Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
  • B65D65/40—Applications of laminates for particular packaging purposes
• • 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
• • 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
  • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
• • 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
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

• the present invention relates to a paper barrier material.
• gas barrier properties particularly oxygen barrier properties
• paper packaging materials in order to impart gas barrier properties to paper packaging materials, as a gas barrier layer on a paper base material, a metal foil made of a metal such as aluminum, a metal vapor deposition film, polyvinyl alcohol or an ethylene-vinyl alcohol copolymer, etc.
• a resin film such as polyvinylidene chloride or polyacrylonitrile, a film coated with these resins, or a ceramic vapor-deposited film on which an inorganic oxide such as silicon oxide or aluminum oxide is vapor-deposited is extruded or laminated on a paper substrate. The method of doing has been mainly used.
• a paper gas barrier material having a gas barrier layer composed of a water-soluble polymer and an inorganic layered compound is disclosed. It is also important to impart water resistance (particularly, water vapor barrier property) to the paper packaging material in order to protect various products to be packaged from deterioration due to water vapor.
• a paper packaging material having gas barrier properties and water vapor barrier properties a paper barrier having a water vapor barrier layer containing a water vapor barrier resin and a pigment and a gas barrier layer containing a polyvinyl alcohol resin and a pigment on a paper base material.
• the packaging material is disclosed (Patent Document 3).
• the barrier property may be significantly reduced when bent.
• the deterioration of the barrier property due to bending is due to the fact that the layer is destroyed around the rigid pigment due to bending, which makes it easier for gas to pass through.
• An object of the present invention is to provide a paper barrier material having excellent bending resistance.
• the means for solving the problems of the present invention are as follows. 1. 1. It has a plurality of gas barrier layers laminated adjacent to each other on a paper substrate, and has a plurality of gas barrier layers. The gas barrier layer located at the top contains a water-soluble polymer, and the pigment content is 15% by weight or less by dry weight. A paper barrier material characterized in that at least one of the other gas barrier layers contains a water-soluble polymer and a pigment, and the content of the pigment is higher than that of the gas barrier layer located at the uppermost portion. 2. 2. 1. The content of the pigment in the gas barrier layer located at the uppermost portion is 5% by weight or less by dry weight. The paper barrier material described in. 3. 3. 1. The pigment is a flat pigment. Or 2. The paper barrier material described in. 4. 1.
• a water vapor barrier layer containing a water vapor barrier resin is provided between the paper substrate and the plurality of gas barrier layers.
• the water-soluble polymer is a polyvinyl alcohol-based resin.
• the paper barrier material described in any of. 6. 1.
• the amount of coating of the gas barrier layer located at the uppermost portion is the smallest among the plurality of gas barrier layers.
• the paper barrier material described in any of. 7. 1.
• the amount of coating of the gas barrier layer located at the uppermost portion is 0.1 g / m 2 or more and 5.0 g / m 2 or less in terms of dry weight.
• the basis weight of the paper substrate is 30 g / m 2 or more and 110 g / m 2 or less.
• ⁇ 8. A flexible packaging bag made of the paper barrier material described in any of the above.
• the paper substrate has a first gas barrier layer and a second gas barrier layer formed on the first gas barrier layer.
• the first gas barrier layer contains a water-soluble polymer and a pigment
• the first gas barrier layer contains a water-soluble polymer and a pigment.
• the second gas barrier layer contains a water-soluble polymer and is A paper barrier material characterized in that the content of the pigment in the second gas barrier layer is 1% by weight or less by dry weight.
• 12. 11 is a flat pigment.
• a water vapor barrier layer containing a water vapor barrier resin is provided between the paper substrate and the first gas barrier layer. Or 12.
• the water-soluble polymer contained in the first and second gas barrier layers is a polyvinyl alcohol-based resin.
• the coating amount of the second gas barrier layer is equal to or less than the coating amount of the first gas barrier layer.
• the amount of the second gas barrier layer coated is 0.1 g / m 2 or more and 5.0 g / m 2 or less in terms of dry weight.
• the basis weight of the paper substrate is 30 g / m 2 or more and 110 g / m 2 or less.
• the paper barrier material of the present invention has excellent bending resistance, and the decrease in barrier property during bending is small. Since the paper barrier material of the present invention is flexible, it can be suitably used for a flexible packaging bag in which bending is likely to occur.
• the present invention has a plurality of gas barrier layers laminated adjacent to each other on a paper substrate.
• the gas barrier layer located at the top contains a water-soluble polymer, and the pigment content is 15% by weight or less by dry weight.
• the present invention relates to a paper barrier material characterized in that at least one of the other gas barrier layers contains a water-soluble polymer and a pigment, and the content of the pigment is higher than that of the gas barrier layer located at the uppermost portion.
• the paper base material is a sheet made of pulp, a filler, and various auxiliaries.
• pulp examples include broadleaf bleached kraft pulp (LBKP), conifer bleached kraft pulp (NBKP), broadleaf unbleached kraft pulp (LUKP), conifer unbleached pulp (NUKP), chemical pulp such as sulphite pulp, stone grind pulp, and thermo.
• Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and used paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp and the like can be used, and can be appropriately blended and used.
• 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.
• an auxiliary agent for papermaking such as a sulfate band, various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers and internal sizing agents can be used.
• a dye, a fluorescent whitening agent, a pH adjusting agent, a defoaming agent, a pitch control agent, a slime control agent and the like can be added as needed.
• the method for producing the paper substrate is not particularly limited, and an acidic papermaking machine, a neutral papermaking machine, or an alkaline papermaking method can be used using a known long net former, on-top hybrid former, gap former machine, or the like.
• Paper base material can be manufactured by papermaking. Further, the paper base material may be one layer or may be composed of two or more layers. Furthermore, it is possible to treat the surface of the paper substrate with various chemicals. Examples of the chemicals used include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water resistant agents, water retaining agents, thickeners, lubricants, and the like.
• Pigments include 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, and satin.
• Inorganic pigments such as 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.
• the method of surface treatment of the paper substrate is not particularly limited, but a known coating device such as a rod metering size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, and a curtain coater should be used. Can be done.
• the paper base material thus obtained includes high-quality paper, medium-quality paper, coated paper, single-gloss paper, kraft paper, single-gloss kraft paper, bleached kraft paper, glassin paper, paperboard, white paperboard, liner, and the like.
• Various known ones can be exemplified.
• the basis weight of the paper base material can be appropriately selected depending on various qualities and handleability desired for the paper barrier material, but usually, it is preferably about 20 g / m 2 or more and 500 g / m 2 or less.
• paper barrier materials used for packaging such as packaging materials for foods, containers, cups, etc.
• those of 25 g / m 2 or more and 400 g / m 2 or less are more preferable, and particularly used for flexible packaging bags described later.
• a material of 30 g / m 2 or more and 110 g / m 2 or less is more preferable.
• the paper barrier material of the present invention has a plurality of gas barrier layers laminated adjacent to each other on a paper base material.
• the number of layers of the gas barrier layer is not particularly limited, but the larger the number, the higher the production cost. Therefore, the number of layers is preferably 4 or less, more preferably 3 or less, and further preferably 2 layers.
• the water-soluble polymer used for the gas barrier layer includes polyvinyl alcohol-based resins such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, casein, soybean protein, and synthetic protein.
• Examples thereof include proteins, oxidized starch, cationized starch, urea phosphate esterified starch, hydroxyethyl etherified starch and other starches, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and other cellulose derivatives, polyvinylpyrrolidone, sodium alginate and the like. Can be done. Among these, polyvinyl alcohol-based resins and cellulose derivatives are preferable, and polyvinyl alcohol-based resins are even more preferable, from the viewpoint of gas barrier properties.
• Pigments used for the gas barrier layer include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, etc.
• Inorganic pigments such as 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.
• the pigment is preferably a flat pigment having a volume of 50% average particle diameter (D50) (hereinafter, also referred to as “average particle diameter”) of 3 ⁇ m or more and an aspect ratio of 10 or more, and has an average particle diameter of 5 ⁇ m or more.
• D50 50% average particle diameter
• the flat pigment has an aspect ratio of 30 or more.
• the gas barrier layer contains a pigment, particularly a flat pigment, a gas such as oxygen passes around the pigment. Therefore, the gas barrier layer containing the pigment has excellent gas barrier properties as compared with the gas barrier layer containing no pigment, and particularly has excellent gas barrier properties in a high humidity atmosphere.
• the gas barrier layer located at the top contains a water-soluble polymer, and the pigment content is 15% by weight or less by dry weight.
• the content of the pigment is preferably small, preferably 5% by weight or less, more preferably 1% by weight or less, and further preferably 0.5% by weight or less. It is more preferably 0.3% by weight or less, further preferably 0.1% by weight or less, and most preferably not contained (0% by weight).
• At least one of the gas barrier layers other than the gas barrier layer located at the top contains a water-soluble polymer and a pigment, and the pigment content is higher than that of the gas barrier layer located at the top. expensive.
• at least one layer of the other gas barrier layer, the layer containing the water-soluble polymer and the pigment and having a higher pigment content than the gas barrier layer located at the top is a blend of the pigment and the water-soluble polymer.
• the ratio (pigment / water-soluble polymer) is preferably 10/100 to 1000/100 in terms of dry weight.
• the ratio of the pigment is less than the above range, the effect of improving the gas barrier property may be small, and the decrease in the barrier property due to bending may be small in the first place. If the ratio of the pigment is larger than the above range, the water-soluble resin may not be able to fill the gaps between the pigments, and the effect of improving the gas barrier property may be reduced. In the present invention, when the pigment is blended in the water-soluble polymer, it is preferable to add and mix the slurry of the pigment.
• a cross-linking agent typified by a polyvalent metal salt or the like can be added to the gas barrier layer. Since the cross-linking agent causes a cross-linking reaction with the water-soluble polymer contained in the gas barrier layer, the number of bonds (cross-linking points) in the gas barrier layer increases. That is, the gas barrier layer has a dense structure and can exhibit good gas barrier properties.
• the type of the cross-linking agent is not particularly limited, and polyvalent metal salts (copper, zinc, silver, iron, potassium, sodium) are matched according to the type of the water-soluble polymer contained in the gas barrier layer.
• the amount of the cross-linking agent to be blended is not particularly limited as long as it is within the range of the paint concentration and the paint viscosity that can be applied, but preferably, 1 part of the cross-linking agent is added to 100 parts by weight of the pigment. It is 5 parts by weight or more and 10 parts by weight or less, and more preferably 3 parts by weight or more and 5 parts by weight or less. If it is less than 1 part by weight, the effect of adding the cross-linking agent may not be sufficiently obtained. On the other hand, if the amount is more than 10 parts by weight, the viscosity of the paint increases remarkably, which may make coating difficult.
• the paper barrier material of the present invention can have a water vapor barrier layer between the paper base material and the first gas barrier layer.
• a surfactant in the first gas barrier layer from the viewpoint of adhesion to the water vapor barrier layer.
• the gas barrier layer contains a surfactant, it is preferable that the gas barrier layer provided on the upper surface thereof also contains the surfactant from the viewpoint of adhesion.
• the ionicity of the surfactant is not limited, and may be any kind of anionic surfactant, cationic surfactant, amphoteric surfactant, and nonionic surfactant, and may be used alone or in two kinds. The above can be used in combination.
• Specific types include silicone-based surfactants, fluorine-based surfactants, alcohol-based surfactants, acetylene-based surfactants having an acetylene group, and acetylene diol-based surfactants having an acetylene group and two hydroxyl groups.
• Agents alkyl sulfonic acid-based surfactants having an alkyl group and sulfonic acid, ester-based surfactants, amide-based surfactants, amine-based surfactants, alkyl ether-based surfactants, phenyl ether-based surfactants, sulfuric acid Examples thereof include ester-based surfactants and phenol-based surfactants.
• the surface tension of the paint for the first gas barrier layer should be adjusted to 10 mN / m or more and 60 mN / m or less from the viewpoint of adhesion to the water vapor barrier layer. Is preferable, and it is more preferable to adjust the temperature to 15 mN / m or more and 50 mN / m or less.
• the surface tension of the paint for the first gas barrier layer is ⁇ 20 mN / m with respect to the wetting tension of the surface of the water vapor barrier layer from the viewpoint of adhesion between the water vapor barrier layer and the first gas barrier layer. .. Further, it is preferable that the surface tension of the upper layer paint is ⁇ 20 mN / m with respect to the wet tension of the lower layer from the viewpoint of adhesion between adjacent layers.
• the gas barrier layer includes various commonly used aids such as dispersants, thickeners, water-retaining agents, defoaming agents, water-resistant agents, dyes, and fluorescent dyes. Agents can be used.
• the water vapor barrier resin contained in the water vapor barrier layer includes styrene / butadiene type, styrene / acrylic type, ethylene / vinyl acetate type, paraffin (WAX) type, butadiene / methyl methacrylate type, and vinyl acetate / butyl acrylate.
• Various copolymers such as systems, maleic anhydride copolymers, synthetic adhesives such as acrylic acid / methyl methacrylate-based copolymers, or their paraffin (WAX) -blended synthetic adhesives, etc. are mixed alone or in combination of two or more. Can be used.
• the styrene-butadiene synthetic adhesive is obtained by emulsion-polymerizing styrene and butadiene as main constituent monomers by combining them with various comonomer for the purpose of modification.
• comonomers include methylmethacryllate, acrylonitrile, acrylamide, hydroxyethyl acrylate, unsaturated carboxylic acids such as itaconic acid, maleic acid and acrylic acid.
• an anionic surfactant such as sodium oleate, soap loginate, sodium alkylallyl sulfonate, sodium dialkyl sulfosuccinate can be used alone or in combination with a nonionic surfactant.
• Amphoteric or cationic surfactants may be used depending on the purpose.
• polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, proteins such as casein, soybean protein, and synthetic protein, and oxidation.
• the above-mentioned starches such as starch, cationized starch, urea phosphate esterified starch, hydroxyethyl etherified starch, cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose and hydroxyethyl cellulose, and water-soluble polymers such as polyvinylpyrrolidone and sodium alginate are used. It can also be used in combination with a water vapor barrier resin.
• pigment in the water vapor barrier layer from the viewpoint of adhesion between the water vapor barrier layer and the gas barrier layer in the configuration having the water vapor barrier layer and the gas barrier layer.
• Pigments include 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, and satin.
• Inorganic pigments such as 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.
• inorganic pigments such as kaolin, mica, and talc having a flat shape are preferable, and kaolin is more preferable, from the viewpoints of improving the water vapor barrier property and suppressing the penetration of the gas barrier layer.
• an inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more alone or in combination of two or more. If the average particle size or aspect ratio of the inorganic pigment used is smaller than the above range, the number of times water vapor detours in the water vapor barrier layer decreases and the distance traveled becomes shorter, resulting in a smaller effect of improving the water vapor barrier property. May become.
• the water vapor barrier layer containing an inorganic pigment having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more has an average particle size of 5 ⁇ m. It is preferable to contain the following pigments. By using a pigment having an average particle size of 5 ⁇ m or less in combination, it is possible to reduce voids in the water vapor barrier layer formed by an inorganic pigment having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more, which is further excellent. A water vapor barrier property is developed.
• the voids formed by the inorganic pigments having a large average particle size in the water vapor barrier layer are filled with the pigments having a small average particle size, and the water vapor.
• an 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 are used in combination, an inorganic pigment having an average particle diameter of 5 ⁇ m or more and an aspect ratio of 10 or more is used.
• the compounding ratio of the pigment having an average particle diameter of 5 ⁇ m or less is 50/50 to 99 / by dry weight. It is preferably 1. 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 water vapor detours in the water vapor barrier layer decreases and the distance traveled becomes short, so that the water vapor barrier property is obtained. The improvement effect of is small.
• the amount exceeds the above range, the voids formed by the inorganic pigment having a large average particle size in the water vapor barrier layer cannot be sufficiently filled with the pigment having an average particle size of 5 ⁇ m or less, so that the water vapor barrier property is further improved. I can't.
• the pigments 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 include kaolin, clay, engineered kaolin, delaminated clay, and heavy calcium carbonate.
• Light calcium carbonate, talc, titanium dioxide, barium sulphate, calcium sulphate, zinc oxide, silicic acid, silicate, colloidal silica, satin white and other inorganic pigments and solid, hollow or core-shell type organic pigments Etc. can be used alone or in combination of two or more.
• the blending amount of the pigment is in the range of 5 parts by weight or more and 200 parts by weight or less in total of the water vapor barrier resin and the water-soluble polymer with respect to 100 parts by weight of the pigment by dry weight. It is preferably used, and more preferably, the total amount of the water vapor barrier resin and the water-soluble polymer is 10 parts by weight or more and 150 parts by weight or less.
• the water vapor barrier layer is usually used with a dispersant, a thickener, a water retention agent, a defoaming agent, a water resistant agent, a dye, a fluorescent dye, and the like.
• Various auxiliaries can be used.
• a cross-linking agent typified by a polyvalent metal salt or the like can be added to the water vapor barrier layer. Since the cross-linking agent causes a cross-linking reaction with the water vapor barrier resin and the water-soluble polymer contained in the water vapor barrier layer, the number of bonds (cross-linking points) in the water vapor barrier layer increases. That is, the water vapor barrier layer has a dense structure and can exhibit good water vapor barrier properties.
• the type of the cross-linking agent is not particularly limited, and the polyvalent metal salt (copper, zinc, silver) is matched with the type of the water vapor barrier resin or the water-soluble polymer contained in the water vapor barrier layer.
• a compound to which a sex 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 amount of the cross-linking agent to be blended is not particularly limited as long as it is within the range of the paint concentration and the paint viscosity that can be applied, but preferably, 1 part of the cross-linking agent is added to 100 parts by weight of the pigment. 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 it is less than 1 part by weight, the effect of adding the cross-linking agent may not be sufficiently obtained. On the other hand, if the amount is more than 10 parts by weight, the viscosity of the paint increases remarkably, which may make coating difficult.
• the cross-linking agent when added to the paint for the water vapor barrier layer, it is preferable to dissolve the cross-linking agent in a polar solvent such as ammonia before adding the cross-linking agent to the paint.
• a polar solvent such as ammonia
• the cross-linking agent and the polar solvent form a bond. Therefore, even if the cross-linking agent is added to the paint, the cross-linking reaction with the water vapor barrier resin or the water-soluble polymer does not occur immediately, and the paint thickens. Can be suppressed.
• the water repellent in the water vapor barrier layer from the viewpoint of improving the water vapor barrier property.
• the water repellent include paraffin-based water repellents mainly composed of alkane compounds, natural oil-based 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 contained.
• paraffin-based water repellent mainly composed of alkane compounds, natural oil-based water repellents derived from animals and plants such as carnauba and lanolin, silicone-containing water repellents containing silicone or silicone compounds, and fluorine compounds.
• fluorine compounds examples thereof include a fluorine-containing water repellent contained.
• the blending amount of the water repellent agent is not particularly limited, but the blending amount of the water repellent agent is the dry weight with respect to 100 parts by weight of the water vapor barrier resin and the water-soluble polymer in total. It is preferable that the amount of the liquid agent is 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, if it exceeds 100 parts by weight, it becomes difficult to uniformly form the gas barrier layer when the gas barrier layer is provided on the water vapor barrier layer, so that the gas barrier property may decrease.
• the wetting tension of the surface of the water vapor barrier layer is preferably 10 mN / m or more and 60 mN / m or less, preferably 15 mN / m or more and 50 mN / m / m, from the viewpoint of improving the water vapor barrier property and adhesion to the gas barrier layer. It is more preferably m or less.
• the coating method of the water vapor barrier layer and the gas barrier layer is not particularly limited, and coating can be performed by a known coating device and coating system.
• the coating device 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.
• examples of the coating system include water-based coating using a solvent such as water, solvent-based coating using a solvent such as an organic solvent, and the like.
• a usual method such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, or a cylinder dryer is used.
• the coating amount thereof is preferably 3 g / m 2 or more and 50 g / m 2 or less in terms of dry weight, and 5 g / m 2 or more and 40 g / m 2 or less. More preferably, it is 7 g / m 2 or more and 30 g / m 2 or less. If the coating amount of the water vapor barrier layer is less than 3 g / m 2 , the improvement of the water vapor barrier property may be hardly expected. On the other hand, if it is more than 50 g / m 2 , the drying load at the time of coating becomes large.
• the water vapor barrier layer is arbitrary, but the number of layers may be one layer or may be composed of two or more layers. When the water vapor barrier layer is composed of two or more layers, it is preferable that the total coating amount of all the water vapor barrier layers is within the above range.
• the coating amount of the gas barrier layer (total of a plurality of gas barrier layers) is preferably 0.2 g / m 2 or more and 20 g / m 2 or less in terms of dry weight. If the coating amount of the gas barrier layer is less than 0.2 / m 2 , it is difficult to form a uniform gas barrier layer, so that sufficient gas barrier properties may not be obtained. On the other hand, if it is more than 20 g / m 2 , the drying load at the time of coating becomes large.
• the coating amount of the gas barrier layer located at the uppermost portion is preferably the smallest among the plurality of gas barrier layers, and is located at the uppermost portion with respect to the total coating amount of 100 parts by weight of the other gas barrier layers. It is more preferable that the coating amount of the gas barrier layer is 1 part by weight or more and 100 parts by weight or less. If the amount of coating of the gas barrier layer located at the uppermost portion is less than 1 part by weight, the bending resistance may not be sufficiently exhibited. Further, when the coating amount of the gas barrier layer located at the uppermost portion exceeds 100 parts by weight, the content of the pigment in the entire gas barrier layer becomes low, and the gas barrier property, particularly the gas barrier property at high humidity may be lowered. ..
• the upper limit of the coating amount of the gas barrier layer located at the uppermost portion is preferably 5 g / m 2 or less in terms of dry weight, and more preferably 4 g / m 2 or less.
• the lower limit of the coating amount of the gas barrier layer located at the uppermost portion is preferably 0.1 g / m 2 or more, more preferably 0.2 g / m 2 or more, and 0.3 g in terms of dry weight. It is more preferably / m 2 or more. If the coating amount of the gas barrier layer located at the uppermost portion is more than 5 g / m 2 , blocking during winding may occur. On the other hand, if it is less than 0.1 g / m 2 , the bending resistance may not be sufficiently exhibited.
• the paper barrier material of the present invention can have a protective layer on at least one surface.
• a paper barrier material having a protective layer a laminate having a paper base material, a water vapor barrier layer (arbitrary), and a plurality of adjacent gas barrier layers is referred to as a paper barrier base paper.
• the protective layer prevents deterioration of the water vapor barrier layer and gas barrier layer of the paper barrier base paper due to moisture in the air, and imparts further water vapor barrier property and gas barrier property to the paper barrier base paper, or oil resistance and solvent resistance. It is possible to impart properties, heat resistance, wear resistance, impact resistance, light resistance, and the like. Further, when the protective layer is a resin layer, heat-sealing property can be imparted.
• the protective layer can be provided on both sides of the paper barrier base paper, it is preferable to have the protective layer on at least the surface on the side having the gas barrier layer.
• the protective layer include a resin layer, a paper layer, a metal foil, and the like, and among these, the resin layer is preferable.
• 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 acid, and polychloride.
• Fossil resource-derived resins such as vinylidene, polyamide (nylon), polyacetal, polycarbonate, polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), biopolyethylene, Biopolyethylene terephthalate, biopolyester and other bio-derived resins can be included.
• the biological resin includes a substance derived from a renewable organic resource as a raw material, and is a polymer material having a number average molecular weight (Mn) of 1,000 or more obtained by chemically or biologically synthesizing the resin. Say.
• biodegradable resins such as polylactic acid (PLA), esterified starch, cellulose acetate, polybutylene succinate (PBS), and polybutylene succinate adipate (PBSA), Any non-biodegradable resin such as 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 finally becomes carbon dioxide and water and circulates to the natural world.
• the resin laminated layer is preferable as the resin layer.
• the resin laminated layer include an extruded laminated layer and a film bonding layer such as a barrier film and a vapor-deposited film.
• the various resins described above are laminated as a resin laminating layer on at least one surface of the paper barrier base paper by an extruding laminating method.
• the resin laminate layer is a film laminating layer
• the above-mentioned various resin films are laminated as a resin laminating layer on at least one surface of the paper barrier base paper by a dry laminating method, a sand laminating method, or the like. ..
• the resin layer can be provided on both sides of the paper barrier base paper, it is preferable to have the resin layer on at least the surface on the side having the gas barrier layer. Further, it is preferable to have a resin layer on the gas barrier layer of the paper barrier base paper.
• examples of the film used for the film bonding layer include the above-mentioned films made of various resins.
• films mainly composed of resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, and polyacrylonitrile, and films made of the above-mentioned various resins are coated with resins such as these polyvinyl alcohols.
• a barrier film such as a vapor-deposited film on which an object is vapor-deposited is preferable, and a vapor-deposited film is more preferable.
• these films can be used by laminating one layer or a plurality of layers.
• the paper barrier material of the present invention can be used as a paper barrier material, or laminated with various resins or the like, or bonded to various general-purpose films, barrier films, aluminum foil, etc., to form packaging materials for foods, containers, and the like. It can be a paper barrier packaging material used for packaging applications such as cups, or a laminate used for industrial materials and the like. Among these, the paper barrier material of the present invention can be suitably used as a paper barrier packaging material used for packaging materials such as foods, containers, cups and the like, and flexible packaging bags for foods and the like. It can be used particularly preferably.
• the flexible packaging bag is a packaging material composed of a highly flexible material, and generally, a thin and flexible material such as paper, film, or aluminum foil is used alone or bonded.
• the shape of the flexible packaging bag is not particularly limited, and examples thereof include a vertical pillow packaging bag, a horizontal pillow packaging bag, a side seal bag, a two-way seal bag, a three-way seal bag, a gusset bag, a bottom gusset bag, and a stand bag.
• the paper barrier material of the present invention When used as a packaging material for foods, especially a flexible packaging bag, it is laminated with a resin having a heat-sealing property to improve the airtightness as a packaging material and oxidize the contents with oxygen. It can protect the product from deterioration due to moisture and moisture, and can extend the storage period. Further, since the flexible packaging material is thin and flexible, bending is likely to occur during manufacturing, transportation, storage, sales, etc., but the paper barrier material of the present invention has excellent bending resistance and bending occurs. However, since the deterioration of the barrier property is suppressed, it is possible to prevent the quality of the contents from being impaired due to unexpected bending. In addition, even when used as a laminate used for industrial materials, it is possible to prevent spoilage and deterioration by suppressing the intrusion of oxygen and moisture, as well as flavor barrier properties that prevent the odor of the solvent from leaking out. The effect of is expected.
• Example 1 (Preparation of paper substrate) Hardwood bleached kraft pulp (LBKP) with a Canadian standard freshness (CSF) of 500 ml and softwood bleached kraft pulp (NBKP) with a CSF of 530 ml were blended in a weight ratio of 80/20 to obtain a raw material pulp.
• Polyamide epichlorohydrin (PAEH) -based resin as a wet paper strength enhancer is 0.15% per absolute dry pulp weight
• polyacrylamide (PAM) having a molecular weight of 10 million as a retention agent is added to the absolute dry pulp weight. After adding 0.08% per pulp, paper was made with a duoformer FM type paper machine at a speed of 300 m / min to obtain a paper having a basis weight of 59 g / m 2 .
• polyvinyl alcohol (PVA117 manufactured by Kuraray Co., Ltd.) prepared to have a solid content concentration of 2% was coated on the obtained paper with a rod metering size press at a total of 1.0 g / m 2 on both sides, dried, and the basis weight was 60 g.
• a base paper of / m 2 was obtained.
• the obtained base paper was smoothed using a chilled calendar at a speed of 300 min / m and a linear pressure of 50 kgf / cm in one pass to obtain a paper substrate.
• the coating liquid 1 for the gas barrier layer is coated on one side so that the coating amount is 5.0 g / m 2 by dry weight, and after drying, the coating liquid for the gas barrier layer is applied onto the coating liquid for the gas barrier layer. 2 was coated on one side so as to have a dry weight of 0.5 g / m 2 , and a paper barrier material was obtained.
• Example 2 A paper barrier material was obtained in the same manner as in Example 1 except that the coating liquid 2 for the gas barrier layer was coated so as to have a dry weight of 2.0 g / m 2 .
• Example 3 A paper barrier material was obtained in the same manner as in Example 1 except that the coating liquid 2 for the gas barrier layer was coated so as to have a dry weight of 4.0 g / m 2 .
• Example 4 A paper barrier material was obtained in the same manner as in Example 1 except that the coating liquid 2 for the gas barrier layer was coated so as to have a dry weight of 0.2 g / m 2 .
• Example 5 Preparation of coating liquid for water vapor barrier layer
• Sodium polyacrylate was added as a dispersant to engineered kaolin (Imelis, Varisurf HX, average particle size 90 ⁇ m, aspect ratio 80-100) (0.2% of pigment), dispersed with a variety mixer, and solid content.
• a kaolin slurry having a concentration of 60% was prepared.
• 100 parts (solid content) of a styrene / acrylic copolymer emulsion manufactured by Saiden Chemical Co., Ltd., X-511-374E
• a water vapor barrier resin 100 parts (solid content) of the pigment.
• a coating liquid for a water vapor barrier layer having a solid content concentration of 45% was obtained. Prior to coating the coating liquid for the first gas barrier layer, the coating liquid for the water vapor barrier layer was coated on one side so as to have a dry weight of 15 g / m 2 , and dried in the same manner as in Example 1. A paper barrier material was obtained.
• Example 1 A paper barrier material was obtained in the same manner as in Example 1 except that the coating liquid 2 for the gas barrier layer was not applied.
• Comparative Example 2 A paper barrier material was obtained in the same manner as in Example 2 except that the gas barrier layer coating liquid 2 was applied instead of the gas barrier layer coating liquid 1 as the first gas barrier layer.
• Comparative Example 3 The paper barrier material was used in the same manner as in Example 2 except that the coating liquid 2 for the gas barrier was an aqueous polyester resin solution (manufactured by GOO CHEMICAL CO., LTD., Plus coat Z-561, high hardness polyester, no gas barrier property). Obtained.
• Reference Example 1 A paper barrier material was obtained in the same manner as in Example 1 except that the coating liquid 2 for the gas barrier layer was coated so as to have a dry weight of 6.0 g / m 2 .
• the paper barrier materials obtained in Examples 1 to 5 of the present invention were excellent in bending resistance and could maintain high oxygen barrier properties even in the presence of creases.
• the paper barrier materials obtained in Examples 1 to 3 and 5 have an oxygen permeability ratio of 1.5 times or less with and without creases under high humidity, and further, Examples 2 and 3
• the ratio of oxygen permeability with creases / without creases under drying was 10 times or less.
• the paper barrier materials obtained in Comparative Examples 1 and 3 are inferior in bending resistance, and the oxygen barrier property is remarkably lowered in the presence of creases, and oxygen permeation with / without creases under drying.
• the ratio of degrees was 100 times or more.
• the paper barrier material obtained in Comparative Example 2 in which the first gas barrier layer did not contain a pigment was originally inferior in oxygen barrier property under high humidity without creases.
• the paper barrier material obtained in Reference Example 1 had blocking during winding after production. When the paper barrier material was pulled out from this winding, the second gas barrier layer was peeled off, so the gas barrier property was not evaluated.
• Reference Example 1 it is presumed that a paper barrier material having better bending resistance than Comparative Example 1 was obtained by preparing drying conditions and preventing blocking.
• Example 6 (Preparation of coating liquid 3 for gas barrier layer) An aqueous solution of ethylene copolymer polyvinyl alcohol (RS-4104, manufactured by Kuraray Co., Ltd.) was prepared so as to have a solid content concentration of 13% to obtain a PVA aqueous solution. Mica slurry (manufactured by Topy Industries, Ltd., product name: NTS-10, aspect ratio: 1500, solid content concentration 10%) is mixed with the obtained PVA aqueous solution so that the solid content is 100:15, and the gas barrier layer is formed. A coating liquid 3 was obtained.
• RS-4104 ethylene copolymer polyvinyl alcohol
• the coating liquid 1 for the gas barrier layer is coated on one side so that the coating amount is 5.0 g / m 2 by dry weight, and after drying, the coating liquid for the gas barrier layer is applied onto the coating liquid for the gas barrier layer.
• 3 was coated on one side so as to have a dry weight of 3.0 g / m 2 , and a paper barrier material was obtained.
• Example 7 Preparation of coating liquid 4 for gas barrier layer
• An aqueous solution of ethylene copolymer polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Excelval HR3010) was prepared so that the solid content concentration was 10%, and a coating liquid 4 for a gas barrier layer was obtained.
• the coating liquid 4 for the gas barrier layer was coated on one side so as to have a dry weight of 3.0 g / m 2 , and the paper barrier material was applied. Obtained.
• Example 8 On the obtained paper substrate, the coating liquid for the water vapor barrier layer is coated on one side so as to have a dry weight of 15 g / m 2 , and after drying, the coating liquid 3 for the gas barrier layer is applied on the coating liquid for the gas barrier layer by the dry weight. Single-sided coating to a dry weight of 3.0 g / m 2 and drying, and then single-sided coating of a gas barrier layer coating liquid 4 to a dry weight of 3.0 g / m 2 to obtain a paper barrier material. Obtained.
• the coating liquid 3 for the gas barrier layer was coated on a paper substrate on one side so as to have a dry weight of 3.0 g / m 2 , to obtain a paper barrier material.
• the paper barrier materials obtained in Examples 6 to 8 of the present invention were excellent in bending resistance and could maintain high oxygen barrier properties even in the presence of creases.
• the paper barrier materials obtained in Examples 7 and 8 have an oxygen permeability of 5 ml / m 2 ⁇ day ⁇ atm or less under drying with creases and an oxygen permeability of 2.9 ml under high humidity. It was less than / m 2 ⁇ day ⁇ atm, and it was possible to maintain a very high oxygen barrier property even in the presence of creases.
• the paper barrier material obtained in Comparative Example 4 was inferior in oxygen barrier property without creases, and the oxygen barrier property was lowered in the presence of creases.

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• 2021
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