviolet rays to cellulose-based raw materials oxidized using an N-oxyl compound, and then performing defibration and dispersion treatment. A fiber dispersion can be obtained with low power consumption. The reason is guessed as follows. A carboxyl group is localized on the surface of the cellulosic raw material oxidized with the N-oxyl compound, and a hydrated layer is formed. Therefore, it is considered that there is a microscopic gap between the raw materials which is not found in ordinary pulp due to the action of the charge repulsion between carboxyl groups. When the raw material is irradiated with ultraviolet rays, active oxygen species having excellent oxidizing power such as ozone are generated from oxygen dissolved in the hydration layer on the surface of the raw material or pore water of the raw material, and this product is oxidized. By modifying the cellulose-based material thus obtained, it is considered that the B-type viscosity of the dispersion in the defibration / dispersion treatment in the next step is significantly reduced, and the fluidity of the dispersion is improved. In addition, the UV irradiation treatment provides a cellulose nanofiber dispersion with excellent transparency, increases the dispersibility in water, makes the gas barrier layer formed after coating more uniform, and exhibits a high level of gas barrier properties. I think that.
　本発明において、セルロースナノファイバーを他の水溶性ガスバリア性樹脂に添加して紙に塗工すると、ガスバリア性のさらなる向上が期待できる。これはセルロースナノファイバーの持つガスバリア性と、塗液の増粘作用による紙への染み込み防止の双方の効果があると考えられる。また、水溶性ガスバリア性樹脂とセルロースナノファイバーは、それぞれ単独で塗工するよりも混合して塗工することで、ガスバリア材料としての相乗効果が得られる。この作用については明らかではないが、水溶性ガスバリア性樹脂の折りたたみ構造によって生じる隙間に、微細なサイズのセルロースナノファイバーが入り込み、非常に高いガスバリア性が実現するものと思われる。このため、セルロースナノファイバーのサイズが微細であるほど、この効果がより顕著になる。さらなる微細化処理の方法としては、例えば先に述べた紫外線照射処理が挙げられ、セルロースナノファイバーを紫外線処理することにより、ガスバリア性を向上させることができる。この処理をしたＣＮＦを用いることにより、ガスバリア層を薄くすることが可能となる。その向上性は、約５０％であり、層厚を半分にすることができる。
　ただし、セルロースナノファイバーを多量に添加した場合には、塗料粘度を増加させるため、撹拌不良を引き起こし、塗工適性を損なうおそれがある。また、バリア材料の柔軟性が損なわれるため、包装用材料として用いる場合に必要となる折り加工適性を有さなくなる。そのため、前記セルロースナノファイバーの好ましい配合量は、水溶性ガスバリア性樹脂１００質量部に対して０．１質量部以上４３質量部以下とし、さらに好ましくは、２５質量部以下である。なお、ガスバリア層として、セルロースナノファイバーと水溶性ガスバリア性樹脂とを含有することにより、紙製バリア材料のガスバリア層暴露表面にヒートシール可能な材料をラミネートする際、紙製バリア材料とヒートシール可能な材料の接着性を向上させることができる。 In the present invention, when cellulose nanofibers are added to other water-soluble gas barrier resins and coated on paper, further improvement in gas barrier properties can be expected. This is considered to have both the gas barrier properties of cellulose nanofibers and the prevention of penetration into paper due to the thickening action of the coating liquid. In addition, the water-soluble gas barrier resin and the cellulose nanofibers can be mixed and applied rather than separately, thereby obtaining a synergistic effect as a gas barrier material. Although it is not clear about this effect | action, it is thought that a very high gas barrier property is implement | achieved by the fine-sized cellulose nanofiber entering into the clearance gap produced by the folding structure of water-soluble gas barrier resin. For this reason, this effect becomes more remarkable, so that the size of a cellulose nanofiber is fine. As a further refinement method, for example, the ultraviolet irradiation treatment described above can be mentioned, and the gas barrier property can be improved by subjecting the cellulose nanofibers to ultraviolet treatment. By using CNF subjected to this treatment, the gas barrier layer can be made thin. The improvement is about 50%, and the layer thickness can be halved.
However, when a large amount of cellulose nanofiber is added, the viscosity of the paint is increased, which may cause poor stirring and impair the coating suitability. Further, since the flexibility of the barrier material is impaired, it does not have the folding processability required when used as a packaging material. Therefore, the preferable compounding quantity of the said cellulose nanofiber shall be 0.1 to 43 mass parts with respect to 100 mass parts of water-soluble gas barrier resin, More preferably, it is 25 mass parts or less. In addition, by containing cellulose nanofiber and water-soluble gas barrier resin as a gas barrier layer, when laminating a heat-sealable material on the gas barrier layer exposed surface of a paper barrier material, heat sealing with the paper barrier material is possible. The adhesion of various materials can be improved.
　水溶性のガスバリア性樹脂とは、カルボキシメチルセルロース、メチルセルロース、カルボキシアルキルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、キトサン、ポリアクリルアミド、ポリアクリル酸、ポリエチレンオキシド、ポリビニルアルコール、エチレン－ビニルアルコール共重合体、ポリメタクリル酸、ポリアミン、ポリビニルピリジン、およびこれらの化合物の塩、ならびにこれらの材料のいずれかであることが好ましく、特に水酸基を持つガスバリア性樹脂であればセルロースナノファイバーとの結合性が高いため、より好ましい。本発明の実施においては、エチレン－ビニルアルコール共重合体またはポリビニルアルコールを用いることで、高いガスバリア性を有するバリア材料を得ることができる。 Water-soluble gas barrier resin is carboxymethylcellulose, methylcellulose, carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, chitosan, polyacrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, ethylene-vinyl alcohol copolymer Preferably, the polymer, polymethacrylic acid, polyamine, polyvinyl pyridine, and salts of these compounds, and any of these materials are used. Especially, a gas barrier resin having a hydroxyl group has high binding properties to cellulose nanofibers. Therefore, it is more preferable. In the practice of the present invention, a barrier material having high gas barrier properties can be obtained by using an ethylene-vinyl alcohol copolymer or polyvinyl alcohol.
　なお、エチレン－ビニルアルコール共重合樹脂(ＥＶＯＨ)は、エチレンと酢酸ビニル共重合物の加水分解により得られる。ポリビニルアルコールのハイガスバリア性や耐油性、透明性を有するとともに、エチレン成分の耐湿性や溶融押出加工性等の特性を併せ持っている。本発明においては、上述した水溶性のガスバリア性樹脂に対して、少量のセルロースナノファイバーを添加して、水溶性のガスバリア性樹脂を改質することが可能となり、紙製ガスバリア材料のガスバリア特性を向上することができる。 The ethylene-vinyl alcohol copolymer resin (EVOH) is obtained by hydrolysis of ethylene and vinyl acetate copolymer. Polyvinyl alcohol has high gas barrier properties, oil resistance, and transparency, and also has properties such as moisture resistance and melt extrusion processability of ethylene components. In the present invention, it is possible to modify the water-soluble gas barrier resin by adding a small amount of cellulose nanofibers to the above-mentioned water-soluble gas barrier resin, thereby improving the gas barrier characteristics of the paper gas barrier material. Can be improved.
　本発明におけるガスバリア性は、標準温度および標準圧力（ＳＴＰ）で０％の相対湿度（％ＲＨ）にて測定したとき、酸素移動速度（ＯＴＲ）が１０ｃｃ／ｍ２／日未満である。より好ましくは３ｃｃ／ｍ２／日未満であることが望ましい。ポリビニルアルコール等の水溶性のガスバリア性樹脂は、上記の効果を奏するために１ｍ２あたり大量の材料を必要とするが、これに、セルロースナノファイバーを混合した場合に、必要量を低下させることができる。 The gas barrier property in the present invention has an oxygen transfer rate (OTR) of less than 10 cc / m 2 / day when measured at 0% relative humidity (% RH) at standard temperature and pressure (STP). More preferably, it is less than 3 cc / m 2 / day. A water-soluble gas barrier resin such as polyvinyl alcohol requires a large amount of material per 1 m 2 in order to achieve the above-mentioned effects. However, when cellulose nanofiber is mixed with this, the required amount can be reduced. it can.
　本発明において紙基材とは、セルロースを主たる構成成分とする、パルプ繊維が絡み合った集合体であり、包装用紙、板紙、段ボール原紙、ラミネート紙等も含まれる。また、バリア材料に高いガスバリア性を持たせるために、紙基材とガスバリア層の間に、目止め層を設けることも有効である。目止め層としてはクレー等の顔料とバインダー樹脂とを含有する塗工層や皮膜性を有する樹脂からなる塗工層を例示することができる。また、液体や水蒸気へのバリアを提供する防湿層を紙基材と酸素バリア層の間、または酸素バリア層の曝露表面、またはその両方に設けることは、高湿度下でのバリア性の低下抑制に有効である。さらに、ガスバリア層の曝露表面には、ヒートシール可能な材料の層を施用してもよい。本発明の紙製バリア材料は、食品包装材、容器、カップ等に成形、加工することができる。 In the present invention, the paper base is an aggregate in which pulp fibers are intertwined mainly composed of cellulose, and includes wrapping paper, paperboard, cardboard base paper, laminated paper and the like. It is also effective to provide a sealing layer between the paper substrate and the gas barrier layer in order to give the barrier material a high gas barrier property. Examples of the sealing layer include a coating layer containing a pigment such as clay and a binder resin, and a coating layer made of a resin having a film property. In addition, providing a moisture barrier layer that provides a barrier to liquids and water vapor between the paper substrate and the oxygen barrier layer, or the exposed surface of the oxygen barrier layer, or both, suppresses the deterioration of barrier properties under high humidity. It is effective for. Furthermore, a layer of heat sealable material may be applied to the exposed surface of the gas barrier layer. The paper barrier material of the present invention can be formed and processed into food packaging materials, containers, cups and the like.
　本発明において、ガスバリア層はセルロースナノファイバーと水溶性ガスバリア性樹脂とを含有する水性の塗工液を紙基材表面に塗工した後、乾燥して設けられる。セルロースナノファイバーを含有する塗工液を塗工する方法としては、２ロールサイズプレスコーター、ゲートロールコーター、ブレードメタリングコーター、ロッドメタリングコーター、ブレードコーター、エアナイフコーター、ロールコーター、ブラッシュコーター、キスコーター、スクイズコーター、カーテンコーター、ダイコーター、バーコーター、グラビアコーター、ディップコーター等の公知の塗工機を用いることができる。また、乾燥は公知の乾燥機を用いることができる。 In the present invention, the gas barrier layer is provided by applying a water-based coating liquid containing cellulose nanofibers and a water-soluble gas barrier resin to the surface of the paper substrate and then drying it. As a method of coating a coating solution containing cellulose nanofibers, a two-roll size press coater, a gate roll coater, a blade metering coater, a rod metering coater, a blade coater, an air knife coater, a roll coater, a brush coater, and a kiss coater. A known coating machine such as a squeeze coater, a curtain coater, a die coater, a bar coater, a gravure coater, or a dip coater can be used. Moreover, a well-known dryer can be used for drying.
　本発明においては、ガスバリア層中に必要に応じてサイズ剤、耐水化剤、撥水剤、染料等の薬品を、本発明の効果を損なわない程度に混合して使用することができるが、より高いガスバリア性を求める場合は、上記助剤は配合されないことが好ましい。 In the present invention, chemicals such as a sizing agent, water-proofing agent, water repellent, and dye can be mixed and used in the gas barrier layer as needed without impairing the effects of the present invention. When a high gas barrier property is required, it is preferable that the auxiliary agent is not blended.
　以下に本発明の実施例を挙げてより具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例および比較例において％、部とあるものはそれぞれ質量％、質量部を示す。また、塗工量を示す値は断りのない限り乾燥後の固形分質量を示す。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, “%” and “part” indicate mass% and mass part, respectively. Moreover, the value which shows a coating amount shows the solid content mass after drying, unless there is a notice.
［実施例１］
　ポリビニルアルコール系樹脂（商品名エクセバール、クラレ（株）、固形分濃度２０％）１００部にセルロースナノファイバー（固形分濃度１％）１部を混合し、塗工液を調製した。この塗工液を塗工紙（商品名オーロラコート、１５７ｇ／ｍ２、日本製紙（株）社製）の塗工面上に固形分で１．０ｇ／ｍ２となるようにマイヤーバーを用いてガスバリア層を塗工し、送風乾燥機を用いて乾燥温度１０５℃で乾燥し、紙製バリア材料を得た。 [Example 1]
One part of cellulose nanofiber (solid content concentration 1%) was mixed with 100 parts of polyvinyl alcohol-based resin (trade name EXEVAL, Kuraray Co., Ltd., solid content concentration 20%) to prepare a coating solution. Using a Mayer bar, this coating solution is applied to the coated surface of coated paper (trade name: Aurora Coat, 157 g / m 2 , manufactured by Nippon Paper Industries Co., Ltd.) at a solid content of 1.0 g / m 2. The gas barrier layer was applied and dried at a drying temperature of 105 ° C. using a blow dryer to obtain a paper barrier material.
［実施例２～９、比較例１～７］
　表１、２に示すように、ガスバリア層の組成に関して、セルロースナノファイバー、ポリビニルアルコール系樹脂、マイカの添加比率、およびガスバリア層の塗工量を変えた以外は、実施例１と同様に紙製バリア材料を得た。 [Examples 2 to 9, Comparative Examples 1 to 7]
As shown in Tables 1 and 2, with respect to the composition of the gas barrier layer, the same as in Example 1, except that the addition ratio of cellulose nanofiber, polyvinyl alcohol resin, mica, and the coating amount of the gas barrier layer was changed. A barrier material was obtained.
＜セルロースナノファイバー分散液の製造＞
　粉末セルロース（日本製紙ケミカル(株)製、粒径２４μｍ）１５ｇ（絶乾）を、ＴＥＭＰＯ（ＳｉｇｍａＡｌｄｒｉｃｈ社）７８ｍｇ(０．５ｍｍｏｌ)と臭化ナトリウム７５５ｍｇ(５ｍｍｏｌ)を溶解した水溶液５００ｍｌに加え、粉末セルロースが均一に分散するまで攪拌した。反応系に次亜塩素酸ナトリウム水溶液（有効塩素５％）５０ｍｌを添加した後、０．５Ｎ塩酸水溶液でｐＨを１０．３に調整し、酸化反応を開始した。反応中は系内のｐＨは低下するが、０．５Ｎ水酸化ナトリウム水溶液を逐次添加し、ｐＨ１０に調整した。２時間反応した後、遠心操作（６０００ｒｐｍ、３０分、２０℃）で酸化した粉末セルロースを分離し、十分に水洗することで酸化処理した粉末セルロースを得た。酸化処理した粉末セルロースの２％(ｗ／ｖ)スラリーをミキサーにより１２，０００ｒｐｍ、１５分処理し、さらに粉末セルローススラリーを超高圧ホモジナイザーにより１４０ＭＰａの発送圧力で５回処理したところ、透明なゲル状分散液が得られた。得られた２％(ｗ／ｖ)のセルロースナノファイバー分散液をさらに希釈して固形分濃度１％(ｗ／ｖ)のセルロースナノファイバー分散液を得た。なお、得られたセルロースナノファイバーのＢ型粘度は８９０（ｍＰａ・ｓ）であった。また、原子間力顕微鏡（ＡＦＭ）の観察より、セルロースナノファイバーの最大繊維径が１０ｎｍ、数平均繊維径が６ｎｍであった。 <Manufacture of cellulose nanofiber dispersion>
Powdered cellulose (Nippon Paper Chemical Co., Ltd., particle size 24 μm) 15 g (absolutely dry) was added to 500 ml of an aqueous solution in which 78 mg (0.5 mmol) of TEMPO (Sigma Aldrich) and 755 mg (5 mmol) of sodium bromide were dissolved. Stir until the cellulose is uniformly dispersed. After adding 50 ml of a sodium hypochlorite aqueous solution (effective chlorine 5%) to the reaction system, the pH was adjusted to 10.3 with a 0.5N hydrochloric acid aqueous solution to start the oxidation reaction. During the reaction, the pH in the system was lowered, but a 0.5N aqueous sodium hydroxide solution was successively added to adjust the pH to 10. After reacting for 2 hours, oxidized powdered cellulose was separated by centrifugal operation (6000 rpm, 30 minutes, 20 ° C.) and sufficiently washed with water to obtain oxidized powdered cellulose. A 2% (w / v) slurry of oxidized powdered cellulose was treated with a mixer at 12,000 rpm for 15 minutes, and the powdered cellulose slurry was further treated with an ultra-high pressure homogenizer five times at a shipping pressure of 140 MPa to obtain a transparent gel A dispersion was obtained. The obtained 2% (w / v) cellulose nanofiber dispersion was further diluted to obtain a cellulose nanofiber dispersion having a solid concentration of 1% (w / v). In addition, the B type viscosity of the obtained cellulose nanofiber was 890 (mPa · s). Further, from observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofibers was 10 nm, and the number average fiber diameter was 6 nm.
　実施例、比較例でそれぞれ作成した紙製バリア材料を用いて下記の測定を行い、結果を表１、２に示した。試験方法を下記に示す。
＜ガスバリア性の測定＞
本試験では、ガスバリア性を酸素の透過度で測定している。これは、食品等の包装資材では、食品の酸化防止が課題になることが多いので、ガスバリア性の代表的な評価指標として酸素透過に着目することとした。
　酸素透過度測定は、ＭＯＣＯＮ社製ＯＸ－ＴＲＡＮ２／２１を使用し、２３℃－０％ＲＨ条件で測定した。 The following measurements were performed using the paper barrier materials prepared in Examples and Comparative Examples, and the results are shown in Tables 1 and 2. The test method is shown below.
<Measurement of gas barrier properties>
In this test, gas barrier properties are measured by oxygen permeability. This is because, in packaging materials such as food, oxidation prevention of food often becomes a problem, so attention was paid to oxygen permeation as a representative evaluation index of gas barrier properties.
Oxygen permeability was measured using OX-TRAN 2/21 manufactured by MOCON under the condition of 23 ° C.-0% RH.
＜折り曲げ適性評価方法＞
それぞれの酸素バリア層用塗工液から、厚さ３０μｍのフィルムを作製し、これを１８０度折り曲げた時に割れるか否かを観察した。
評価基準
　○：フィルムに亀裂が入らない。
　×：フィルムに亀裂が入る。または、フィルムが断裂する。 <Bending aptitude evaluation method>
A film having a thickness of 30 μm was prepared from each oxygen barrier layer coating solution, and it was observed whether or not the film was broken when it was bent 180 degrees.
Evaluation criteria ○: The film does not crack.
X: The film is cracked. Or the film is torn.
＜ラミネート接着性＞
　酸素バリア層上に２０μｍの厚みのポリエチレン層を押し出しラミネートし、ラミネート後のそれぞれのサンプルに対して、粘着テープ剥離試験を行い、剥離の状態を観察した。粘着テープとしてはニチバン社製、１５ｍｍ幅の透明テープを用い、酸素バリア層上に粘着テープを貼り付け、手で数回擦った後、粘着テープを剥離した。
評価基準
　◎：ガスバリア層とポリエチレンの密着が良好で、粘着テープ全面において紙基材が破壊されている。
　○：紙基材が一部破壊されている。
　×：ガスバリア層とポリエチレンの間で剥離が発生している。 <Laminate adhesion>
A polyethylene layer having a thickness of 20 μm was extruded and laminated on the oxygen barrier layer, and an adhesive tape peeling test was performed on each sample after lamination to observe the peeling state. As a pressure-sensitive adhesive tape, a 15 mm wide transparent tape manufactured by Nichiban Co., Ltd. was used. The pressure-sensitive adhesive tape was attached on the oxygen barrier layer and rubbed several times by hand, and then the pressure-sensitive adhesive tape was peeled off.
Evaluation criteria A: Adhesion between the gas barrier layer and the polyethylene is good, and the paper substrate is destroyed on the entire surface of the adhesive tape.
○: The paper base material is partially destroyed.
X: Peeling has occurred between the gas barrier layer and the polyethylene.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明に相当する実施例で得られた紙製バリア材料については、ガスバリア層の塗工量が小さくても酸素バリア性、折り曲げ適性、ラミネート接着性ともに優れていた。
　なお、ポリビニルアルコール塗布量１０ｇ／ｍ２、１５ｇ／ｍ２でそれぞれの酸素透過度は８．１、４．２であった。したがって、酸素透過度３．０を満足するには少なくともポリビニルアルコールの塗布量は１５ｇ／ｍ２以上必要とする。  The paper barrier materials obtained in the examples corresponding to the present invention were excellent in oxygen barrier properties, bendability and laminate adhesion even when the coating amount of the gas barrier layer was small.
The oxygen permeability was 8.1 and 4.2 at polyvinyl alcohol coating amounts of 10 g / m 2 and 15 g / m 2 , respectively. Therefore, in order to satisfy the oxygen permeability of 3.0, at least the coating amount of polyvinyl alcohol needs to be 15 g / m 2 or more.
　実施例１～９より、ポリビニルアルコール系樹脂１００部に対して、１～４３部のセルロースナノファイバーを添加することにより、酸素透過量が低減されることがわかる。
　５．０ｇ／ｍ２の塗工量である実施例４と比較例２を対比すると、酸素透過度は、０．１４：１３．２と約１００倍の差がある。また、１．０ｇ／ｍ２の塗工量である実施例１と比較例１とは酸素透過度が２．８：３２と約１０倍である。このことは、本発明ではＣＮＦの層厚依存度が１０倍程度の改善性を発揮することを示している。
　また、ポリビニルアルコール系樹脂にセルロースナノファイバーを添加することによりラミネート接着性が向上した。
　ただし、比較例４，５のようにセルロースナノファイバーの添加量が多すぎると、折り曲げ適性が悪化した。折り曲げ特性は、折り曲げ加工を伴う容器等の性能に影響する指標である。ヒートシールのような折り曲げ加工の影響を無視しえるような場合は、この指標は必要ない。
　さらに、実施例９に示すようにマイカに代表される層状珪酸等の扁平な顔料を少量添加することで、よりガスバリア性を向上させることができた。 From Examples 1 to 9, it can be seen that by adding 1 to 43 parts of cellulose nanofiber to 100 parts of polyvinyl alcohol resin, the amount of oxygen permeation is reduced.
When Example 4 having a coating amount of 5.0 g / m 2 is compared with Comparative Example 2, the oxygen permeability is 0.14: 13.2, which is about 100 times different. Further, Example 1 and Comparative Example 1 having a coating amount of 1.0 g / m 2 have an oxygen permeability of 2.8: 32, which is about 10 times. This indicates that the present invention exhibits an improvement of about 10 times the dependency of CNF on the layer thickness.
Moreover, the lamination adhesiveness improved by adding a cellulose nanofiber to polyvinyl alcohol-type resin.
However, when there was too much addition amount of a cellulose nanofiber like the comparative examples 4 and 5, bendability deteriorated. The folding characteristic is an index that affects the performance of a container or the like accompanied by a bending process. This indicator is not necessary when the influence of bending such as heat sealing can be ignored.
Furthermore, as shown in Example 9, gas barrier properties could be further improved by adding a small amount of a flat pigment such as layered silicic acid represented by mica.
［実施例１０］
　ポリビニルアルコール系樹脂（商品名エクセバール、クラレ（株）、固形分濃度１０％）１００部にセルロースナノファイバー（固形分濃度１％）１０部を混合し、この混合液に対しイソプロピルアルコールを１１部の割合で添加して塗工液を調整した。この塗工液をポリエチレン片面ラミネート紙（紙の坪量：２００ｇ／ｍ２、ポリエチレン厚さ：２０μｍ）のラミネート面上に固形分で０．５ｇ／ｍ２となるようにマイヤーバーを用いて塗工し、送風乾燥機を用いて乾燥温度８０℃で乾燥し、紙製バリア材料を得た。 [Example 10]
10 parts of cellulose nanofiber (solid content concentration 1%) is mixed with 100 parts of polyvinyl alcohol resin (trade name EXEVAL, Kuraray Co., Ltd., solid content concentration 10%), and 11 parts of isopropyl alcohol is mixed with this mixed solution. The coating liquid was adjusted by adding at a ratio. This coating solution is applied on a laminated surface of polyethylene single-sided laminated paper (paper basis weight: 200 g / m 2 , polyethylene thickness: 20 μm) using a Meyer bar so that the solid content is 0.5 g / m 2. And dried using a blow dryer at a drying temperature of 80 ° C. to obtain a paper barrier material.
[実施例１１]
　実施例１～１０と同様に酸化処理した粉末セルロースを得た後、２５４ｎｍの紫外線を照射する２０Ｗ低圧水銀ランプで０．５時間処理した。紫外線処理した酸化パルプスラリーを超高圧ホモジナイザー（処理圧１４０ＭＰａ）で１０回処理したところ、透明なゲル状のセルロースナノファイバー分散液が得られ、分散液の１％（ｗ／ｖ）でのＢ型粘度（６０ｒｐｍ、２０℃）は７００ ｍＰａ・ｓであった。このセルロースナノファイバー分散液を用いた以外は実施例１０と同様にして、紙製バリア材料を得た。なお、原子間力顕微鏡（ＡＦＭ）の観察より、セルロースナノファイバーの最大繊維径が１０ｎｍ、数平均繊維径が６ｎｍであった。
[実施例１２]
　紫外線の波長を３８０ｎｍにした以外は実施例１１と同様にして紙製バリア材料を得た。なお、原子間力顕微鏡（ＡＦＭ）の観察より、セルロースナノファイバーの最大繊維径が１０ｎｍ、数平均繊維径が６ｎｍ、分散液の１％（ｗ／ｖ）でのＢ型粘度（６０ｒｐｍ、２０℃）は８００ ｍＰａ・ｓであった。
[実施例１３]
　紫外線の照射時間を６時間にした以外は実施例１１と同様にして紙製バリア材料を得た。なお、原子間力顕微鏡（ＡＦＭ）の観察より、セルロースナノファイバーの最大繊維径が１０ｎｍ、数平均繊維径が６ｎｍ、分散液の１％（ｗ／ｖ）でのＢ型粘度（６０ｒｐｍ、２０℃）は３２０ ｍＰａ・ｓであった。 [Example 11]
After obtaining powdered cellulose oxidized in the same manner as in Examples 1 to 10, it was treated with a 20 W low-pressure mercury lamp that irradiates 254 nm ultraviolet light for 0.5 hour. Ultraviolet-treated oxidized pulp slurry was treated 10 times with an ultra-high pressure homogenizer (treatment pressure 140 MPa), and a transparent gel-like cellulose nanofiber dispersion was obtained. Type B at 1% (w / v) of the dispersion The viscosity (60 rpm, 20 ° C.) was 700 mPa · s. A paper barrier material was obtained in the same manner as in Example 10 except that this cellulose nanofiber dispersion was used. From observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofiber was 10 nm, and the number average fiber diameter was 6 nm.
[Example 12]
A paper barrier material was obtained in the same manner as in Example 11 except that the wavelength of the ultraviolet light was changed to 380 nm. From observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofibers is 10 nm, the number average fiber diameter is 6 nm, and the B-type viscosity (60 rpm, 20 ° C.) at 1% (w / v) of the dispersion. ) Was 800 mPa · s.
[Example 13]
A paper barrier material was obtained in the same manner as in Example 11 except that the ultraviolet irradiation time was changed to 6 hours. From observation with an atomic force microscope (AFM), the maximum fiber diameter of the cellulose nanofibers is 10 nm, the number average fiber diameter is 6 nm, and the B-type viscosity (60 rpm, 20 ° C.) at 1% (w / v) of the dispersion. ) Was 320 mPa · s.
[比較例８］
　実施例１０を基本とし、ＰＶＡとＣＮＦを別々に塗工した紙製バリア材料を作成して試験した。
　ポリビニルアルコール系樹脂（ＰＶＡ）（商品名エクセバール、クラレ（株）、固形分濃度１０％）１００部に対してイソプロピルアルコールを1０部配合したＰＶＡ塗工液（Ａ）を調整した。セルロースナノファイバー（固形分濃度１％）１０部に対してイソプロピルアルコールを１部の割合でそれぞれ塗工液（Ｂ）を調整した。その後、固形分を０．４５ｇ／ｍ２としたポリビニルアルコール系樹脂を含有した塗工液（Ａ）を準備した。固形分を０．０５ｇ／ｍ２としたセルロースナノファイバーを含有した塗工液（Ｂ）を準備した。（Ａ）（Ｂ）の順で別々に塗工した。 [Comparative Example 8]
Based on Example 10, a paper barrier material coated with PVA and CNF separately was prepared and tested.
A PVA coating solution (A) in which 10 parts of isopropyl alcohol was blended with 100 parts of polyvinyl alcohol-based resin (PVA) (trade name EXVAL, Kuraray Co., Ltd., solid content concentration 10%) was prepared. The coating liquid (B) was adjusted at a ratio of 1 part of isopropyl alcohol to 10 parts of cellulose nanofiber (solid content concentration 1%). Then, the coating liquid (A) containing the polyvinyl alcohol-type resin which made solid content 0.45g / m < 2 > was prepared. A coating liquid (B) containing cellulose nanofibers having a solid content of 0.05 g / m 2 was prepared. (A) It coated separately in the order of (B).
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000003
 
　実施例１０と比較例８から、セルロースナノファイバーと水溶性ガスバリア性樹脂は別々に塗工するよりも、混合で塗工することで高いガスバリア性が発現した。またセルロースナノファイバーの製造工程に紫外線の照射を加えた実施例１１、１３では、照射時間が長くなるほどガスバリア性がさらに向上した。なお、紫外線波長は実施例１１の２５４ｎｍでの処理の方が、実施例１２の３８０ｎｍでの処理よりも効果が高かった。
　実施例１３と実施例３を対比すると、酸素透過度は同程度である。これはＵＶ処理した実施例１１は、実施例３の約半分のＣＮＦ量であるので、ＵＶ処理によって２倍以上のガスバリア性を向上させることができることを示している。
  From Example 10 and Comparative Example 8, the cellulose nanofiber and the water-soluble gas barrier resin exhibited a high gas barrier property by applying them by mixing rather than applying them separately. Further, in Examples 11 and 13 in which ultraviolet ray irradiation was added to the production process of cellulose nanofiber, the gas barrier property was further improved as the irradiation time became longer. In addition, as for the ultraviolet wavelength, the treatment at 254 nm in Example 11 was more effective than the treatment at 380 nm in Example 12.
When Example 13 and Example 3 are compared, the oxygen permeability is comparable. This indicates that the UV-treated Example 11 has about half the amount of CNF compared to Example 3, so that the gas barrier property can be improved by twice or more by the UV treatment.

Claims (6)

  1. 　紙基材の少なくとも一方の表面に、セルロースナノファイバーと水溶性ガスバリア性樹脂とを含有するガスバリア層を設けた紙製バリア材料であって、前記ガスバリア層中のセルロースナノファイバーと水溶性ガスバリア性樹脂の含有重量比が水溶性ガスバリア性樹脂１００質量部に対し、セルロースナノファイバー０．１質量部以上４３質量部以下である、紙製バリア材料。 A paper barrier material in which a gas barrier layer containing cellulose nanofibers and a water-soluble gas barrier resin is provided on at least one surface of a paper substrate, the cellulose nanofibers in the gas barrier layer and the water-soluble gas barrier resin A paper-made barrier material in which the content weight ratio is 0.1 to 43 parts by mass of cellulose nanofibers with respect to 100 parts by mass of the water-soluble gas barrier resin.
  2. 　ガスバリア性が、標準温度および標準圧力（ＳＴＰ）で０％の相対湿度（％ＲＨ）にて測定したとき、酸素移動速度（ＯＴＲ）が１０ｃｃ／ｍ２／日未満であることを特徴とする請求項１記載の紙製バリア材料。 The gas barrier property has an oxygen transfer rate (OTR) of less than 10 cc / m 2 / day when measured at 0% relative humidity (% RH) at standard temperature and pressure (STP). Item 2. A paper barrier material according to Item 1.
  3. 　ガスバリア性が、３ｃｃ／ｍ２／日未満であることを特徴とする請求項２記載の紙製バリア材料。 The paper barrier material according to claim 2 , wherein the gas barrier property is less than 3 cc / m 2 / day.
  4. 　前記水溶性ガスバリア性樹脂が、カルボキシメチルセルロース、メチルセルロース、カルボキシアルキルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、キトサン、ポリアクリルアミド、ポリアクリル酸、ポリエチレンオキシド、ポリビニルアルコール、エチレン－ビニルアルコール共重合体、ポリメタクリル酸、ポリアミン、ポリビニルピリジン、およびこれらの化合物の塩、ならびにこれらの材料のいずれかの混合物のうち少なくとも１種である、請求項１～３のいずれかに記載の紙製バリア材料。 The water-soluble gas barrier resin is carboxymethylcellulose, methylcellulose, carboxyalkylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, chitosan, polyacrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, ethylene-vinyl alcohol copolymer. The paper barrier material according to any one of claims 1 to 3, which is at least one of polymethacrylic acid, polyamine, polyvinylpyridine, salts of these compounds, and a mixture of any of these materials.
  5. 　ガスバリア層にマイカを添加したことを特徴とする請求項１～４のいずれかに記載の紙製バリア材料。 The paper barrier material according to any one of claims 1 to 4, wherein mica is added to the gas barrier layer.
  6. 　前記セルロースナノファイバーが、紫外線照射処理を施されていることを特徴とする請求項１～５のいずれかに記載の紙製バリア材料。  The paper barrier material according to any one of claims 1 to 5, wherein the cellulose nanofiber is subjected to an ultraviolet irradiation treatment.
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