WO2019189229A1 - Matériau barrière en papier - Google Patents

Matériau barrière en papier Download PDF

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Publication number
WO2019189229A1
WO2019189229A1 PCT/JP2019/012953 JP2019012953W WO2019189229A1 WO 2019189229 A1 WO2019189229 A1 WO 2019189229A1 JP 2019012953 W JP2019012953 W JP 2019012953W WO 2019189229 A1 WO2019189229 A1 WO 2019189229A1
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WO
WIPO (PCT)
Prior art keywords
coating layer
water vapor
paper
barrier coating
barrier
Prior art date
Application number
PCT/JP2019/012953
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English (en)
Japanese (ja)
Inventor
岡本　匡史
悟司 津田
泰弘 山下
健太 渡辺
眞紀 畠田
Original Assignee
日本製紙株式会社
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Filing date
Publication date
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Publication of WO2019189229A1 publication Critical patent/WO2019189229A1/fr

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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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/72—Coated paper characterised by the paper substrate
    • D21H19/76—Coated paper characterised by the paper substrate the substrate having specific absorbent properties
    • D21H19/78—Coated paper characterised by the paper substrate the substrate having specific absorbent properties being substantially impervious to the coating
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the first invention of the present invention relates to a paper barrier material having excellent barrier properties
  • the second and third inventions of the present invention relate to a paper barrier material having excellent water vapor barrier properties.
  • gas barrier properties and water vapor barrier properties are important because they affect the preservation of contents in a wide range of fields such as packaging materials and containers for food, cosmetics, agricultural chemicals, pharmaceuticals, miscellaneous goods, building materials, industrial materials, etc. Performance.
  • a gas barrier property is imparted to a paper packaging material by providing a metal foil or a metal vapor-deposited film made of a metal such as aluminum as a gas barrier layer on a paper base material (base paper), polyvinyl alcohol or ethylene-vinyl alcohol.
  • Polymer films resin films such as polyvinylidene chloride, polyacrylonitrile, etc., or films coated with these resins, and ceramic vapor-deposited films deposited with inorganic oxides such as silicon oxide and aluminum oxide, are extruded onto paper substrates (base paper). Laminating or pasting methods have been mainly used.
  • Other paper packaging materials with gas barrier properties other than those described above include paper gas barrier materials having a gas barrier layer composed of a water-soluble polymer and an inorganic layered compound (Patent Documents 1 and 2), and a specific vinyl on the coating layer.
  • a paper gas barrier material (Patent Document 2) provided with a barrier layer made of an alcohol polymer is disclosed.
  • Patent Document 3 a barrier material obtained by adding a water vapor barrier property to a gas barrier property.
  • Patent Document 4 a barrier material obtained by adding a water vapor barrier property to a gas barrier property.
  • Patent Document 5 a resin composition that defines the melting point of the resin contained in the gas barrier layer is also disclosed (Patent Document 5).
  • the present invention provides a paper barrier material having excellent barrier properties and low environmental impact, and an excellent and uniform coating of a coating liquid having barrier properties on a paper substrate.
  • An object is to provide a paper barrier material having a water vapor barrier property and a low environmental load, and to provide a paper barrier material having a good water vapor barrier property and a low environmental load.
  • the present invention provides the following [1] to [20].
  • the paper barrier material satisfying the condition (1) is the first invention
  • the paper barrier material satisfying the condition (2) is the second invention
  • the paper barrier material satisfying the condition (3) is the third invention.
  • the barrier coating layer contains a pigment
  • the barrier coating layer contains at least two types of flat inorganic pigment A and flat inorganic pigment B in an amount of 50% by weight or more based on the total pigment of the barrier coating layer. .
  • the barrier coating layer is a water vapor barrier coating layer, the water vapor barrier coating layer contains a water vapor barrier resin, and the drip oil absorption of the paper substrate is 50 seconds or more.
  • the barrier coating layer is a water vapor barrier coating layer, and the water vapor barrier coating layer has at least a water vapor barrier resin A having a melting point of 110 ° C. or more and a water vapor barrier resin having a melting point of less than 110 ° C. Contains B. [2].
  • the barrier coating layer contains a pigment, and the barrier coating layer contains at least two types of flat inorganic pigment A and flat inorganic pigment B in an amount of 50% by weight or more based on the total pigment of the barrier coating layer.
  • the paper barrier material according to [1]. [3].
  • the barrier coating layer is a water vapor barrier coating layer, the water vapor barrier coating layer contains a water vapor barrier resin, and the drip oil absorption of the paper substrate is 50 seconds or more [1 ] The paper barrier material as described in]. [9].
  • the water vapor barrier coating layer further contains a pigment, and the content of the water vapor barrier resin with respect to 100 parts by weight of the pigment is 30 parts by weight or more and 350 parts by weight or less when absolutely dry [8] The paper barrier material described in 1. [10].
  • the paper barrier material according to [8] or [9] further comprising a gas barrier coating layer on the paper base material.
  • the barrier coating layer is a water vapor barrier coating layer, and the water vapor barrier coating layer contains at least a water vapor barrier resin A having a melting point of 110 ° C. or more and a water vapor barrier resin B having a melting point of less than 110 ° C.
  • the paper barrier material according to [11], wherein the water vapor barrier resin A and the water vapor barrier resin B are water-soluble or water-dispersible water-based resins.
  • the paper barrier material according to [12] wherein the water vapor barrier resin A is a water-soluble water-based resin, and the water vapor barrier resin B is a water-dispersible water-based resin.
  • a paper barrier material further comprising a protective layer on at least one surface of the paper barrier material according to any one of [1] to [14]. [16]. [1] A packaging material using the paper barrier material according to any one of [15]. [17]. A bag using the paper barrier material according to any one of [1] to [15]. [18]. [1] A tray using the paper barrier material according to any one of [15]. [19]. A cup using the paper barrier material according to any one of [1] to [15]. [20]. A liquid paper container using the paper barrier material according to any one of [1] to [15].
  • the paper barrier material which has the outstanding barrier property can be provided. Further, by adding a specific amount of at least two kinds of flat inorganic pigments to at least one barrier coating layer, better barrier properties can be imparted. Furthermore, the barrier coating layer has both a water vapor barrier property and a gas barrier property, or the barrier coating layer is a combination of a water vapor barrier coating layer having a water vapor barrier property and a gas barrier coating layer having a gas barrier property. A paper barrier material having both excellent gas barrier properties and water vapor barrier properties can be provided. In addition, because the main component is paper made from biomass, which is a sustainable raw material, carbon dioxide emissions from production to disposal can be reduced and production can be reduced compared to films derived from fossil resources. Due to its degradability, it is less likely to cause environmental pollution during disposal and has a low environmental impact.
  • Second invention it is possible to provide a paper barrier material having an excellent water vapor barrier property, in which a coating liquid having a barrier property is effectively and uniformly coated on a paper base material. it can. Furthermore, by providing a gas barrier coating layer on the paper substrate, a paper barrier material having both excellent gas barrier properties and water vapor barrier properties can be provided.
  • the main component is paper made from biomass, which is a sustainable raw material, carbon dioxide emissions from production to disposal can be reduced and production can be reduced compared to films derived from fossil resources. Due to its degradability, it is less likely to cause environmental pollution during disposal and has a low environmental impact.
  • steam barrier property can be provided.
  • the paper barrier material which has the outstanding water vapor
  • a paper barrier material having both excellent gas barrier properties and water vapor barrier properties can be provided.
  • the main component is paper made from biomass, which is a sustainable raw material, carbon dioxide emissions from production to disposal can be reduced and production can be reduced compared to films derived from fossil resources. Due to its degradability, it is less likely to cause environmental pollution during disposal and has a low environmental impact.
  • the present invention relates to a paper barrier material, which is a paper barrier material having at least one barrier coating layer on a paper substrate, and satisfies any one or more of the following conditions (1) to (3): .
  • the barrier coating layer contains a pigment, and the barrier coating layer contains at least two types of flat inorganic pigment A and flat inorganic pigment B in an amount of 50% by weight or more based on the total pigment of the barrier coating layer.
  • the barrier coating layer is a water vapor barrier coating layer, the water vapor barrier coating layer contains a water vapor barrier resin, and the drip oil absorption of the paper substrate is 50 seconds or more.
  • the barrier coating layer is a water vapor barrier coating layer, and the water vapor barrier coating layer has at least a water vapor barrier resin A having a melting point of 110 ° C. or more and a water vapor barrier resin having a melting point of less than 110 ° C. Contains B.
  • the first invention of the present invention is a paper barrier material in which a barrier coating layer containing at least one pigment is provided on a paper substrate (hereinafter sometimes referred to as “base paper”).
  • the barrier coating layer contains at least two types of flat inorganic pigment A and flat inorganic pigment B in an amount of 50% by weight or more based on the total pigment of the barrier coating layer.
  • the barrier coating layer of the first invention preferably has water vapor barrier properties and / or gas barrier properties, and more preferably has at least water vapor barrier properties.
  • the barrier coating layer has both a water vapor barrier property and a gas barrier property, or the barrier coating layer is a combination of a water vapor barrier coating layer having a water vapor barrier property and a gas barrier coating layer having a gas barrier property. It is preferable because a paper barrier material having both excellent gas barrier properties and water vapor barrier properties can be obtained.
  • the barrier coating layer is a combination of a water vapor barrier coating layer having a water vapor barrier property and a gas barrier coating layer having a gas barrier property
  • the configuration order of each layer is not particularly limited.
  • the layers are preferably laminated in the order of the gas barrier coating layer. These coating layers can be formed by applying a coating solution mainly containing water as a medium with various coating apparatuses and drying.
  • the paper barrier material having the water vapor barrier coating layer and the gas barrier coating layer in this order has both excellent water vapor barrier properties and gas barrier properties is presumed as follows.
  • polymers such as water-soluble polymers and water-dispersible polymers are generally used as the gas barrier resin used in the gas barrier coating layer, and the gas barrier coating layer and water vapor barrier are formed on the paper substrate.
  • coating layers are provided in this order, they contain polymers such as water-soluble polymers and water-dispersible polymers due to moisture in the paper substrate and moisture in the air that permeates through the paper substrate. Gas barrier coating layer tends to deteriorate.
  • the water vapor barrier coating layer can be used for gas barrier coating such as moisture in the paper substrate.
  • the influence (deterioration) on the construction layer can be effectively suppressed.
  • steam barrier coating layer and a gas barrier coating layer in this order has favorable water vapor
  • the paper barrier material of the first invention has a barrier coating layer containing at least one pigment on at least one surface on a paper substrate, and at least two types of flat inorganic pigments in the barrier coating layer A and the flat inorganic pigment B are contained in an amount of 50% by weight or more based on the total pigment of the barrier coating layer.
  • the barrier coating layer preferably has a water vapor barrier property and / or a gas barrier property, and more preferably has at least a water vapor barrier property.
  • the barrier coating layer may have both water vapor barrier properties and gas barrier properties, or the barrier coating layer may be a combination of a water vapor barrier coating layer having water vapor barrier properties and a gas barrier coating layer having gas barrier properties. It is more preferable that the paper substrate, the water vapor barrier coating layer, and the gas barrier coating layer are laminated in this order.
  • the water vapor barrier resin contained in the barrier coating layer is a water-soluble or water-dispersible water-based resin having water vapor barrier properties, such as styrene / butadiene, styrene / acrylic, ethylene ⁇ Various acetates such as vinyl acetate, paraffin (WAX), polyester resin, butadiene / methyl methacrylate, vinyl acetate / butyl acrylate, maleic anhydride copolymer, acrylic acid / methyl methacrylate copolymer, etc.
  • These synthetic adhesives or their paraffin (WAX) blended synthetic adhesives can be used alone or in combination of two or more.
  • the gas barrier resin contained in the barrier coating layer is a polymer having gas barrier properties, such as a water-soluble polymer and a water-dispersible polymer.
  • Water-soluble polymers include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, polyvinyl alcohol such as ethylene copolymerized polyvinyl alcohol, proteins such as casein, soy protein, synthetic protein, oxidized starch, cationized starch, urea Examples thereof include starches such as phosphate esterified starch and hydroxyethyl etherified starch, cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose and hydroxyethyl cellulose, polyvinylpyrrolidone, and sodium alginate.
  • polyvinyl alcohols and cellulose derivatives are preferable, and polyvinyl alcohols are more preferable.
  • the water-dispersible polymer include polyvinylidene chloride, ethylene vinyl acetate resin, and modified polyolefin resin.
  • At least two types of flat inorganic pigment A and flat inorganic pigment B are contained in at least one barrier coating layer.
  • the flat inorganic pigment A and the flat inorganic pigment B various known flat inorganic pigments such as kaolin, talc, clay, bentonite, saponite, steven knight, montmorillonite and mica can be used.
  • the total amount of the inorganic pigment A and the flat inorganic pigment B is 50% by weight or more based on the total pigment of the barrier coating layer. The amount is preferably 60% by weight or more, more preferably 70% by weight or more based on the total pigment.
  • the barrier coating layer moves with less frequency of detouring water vapor or gas. Since the distance is short, various barrier properties, particularly water vapor barrier properties and gas barrier properties are insufficient.
  • the flat inorganic pigment A is preferably mica.
  • Mica is a kind of mineral mainly composed of silicon.
  • tetrahedrons composed of silicon and oxygen are connected in a sheet shape, and this continuous structure forms a highly flat shape.
  • the swellable mica is preferable because it swells by taking water molecules between the sheet-like structures and swells and cleaves finely.
  • the barrier coating layer is a combination of a water vapor barrier coating layer containing a pigment and a gas barrier coating layer
  • the content ratio of the flat inorganic pigment other than mica and mica in the water vapor barrier coating layer is
  • the flat inorganic pigment other than mica / mica 60/40 to 5/95 (solid content ratio)
  • the adhesion between the water vapor barrier coating layer and the gas barrier coating layer is improved, and the water vapor barrier property and gas barrier property are high.
  • it is 55/50 to 10/90, and still more preferably 50/45 to 15/85.
  • the flat inorganic pigment B preferably has an aspect ratio of 10 or more.
  • the flat inorganic pigment B having an aspect ratio of 10 or more include kaolin, talc, clay, bentonite, saponite, steven knight, and montmorillonite.
  • kaolin, bentonite, and montmorillonite are preferable, and kaolin and bentonite are more preferable from the viewpoints of both improvement of water vapor barrier properties and suppression of permeation of the gas barrier layer.
  • the flat inorganic pigment A is mica and the flat inorganic pigment B has an aspect ratio of 10 or more, the number of times the water vapor or gas bypasses the barrier coating layer increases, and the moving distance becomes longer.
  • the effect of improving the property and gas barrier property is increased.
  • the aspect ratio is preferably 30 or more, more preferably 90 or more.
  • the aspect ratio of the flat inorganic pigment B is a value obtained by photographing the powder particles of the flat inorganic pigment B with an electron microscope and dividing the diameter by the thickness for 100 randomly extracted particles. Yes, the flatness of the flat inorganic pigment B increases as the aspect ratio value increases.
  • the content ratio of the flat inorganic pigment A and the flat inorganic pigment B is: flat inorganic pigment A / flat inorganic pigment
  • B 60/40 to 5/95 (solid content ratio)
  • mica and the flat inorganic pigment B effectively fill the voids in the barrier coating layer, so that the water vapor barrier property and gas barrier property are improved. It is preferable because it becomes larger. More preferably, it is 50/45 to 10/90, and still more preferably 55/50 to 15/85.
  • inorganic pigments such as calcium carbonate, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin white
  • An organic pigment such as a real type, a hollow type, or a core-shell type may be used alone or in combination of two or more.
  • the total amount of the water vapor barrier resin and the gas barrier resin is 11 parts by weight based on 100 parts by weight of the total pigment contained in the barrier coating layer.
  • the amount is preferably 1300 parts by weight or less.
  • the barrier coating layer is a combination of a water vapor barrier coating layer and a gas barrier coating layer, and when the water vapor barrier coating layer contains a pigment, 100 parts by weight of the total pigment contained in the water vapor barrier coating layer
  • the water vapor barrier resin is preferably 10 parts by weight or more and 300 parts by weight or less, and more preferably 30 parts by weight or more and 250 parts by weight or less by dry weight.
  • the gas barrier resin When the pigment is contained in the gas barrier coating layer, the gas barrier resin may be 1 part by weight or more and 1000 parts by weight or less by dry weight with respect to 100 parts by weight of the total pigment contained in the gas barrier coating layer. preferable.
  • the pigment when the pigment is contained in the barrier coating layer, it is preferable to add and mix the slurry of the pigment into the water vapor barrier resin or the gas barrier resin.
  • a crosslinking agent typified by a polyvalent metal salt or the like can be added to the barrier coating layer. Since the crosslinking agent causes a crosslinking reaction with the water vapor barrier resin or gas barrier resin contained in the barrier coating layer, the number of bonds (crosslinking points) in the barrier coating layer increases. That is, the barrier coating layer has a dense structure and can exhibit good water vapor barrier properties and gas barrier properties.
  • the type of the crosslinking agent is not particularly limited, and in accordance with the type of the water vapor barrier resin or the gas barrier resin contained in the barrier coating layer, a polyvalent metal salt (copper, zinc, Multivalent metals such as silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium and carbonate ions, sulfate ions, nitrate ions, phosphate ions, silicate ions, nitrogen oxides, boron oxides, etc.
  • a compound to which an ionic substance is bound) an amine compound, an amide compound, an aldehyde compound, a hydroxy acid, and the like can be appropriately selected and used.
  • the blending amount of the crosslinking agent can be blended without particular limitation as long as it is within the range of the concentration and viscosity of the coating liquid that can be coated, but preferably the crosslinking agent is used with respect to 100 parts by weight of the pigment. Is 1 part by weight or more and 10 parts by weight or less, more preferably 3 parts by weight or more and 5 parts by weight or less. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained.
  • the amount is more than 10 parts by weight, the viscosity of the coating solution is remarkably increased, and coating may be difficult.
  • a crosslinking agent when adding a crosslinking agent to the coating liquid for barrier coating layers, it is preferable to add, after dissolving a crosslinking agent in polar solvents, such as ammonia.
  • polar solvents such as ammonia.
  • the crosslinking agent is dissolved in a polar solvent, a bond is formed between the crosslinking agent and the polar solvent. Therefore, even if added to the coating solution, a crosslinking reaction with the water vapor barrier resin or gas barrier resin does not occur immediately. Can be prevented. In that case, the polar solvent component is volatilized by drying after coating on the paper substrate, and it is estimated that a cross-linking reaction with the water vapor barrier resin or gas barrier resin occurs to form a dense barrier coating layer.
  • the barrier coating layer can contain a water repellent.
  • water repellents include paraffinic water repellents mainly composed of alkane compounds, natural oil and fat water repellents derived from animals and plants such as carnauba and lanolin, silicone-containing water repellents containing silicone or silicone compounds, and fluorine compounds. Examples thereof include a fluorine-containing water repellent.
  • These water repellents can be used alone or in combination of two or more.
  • the blending amount of the water repellent is not particularly limited, but the blending amount of the water repellent is 1 part by weight of the water repellent with respect to 100 parts by weight of the water vapor barrier resin in dry weight.
  • the amount is preferably 100 parts by weight or less. If the blending amount of the water repellent is less than 1 part by weight, the effect of improving the water vapor barrier property may not be sufficiently obtained.
  • the amount exceeds 100 parts by weight, a paper base, a water vapor barrier coating layer, and a gas barrier coating layer are laminated in this order, and when the water vapor barrier coating layer contains a water repellent, Since it becomes difficult to form a layer uniformly, gas barrier property may fall.
  • the water vapor barrier coating is performed from the viewpoint of improvement of water vapor barrier properties and adhesion to the gas barrier coating layer.
  • the wetting tension on the surface of the work layer can be 10 mN / m or more and 60 mN / m or less, and if it is 15 mN / m or more and 50 mN / m or less, the effect is more exhibited.
  • the barrier coating layer may contain a surfactant.
  • a surfactant in the first invention, may contain a surfactant.
  • the ionicity of the surfactant there is no limitation on the ionicity of the surfactant, and any one of anionic surfactant, cationic surfactant, amphoteric surfactant and nonionic surfactant can be used alone or in combination of two or more. Can be used in combination.
  • Specific types include silicone surfactants, fluorine surfactants, alcohol surfactants, acetylene surfactants having an acetylene group, and acetylenic diol surfactants having an acetylene group and two hydroxyl groups.
  • Agents alkyl sulfonic acid surfactants having an alkyl group and sulfonic acid, ester surfactants, amide surfactants, amine surfactants, alkyl ether surfactants, phenyl ether surfactants, sulfuric acid Examples thereof include ester surfactants and phenol surfactants.
  • an acetylenic diol surfactant which has a large effect of improving the leveling property of the gas barrier coating layer coating solution.
  • gas barrier property since the uniformity of a gas barrier coating layer will improve if the leveling property of the coating liquid for gas barrier coating layers improves, gas barrier property will improve.
  • the coating for the gas barrier coating layer is preferably adjusted to 10 mN / m or more and 60 mN / m or less, and more preferably adjusted to 15 mN / m or more and 50 mN / m or less in order to exhibit more effects.
  • the surface tension of the gas barrier coating layer coating liquid is ⁇ 20 mN / m with respect to the wet tension of the water vapor barrier coating layer surface, so that the adhesion between the water vapor barrier coating layer and the gas barrier coating layer is improved.
  • the barrier coating layer of the first invention includes the above-described water vapor barrier resin, gas barrier resin, other resins, pigments, water repellents, surfactants, dispersants, thickeners, water retention agents, antifoams Various commonly used auxiliaries such as agents, water resistance agents, dyes, fluorescent dyes and the like can be used.
  • the coating method of the barrier coating layer is not particularly limited, and it can be applied by a known coating apparatus and coating system.
  • the coating apparatus include a blade coater, a bar coater, a roll coater, an air knife coater, a reverse roll coater, a curtain coater, a spray coater, a size press coater, and a gate roll coater.
  • the coating system an aqueous coating mainly using water as a medium is preferable.
  • a method for drying the barrier coating layer for example, usual methods such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, a cylinder dryer, and the like are used.
  • the coating amount of the barrier coating layer is preferably set to 3.2 g / m 2 or more 70 g / m 2 or less by dry weight, 5.2 g / M 2 or more and 60 g / m 2 or less is more preferable, and 7.2 g / m 2 or more and 40 g / m 2 or less is more preferable.
  • the coating amount of the water vapor barrier coating layer is 3.0 g / m 2 or more and 50 g / m 2 or less in terms of dry weight.
  • the water vapor barrier coating layer may be a single layer or a multilayer of two or more layers.
  • the total coating amount of all the water vapor barrier coating layers is preferably within the above range.
  • the coating amount of the gas barrier coating layer is preferably in a 0.2 g / m 2 or more 20 g / m 2 or less by dry weight. If the coating amount of the gas barrier coating layer is less than 0.2 g / m 2 , it may be difficult to form a uniform gas barrier layer, so that sufficient gas barrier properties may not be obtained. On the other hand, when it is more than 20 g / m 2 , the drying load during coating increases.
  • the gas barrier coating layer may be a single layer or a multilayer of two or more layers. When the gas barrier coating layer is composed of two or more layers, the total coating amount of all the gas barrier coating layers is preferably within the above range.
  • the paper base is a sheet mainly made of pulp, and may contain a filler and various auxiliaries.
  • Pulp includes chemical pulp such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), softwood unbleached kraft pulp (NUKP), sulfite pulp, stone grind pulp, thermo Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and waste paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp, etc., polyester resin fiber such as polyethylene terephthalate, polyolefin resin fiber such as polypropylene and polyethylene Synthetic fibers such as polyamide resin fibers such as nylon and halogen-containing resin fibers such as polyvinyl chloride can be used, and they can be used by appropriately blending them.
  • LLKP hardwood bleached kraft pulp
  • NKP softwood bleached kraft pulp
  • LKP hardwood unbleached kraft pulp
  • filler known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, and synthetic resin filler can be used.
  • sulfuric acid bands and various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers and internal additive sizing agents, etc. Can be used.
  • dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
  • the production method (paper making) of the paper base material is not particularly limited, and it is possible to use a known long net former machine, on-top hybrid former machine, gap former machine, Yankee machine, etc.
  • a paper base material can be manufactured by paper making by paper making or alkali paper making.
  • the paper substrate may be a single layer or may be composed of two or more layers.
  • the surface of the paper substrate can be treated with various chemicals. Examples of the drug used include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agent, water-resistant agent, water retention agent, thickener, lubricant, etc. These can be used alone or in admixture of two or more.
  • pigments kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin
  • An inorganic pigment such as white and an organic pigment such as a solid type, a hollow type, or a core-shell type can be used alone or in admixture of two or more.
  • the surface treatment method of the paper substrate is not particularly limited, but a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • Paper bases obtained in this way include fine paper, medium paper, coated paper, glossy paper, kraft paper, glossy kraft paper, bleached kraft paper, glassine paper, paperboard, white paperboard, liners, etc.
  • Various well-known things can be illustrated.
  • the paper base material of the first invention Since the paper base material of the first invention is mainly applied with a coating solution containing water as a medium, the strength when the paper base material is wetted with water is preferably not less than a certain level. Therefore, the wet tensile strength in the paper making direction (MD) is preferably 300 N / m or more.
  • the paper base material of the first invention may be an optimum basis weight according to the use, but generally it is about 30 g / m 2 to 600 g / m 2 , 30 g / m 2 to 500 g / m 2 Is often used.
  • a protective layer may be further provided on at least one surface of the paper barrier material of the first invention.
  • the protective layer prevents the influence (deterioration) of the paper barrier material on the barrier coating layer due to moisture in the air, scratching or cracking of the barrier coating layer, and further increases the water vapor barrier property of the paper barrier material.
  • Gas barrier properties can be imparted, or oil resistance, solvent resistance, heat resistance, wear resistance, impact resistance, light resistance, water resistance, and the like can be imparted.
  • heat sealability can also be provided.
  • the protective layer can be provided on both surfaces of the paper barrier material, but it is preferable to have at least the surface on the side having the barrier coating layer. Furthermore, it is possible to have a protective layer on the gas barrier coating layer of the paper barrier material that has the water vapor barrier coating layer and the gas barrier coating layer in this order on the paper base material. It is preferable for preventing the influence (deterioration) on the work layer and the gas barrier coating layer.
  • the protective layer include a resin layer, a paper layer, and a metal foil. Among these, a resin layer is preferable. However, in applications where biodegradability is required, the protective layer preferably has biodegradability such as a biodegradable resin.
  • the resin of the resin layer includes polyester, polyvinyl alcohol, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene, polyvinyl chloride, acrylonitrile / butadiene / styrene, acrylonitrile / styrene, polymethylmethacrylic, polychlorinated.
  • Resin derived from fossil resources such as vinylidene, polyamide (nylon), polyacetal, polycarbonate, polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), biopolyethylene, Biological resins such as biopolyethylene terephthalate and biopolyurethane can be included.
  • the bio-derived resin includes a high-molecular material having a number average molecular weight (Mn) of 1,000 or more obtained by chemically or biologically synthesizing a material derived from an organic resource that can be regenerated as a raw material.
  • Mn number average molecular weight
  • polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and the like are biodegradable.
  • Any of non-biodegradable resins such as resin, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyamide (nylon), and biopolyethylene can be used.
  • the biodegradable resin is a resin that is decomposed to the molecular level by the action of microorganisms and eventually circulates into the natural world as carbon dioxide and water.
  • the resin layer is preferably a resin laminate layer.
  • the resin laminate layer include an extruded laminate layer, and a film bonding layer such as a barrier film and a vapor deposition film.
  • the resin laminate layer is an extruded laminate layer
  • the above-described various resins are laminated on at least one surface of the paper barrier material as a resin laminate layer by an extrusion lamination method.
  • the resin laminate layer is a film bonding layer
  • the above-mentioned various resin films are bonded as a resin laminate layer on at least one surface of the paper barrier material by a dry lamination method, a sand lamination method, or the like. .
  • examples of the film used for the film bonding layer include the above-described various resin films.
  • films mainly composed of resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, and the above-mentioned various resin films are coated with these resins such as polyvinyl alcohol.
  • Film a film obtained by bonding a metal foil made of various metals such as aluminum to the above-mentioned various resin films, an inorganic oxide such as silicon oxide or aluminum oxide, or various metals such as aluminum on the above-mentioned various resin films
  • a barrier film such as a vapor deposition film on which an object is vapor-deposited is preferable, and a vapor deposition film is more preferable. Depending on the purpose, these films can be used by laminating one or more layers.
  • the paper barrier material of the first invention preferably has the following barrier properties.
  • the following barrier property value is a value measured in a state where the above-described protective layer is not formed.
  • the paper barrier material of the first invention has excellent barrier properties without using various films and metal foils. (1) Water vapor permeability at a temperature of 40 ⁇ 0.5 ° C. and a relative humidity difference of 90 ⁇ 2% is 50 g / m 2 ⁇ day or less (2) Temperature: oxygen permeability at 23 ° C.
  • the second invention is a paper barrier material in which at least a water vapor barrier coating layer is provided on a paper base material (hereinafter sometimes referred to as “base paper”).
  • base paper a paper base material
  • a gas barrier coating layer may be further provided on the paper substrate.
  • the order of construction of each layer is not particularly limited, it is preferable that the layers are laminated in the order of a paper substrate, a water vapor barrier coating layer, and a gas barrier coating layer.
  • These coating layers can be formed by applying a coating solution mainly containing water as a medium with various coating apparatuses and drying.
  • the paper barrier material having the water vapor barrier coating layer and the gas barrier coating layer in this order has both excellent water vapor barrier properties and gas barrier properties is presumed as follows.
  • the resin having gas barrier properties used in the gas barrier coating layer polymers such as water-soluble polymers and water-dispersible polymers are generally used as exemplified below, and the gas barrier coating layer on the paper substrate,
  • the water vapor barrier coating layer is provided in this order, the water-soluble polymer or water-dispersible polymer can be absorbed by water in the paper base or in the air that permeates through the paper base.
  • the gas barrier coating layer contained tends to deteriorate.
  • the water vapor barrier coating layer can be used for gas barrier coating such as moisture in the paper substrate.
  • the influence (deterioration) on the construction layer can be effectively suppressed.
  • steam barrier coating layer and a gas barrier coating layer in this order has favorable water vapor
  • the paper base is a sheet mainly made of pulp, and may contain a filler and various auxiliaries.
  • Pulp includes chemical pulp such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), softwood unbleached kraft pulp (NUKP), sulfite pulp, stone grind pulp, thermo Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and waste paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp, etc., polyester resin fiber such as polyethylene terephthalate, polyolefin resin fiber such as polypropylene and polyethylene Synthetic fibers such as polyamide resin fibers such as nylon and halogen-containing resin fibers such as polyvinyl chloride can be used, and they can be used by appropriately blending them.
  • LLKP hardwood bleached kraft pulp
  • NKP softwood bleached kraft pulp
  • LKP hardwood unbleached kraft pulp
  • filler known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, and synthetic resin filler can be used.
  • sulfuric acid bands and various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers and internal additive sizing agents, etc. Can be used.
  • dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
  • the production method (paper making) of the paper base material is not particularly limited, and it is possible to use a known long net former machine, on-top hybrid former machine, gap former machine, Yankee machine, etc.
  • a paper base material can be manufactured by paper making by paper making or alkali paper making.
  • the paper substrate may be a single layer or may be composed of two or more layers.
  • the surface of the paper substrate can be treated with various chemicals. Examples of the drug used include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agent, water-resistant agent, water retention agent, thickener, lubricant, etc. These can be used alone or in admixture of two or more.
  • pigments kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin
  • An inorganic pigment such as white and an organic pigment such as a solid type, a hollow type, or a core-shell type can be used alone or in admixture of two or more.
  • the surface treatment method of the paper substrate is not particularly limited, but a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • Paper bases obtained in this way include fine paper, medium paper, coated paper, glossy paper, kraft paper, glossy kraft paper, bleached kraft paper, glassine paper, paperboard, white paperboard, liners, etc.
  • Various well-known things can be illustrated.
  • the paper base material of the second invention has a drip oil absorption of 50 seconds or more, preferably 100 seconds or more.
  • the water vapor barrier coating layer is compared with the pigment component and the resin component.
  • the resin component tends to increase.
  • Most of the water vapor barrier resins are oleophilic resins, and the drip oil absorption of the paper substrate is 50 seconds or more in order to suppress penetration into the paper substrate.
  • the drip oil absorption of the paper substrate When the drip oil absorption of the paper substrate is 50 seconds or more, these water vapor barrier resin components tend to stay on the surface of the paper, and a uniform film that effectively exhibits the water vapor barrier property is easily generated. As a result, good water vapor barrier properties can be obtained.
  • the drip oil absorption of the paper substrate can be adjusted by the surface treatment conditions, the amount of the internal additive, the amount of the internal additive, and the like.
  • the paper base material of the second invention Since the paper base material of the second invention is mainly applied with a coating solution containing water as a medium, the strength when the paper base material is wet with water is preferably not less than a certain level. Therefore, the wet tensile strength in the paper making direction (MD) is preferably 300 N / m or more.
  • the paper substrate of the second invention may have an optimum basis weight depending on the application, but generally it is about 30 g / m 2 to 600 g / m 2 and 30 g / m 2 to 500 g / m 2 . Is often used.
  • the paper barrier material of the second invention has a water vapor barrier coating layer on at least one surface on the paper substrate.
  • the paper substrate, the water vapor barrier coating layer, and the gas barrier coating layer are preferably laminated in this order.
  • the water vapor barrier resin to be contained in the water vapor barrier coating layer is a water-soluble or water-dispersible water-based resin having water vapor barrier properties, such as styrene / butadiene, styrene / acrylic.
  • Various copolymers such as ethylene / vinyl acetate, paraffin (WAX), polyester resin, butadiene / methyl methacrylate, vinyl acetate / butyl acrylate, maleic anhydride copolymer, acrylic acid / methyl methacrylate copolymer
  • Synthetic adhesives such as coalescence, or paraffin (WAX) blended synthetic adhesives or the like can be used alone or in admixture of two or more.
  • the second invention it is preferable to use a mixture of two or more. Moreover, in order to improve the adhesiveness of a water vapor
  • polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, proteins such as casein, soy protein, and synthetic protein, oxidation Starch, cationized starch, urea phosphated starch, starch such as hydroxyethyl etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, water-soluble polymers such as polyvinylpyrrolidone, sodium alginate, etc. It can also be used in combination with a water vapor barrier resin.
  • the water vapor barrier coating layer contains a pigment in terms of adhesion between the water vapor barrier coating layer and the gas barrier coating layer in the configuration having the water vapor barrier coating layer and the gas barrier coating layer.
  • Inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white, etc.
  • Organic pigments such as hollow type or core-shell type can be used alone or in combination of two or more.
  • inorganic pigments such as kaolin, talc, clay and mica having a flat shape are preferable, and kaolin and mica are more preferable.
  • inorganic pigments having a volume 50% average particle diameter (D50) (hereinafter also referred to as “average particle diameter”) of 5 ⁇ m or more and an aspect ratio of 10 or more alone or in combination. If the average particle size or aspect ratio of the inorganic pigment used is smaller than the above range, the number of times that the water vapor bypasses the water vapor barrier coating layer is reduced, and the moving distance is shortened. As a result, the water vapor barrier property is improved. May become smaller.
  • the water vapor barrier resin when the pigment is contained in the water vapor barrier coating layer, is preferably contained in the range of 30 parts by weight to 350 parts by weight with respect to 100 parts by weight of the dry pigment. More preferably, it is 50 weight part or more, More preferably, it is 80 weight part or more. Further, it is more preferably 250 parts by weight or less, and still more preferably 200 parts by weight or less.
  • a crosslinking agent represented by a polyvalent metal salt or the like can be added to the water vapor barrier coating layer. Since the crosslinking agent causes a crosslinking reaction with the water vapor barrier resin or water-soluble polymer contained in the water vapor barrier coating layer, the number of bonds (crosslinking points) in the water vapor barrier coating layer increases. That is, the water vapor barrier coating layer has a dense structure and can exhibit good water vapor barrier properties.
  • the type of the crosslinking agent is not particularly limited, and in accordance with the type of the water vapor barrier resin or water-soluble polymer contained in the water vapor barrier coating layer, a polyvalent metal salt (copper, Multivalent metals such as zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide, boron oxide Etc.), amine compounds, amide compounds, aldehyde compounds, hydroxy acids and the like can be appropriately selected and used.
  • a polyvalent metal salt copper, Multivalent metals such as zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide, boron oxide Etc.
  • a polyvalent metal salt from the viewpoint of expression of a crosslinking effect. More preferably, potassium alum is used.
  • the amount of the crosslinking agent can be blended without particular limitation as long as it is within the range of the paint concentration and the paint viscosity that can be applied, but preferably the crosslinking agent is 1 with respect to 100 parts by weight of the pigment. It is not less than 10 parts by weight and more preferably not less than 3 parts by weight and not more than 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, when the amount is more than 10 parts by weight, the viscosity of the coating material is remarkably increased and coating may be difficult.
  • the crosslinking agent when added to the paint for the water vapor barrier coating layer, it is preferable that the crosslinking agent is dissolved in a polar solvent such as ammonia and then added to the coating.
  • a polar solvent such as ammonia
  • a bond is formed between the cross-linking agent and the polar solvent, so that even if added to the paint, a cross-linking reaction with the water vapor barrier resin or water-soluble polymer does not occur immediately. Can be suppressed.
  • the polar solvent component when the polar solvent component is volatilized by drying after coating on the paper substrate, a crosslinking reaction with the water vapor barrier resin or water-soluble polymer occurs, and a dense water vapor barrier coating layer is formed. Guessed.
  • a water repellent may be contained in the water vapor barrier coating layer in order to improve the water vapor barrier property.
  • water repellents include paraffinic water repellents mainly composed of alkane compounds, natural oil and fat water repellents derived from animals and plants such as carnauba and lanolin, silicone-containing water repellents containing silicone or silicone compounds, and fluorine compounds. Examples thereof include a fluorine-containing water repellent.
  • These water repellents can be used alone or in combination of two or more.
  • the blending amount of the water repellent is not particularly limited, but the blending amount of the water repellent is 100 parts by weight in total of the water vapor barrier resin and the water-soluble polymer in dry weight.
  • the water repellent is preferably 1 part by weight or more and 100 parts by weight or less. If the blending amount of the water repellent is less than 1 part by weight, the effect of improving the water vapor barrier property may not be sufficiently obtained. On the other hand, when the amount exceeds 100 parts by weight, the gas barrier coating layer is difficult to form uniformly when the gas barrier coating layer is provided on the water vapor barrier coating layer, so that the gas barrier property may be lowered.
  • the wet tension on the surface of the water vapor barrier coating layer can be 10 mN / m or more and 60 mN / m or less, and 15 mN If it is / m or more and 50 mN / m or less, an effect will be exhibited more.
  • the water vapor barrier coating layer includes the above water vapor barrier resin, water-soluble polymer, pigment, cross-linking agent, water repellent, dispersant, thickener, water retention agent, antifoaming agent, Various commonly used auxiliaries such as water-resistant agents, dyes, fluorescent dyes and the like can be used.
  • the gas barrier coating layer may contain a polymer having gas barrier properties, such as a water-soluble polymer and a water-dispersible polymer.
  • the water-soluble polymer used in the gas barrier coating layer includes polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, casein, soybean protein, and synthetic protein.
  • polyvinyl alcohols and cellulose derivatives are preferable, and polyvinyl alcohols are more preferable.
  • water-dispersible polymer used for the gas barrier coating layer include polyvinylidene chloride, ethylene vinyl acetate resin, and modified polyolefin resin.
  • a gas barrier coating layer contains a pigment from the viewpoint of improving the gas barrier property.
  • pigments used in the gas barrier coating layer kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, Inorganic pigments such as silicic acid, silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, and core-shell type can be used alone or in combination of two or more.
  • flat inorganic pigments such as kaolin, talc, clay and mica from the viewpoint of gas barrier properties, and flat inorganic pigments having an average particle diameter of 3 ⁇ m or more and an aspect ratio of 10 or more are used. It is more preferable to use a flat inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 30 or more.
  • a gas barrier coating layer contains a pigment
  • a gas such as oxygen passes around the pigment.
  • a gas barrier coating layer made of a polymer such as a water-soluble polymer or a water-dispersible polymer that does not contain a pigment.
  • a gas barrier coating layer containing an inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more can further contain a pigment having an average particle diameter of 5 ⁇ m or less.
  • voids in the gas barrier coating layer formed of an inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more can be further reduced. Gas barrier properties are exhibited. That is, when the gas barrier coating layer contains pigments having different average particle sizes, the voids formed by the inorganic pigment having a large average particle size are filled with the pigment having a small average particle size in the gas barrier coating layer. Since gas such as oxygen bypasses the pigment and passes through, it is presumed that it has a high gas barrier property as compared with a gas barrier coating layer not containing a pigment having a different average particle size.
  • the inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more and a pigment having an average particle diameter of 5 ⁇ m or less when used in combination, the inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more.
  • the blending ratio of the pigment having an average particle size of 5 ⁇ m or less can be 50/50 to 99/1 in terms of dry weight. If the blending ratio of the inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more is less than the above range, the number of times that a gas such as oxygen bypasses the gas barrier coating layer is reduced, and the moving distance is shortened. In addition, the gas barrier property improving effect may be reduced.
  • the void formed by the inorganic pigment having a large average particle size in the gas barrier coating layer cannot be sufficiently filled with the pigment having an average particle size of 5 ⁇ m or less, and therefore further improvement in gas barrier properties is observed. I can't.
  • the pigment having an average particle size of 5 ⁇ m or less used in combination with an inorganic pigment having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more includes kaolin, clay, engineered kaolin, delaminated clay, heavy carbonate Inorganic pigments such as calcium, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, and core-shell type Can be used alone or in admixture of two or more. Among these pigments, it is preferable to use heavy calcium carbonate.
  • Inorganic pigments such as calcium, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin white
  • organic pigments such as solid type, hollow type, and core-shell type Can be used alone or in
  • the blending ratio of the pigment, the water-soluble polymer and the water-dispersible polymer is dry weight, and the pigment / (water-soluble polymer and water-dispersible polymer).
  • the sum of the above) is preferably 1/100 to 1000/100. If the ratio of the pigment is out of the above range, the gas barrier property improving effect may be reduced.
  • the pigment when the pigment is blended into the water-soluble polymer or the water-dispersible polymer, it is preferable to add and mix the slurry of the pigment.
  • a crosslinking agent typified by a polyvalent metal salt or the like can be added to the gas barrier coating layer. Since the crosslinking agent causes a crosslinking reaction with a polymer such as a water-soluble polymer or a water-dispersible polymer contained in the gas barrier coating layer, the number of bonds (crosslinking points) in the gas barrier coating layer increases. That is, the gas barrier coating layer has a dense structure and can exhibit good gas barrier properties.
  • the type of the crosslinking agent is not particularly limited, and a polyvalent metal is selected according to the type of polymer such as a water-soluble polymer or water-dispersible polymer contained in the gas barrier coating layer.
  • Salt copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium and other polyvalent metals, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide ,
  • an amine compound, an amide compound, an aldehyde compound, a hydroxy acid, and the like can be appropriately selected and used.
  • it is preferable to use a polyvalent metal salt from a viewpoint of expression of a crosslinking effect and it is more preferable to use potassium alum.
  • the amount of the crosslinking agent can be blended without particular limitation as long as it is within the range of the paint concentration and the paint viscosity that can be applied, but preferably the crosslinking agent is 1 with respect to 100 parts by weight of the pigment. It is not less than 10 parts by weight and more preferably not less than 3 parts by weight and not more than 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, when the amount is more than 10 parts by weight, the viscosity of the coating material is remarkably increased and coating may be difficult.
  • a surfactant in order to improve the adhesion to the water vapor barrier coating layer, can be contained in the gas barrier coating layer.
  • a surfactant can be contained in the gas barrier coating layer.
  • any one of anionic surfactant, cationic surfactant, amphoteric surfactant and nonionic surfactant can be used alone or in combination of two or more. Can be used in combination.
  • Specific types include silicone surfactants, fluorine surfactants, alcohol surfactants, acetylene surfactants having an acetylene group, and acetylenic diol surfactants having an acetylene group and two hydroxyl groups.
  • alkyl sulfonic acid surfactants having an alkyl group and sulfonic acid examples thereof include ester surfactants and phenol surfactants.
  • ester surfactants and phenol surfactants examples thereof include ester surfactants and phenol surfactants.
  • uniformity of a gas barrier coating layer will improve if the leveling property of a coating material improves, gas barrier property will improve.
  • the surface tension of the gas barrier coating layer paint can be adjusted to 10 mN / m or more and 60 mN / m or less, and more effective. Is preferably adjusted to 15 mN / m or more and 50 mN / m or less.
  • the surface tension of the coating for the gas barrier coating layer is set to ⁇ 20 mN / m with respect to the wet tension on the surface of the water vapor barrier coating layer. To preferred.
  • the gas barrier coating layer includes the above-mentioned water-soluble polymer, water-dispersible polymer, pigment, crosslinking agent, surfactant, dispersant, thickener, water retention agent, antifoaming agent, Various commonly used auxiliaries such as water-resistant agents, dyes, fluorescent dyes and the like can be used.
  • the method for coating the water vapor barrier coating layer and the gas barrier coating layer is not particularly limited, and coating can be performed with a known coating apparatus and coating system.
  • the coating apparatus include a blade coater, a bar coater, a roll coater, an air knife coater, a reverse roll coater, a curtain coater, a spray coater, a size press coater, and a gate roll coater.
  • the coating system an aqueous coating mainly using water as a medium is preferable.
  • a method for drying the water vapor barrier coating layer and the gas barrier coating layer for example, usual methods such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, and a cylinder dryer are used.
  • the coating amount of the water vapor barrier coating layer is preferably 3 g / m 2 or more and 50 g / m 2 or less by dry weight, and more preferably 5 g / m 2 or more and 40 g / m 2 or less. Preferably, it is more preferably 7 g / m 2 or more and 20 g / m 2 or less.
  • the coating amount of the water vapor barrier coating layer is less than 3 g / m 2 , it becomes difficult to completely coat the paper substrate with the coating liquid, and sufficient water vapor barrier properties cannot be obtained. The work layer may penetrate into the paper substrate, and sufficient gas barrier properties may not be obtained.
  • the water vapor barrier coating layer may be a single layer or a multilayer of two or more layers.
  • the total coating amount of all the water vapor barrier coating layers is preferably within the above range.
  • the coating amount of the gas barrier coating layer is preferably 0.2 g / m 2 or more and 20 g / m 2 or less by dry weight. If the coating amount of the gas barrier coating layer is less than 0.2 g / m 2 , it may be difficult to form a uniform gas barrier coating layer, so that sufficient gas barrier properties may not be obtained. On the other hand, when it is more than 20 g / m 2 , the drying load during coating increases.
  • the gas barrier coating layer may be a single layer or a multilayer of two or more layers. When the gas barrier coating layer is composed of two or more layers, the total coating amount of all the gas barrier coating layers is preferably within the above range.
  • a protective layer may be further provided on at least one surface of the paper barrier material of the second invention.
  • the protective layer prevents the influence (deterioration) of the water barrier coating layer and the gas barrier coating layer of the paper barrier material due to moisture in the air, scratching and cracking of the barrier coating layer, etc. on the paper barrier material. Further water vapor barrier properties and gas barrier properties can be imparted, or oil resistance, solvent resistance, heat resistance, wear resistance, impact resistance, light resistance, water resistance and the like can be imparted. Moreover, when a protective layer is a resin layer, heat sealability can also be provided.
  • the protective layer can be provided on both sides of the paper barrier material, but is preferably provided on at least the side having the water vapor barrier coating layer. Furthermore, it is possible to have a protective layer on the gas barrier coating layer of the paper barrier material that has the water vapor barrier coating layer and the gas barrier coating layer in this order on the paper base material. It is preferable for preventing the influence (deterioration) on the work layer and the gas barrier coating layer.
  • the protective layer include a resin layer, a paper layer, and a metal foil. Among these, a resin layer is preferable. However, in applications where biodegradability is required, the protective layer preferably has biodegradability such as a biodegradable resin.
  • the resin of the resin layer includes polyester, polyvinyl alcohol, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene, polyvinyl chloride, acrylonitrile / butadiene / styrene, acrylonitrile / styrene, polymethylmethacrylic, polychlorinated.
  • Resin derived from fossil resources such as vinylidene, polyamide (nylon), polyacetal, polycarbonate, polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), biopolyethylene, Biological resins such as biopolyethylene terephthalate and biopolyurethane can be included.
  • the bio-derived resin includes a high-molecular material having a number average molecular weight (Mn) of 1,000 or more obtained by chemically or biologically synthesizing a material derived from an organic resource that can be regenerated as a raw material.
  • Mn number average molecular weight
  • polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and the like are biodegradable.
  • Any of non-biodegradable resins such as resin, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyamide (nylon), and biopolyethylene can be used.
  • the biodegradable resin is a resin that is decomposed to the molecular level by the action of microorganisms and eventually circulates into the natural world as carbon dioxide and water.
  • the resin layer is preferably a resin laminate layer.
  • the resin laminate layer include an extruded laminate layer, and a film bonding layer such as a barrier film and a vapor deposition film.
  • the resin laminate layer is an extruded laminate layer
  • the above-described various resins are laminated on at least one surface of the paper barrier material as a resin laminate layer by an extrusion lamination method.
  • the resin laminate layer is a film bonding layer
  • the above-mentioned various resin films are bonded as a resin laminate layer on at least one surface of the paper barrier material by a dry lamination method, a sand lamination method, or the like. .
  • examples of the film used for the film bonding layer include the above-mentioned various resin films.
  • films mainly composed of resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, and the above-mentioned various resin films are coated with these resins such as polyvinyl alcohol.
  • Film a film obtained by bonding a metal foil made of various metals such as aluminum to the above-mentioned various resin films, an inorganic oxide such as silicon oxide or aluminum oxide, or various metals such as aluminum on the above-mentioned various resin films
  • a barrier film such as a vapor deposition film on which an object is vapor-deposited is preferable, and a vapor deposition film is more preferable. Depending on the purpose, these films can be used by laminating one or more layers.
  • the paper barrier material of the second invention preferably has the following barrier properties.
  • the following barrier property value is a value measured in a state where the above-described protective layer is not formed.
  • the paper barrier material of the second invention has excellent barrier properties without using various films and metal foils.
  • (1) Water vapor permeability at a temperature of 40 ⁇ 0.5 ° C. and a relative humidity difference of 90 ⁇ 2% is 200 g / m 2 ⁇ day or less. 2 ⁇ day ⁇ atm or less More preferably, it has the following barrier properties.
  • the third invention is a paper barrier material in which at least a water vapor barrier coating layer is provided on a paper substrate (hereinafter sometimes referred to as “base paper”).
  • a gas barrier coating layer may be further provided on the paper substrate.
  • the order of construction of each layer is not particularly limited, it is preferable that the layers are laminated in the order of a paper substrate, a water vapor barrier coating layer, and a gas barrier coating layer.
  • These coating layers can be formed by applying a coating solution mainly containing water as a medium with various coating apparatuses and drying.
  • the paper barrier material having the water vapor barrier coating layer and the gas barrier coating layer in this order has both excellent water vapor barrier properties and gas barrier properties is presumed as follows.
  • the resin having gas barrier properties used in the gas barrier coating layer polymers such as water-soluble polymers and water-dispersible polymers are generally used as exemplified below, and the gas barrier coating layer on the paper substrate,
  • the water vapor barrier coating layer is provided in this order, the water-soluble polymer or water-dispersible polymer can be absorbed by water in the paper base or in the air that permeates through the paper base.
  • the gas barrier coating layer contained tends to deteriorate.
  • the water vapor barrier coating layer can be used for gas barrier coating such as moisture in the paper substrate.
  • the influence (deterioration) on the construction layer can be effectively suppressed.
  • steam barrier coating layer and a gas barrier coating layer in this order has favorable water vapor
  • the paper base is a sheet mainly made of pulp, and may contain a filler and various auxiliaries.
  • Pulp includes chemical pulp such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), softwood unbleached kraft pulp (NUKP), sulfite pulp, stone grind pulp, thermo Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and waste paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp, etc., polyester resin fiber such as polyethylene terephthalate, polyolefin resin fiber such as polypropylene and polyethylene Synthetic fibers such as polyamide resin fibers such as nylon and halogen-containing resin fibers such as polyvinyl chloride can be used, and they can be used by appropriately blending them.
  • LLKP hardwood bleached kraft pulp
  • NKP softwood bleached kraft pulp
  • LKP hardwood unbleached kraft pulp
  • filler known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, and synthetic resin filler can be used.
  • sulfuric acid bands and various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers and internal additive sizing agents, etc. Can be used.
  • dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
  • the production method (paper making) of the paper base material is not particularly limited, and it is possible to use a known long net former machine, on-top hybrid former machine, gap former machine, Yankee machine, etc.
  • a paper base material can be manufactured by paper making by paper making or alkali paper making.
  • the paper substrate may be a single layer or may be composed of two or more layers.
  • it is possible to treat the surface of the paper substrate with various chemicals. Examples of the drug used include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agent, water-resistant agent, water retention agent, thickener, lubricant, etc. These can be used alone or in admixture of two or more.
  • pigments kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin
  • An inorganic pigment such as white and an organic pigment such as a solid type, a hollow type, or a core-shell type can be used alone or in admixture of two or more.
  • the surface treatment method of the paper substrate is not particularly limited, but a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • Paper bases obtained in this way include fine paper, medium paper, coated paper, glossy paper, kraft paper, glossy kraft paper, bleached kraft paper, glassine paper, paperboard, white paperboard, liners, etc.
  • Various well-known things can be illustrated.
  • the paper base material of the third invention is mainly applied with a coating solution containing water as a medium, it is preferable that the strength when the paper base material is wet is more than a certain level. Therefore, the wet tensile strength in the paper making direction (MD) is preferably 300 N / m or more.
  • the paper base material of the third invention may have an optimum basis weight according to the use, but in general, about 30 g / m 2 to 600 g / m 2 , 30 g / m 2 to 500 g / m 2 Is often used.
  • the paper barrier material of the third invention has a water vapor barrier coating layer on at least one surface on the paper substrate.
  • the paper substrate, the water vapor barrier coating layer, and the gas barrier coating layer are preferably laminated in this order.
  • the water vapor barrier resin to be contained in the water vapor barrier coating layer is a water-soluble or water-dispersible water-based resin having water vapor barrier properties, such as styrene / butadiene, styrene / acrylic.
  • Various copolymers such as ethylene / vinyl acetate, paraffin (WAX), polyester resin, butadiene / methyl methacrylate, vinyl acetate / butyl acrylate, maleic anhydride copolymer, acrylic acid / methyl methacrylate copolymer
  • Synthetic adhesives such as coalescence, or paraffin (WAX) blended synthetic adhesives or the like can be used alone or in admixture of two or more. In the third invention, it is preferable to use a mixture of two or more.
  • the water vapor barrier coating layer of the third invention contains at least a water vapor barrier resin A having a melting point of 110 ° C. or higher and a water vapor barrier resin B having a melting point of less than 110 ° C.
  • a resin water-dispersible resin
  • a resin such as an emulsion system in which particles are dispersed in water forms a film (film formation) between the particles as drying progresses.
  • the temperature range at which a water-dispersible resin forms a film is considered to be the melting point of the resin dispersed in water.
  • water-soluble resin when the water-soluble resin is dried, water as a solvent evaporates, and the resin dissolved in water is cured to form a film (film formation).
  • the temperature range in which the water-soluble resin is cured depends on the inherent melting point of the resin dissolved in water.
  • the temperature zone for forming a film is the temperature zone for curing the water-soluble resin (the melting point of the resin dissolved in water) ) Contains those having a temperature of 110 ° C. or higher and those having a temperature lower than 110 ° C.
  • the melting point of each resin satisfies the above range, the melting point is more than a certain distance across the vicinity of the boiling point of water, so the film formation proceeds in order from the low melting point, and the same quality resin film can be formed in layers It is estimated that the water vapor barrier property is excellent.
  • the water vapor barrier resin A having a melting point of 110 ° C. or higher is a water-soluble resin
  • the water vapor barrier resin B having a melting point of less than 110 ° C. is a water dispersible resin.
  • steam barrier resin can be measured by detecting the peak of endothermic reaction using a differential scanning calorimeter (DSC), for example.
  • polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, proteins such as casein, soy protein, and synthetic protein, oxidation Starch, cationized starch, urea phosphated starch, starch such as hydroxyethyl etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, water-soluble polymers such as polyvinylpyrrolidone, sodium alginate, etc. It can also be used in combination with a water vapor barrier resin.
  • the water vapor barrier coating layer contains a pigment in the configuration having the water vapor barrier coating layer and the gas barrier coating layer from the viewpoint of adhesion between the water vapor barrier coating layer and the gas barrier coating layer.
  • Inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white, etc.
  • Organic pigments such as hollow type or core-shell type can be used alone or in combination of two or more.
  • flat inorganic pigments such as kaolin, talc, clay, and mica, which are flat in shape, are preferable from the viewpoints of improving water vapor barrier properties and suppressing penetration of the gas barrier coating layer, and kaolin and mica are more preferable.
  • flat inorganic pigments having a volume 50% average particle diameter (D50) (hereinafter also referred to as “average particle diameter”) of 5 ⁇ m or more and an aspect ratio of 10 or more singly or in combination. It is more preferable to use a mixture of two or more.
  • D50 volume 50% average particle diameter
  • the average particle size or aspect ratio of the inorganic pigment used is smaller than the above range, the number of times that the water vapor bypasses the water vapor barrier coating layer is reduced, and the moving distance is shortened. As a result, the water vapor barrier property is improved. May become smaller.
  • the total amount of the water vapor barrier resin and the water-soluble polymer ranges from 30 parts by weight to 350 parts by weight with respect to 100 parts by weight of the dry pigment. It is preferable to contain. More preferably, it is 50 weight part or more, More preferably, it is 80 weight part or more. Further, it is more preferably 250 parts by weight or less, and still more preferably 200 parts by weight or less.
  • a crosslinking agent represented by a polyvalent metal salt or the like can be added to the water vapor barrier coating layer. Since the crosslinking agent causes a crosslinking reaction with the water vapor barrier resin or water-soluble polymer contained in the water vapor barrier coating layer, the number of bonds (crosslinking points) in the water vapor barrier coating layer increases. That is, the water vapor barrier coating layer has a dense structure and can exhibit good water vapor barrier properties.
  • the type of the crosslinking agent is not particularly limited, and in accordance with the type of the water vapor barrier resin or water-soluble polymer contained in the water vapor barrier coating layer, a polyvalent metal salt (copper, Multivalent metals such as zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide, boron oxide Etc.), amine compounds, amide compounds, aldehyde compounds, hydroxy acids and the like can be appropriately selected and used.
  • a polyvalent metal salt copper, Multivalent metals such as zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide, boron oxide Etc.
  • a polyvalent metal salt from the viewpoint of expression of a crosslinking effect. More preferably, potassium alum is used.
  • the amount of the crosslinking agent can be blended without particular limitation as long as it is within the range of the paint concentration and the paint viscosity that can be applied, but preferably the crosslinking agent is 1 with respect to 100 parts by weight of the pigment. It is not less than 10 parts by weight and more preferably not less than 3 parts by weight and not more than 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, when the amount is more than 10 parts by weight, the viscosity of the coating material is remarkably increased and coating may be difficult.
  • a crosslinking agent when added to the water vapor barrier coating layer paint, it is preferable to dissolve the crosslinking agent in a polar solvent such as ammonia before adding it to the paint.
  • a polar solvent such as ammonia
  • a bond is formed between the cross-linking agent and the polar solvent, so that even if added to the paint, a cross-linking reaction with the water vapor barrier resin or water-soluble polymer does not occur immediately. Can be suppressed.
  • the polar solvent component when the polar solvent component is volatilized by drying after coating on the paper substrate, a crosslinking reaction with the water vapor barrier resin or water-soluble polymer occurs, and a dense water vapor barrier coating layer is formed. Guessed.
  • a water repellent may be contained in the water vapor barrier coating layer in order to improve the water vapor barrier property.
  • water repellents include paraffinic water repellents mainly composed of alkane compounds, natural oil and fat water repellents derived from animals and plants such as carnauba and lanolin, silicone-containing water repellents containing silicone or silicone compounds, and fluorine compounds. Examples thereof include a fluorine-containing water repellent.
  • These water repellents can be used alone or in combination of two or more.
  • the blending amount of the water repellent is not particularly limited.
  • the water repellent is preferably 1 part by weight or more and 100 parts by weight or less. If the blending amount of the water repellent is less than 1 part by weight, the effect of improving the water vapor barrier property may not be sufficiently obtained. On the other hand, when the amount exceeds 100 parts by weight, the gas barrier coating layer is difficult to form uniformly when the gas barrier coating layer is provided on the water vapor barrier coating layer, so that the gas barrier property may be lowered.
  • the wet tension of the water vapor barrier coating layer surface can be 10 mN / m or more and 60 mN / m or less, and 15 mN If it is / m or more and 50 mN / m or less, an effect will be exhibited more.
  • the water vapor barrier coating layer includes the above water vapor barrier resin, water-soluble polymer, pigment, crosslinking agent, water repellent, dispersant, thickener, water retention agent, antifoaming agent, Various commonly used auxiliaries such as water-resistant agents, dyes, fluorescent dyes and the like can be used.
  • the gas barrier coating layer may contain a polymer having gas barrier properties, such as a water-soluble polymer and a water-dispersible polymer.
  • the water-soluble polymer used in the gas barrier coating layer includes polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, casein, soy protein, and synthetic protein.
  • polyvinyl alcohols and cellulose derivatives are preferable, and polyvinyl alcohols are more preferable.
  • Examples of the water-dispersible polymer used for the gas barrier coating layer include polyvinylidene chloride, ethylene vinyl acetate resin, and modified polyolefin resin.
  • inclusion of a pigment in the gas barrier coating layer is preferable from the viewpoint of improving gas barrier properties.
  • pigments used in the gas barrier coating layer kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, Inorganic pigments such as silicic acid, silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, and core-shell type can be used alone or in combination of two or more.
  • flat inorganic pigments such as kaolin, talc, clay, and mica that are flat in terms of gas barrier properties, and flat inorganic pigments having an average particle diameter of 3 ⁇ m or more and an aspect ratio of 10 or more. It is more preferable to use a flat inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 30 or more.
  • a gas barrier coating layer contains a pigment
  • a gas such as oxygen passes around the pigment.
  • a gas barrier coating layer made of a polymer such as a water-soluble polymer or a water-dispersible polymer that does not contain a pigment.
  • a gas barrier coating layer containing a flat inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more can further contain a pigment having an average particle diameter of 5 ⁇ m or less.
  • voids in the gas barrier coating layer formed of a flat inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more can be further reduced.
  • Excellent gas barrier properties That is, when the gas barrier coating layer contains pigments having different average particle sizes, the voids formed by the inorganic pigment having a large average particle size are filled with the pigment having a small average particle size in the gas barrier coating layer. Since gas such as oxygen bypasses the pigment and passes through, it is presumed that it has a high gas barrier property as compared with a gas barrier coating layer not containing a pigment having a different average particle size.
  • the flat inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more when used in combination with a pigment having an average particle diameter of 5 ⁇ m or less, the flatness having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more.
  • the blending ratio of the inorganic pigment and the pigment having an average particle diameter of 5 ⁇ m or less can be 50/50 to 99/1 by dry weight.
  • the gas barrier property improving effect may be reduced.
  • the void formed by the inorganic pigment having a large average particle size in the gas barrier coating layer cannot be sufficiently filled with the pigment having an average particle size of 5 ⁇ m or less, and therefore further improvement in gas barrier properties is observed. I can't.
  • the pigment having an average particle diameter of 5 ⁇ m or less used in combination with a flat inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more includes kaolin, clay, engineered kaolin, delaminated clay, heavy Inorganic pigments such as calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, or core-shell type Etc. can be used alone or in admixture of two or more. Among these pigments, it is preferable to use heavy calcium carbonate.
  • the blending ratio of the pigment, the water-soluble polymer and the water-dispersible polymer is dry weight, and the pigment / (water-soluble polymer and water-dispersible polymer).
  • the sum of the above) is preferably 1/100 to 1000/100. If the ratio of the pigment is out of the above range, the gas barrier property improving effect may be reduced.
  • the pigment when the pigment is blended in the water-soluble polymer or the water-dispersible polymer, it is preferable to add and mix the slurry of the pigment.
  • a crosslinking agent typified by a polyvalent metal salt or the like can be added to the gas barrier coating layer. Since the crosslinking agent causes a crosslinking reaction with a polymer such as a water-soluble polymer or a water-dispersible polymer contained in the gas barrier coating layer, the number of bonds (crosslinking points) in the gas barrier coating layer increases. That is, the gas barrier coating layer has a dense structure and can exhibit good gas barrier properties.
  • the type of the crosslinking agent is not particularly limited, and a polyvalent metal is selected according to the type of polymer such as a water-soluble polymer or water-dispersible polymer contained in the gas barrier coating layer.
  • Salt copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium and other polyvalent metals, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide ,
  • an amine compound, an amide compound, an aldehyde compound, a hydroxy acid, and the like can be appropriately selected and used.
  • it is preferable to use a polyvalent metal salt from a viewpoint of expression of a crosslinking effect and it is more preferable to use potassium alum.
  • the amount of the crosslinking agent can be blended without particular limitation as long as it is within the range of the paint concentration and the paint viscosity that can be applied, but preferably the crosslinking agent is 1 with respect to 100 parts by weight of the pigment. It is not less than 10 parts by weight and more preferably not less than 3 parts by weight and not more than 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, when the amount is more than 10 parts by weight, the viscosity of the coating material is remarkably increased and coating may be difficult.
  • surfactant in order to improve adhesiveness with a water vapor
  • ionicity of the surfactant there is no limitation on the ionicity of the surfactant, and any one of anionic surfactant, cationic surfactant, amphoteric surfactant and nonionic surfactant can be used alone or in combination of two or more. Can be used in combination. Specific types include silicone surfactants, fluorine surfactants, alcohol surfactants, acetylene surfactants having an acetylene group, and acetylenic diol surfactants having an acetylene group and two hydroxyl groups.
  • alkyl sulfonic acid surfactants having an alkyl group and sulfonic acid examples thereof include ester surfactants and phenol surfactants.
  • ester surfactants and phenol surfactants examples thereof include ester surfactants and phenol surfactants.
  • uniformity of a gas barrier coating layer will improve if the leveling property of a coating material improves, gas barrier property will improve.
  • the surface tension of the gas barrier coating layer paint can be adjusted to 10 mN / m or more and 60 mN / m or less, and more effective. Is preferably adjusted to 15 mN / m or more and 50 mN / m or less.
  • the surface tension of the coating for the gas barrier coating layer is set to ⁇ 20 mN / m with respect to the wet tension on the surface of the water vapor barrier coating layer. To preferred.
  • the gas barrier coating layer includes the above-mentioned water-soluble polymer, water-dispersible polymer, pigment, crosslinking agent, surfactant, dispersant, thickener, water retention agent, antifoaming agent, Various commonly used auxiliaries such as water-resistant agents, dyes, fluorescent dyes and the like can be used.
  • the method for coating the water vapor barrier coating layer and the gas barrier coating layer is not particularly limited, and the coating can be performed by a known coating apparatus and coating system.
  • the coating apparatus include a blade coater, a bar coater, a roll coater, an air knife coater, a reverse roll coater, a curtain coater, a spray coater, a size press coater, and a gate roll coater.
  • the coating system an aqueous coating mainly using water as a medium is preferable.
  • a method for drying the water vapor barrier coating layer and the gas barrier coating layer for example, usual methods such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, and a cylinder dryer are used.
  • the coating amount of the water vapor barrier coating layer is preferably 3 g / m 2 or more and 50 g / m 2 or less in terms of dry weight, and more preferably 5 g / m 2 or more and 40 g / m 2 or less. Preferably, it is more preferably 7 g / m 2 or more and 20 g / m 2 or less.
  • the coating amount of the water vapor barrier coating layer is less than 3 g / m 2 , it becomes difficult to completely coat the paper substrate with the coating liquid, and sufficient water vapor barrier properties cannot be obtained. The work layer may penetrate into the paper substrate, and sufficient gas barrier properties may not be obtained.
  • the water vapor barrier coating layer may be a single layer or a multilayer of two or more layers.
  • the total coating amount of all the water vapor barrier coating layers is preferably within the above range.
  • the coating amount of the gas barrier coating layer is preferably in a 0.2 g / m 2 or more 20 g / m 2 or less by dry weight. If the coating amount of the gas barrier coating layer is less than 0.2 g / m 2 , it may be difficult to form a uniform gas barrier coating layer, so that sufficient gas barrier properties may not be obtained. On the other hand, when it is more than 20 g / m 2 , the drying load during coating increases.
  • the gas barrier coating layer may be a single layer or a multilayer of two or more layers. When the gas barrier coating layer is composed of two or more layers, the total coating amount of all the gas barrier coating layers is preferably within the above range.
  • a protective layer may be further provided on at least one surface of the paper barrier material of the third invention.
  • the protective layer prevents the influence (deterioration) of the water barrier coating layer and the gas barrier coating layer of the paper barrier material due to moisture in the air, scratching and cracking of the barrier coating layer, etc. on the paper barrier material. Further water vapor barrier properties and gas barrier properties can be imparted, or oil resistance, solvent resistance, heat resistance, wear resistance, impact resistance, light resistance, water resistance and the like can be imparted. Moreover, when a protective layer is a resin layer, heat sealability can also be provided.
  • the protective layer can be provided on both sides of the paper barrier material, but is preferably provided on at least the side having the water vapor barrier coating layer. Furthermore, it is possible to have a protective layer on the gas barrier coating layer of the paper barrier material that has the water vapor barrier coating layer and the gas barrier coating layer in this order on the paper base material. It is preferable for preventing the influence (deterioration) on the work layer and the gas barrier coating layer.
  • the protective layer include a resin layer, a paper layer, and a metal foil. Among these, a resin layer is preferable. However, in applications where biodegradability is required, the protective layer preferably has biodegradability such as a biodegradable resin.
  • the resin of the resin layer includes polyester, polyvinyl alcohol, polypropylene, polyethylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polymethylpentene, polyvinyl chloride, acrylonitrile / butadiene / styrene, acrylonitrile / styrene, polymethylmethacrylic, polychlorinated.
  • Resin derived from fossil resources such as vinylidene, polyamide (nylon), polyacetal, polycarbonate, polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), biopolyethylene, Biological resins such as biopolyethylene terephthalate and biopolyurethane can be included.
  • the bio-derived resin includes a high-molecular material having a number average molecular weight (Mn) of 1,000 or more obtained by chemically or biologically synthesizing a material derived from an organic resource that can be regenerated as a raw material.
  • Mn number average molecular weight
  • polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and the like are biodegradable.
  • Any of non-biodegradable resins such as resin, polyethylene, polypropylene, polyester, polyethylene terephthalate, polyamide (nylon), and biopolyethylene can be used.
  • the biodegradable resin is a resin that is decomposed to the molecular level by the action of microorganisms and eventually circulates into the natural world as carbon dioxide and water.
  • the resin layer is preferably a resin laminate layer.
  • the resin laminate layer include an extruded laminate layer, and a film bonding layer such as a barrier film and a vapor deposition film.
  • the resin laminate layer is an extruded laminate layer
  • the above-described various resins are laminated on at least one surface of the paper barrier material as a resin laminate layer by an extrusion lamination method.
  • the resin laminate layer is a film bonding layer
  • the above-mentioned various resin films are bonded as a resin laminate layer on at least one surface of the paper barrier material by a dry lamination method, a sand lamination method, or the like. .
  • examples of the film used for the film bonding layer include the above-mentioned various resin films.
  • films mainly composed of resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, polyacrylonitrile, and the above-mentioned various resin films are coated with these resins such as polyvinyl alcohol.
  • Film a film obtained by bonding a metal foil made of various metals such as aluminum to the above-mentioned various resin films, an inorganic oxide such as silicon oxide or aluminum oxide, or various metals such as aluminum on the above-mentioned various resin films
  • a barrier film such as a vapor deposition film on which an object is vapor-deposited is preferable, and a vapor deposition film is more preferable. Depending on the purpose, these films can be used by laminating one or more layers.
  • the paper barrier material of the third invention preferably has the following barrier properties.
  • the following barrier property value is a value measured in a state where the above-described protective layer is not formed.
  • the paper barrier material of the third invention has excellent barrier properties without using various films and metal foils.
  • (1) Water vapor permeability at a temperature of 40 ⁇ 0.5 ° C. and a relative humidity difference of 90 ⁇ 2% is 200 g / m 2 ⁇ day or less. 2 ⁇ day ⁇ atm or less More preferably, it has the following barrier properties.
  • the paper barrier material of the present invention is a paper barrier material or laminated with various resins, etc., laminated with various general purpose films, barrier films, aluminum foil, etc. It can be a packaging material used for packaging applications such as paper containers, cardboard boxes, trays, cups, liquid paper containers, etc., or a laminate used for industrial materials and building materials. Among these, it can be suitably used as a packaging material used for packaging applications such as packaging materials for foods, bags, paper containers, cardboard boxes, trays, cups, liquid paper containers, etc. It can be particularly preferably used.
  • the soft packaging material is a packaging material composed of a material rich in flexibility. Generally, a thin flexible material such as paper, film, aluminum foil, etc. is used alone or bonded. Refers to packaging material.
  • the packaging material which maintains a solid shape by putting the contents, such as a bag, is pointed out.
  • the paper barrier material of the present invention is used as a packaging material such as food, particularly as a soft packaging material, it is laminated with a resin having heat sealability to improve the sealing property as a packaging material and oxidize the contents with oxygen. Protects against deterioration due to moisture and humidity, and can extend the storage period.
  • a resin having heat sealability to improve the sealing property as a packaging material and oxidize the contents with oxygen.
  • it is possible to prevent decay and deterioration by suppressing the intrusion of oxygen and moisture, and to prevent the odor of solvent from leaking out. Effects such as barrier properties are expected.
  • the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
  • the part and% in an example show a weight part and weight%, respectively.
  • the obtained paper barrier material was tested based on the following evaluation method.
  • Water vapor permeability Measured using a moisture permeability measuring instrument (Dr. Lyssy, L80-4000) under conditions of a temperature of 40 ⁇ 0.5 ° C. and a relative humidity difference of 90 ⁇ 2%. In addition, it measured using the paper-made barrier materials before providing a protective layer.
  • Oxygen permeability Measured using an oxygen permeability measuring device (manufactured by MOCON, OX-TRAN 2/21) under conditions of 23 ° C.-0% RH and 23 ° C.-85% RH. In addition, it measured using the paper-made barrier materials before providing a protective layer.
  • Aspect ratio of flat inorganic pigment measured by the method described above.
  • Drip oil absorption One drop (10 ⁇ l) of general light oil (light oil No. 2) was dropped by its own weight onto the sample with a syringe, and the time until it penetrated into the sample and the liquid surface became dull was measured.
  • Melting point Measured by detecting the endothermic reaction peak using a differential scanning calorimeter (Shimadzu Corporation, DSC-60Plus).
  • Example of the first invention [Example 1] (Preparation of paper substrate 1) 100 parts by weight of hardwood kraft pulp (LBKP) having a Canadian standard freeness (CSF) of 320 ml was used as a raw material pulp. The raw material pulp was made with a long paper machine to obtain a paper having a basis weight of 63.0 g / m 2 . Next, starch (manufactured by Sanus Co., Ltd., Low Cons) prepared to a solid content concentration of 3% was applied to the obtained paper in a total amount of 1.0 g / m 2 and dried, and the speed was 300 min / m using a chilled calendar. The paper substrate 1 having a basis weight of 64.0 g / m 2 was obtained by performing a smoothing process with a linear pressure of 50 kgf / cm 1 pass.
  • LLKP hardwood kraft pulp
  • CSF Canadian standard freeness
  • mica slurry and kaolin slurry are mixed so that mica is 50 parts (solid content) and kaolin is 50 parts (solid content), and 100 parts of pigment (solid content) is styrene / acrylic as a water vapor barrier resin.
  • a copolymer emulsion (manufactured by Seiden Chemical Co., Ltd., product name: Cybinol X-511-374E) was blended to 100 parts (solid content), and a paraffinic water repellent (manufactured by Maruyoshi Chemical Co., Ltd., product name: MYE-35G, a wax-containing polyethylene emulsion) was blended so as to be 100 parts (solid content) with respect to 100 parts of pigment to obtain a coating solution A1 for a water vapor barrier coating layer having a solid content concentration of 22%.
  • a paraffinic water repellent manufactured by Maruyoshi Chemical Co., Ltd., product name: MYE-35G, a wax-containing polyethylene emulsion
  • gas barrier coating layer coating solution B1 As a gas barrier resin, an aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., product name: PVA117) is prepared so as to have a solid content concentration of 10%. In the obtained aqueous polyvinyl alcohol solution, 100 parts of polyvinyl alcohol (solid content) is silicone-based. A surfactant (manufactured by San Nopco, product name: SN wet 125) was blended so as to be 1 part (solid content) to obtain a coating liquid B1 for a gas barrier coating layer.
  • PVA117 polyvinyl alcohol
  • a surfactant manufactured by San Nopco, product name: SN wet 125
  • the coating solution A1 for the water vapor barrier coating layer is coated on one side using a blade coater so that the coating weight is 15 g / m 2 by dry weight, and then dried.
  • One-side coating and drying were performed using a roll coater so that the coating amount B1 for gas barrier coating layer was 5.0 g / m 2 by dry weight to obtain a paper barrier material.
  • Example 2 Use kaolin (product name: Capim CC, aspect ratio: 15) instead of kaolin (product name: Varisurf HX, product name: Varisurf HX, aspect ratio: 100) of the coating liquid A1 for the water vapor barrier coating layer.
  • a paper barrier material was obtained in the same manner as in Example 1 except that.
  • Example 3 As a flat inorganic pigment B, bentonite (manufactured by Kunimine Kogyo Co., Ltd., product name: Kunipia F, aspect ratio: 400) is added sodium pyrophosphate as a dispersing agent (0.4 parts of inorganic pigment), dispersed with a variety mixer and solid A bentonite slurry having a partial concentration of 15% was prepared.
  • the bentonite slurry 50 parts (solid content) was used instead of 50 parts (solid content) of kaolin slurry (product name: Varisurf HX, aspect ratio: 100, manufactured by Imeris Co., Ltd.) of the coating liquid A1 for the water vapor barrier coating layer. Except for the above, a paper barrier material was obtained in the same manner as in Example 1.
  • Example 4 Preparation of coating solution A2 for water vapor barrier coating layer
  • mica slurry manufactured by Topy Industries, product name: NTS-10, aspect ratio: 1500, solid content concentration: 10%
  • flat inorganic pigment B kaolin (manufactured by Imeris Co., Ltd., product name: Balisurf HX, aspect ratio: 100) was added sodium polyacrylate as a dispersant (0.2 parts of inorganic pigment) and dispersed with a variety mixer.
  • a kaolin slurry having a solid content of 60% was prepared.
  • a heavy calcium carbonate slurry (manufactured by PMMA Tech, product name: FMT-90, solid content concentration 60%) was prepared.
  • the mica slurry, kaolin slurry and heavy calcium carbonate slurry are mixed so that the mica is 54 parts (solid content), the kaolin is 36 parts (solid content), and the heavy calcium carbonate is 10 parts (solid content).
  • 100 parts (solid content) of styrene / acrylic copolymer emulsion product name: Cybinol X-511-374E) as a water vapor barrier resin with respect to 100 parts (solid content) of pigment.
  • a paraffinic water repellent manufactured by Maruyoshi Chemical Co., Ltd., product name: MYE-35G, wax-containing polyethylene emulsion
  • a coating solution A2 for a water vapor barrier coating layer having a concentration of 22% was obtained.
  • a paper barrier material was obtained in the same manner as in Example 1, except that the water vapor barrier coating layer coating liquid A2 was used instead of the water vapor barrier coating layer coating liquid A1.
  • Example 5 Example 1 except that the mixing ratio of mica and kaolin in the coating solution A1 for the water vapor barrier coating layer was mixed so that mica was 60 parts (solid content) and kaolin was 40 parts (solid content). Thus, a paper barrier material was obtained.
  • Example 6 Example 1 except that the mixing ratio of mica and kaolin in the coating solution A1 for the water vapor barrier coating layer was mixed so that mica was 30 parts (solid content) and kaolin was 70 parts (solid content). Thus, a paper barrier material was obtained.
  • Example 7 As a flat inorganic pigment A, bentonite (manufactured by Kunimine Kogyo Co., Ltd., product name: Kunipia F, aspect ratio: 400) was added sodium pyrophosphate as a dispersing agent (0.4 parts of inorganic pigment), dispersed with a variety mixer and solid A bentonite slurry having a partial concentration of 15% was prepared.
  • the bentonite slurry 50 described above was replaced with 50 parts (solid content) of mica slurry (product name: NTS-10, aspect ratio: 1500, solid content concentration 10%, manufactured by Topy Industries, Ltd.) of the coating liquid A1 for the water vapor barrier coating layer.
  • a paper barrier material was obtained in the same manner as in Example 1 except that the part (solid content) was used.
  • the paper barrier materials of Examples 1 to 7 are superior to the paper barrier material of Comparative Example 1 in water vapor barrier properties and gas barrier properties.
  • Example 8 (Preparation of paper substrate 2) 100 parts by weight of hardwood kraft pulp (LBKP) having a Canadian standard freeness (CSF) of 320 ml was used as a raw material pulp. The raw material pulp was made with a long paper machine to obtain a paper having a basis weight of 63.0 g / m 2 . Next, starch (manufactured by Sanus Co., Ltd., Locons) prepared to a solid content concentration of 3% is applied to the obtained paper at 1.0 g / m 2 in total on both sides, dried, and the speed is 300 min / m using a chilled calendar. performs smoothing processing with linear pressure of 50 kgf / cm 1 pass, to give a paper substrate 2 having a basis weight of 64.0 g / m 2. The drip oil absorption of the paper substrate 2 was 100 seconds.
  • LLKP hardwood kraft pulp
  • CSF Canadian standard freeness
  • a paraffinic water repellent (Maruyoshi Chemical Co., Ltd., MYE-35G, wax-containing polyethylene emulsion) is blended so as to be 100 parts (solid content), and a coating solution for a water vapor barrier coating layer having a solid content concentration of 45%. A3 was obtained.
  • gas barrier coating layer coating solution B2 An aqueous solution of polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) was prepared so as to have a solid content concentration of 10%.
  • aqueous polyvinyl alcohol solution 100 parts of polyvinyl alcohol (solid content) is blended with 1 part (solid content) of silicone surfactant (manufactured by San Nopco, SN wet 125), and gas barrier coating is performed.
  • Layer coating liquid B2 was obtained.
  • one-side coating is performed using a blade coater at a coating speed of 300 m / min so that the coating amount A3 of the water vapor barrier coating layer is 15 g / m 2 in dry weight.
  • the coating liquid B2 for gas barrier coating layer is coated on one side using a roll coater at a coating speed of 300 m / min so that the coating weight is 5.0 g / m 2 in terms of dry weight.
  • a barrier material made was obtained.
  • Example 9 (Preparation of paper base 3) Canadian standard freeness (CSF) 500 ml of hardwood kraft pulp (LBKP) and CSF 530 ml of softwood kraft pulp (NBKP) were blended at a weight ratio of 80/20 to obtain raw pulp. The raw pulp was made with a long paper machine to obtain a paper with a basis weight of 59.0 g / m 2 . Next, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117) prepared to a solid content concentration of 2% was applied to the obtained paper in a total amount of 1.0 g / m 2 and dried, and the speed was 300 min / using a chilled calendar.
  • CSF Canadian standard freeness
  • LKP hardwood kraft pulp
  • NKP softwood kraft pulp
  • a paper barrier material was obtained in the same manner as in Example 8 except that the paper base 3 was used instead of the paper base 2.
  • Example 10 (Production of paper barrier material)
  • the coating solution A3 for the water vapor barrier coating layer was the same as in Example 8 except that one side coating and drying were performed using a blade coater at a coating speed of 300 m / min so that the coating weight was 12 g / m 2 by dry weight. Thus, a paper barrier material was obtained.
  • Example 11 Preparation of water vapor barrier coating layer coating solution A4
  • engineered kaolin manufactured by Imeris Co., Ltd., Varisurf HX, particle size 9.0 ⁇ m, aspect ratio 80-100
  • dispersant 0.2 parts of pigment
  • solid content concentration A 60% kaolin slurry was prepared.
  • Example 12 A paper product was prepared in the same manner as in Example 8 except that low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., product name: LC602A) was laminated on both sides of the paper barrier material obtained in Example 8 by coextrusion lamination to a thickness of 30 ⁇ m. A barrier material was obtained.
  • low-density polyethylene manufactured by Nippon Polyethylene Co., Ltd., product name: LC602A
  • Example 13 (Preparation of paper substrate 4) 100 parts by weight of hardwood kraft pulp (LBKP) having a Canadian standard freeness (CSF) of 320 ml was used as a raw material pulp. The raw material pulp was made with a long paper machine to obtain a paper with a basis weight of 62.5 g / m 2 . Next, starch (manufactured by Sanus Co., Ltd., Lawcons) prepared to a solid content concentration of 4% is applied to the obtained paper, 1.5 g / m 2 in total on both sides, dried, and a speed of 300 min / m using a chilled calendar.
  • LLKP hardwood kraft pulp
  • CSF Canadian standard freeness
  • the paper substrate 4 having a basis weight of 64.0 g / m 2 was obtained by performing a smoothing process with a linear pressure of 50 kgf / cm 1 pass.
  • the drip oil absorption of the paper substrate 4 was 150 seconds.
  • a paper barrier material was obtained in the same manner as in Example 8 except that the paper base 4 was used instead of the paper base 2.
  • Example 14 (Preparation of paper substrate 5) Canadian standard freeness (CSF) 500 ml of hardwood kraft pulp (LBKP) and CSF 530 ml of softwood kraft pulp (NBKP) were blended at a weight ratio of 80/20 to obtain raw pulp. The raw material pulp was made with a long paper machine to obtain a paper with a basis weight of 58.5 g / m 2 .
  • CSF Canadian standard freeness
  • LKP hardwood kraft pulp
  • NNKP softwood kraft pulp
  • polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) prepared to a solid content concentration of 3% was applied to the obtained paper at a total of 1.5 g / m 2 on both sides, dried, and a speed of 300 min / m, smoothing was performed with a linear pressure of 50 kgf / cm 1 pass to obtain a paper substrate 5 having a basis weight of 60.0 g / m 2 .
  • the drip oil absorption of the paper substrate 5 was 80 seconds.
  • a paper barrier material was obtained in the same manner as in Example 8 except that the paper base 5 was used instead of the paper base 2.
  • [Comparative Example 2] (Preparation of paper substrate 6) 100 parts by weight of hardwood kraft pulp (LBKP) having a Canadian standard freeness (CSF) of 320 ml was used as a raw material pulp. The raw pulp was made with a long paper machine to obtain a paper with a basis weight of 64.0 g / m 2 . Subsequently, using a chilled calendar, smoothing was performed at a speed of 300 min / m and a linear pressure of 50 kgf / cm 1 pass to obtain a paper base 6 having a basis weight of 64.0 g / m 2 . The drip oil absorption of the paper substrate 6 was 13 seconds. (Production of paper barrier material) A paper barrier material was obtained in the same manner as in Example 8 except that the paper base 6 was used instead of the paper base 2.
  • LLKP hardwood kraft pulp
  • CSF Canadian standard freeness
  • a paper barrier material was obtained in the same manner as in Example 8 except that the paper base 7 was used instead of the paper base 2.
  • the water vapor barrier property is excellent even if the coating amount of the water vapor barrier coating layer is the same. Moreover, when the content of the water vapor barrier resin with respect to 100 parts by weight of the pigment contained in the water vapor barrier coating layer is 30 parts by weight or more and 350 parts by weight or less when absolutely dry, the coating amount of the water vapor barrier coating layer is Even the same, the water vapor barrier property is excellent.
  • Example 15 (Preparation of paper substrate 8) 100 parts by weight of hardwood kraft pulp (LBKP) having a Canadian standard freeness (CSF) of 320 ml was used as a raw material pulp. The raw material pulp was made with a long paper machine to obtain a paper having a basis weight of 63.0 g / m 2 . Next, starch (manufactured by Sanus Co., Ltd., Low Cons) prepared to a solid content concentration of 3% was applied to the obtained paper in a total amount of 1.0 g / m 2 and dried, and the speed was 300 min / m using a chilled calendar. The paper substrate 8 having a basis weight of 64.0 g / m 2 was obtained by performing a smoothing process with a linear pressure of 50 kgf / cm 1 pass.
  • LLKP hardwood kraft pulp
  • CSF Canadian standard freeness
  • water vapor barrier resin B (acrylic resin, manufactured by Sumitomo Seika Co., Ltd., Saixen N, melting point 90 ° C.), and paraffinic water repellent (manufactured by Maruyoshi Chemical Co., Ltd., MYE-35G) , Wax-containing polyethylene emulsion) was blended to 100 parts (solid content) to obtain a water vapor barrier coating layer coating solution A5 having a solid content concentration of 45%.
  • gas barrier coating layer coating solution B3 An aqueous solution of polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) was prepared so as to have a solid content concentration of 10%.
  • aqueous polyvinyl alcohol solution 100 parts of polyvinyl alcohol (solid content) is blended with 1 part (solid content) of silicone surfactant (manufactured by San Nopco, SN wet 125), and gas barrier coating is performed.
  • a layer coating solution B3 was obtained.
  • one-side coating is performed using a blade coater at a coating speed of 300 m / min so that the coating amount A5 of the water vapor barrier coating layer is 15 g / m 2 by dry weight.
  • the coating solution B3 for gas barrier coating layer is coated on one side using a roll coater at a coating speed of 300 m / min so that the coating weight is 5.0 g / m 2 by dry weight.
  • a barrier material made was obtained.
  • Example 16 (Preparation of water vapor barrier coating layer coating solution A6) Water vapor barrier resin A (polyethylene resin, manufactured by Mitsui Chemicals, Chemipearl W400, melting point 110 ° C.) 60 parts (solid content), water vapor barrier resin B (acrylic resin, manufactured by Sumitomo Seika Co., Ltd., Syxen N, melting point) 90 ° C.) was changed to 40 parts (solid content), and a water vapor barrier coating layer coating solution A6 was obtained in the same manner as in Example 15. (Production of paper barrier material) A paper barrier material was obtained in the same manner as in Example 15 except that the water vapor barrier coating layer coating liquid A6 was used instead of the water vapor barrier coating layer coating liquid A5.
  • Example 17 (Preparation of coating solution A7 for water vapor barrier coating layer)
  • Water vapor barrier resin A polyethylene resin, manufactured by Mitsui Chemicals, Chemipearl W400, melting point 110 ° C.) 40 parts (solid content)
  • water vapor barrier resin B acrylic resin, manufactured by Sumitomo Seika Co., Ltd., Syxen N, melting point) 90 ° C.
  • a water vapor barrier coating layer coating solution A7 was obtained in the same manner as in Example 15.
  • a paper barrier material was obtained in the same manner as in Example 15 except that the water vapor barrier coating layer coating liquid A7 was used instead of the water vapor barrier coating layer coating liquid A5.
  • the water vapor barrier coating layer contains at least a water vapor barrier resin A having a melting point of 110 ° C. or more and a water vapor barrier resin B having a melting point of less than 110 ° C., Excellent gas barrier properties.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un matériau barrière en papier qui présente d'excellentes propriétés de barrière et une charge environnementale réduite. La solution selon l'invention porte sur un matériau barrière en papier qui comprend un matériau de base en papier et au moins une couche de revêtement barrière disposée sur ce dernier, et qui est caractérisé en ce qu'il satisfait à une ou plusieurs des conditions (1) à (3) suivantes. 1) La couche de revêtement barrière contient un pigment, et la couche de revêtement barrière contient 50 % en poids au minimum d'au moins deux types de pigments inorganiques plats A et B par rapport à l'ensemble du pigment dans la couche de revêtement barrière. (2) La couche de revêtement barrière est une couche de revêtement barrière contre la vapeur d'eau, la couche de revêtement barrière contre la vapeur d'eau contient une résine à propriété de barrière contre la vapeur d'eau, et le matériau de base en papier a une capacité d'absorption de condensat supérieure ou égale à 50 secondes. (3) La couche de revêtement barrière est une couche de revêtement barrière contre la vapeur d'eau, et la couche de revêtement barrière contre la vapeur d'eau contient au moins une résine A à propriété de barrière contre la vapeur d'eau ayant un point de fusion supérieur ou égal à 110 °C, et une résine B à propriété de barrière contre la vapeur d'eau ayant un point de fusion inférieur à 110° C.
PCT/JP2019/012953 2018-03-28 2019-03-26 Matériau barrière en papier WO2019189229A1 (fr)

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WO2021106926A1 (fr) * 2019-11-27 2021-06-03 王子ホールディングス株式会社 Stratifié de papier
JPWO2021166910A1 (fr) * 2020-02-18 2021-08-26
CN113774712A (zh) * 2020-06-09 2021-12-10 新川创新股份有限公司 涂料组合物以及纸材
WO2021251449A1 (fr) * 2020-06-10 2021-12-16 日本製紙株式会社 Matériau de base en papier à dépôt en phase vapeur
WO2022264136A1 (fr) * 2021-06-14 2022-12-22 Melodea Ltd. Procédés de métallisation et produits formés à partir de ceux-ci
JP7245951B1 (ja) 2022-10-14 2023-03-24 大王製紙株式会社 バリア紙、産業用材、包装材及び積層体
WO2023245223A1 (fr) 2022-06-24 2023-12-28 Mondi Ag Papier repoussant les graisses

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JPH07119080A (ja) * 1993-10-15 1995-05-09 Nisshin Chem Ind Co Ltd 防湿、易離解性コート剤
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WO2021106926A1 (fr) * 2019-11-27 2021-06-03 王子ホールディングス株式会社 Stratifié de papier
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CN113774712A (zh) * 2020-06-09 2021-12-10 新川创新股份有限公司 涂料组合物以及纸材
WO2021251449A1 (fr) * 2020-06-10 2021-12-16 日本製紙株式会社 Matériau de base en papier à dépôt en phase vapeur
WO2022264136A1 (fr) * 2021-06-14 2022-12-22 Melodea Ltd. Procédés de métallisation et produits formés à partir de ceux-ci
WO2023245223A1 (fr) 2022-06-24 2023-12-28 Mondi Ag Papier repoussant les graisses
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