Classifications

• • 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
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/30—Multi-ply
• • 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
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • 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
  • D21H19/80—Paper comprising more than one coating
  • D21H19/82—Paper comprising more than one coating superposed
• • 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
  • D21H19/84—Paper comprising more than one coating on both sides of the substrate
• • 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
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/16—Sizing or water-repelling agents
• • 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
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
  • D21H27/10—Packing paper
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • 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
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/12—Coating on the layer surface on paper layer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/26—Polymeric coating
• • 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
  • B32B2255/00—Coating on the layer surface
  • B32B2255/28—Multiple coating on one surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/72—Density
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/70—Food packaging
• • 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
  • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

• the present disclosure relates to a barrier laminate and a packaging bag using the same.
• Packaging materials that have gas barrier properties such as oxygen barrier properties and water vapor barrier properties added to paper base materials have traditionally been used in the packaging of foods, medical products, electronic components, etc. to prevent the quality of the contents from deteriorating. It's been getting worse.
• a common method for imparting water vapor barrier properties and gas barrier properties to a paper base material is to laminate a synthetic resin film with excellent gas barrier properties onto the paper base material.
• materials in which a synthetic resin film or the like is laminated onto a paper base material have an environmental problem because it is difficult to recycle the paper or synthetic resin after use.
• Patent Document 1 describes a technology for controlling the hydroxyl groups and acid groups of a resin used in the gas barrier layer in a paper barrier material in which a gas barrier layer and a heat seal layer are provided in this order on a paper base material. ing.
• the paper barrier material described in Patent Document 1 has a single-layer barrier layer, which makes it possible to reduce the amount of plastic material used. However, it cannot be said to be sufficient from the viewpoint of water vapor barrier properties.
• the present disclosure achieves both high water vapor barrier properties and gas barrier properties with a small number of layers (for example, even if the barrier layer is a single layer), and can further reduce the burden on the environment by reducing the coating amount of the barrier layer. Provides a barrier laminate with excellent barrier properties.
• the barrier layer is a single layer,
• the water vapor permeability of the barrier layer at 40° C. and 90% RH is less than 50 g/m 2 ⁇ day,
• the oxygen permeability of the barrier layer at 23° C. and 50% RH is 10.0 mL/m 2 ⁇ day ⁇ atm or less,
• the water vapor permeability of the barrier laminate measured at 40° C. and 90% RH in accordance with JIS-Z-0208:1976 is less than 50 g/m 2 ⁇ day,
• the barrier layer contains hydroxy polyurethane and a swellable layered silicate.
• a barrier laminate having a barrier layer on at least one surface of a paper base material The barrier layer is a barrier laminate containing hydroxy polyurethane, a swellable layered silicate, and a cationic resin.
• ⁇ 7> The barrier laminate according to any one of ⁇ 2> to ⁇ 6>, wherein the content of the swellable layered silicate in the barrier layer is 5.0 to 30.0% by mass.
• the barrier layer further includes at least one selected from the group consisting of a water-suspended polymer other than hydroxypolyurethane and a water-soluble polymer other than hydroxypolyurethane,
• the water-suspended polymer contains at least one selected from the group consisting of a styrene-butadiene copolymer, an acrylic resin, an olefin-unsaturated carboxylic acid copolymer, and a polyolefin resin
• the water-soluble polymer is selected from the group consisting of vinyl alcohol polymers, (meth)acrylic acid polymers, polyethylene glycols, water-soluble polyamides, polyacrylamide, polyamines, polycarboxylic acids, and water-soluble cellulose derivatives.
• the total content of the water-suspended polymer other than the hydroxypolyurethane and the water-soluble polymer other than the hydroxypolyurethane in the barrier layer is 2.0 to 50.0% by mass. Barrier laminate described.
• the barrier laminate further has a heat seal layer on the side on which the barrier layer is laminated,
• the heat seal strength when peeled using a tensile tester using a sample obtained by heat sealing the heat seal layers of the barrier laminate under the conditions of 150° C., 0.2 MPa, and 1 second was 2.
• ⁇ 12> The oxygen permeability at 23° C.
• ⁇ 1> to ⁇ 11 The barrier laminate according to any one of the above.
• ⁇ 13> A packaging bag using the barrier laminate according to any one of ⁇ 1> to ⁇ 12>.
• the range “X to Y” means “X or more and Y or less”.
• the upper and lower limits of each numerical range can be arbitrarily combined.
• operations and measurements of physical properties, etc. are performed under conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH.
• At least one aspect of the present disclosure is a barrier laminate having a barrier layer on at least one surface of a paper base material,
• the barrier layer is a single layer,
• the water vapor permeability of the barrier layer at 40° C. and 90% RH is less than 50 g/m 2 ⁇ day;
• the oxygen permeability of the barrier layer at 23° C. and 50% RH is 10.0 mL/m 2 ⁇ day ⁇ atm or less,
• the water vapor permeability of the barrier laminate measured at 40° C. and 90% RH in accordance with JIS-Z-0208:1976 is less than 50 g/m 2 ⁇ day,
• the oxygen permeability at 23° C. and 50% RH when a CPP film is bonded to the barrier laminate is 10 mL/m 2 ⁇ day ⁇ atm or less,
• the recovery rate of pulp after redisintegrating the barrier laminate is 85% by mass or more.
• At least one aspect of the present disclosure is a barrier laminate having a barrier layer on at least one surface of a paper base material
• the barrier layer relates to a barrier laminate containing (A) hydroxy polyurethane, (B) swellable layered silicate, and (C) cationic resin.
• the barrier layer containing the components (A) to (C) above alone exhibits excellent water vapor barrier properties and gas barrier properties; It's okay.
• the present inventors have developed a barrier laminate that can achieve both high water vapor barrier properties and gas barrier properties with a small number of layers (for example, even if the barrier layer is a single layer), and can further reduce the coating amount of the barrier layer. I considered it carefully.
• the inventors have also found that the above-mentioned problems can be solved by forming the above-mentioned barrier laminate.
• the water vapor permeability of the barrier laminate measured at 40° C. and 90% RH according to JIS-Z-0208:1976 is less than 50 g/m 2 ⁇ day.
• the water vapor permeability is preferably 40 g/m 2 ⁇ day or less, more preferably 30 g/m 2 ⁇ day or less, even more preferably 20 g/m 2 ⁇ day or less, and 15 g/m 2 ⁇ day or less. It is even more preferable that it is 2 ⁇ day or less, it is especially preferable that it is 10 g/m 2 ⁇ day or less, and it is especially preferable that it is 8 g/m 2 ⁇ day or less.
• a content within the above range indicates that the water vapor barrier property is extremely high.
• the lower limit is not particularly limited as the lower the better, but it is preferably 0 g/m 2 ⁇ day or more, 1 g/m 2 ⁇ day or more, 2 g/m 2 ⁇ day or more, or 3 g/m 2 ⁇ day or more.
• the water vapor permeability can be controlled, for example, by selecting the thickness of the barrier layer and the components contained in the barrier layer.
• the oxygen permeability at 23° C. and 50% RH when the CPP film is bonded to the barrier laminate is 10.0 mL/m 2 ⁇ day ⁇ atm or less.
• the oxygen permeability is preferably 8.0 mL/m 2 ⁇ day ⁇ atm or less, more preferably 5.0 mL/m 2 ⁇ day ⁇ atm or less, and 3.0 mL/m 2 ⁇ day ⁇ It is more preferably at most 2.0 mL/m 2 ⁇ day ⁇ atm, even more preferably at most 1.5 mL/m 2 ⁇ day ⁇ atm, even more preferably at most 1.0 mL/m 2 ⁇ day ⁇ atm.
• the oxygen barrier property is very high.
• the lower limit is not particularly limited because the lower the better, but it is preferably 0.0 mL/m 2 ⁇ day ⁇ atm or more, and 0.1 mL/m 2 ⁇ day ⁇ atm or more.
• the oxygen permeability can be controlled, for example, by selecting the thickness of the barrier layer and the components contained in the barrier layer.
• the barrier laminate has a barrier layer on at least one side of the paper base material.
• the barrier layer is a single layer.
• the water vapor permeability of the barrier layer at 40° C. and 90% RH is less than 50 g/m 2 ⁇ day.
• the water vapor permeability of the barrier layer is preferably 40 g/m 2 ⁇ day or less, more preferably 30 g/m 2 ⁇ day or less, even more preferably 20 g/m 2 ⁇ day or less, It is even more preferably 15 g/m 2 ⁇ day or less, even more preferably 10 g/m 2 ⁇ day or less, and particularly preferably 8 g/m 2 ⁇ day or less.
• the lower limit is not particularly limited as the lower the better, but it is preferably 0 g/m 2 ⁇ day or more, 1 g/m 2 ⁇ day or more, 2 g/m 2 ⁇ day or more, or 3 g/m 2 ⁇ day or more.
• the water vapor permeability of the barrier layer is measured by the measuring method described in Examples below.
• the oxygen permeability of the barrier layer at 23° C. and 50% RH is 10.0 mL/m 2 ⁇ day ⁇ atm or less.
• the oxygen permeability of the barrier layer is preferably 8.0 mL/m 2 ⁇ day ⁇ atm or less, more preferably 5.0 mL/m 2 ⁇ day ⁇ atm or less, and 3.0 mL/m 2 - It is more preferably less than 2.0 mL/m 2 - day - atm, even more preferably less than 2.0 mL/m 2 - day - atm, even more preferably less than 1.0 mL/m 2 - day - atm, and 0 It is even more preferable that it is .7 mL/m 2 ⁇ day ⁇ atm or less, and particularly preferably that it is 0.5 L/m 2 ⁇ day ⁇ atm or less.
• the lower limit is not particularly limited because the lower the better, but it is preferably 0.0 mL/m 2 ⁇ day ⁇ atm or more, and 0.1 mL/m 2 ⁇ day ⁇ atm or more.
• the oxygen permeability of the barrier layer is measured by the measuring method described in Examples below.
• the fact that the barrier layer satisfies the above water vapor permeability and oxygen permeability indicates that the single barrier layer has very high water vapor barrier properties and gas barrier properties. Since the above-mentioned high water vapor barrier properties and gas barrier properties can be achieved with a single layer, the coating amount of the barrier layer can be reduced, and the weight of the product can be reduced.
• the barrier layer of the barrier laminate contains hydroxypolyurethane, a swellable phyllosilicate, and a cationic resin, so that the labyrinth effect caused by the swellable phyllosilicate can be efficiently suppressed. It can be expressed well.
• the barrier layer is a single layer can be confirmed by preparing a cross section along the direction perpendicular to the plane of the paper and observing it with an electron microscope. Alternatively, it can be confirmed by non-destructive observation using X-ray CT.
• the water vapor permeability and oxygen permeability can be set within the above ranges by selecting the material used for the barrier layer.
• the recovery rate of pulp after redisintegrating the barrier laminate is 85% by mass or more.
• the fact that the recovery rate is within the above range indicates that the content of pulp in the barrier laminate is high and the recyclability is high.
• the recovery rate of the pulp is preferably 88% by mass or more, more preferably 90% by mass or more, and even more preferably 92% by mass or more.
• the upper limit is not particularly limited, but is preferably 99% by mass or less, 98% by mass or less, and 97% by mass or less.
• the recovery rate of the pulp can be controlled by the coating amount of the barrier layer, the content of the layered inorganic compound (swellable layered silicate) in the barrier layer, the basis weight of the paper base material, and the like.
• the oxygen permeability at 23°C and 85% RH when the CPP film is bonded to the barrier laminate is preferably 10.0 mL/m 2 ⁇ day ⁇ atm or less, and 8.0 mL/m It is more preferably at most 2.day atm, even more preferably at most 5.0 mL/m 2.day atm, even more preferably at most 3.0 mL/m 2.day atm, It is particularly preferably 2.0 mL/m 2 ⁇ day ⁇ atm or less, even more preferably 1.5 mL/m 2 ⁇ day ⁇ atm or less, and 1.0 mL/m 2 ⁇ day ⁇ atm or less is particularly preferred.
• the lower limit is not particularly limited because the lower the better, but it is preferably 0.0 mL/m 2 ⁇ day ⁇ atm or more, and 0.1 mL/m 2 ⁇ day ⁇ atm or more.
• the oxygen permeability at 5% RH can be set within the above range by selecting the material used for the barrier layer. Each material of the barrier laminate will be explained below.
• the barrier laminate includes a paper base.
• the paper base material is not particularly limited, and any known paper material can be used.
• the pulp constituting the paper base material preferably has plant-derived pulp as its main component, and has wood pulp as its main component. Examples of the wood pulp include hardwood pulp and softwood pulp. Non-wood pulps include cotton pulp, hemp pulp, kenaf pulp, bamboo pulp, and the like. Materials other than pulp fibers, such as synthetic fibers such as rayon fibers and nylon fibers, may also be blended as sub-paper materials as long as they do not impair the effects of the present invention.
• the paper base material include bleached kraft paper, unbleached kraft paper, high-quality paper, paperboard, liner paper, coated paper, single-gloss bleached kraft paper, glassine paper, and graphene paper.
• bleached kraft paper unbleached kraft paper, high-quality paper, and single-gloss bleached kraft paper. More preferred are bleached kraft paper and single gloss bleached paper, and even more preferred is single gloss bleached kraft paper.
• Additives may be added to the paper base material.
• additives include pH adjusters (sodium hydrogen carbonate, sodium hydroxide, etc.), dry paper strength agents (polyacrylamide, starch, etc.), wet paper strength agents (polyamide polyamine epichlorohydrin resin, melamine-formaldehyde resin, (urea-formaldehyde resin), internal sizing agents (rosin type, alkyl ketene dimer, etc.), drainage retention improvers, antifoaming agents, fillers (calcium carbonate, talc, etc.), dyes, etc.
• pH adjusters sodium hydrogen carbonate, sodium hydroxide, etc.
• dry paper strength agents polyacrylamide, starch, etc.
• wet paper strength agents polyamide polyamine epichlorohydrin resin, melamine-formaldehyde resin, (urea-formaldehyde resin), internal sizing agents (rosin type, alkyl ketene dimer, etc.), drainage retention improvers
• the basis weight of the paper base material is not particularly limited, but for example, if it is used for packaging bags, it is preferably 20 g/m 2 or more and 150 g/m 2 or less, more preferably 30 g/m 2 or more and 100 g/m 2 or less, and 40 g/m 2 or more. More preferably, it is not less than m 2 and not more than 70 g/m 2 .
• the basis weight of the paper base material is measured in accordance with JIS P 8124:2011.
• the paper thickness of the paper base material is not particularly limited, but for example, for use in packaging bags, it is preferably 20 ⁇ m or more and 150 ⁇ m or less, more preferably 25 ⁇ m or more and 100 ⁇ m or less, and even more preferably 30 ⁇ m or more and 50 ⁇ m or less.
• the paper thickness of the paper base material is measured in accordance with JIS P 8118:2014.
• the smoothness of the paper base material is not particularly limited.
• the Oken type smoothness of the surface on which the barrier layer is provided is preferably 5 seconds or more, more preferably 10 seconds or more.
• the upper limit is not particularly limited, for example, it is preferably 2000 seconds or less, and more preferably 1000 seconds or less.
• the Oken smoothness of the paper base material is measured in accordance with JIS P 8155:2010.
• Examples of the method for manufacturing the paper base material include a method of making paper from a paper stock containing pulp.
• the paper stock may further contain an additive.
• Examples of the additive include the additives listed above.
• Paper stock can be prepared by adding additives to pulp slurry. Pulp slurry is obtained by beating pulp in the presence of water.
• the pulp beating method and beating device are not particularly limited, and may be the same as known beating methods and beating devices.
• the content of pulp in the paper stock is not particularly limited, and may be within a commonly used range. For example, it is 60% by mass or more and less than 100% by mass with respect to the total mass of the paper stock.
• Paper making can be carried out using standard methods. For example, there is a method in which paper stock is cast on a wire or the like, dehydrated to obtain a wet paper, and if necessary, multiple wet papers are stacked, and this single-layer or multi-layer wet paper is pressed and dried. . At this time, if a plurality of wet papers are not stacked, a single-layer paper will be obtained, and if a plurality of wet papers are stacked, a multi-layer paper will be obtained. When stacking a plurality of wet papers, an adhesive may be applied to the surface of the wet paper (the surface on which other wet papers are stacked).
• the barrier laminate has a single barrier layer on at least one side of the paper base material.
• the barrier layer exhibits high water vapor barrier properties and gas barrier properties.
• the material used for the barrier layer is not particularly limited as long as it can exhibit the above water vapor barrier properties and gas barrier properties.
• the following known resins may be used.
• resins that can be used for the barrier layer include polyolefin resins (polyethylene, polypropylene, etc.), vinyl chloride resins, styrene resins, styrene/butadiene copolymers, acrylonitrile/styrene copolymers, acrylonitrile/butadiene copolymers, ABS resins, AAS resin, AES resin, vinylidene chloride resin, polyurethane resin, poly-4-methylpentene-1 resin, polybutene-1 resin, vinylidene fluoride resin, vinyl fluoride resin, fluororesin, polycarbonate resin, polyamide resin, acetal resin, Polyphenylene oxide resin, polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), polyphenylene sulfide resin, polyimide resin, polysulfone resin, polyether sulfone resin, aromatic polyester resin, polyarylate resin, olefin/unsaturated
• the barrier layer preferably contains hydroxypolyurethane in order to exhibit high water vapor barrier properties and gas barrier properties.
• Hydroxy polyurethane refers to polyurethane having hydroxyl groups.
• the hydroxyl value of the hydroxy polyurethane is preferably 100 to 500 mgKOH/g, more preferably 150 to 400 mgKOH/g, and still more preferably 200 to 350 mgKOH/g.
• Hydroxy polyurethane may have acid groups.
• the acid value of the hydroxy polyurethane is preferably 50 to 100 mgKOH/g, more preferably 10 to 70 mgKOH/g, and even more preferably 15 to 60 mgKOH/g.
• the acid value and hydroxyl value of hydroxy polyurethane can be measured by a titration method in accordance with JIS K 1557:2007.
• hydroxy polyurethanes can be used. Examples include HPU W-001, HPU W-003, and HPU-W013A (all manufactured by Dainichiseika Kagyo Co., Ltd.).
• the content of hydroxy polyurethane in the barrier layer is preferably 30.0 to 80.0% by mass, more preferably 40.0 to 75.0% by mass, and 50.0 to 70.0% by mass. It is more preferably 55.0 to 68.0% by mass, even more preferably 60.0 to 66.0% by mass. Within the above range, it becomes easier to improve water vapor barrier properties and gas barrier properties. Further, within the above range, the strength of the barrier layer will be good, and when a heat sealing layer is provided on the barrier layer, the heat sealability will be good.
• the barrier layer preferably further includes at least one selected from the group consisting of water-suspended polymers other than hydroxypolyurethane and water-soluble polymers other than hydroxypolyurethane.
• the water-suspended polymer or water-soluble polymer can be selected from those mentioned above as resins that can be used in the barrier layer.
• the water-suspended polymer other than hydroxypolyurethane may contain at least one selected from the group consisting of a styrene/butadiene copolymer, an acrylic resin, an olefin/unsaturated carboxylic acid copolymer, and a polyolefin resin.
• Water-soluble polymers other than hydroxypolyurethane are from the group consisting of vinyl alcohol polymers, (meth)acrylic acid polymers, polyethylene glycols, water-soluble polyamides, polyacrylamide, polyamines, polycarboxylic acids, and water-soluble cellulose derivatives. It is preferable to include at least one selected from the group consisting of vinyl alcohol-based polymers and (meth)acrylic acid-based polymers.
• the film formability of the barrier layer can be improved, and the water vapor barrier properties and gas barrier properties can be improved.
• water-soluble polymers are more effective in improving film formability than water-suspended polymers.
• the barrier layer preferably contains a water-suspended polymer and a water-soluble polymer.
• the water-suspended polymer is preferably an olefin/unsaturated carboxylic acid copolymer, and more preferably an ethylene/(meth)acrylic acid copolymer.
• a vinyl alcohol polymer is preferable.
• the ratio by mass of the water-suspended polymer content and the water-soluble polymer content is preferably 20:1 to 1: 2, more preferably 10:1 to 2:3, still more preferably 5:1 to 3:4, even more preferably 4:1 to 4:5.
• Styrene-butadiene copolymers are made by combining styrene compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene with 1,3-butadiene, isoprene (2-methyl-1,3 -butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc., and other compounds copolymerizable with these monomers. It is a copolymer. Styrene is preferred as the styrene compound, and 1,3-butadiene is preferred as the butadiene compound.
• the acid-modified styrene-butadiene copolymer binder includes LX407S12 (manufactured by Nippon Zeon Co., Ltd.).
• Styrene/acrylic copolymers combine styrene compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene with acrylic acid, methacrylic acid, (meth)acrylic ester, and ) Emulsion polymerization of monomers consisting of acrylic compounds such as acrylamide propane sulfonic acid, sulfoalkyl sodium (meth)acrylate (alkyl group has 2 to 3 carbon atoms), and other compounds copolymerizable with these.
• styrene compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene with acrylic acid, methacrylic acid, (meth)acrylic ester, and ) Emulsion polymerization of monomers consisting of acrylic compounds such as acrylamide propane sulf
• the (meth)acrylic ester is preferably an acrylic alkyl ester, and the alkyl group preferably has 1 to 6 carbon atoms.
• styrene/acrylic copolymers can also be used.
• examples of the styrene-acrylic copolymer binder include JONCRYL HSL-9012 (manufactured by BASF).
• Olefin/unsaturated carboxylic acid copolymers include olefins, especially ⁇ -olefins such as propylene, or ethylene, and acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, fumaric acid, maleic acid, butene tricarboxylic acid.
• Unsaturated carboxylic acids such as acids, unsaturated polycarboxylic acid alkyl esters having at least one carboxy group, such as itaconic acid monoethyl ester, fumaric acid monobutyl ester, and maleic acid monobutyl ester, and copolymerizable with these. It is a copolymer obtained by emulsion polymerization of monomers made of other compounds.
• ethylene or ⁇ -olefin is preferable, and ethylene is more preferable.
• unsaturated carboxylic acid monomer acrylic acid, methacrylic acid, itaconic acid, fumaric acid, etc. are suitable.
• olefin/unsaturated carboxylic acid copolymer examples include, for example, an aqueous dispersion of an ethylene/acrylic acid copolymer ammonium salt such as Zaixen (registered trademark) AC (copolymerization ratio of acrylic acid 20%, Sumitomo It is commercially available as (manufactured by Seikasha) and can be easily obtained and used.
• Zaixen registered trademark
• AC copolymerization ratio of acrylic acid 20%, Sumitomo It is commercially available as (manufactured by Seikasha) and can be easily obtained and used.
• polyolefin resin a polymer of ethylene or an ⁇ -olefin is preferable, and polyethylene is more preferable.
• commercially available polyolefins can also be used.
• the polyolefin resin binder includes HYDRECT HS (manufactured by DIC).
• vinyl alcohol polymers include polyvinyl alcohol.
• the saponification degree of polyvinyl alcohol is preferably 85.0 to 99.5 mol%, more preferably 90.0 to 99.0 mol%.
• Commercially available polyvinyl alcohol can also be used. Examples include the EXCEVAL series (manufactured by Kuraray).
• Examples of the (meth)acrylic acid polymer include polyacrylic acid, polymethacrylic acid, and salts thereof.
• Examples of the salt include sodium poly(meth)acrylate and ammonium poly(meth)acrylate.
• Commercially available (meth)acrylic acid polymers can also be used.
• examples of the aqueous ammonium polyacrylate solution include Aron A-30 (manufactured by Toagosei Co., Ltd.).
• water-soluble polymers such as polyethylene glycol, water-soluble polyamide, polyacrylamide, polyamine, polycarboxylic acid, and water-soluble cellulose derivatives can be used.
• the polycarboxylic acid include polymaleic acid, acrylic acid-maleic acid copolymer, and polyglucuronic acid.
• water-soluble cellulose derivatives include methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, and methylhydroxyethylcellulose.
• the weight average molecular weight of the water-suspended polymer and water-soluble polymer is preferably 10,000 or more, more preferably 20,000 or more, and preferably 10,000,000 or less, more preferably 5,000,000 or less.
• the weight average molecular weight of the water-suspended polymer is measured using gel permeation chromatography (standard substance: polystyrene).
• the weight average molecular weight of the water-soluble polymer is measured using gel permeation chromatography (standard substance: polyethylene glycol).
• the total content of water-suspended polymers other than hydroxypolyurethane and water-soluble polymers other than hydroxypolyurethane in the barrier layer is preferably from 2.0 to 50.0% by mass, and from 5.0 to 45% by mass. It is more preferably 0% by mass, even more preferably 10.0 to 35.0% by mass, and even more preferably 15.0 to 25.0% by mass. Within the above range, it becomes easier to improve water vapor barrier properties and gas barrier properties, and the heat sealability also becomes better.
• the barrier layer may contain a layered inorganic compound in order to more easily improve water vapor barrier properties and gas barrier properties.
• the layered inorganic compound has a tabular shape.
• the plate-like layered inorganic compound can be easily laminated substantially parallel to the plane (surface) of the paper base material. In this case, since the area where the layered inorganic compound does not exist becomes smaller in the planar direction, the permeation of water vapor is likely to be suppressed.
• the layered inorganic compounds in the thickness direction are arranged parallel to the plane of the paper base material, water vapor in the layer passes through the layered inorganic compounds while bypassing the layered inorganic compounds, and due to the labyrinth effect, Water vapor transmission is suppressed. As a result, the barrier layer tends to exhibit excellent water vapor barrier properties.
• the average thickness of the layered inorganic compound is preferably 200 nm or less.
• the average thickness of the layered inorganic compound is preferably 120 nm or less, more preferably 50 nm or less, even more preferably 25 nm or less, and particularly preferably 10 nm or less.
• the smaller the thickness of the layered inorganic compound the greater the number of laminated layers of the layered inorganic compound in the barrier layer, so that high water vapor barrier properties can be exhibited.
• the lower limit of the thickness of the layered inorganic compound is not particularly limited, it is preferably 2 nm or more.
• the average thickness of the layered inorganic compound contained in the barrier layer is determined as follows.
• An enlarged photograph of the cross section of the barrier layer is taken using an electron microscope. At this time, the magnification is set so that about 20 to 30 layered inorganic compounds are included in the screen. Measure the thickness of each layered inorganic compound in the screen. Then, the average value of the obtained thicknesses is calculated and set as the average thickness of the layered inorganic compound.
• the average length of the layered inorganic compound is preferably 1 ⁇ m or more and 100 ⁇ m or less. When the average length is 1 ⁇ m or more, the layered inorganic compound is likely to be arranged parallel to the paper base material. Moreover, when the average length is 100 ⁇ m or less, there is little concern that a part of the layered inorganic compound will protrude from the barrier layer.
• the average length of the layered inorganic compound is more preferably 50 ⁇ m or less, even more preferably 30 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
• the average length of the layered inorganic compound contained in the barrier layer is determined as follows. An enlarged photograph of the cross section of the barrier layer is taken using an electron microscope.
• the magnification is set so that about 20 to 30 layered inorganic compounds are included in the screen. Measure the length of each layered inorganic compound in the screen. Then, the average value of the obtained lengths is calculated and set as the average length of the layered inorganic compound. Note that the length of the layered inorganic compound is sometimes described in terms of particle diameter.
• the layered inorganic compound preferably has an aspect ratio of 50 or more.
• the aspect ratio of the layered inorganic compound is preferably 80 or more, more preferably 300 or more, and particularly preferably 500 or more.
• the larger the aspect ratio the lower the amount of layered inorganic compound added.
• the upper limit of the aspect ratio is not particularly limited, and from the viewpoint of the viscosity of the coating liquid, it is preferably about 10,000 or less, more preferably about 5,000 or less, and even more preferably about 2,000 or less.
• the aspect ratio is the value obtained by taking an enlarged photograph of the cross section of the barrier layer using an electron microscope and dividing the average length of the obtained layered inorganic compound by its average thickness, as described above. be.
• layered inorganic compounds include mica such as mica group and brittle mica group, bentonite, kaolinite (kaolin mineral), pyrophyllite, talc, smectite, vermiculite, chlorite, septechlorite, serpentine, and stilp. Examples include nomelene and montmorillonite.
• mica and bentonite examples include synthetic mica (e.g., swellable mica, non-swellable mica), muscovite, sericite, phlogopite, biotite, and fluorine.
• examples include phlogopite (artificial mica), red mica, soda mica, vanadium mica, illite, chimney mica, paragonite, and brittle mica.
• bentonite includes montmorillonite.
• the barrier layer preferably comprises a swellable layered silicate, such as swellable mica.
• the barrier layer comprises a hydroxy polyurethane and a swellable layered silicate.
• a swellable layered silicate is a layered inorganic compound that is swellable in water and whose layers are easily cleaved by shearing to a thickness on the order of nanometers.
• a thin swellable phyllosilicate with a high aspect ratio is dispersed in the hydroxypolyurethane resin film, which inherently has high gas barrier performance, and the labyrinth effect further enhances the Demonstrates high gas barrier performance.
• the swellable layered silicate include sodium tetrasilicon mica, sodium hectorite, lithium taeniolite, fluorophlogopite, sodium smectite, and sodium montmorillonite.
• the swellable layered silicate is preferably a swellable mica such as sodium tetrasilicate mica.
• examples of swellable mica include NTO-05 (manufactured by Topy Industries) and Somasif ME300B-4T (manufactured by Katakura Co-op Agri).
• the content of the swellable layered silicate in the barrier layer is preferably 5.0 to 30.0% by mass, more preferably 10.0 to 25.0% by mass, and 13.0 to 24% by mass. More preferably, it is .0% by mass. Within the above range, it becomes easier to improve water vapor barrier properties and gas barrier properties.
• the barrier layer preferably contains a cationic resin in addition to the hydroxypolyurethane and the swellable layered silicate.
• a cationic resin in addition to the hydroxypolyurethane and the swellable layered silicate.
• gas barrier properties and water vapor barrier properties, particularly water vapor barrier properties are greatly improved, making it easier to achieve the above-mentioned specific ranges of oxygen permeability and water vapor permeability.
• Swellable layered silicate particles tend to be anionically charged on the particle surface and cationically charged on the particle end surfaces, so the surface and end surfaces tend to attract each other and form a card house aggregate structure.
• the anionic groups on the particle surface can be blocked with cations, and the card house aggregate structure can be destroyed. Therefore, steric aggregation of the swellable phyllosilicate can be suppressed, the swellable phyllosilicate can be aligned parallel to the plane of the paper base material, and the labyrinth effect can be sufficiently expressed. As a result, extremely high gas barrier properties and water vapor barrier properties can be exhibited.
• cationic resins include polyalkylene polyamines, polyamide compounds, modified polyamide compounds, polyamide amine-epihalohydrin or formaldehyde condensation reaction products, polyamine-epihalohydrin or formaldehyde condensation reaction products, polyamide polyurea-epihalohydrin or formaldehyde condensation products.
• the cationic resin is preferably a modified polyamide compound, more preferably a modified polyamide resin.
• modified polyamide resins may be used, such as SPI203(50)H, manufactured by Taoka Chemical Industry, etc.
• the content of the cationic resin in the barrier layer may be appropriately selected depending on the type of material used for the barrier layer, such as hydroxy polyurethane and swellable layered silicate. From the viewpoint of further improving barrier properties and/or heat sealability, the content of the cationic resin in the barrier layer is preferably 1.0 to 20.0% by mass, and preferably 1.0 to 10.0% by mass. is more preferably 1.5 to 8.0% by mass, even more preferably 1.8 to 5.0% by mass, and even more preferably 2.0 to 3.0% by mass. Particularly preferred.
• the surface charge of the cationic resin is preferably 0.1 to 10 meq/g, more preferably 0.1 to 5.0 meq/g, and preferably 0.1 to 4.0 meq/g. It is more preferably 0.1 to 2.0 meq/g, even more preferably 0.2 to 1.0 meq/g.
• the surface charge of the cationic resin is at least the above lower limit, the effect of adding the cationic resin can be more fully obtained.
• the surface charge is below the above upper limit, the effect of the cationic resin can be more fully exhibited while suppressing aggregation of the swellable layered silicate. Note that the surface charge of the cationic resin is measured by the method described below.
• a sample polymer is dissolved in water to obtain a solution with a polymer concentration of 1 ppm.
• a charge analyzer Mutek PCD-04 manufactured by BTG
• 0.001N sodium polyethylene sulfonate is added dropwise to the solution to measure the amount of charge.
• Dispersants, surfactants, antifoaming agents, wetting agents, dyes, color adjusters, thickeners, etc. may be added to the barrier layer as necessary to the extent that the above-mentioned specific barrier properties are not impaired. is possible.
• the coating amount of the barrier layer is not particularly limited, but from the viewpoint of barrier properties, the solid content after drying is preferably 1 g/m 2 or more, more preferably 2 g/m 2 or more, and From the viewpoint of performance, it is preferably 15 g/m 2 or less, more preferably 10 g/m 2 or less, even more preferably 8 g/m 2 or less, and even more preferably 6 g/m 2 or less.
• the thickness of the barrier layer is preferably 1 to 20 ⁇ m, more preferably 2 to 10 ⁇ m.
• the method of forming the barrier layer is not particularly limited.
• a barrier layer coating containing at least one resin selected from the group consisting of water-suspending polymers other than hydroxypolyurethane and water-soluble polymers, hydroxypolyurethane, a swellable layered silicate, and a cationic resin dispersed in a solvent may be used.
• the solvent for the barrier layer coating solution is not particularly limited, and water or organic solvents such as ethanol, isopropyl alcohol, methyl ethyl ketone, and toluene can be used.
• an aqueous medium is preferable as a dispersion medium for the barrier layer coating liquid, and water is more preferable.
• the aqueous medium is a medium containing 50% by mass or more of water.
• the device used for coating the barrier layer coating solution is not particularly limited, and may be appropriately selected from commonly used coating devices.
• coating devices For example, air knife coater, blade coater, gravure coater, rod blade coater, roll coater, reverse roll coater, Meyer bar coater, curtain coater, die slot coater, Champlex coater, metering blade type size press coater, short dwell coater,
• Various known coating devices such as a spray coater, a gate roll coater, and a lip coater can be used.
• the barrier laminate may further include a heat seal layer on the side on which the barrier layer is laminated.
• the heat seal layer does not satisfy both the water vapor permeability and oxygen permeability ranges of the barrier layer, for example.
• the heat seal layer may satisfy either the water vapor permeability or oxygen permeability range of the barrier layer described above, for example.
• the heat seal layer may have barrier properties such as water vapor barrier properties and gas barrier properties.
• the heat seal layer may satisfy at least one or both of the water vapor permeability and oxygen permeability ranges of the barrier layer described above.
• the heat seal layer is a layer that is melted and bonded by heating, ultrasonic waves, etc.
• the heat seal layer preferably contains a water-dispersible resin.
• water-dispersible resins include those mentioned above as water-dispersible polymers other than hydroxypolyurethane, preferably polyolefin resins, styrene/acrylic copolymers, ethylene-(meth)acrylic acid copolymers, etc.
• examples include acrylic resins, ethylene-vinyl acetate copolymers, polyester resins, rubber resins, urethane resins, and polyamide resins.
• lubricants such as paraffin wax, carnauba wax, and polyolefin wax, and pigments such as silica and kaolin may be added for the purpose of preventing blocking and improving oil resistance.
• the heat seal layer is preferably a layer containing at least one resin selected from the group consisting of a styrene/acrylic copolymer and a polyolefin resin.
• a resin selected from the group consisting of a styrene/acrylic copolymer and a polyolefin resin.
• Commercially available materials include styrene acrylic aqueous dispersion (product name: XP8829, manufactured by Seiko PMC), polyolefin aqueous dispersion (product name: Rhobarr320, manufactured by Dow), and the like.
• the water vapor permeability of the heat seal layer at 40° C. and 90% RH is, for example, about 1 to 100 g/m 2 ⁇ day when converted to a thickness of 20 ⁇ m.
• the oxygen permeability of the heat seal layer at 23° C. and 50% RH is, for example, about 1 to 100 mL/m 2 ⁇ day ⁇ atm when converted to a thickness
• the coating amount of the heat seal layer is not particularly limited, but from the viewpoint of heat sealability, the solid content after drying is preferably 1 g/m 2 or more, more preferably 2 g/m 2 or more, and, From the viewpoint of redisintegrability, it is preferably 15 g/m 2 or less, more preferably 10 g/m 2 or less, even more preferably 8 g/m 2 or less, and even more preferably 6 g/m 2 or less.
• the thickness of the heat seal layer is preferably 0.5 to 20 ⁇ m, more preferably 1 to 10 ⁇ m.
• the method of forming the heat seal layer is not particularly limited.
• a heat seal layer coating liquid is prepared by dispersing a water-dispersible resin in a solvent. It is preferable to apply the obtained heat-seal layer coating liquid onto a barrier layer of a paper base material and dry it to form a heat-seal layer.
• the solvent for the heat seal layer coating liquid is not particularly limited, and water or organic solvents such as ethanol, isopropyl alcohol, methyl ethyl ketone, and toluene can be used. Among these, from the viewpoint of not causing the problem of volatile organic solvents, an aqueous medium is preferable as a dispersion medium for the heat seal layer coating liquid, and water is more preferable.
• the total coating amount of the barrier layer and the heat seal layer is preferably 12 g/m 2 or less, more preferably 11 g/m 2 or less. Being within the above range means that even if the layer is thin, it can exhibit very high gas barrier properties and water vapor barrier properties. Furthermore, within the above range, the recovery rate of pulp can be easily increased, the weight of the product can be further reduced, and the biodegradation performance can be further improved.
• the lower limit of the coating amount is not particularly limited, but is preferably 2 g/m 2 or more, more preferably 5 g/m 2 or more, and still more preferably 8 g/m 2 or more.
• the heat-sealing strength was 2.0N when the heat-sealing layers of the barrier laminate were peeled using a tensile tester using a sample obtained by heat-sealing the heat-sealing layers at 150°C, 0.2MPa, and 1 second. /15mm or more, more preferably 2.5N/15mm or more, even more preferably 2.8N/15mm or more, even more preferably 3.0N/15mm or more.
• the upper limit is not particularly limited, but is preferably 10.0 N/15 mm or less, 7.0 N/15 mm or less, 5.0 N/15 mm or less, and 4.0 N/15 mm or less.
• the barrier laminate may have other layers in addition to the barrier layer and heat seal layer described above.
• the other layer may have barrier properties such as a water vapor barrier layer and a gas barrier layer.
• the method for manufacturing the barrier laminate is not particularly limited, and any known method may be employed.
• the method for producing a barrier laminate includes the step of first coating a barrier layer coating liquid on a paper base material to form a barrier layer. If necessary, the method may include a step of forming a heat seal layer by applying a heat seal layer coating liquid to the surface of the paper base coated with the barrier layer.
• the formation of each layer is as described above. Note that each layer may be formed by sequentially applying and drying a coating liquid, or may be formed by simultaneously applying multiple layers and then drying.
• the drying equipment for drying each coating layer is not particularly limited, and any known equipment can be used. Examples of the drying equipment include a hot air dryer, an infrared dryer, a gas burner, and a hot plate.
• the barrier laminate has a barrier layer on at least one surface of the paper base material.
• the barrier laminate preferably has a paper base material, a barrier layer, and a heat seal layer in this order.
• the barrier laminate may be a laminate consisting only of a paper base material and a single barrier layer, or may be a laminate consisting only of a paper base material, a single barrier layer, and a heat seal layer.
• a second aspect of the present disclosure is a barrier laminate having a barrier layer on at least one surface of a paper base material, the barrier layer comprising (A) hydroxy polyurethane, (B) swellable A barrier laminate containing a layered silicate and (C) a cationic resin is provided.
• the barrier layer comprising (A) hydroxy polyurethane, (B) swellable A barrier laminate containing a layered silicate and (C) a cationic resin.
• the barrier layer containing the components (A) to (C) above exhibits excellent water vapor barrier properties and gas barrier properties even with one layer, but may have two or more layers. Furthermore, in the second embodiment, when the film further includes another layer (for example, a heat seal layer), the other layer may have barrier properties such as a water vapor barrier layer and a gas barrier layer. That is, in the second embodiment, the water vapor permeability and oxygen permeability may include contributions from other layers in addition to the barrier layer containing the components (A) to (C).
• the barrier laminate can be suitably used as a packaging material for foods, cosmetics, daily necessities, medical products, electronic parts, and the like. Since the barrier laminate has very high water vapor barrier properties and gas barrier properties, it can also be suitably used as a packaging material for contents having aromas and odors. It can also be suitably used as a packaging material for foods, cosmetics, daily necessities, medical products, electronic parts, etc. that are exposed to high humidity conditions. Barrier laminates are suitable for use in soft packaging materials such as wrapping paper, packaging bags, lids, and labels; liquid containers such as milk cartons; packaging containers such as cups, trays, plates, lidding materials, and laminated tubes; etc. be able to. The contents to be packaged may be liquid, solid (granules, powder, etc.), or gel.
• a packaging bag according to another embodiment of the present disclosure is a packaging bag using the barrier laminate described above.
• Examples of packaging bags include standing pouch type, side seal type, two side seal type, three side seal type, four side seal type, envelope sticker type, gasho sticker type (pillow seal type), pleated seal type, and flat bottom seal type.
• Forms include a type, a square bottom seal type, and a gusset type.
• the packaging bag of this embodiment is one in which a barrier laminate having a heat seal layer is folded or two layers are stacked so that the heat seal layers face each other, and the peripheral edges of the barrier laminate are heat sealed to obtain the above form. It may be. Further, the packaging bag may be made by folding or stacking two barrier laminates and bonding the peripheral edges thereof with an adhesive so as to have the above-mentioned configuration.
• the oxygen permeability of the barrier laminate was measured using an oxygen permeability measuring device (OX-TRAN2/22, manufactured by MOCON) under conditions of a temperature of 23° C. and a relative humidity of 50%. Specifically, 5 g/m of isocyanate adhesive (manufactured by DIC Corporation, a mixture of 10 parts of Dick Dry LX-500 and 1 part of Dick Dry KW-75) was applied to the barrier layer surface of the barrier laminate. After coating 2 , a 20 ⁇ m thick CPP film (non-oriented polypropylene film: manufactured by Hokuetsu Kasei Co., Ltd., GP-32) was laminated to form a laminated sheet.
• OX-TRAN2/22 oxygen permeability measuring device
• the oxygen permeability of the laminated sheet was measured at a temperature of 23° C. and a relative humidity of 50% in accordance with JIS K7126-2:2006.
• the thickness of the heat seal layer can be measured by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like.
• the oxygen permeability of the heat seal layer alone can be estimated by applying the heat seal layer to an unstretched polypropylene film or PET film so that the thickness of the heat seal layer is the same as that measured.
• Step 3 From the oxygen permeability of the barrier laminate in step 1 and the oxygen permeability of the heat seal layer alone in step 2, calculate the oxygen permeability of the barrier layer alone based on the following formula. At this time, the oxygen permeability of the paper base material must not be taken into account if glassine paper is not used as the paper base material (as a guideline, if the total light transmittance of the barrier laminate is less than 60%). good.
• 1/P 1/P 1 +1/P 2 +...+1/P n
• P Oxygen permeability of the barrier laminate
• P 1 , P 2 ,...P n Oxygen permeability of each layer
• the barrier laminate has a layer structure of paper base material/barrier layer/heat seal layer
• the calculation is performed as follows.
• the layer structure of the barrier laminate can be analyzed by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like.
• Procedure 1 Measure the oxygen permeability of the barrier laminate.
• the oxygen permeability of the barrier laminate can be measured by the method described above.
• Step 2 Analyze the material and thickness of the heat seal layer.
• the material of the heat seal layer can be analyzed by pyrolysis GC/MS, FT-IR analysis, Raman spectrum analysis, etc.
• the thickness of the heat seal layer can be measured by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like.
• the oxygen permeability of the heat seal layer alone can be estimated from the material and thickness of the heat seal layer.
• Step 3 From the oxygen permeability of the barrier laminate in step 1 and the oxygen permeability of the heat seal layer alone in step 2, calculate the oxygen permeability of the barrier layer alone based on the following formula. At this time, the oxygen permeability of the paper base material must not be taken into account if glassine paper is not used as the paper base material (as a guideline, if the total light transmittance of the barrier laminate is less than 60%). good.
• 1/P 1/P 1 +1/P 2 +...+1/P n
• P Oxygen permeability of the barrier laminate
• P 1 , P 2 ,...P n Oxygen permeability of each layer
• the water vapor permeability of the barrier layer at 40° C. and 90% RH can be calculated by the following procedure. (If materials for layers other than the barrier layer, such as heat seal layer, are available) For example, when the barrier laminate has a layer structure of paper base material/barrier layer/heat seal layer, the calculation is performed as follows. Note that the layer structure of the barrier laminate can be analyzed by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like (analysis method). Procedure 1: Measure the water vapor permeability of the barrier laminate. The water vapor permeability of the barrier laminate can be measured by the method described above. Step 2: Analyze the thickness of the heat seal layer.
• the thickness of the heat seal layer can be measured by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like.
• the water vapor permeability of the heat-sealing layer alone can be estimated by applying the heat-sealing layer to an unstretched polypropylene film or PET film so as to have the measured thickness of the heat-sealing layer.
• Step 3 From the water vapor permeability of the barrier laminate in Step 1 and the water vapor permeability of the heat seal layer alone in Step 2, calculate the water vapor permeability of the barrier layer alone based on the following formula.
• the oxygen permeability of the paper base material must not be taken into account if glassine paper is not used as the paper base material (as a guideline, if the total light transmittance of the barrier laminate is less than 60%). good.
• 1/P 1/P1+1/P2+...+1/Pn
• P water vapor permeability of barrier laminate
• P1, P2,...Pn water vapor permeability of each layer
• the barrier laminate has a layer structure of paper base material/barrier layer/heat seal layer
• the layer structure of the barrier laminate can be analyzed by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like (analysis method).
• Procedure 1 Measure the water vapor permeability of the barrier laminate.
• the water vapor permeability of the barrier laminate can be measured by the method described above.
• Step 2 Analyze the material and thickness of the heat seal layer.
• the material of the heat seal layer can be analyzed by pyrolysis GC/MS, FT-IR analysis, Raman spectrum analysis, etc.
• the thickness of the heat seal layer can be measured by cross-sectional observation using an electron microscope, X-ray CT measurement, or the like.
• the water vapor permeability of the heat seal layer alone can be estimated from the material and thickness of the heat seal layer.
• Step 3 From the water vapor permeability of the barrier laminate in Step 1 and the water vapor permeability of the heat seal layer alone in Step 2, calculate the water vapor permeability of the barrier layer alone based on the following formula.
• the oxygen permeability of the paper base material must not be taken into account if glassine paper is not used as the paper base material (as a guideline, if the total light transmittance of the barrier laminate is less than 60%). good.
• 1/P 1/P1+1/P2+...+1/Pn
• P water vapor permeability of barrier laminate
• P1, P2,...Pn water vapor permeability of each layer
• a barrier laminate with an absolutely dry mass of 30 g was torn by hand into 3 to 4 cm square pieces and soaked in tap water at 20° C. overnight. After diluting with tap water so that the concentration of the barrier laminate was 2.5% by mass, it was disintegrated for 20 minutes at a rotation speed of 3000 rpm using a TAPPI standard disintegrator (manufactured by Kumagai Riki Co., Ltd.).
• Pulp recovery rate (%) ⁇ absolute dry mass (g) of barrier laminate subjected to test - absolute dry mass (g) of undisintegrated material ⁇ /absolute dry mass of barrier laminate subjected to test x 100
• the heat-sealed test piece was cut into 15 mm width, and T-shaped peeling was performed at a tensile speed of 300 mm/min using a tensile tester (Tensilon Universal Material Tester RTC-1250A, manufactured by A&D Co., Ltd.). The maximum load recorded was taken as the heat seal peel strength (N/15 mm).
• Example 1 Aqueous dispersion of layered inorganic compound (swellable mica (sodium tetrasilicon mica), average length 6.3 ⁇ m, aspect ratio approximately 1000, thickness approximately 5 nm, solid content concentration 6% by mass, product name: NTO-05, Topy (Industrial product) 33.3 parts by mass, and 6.8 parts by mass of a self-emulsifying emulsion of ethylene/acrylic acid copolymer (solid content concentration 29.2% by mass, product name: Zaixen AC, manufactured by Sumitomo Seika Chemical) while stirring.
• layered inorganic compound swellable mica (sodium tetrasilicon mica), average length 6.3 ⁇ m, aspect ratio approximately 1000, thickness approximately 5 nm, solid content concentration 6% by mass, product name: NTO-05, Topy (Industrial product) 33.3 parts by mass, and 6.8 parts by mass of a self-emulsifying emulsion of ethylene/acrylic acid copolymer (solid content
• a barrier layer coating solution was added to make the solid content concentration 19% by mass to obtain a barrier layer coating solution.
• the above barrier layer coating solution was applied to one side of a paper base material of 50 g/m 2 (single gloss bleached kraft paper, manufactured by Oji F-Tex Co., Ltd.) so that the solid content was 5 g/m 2 and heated to 120°C. was dried for 1 minute to form a barrier layer.
• a coating liquid for the heat seal layer a styrene acrylic aqueous dispersion (solid content concentration 48% by mass, product name: XP8829, manufactured by Seiko PMC) was diluted with water to a solid content concentration of 22% by mass, and the solid content was 5 g.
• the heat seal layer has an oxygen permeability of more than 10.0 mL/m 2 ⁇ day ⁇ atm at 23° C. and 50% RH, and does not correspond to the barrier layer in the first embodiment.
• Example 2 Same as Example 1 except that the self-emulsifying emulsion of ethylene/acrylic acid copolymer in the barrier layer coating liquid was 13.7 parts by mass, and the self-emulsifying aqueous emulsion of hydroxypolyurethane was 20.0 parts by mass.
• a barrier layer and a heat-sealing layer were formed on the paper base material to obtain a heat-sealable barrier laminate.
• Example 3 A barrier layer and a heat-sealable layer were formed on a paper base material in the same manner as in Example 1, except that the swellable mica in the barrier layer coating liquid was changed to 50 parts by mass, and a heat-sealable barrier laminate was obtained. Obtained.
• Example 4 A barrier layer and a heat seal layer were formed on the paper base material in the same manner as in Example 1, except that the paper base material was bleached kraft paper 70 g/m 2 (OK bleached kraft, manufactured by Oji Materia Co., Ltd.), A heat-sealable barrier laminate was obtained.
• Example 5 Other than changing the self-emulsifying emulsion of ethylene-acrylic acid copolymer to 5.1 parts by mass of styrene-acrylic copolymer binder (solid content concentration 39% by mass, product name: JONCRYL HSL-9012, manufactured by BASF) A barrier layer and a heat seal layer were formed on a paper base material in the same manner as in Example 1 to obtain a heat sealable barrier laminate.
• Example 6 Other than changing the self-emulsifying emulsion of ethylene/acrylic acid copolymer to 4.3 parts by mass of acid-modified styrene-butadiene copolymer binder (solid content concentration 46% by mass, product name: LX407S12, manufactured by Nippon Zeon Co., Ltd.) A barrier layer and a heat seal layer were formed on a paper base material in the same manner as in Example 1 to obtain a heat sealable barrier laminate.
• Example 7 Same as Example 1 except that the self-emulsifying emulsion of ethylene/acrylic acid copolymer was changed to 8.7 parts by mass of polyolefin resin binder (solid content concentration 23% by mass, product name: HYDRECT HS, manufactured by DIC). A barrier layer and a heat-sealing layer were formed on the paper base material to obtain a heat-sealable barrier laminate.
• Example 8 A barrier layer and a heat-sealable layer were formed on a paper base material in the same manner as in Example 1, except that the cationic resin in the barrier layer coating solution was 1.90 parts by mass, and a heat-sealable barrier laminate was obtained. I got a body.
• Example 9 20.0 parts by mass of an aqueous solution of a self-emulsifying emulsion of ethylene/acrylic acid copolymer dissolved in water with polyvinyl alcohol (product name: EXCEVAL HR-3010, manufactured by Kuraray Co., Ltd.) at a solid content concentration of 10% by mass.
• a barrier layer and a heat-sealing layer were formed on a paper base material in the same manner as in Example 1, except that the above was changed to obtain a heat-sealable barrier laminate.
• Example 10 A barrier layer and A heat-sealable layer was formed to obtain a heat-sealable barrier laminate.
• the heat seal layer has a water vapor permeability of 50 g/m 2 ⁇ day or more at 40°C and 90% RH, and an oxygen permeability of 10.0 mL/m 2 ⁇ day at 23°C and 50% RH. ATM, and does not correspond to the barrier layer in the first embodiment.
• Example 11 A self-emulsifying emulsion of ethylene/acrylic acid copolymer was mixed with an aqueous ammonium polyacrylate solution (solid content concentration 30% by mass, product name: Aron A-30, manufactured by Toagosei Co., Ltd.) so that the solid content concentration was 5% by mass.
• a barrier layer and a heat-sealing layer were formed on a paper base material in the same manner as in Example 1, except that the aqueous solution was changed to 40.0 parts by mass, and a heat-sealable barrier laminate was obtained.
• Example 12 The number of parts added of the self-emulsifying emulsion of ethylene/acrylic acid copolymer was changed to 3.4 parts by mass, and the solid content concentration of polyvinyl alcohol (product name: EXCEVAL HR-3010, manufactured by Kuraray Co., Ltd.) was increased to 10% by mass.
• a barrier layer and a heat-sealing layer were formed on a paper base material in the same manner as in Example 10, except that 10.0 parts by mass of an aqueous polyvinyl alcohol solution dissolved in water was added to the barrier layer coating solution. A sealable barrier laminate was obtained.
• Example 13 The self-emulsifying emulsion of hydroxy polyurethane in the barrier layer coating liquid was 31.7 parts by mass, the self-emulsifying aqueous emulsion of ethylene-acrylic acid copolymer was 1.7 parts by mass, and the cationic resin was 1.90 parts by mass.
• a barrier layer and a heat seal layer were formed on a paper base material in the same manner as in Example 10, except that the coating amount of the heat seal layer was changed to 3 g/m 2 (solid content equivalent). A sealable barrier laminate was obtained.
• Example 14 A barrier layer was formed on a paper base material to obtain a barrier laminate in the same manner as in Example 1 except that the heat seal layer coating liquid was not applied.
• Example 15 Except that the swelling mica in the barrier layer coating liquid was changed to 83.3 parts by mass, the cationic resin was changed to 5.7 parts by mass, and the coating amount of the heat seal layer was changed to 3 g/m 2 (solid content equivalent).
• a barrier layer and a heat-sealing layer were formed on a paper base material to obtain a heat-sealable barrier laminate.
• Example 16 The number of parts added of the self-emulsifying emulsion of ethylene/acrylic acid copolymer was changed to 5.1 parts by mass, and the solid content concentration of polyvinyl alcohol (product name: EXCEVAL RS-1717, manufactured by Kuraray Co., Ltd.) was changed to 10% by mass.
• Example 10 except that 5.0 parts by mass of a polyvinyl alcohol aqueous solution dissolved in water was added to the barrier layer coating solution and the coating amount of the heat seal layer was changed to 3 g/m 2 (solid content equivalent).
• a barrier layer and a heat-sealing layer were formed on a paper base material to obtain a heat-sealable barrier laminate.
• Example 1 The same procedure as in Example 1 was carried out, except that the self-emulsifying emulsion of ethylene/acrylic acid copolymer in the barrier layer coating liquid was 34.2 parts by mass, and the self-emulsifying aqueous emulsion of hydroxypolyurethane was 0 parts by mass.
• a barrier layer and a heat seal layer were formed on a paper base material to obtain a heat sealable barrier laminate.
• Example 2 A barrier layer and a heat seal layer were formed on a paper base material in the same manner as in Example 1, except that the swellable mica and cationic resin in the barrier layer coating liquid were 0 parts by mass, A heat-sealable barrier laminate was obtained.
• Example 3 A barrier layer and a heat-sealable layer were formed on a paper base material in the same manner as in Example 1, except that the cationic resin in the barrier layer coating solution was 0 parts by mass, and a heat-sealable barrier laminate was obtained. Obtained.
• Example 4 A barrier layer and a heat-sealable layer were formed on a paper base material in the same manner as in Example 1, except that the cationic resin in the barrier layer coating solution was 18.9 parts by mass, and a heat-sealable barrier laminate was obtained. I got a body.
• Kaolin engineered kaolin, average length 0.89 ⁇ m, aspect ratio approx. 33, thickness approx. 27 nm, solid content concentration 100% by mass, product name: Contour Extreme, manufactured by Imerys
• a barrier layer and a heat-sealing layer were formed on a paper base material in the same manner as in Example 1, except that the amount was 2 parts by mass, to obtain a heat-sealable barrier laminate.
• a self-emulsifying aqueous emulsion of hydroxy polyurethane for the barrier layer coating liquid is prepared by dissolving polyvinyl alcohol (product name: EXCEVAL AQ-4104, manufactured by Kuraray Co., Ltd.) in water to a solid content concentration of 10% by mass.
• a barrier layer and a heat seal layer were formed on a paper base material in the same manner as in Example 1, except that the amount was changed to .0 part by mass, to obtain a heat sealable barrier laminate.
• Packaging bags were produced by forming the paper laminates of Examples and Comparative Examples into pillow-shaped packaging bags and heat-sealing them. Cut one side of the resulting packaging bag, and add a heat seal checker (product name: Ageless Seal Check, manufactured by Mitsubishi Gas Chemical Co., Ltd., ingredients: high-boiling ester, high-boiling hydrocarbon, vegetable oil, azo oil-soluble dye) into the packaging bag. ) was dropped to evaluate the presence or absence of liquid leakage at the sealing part.
• A The heat seal checker liquid does not leak and is sealed.
• B The heat seal checker liquid leaks, pinholes occur, and there is no adhesion.
• the formulation (ratio of mass parts of solid content), physical properties, evaluation results, oxygen permeability and water vapor permeability of the barrier layer itself, and content ratio of each material in the barrier layer (mass %) of each obtained barrier laminate. ) are shown in Tables 1 to 3.
• the unit of coating amount is g/ m2
• the unit of oxygen permeability is mL/ m2 ⁇ day ⁇ atm
• the unit of water vapor permeability (measured under the conditions of 40°C and 90% RH).
• the unit of heat seal strength is N/15 mm.
• Redisintegration property is the recovery rate (% by mass) of pulp after redisintegration of the barrier laminate.
• the oxygen permeability of the barrier layer is the oxygen permeability of the barrier layer at 23°C and 50% RH
• the water vapor permeability of the barrier layer is the water vapor permeability of the barrier layer at 40°C and 90% RH. shows.
• water-suspended polymer, etc. indicates the total content of water-suspended polymers other than hydroxypolyurethane and water-soluble polymers other than hydroxypolyurethane.
• the oxygen permeability of the barrier layer alone was measured using an oxygen permeability measuring device (OX-TRAN2/22, manufactured by MOCON) under conditions of a temperature of 23° C. and a relative humidity of 50%.
• a barrier layer coating solution was applied to a paper base material (single gloss bleached kraft paper, basis weight 50 g/m 2 , manufactured by Oji F-Tex Co., Ltd.) using the formulation and coating amount of each example and comparative example. and dried at 120° C. for 1 minute to form a barrier layer.
• Water vapor permeability of barrier layer was determined by applying the barrier layer coating solution to a paper base material (single gloss bleached kraft paper, basis weight 50 g/m 2 , manufactured by Oji F-Tex Co., Ltd.) using the formulation and coating amount of each example and comparative example. After drying at 120°C for 1 minute to form a barrier layer, it was dried in accordance with JIS-Z-0208:1976 (cup method) B method (40°C ⁇ 0.5°C, relative humidity 90% ⁇ 2%). The measurement was made with the side on which the barrier layer was provided facing inside.
• a paper base material single gloss bleached kraft paper, basis weight 50 g/m 2 , manufactured by Oji F-Tex Co., Ltd.
• Example 14 no adhesion was observed in the measurement of heat seal strength.

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