WO2022030118A1 - Corps barrière multicouche et sac d'emballage - Google Patents

Corps barrière multicouche et sac d'emballage Download PDF

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Publication number
WO2022030118A1
WO2022030118A1 PCT/JP2021/023359 JP2021023359W WO2022030118A1 WO 2022030118 A1 WO2022030118 A1 WO 2022030118A1 JP 2021023359 W JP2021023359 W JP 2021023359W WO 2022030118 A1 WO2022030118 A1 WO 2022030118A1
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WIPO (PCT)
Prior art keywords
water vapor
less
resin
barrier laminate
layer
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PCT/JP2021/023359
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English (en)
Japanese (ja)
Inventor
三代子 田中
友史 磯▲崎▼
正啓 鶴原
裕太 社本
泰友 野一色
Original Assignee
王子ホールディングス株式会社
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Priority to JP2022541141A priority Critical patent/JPWO2022030118A1/ja
Publication of WO2022030118A1 publication Critical patent/WO2022030118A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—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
    • D21H19/72—Coated paper characterised by the paper 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed

Definitions

  • the present disclosure relates to a barrier laminate and a packaging bag using the same.
  • Packaging materials that have a water vapor barrier property or a gas barrier property, especially an oxygen barrier property, have been conventionally used in packaging of foods, medical products, electronic parts, etc. in order to prevent deterioration of the quality of the contents. ing.
  • Patent Document 1 proposes a paper barrier material in which a water vapor barrier layer and a gas barrier layer are provided in this order on a paper base material.
  • the packaging bag may be required to have visibility of the contents so that the contents and the remaining amount can be seen from the outside.
  • the paper barrier material described in Patent Document 1 has low transparency and is used as a packaging bag. Sometimes there is a problem that the visibility of the contents is poor.
  • the present disclosure provides a barrier laminate having excellent visibility of the contents when used as a packaging bag and having a good barrier property.
  • ⁇ 1> A barrier laminate having an anchor coat layer and a water vapor barrier layer on at least one surface of a paper substrate in this order, and the total light transmittance measured in accordance with JIS K 7631-1: 1997. Is 65% or more, and the arithmetic mean height of the surface on the water vapor barrier layer side measured in accordance with JIS B 0601: 2001 is 75 ⁇ m or less.
  • ⁇ 2> The barrier laminate according to ⁇ 1>, wherein the haze measured according to JIS K 7136: 2000 is 90% or less.
  • ⁇ 3> The barrier laminate according to ⁇ 1> or ⁇ 2>, wherein the maximum height of the surface on the water vapor barrier layer side measured in accordance with JIS B 0601: 2001 is 550 ⁇ m or less.
  • ⁇ 4> The barrier laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the irregular freeness of the pulp fibers constituting the paper substrate is 100 mL or more and 600 mL or less.
  • ⁇ 5> The barrier laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the coating amount of the water vapor barrier layer is 2 g / m 2 or more and 8 g / m 2 or less as the solid content after drying. ..
  • ⁇ 6> Of ⁇ 1> to ⁇ 5>, wherein the anchor coat layer and the water vapor barrier layer are provided in this order on one surface of the paper substrate, and the resin layer is provided on the other surface of the paper substrate.
  • the barrier laminate according to any one. ⁇ 7> The barrier laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the water vapor transmission rate under the conditions of 40 ° C. and 90% RH is 20 g / m 2 ⁇ day or less.
  • ⁇ 8> The barrier laminate according to any one of ⁇ 1> to ⁇ 7>, wherein the oxygen permeability under the conditions of 23 ° C. and 50% RH is 5 mL / ( m 2.24 h ⁇ atm) or less.
  • the resin constituting the anchor coat layer contains a polyester resin.
  • the water vapor barrier layer contains a water-dispersible resin binder and contains.
  • the water-dispersible resin binder is one of ⁇ 1> to ⁇ 10>, which comprises at least one selected from the group consisting of a styrene / acrylic copolymer and an olefin / unsaturated carboxylic acid copolymer.
  • ⁇ 12> The barrier laminate according to ⁇ 11>, wherein the water vapor barrier layer further contains a cationic resin and a layered inorganic compound.
  • ⁇ 13> The barrier laminate according to any one of ⁇ 1> to ⁇ 12>, which is a packaging material.
  • ⁇ 14> A packaging bag using the barrier laminate according to any one of ⁇ 1> to ⁇ 12>.
  • X to Y indicating a range means “X or more and Y or less”.
  • the upper and lower limits of each numerical range can be arbitrarily combined.
  • the operation and the measurement of physical properties are performed under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 50% RH.
  • the barrier laminate according to the embodiment of the present invention (hereinafter, also simply referred to as “barrier laminate”) has an anchor coat layer and a water vapor barrier layer on at least one surface of a paper substrate in this order, and is JIS.
  • the total light transmittance measured according to K 7631-1: 1997 is 65% or more, and the arithmetic mean height of the surface on the water vapor barrier layer side measured according to JIS B 0601: 2001 is 75 ⁇ m or less.
  • the barrier laminate of the present embodiment has excellent visibility of the contents when used as a packaging bag and has good barrier properties.
  • the present embodiment will be described in detail.
  • the irregular freeness of the pulp fibers constituting the paper substrate is preferably 100 mL or more, more preferably 150 mL or more, still more preferably 200 mL or more, from the viewpoint of dimensional stability of the paper substrate. Is. Further, the irregular freeness of the pulp fiber constituting the paper base material is preferably 600 mL or less, more preferably 500 mL or less, still more preferably 400 mL or less, from the viewpoint of the transparency of the paper base material.
  • Known methods can be used for beating pulp to prepare anomalous freeness.
  • “irregular freeness” means that the pulp sampling amount is changed from 3 g to 0.3 g and the JIS standard screen plate is changed to 80 mesh wire in the Canadian standard freeness method specified in JIS P 8121: 2012. It is the freeness (degree of drainage) measured in the above.
  • the anomalous freeness of the pulp constituting the paper substrate is measured by the above-mentioned method using the pulp dissociated according to JIS P 820-1: 2012 as a sample.
  • the irregular freeness of the pulp fiber constituting the paper base material is also referred to as "the irregular freeness of the dissociated pulp". Examples of the paper base material having an irregular freeness of 100 mL or more and 600 mL or less of the constituent pulp fibers include glassine paper.
  • the glassine paper which shows a high total light transmittance with a particularly high tapping is also called a glassine paper. It is preferable to use graphan paper as the paper base material because a barrier laminate having excellent gas barrier properties can be obtained without further providing a gas barrier layer.
  • glassine paper has softwood chemical pulp as a main component as a pulp raw material, is highly beaten, is made into paper with acidity or neutrality, and is finished by compression processing with a super calendar or the like.
  • pulp for example, chemical pulp made of softwood such as spruce and hemlock is optimal, but other than that, chemical pulp made of hardwood, mechanical pulp, used paper, synthetic pulp and the like are mixed and blended. May be good.
  • Additives may be added to the paper substrate.
  • the additive include a pH adjuster (sodium hydrogen carbonate, sodium hydroxide, etc.), a dry paper strength agent (polyacrylamide, starch, etc.), a wet paper strength agent (polyamide polyamine epichlorohydrin resin, melamine-formaldehyde resin, etc.). Any of urea-formaldehyde resin), internal sizing agent (rosin-based, alkyl ketene dimer, etc.), drainage yield improving agent, defoaming agent, filler (calcium carbonate, talc, etc.), dye, etc. may be mentioned. These additives may be used alone or in combination of two or more. The content of the additive is not particularly limited and may be in the range usually used.
  • the basis weight of the paper substrate is not particularly limited, but for example, for packaging bag applications, 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 30 g / m /. More preferably, it is m 2 or more and 50 g / m 2 or less.
  • the basis weight of the paper substrate is measured according to JIS P 8124: 2011.
  • the paper thickness of the paper base material is not particularly limited, but for example, for packaging bag applications, it is preferably 20 ⁇ m or more and 150 ⁇ m or less, more preferably 25 ⁇ m or more and 100 ⁇ m or less, and further preferably 30 ⁇ m or more and 50 ⁇ m or less.
  • the paper thickness of the paper substrate is measured according to JIS P 8118: 2014.
  • the total light transmittance of the paper substrate is preferably 65% or more, more preferably 70% or more, still more preferably 75%, from the viewpoint of obtaining a barrier laminate having excellent visibility of the contents when used as a packaging bag. As described above, it is more preferably 80% or more, and may be 100%, and from the viewpoint of accessibility, it is preferably 95% or less, more preferably 90% or less.
  • the total light transmittance of the paper substrate is measured according to JIS K 7375: 2008.
  • the smoothness of the paper base material is not particularly limited, but the Oken-type smoothness of the surface on which the anchor coat layer and the water vapor barrier layer of the paper base material are provided is preferably 500 seconds or more and 1500 seconds or less. Further, when the resin layer described later is provided, the Oken-type smoothness of the surface on which the resin layer of the paper substrate is provided is preferably 1000 seconds or more and 2000 seconds or less. The Oken smoothness of the paper substrate is measured according to JIS P 8155: 2010.
  • Examples of the method for producing a paper base material include a method of making a paper material containing pulp.
  • the paper material may further contain an additive.
  • Examples of the additive include the additives mentioned above.
  • Paper charges can be prepared by adding additives to the pulp slurry.
  • Pulp slurry is obtained by beating the 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 material is not particularly limited and may be in the range usually used. For example, it is 60% by mass or more and less than 100% by mass with respect to the total mass of the paper material.
  • Papermaking can be done by the standard method. For example, there is a method in which a paper material is cast on a wire or the like, dehydrated to obtain a wet paper, a plurality of wet papers are stacked as needed, and the single-layer or multi-layer wet paper is pressed and dried. .. At this time, when a plurality of wet papers are not stacked, a single-layer paper is obtained, and when a plurality of wet papers are stacked, a multi-layer paper is obtained. When stacking a plurality of wet papers, an adhesive may be applied to the surface of the wet papers (the surface on which other wet papers are stacked).
  • the barrier laminate of the present embodiment has an anchor coat layer between the paper base material and the water vapor barrier layer.
  • the highly transparent paper substrate (particularly, graphan paper) has a large specific surface area of cellulose because it has been beaten. Therefore, there are many hydrogen bonds between celluloses, and water easily enters the portion. Therefore, when a water-based water vapor barrier layer coating liquid is applied to a highly transparent paper base material, the coating liquid permeates the paper base material and a large number of wrinkles are generated in the drying process (that is, water vapor). The surface roughness of the surface on the barrier layer side increases).
  • the obtained barrier laminate is inferior in the visibility of the contents when it is made into a packaging bag (Comparative Examples 1 to 4 described later).
  • the permeation of the water vapor barrier layer coating liquid into the paper base material is suppressed, and the drying process is performed.
  • the occurrence of wrinkles can be reduced (that is, the surface roughness of the surface on the water vapor barrier layer side becomes smaller).
  • the obtained barrier laminate has excellent visibility of the contents when it is used as a packaging bag.
  • the method for producing the barrier laminate preferably includes the following steps. (1) An anchor coat layer coating liquid in which a resin constituting an anchor coat layer is dissolved or dispersed in an organic solvent or a mixed solvent of an organic solvent and water (more preferably an organic solvent) is applied to at least one surface of a paper substrate. (2) A step of applying a water vapor barrier layer coating liquid on the obtained anchor coat layer and drying it to form a water vapor barrier layer.
  • the resin constituting the anchor coat layer (hereinafter, also referred to as “resin for anchor coat layer”) is not particularly limited as long as it can exhibit the above effects, but is preferably polyester resin, urethane resin, acrylic resin, vinyl chloride. -Vinyl acetate copolymer, ethylene-vinyl acetate, ethylene acrylic resin, modified products thereof and the like can be mentioned.
  • the resin for the anchor coat layer preferably contains a polyester resin, and more preferably a polyester resin.
  • the resin for the anchor coat layer may be used alone or in combination of two or more.
  • the resin for the anchor coat layer either a synthetic product or a commercially available product may be used, and as the commercially available product, the one used in the examples or the like can be used.
  • other components may be added in addition to the above resin for the anchor coat layer.
  • other components include pigments; lubricants; defoamers; viscosity modifiers; surfactants, leveling agents such as alcohols, and colorants such as color dyes.
  • the total content of the other components is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less in the solid content of the anchor coat layer.
  • the method for forming the anchor coat layer is not particularly limited, but for example, an anchor coat layer coating liquid containing at least a resin for the anchor coat layer is prepared, and the coating liquid is applied to at least one surface of the paper substrate. By drying, the anchor coat layer can be formed.
  • the anchor coat layer resin is dissolved or dispersed in an organic solvent or a mixed solvent of an organic solvent and water to dissolve or disperse the anchor coat layer. It is preferable to prepare a coating liquid.
  • the organic solvent is not particularly limited, and examples thereof include acetone, methanol, ethanol, isopropanol, n-propanol, butanol, ethyl acetate, propyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether, and hexane.
  • the mass ratio of the organic solvent to water (organic solvent / water) in the anchor coat layer coating liquid is preferably 99/1 or more and less than 20/80.
  • the device used for coating the anchor coat layer coating liquid 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, Mayer bar coater, curtain coater, die slot coater, champlex coater, metering blade type size press coater, short dwell coater, etc.
  • coating devices such as a spray coater, a gate roll coater, and a lip coater.
  • the drying conditions of the anchor coat layer are not particularly limited, but the drying temperature is preferably 50 to 100 ° C., and the drying time is preferably 5 to 60 seconds.
  • the drying equipment for drying the coated anchor coat layer is not particularly limited, and known equipment can be used.
  • Examples of the drying equipment include a hot air dryer, an infrared dryer, an explosion-proof dryer, a gas burner, a hot plate, and the like.
  • the coating amount of the anchor coat layer is preferably 0.1 g / m 2 or more, more preferably 0.3 g / m 2 or more, from the viewpoint of suppressing the penetration of the anchor coat layer coating liquid into the paper substrate. ..
  • the upper limit of the coating amount of the anchor coat layer is not particularly limited, but is preferably 3.0 g / m 2 or less, more preferably 2.0 g / m 2 or less, and further preferably 1.0 g / m 2 or less.
  • the amount of coating of the anchor coat layer is the amount of coating after drying.
  • the water vapor barrier layer is a layer having a water vapor barrier property that blocks the permeation of water vapor.
  • the barrier laminate according to the present embodiment preferably has a water vapor barrier layer on at least one outermost layer of the paper substrate. By providing the water vapor barrier layer on the outermost layer, the heat sealability can be exhibited without providing the sealant layer.
  • the water vapor barrier layer according to the present embodiment preferably contains a water-dispersible resin binder.
  • the water-dispersible resin binder is a resin binder that is not water-soluble but is finely dispersed in water like an emulsion or a suspension.
  • Examples of the polymer that forms the skeleton of the water-dispersible resin binder include polyolefin resins (polyethylene, polypropylene, etc.), vinyl chloride resins, styrene resins, styrene / butadiene copolymers, acrylonitrile / styrene copolymers, and acrylonitrile / butadiene copolymers.
  • ABS resin 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, polyallylate resin, olefin / unsaturated carboxylic acid Examples thereof include polymers and modified products thereof.
  • the polymer that forms the skeleton of the water-dispersible resin binder of the water vapor barrier layer is a group consisting of a styrene / butadiene-based copolymer, a styrene / acrylic-based copolymer, and an olefin / unsaturated carboxylic acid-based copolymer. It is preferably one or more selected from the above, and more preferably one or more selected from the group consisting of a styrene / acrylic copolymer and an olefin / unsaturated carboxylic acid copolymer.
  • Styrene-butadiene copolymers include styrene compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, pt-butylstyrene and chlorostyrene, and 1,3-butadiene and isoprene (2-methyl-1,3).
  • -Butadiene 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and other butadiene compounds, and other compounds that can be copolymerized with these compounds are emulsified and polymerized. It is a copolymer.
  • Styrene is preferable as the styrene-based compound
  • 1,3-butadiene is preferable as the butadiene-based compound.
  • the styrene / acrylic copolymer includes styrene compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene, and acrylic acid, methacrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid ester. ) Emulsion polymerization of a monomer composed of acrylic compounds such as acrylamide propane sulfonic acid and (meth) acrylic acid sulfoalkyl sodium salt (alkyl group having 2 or more and 3 or less carbon atoms) and other compounds copolymerizable with these compounds.
  • the styrene-based compound styrene is preferable, and as the acrylic-based compound, acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester are suitable, and acrylic acid and acrylic acid ester are more preferable.
  • the (meth) acrylic acid ester is preferably an acrylic acid alkyl ester, and the alkyl group preferably has 1 to 6 carbon atoms.
  • the water-dispersible resin binder is a styrene / acrylic copolymer, it is also preferable that the water vapor barrier layer is made of a styrene / acrylic copolymer.
  • Olefin / unsaturated carboxylic acid-based copolymers include olefins, especially ⁇ -olefins such as propylene or ethylene, acrylic acid, methacrylic acid, crotonic acid, silicate, itaconic acid, fumaric acid, maleic acid, butentricarboxylic acid.
  • Unsaturated polycarboxylic acid alkyl esters with at least one carboxy group and copolymerizable with unsaturated carboxylic acids such as acids, itaconic acid monoethyl esters, fumaric acid monobutyl esters and maleic acid monobutyl esters. It is a copolymer obtained by emulsifying and polymerizing a monomer composed 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 and the like are suitable.
  • the olefin / unsaturated carboxylic acid-based copolymer for example, an aqueous dispersion of an ethylene / acrylic acid copolymer ammonium salt may be used as Zyxene ((registered trademark) AC) (copolymerization ratio of acrylic acid: 20%, etc.). It is commercially available as Sumitomo Seika Co., Ltd.) and can be easily obtained and used.
  • the water vapor barrier layer contains a cationic resin and a layered inorganic compound
  • the water-dispersible resin binder is preferably an anionic binder.
  • the anionic binder include a binder containing a monomer unit containing an anionic group.
  • the anionic binder is preferably a binder containing a monomer unit containing a carboxy group.
  • the planar portion of the layered inorganic compound is anionic, but when the cationic resin is adsorbed, the surface becomes cationic, and as a result, the affinity with the anionic binder is enhanced. Conceivable.
  • the anionic binder the above-mentioned olefin / unsaturated carboxylic acid-based copolymer and the like are preferable.
  • the content of the unsaturated carboxylic acid-based monomer unit of the olefin / unsaturated carboxylic acid-based copolymer is preferably 1 mol% or more, more preferably 10 mol% or more, and preferably 50 mol% or less. It is preferably 30 mol% or less. When the content of the unsaturated carboxylic acid-based monomer is within the above range, the dispersibility of the layered inorganic compound is excellent.
  • the weight average molecular weight of the water-dispersible resin binder is preferably 10,000 or more, more preferably 20,000 or more, and preferably 10 million or less, from the viewpoint of viscosity and strength when applied to a paper substrate. It is preferably 5 million or less.
  • the content of the water-dispersible resin binder is not particularly limited, but is preferably 20% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably, in the total solid content of the water vapor barrier layer. Is 70% by mass or more.
  • the content of the water-dispersible resin binder is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less with respect to the total solid content mass contained in the water vapor barrier layer. Is more preferable, and 80% by mass or less is particularly preferable.
  • the water vapor barrier layer preferably contains a layered inorganic compound.
  • the form of the layered inorganic compound is a flat plate.
  • a mixed solution of a layered inorganic compound, a cationic resin and a water-dispersible resin binder is prepared and coated on a paper substrate, a water vapor barrier layer is formed.
  • the flat layered inorganic compounds are arranged in a state of being laminated substantially parallel to the plane (surface) of the paper substrate. Then, in the plane direction, the area where the layered inorganic compound does not exist becomes small, so that the permeation of water vapor is suppressed.
  • the water vapor in the layer permeates while bypassing the layered inorganic compound, and the maze effect causes the water vapor to permeate. Permeation of water vapor is suppressed. As a result, the water vapor barrier layer can 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, further preferably 25 nm or less, and particularly preferably 10 nm or less.
  • the lower limit of the thickness of the layered inorganic compound is not particularly limited, but is preferably 2 nm or more.
  • the average thickness of the layered inorganic compound in the state of being contained in the water vapor barrier layer is obtained as follows.
  • a magnified photograph of the cross section of the water vapor 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 contained in the screen. The thickness of each layered inorganic compound in the screen is measured. Then, the average value of the obtained thickness is calculated and used 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 compounds are likely to be arranged in parallel with the paper substrate. Further, when the average length is 100 ⁇ m or less, there is little concern that a part of the layered inorganic compound protrudes from the water vapor barrier layer.
  • the average length of the layered inorganic compound is more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the average length of the layered inorganic compound in the state of being contained in the water vapor barrier layer is obtained as follows.
  • a magnified photograph of the cross section of the water vapor 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 contained in the screen. The length of each layered inorganic compound in the screen is measured. Then, the average value of the obtained lengths is calculated and used as the average length of the layered inorganic compound.
  • the length of the layered inorganic compound may be described by the expression of particle size.
  • 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 more the permeation of water vapor is suppressed and the water vapor barrier property is improved. Further, the larger the aspect ratio, the smaller the amount of the layered inorganic compound added.
  • the upper limit of the aspect ratio is not particularly limited, and is preferably about 10,000 or less, more preferably about 5,000 or less, and even more preferably about 2,000 or less from the viewpoint of the viscosity of the coating liquid.
  • the aspect ratio is a value obtained by taking a magnified photograph of the cross section of the water vapor barrier layer using an electron microscope and dividing the average length of the obtained layered inorganic compound by the average thickness, as described above. Is.
  • layered inorganic compounds include mica such as mica and brittle mica, bentonite, kaolinite (kaolin mineral), pyrophyllite, talc, smectite, vermiculite, chlorite, septe chlorite, serpentine, and stirp. Examples include nomelane and montmorillonite.
  • mica examples include synthetic mica (eg, swelling mica, non-swelling mica), white mica (mascobite), silk mica (serisite), gold mica (frocopite), black mica (biotight), and fluorine.
  • synthetic mica eg, swelling mica, non-swelling mica
  • white mica mascobite
  • silk mica silk mica
  • gold mica frocopite
  • black mica biotight
  • fluorine examples include gold mica (artificial mica), red mica, soda mica, vanajin mica, illite, chimmica, paragonite, and brittle mica.
  • bentonite montmorillonite can be mentioned.
  • the content of the layered inorganic compound is preferably 80% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less in the total solid content of the water vapor barrier layer.
  • the content of the layered inorganic compound is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, still more preferably 5% by mass or more.
  • the water vapor barrier layer preferably contains a cationic resin.
  • the layered inorganic compound tends to be charged anionicly in the flat portion of the flat plate shape and cationically charged in the edge portion, the layered inorganic compound may have a so-called card house structure in which the layered inorganic compounds are three-dimensionally aggregated with each other. Are known. Due to this card house structure, the aqueous dispersion of the layered inorganic compound has a very high viscosity.
  • the aqueous dispersion of the layered inorganic compound exhibits thixotropy.
  • the cationic resin is adsorbed on the anionic flat portion of the layered inorganic compound, and the card house structure is destroyed.
  • the three-dimensional aggregation of the layered inorganic compound is suppressed, and the flat plate-shaped layered inorganic compound is easily laminated in parallel with the plane of the paper substrate, which leads to the improvement of the water vapor barrier property.
  • cationic resin examples include polyalkylene polyamines, polyamide compounds, modified polyamide compounds, polyamideamine-epihalohydrin or formaldehyde condensation reaction products, polyamine-epihalohydrin or formaldehyde condensation reaction products, polyamide polyurea-epihalohydrin or formaldehyde condensation.
  • the cationic resin is preferably a modified polyamide compound, and more preferably a modified polyamide resin.
  • the modified polyamide resin a commercially available one may be used, and examples thereof include SPI203 (50) H and Taoka Chemical Industry Co., Ltd.
  • the content of the cationic resin in the water vapor barrier layer may be appropriately selected according to the type of the layered inorganic compound used in the water vapor barrier layer and the water-dispersible resin binder, but from the viewpoint of improving the barrier property, the layered inorganic material may be appropriately selected.
  • the layered inorganic material may be appropriately selected.
  • 100 parts by mass of the compound 1 part by mass or more and 300 parts by mass or less is preferable, 3 parts by mass or more and 250 parts by mass or less is more preferable, 5 parts by mass or more and 200 parts by mass or less is further preferable, and 10 parts by mass or more and 150 parts by mass or less.
  • the following is particularly preferable, and 20 parts by mass or more and 100 parts by mass or less are most preferable.
  • the content of the cationic resin is preferably 0.1 part by mass or more and 20 parts by mass or less, and more preferably 0.3 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the water-dispersible resin binder of the water vapor barrier layer. It is preferable, and more preferably 1 part by mass or more and 15 parts by mass or less.
  • the water vapor barrier layer preferably contains a water-dispersible resin binder and, if necessary, a layered inorganic compound and a cationic resin.
  • a water-dispersible resin binder preferably contains a water-dispersible resin binder and, if necessary, a layered inorganic compound and a cationic resin.
  • cationic resins and water-dispersible resin binders a dispersant, a surfactant, an antifoaming agent, a wetting agent, a dye, a color adjuster, and a thickener are added to the water vapor barrier layer as needed. Etc. can be added.
  • the coating amount of the water vapor barrier layer is 1 g / m 2 or more, more preferably 2 g / m 2 or more, and preferably 15 g / m 2 or less, more preferably 10 g / m 2 or more as the solid content after drying. It is m 2 or less, more preferably 8 g / m 2 or less, and even more preferably 5 g / m 2 or less.
  • the method for forming the water vapor barrier layer is not particularly limited, but a water vapor barrier layer coating liquid in which a water-dispersible resin binder and, if necessary, a layered inorganic compound and a cationic resin are dispersed in a solvent is applied and dried, and the water vapor barrier is formed. It is preferable to form a layer.
  • the equipment used for coating and drying is not particularly limited, and examples thereof include those exemplified in the above section (Method for forming an anchor coat layer).
  • the solvent of the water vapor barrier layer coating liquid is not particularly limited, and water or an organic solvent such as ethanol, isopropyl alcohol, methyl ethyl ketone, and toluene can be used. Among these, water is preferable as the dispersion medium of the water vapor barrier layer coating liquid from the viewpoint of not causing the problem of the volatile organic solvent.
  • the barrier laminate according to the present embodiment preferably has a resin layer on the other surface of the paper substrate (the surface on which the water vapor barrier layer is not provided) for the purpose of further improving transparency. That is, it is preferable that the anchor coat layer and the water vapor barrier layer are provided in this order on one surface of the paper substrate, and the resin layer is provided on the other surface of the paper substrate. It is considered that by providing the resin layer on the other surface of the paper base material, the surface unevenness of the paper base material is covered, the scattering of light is suppressed, and the transparency is improved.
  • the resin constituting the resin layer (hereinafter, also referred to as “resin for resin layer”) is not particularly limited, but a resin having an effect of improving the transparency or smoothness of the paper substrate is preferable, and for example, varnish and acrylic. Examples thereof include resin, urethane resin, polyester resin, and ethylene acrylic resin. Urethane resin is preferable.
  • the resin for the resin layer may be used alone or in combination of two or more.
  • the resin for the resin layer either a synthetic product or a commercially available product may be used, and as the commercially available product, the one used in the examples or the like can be used.
  • the resin layer may contain other components in addition to the resin for the resin layer.
  • other components include metal powders; pigments; lubricants; defoamers; viscosity modifiers; surfactants, leveling agents such as alcohols; colorants such as coloring dyes, and the like.
  • the resin layer contains, for example, zinc oxide powder as an ultraviolet inhibitor.
  • the ultraviolet transmittance of the barrier laminated body at a wavelength of 350 nm with the light entering surface as the surface on the water vapor barrier layer side is preferably 0 to 25%, more preferably 1 to 4%.
  • the resin layer is obtained by preparing a resin layer coating liquid containing at least a resin for a resin layer, applying the coating liquid to at least one surface of a paper substrate, and drying the coating liquid.
  • a resin layer coating liquid is prepared by dissolving or dispersing the resin for the resin layer in an organic solvent or a mixed solvent of an organic solvent and water, and the coating liquid is applied onto the above-mentioned paper substrate. ..
  • the solvent of the resin layer coating liquid an organic solvent or a mixed solvent of an organic solvent and water is used.
  • the organic solvent is not particularly limited, and examples thereof include those exemplified in the above section (Method for forming an anchor coat layer).
  • the mass ratio of the organic solvent to water (organic solvent / water) in the resin layer coating liquid is preferably 99/1 or more and less than 20/80.
  • the device used for coating and drying the resin layer is not particularly limited, and examples thereof include those exemplified in the above section (Method for forming an anchor coat layer).
  • the drying conditions of the resin layer are not particularly limited, but the drying temperature is preferably 50 to 100 ° C., and the drying time is preferably 5 to 60 seconds.
  • the coating amount of the resin layer is preferably 0.1 g / m 2 or more, more preferably 0.3 g / m 2 or more, from the viewpoint of suppressing the penetration of the water vapor barrier layer coating liquid into the paper substrate.
  • the upper limit of the coating amount of the anchor coat layer is not particularly limited, but is preferably 3.0 g / m 2 or less, more preferably 2.0 g / m 2 or less, and further preferably 1.0 g / m 2 or less.
  • the amount of coating of the anchor coat layer is the amount of coating after drying.
  • the barrier laminate may further have a sealant layer on at least one outermost layer.
  • the sealant layer is a layer that is melted and adhered by heating, ultrasonic waves, or the like.
  • the sealant layer preferably contains a water-dispersible resin or a biodegradable resin.
  • the water-dispersible resin include those described above as the polymer serving as the skeleton of the water-dispersible resin binder of the water vapor barrier layer.
  • Biodegradable resin examples include, but are not limited to, polylactic acid, polybutylene succinate, polybutylene succinate adipate, polybutylene adipate terephthalate, 3-hydroxybutanoic acid / 3-hydroxyhexanoic acid copolymer, and the like.
  • a commercially available product may be used as the biodegradable resin, and examples thereof include "Randy PL series (trade name)” manufactured by Miyoshi Oil & Fat Co., Ltd. as polylactic acid.
  • the thickness of the sealant layer is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the coating amount of the sealant layer is preferably 0.5 g / m 2 or more, more preferably 1 g / m 2 or more, and preferably 50 g / m 2 or less, more preferably 30 g / m 2 as a solid content. It is less than or equal to, more preferably 10 g / m 2 or less.
  • ⁇ Physical characteristics of barrier laminate> (Moisture vapor transmission rate)
  • the water vapor transmission rate of the barrier laminate is measured by the method described in Examples. The water vapor transmission rate can be controlled, for example, by selecting the thickness of the water vapor barrier layer and / and the components contained in the water vapor barrier layer.
  • the oxygen permeability of the barrier laminate is preferably 20 mL / m 2.24 h ⁇ atm or less, more preferably 10 mL /. It is m 2.24 h ⁇ atm or less, more preferably 5 mL / m 2.24 h ⁇ atm or less, still more preferably 3 mL / m 2.24 h ⁇ atm or less, and particularly preferably 2 mL / m 2.24 h ⁇ atm or less.
  • the oxygen permeability of the barrier laminate is measured by the method described in the Examples.
  • the lower the oxygen permeability, the more preferable, so the lower limit is not particularly limited, but preferably 0 mL / m 2.24 h ⁇ atm or more, 0.1 mL / m 2.24 h ⁇ atm or more, 0.5 mL / m 2.24 h ⁇ atm. That is all.
  • Oxygen permeability can be controlled, for example, by the thickness and / and type of paper substrate.
  • the total light transmittance of the barrier laminate according to the present embodiment is 65% or more, preferably 70% or more, more preferably 75% or more, from the viewpoint of visibility of the contents when it is made into a packaging bag. Even more preferably 80% or more, still more preferably 82% or more.
  • the upper limit of the total light transmittance of the barrier laminated body is not particularly limited, but is usually 100% or less, preferably 95% or less, and more preferably 90% or less.
  • the total light transmittance of the barrier layer is measured according to JIS K 7631-1: 1997. The total light transmittance can be controlled by, for example, the thickness and / and type of the paper substrate.
  • the haze of the barrier laminate according to the present embodiment is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, from the viewpoint of visibility of the contents when made into a packaging bag.
  • the lower limit of the haze of the barrier laminate is not particularly limited, but is usually 0% or more, preferably 10% or more, more preferably 20% or more, still more preferably 50% or more, still more preferably 70% or more.
  • the haze of the barrier laminate is measured according to JIS K 7136: 2000.
  • the haze of the barrier laminate can be controlled, for example, by the thickness and / or smoothness (surface roughness) of the coating layer (anchor coat layer and water vapor barrier layer).
  • the smoothness (surface roughness) of the coating layer can be controlled by the coating method of the coating layer.
  • the haze of the barrier laminate can also be controlled by the thickness and / and type of the paper substrate.
  • the surface roughness of the barrier laminate according to the present embodiment is an arithmetic mean of the surface on the water vapor barrier layer side measured in accordance with JIS B 0601: 2001 from the viewpoint of visibility of the contents when it is made into a packaging bag.
  • the height is 75 ⁇ m or less, preferably 70 ⁇ m or less.
  • the lower limit is not particularly limited, but is preferably 0 ⁇ m or more, 20 ⁇ m or more, 30 ⁇ m or more, and 50 ⁇ m or more.
  • the surface on the water vapor barrier layer side refers to the surface on the side where the water vapor barrier layer exists with reference to the paper substrate.
  • the arithmetic mean height is, for example, a coating method of a coating layer (anchor coat layer and a water vapor barrier layer) (for example, selecting a coating method having high surface smoothness such as bar coating or blade coating). And / or can be controlled by the calendering of the paper substrate.
  • the surface roughness of the barrier laminate according to the present embodiment is the maximum height of the surface on the water vapor barrier layer side measured in accordance with JIS B 0601: 2001 from the viewpoint of visibility of the contents when it is made into a packaging bag. It is preferably 550 ⁇ m or less, more preferably 500 ⁇ m or less.
  • the lower limit is not particularly limited, but is preferably 0 ⁇ m or more, 150 ⁇ m or more, and 250 ⁇ m or more.
  • the maximum height is, for example, a coating method of a coating layer (anchor coat layer and a water vapor barrier layer) (for example, selecting a coating method having high surface smoothness such as bar coating or blade coating). Or / as well as can be controlled by the calendering of the paper substrate.
  • the barrier laminate of the present embodiment is used as a packaging material for foods, cosmetics, daily miscellaneous goods, detergents, soaps, powders, precision machinery, etc., taking advantage of the excellent visibility of the contents when used as a packaging bag. It can be suitably used. Therefore, the present invention also provides a packaging bag made of the barrier laminate.
  • Example 1 Water dispersion of plate-like inorganic compound (swellable mica, average particle size 6.3 ⁇ m, aspect ratio about 1000, average thickness about 5 nm, solid content 6%, product name: NTS-10NC, manufactured by Topy Industries) 30.0 34.2 parts of an aqueous emulsion of an ethylene / acrylic acid copolymer (solid content 29.2%, product name: Zyxen AC, manufactured by Sumitomo Seika Chemicals) was added to the parts while stirring, and the mixture was stirred.
  • plate-like inorganic compound swellable mica, average particle size 6.3 ⁇ m, aspect ratio about 1000, average thickness about 5 nm, solid content 6%, product name: NTS-10NC, manufactured by Topy Industries
  • the steam barrier layer coating liquid A as a steam barrier layer is applied to the upper layer of the anchor coat layer with a Mayer bar so that the coating amount after drying is 3.0 g / m 2 , and then 120 in a hot air dryer. It was dried at ° C. for 1 minute to form a water vapor barrier layer, and a barrier laminate was obtained.
  • Example 2 Barrier property as in Example 1 except that a styrene acrylic resin aqueous dispersion (solid content: 40%, product name: XP8812, manufactured by Seiko PMC Corporation) was used instead of the water vapor barrier layer coating liquid A. A laminate was produced.
  • a styrene acrylic resin aqueous dispersion solid content: 40%, product name: XP8812, manufactured by Seiko PMC Corporation
  • Example 3 A UV-cutting agent containing a solvent-based urethane resin on the surface of the barrier laminate obtained in Example 1 on which the water vapor barrier layer is not provided (highly smooth surface of graphan paper, Oken-type smoothness of 1710 seconds).
  • After coating to 0.5 g / m 2 it was dried at 80 ° C. for 10 seconds in an explosion-proof dryer to form a resin layer, and a barrier laminate was obtained.
  • Example 4 A UV-cutting agent containing a solvent-based urethane resin on the surface of the barrier laminate obtained in Example 2 on the side where the water vapor barrier layer is not provided (highly smooth surface of graphan paper, Oken-type smoothness of 1710 seconds).
  • After coating to 0.5 g / m 2 it was dried at 80 ° C. for 10 seconds in an explosion-proof dryer to form a resin layer, and a barrier laminate was obtained.
  • a styrene acrylic resin aqueous dispersion solid content: 40%, product name: XP8812, manufactured by Seiko PMC Corporation
  • Example 5 Except that the paper base material was bleached kraft paper (manufactured by Oji Materia Co., Ltd., irregular freeness 700 mL of constituent pulp, basis weight 50 g / m 2 , paper thickness 60 ⁇ m, total light transmittance 47%), as in Example 1. Similarly, an anchor coat layer and a steam barrier layer were formed on one surface of the paper substrate to prepare a barrier laminate.
  • bleached kraft paper manufactured by Oji Materia Co., Ltd., irregular freeness 700 mL of constituent pulp, basis weight 50 g / m 2 , paper thickness 60 ⁇ m, total light transmittance 47%), as in Example 1.
  • an anchor coat layer and a steam barrier layer were formed on one surface of the paper substrate to prepare a barrier laminate.
  • Example 6 ⁇ Comparative Example 6> Except that the paper base material was bleached kraft paper (manufactured by Oji Materia Co., Ltd., irregular freeness 700 mL of constituent pulp, basis weight 50 g / m 2 , paper thickness 60 ⁇ m, total light transmittance 47%), as in Example 2. Similarly, an anchor coat layer and a steam barrier layer were formed on one surface of the paper substrate to prepare a barrier laminate.
  • Oxygen permeability Using an oxygen permeability measuring device (OX-TRAN2 / 22 manufactured by MOCON), barrier property under atmospheric pressure at a temperature of 23 ° C and a relative humidity of 50% (low humidity condition). The oxygen permeability of the laminate was measured. The lower the oxygen permeability value, the better the oxygen barrier property.
  • the results are shown in Table 1 above.
  • the barrier laminates of Examples 1 to 4 had excellent visibility of the contents when used as a packaging bag, and had good water vapor barrier properties and gas barrier properties.
  • the surface roughness is reduced by providing the resin layer on the other surface of the paper base material. It is considered that the reason for this is that the solvent coating on both sides of the paper base material suppresses the deflection that occurs during coating on only one side.
  • the barrier laminates of Comparative Examples 1 to 4 in which the water vapor barrier layer was water-based coated without applying the anchor coating agent were wrinkled in the drying process, and the visibility of the contents when used as a packaging bag was obtained. Was scarce.
  • the barrier-type laminates of Comparative Examples 5 to 6 in which bleached kraft paper was used instead of graphan paper as the paper base material had poor visibility of the contents when used as a packaging bag and had low gas barrier properties.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un corps barrière multicouche qui présente de bonnes propriétés de barrière et qui forme un sac d'emballage présentant une excellente visibilité du contenu. L'invention concerne également un corps barrière multicouche qui comprend séquentiellement, sur au moins une surface d'un matériau de base en papier, une couche de revêtement d'ancrage et une couche barrière contre la vapeur d'eau dans cet ordre, dans lequel : la transmittance totale de la lumière telle que déterminée selon JIS K 7361-1 (1997) est de 65 % ou plus ; et la hauteur moyenne arithmétique de la surface latérale de la couche barrière contre la vapeur d'eau telle que déterminée selon JIS B 0601 (2001) est de 75 μm ou moins.
PCT/JP2021/023359 2020-08-05 2021-06-21 Corps barrière multicouche et sac d'emballage WO2022030118A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5421474A (en) * 1977-07-19 1979-02-17 Daicel Chem Ind Ltd Coated thin paper
JP2006142566A (ja) * 2004-11-17 2006-06-08 Japan Tobacco Inc 包装紙及び包装紙を使用したシガレットパッケージ並びに包装紙の製造方法及び装置
JP2016210503A (ja) * 2015-05-01 2016-12-15 旭化成株式会社 プレススルーパック包装体用蓋材及びその製造方法、並びにプレススルーパック包装体
JP2017124564A (ja) * 2016-01-15 2017-07-20 王子ホールディングス株式会社 ヒートシールシートおよびプレススルー包装体
JP2019210473A (ja) * 2018-06-04 2019-12-12 積水フーラー株式会社 熱可塑性樹脂フィルム、溶融袋及び包装ホットメルト接着剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5421474A (en) * 1977-07-19 1979-02-17 Daicel Chem Ind Ltd Coated thin paper
JP2006142566A (ja) * 2004-11-17 2006-06-08 Japan Tobacco Inc 包装紙及び包装紙を使用したシガレットパッケージ並びに包装紙の製造方法及び装置
JP2016210503A (ja) * 2015-05-01 2016-12-15 旭化成株式会社 プレススルーパック包装体用蓋材及びその製造方法、並びにプレススルーパック包装体
JP2017124564A (ja) * 2016-01-15 2017-07-20 王子ホールディングス株式会社 ヒートシールシートおよびプレススルー包装体
JP2019210473A (ja) * 2018-06-04 2019-12-12 積水フーラー株式会社 熱可塑性樹脂フィルム、溶融袋及び包装ホットメルト接着剤

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