EP2777934B1 - Matériau d'emballage à papier barrière - Google Patents

Matériau d'emballage à papier barrière Download PDF

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Publication number
EP2777934B1
EP2777934B1 EP12847115.8A EP12847115A EP2777934B1 EP 2777934 B1 EP2777934 B1 EP 2777934B1 EP 12847115 A EP12847115 A EP 12847115A EP 2777934 B1 EP2777934 B1 EP 2777934B1
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EP
European Patent Office
Prior art keywords
barrier layer
water vapor
paper
vapor barrier
coating
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP12847115.8A
Other languages
German (de)
English (en)
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EP2777934A4 (fr
EP2777934A1 (fr
Inventor
Masashi Okamoto
Takaharu Noda
Takeshi Nakayama
Masatsugu Kato
Akinobu Chatani
Masaaki Fukunaga
Yukiko Sato
Junichi Hayakawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper Co Ltd
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Publication of EP2777934A1 publication Critical patent/EP2777934A1/fr
Publication of EP2777934A4 publication Critical patent/EP2777934A4/fr
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • 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
    • D21H19/822—Paper comprising more than one coating superposed two superposed coatings, both being pigmented
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • the present invention relates to a paper-based barrier material used for a food packaging material, a food container, or a food cup.
  • gas barrier property in particular, an oxygen barrier property
  • Paper packaging materials have hitherto been provided to which a gas barrier property is imparted by laminating a metal foil or a film on a paper base material.
  • the material forming the barrier layer include: a metal foil or a metal vapor deposited film made of a metal such as aluminum; a resin film made of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride or polyacrylonitrile; a film coated with such a resin; and a ceramic vapor-deposited film which is further coated with a vapor-deposited inorganic oxide such as silicon oxide or aluminum oxide.
  • Patent Literature 1 paper gas barrier materials having a gas barrier layer made of a water soluble polymer and an inorganic layered compound have been disclosed in Patent Literature 1 and Patent Literature 2.
  • Patent Literature 2 A paper gas barrier material in which a barrier layer made of a specific vinyl alcohol-based polymer is provided on a coating layer is disclosed in Patent Literature 2.
  • a waterproofness in particular, a water vapor barrier property
  • a paper packaging material for the purpose of protecting various products to be packaged from the degradation due to water vapor.
  • a paper packaging material has been proposed in which a water vapor barrier property is imparted by extrusion lamination of or pasting of a resin film excellent in water vapor barrier property onto a paper base material, or alternatively, by extrusion lamination of or pasting of, for example, a film coated with such a resin excellent in water vapor barrier property on a paper base material.
  • a packaging paper having a moistureproof layer composed of a synthetic resin latex, a wax and inorganic fine particles is disclosed in Patent Literature 3.
  • a packaging material in which both of a gas barrier property and a water vapor barrier are imparted to a paper packaging material
  • a packaging material in which a resin having a gas barrier property and a resin having a water vapor barrier property are laminated on a paper base material.
  • Patent Literature 4 discloses a packaging material comprising a base material layer made of paper, a clay coat layer containing clay formed on the base material layer and a barrier layer formed on the clay coat layer.
  • the clay coat layer preferably contains at least one of kaolin, talc, calcium carbonate and titanium dioxide (abstract).
  • the clay coat layer can contain styrene butadiene latex as a binder resin (paragraph [0020]).
  • Patent Literature 5 describes a thermal recording material which, in addition to thermal recording layers, contains an intermediate layer comprising modified polyvinyl alcohol and synthetic mica particles (abstract).
  • Patent Literature 6 discloses a laminate which has gas barrier and moisture barrier properties.
  • the laminate comprises a gas barrier layer consisting essentially of microfibrous cellulose, which is formed on one surface of a paper support and a moistureproof layer comprising a pigment and a synthetic resin latex formed on the gas barrier layer (abstract).
  • a packaging material in which by extrusion lamination of a resin having a gas barrier property and a resin having a water vapor barrier property on a paper base material (base paper), both barrier layers are formed on the paper base material has a problem that the packaging material cannot cope with the required quality because the types of the resins capable of being extrusion laminated are limited.
  • a packaging material in which multilayers are laminated on a paper base material in order to establish the compatibility between the gas barrier property and the water vapor barrier property finds difficulty in recycling of the paper and the laminated layers.
  • the multilayer laminated packaging material also offers a problem such that the carbon dioxide emission amount in the production thereof is large.
  • specific adhesive resins are sometimes required to be used between the respective laminated layers, to offer another problem that the production of the multilayer laminated packaging material is cumbersome.
  • a packaging material in which a paper base material is coated with a resin having a gas barrier property and a resin having a water vapor barrier property and the types of the usable resins are scarcely limited, and various required qualities can be coped with.
  • a packaging material to which both of the gas barrier property and the water vapor barrier property are imparted for example, in the case where the moistureproof layer of Patent Literature 3 is disposed on the packaging material having a gas barrier property of Patent Literature 1 or Patent Literature 2, offers a problem that although a satisfactory water vapor barrier property is obtained, no gas barrier property is obtained.
  • the gas barrier layer of Patent Literature 1 or Patent Literature 2 is disposed on a moistureproof paper having the moistureproof layer of Patent Literature 3, the surface tension of the moistureproof layer, hence the gas barrier layer is not uniformly formed due to repellency, and hence no sufficient gas barrier property can be obtained.
  • the present invention takes as its object the provision of a paper based barrier packaging material simultaneously having both of an excellent gas barrier property and an excellent water vapor barrier property.
  • a paper based barrier packaging material comprising a plurality of coating layers disposed on a paper base material, wherein the plurality of coating layers includes a water vapor barrier layer formed on the paper base material and a gas barrier layer formed on the water vapor barrier layer, wherein a resin selected from the group consisting of styrene-butadiene-based resins, styrene-acrylic resins, ethylene-vinyl acetate-based resins, butadiene-methyl methacrylate-based resins, vinyl acetate-butyl acrylate-based copolymers, maleic anhydride copolymer and acrylic acid-methyl methacrylate-based copolymer or a mixture of two or more thereof is used as a binder resin in the water vapor barrier layer, wherein a polyvinyl alcohol resin is used as a binder resin in the gas barrier layer, and wherein the water vapor barrier layer includes kaolin having an average particle size of 5 ⁇ m or more and
  • the present invention is a paper based barrier packaging material (hereinafter, sometimes referred to as a "packaging material”) including a water vapor barrier layer and a gas barrier layer disposed in this order on a paper base material (hereinafter, sometimes referred to as a "base paper").
  • the two types of barrier layers are each formed by applying an aqueous coating material, and to the coating material, a polymer binder as a main additive, a pigment, and a cross-linking agent are added.
  • the water vapor barrier layer or the gas barrier layer is formed by coating with a coating material including a polymer as a binder resin and using water as a dispersion medium.
  • a coating material including a polymer as a binder resin and using water as a dispersion medium.
  • the paper based barrier packaging material of the present invention includes the water vapor barrier layer formed on a paper base material and further the gas barrier layer on the water vapor barrier layer simultaneously has both of an excellent water vapor barrier property and an excellent gas barrier property are inferred as follows.
  • the paper based barrier packaging material of the present invention has a satisfactory water vapor barrier property and a satisfactory gas barrier property.
  • the paper based barrier packaging material of the present invention is usually used in such a way that the side of the gas barrier layer is the side of the content (article to be packaged) and the side of the paper layer is the atmospheric side (outer surface).
  • the permeation of the atmospheric moisture into the interior can be prevented, and hence when the article to be packaged is a dry substance, the structure of the present invention is effective.
  • a resin extrusion laminated layer or a film laminate layer is additionally formed on the gas barrier layer to be the inner side.
  • the paper base material is a sheet includes pulp, a filler, and various additives.
  • the pulp include: chemical pulps such as leaf bleached kraft pulp (LBKP), needle bleached kraft pulp (NBKP) and sulfite pulp; mechanical pulps such as stone-ground pulp and thermomechanical pulp; and non-wood fibers obtained from kenaf, bamboo, and hemp. These materials can be appropriately mixed to be used.
  • the chemical pulps such as leaf bleached kraft pulp (LBKP) and needle bleached kraft pulp (NBKP) are preferable.
  • the chemical pulps are suitable, for example, for the reasons that contamination of the base paper hardly occurs, temporal discoloration hardly occurs when used paper containers are collected as waste paper raw materials to be recycled, and chemical pulps have a high degree of whiteness to result in satisfactory surface touch at the time of printing so as to enhance the value in use as packaging materials.
  • the usable filler examples include heretofore known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, precipitated calcium carbonate, titanium oxide, zeolite and synthetic resin fillers.
  • the following papermaking internal aids can also be used: aluminum sulfate; various anionic, cationic, nonionic, or amphoteric yield improvers; a freeness improver, a paper-strengthening agent and an internal sizing agent.
  • a dye, a fluorescent whitening agent, a pH adjuster, an antifoaming agent, a pitch control agent, and a slime control agent can also be added.
  • the method of the production (paper making) of the paper base material is not particularly limited; paper base materials can be produced by using heretofore known fourdrinier former, on-top hybrid former and gap former machines, and by performing paper making with acidic paper making, neutral paper making, alkaline paper making methods.
  • the paper base material is preferably a material generally used for coated papers, having a basis weight of about 25 to 400 g/m 2 .
  • the surface of the paper base material can be treated with various chemicals.
  • Examples of the chemicals to be used may include: oxidized starch, hydroxyethyl etherified starch, oxygen-modified starch, polyacrylamide, polyvinyl alcohol, a surface sizing agent, a waterproofing agent, a water retention agent, a thickener and a lubricant; these can be used each alone or in combinations of two or more thereof.
  • the method of the surface treatment of the paper base material is not particularly limited; however, heretofore known coating apparatuses such as a rod metering size press, a pond type size press, a gate roll coater, a spray coater, a blade coater and a curtain coater can be used.
  • the polymer to be used as the main component of the coating layer forming the water vapor barrier layer or the gas barrier layer is suitably a resin for which water can be used as a dispersion medium.
  • the dosage form include a polymer aqueous solution and a form of a polymer emulsion.
  • the polymer corresponds to the binder of the coating material for forming a coating layer.
  • the resins to be included in the water vapor barrier layer are used each alone or as mixtures of two or more thereof: copolymers such as styrene-butadiene-based, styrene-acrylic, ethylene-vinyl acetate-based, butadiene-methyl methacrylate-based, vinyl acetate-butyl acrylate-based copolymers; maleic anhydride copolymer; and acrylic acid-methyl methacrylate-based copolymer.
  • styrene-butadiene-based resin is preferable from the viewpoint of the water vapor barrier property.
  • styrene-butadiene-based synthetic resin is a resin synthesized with emulsion polymerization by using styrene and butadiene as the main constituent monomers in combination with various comonomers aiming at modification.
  • the comonomer include: methyl methacrylate, acrylonitrile, acrylamide and hydroxyethyl acrylate; and unsaturated carboxylic acids such as itaconic acid, maleic acid and acrylic acid.
  • the resins are used as emulsion-type coating materials prepared by emulsification with water as a dispersant.
  • the emulsifier include anionic surfactants such as sodium oleate, rosin acid soap, sodium alkyl allyl sulfonate and sodium dialkyl sulfosuccinate. These can be used each alone or in combinations with nonionic surfactants. Moreover, if necessary, amphoteric or cationic surfactants may also be used.
  • the coating material to form the water vapor barrier layer preferably does not include water-repellent components such as a hydrocarbon, a silicone-based resin, a fluorine-based resin, a fatty acid and an ester between a fatty acid and an alcohol.
  • water-repellent components such as a hydrocarbon, a silicone-based resin, a fluorine-based resin, a fatty acid and an ester between a fatty acid and an alcohol.
  • conventional packaging materials having a water vapor barrier property are generally provided with water-repellent component-containing resins.
  • the water-repellent component degrades the affinity between the water vapor barrier layer and the gas barrier layer, and accordingly, the moisture or gas permeating from one of these layers unpreferably promotes interfacial peeling.
  • the inclusion of a pigment in the water vapor barrier layer improves the water vapor barrier property, and also improves the adhesion between the water vapor barrier layer and the gas barrier layer.
  • the water vapor barrier property is improved by using a pigment large in particle size and a pigment small in particle size in combination.
  • the large pigment kaolin having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more is used.
  • a flat pigment is distributed parallel to the coating layer, the water vapor permeating into the water vapor barrier layer is blocked by the flat pigment with respect to the movement in the thickness direction and is made to move in a detour so as to elongate the path of the passage of the water vapor through the water vapor barrier layer, and hence the barrier property is improved.
  • the aspect ratio of the added pigment is small, the number of times of detour of the water vapor in the coating layer is decreased, accordingly the distance of the movement of the water vapor is reduced, and consequently the pigment small in aspect ratio is inferior to the flat pigment having a large particle size.
  • a flat pigment can be expected to have the same effect as described above on the gas barrier layer.
  • the water vapor barrier property can be further improved.
  • the pigment having a small particle size is not required to be flat.
  • the water vapor barrier layer further includes a pigment having an average particle size of 5 ⁇ m or less.
  • a pigment having an average particle size of 5 ⁇ m or less is interposed between the kaolin particles present in a multilayered manner, having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more, and consequently, the water vapor being forced to move along the flat plane of kaolin is blocked in its movement by the smaller pigment particles.
  • the water vapor barrier layer since pigments different in flatness and average particle size are included in the water vapor barrier layer, a state occurs in which in the water vapor barrier layer, the pigment of smaller particle size is filled in the voids formed between the adjacent flat pigment particles large in particle size, accordingly the water vapor passes all the way around the pigments, and hence the water vapor barrier layer including the pigments different in average particle size exhibits a higher water vapor barrier property as compared to the water vapor barrier layer including no pigment smaller in particle size.
  • the mixing ratio between kaolin having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more and the pigment having an average particle size of 5 ⁇ m or less is 50/50 to 99/1 in terms of dry weight.
  • the ratio of kaolin having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more is smaller than the foregoing range, the detour distance of the water vapor in the coating layer is short, and hence no sufficient water vapor barrier property can be obtained.
  • the ratio of kaolin having an average particle size of 5 ⁇ m or more and an aspect ratio of 10 or more is larger than the foregoing range, the voids formed by the large particle size pigment in the coating layer cannot be sufficiently filled by the pigment having an average particle size of 5 ⁇ m or less, and hence no improvement of the water vapor barrier property is found.
  • the following pigments can be used each alone or as mixtures of two or more thereof: inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicates, colloidal silica and satin white; and organic pigments such as a dense-type pigment, a hollow-type pigment, or a core-shell type pigment. Among these pigments, heavy calcium carbonate is preferable.
  • the mixing amounts of the resin and the pigments in the water vapor barrier layer are such that a resin is used in an amount of preferably 5 to 200 parts by weight and more preferably 20 to 150 parts by weight (dry weight) in relation to 100 parts by weight (dry weight) of the pigment.
  • a resin is used in an amount of preferably 5 to 200 parts by weight and more preferably 20 to 150 parts by weight (dry weight) in relation to 100 parts by weight (dry weight) of the pigment.
  • various usually used aids such as a dispersant, a thickener, a water retention agent, an antifoaming agent, a waterproofing agent, a dye and a fluorescent dye.
  • a cross-linking agent typified by a multivalent metal salt
  • the cross-linking agent causes a cross-linking reaction with the binder included in the water vapor barrier layer, and accordingly the number of the bonds (the number of the cross-linked points) in the water vapor barrier layer is increased.
  • the water vapor barrier layer becomes dense in structure, and consequently exhibits a satisfactory water vapor barrier property.
  • the type of the cross-linking agent is not particularly limited; the cross-linking agent appropriately according to the type of the binder included in the water vapor barrier layer from the following can be used: multivalent metal salts (the compounds produced by bonding the multivalent metals such as copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium and titanium with the ionic substances such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide and boron oxide); and amine compounds, amide compounds, aldehyde compounds, and hydroxy acids.
  • multivalent metal salts the compounds produced by bonding the multivalent metals such as copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium and titanium with the ionic substances such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion,
  • the cross-linking agent can be mixed without being particularly limited with respect to the mixing amount thereof.
  • a multivalent metal salt when a styrene-based water vapor barriering resin exhibiting excellent effects in the water vapor barrier property, such as a styrene-butadiene-based resin or a styrene-acrylic-based resin is used; in particular, potassium alum is more preferable.
  • the addition amount of the cross-linking agent is 1 to 10 parts by weight and more preferably 3 to 5 parts by weight in relation to 100 parts by weight of the binder resin used in the water vapor barrier layer.
  • the addition amount of the cross-linking agent is less than 1 part by weight, no sufficient effect is obtained, and when the addition amount of the cross-linking agent is larger than 10 parts by weight, the viscosity of the coating liquid is remarkably increased to make the coating operation difficult.
  • a cross-linking agent when added to the coating liquid to form the water vapor barrier layer, it is preferable to add the cross-linking agent to the coating liquid after the cross-linking agent is dissolved in a polar solvent such as ammonium hydroxide solution.
  • a polar solvent such as ammonium hydroxide solution.
  • the contact angle with water of the surface of the water vapor barrier layer disposed on the paper base material is preferably less than 90°, more preferably less than 85° and furthermore preferably less than 80°.
  • the contact angle with water is 90° or more, it is difficult to dispose a uniform gas barrier layer on the water vapor barrier layer, and it is difficult to exhibit a high gas barrier property.
  • the contact angle with water is less than 90°, it is possible to suppress the repulsion between the water vapor barrier layer and the gas barrier layer so as to suppress the peeling between these two layers.
  • the contact angle serves as a measure with which the affinity between the water vapor barrier layer and the gas barrier layer is inferred.
  • the water soluble polymer used as the binder resin of the coating material to form the gas barrier layer is a polyvinyl alcohol resin.
  • examples of the pigments used in the gas barrier layer include: inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white and mica; and organic pigments such as a dense-type pigment, a hollow-type pigment and a core-shell type pigment. These can be used each alone or as mixtures of two or more thereof. Among these, from the viewpoint of the gas barrier property, it is preferable to use an inorganic pigment.
  • inorganic pigments such as kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, precipitated calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white and mica
  • organic pigments such as a dense-
  • an inorganic pigment in particular, kaolin
  • an inorganic pigment in particular, kaolin
  • an inorganic pigment in particular, kaolin
  • a gas such as oxygen passes around the pigment. Consequently, as compared to the gas barrier layer formed of a water soluble polymer including no pigment, the gas barrier layer formed of a water soluble polymer including a pigment has a satisfactory water vapor barrier property and an excellent gas barrier property in a high-humidity atmosphere.
  • the mixing ratio (in terms of dry weights) between the pigment and the water soluble polymer included in the gas barrier layer is preferably such that the ratio pigment /water soluble polymer is 1/100 to 1000/100. When the proportion of the pigment falls outside the foregoing range, no sufficient gas barrier property is exhibited.
  • a cross-linking agent typified by a multivalent metal salt to the gas barrier layer.
  • the cross-linking agent bonds the hydroxyl groups in the water soluble polymer to each other through cross-linked structure, hence the amount of the hydroxyl groups having the loosened bonds (or broken bonds) when the humidity becomes high is decreased to improve the waterproofness of the whole layer, and thus the degradation of the oxygen barrier property under a high humidity can be suppressed.
  • the type of the cross-linking agent is not particularly limited; the cross-linking agent appropriately according to the type of the binder included in the water vapor barrier layer from the following can be used: multivalent metal salts (the compounds produced by bonding the multivalent metals such as copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium and titanium with the ionic substances such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide and boron oxide); and amine compounds, amide compounds, aldehyde compounds, and hydroxy acids.
  • multivalent metal salts the compounds produced by bonding the multivalent metals such as copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium and titanium with the ionic substances such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion,
  • the cross-linking agent can be mixed without being particularly limited with respect to the mixing amount thereof.
  • a multivalent metal salt it is preferable to use a multivalent metal salt and it is more preferable to use potassium alum when a styrene-based water vapor barrier resin exhibiting excellent effects in the water vapor barrier property, such as a styrene-butadiene-based resin or a styrene-acrylic-based resin is used.
  • the addition amount of the cross-linking agent is 1 to 10 parts by weight and more preferably 3 to 5 parts by weight in relation to 100 parts by weight of the resin used in the gas barrier layer.
  • the addition amount of the cross-linking agent is less than 1 part by weight, no sufficient effect is obtained, and when the addition amount of the cross-linking agent is larger than 10 parts by weight, the viscosity of the coating liquid is remarkably increased to make the coating operation difficult.
  • a pigment when a pigment is mixed in a water soluble polymer, it is preferable to add and mix a pigment which is water-dispersed and slurried.
  • the gas barrier layer in addition to the water soluble polymer and the pigment, various usually used aids such as a dispersant, a thickener, a water retention agent, an antifoaming agent, a waterproofing agent, a dye and a fluorescent dye.
  • various usually used aids such as a dispersant, a thickener, a water retention agent, an antifoaming agent, a waterproofing agent, a dye and a fluorescent dye.
  • the coating methods of the water vapor barrier layer and the gas barrier layer are not particularly limited, and heretofore known coating apparatuses can be used.
  • a coating apparatus include: a blade coater, a bar coater, a roll coater, an air knife coater, a reverse roll coater, a curtain coater, a spray coater, a size press coater and a gate roll coater.
  • a steam heating heater a gas heater, an infrared heater, an electric heater, a hot air heating heater, a microwave, and a cylinder dryer.
  • the coating amount of the water vapor barrier layer is preferably set at 4 to 30 g/m 2 , more preferably 6 to 25 g/m 2 and furthermore preferably 10 to 20 g/m 2 in terms of dry weight.
  • the coating amount is 3 g/m 2 or less, there occur a problem that it is difficult for the coating liquid to perfectly coat the base paper, and hence no sufficient water vapor barrier property is obtained, and a problem that the gas barrier layer penetrates into the paper base material, and hence a uniform gas barrier property is not obtained.
  • the coating amount is 30 g/m 2 or more, the drying load at the time of coating operation becomes large, unpreferably from the viewpoint of both of the operational aspect and the cost aspect.
  • the coating amount of the gas barrier layer is preferably set at 0.2 to 10 g/m 2 in terms of dry weight.
  • the coating amount is less than 0.2 g/m 2 , no uniform gas barrier layer can be formed, and hence there is problem that no sufficient gas barrier property is obtained.
  • the coating amount is 10 g/m 2 or more, the drying load at the time of coating operation becomes large, unpreferably from the viewpoint of both of the operational aspect and the cost aspect.
  • a sealant layer made of a polymer such as polyethylene, polypropylene or polyvinyl acetate on the paper based barrier packaging material including a water vapor barrier layer and a gas barrier layer disposed on a paper base material.
  • the method for laminating the sealant layer is not particularly limited; it is possible to use a conventional, heretofore known methods such as a melt-extrusion lamination method, a dry lamination method using a film and a direct melt coating method.
  • a raw material pulp was prepared by mixing, with a weight ratio of 80/20, a leaf bleached kraft pulp (LBKP) having a Canadian standard freeness (CSF) of 500 ml and a needle bleached kraft pulp (NBKP) having a CSF of 530 ml.
  • LKP leaf bleached kraft pulp
  • NKP needle bleached kraft pulp
  • polyacrylamide (PAM) having a molecular weight of 2,500,000 as a dry paper-strengthening agent in an amount of 0.1% in relation to the bone-dry weight of the pulp, alkyl ketene dimer (AKD) as sizing agent in an amount of 0.35% in relation to the bone-dry weight of the pulp, a polyamide epichlorohydrin (PAEH)-based resin as a wet paper-strengthening agent in an amount of 0.15% in relation to the bone-dry weight of the pulp, and further polyacrylamide (PAM) having a molecular weight of 10,000,000 as a yield improver in an amount of 0.08% in relation to the bone-dry weight of the pulp were added; and then paper making was performed with a duo former FM-type paper making machine at a rate of 300 m/min to yield a paper having a basis weight of 59 g/m 2 .
  • both faces of the obtained paper were coated with polyvinyl alcohol (PVA 117, manufactured by Kuraray Co., Ltd.) regulated to a solid content concentration of 2% in an amount of 1.0 g/m 2 by using a rod metering size press, and dried to yield a base paper having a basis weight of 60 g/m 2 .
  • the base paper obtained was subjected to a smoothing treatment with a chilled calender at a rate of 300 min/m and at a linear load of 4.9 N/m (50 kgf/cm), in a single pass.
  • Polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) was regulated so as to have a solid content concentration of 10% to yield a coating liquid B.
  • the base paper obtained was single-side coated with the coating liquid A so as to have a coating amount (dry amount) of 12 g/m 2 at a coating speed of 300 m/min with a blade coater and dried; subsequently, the coated side was single-side coated with the coating liquid B so as to have a coating amount (dry amount) of 2.0 g/m 2 at a coating speed of 300 m/min with a roll coater to yield a paper based barrier packaging material.
  • the coating liquid for the oxygen barrier layer to the large particle size engineered kaolin (Barrisurf HX, manufactured by Imerys Minerals Ltd.), sodium polyacrylate was added as a dispersant (in an amount of 0.2 part in relation to the inorganic pigment), and the resulting mixture was dispersed with a Serie mixer to prepare a large particle size kaolin slurry having a solid content concentration of 55%.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the oxygen barrier layer, potassium alum (aluminum potassium sulfate dodecahydrate, manufactured by Kanto Chemical Co., Inc.) was dissolved so as for the concentration to be 5%, the obtained potassium alum aqueous solution was mixed in an amount of 3 parts in terms of the solid content in relation to polyvinyl alcohol, to prepare a coating liquid having a solid content concentration of 10%, and the thus obtained coating liquid was used.
  • potassium alum aluminum potassium sulfate dodecahydrate, manufactured by Kanto Chemical Co., Inc.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, a coating liquid in which a heavy calcium carbonate slurry (FMT-75, average particle size: 1.6 ⁇ m, aspect ratio: 1, manufactured by Fimatec Ltd.) was mixed in and stirred with the pigment of the coating liquid A so as for the pigment mixing ratio to be 75:25 was used.
  • a coating liquid in which a heavy calcium carbonate slurry FMT-75, average particle size: 1.6 ⁇ m, aspect ratio: 1, manufactured by Fimatec Ltd.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the potassium alum aqueous solution dissolved in Example 3 was mixed in an amount of 3 parts in relation to the pigment in the coating liquid obtained in Example 5 to prepare a coating liquid having a solid content concentration of 50%, and the thus obtained coating liquid was used.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the oxygen barrier layer, the coating liquid obtained in Example 4 was used, and in the coating liquid for the water vapor barrier layer, the coating liquid obtained in Example 5 was used.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the oxygen barrier layer, the coating liquid obtained in Example 4 was used, and in the coating liquid for the water vapor barrier layer, the coating liquid obtained in Example 6 was used.
  • a paper based barrier packaging material was obtained in the same manner as in Example 2 except that in the coating liquid for the oxygen barrier layer, the large particle size engineered kaolin in the coating liquid obtained in Example 2 was altered to mica (B-82, particle size: 180 ⁇ m, manufactured by Matsuo Sangyo Co., Ltd.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the oxygen barrier layer, the large particle size engineered kaolin in the coating liquid obtained in Example 1 was altered to montmorillonite (Nikka Knight A-36, particle size: 400 ⁇ m, manufactured by Toshin Chemicals Co., Ltd.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the large particle size engineered kaolin in the coating liquid obtained in Example 1 was altered to mica (B-82, particle size: 180 ⁇ m, manufactured by Matsuo Sangyo Co., Ltd.), the pigment dispersion concentration was altered to 20%, and the coating liquid concentration was altered to 30%.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the large particle size engineered kaolin in the coating liquid obtained in Example 1 was altered to montmorillonite (Nikka Knight A-36, particle size: 400 ⁇ m, manufactured by Toshin Chemicals Co., Ltd.), the pigment dispersion concentration was altered to 20%, the coating liquid concentration was altered to 30%, and the coating amount was altered to 9 g/m 2 .
  • montmorillonite Nakka Knight A-36, particle size: 400 ⁇ m, manufactured by Toshin Chemicals Co., Ltd.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the styrene-butadiene-based latex in Example 1 was altered to an acrylic-styrene-based copolymer emulsion (Saivinol X-511-374E, manufactured by Saiden Chemical Industry Co., Ltd.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the latex was altered to a styrene-butadiene-based latex (L7360, manufactured by Asahi Kasei Chemicals Corp.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the pigment used in the coating liquid was altered from the large particle size engineered kaolin (Barrisurf HX, manufactured by Imerys Minerals Ltd.) to the large particle size engineered kaolin (Capim CC, particle size: 8.0 ⁇ m, aspect ratio: 10 to 15, manufactured by Imerys Minerals Ltd.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the pigment used in the coating liquid was altered from the large particle size engineered kaolin (Barrisurf HX, manufactured by Imerys Minerals Ltd.) to a fine particle kaolin (Hydragloss, average particle size: 0.3 ⁇ m, aspect ratio: 10 to 15, manufactured by KaMin LLC).
  • the large particle size engineered kaolin (Barrisurf HX, manufactured by Imerys Minerals Ltd.)
  • a fine particle kaolin Heydragloss, average particle size: 0.3 ⁇ m, aspect ratio: 10 to 15, manufactured by KaMin LLC).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the pigment used in the coating liquid was altered from the large particle size engineered kaolin (Barrisurf HX, manufactured by Imerys Minerals Ltd.) to a second grade kaolin (KCS, average particle size: 3.6 ⁇ m, aspect ratio: 10 to 15, manufactured by Imerys Minerals Ltd.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the latex used in the coating liquid was altered to a styrene-butadiene-based latex (PNT7889, manufactured by ZEON Corp.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the latex used in the coating liquid was altered to a styrene-butadiene-based latex (L7360, Asahi Kasei Chemicals Corp.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the latex used in the coating liquid was altered to an acrylic copolymer latex (E316, manufactured by Asahi Kasei Chemicals Corp.).
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the coating liquid for the water vapor barrier layer, the latex used in the coating liquid was altered to an acrylic copolymer aqueous emulsion (EK-61, manufactured by Saiden Chemical Industry Co., Ltd.).
  • EK-61 acrylic copolymer aqueous emulsion
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that the coating amount of the coating liquid A was altered from 12 g/m 2 to 6 g/m 2 in terms of dry weight.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that the coating amount of the coating liquid A was altered from 12 g/m 2 to 15 g/m 2 in terms of dry weight.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that the coating amount of the coating liquid B was altered from 2 g/m 2 to 1 g/m 2 in terms of dry weight.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that the coating amount of the coating liquid B was altered from 2 g/m 2 to 4 g/m 2 in terms of dry weight.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the preparation of the coating liquid for the water vapor barrier layer, the mixing amount of the styrene-butadiene-based latex (PNT7868, manufactured by ZEON Corp.) was altered from 100 parts to 50 parts (solid content) in relation to the pigment.
  • the mixing amount of the styrene-butadiene-based latex (PNT7868, manufactured by ZEON Corp.) was altered from 100 parts to 50 parts (solid content) in relation to the pigment.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that in the preparation of the coating liquid for the water vapor barrier layer, the mixing amount of the styrene-butadiene-based latex (PNT7868, manufactured by ZEON Corp.) was altered from 100 parts to 150 parts (solid content) in relation to the pigment.
  • the mixing amount of the styrene-butadiene-based latex (PNT7868, manufactured by ZEON Corp.) was altered from 100 parts to 150 parts (solid content) in relation to the pigment.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that the gas barrier layer and the water vapor barrier layer were disposed in this order on the paper base material.
  • a paper based barrier packaging material was obtained in the same manner as in Example 1 except that no water vapor barrier layer was disposed.
  • Example 1 A paper based barrier packaging material was obtained in the same manner as in Example 1 except that no gas barrier layer was disposed.
  • [Table 1] Coating amount of water vapor barrier layer Contact angle after coating of water vapor barrier layer Water vapor permeability Coating amount of oxygen barrier layer Oxygen permeability (under dry condition) Oxygen permeability (under high humidity) g/m 2 ° g/m 2 ⁇ day g/m 2 g/m 2 ⁇ day g/m 2 ⁇ day Example 1 12.0 75 250 2.0 1.0 200 Example 2 12.0 75 250 2.0 1.0 80 Example 3 12.0 75 250 2.0 1.0 150 Example 4 12.0 75 250 2.0 1.0 50 Example 5 12.0 75 200 2.0 1.0 200 Example 6 12.0 75 150 2.0 1.0 200 Example 7 12.0 75 200 2.0 1.0 50 Example 8 12.0 75 150 2.0 1.0 50 Example 9 12.0 75 250 2.0 1.0 80 Example 10 12.0 75 250 2.0 1.0 80 Example 11 9.0 75 300 2.0 1.0 200 Example 12 9.0 75 300 2.0 1.0 200 Example 13 12.0 90 250 2.0 1.0

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Packages (AREA)
  • Wrappers (AREA)

Claims (6)

  1. Matériau d'emballage barrière à base de papier comprenant une pluralité de couches de revêtement disposées sur un matériau à base de papier, la pluralité de couches de revêtement incluant une couche formant barrière à la vapeur d'eau formée sur le matériau à base de papier et une couche formant barrière au gaz formée sur la couche formant barrière à la vapeur d'eau,
    dans lequel une résine sélectionnée à partir du groupe constitué de résines à base de styrène butadiène, de résines acryliques styrènes, de résines à base d'acétate de vinyle éthylène, de résines à base de méthacrylate de méthyle butadiène, de copolymères à base d'acrylate de butyle - acétate de vinyle, de copolymère anhydride maléique et de copolymère à base de méthacrylate de méthyle - acide acrylique, ou bien d'un mélange de deux ou plus parmi ceux-ci, est utilisée comme résine de liant dans la couche formant barrière à la vapeur d'eau,
    dans lequel une résine d'alcool polyvinylique est utilisée comme résine de liant dans la couche formant barrière au gaz, et
    dans lequel la couche formant barrière à la vapeur d'eau inclut du kaolin présentant une taille moyenne de particules de 5 µm ou plus et un rapport de forme de 10 ou plus, ainsi qu'un pigment présentant une taille moyenne de particules de 5 µm ou moins,
    dans lequel le rapport de mélange entre ledit kaolin présentant une taille moyenne de particules de 5 µm ou plus et un rapport de forme de 10 ou plus et ledit pigment présentant une taille moyenne de particules de 5 µm ou moins est de 50 / 50 ou de 99/1 en termes de poids sec.
  2. Matériau d'emballage barrière à base de papier selon la revendication 1, dans lequel la résine de liant de la couche formant barrière à la vapeur d'eau est une résine synthétique à base de butadiène - styrène.
  3. Matériau d'emballage barrière à base de papier selon la revendication 1, dans lequel le matériau de revêtement formant la couche formant barrière à la vapeur d'eau inclut un agent de réticulation.
  4. Matériau d'emballage barrière à base de papier selon la revendication 1, dans lequel la couche formant barrière au gaz inclut du kaolin présentant une taille moyenne de particules de 5 µm ou plus et un rapport de forme de 10 ou plus.
  5. Matériau d'emballage barrière à base de papier selon la revendication 1, dans lequel le matériau de revêtement formant la couche formant barrière au gaz inclut un agent de réticulation.
  6. Matériau d'emballage barrière à base de papier selon la revendication 1, dans lequel la quantité de revêtement de la couche formant barrière à la vapeur d'eau est de 4 à 30 g/m2 en termes de poids sec et la quantité de revêtement de la couche formant barrière au gaz est de 0,2 à 10 g/m2 en termes de poids sec.
EP12847115.8A 2011-11-10 2012-11-09 Matériau d'emballage à papier barrière Active EP2777934B1 (fr)

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EP2777934A1 (fr) 2014-09-17
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