WO2021095780A1 - Stratifié de papier - Google Patents

Stratifié de papier Download PDF

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Publication number
WO2021095780A1
WO2021095780A1 PCT/JP2020/042116 JP2020042116W WO2021095780A1 WO 2021095780 A1 WO2021095780 A1 WO 2021095780A1 JP 2020042116 W JP2020042116 W JP 2020042116W WO 2021095780 A1 WO2021095780 A1 WO 2021095780A1
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WO
WIPO (PCT)
Prior art keywords
paper
mass
resin layer
less
paper laminate
Prior art date
Application number
PCT/JP2020/042116
Other languages
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to JP2021514141A priority Critical patent/JP6901058B1/ja
Publication of WO2021095780A1 publication Critical patent/WO2021095780A1/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
    • 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
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed

Definitions

  • the present invention relates to a paper laminate.
  • Packaging materials that have water vapor barrier properties and gas barrier properties (particularly oxygen barrier properties) added to the paper base material have been conventionally used in packaging foods, medical products, electronic parts, etc. in order to prevent deterioration of the quality of the contents. Has been done.
  • 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 water vapor barrier layer contains a water vapor barrier resin and a water repellent
  • the gas barrier layer contains a water-soluble polymer and a surfactant.
  • Patent Document 2 proposes a paper barrier packaging material in which a water vapor barrier layer and a gas barrier layer are provided on a paper base material.
  • the water vapor barrier layer contains 50 to 100% by weight of kaolin having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more with respect to all pigments, and the binder resin of the gas barrier layer is a polyvinyl alcohol resin.
  • an object of the present invention is to provide a paper laminate having excellent disintegration property and high barrier property.
  • the present inventors have provided a resin layer and a protective layer on a specific paper substrate, and the resin layer is a water-suspendable polymer, a plate-like inorganic compound having a specific aspect ratio, and a cation. It has been found that a paper laminate containing a sex resin and a protective layer containing a water-soluble polymer solves the above-mentioned problems. That is, the present invention relates to the following paper laminate. ⁇ 1>: A paper laminate having a paper base material and a resin layer and a protective layer on at least one surface of the paper base material, and the density of the paper base material is 0.50 g / cm 3 or more and 0.
  • one side of the paper substrate is a smooth surface
  • the smooth surface is measured in accordance with JIS P 8155: 2010, and the smoothness of the smooth surface is 100 seconds or more.
  • the water-suspendable polymer contained in the resin layer is composed of an olefin / unsaturated carboxylic acid-based copolymer, a styrene / butadiene-based copolymer, and a styrene / acrylic-based copolymer.
  • ⁇ 4> The method according to any one of ⁇ 1> to ⁇ 3>, wherein the plate-like inorganic compound contained in the resin layer contains at least one selected from the group consisting of synthetic mica, bentonite and kaolin. Paper laminate.
  • ⁇ 5> The content of the plate-like inorganic compound contained in the resin layer is 0.1 part by mass or more and 800 parts by mass or less with respect to 100 parts by mass of the water-suspendable polymer, ⁇ 1.
  • ⁇ 6> The paper laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the thickness of the plate-like inorganic compound contained in the resin layer is 200 nm or less.
  • ⁇ 7> The content ratio of the plate-like inorganic compound contained in the resin layer is 0.1% by mass or more and 80% by mass or less in the total solid content of the resin layer, ⁇ 1> to ⁇ 6>.
  • ⁇ 8> The method according to any one of ⁇ 1> to ⁇ 7>, wherein the water-soluble polymer contained in the protective layer contains at least one selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol.
  • the paper substrate has a Wangken-type smoothness of the surface opposite to the smooth surface measured in accordance with JIS P 8155: 2010, which is less than 100 seconds, ⁇ 1> to ⁇ 9. > The paper laminate according to any one of.
  • ⁇ 11> The content of the cationic resin contained in the resin layer is 0.5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the plate-shaped inorganic compound, ⁇ 1> to The paper laminate according to any one of ⁇ 10>.
  • ⁇ 12> The content of the cationic resin contained in the resin layer is 0.1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the water-suspended polymer, ⁇ 1. > To ⁇ 11>.
  • the paper laminate according to any one of. ⁇ 13> The paper laminate according to any one of ⁇ 1> to ⁇ 12>, which further has a sealant layer on at least one outermost layer.
  • ⁇ 14> The paper laminate according to any one of ⁇ 1> to ⁇ 13>, which is a packaging material.
  • the present embodiment The embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail.
  • the following embodiments are examples for explaining the present invention, and are not limited to the contents of the present invention.
  • the present invention can be appropriately modified and implemented within the scope of the gist thereof.
  • the preferred provisions can be arbitrarily adopted, and it can be said that the combination of preferable ones is more preferable.
  • the paper laminate of the present embodiment is a paper laminate having a paper substrate and a resin layer and a protective layer on at least one surface of the paper substrate, and the density of the paper substrate is 0.50 g / cm. 3 or more and 0.90 g / cm 3 or less, one side of the paper substrate is a smooth surface, and the smooth surface measured according to JIS P 8155: 2010 has a smooth surface of 100 seconds or more.
  • the resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin, and the protective layer contains a water-soluble polymer.
  • the paper laminate of the present embodiment has excellent disintegration property and high barrier property.
  • a surface having a higher Oken-type smoothness than the other surface is called a smooth surface
  • a surface having a lower Oken-type smoothness is called a non-smooth surface.
  • the smooth surface of the paper base material has an Oken-type smoothness of the above lower limit or more and the density is within the above range, the shrinkage of fibers is suppressed, so that the paper has high disintegration property and has a good texture. Become. If the texture is good, when the paint is applied, there is little unevenness of penetration and a highly uniform coating film can be obtained. Therefore, it is considered that the paper laminate of the present embodiment has excellent disintegration property and exhibits high barrier property.
  • the paper laminate of the present embodiment has a paper base material and a resin layer and a protective layer on at least one surface of the paper base material.
  • the paper base material may have a resin layer and a protective layer on one side, or may have a resin layer and a protective layer on both sides. From the viewpoint of production efficiency, it is preferable to have a resin layer and a protective layer on one side. In the present embodiment, even if the resin layer and the protective layer are provided on only one side, sufficient barrier properties, particularly oxygen barrier properties, can be exhibited.
  • a barrier property it refers to a water vapor barrier property or a gas barrier property (particularly an oxygen barrier property).
  • one surface of the paper base material is a smooth surface.
  • the other surface of the paper base material is the surface opposite to the smooth surface.
  • the surface on which the resin layer and the protective layer of the paper base material are provided may be a smooth surface or a surface opposite to the smooth surface.
  • the resin layer and the protective layer may be provided in this order from the side closer to the paper base material on at least one surface of the paper base material, and the protective layer and the resin layer may be provided from the side closer to the paper base material. And may have in this order.
  • the protective layer is directly formed on the resin layer. Since the protective layer is directly formed on the resin layer, the resin layer is easily dispersed in water by the mechanical dissociation action from both the paper base material side and the protective layer side, and the effect of the paper base material in the present embodiment. Can be demonstrated more regretfully.
  • the resin layer is directly formed on the paper base material. Since the resin layer is directly formed on the paper base material, the adhesion between the resin layer and the paper base material can be enhanced, and the barrier property of the paper laminate can be further improved.
  • the paper laminate of the present embodiment conforms to JIS Z 0208: 1976 (cup method) B method (temperature 40 ° C. ⁇ 0.5 ° C., relative humidity 90% ⁇ 2%) from the viewpoint of further improving the water vapor barrier property.
  • the water vapor permeability of the paper laminate of the present embodiment which is measured by arranging the resin layer of the paper laminate so as to come to the inside (low humidity side), is preferably 20.0 g / (m 2 ⁇ .
  • the lower limit is not particularly limited, but is, for example, 0.01 g / (m 2 ⁇ day) or more.
  • the oxygen permeability of the paper laminate of the present embodiment measured under the conditions of a temperature of 23 ° C. and a relative humidity of 50% under atmospheric pressure is from the viewpoint of further improving the gas barrier property.
  • the lower limit for the oxygen permeability of the paper stack is preferably as low as possible in the present embodiment is not limited particularly, but for example 0.01cc / (m 2 ⁇ day ⁇ atm) or more.
  • the dissociation rate of the paper laminate of the present embodiment is preferably 92.5% or more, more preferably 93.0% or more, from the viewpoint of further improving the dissociation property. It is more preferably 94.0% or more, still more preferably 95.0% or more, still more preferably 96.0% or more, and for example 100% or less.
  • the dissociation rate of the paper laminate of the present embodiment is preferably 87.0% or more, more preferably 88.0% or more from the viewpoint of further improving the dissociation property. , More preferably 88.5% or more, even more preferably 89.0% or more, and for example 100% or less.
  • the disintegration rate is determined by dissociating the paper laminate of the present embodiment in accordance with JIS P 8220: 2012, and collecting and drying the sample on the screen 10 minutes after the start of disaggregation to determine the mass ratio (%) of the residue. Calculated and calculated by the mass ratio of 100-residue.
  • the paper substrate in the present embodiment has a density of 0.50 g / cm 3 or more and 0.90 g / cm 3 or less, and is preferably 0.70 g / cm 3 or more, more preferably 0, from the viewpoint of being used as wrapping paper. It is .73 g / cm 3 or more, and is preferably 0.85 g / cm 3 or less, more preferably 0.83 g / cm 3 or less, from the viewpoint of further improving the disintegration property. Density is a value measured in accordance with JIS P 8118: 1998.
  • the smooth surface has a smoothness of 100 seconds or more.
  • the Oken-type smoothness of the smooth surface is preferably 200 seconds or longer, preferably 250 seconds or longer, more preferably 300 seconds or longer, further preferably 350 seconds or longer, from the viewpoint of further improving the disintegration property and barrier property of the paper laminate. It is preferable, and 400 seconds or more is more preferable.
  • the Oken-type smoothness of the smooth surface is preferably 1000 seconds or less, more preferably 800 seconds or less, further preferably 600 seconds or less, from the viewpoint of further improving the barrier property, texture and opacity of the paper laminate. More preferably 500 seconds or less, and even more preferably 450 seconds or less.
  • the surface opposite to the smooth surface may have a Wangken-type smoothness smaller than that of the smooth surface, and is not particularly limited, but is preferably 1 second or longer, more preferably 10 seconds or longer, and preferably 100 seconds or longer. It is small, more preferably 90 seconds or less, still more preferably 50 seconds or less.
  • the Oken type smoothness is a value measured in accordance with JIS P 8155: 2010.
  • Examples of the pulp constituting the paper base material include wood pulp and non-wood pulp.
  • Examples of wood pulp include softwood pulp and hardwood pulp. From the viewpoint of improving the air permeability and moisture permeability of the paper base material to improve the disintegration property, it is preferable that 40% by mass or more of the total pulp constituting the paper base material is hardwood pulp, and 50% by mass or more is hardwood pulp. It is more preferable to do so.
  • the upper limit of the amount of hardwood pulp used is, for example, 100% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less of the total pulp constituting the paper base material.
  • the fibers of softwood pulp are long, from the viewpoint of increasing the tensile strength of the paper base material, it is preferable that 5% by mass or more of the total pulp constituting the paper base material is softwood pulp, and 10% by mass or more. Is more preferable.
  • the upper limit of the amount of softwood pulp used is, for example, 60% by mass or less, preferably 50% by mass or less of the total pulp constituting the paper base material.
  • non-wood pulp examples 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 be blended as auxiliary materials as long as the effects of the present invention are not impaired.
  • the paper substrate can be obtained, for example, by making a papermaking material containing pulp slurry as a main component.
  • Pulp slurries are obtained from wood or non-wood raw material chips through steps such as cooking, washing and bleaching.
  • the cooking method, washing method, bleaching method, etc. are not particularly limited.
  • the pulp slurry obtained through these steps is further beaten in the presence of water.
  • the freeness of pulp is not particularly limited, and is preferably 150 mL CSF or more, more preferably 250 mL CSF or more, and preferably 600 mL CSF or less, more preferably 500 mL CSF or less.
  • the desired density can be suitably adjusted. That is, by setting the freeness to 150 mL CSF or more, the density of the paper base material can be lowered and the air permeability and moisture permeability can be improved.
  • the freeness to 600 mL CSF or less the density of the paper base material can be increased and the barrier property of the smooth surface can be enhanced.
  • freeness is the Canadian standard freeness according to JIS P8121-2: 2012. Known methods can be used for beating pulp to control freeness.
  • a filler may be added to the paper base material as appropriate.
  • Fillers include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, gypsum, calcined kaolin, white carbon, amorphous silica, delaminated kaolin, diatomaceous soil, magnesium carbonate, aluminum hydroxide, calcium hydroxide. , Magnesium hydroxide, zinc hydroxide, titanium dioxide and the like can be exemplified.
  • paper base materials include, for example, sizing agents, paper strength enhancers, yield improvers, drainage improvers, pH adjusters, fabric softeners, antistatic agents, defoamers, and the like.
  • the internal additive for papermaking can be added as needed.
  • the sizing agent include rosin-based, alkyl ketene dimer-based, alkenyl succinic anhydride-based, styrene-acrylic, higher fatty acid-based, and petroleum resin-based sizing agents.
  • the basis weight of the paper substrate is not particularly limited, but from the viewpoint of obtaining a desired density and thickness, 20 g / m 2 or more is preferable, 30 g / m 2 or more is more preferable, 40 g / m 2 or more is further preferable, and 100 g / m 2 or less, and more preferably not more than 90g / m 2, 80g / m 2 or less is more preferred.
  • a known wet paper machine for example, a long net paper machine, a gap former type paper machine, a circular net type paper machine, a short net type paper machine, or the like is appropriately selected and used. be able to.
  • the wet paper formed by the paper machine is conveyed by felt and dried by a dryer.
  • a multi-stage cylinder dryer may be used as a pre-dryer before drying the dryer.
  • the wet paper may be smoothed by an on-machine breaker stack in a semi-dry state, or may be smoothed by an on-machine or off-machine calendar in a dry state.
  • Single glossy paper is preferable.
  • Single-gloss paper is paper obtained by pressing and drying it with a Yankee dryer. The single-gloss paper is dried while in contact with a Yankee dryer or the like during papermaking (restraint drying), so that the shrinkage of the fibers is suppressed, so that the paper has high disintegration property and a good texture. If the texture is good, when the paint is applied, there is little unevenness of penetration and a highly uniform coating film can be obtained. Therefore, it is considered that when single-glossy paper is used as the paper base material, the disintegration property is excellent and the barrier property is further enhanced.
  • the paper base material by using single-gloss paper as the paper base material, the pressure applied to the paper base material during smoothing is small, so that the paper base material has even higher air permeability and moisture permeability, and even if a resin layer and a protective layer are provided. It can exhibit excellent disintegration property and enhance recyclability. Further, since one surface of the paper base material is a smooth surface and has a high density, it can contribute to the improvement of the barrier property, which is contrary to having the air permeability and the moisture permeability. Further, the paper base material in the present embodiment is not particularly limited as long as it is a paper generally used with plant-derived pulp as a main component.
  • the paper base material in the present embodiment include bleached or unbleached kraft paper, single-gloss paper, high-quality paper, paperboard, liner paper, coated paper, glassin paper, and graphan paper.
  • single-gloss paper, bleached or unbleached kraft paper is preferable, and bleached kraft paper, single-gloss paper, and single-gloss bleached kraft paper are preferable from the viewpoint of improving disintegration, and not from the viewpoint of improving opacity.
  • Bleached kraft paper and unbleached kraft paper are preferable.
  • the resin layer in this embodiment is formed on at least one surface of the paper base material.
  • a resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin.
  • a microscopic magnified photograph of the resin layer is taken, it is possible to form a dense film without voids, which is clearly different from the conventional one.
  • the dense film structure of the resin layer without voids exhibits excellent water vapor barrier properties.
  • the resin layer is formed on the paper base material and the protective layer is directly formed on the resin layer, it also contributes to the formation of a uniform protective layer and exhibits further excellent gas barrier property and water vapor barrier property. be able to.
  • the water-suspendable polymer is a polymer that can be suspended in water, and facilitates the preparation of a coating material using water as a dispersion medium when forming a resin layer. Since the water-suspendable polymer functions as a binder in the formation of the resin layer, the resin layer containing a plate-like inorganic compound or the like can be uniformly formed.
  • the water-suspendable polymer is preferably a thermoplastic resin from the viewpoint of giving flexibility to the resin layer and enhancing durability during processing, and is an olefin / unsaturated carboxylic acid-based copolymer and a styrene / butadiene-based copolymer. , And one or more selected from the group consisting of styrene / acrylic copolymers, and more preferably one or more selected from the above group.
  • the olefin / unsaturated carboxylic acid-based copolymer is a copolymer of an olefin-based monomer and an unsaturated carboxylic acid-based monomer.
  • an olefin-based monomer and an unsaturated carboxylic acid-based monomer is a copolymer obtained by emulsifying and polymerizing.
  • the olefin-based monomer of the olefin / unsaturated carboxylic acid-based copolymer include ethylene; ⁇ -olefins such as propylene and butylene, and among these, ethylene is preferable.
  • the unsaturated carboxylic acid-based monomer of the olefin / unsaturated carboxylic acid-based copolymer includes an unsaturated carboxylic acid monomer and an ester monomer of an unsaturated carboxylic acid that forms a carboxylic acid by hydrolysis.
  • Examples of the unsaturated carboxylic acid-based monomer of the olefin / unsaturated carboxylic acid-based copolymer include acrylic acid, methacrylic acid, crotonic acid, silicic acid, itaconic acid, fumaric acid, maleic acid, butentricarboxylic acid and the like.
  • Unsaturated carboxylic acid and its ester examples thereof include unsaturated polycarboxylic acid monoalkyl esters having at least one carboxy group, such as itaconic acid monoethyl ester, fumaric acid monobutyl ester, and maleic acid monobutyl ester.
  • the unsaturated carboxylic acid-based monomer constituting the olefin / unsaturated carboxylic acid-based copolymer may be used alone or in combination of two or more.
  • the olefin / unsaturated carboxylic acid-based copolymer may be copolymerized with a small amount of an olefin and other monomers copolymerizable with the unsaturated carboxylic acid-based monomer.
  • the olefin / unsaturated carboxylic acid-based copolymer is preferably one or more selected from the group consisting of ethylene / acrylic acid-based copolymers and ethylene / methacrylic acid-based copolymers, and ethylene.
  • -Acrylic acid copolymer ethylene / methacrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl methacrylate copolymer , Ethylene / butyl acrylate copolymer, and one or more selected from the group consisting of ethylene / butyl methacrylate copolymer, and more preferably ethylene / acrylate copolymer.
  • 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 plate-like inorganic compound is excellent.
  • the weight average molecular weight of the olefin / unsaturated carboxylic acid-based copolymer is preferably 10,000 or more, more preferably 100,000 or more, and preferably 100,000 or more, from the viewpoint of viscosity and strength when applied to a paper substrate. It is 10 million or less, more preferably 5 million or less.
  • the weight average molecular weight of the olefin / unsaturated carboxylic acid-based copolymer can be determined by a standard polystyrene-equivalent value measured by gel filtration chromatography.
  • a commercially available product may be used as the olefin / unsaturated carboxylic acid-based copolymer, and examples thereof include "Zyxen (trade name)” manufactured by Sumitomo Seika Chemical Co., Ltd.
  • styrene-butadiene copolymer examples include styrene-butadiene rubber (SBR) and modified styrene-butadiene rubber (modified SBR).
  • modified SBR examples of the modified styrene-butadiene rubber include acid-modified styrene-butadiene rubber (acid-modified SBR).
  • Commercially available products may be used as the styrene-butadiene copolymer, and examples thereof include "Nipol LX407S series (trade name)" and “Nipol LX407BP series (trade name)” manufactured by Zeon Corporation.
  • the styrene / acrylic copolymer is a copolymer of a styrene compound and an acrylic compound, and includes, for example, a styrene compound and an acrylic compound, and other compounds capable of copolymerizing with these, if necessary. It is a copolymer obtained by emulsifying and polymerizing a monomer containing. Examples of the styrene compound include styrene, ⁇ -methylstyrene, vinyltoluene, pt-butylstyrene, chlorostyrene and the like.
  • acrylic compound examples include unsaturated carboxylic acid-based monomers such as acrylic acid and methacrylic acid; unsaturated carboxylic acid ester-based monomers such as acrylic acid ester and methacrylic acid ester.
  • Other compounds include, for example, unsaturated carboxylic acid-based monomers such as crotonic acid, silicic acid, itaconic acid, fumaric acid, maleic acid, butentricarboxylic acid; itaconic acid monoethyl ester, fumaric acid monobutyl ester and Unsaturated polycarboxylic acid alkyl ester-based monomer having at least one carboxyl group such as maleic acid monobutyl ester; unsaturated sulfone such as acrylamide propane sulfonic acid, sulfoethyl acrylate sodium salt, sulfopropyl sodium methacrylate salt and the like Examples thereof include acid-based monomers and salts thereof.
  • styrene-based compound styrene and the like are preferable, as the acrylic-based compound, acrylic acid and methacrylic acid are preferable, and as other compounds, itaconic acid, fumaric acid and the like are preferable.
  • Commercially available products may be used as the styrene / acrylic copolymer, and examples thereof include "Harville Series C-3 (trade name)” manufactured by Daiichi Paint Mfg. Co., Ltd. and "ACRONAL 4160” manufactured by BASF. Be done.
  • the content ratio of the water-suspendable polymer is not particularly limited, but is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and 50% by mass or more in the total solid content of the resin layer. Is more preferable, 60% by mass or more is further preferable, 95% by mass or less is preferable, and 90% by mass or less is more preferable.
  • the plate-like inorganic compound has an aspect ratio of 50 or more, preferably 80 or more, more preferably 200 or more, still more preferably 300 or more, still more preferably 500 or more.
  • the larger the aspect ratio the longer the moving distance of water vapor and gas becomes. Due to the maze effect, the water vapor barrier property and the gas barrier property can be improved. Further, the larger the aspect ratio, the higher the water vapor barrier property can be exhibited with a smaller content.
  • the upper limit of the aspect ratio is not particularly limited, but is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 2,000 or less, from the viewpoint of availability, viscosity when forming a resin layer on a paper substrate, and the like. is there.
  • the aspect ratio of the plate-like inorganic compound is such that at least 30 plates are taken by taking a magnified photograph using an electron microscope for a cross section in a thickness direction (vertical direction of the resin layer) parallel to the direction in which the resin layer is applied.
  • the average length and thickness are obtained by measuring the length and thickness of the state-inorganic compound and performing arithmetic averaging. Then, the value obtained by dividing the average length of the plate-shaped inorganic compound by the average thickness is defined as the aspect ratio of the plate-shaped inorganic compound.
  • the plate-like inorganic compound is not particularly limited as long as it has the above aspect ratio, but preferably contains one or more selected from the group consisting of synthetic mica, bentonite, and kaolin, and is selected from the above group1 More preferably, it is more than one species, more preferably one or more species selected from the group consisting of synthetic mica and kaolin, and even more preferably synthetic mica.
  • the thickness (average thickness) of the plate-like inorganic compound is preferably 200 nm or less, more preferably 120 nm or less, still more preferably 80 nm or less, still more preferably 50 nm or less.
  • the lower limit of the thickness is not particularly limited, but is preferably 1 nm or more from the viewpoint of availability, viscosity when forming the resin layer on the paper substrate, and the like.
  • the length (average length) of the plate-shaped inorganic compound is preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the length is 1 ⁇ m or more, the plate-like inorganic compound tends to be arranged parallel to the paper substrate. Further, when the length is 100 ⁇ m or less, there is little concern that a part of the plate-like inorganic compound protrudes from the resin layer.
  • the length of the plate-shaped inorganic compound may be described by the expression of particle size.
  • the content of the plate-like inorganic compound contained in the resin layer is not particularly limited, and is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the water-suspendable polymer. , More preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 800 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 100 parts by mass or less. It is more preferably 80 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less.
  • the content of the plate-shaped inorganic compound is 0.1 part by mass or more with respect to 100 parts by mass of the water-suspending polymer, the water vapor barrier property is likely to be exhibited.
  • it is 800 parts by mass or less, it is possible to further suppress the exposure of a part of the plate-like inorganic compound from the layer surface, and it is possible to further improve the water vapor barrier property.
  • the protective layer is directly formed on the resin layer, the coatability of the protective layer is improved, the uniform protective layer is easily formed, and the gas barrier property is easily improved.
  • the ratio of the plate-like inorganic compound contained in the resin layer is not particularly limited, and from the viewpoint of improving the water vapor barrier property and the gas barrier property, it is preferably 0.1% by mass or more based on the total solid amount of the resin layer, and 1 mass by mass. % Or more is more preferable, 2% by mass or more is further preferable, 5% by mass or more is further preferable, and 10% by mass or more is further preferable.
  • it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and 40% by mass or less. It is more preferably 30% by mass or less, and further preferably 20% by mass or less. From the viewpoint of being effective with a smaller content, synthetic mica having a large aspect ratio and a small thickness can be preferably used among the plate-like inorganic compounds.
  • the resin layer contains a cationic resin.
  • the plate-shaped inorganic compound has a so-called card house structure in which the plate-shaped inorganic compounds are three-dimensionally connected to each other because the plate-shaped flat portion is easily charged anionic and the edge portion is easily charged cationically. It has been known. Due to this card house structure, the viscosity of the aqueous dispersion of the plate-like inorganic compound becomes very high.
  • the aqueous dispersion of the plate-like inorganic compound exhibits thixotropy. It is considered that when an appropriate cationic resin is added to the aqueous dispersion of the plate-shaped inorganic compound, the cationic resin is adsorbed on the anionically charged flat portion of the plate-shaped inorganic compound, and the card house structure is destroyed. Be done. As a result, it is presumed that the three-dimensional connection of the plate-shaped inorganic compounds is suppressed, the plate-shaped inorganic compounds are easily laminated in parallel with the plane of the paper substrate, and the water vapor barrier property is improved. Furthermore, it is estimated that the gas barrier property is also improved.
  • cationic resin examples include polyamine resins, modified polyamide resins (for example, cationic modified polyamide resins such as amine-modified polyamide resins), polyamide epichlorohydrin resins, polyethyleneimine resins, polyalkylene polyamine resins, polyamide compounds, and polyamides.
  • Amin / epihalohydrin or formaldehyde condensation reaction product polyamine / epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea / epihalohydrin or formaldehyde condensation reaction product, polyamine polyurea / epihalohydrin or formaldehyde condensation reaction product, polyamide amine polyurea / epihalohydrin
  • the formaldehyde condensation reaction product, polyamide polyurea compound, polyamine polyurea compound, polyamideamine polyurea compound and polyamideamine compound polyvinylpyridine, amino-modified acrylamide compound, polyvinylamine resin, polydialyldimethylammonium chloride and the like can be mentioned. it can.
  • the cationic resin is preferably at least one selected from polyamine resin, modified polyamide resin, and polyethyleneimine resin, more preferably modified polyamide resin, and further preferably cationic modified polyamide resin. It is a resin, more preferably an amine-modified polyamide resin.
  • the content of the cationic resin contained in the resin layer is preferably 0.5 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the plate-shaped inorganic compound from the viewpoint of further improving the water vapor barrier property. More than parts, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, still more preferably 60 parts by mass or more, and preferably 300 parts by mass or less, more preferably 250 parts by mass. Parts or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less.
  • the content of the cationic resin contained in the resin layer is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the water-suspendable polymer, from the viewpoint of further improving the water vapor barrier property.
  • 1 part by mass or more more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 100 parts by mass or less, more preferably 100 parts by mass or more. It is 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.
  • the proportion of the cationic resin contained in the resin layer is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass, based on the total solid content of the resin layer.
  • the above is more preferable, 1% by mass or more is further preferable, 5% by mass or more is further preferable, 20% by mass or less is preferable, and 15% by mass or less is more preferable.
  • the resin layer may contain pigments, dispersants other than the above-mentioned cationic resins, surfactants, defoaming agents, as appropriate.
  • Auxiliary agents such as wetting agents, dyes, color modifiers, thickeners, and water-soluble polymers can be added.
  • the thickness of the resin layer is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the amount of the resin layer formed (hereinafter, also referred to as the coating amount) is preferably 1 g / m 2 or more, more preferably 3 g / m 2 or more, and preferably 30 g / m 2 or less as a solid content. , More preferably 20 g / m 2 or less.
  • the protective layer in this embodiment is formed on at least one surface of the paper substrate.
  • a protective layer contains a water-soluble polymer.
  • the protective layer may be formed on a resin layer or a paper base material. When formed on the resin layer, it is excellent in gas barrier property, particularly oxygen barrier property, and can protect the resin layer to improve the barrier property. In addition, it is possible to improve the disintegration property in the presence of water and obtain a paper laminate having better recyclability. On the other hand, by forming the protective layer on the paper base material, a more uniform resin layer can be formed and the barrier property can be further improved.
  • Water-soluble polymer examples include polyvinyl alcohol, modified polyvinyl alcohol, starch and its derivatives, cellulose derivatives, polyvinylpyrrolidone, urethane resins, polyacrylic acids and salts thereof, casein, polyethyleneimine and the like.
  • polyvinyl alcohol completely saponified or partially saponified polyvinyl alcohol, modified polyvinyl alcohol, and polyethyleneimine are preferable because they have more excellent gas barrier properties, and one or more selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol is selected. It is more preferable to include, and it is further preferable that it is one or more selected from the above group.
  • modified polyvinyl alcohol include ethylene-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, and diacetone-modified polyvinyl alcohol.
  • the content of the water-soluble polymer is preferably 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less based on the total solid content of the protective layer.
  • the protective layer may contain the above-mentioned plate-like inorganic compound.
  • the plate-like inorganic compound is preferably at least one selected from the group consisting of synthetic mica, bentonite and kaolin from the viewpoint of improving the barrier property.
  • the plate-shaped inorganic compound contained in the protective layer may be of the same type as the plate-shaped inorganic compound contained in the resin layer, or may be of a different type.
  • the content of the plate-shaped inorganic compound is not particularly limited, but is preferably 1 part by mass or more and 5 parts by mass with respect to 100 parts by mass of the water-soluble polymer of the protective layer.
  • the plate-like inorganic compounds it is preferable to contain 5 parts by mass or more and 15 parts by mass or less of synthetic mica having a large aspect ratio and a small thickness with respect to 100 parts by mass of the water-soluble polymer of the protective layer. Further, when synthetic mica is used in combination with another plate-shaped inorganic compound (for example, kaolin), the content of the other plate-shaped inorganic compound is preferably 20 with respect to 100 parts by mass of the water-soluble polymer of the protective layer. It is at least 80 parts by mass, and preferably 80 parts by mass or less.
  • the protective layer is appropriately composed of a plate-like inorganic compound, a pigment, a cationic resin, a dispersant other than the above-mentioned cationic resin, a surfactant, a defoaming agent, a wetting agent, and a dye.
  • Tone adjusters, thickeners and other auxiliaries can be added.
  • the thickness of the protective layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the amount of the protective layer formed (hereinafter, also referred to as the coating amount) is preferably 0.1 g / m 2 or more, more preferably 0.5 g / m 2 or more, and preferably 10 g as the solid content. / M 2 or less, more preferably 5 g / m 2 or less.
  • the sealant layer is on the layer farthest from the paper base material on the side where the resin layer and the protective layer are formed, or on the layer farthest from the paper base material on the side where the resin layer and the protective layer are not formed (resin). It can be formed on one or both of (on the paper substrate if there is no other layer on the side that does not form the layer and the protective layer).
  • the sealant layer is a layer that melts and adheres by heating or ultrasonic waves, and is a layer that can bond the paper laminates to each other by heat sealing or the like.
  • the sealant layer is formed by laminating synthetic resins such as polyolefin (polyethylene, polypropylene, etc.), modified polyolefin, ethylene-vinyl acetate polymer, polyvinyl acetate polymer, etc. by melt extrusion laminating method or dry laminating method. Can be done.
  • the sealant layer can also be formed by applying, for example, an emulsified dispersion of a synthetic resin such as a polyolefin, a modified polyolefin, an ethylene-vinyl acetate polymer, or a polyvinyl acetate polymer.
  • the sealant layer preferably contains a biodegradable resin.
  • the biodegradable resin are not particularly limited, and for example, polylactic acid (PLA).
  • PBS Polybutylene succinate
  • PBSA Polybutylene succinate adipate
  • PHBH 3-hydroxybutanoic acid / 3-hydroxyhexanoic acid copolymer
  • 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 amount of the sealant layer formed is preferably 1 g / m 2 or more, more preferably 3 g / m 2 or more, and preferably 50 g / m 2 or less and more preferably 30 g / m 2 or less as a solid content. ..
  • a resin layer and a protective layer are formed on at least one surface of the paper base material, and a sealant layer is formed if necessary.
  • the method for forming each layer is not particularly limited, but it is preferable that at least the resin layer and the protective layer are formed by a coating method.
  • a resin layer paint is applied on a paper base material, dried to form a resin layer, and a protective layer paint is further applied on the resin layer. It may be dried to form a protective layer.
  • Each layer may be formed by sequentially applying and drying the paint, or may be formed by simultaneously applying multiple layers and then drying.
  • the simultaneous multilayer coating the coating layers on the front surface and the back surface of the paper substrate may be coated simultaneously on both sides, or the lower layer and the upper layer on one side may be coated simultaneously.
  • the coating equipment for applying paint, and known equipment may be used.
  • the coating equipment include a Mayer bar, a blade coater, a bar coater, an air knife coater, a slit die coater, a curtain coater, a gravure coater, a micro gravure coater, a gate roll coater, and a size press coater.
  • a coater that scrapes the coated surface such as a Mayer bar, a blade coater, a bar coater, an air knife coater, and a slit die coater is preferable because it promotes the orientation of the plate-like inorganic compound.
  • the drying equipment for drying the coating layer is not particularly limited, and known equipment can be used. Examples of the drying equipment include a hot air dryer, an infrared dryer, a gas burner, a hot plate, and the like. Further, the drying temperature may be appropriately set in consideration of the drying time and the like.
  • the solvent for the coating material is not particularly limited, and for example, water or an organic solvent such as ethanol, isopropyl alcohol, methyl ethyl ketone or toluene can be used.
  • water is preferable as the dispersion medium of the coating material from the viewpoint of not causing the problem of the volatile organic solvent. That is, the coating material for the resin layer and the protective layer is preferably an aqueous composition.
  • the solid content concentration of the coating material is not particularly limited and may be appropriately selected from the viewpoint of coatability and easiness of drying, but is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass. It is more than 80% by mass, more preferably 70% by mass or less, still more preferably 60% by mass or less.
  • the paper laminate of the present embodiment can be suitably used as a packaging material for foods such as coffee, confectionery, milk, pharmaceuticals, medical products, electronic parts, etc. by taking advantage of the above-mentioned excellent water vapor barrier property and gas barrier property. it can. Among these, since it has resistance to cracking, it can be suitably used for flexible packaging materials, paper containers for heavy bags, packaging containers such as milk cartons, and the like.
  • Example 1 Preparation of aqueous dispersion of plate-shaped inorganic compound
  • Plate-shaped inorganic compound engineered kaolin, particle size 10 ⁇ m, aspect ratio 100, thickness 100 nm, trade name: Varisurf HX, manufactured by Imeris
  • a 55% aqueous dispersion A was obtained.
  • the smooth surface of single-gloss bleached kraft paper manufactured by Oji Materia Co., Ltd.
  • the opposite surface hereinafter, also referred to as non-glossy surface or non-smooth surface
  • the opposite surface was coated with a Mayer bar and then dried in a hot air dryer at 120 ° C. for 1 minute to form a resin layer (thickness: 12 ⁇ m).
  • the resin layer is coated with a Mayer bar so that the coating amount after drying is 3.0 g / m 2, and then dried in a hot air dryer at 120 ° C.
  • the single-gloss bleached kraft paper used as the paper base material has a basis weight of 65 g / m 2 , a thickness of 62 ⁇ m, a density of 0.76 g / m 3 , a smooth surface of Oken type smoothness of 427 seconds, and a non-smooth surface of Oken type.
  • the smoothness was 17 seconds.
  • Example 2 Preparation of resin layer paint Water dispersion B of plate-shaped inorganic compound (synthetic mica, particle size 6 ⁇ m, aspect ratio 1200, thickness 5 nm, solid content 6%, trade name: NTO-05, manufactured by Topy Industry Co., Ltd.) 30 Self-emulsifying polyolefin dispersion (solid content 29.2%, trade name: Zyxen AC, manufactured by Sumitomo Seika Co., Ltd., ethylene / acrylic acid) as an olefin / unsaturated carboxylic acid-based copolymer in 0.0 part. Copolymer) 34.2 parts was added and stirred.
  • plate-shaped inorganic compound synthetic mica, particle size 6 ⁇ m, aspect ratio 1200, thickness 5 nm, solid content 6%, trade name: NTO-05, manufactured by Topy Industry Co., Ltd.
  • Self-emulsifying polyolefin dispersion solid content 29.2%, trade name: Zyxen AC, manufactured by Sumito
  • the smooth surface of single-gloss bleached kraft paper manufactured by Oji Materia Co., Ltd.
  • the opposite surface was coated with a Mayer bar and then dried in a hot air dryer at 120 ° C. for 1 minute to form a resin layer (thickness: 6 ⁇ m).
  • the resin layer is coated with a Mayer bar so that the coating amount after drying is 3.0 g / m 2, and then dried in a hot air dryer at 120 ° C. for 1 minute.
  • a protective layer (thickness: 3 ⁇ m) was formed to obtain a paper laminate.
  • the single-gloss bleached kraft paper used as the paper base material has a basis weight of 65 g / m 2 , a thickness of 62 ⁇ m, a density of 0.76 g / m 3 , a smooth surface of Oken type smoothness of 427 seconds, and a non-smooth surface of Oken type. The smoothness was 17 seconds.
  • Example 3 In the production of the paper laminate of Example 1, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji Materia Co., Ltd.) A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the smooth surface (glossy surface) of (manufactured by).
  • Example 4 In the production of the paper laminate of Example 1, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji F-Tex Co., Ltd.) A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by the company).
  • the single-gloss bleached kraft paper used as the paper base material has a basis weight of 50 g / m 2 , a thickness of 62.3 ⁇ m, a density of 0.80 g / cm 3 , a smooth surface of Oken-style smoothness of 287 seconds, and a non-smooth surface of King. The sharpness was 17 seconds.
  • Example 5 In the production of the paper laminate of Example 2, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji F-Tex Co., Ltd.) A paper laminate was obtained in the same manner as in Example 2 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by the company).
  • Example 6 In the production of the paper laminate of Example 2, instead of the surface opposite to the smooth surface (non-smooth surface) of the single gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single gloss bleached kraft paper (Oji F-Tex Co., Ltd.) A paper laminate was obtained in the same manner as in Example 2 except that a resin layer and a protective layer were formed on the smooth surface (glossy surface) of (manufactured by the company).
  • Example 7 In the paper laminate of Example 4, 6 g / m 2 of an aqueous heat sealant (main component: modified polyolefin resin) was further applied onto the protective layer to form a sealant layer (thickness: 6 ⁇ m). A paper laminate was obtained.
  • main component modified polyolefin resin
  • Example 8 In the paper laminate of Example 5, 6 g / m 2 of an aqueous heat sealant (main component: modified polyolefin resin) was further applied onto the protective layer to form a sealant layer (thickness: 6 ⁇ m). A paper laminate was obtained.
  • main component modified polyolefin resin
  • Example 9 In the production of the paper laminate of Example 1, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss unbleached kraft paper (Tenma Special) A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by Paper Manufacturing Co., Ltd.).
  • the single-gloss unbleached kraft paper used as the paper base material has a basis weight of 50 g / m 2 , a thickness of 65 ⁇ m, a density of 0.80 g / cm 3 , a smooth surface of Oken type smoothness of 213 seconds, and a non-smooth surface of Oken.
  • the formula smoothness was 25 seconds.
  • Example 10 In the production of the paper laminate of Example 2, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss unbleached kraft paper (Tenma Special) A paper laminate was obtained in the same manner as in Example 2 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by Paper Manufacturing Co., Ltd.).
  • Example 1 In the production of the paper laminate of Example 1, bleached kraft paper (manufactured by Oji Materia Co., Ltd.) was used instead of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), and further on one side of the bleached kraft paper. A paper laminate was obtained in the same manner as in Example 1 except that the resin layer and the protective layer were formed.
  • the bleached kraft paper used as the paper substrate has a basis weight of 50 g / m 2 , a thickness of 60 ⁇ m, a density of 0.76 g / m 3 , a Oken-type smoothness on one side for 63 seconds, and a Oken-type smoothness on the other side.
  • the degree was 45 seconds.
  • the bleached kraft paper used as the paper substrate has a basis weight of 50 g / m 2 , a thickness of 60 ⁇ m, a density of 0.76 g / m 3 , a Oken-type smoothness on one side for 63 seconds, and a Oken-type smoothness on the other side.
  • the degree was 45 seconds.
  • Example 4 In the production of the paper laminate of Example 1, unbleached kraft paper (manufactured by Oji Materia Co., Ltd.) is used instead of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), and one of the unbleached kraft papers is further produced. A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the surface.
  • the unbleached kraft paper used as the paper base material has a basis weight of 50 g / m 2 , a thickness of 74 ⁇ m, a density of 0.68 g / cm 3 , a Wangken type smoothness on one side of 18 seconds, and a Wangken type on the other side.
  • the smoothness was 17 seconds.
  • oxygen permeability measuring device OX-TRAN2 / 20 manufactured by MOCON
  • the paper laminate is used under atmospheric pressure at a temperature of 23 ° C and a relative humidity of 50% (low humidity condition). Oxygen permeability was measured. The lower the oxygen permeability value, the better the oxygen barrier property.
  • Dissociation rate The obtained paper laminate was dissociated in accordance with JIS P 8220: 2012. At this time, the mass ratio (%) of the residue was calculated by collecting and drying the sample on the screen 10 minutes after the start of dissociation, and the mass ratio of 100-residue was defined as the dissociation rate (%).
  • the texture of the obtained paper laminate was measured using the total texture (Mk systems, 3D sheet analyzer). RANGE was set to 1, and the measurement surface was the surface with higher smoothness.
  • the opacity of the obtained paper laminate was measured according to JIS P 8149: 2000. The opacity of the surface with the higher smoothness was measured.
  • the paper laminates of Comparative Examples 1 and 2 had a low disintegration rate and were inferior in dissociation property.
  • the paper laminate of Comparative Example 3 having no resin layer and protective layer on at least one surface of the paper base material had high water vapor permeability and oxygen permeability, and was inferior in barrier property.
  • Table 2 shows a comparison between Examples 9 to 10 in which single-gloss unbleached kraft paper was used as the paper base material and unbleached kraft paper having a smoothness of 100 seconds or more and no smooth surface as the paper base material. Comparison with Example 4.
  • the paper laminates of Examples 9 to 10 had low water vapor permeability and oxygen permeability, and had a high dissociation rate. That is, the paper laminates of Examples 9 to 10 were excellent in disintegration property and had high barrier property.
  • the paper laminate of Comparative Example 4 had a low disintegration rate and was inferior in dissociation property. Further, the paper laminate of Comparative Example 4 had high water vapor permeability and was inferior in water vapor barrier property.
  • Examples 9 to 10 using the single-gloss unbleached kraft paper as the paper base material had higher opacity than Examples 1 to 8 using the single-gloss bleached kraft paper. Therefore, the paper laminates of Examples 9 to 10 are more excellent in that the contents are difficult to see through when used as a packaging material.

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

Abstract

Le but principal de la présente invention est de fournir un stratifié de papier qui présente d'excellentes propriétés de séparation et des propriétés barrières élevées. L'invention concerne plus précisément un stratifié de papier comportant un substrat de papier, et une couche de résine et une couche protectrice sur au moins une surface du substrat de papier, la densité du substrat de papier étant de 0.50g/cm3 à 0,90 g/cm3 inclus, la surface sur un côté du substrat de papier est une surface lisse, le lissé de type Oken de la surface lisse, lorsqu'il est mesuré selon la norme JIS P 8155: 2010 est d'au moins 100 secondes, la couche de résine contient un polymère dispersible dans l'eau, un composé inorganique en forme de plaque ayant un rapport d'aspect de 50 ou plus et une résine cationique, et la couche de protection contient un polymère soluble dans l'eau.
PCT/JP2020/042116 2019-11-14 2020-11-11 Stratifié de papier WO2021095780A1 (fr)

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WO2022270321A1 (fr) * 2021-06-24 2022-12-29 Ｄｉｃグラフィックス株式会社 Corps stratifié et papier d'emballage ou récipient utilisant un tel corps stratifié
JP7317262B2 (ja) 2021-06-24 2023-07-28 Ｄｉｃグラフィックス株式会社 積層体、及び該積層体を用いた包装紙又は容器
WO2023067852A1 (fr) * 2021-10-19 2023-04-27 Dic株式会社 Produit stratifié et matériau d'emballage
JP7290204B1 (ja) * 2021-10-19 2023-06-13 Dic株式会社 積層体及び包装材

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