WO2019187717A1 - Procédé de fabrication d'un substrat barrière pour la fabrication de papier - Google Patents

Procédé de fabrication d'un substrat barrière pour la fabrication de papier Download PDF

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Publication number
WO2019187717A1
WO2019187717A1 PCT/JP2019/005019 JP2019005019W WO2019187717A1 WO 2019187717 A1 WO2019187717 A1 WO 2019187717A1 JP 2019005019 W JP2019005019 W JP 2019005019W WO 2019187717 A1 WO2019187717 A1 WO 2019187717A1
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WO
WIPO (PCT)
Prior art keywords
water vapor
barrier layer
vapor barrier
paper
water
Prior art date
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PCT/JP2019/005019
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English (en)
Japanese (ja)
Inventor
聡美 早川
博 紺屋本
有理 大石
悟司 津田
Original Assignee
日本製紙株式会社
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Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2019543870A priority Critical patent/JP6600766B1/ja
Publication of WO2019187717A1 publication Critical patent/WO2019187717A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/32—Addition to the formed paper by contacting paper with an excess of material, e.g. from a reservoir or in a manner necessitating removal of applied excess material from the paper
    • D21H23/34—Knife or blade type coaters

Definitions

  • the present invention relates to a method for producing a paper barrier substrate having a very uniform appearance and / or a very homogeneous coating layer.
  • Patent Document 1 proposes a paper barrier packaging material in which a water vapor barrier layer and a gas barrier layer are provided on a paper substrate by coating.
  • a blade-type coating method (hereinafter also referred to as a blade coating method), which is a contact-type coating method, is used.
  • the blade coating method is a coating method (smooth coating method) in which a coating liquid mainly composed of water is applied to a base paper, and then the excess coating liquid is scraped off by a blade to finish the desired coating amount. The smoothness of the coating layer surface is good.
  • the coating liquid when the coating liquid passes through the blade, the coating liquid is pressurized by the blade, the moisture in the coating liquid penetrates into the paper, and when this moisture dries, the paper shrinks, Striped unevenness may occur and the coated surface may be inferior.
  • a very strong shear stress is applied to the coating solution when passing through the blade, more coating solution is scraped off than expected, and the coating layer having a desired film thickness is uniform in the width direction. Adjustment may be required to obtain the coating amount.
  • the present invention relates to a method for producing a paper barrier substrate having a very uniform appearance and / or a method for producing a paper barrier substrate having a very uniform coating layer, in which the coating amount can be easily adjusted.
  • the purpose is to provide.
  • the present invention provides the following [1] to [12].
  • [1] A process for forming a water vapor barrier layer by applying a water vapor barrier layer coating solution containing at least a water vapor barrier resin and a pigment on a paper substrate by a blade coating method;
  • the high shear viscosity at a solid content concentration of 32% by weight and a temperature of 30 ° C. is 11.5 mPa ⁇ s or more and 20 mPa ⁇ s or less.
  • the water vapor barrier layer coating solution contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
  • the manufacturing method that satisfies the condition (1) is the first invention
  • the manufacturing method that satisfies the condition (2) is the second invention.
  • the manufacturing method which is 1st invention coats the coating liquid for water vapor
  • concentration of coating liquid is 32 weight%, High shear viscosity in 30 degreeC of temperature
  • the ratio is set to 11.5 mPa ⁇ s to 20 mPa ⁇ s, it is possible to form a water vapor barrier layer having a very uniform and beautiful appearance with little streak-like unevenness.
  • the water vapor barrier layer coated by the production method of the first invention has extremely excellent surface uniformity, even when a gas barrier layer or the like is coated on this water vapor barrier layer, it is excellent in smoothness and uniformity. The appearance can be maintained.
  • the coating liquid for the water vapor barrier layer of the first invention it is possible to apply with a uniform coating amount over the entire coating width, and there is little variation in performance between the end portion and the central portion. Since the entire coated surface can be used, the yield can be increased.
  • the coating solution for water vapor barrier layer having a solid content concentration of 32% by weight and a B-type viscosity at a temperature of 30 ° C. of 1500 mPa ⁇ s or less is excellent in liquid feeding property and handling property of the coating solution, and should be stably applied. Can do.
  • a water vapor barrier layer coating solution having a solid content concentration of 32% by weight and a pH at a temperature of 30 ° C. of 8.0 or more and 13.0 or less can be applied with high shear viscosity, and has a uniform appearance.
  • a barrier substrate made can be obtained.
  • a water vapor barrier layer coating liquid having a solid content concentration of 25 wt% or more and 44 wt% or less makes it easy to obtain a desired water vapor barrier property and facilitates the preparation of the coating liquid.
  • the manufacturing method which is 2nd invention applies the coating liquid for water vapor
  • steam barrier layers is a floating type water retention agent or adsorption type water retention.
  • an agent By containing an agent, it becomes easy to adjust to a desired coating amount.
  • coating can be performed with a uniform coating amount over the entire coating width, and an extremely uniform coating layer can be obtained. Therefore, the water vapor barrier layer coated by the production method according to the second invention has little variation in performance between the end portion and the central portion, can utilize the entire coated surface, and can increase the yield.
  • the water vapor barrier layer applied by the production method according to the second invention has few streaky irregularities, has a beautiful appearance, and has a very uniform appearance.
  • the water vapor barrier layer of the second invention coated with a coating solution for a water vapor barrier layer containing a floating reversed phase type water retention agent has very little streak-like unevenness and has a very beautiful appearance.
  • the water vapor barrier layer coated by the production method according to the second invention has extremely excellent surface uniformity, even when a gas barrier layer or the like is coated on the water vapor barrier layer, it is excellent in smoothness and uniformity. The appearance can be maintained.
  • the water-retaining agent is basically hydrophilic, but the water-retaining agent is 0.01 to 1.5 parts by weight with respect to 100 parts by weight of the pigment.
  • the water vapor barrier property can be kept high.
  • the coating solution for water vapor barrier layer having a pH of 8.0 or more and 13.0 or less easily exhibits the performance of the water retention agent, and it is easy to apply a water vapor barrier layer having a desired coating amount.
  • a water vapor barrier layer coating liquid having a solid content concentration of 25 wt% or more and 44 wt% or less makes it easy to obtain a desired water vapor barrier property and facilitates the preparation of the coating liquid.
  • the present invention relates to a method for producing a paper barrier substrate, and a water vapor barrier layer coating method is applied by applying a water vapor barrier layer coating solution containing at least a water vapor barrier resin and a pigment on a paper substrate by a blade coating method.
  • a water vapor barrier layer coating solution containing at least a water vapor barrier resin and a pigment on a paper substrate by a blade coating method.
  • Forming a layer The following condition (1) and / or (2) is satisfied.
  • the high shear viscosity at a solid content concentration of 32% by weight and a temperature of 30 ° C. is 11.5 mPa ⁇ s or more and 20 mPa ⁇ s or less.
  • the water vapor barrier layer coating solution contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
  • the first invention of the present invention relates to a method for producing a paper barrier substrate, wherein a coating solution for a water vapor barrier layer containing at least a water vapor barrier resin and a pigment is coated on the paper substrate by a blade coating method. And having a step of forming a water vapor barrier layer, and having a solid content concentration of 32% by weight and a high shear viscosity at a temperature of 30 ° C. of 11.5 mPa ⁇ s to 20 mPa ⁇ s.
  • the second invention of the present invention relates to a method for producing a paper barrier substrate, wherein a coating solution for a water vapor barrier layer containing at least a water vapor barrier resin and a pigment is coated on the paper substrate by a blade coating method. And forming a water vapor barrier layer, and the water vapor barrier layer coating liquid contains a floating water retention agent or an adsorption water retention agent.
  • Paper barrier substrate 1st invention, 2nd invention WHEREIN:
  • the paper barrier base material apply
  • a known apparatus used for blade coating can be used.
  • a bevel blade coater, a vent blade coater, a bar blade coater and the like can be mentioned.
  • the coating solution for the water vapor barrier layer of the first invention is a coating solution mainly containing water in which at least a water vapor barrier resin and a pigment are dissolved and dispersed, and has a solid content concentration of 32% by weight and a temperature.
  • the high shear viscosity (hereinafter simply referred to as high shear viscosity) at 30 ° C. is 11.5 mPa ⁇ s or more and 20 mPa ⁇ s or less.
  • the film thickness after passing through the blade can be maintained, and a coating layer having a desired film thickness can be easily obtained.
  • the high shear viscosity is less than 11.5 mPa ⁇ s, a coating layer having a lot of streaky irregularities and a non-uniform surface appearance is obtained.
  • the high shear viscosity is larger than 20 mPa ⁇ s, scraping off of the excessive coating liquid by the blade becomes unstable, and it becomes difficult to uniformly control the coating amount over the entire coating width. For this reason, performance variation increases between the end portion and the center portion, and the yield decreases.
  • the high shear viscosity of the water vapor barrier layer coating solution is preferably 12 mPa ⁇ s or more, and more preferably 13 mPa ⁇ s or more. Moreover, it is preferable that it is 19 mPa * s or less, and it is more preferable that it is 18 mPa * s or less.
  • streaky unevenness is not a streaky coating defect having a width of 1 mm or less caused by foreign matter sandwiched between an applicator and a blade, but water in the coating liquid pressurized by the blade.
  • the high shear viscosity is a value measured at a rotational speed of 8800 rpm using an E bob using a high shear viscometer.
  • DV-10 manufactured by Kaltec Scientific can be used.
  • the water vapor barrier layer coating liquid used in the first invention preferably has a solid content concentration of 32% by weight and a B-type viscosity at a temperature of 30 ° C. of 1500 mPa ⁇ s or less.
  • a B-type viscosity is more preferably 1000 mPa ⁇ s or less.
  • the B-type viscosity of the coating solution was measured using a Brookfield viscometer (B-type viscometer). It is a value measured at a rotational speed of 60 rpm using 3 rotors.
  • the water vapor barrier layer coating liquid used in the first invention preferably has a solid content concentration of 32% by weight and a pH at a temperature of 30 ° C. of 8.0 to 13.0. Moreover, it is more preferable that it is 8.5 or more, and it is still more preferable that it is 9.0 or more. Further, it is more preferably 12.0 or less, further preferably 11.0 or less, and particularly preferably 10.0 or less. It is preferable that the pH of the coating solution for the water vapor barrier layer is in the above range because the high shear viscosity can be easily within a predetermined range.
  • the water vapor barrier layer coating solution used in the first invention preferably has a solid content concentration in the range of 25 wt% to 44 wt%. Moreover, it is more preferable that it is 30 weight% or more, and it is more preferable that it is 40 weight% or less. It is preferable that the solid content concentration of the coating solution for the water vapor barrier layer is in the above range because desired water vapor barrier properties can be easily obtained and the coating solution can be easily prepared.
  • Water vapor barrier resins include styrene / butadiene, styrene / acrylic, ethylene / vinyl acetate, paraffin (WAX), butadiene / methyl methacrylate, vinyl acetate / butyl acrylate, and other copolymers, anhydrous maleic Synthetic adhesives such as acid copolymers, acrylic acid / methyl methacrylate copolymers, or their paraffin (WAX) blended synthetic adhesives can be used alone or in admixture of two or more.
  • WAX paraffin
  • the styrene / butadiene synthetic adhesive is one obtained by emulsion polymerization by combining styrene and butadiene as main constituent monomers and various comonomers intended for modification.
  • comonomers include methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, unsaturated carboxylic acids such as itaconic acid, maleic acid, and acrylic acid.
  • anionic surfactants such as sodium oleate, rosin acid soap, sodium alkylallylsulfonate, sodium dialkylsulfosuccinate and the like can be used alone or in combination with a nonionic surfactant.
  • amphoteric or cationic surfactants can also be used.
  • the styrene / acrylic synthetic adhesive is obtained by emulsion polymerization by combining styrene and acrylic as main constituent monomers and various comonomers intended for modification.
  • polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, proteins such as casein, soy protein, and synthetic protein, oxidation Starch, cationized starch, urea phosphated starch, starch such as hydroxyethyl etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, water-soluble polymers such as polyvinylpyrrolidone, sodium alginate, etc. It can also be used in combination with a water vapor barrier resin.
  • the pigment enhances the water vapor barrier property of the water vapor barrier layer, and can improve the adhesion between the water vapor barrier layer and the gas barrier layer when a gas barrier layer is applied on the water vapor barrier layer.
  • kaolin, clay, engineered kaolin, delaminated clay heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin
  • An inorganic pigment such as white and an organic pigment such as a solid type, a hollow type, or a core-shell type can be used alone or in admixture of two or more.
  • inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferred. preferable.
  • inorganic pigments having an aspect ratio of 10 or more are preferably used alone or in combination of two or more. The aspect ratio is more preferably 100 or more, and even more preferably 200 or more. Further, it is more preferable to use an inorganic pigment having a volume 50% average particle diameter (D50) (hereinafter also referred to as “average particle diameter”) of 5 ⁇ m or more singly or in combination.
  • D50 volume 50% average particle diameter
  • the water vapor barrier layer containing an inorganic pigment having an average particle size of 5 ⁇ m or more further contains a pigment having an average particle size of 5 ⁇ m or less. You may let them.
  • a pigment having an average particle diameter of 5 ⁇ m or less in combination, voids in the water vapor barrier layer formed of an inorganic pigment having an average particle diameter of 5 ⁇ m or more can be reduced, so that further excellent water vapor barrier properties are exhibited. .
  • the void formed by the inorganic pigment having a large average particle size in the water vapor barrier layer is filled with the pigment having a small average particle size. Since it bypasses the pigment, it is presumed that it has a higher water vapor barrier property than a water vapor barrier layer that does not contain a pigment having a different average particle size.
  • an inorganic pigment having an average particle size of 5 ⁇ m or more and a pigment having an average particle size of 5 ⁇ m or less are used in combination, an inorganic pigment having an average particle size of 5 ⁇ m or more and a pigment having an average particle size of 5 ⁇ m or less
  • the ratio is preferably 50/50 to 99/1 by dry weight. If the blending ratio of the inorganic pigment having an average particle size of 5 ⁇ m or more is less than the above range, the number of times that the water vapor bypasses the water vapor barrier layer is reduced, and the moving distance is shortened. Sometimes.
  • the void formed by the inorganic pigment having a large average particle diameter in the water vapor barrier layer cannot be sufficiently filled with the pigment having an average particle diameter of 5 ⁇ m or less, and therefore further improvement of the water vapor barrier property is observed. I can't.
  • the pigment having an average particle size of 5 ⁇ m or less used in combination with an inorganic pigment having an average particle size of 5 ⁇ m or more includes kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, Inorganic pigments such as talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, or core-shell type, alone or 2 A mixture of more than one type can be used. Among these pigments, it is preferable to use heavy calcium carbonate.
  • the blending amount of the pigment is within a range of 5 parts by weight or more and 200 parts by weight or less in total of the water vapor barrier resin and the water-soluble polymer with respect to 100 parts by weight of the dry pigment. It is preferably used, and more preferably 10 parts by weight or more and 150 parts by weight or less in total of the water vapor barrier resin and the water-soluble polymer.
  • a crosslinking agent typified by a polyvalent metal salt can be added to the water vapor barrier layer. Since the crosslinking agent causes a crosslinking reaction with the water vapor barrier resin or the water-soluble polymer contained in the water vapor barrier layer, the number of bonds (crosslinking points) in the water vapor barrier layer increases. That is, the water vapor barrier layer has a dense structure and can exhibit good water vapor barrier properties.
  • the type of the crosslinking agent is not particularly limited, and in accordance with the type of the water vapor barrier resin or water-soluble polymer contained in the water vapor barrier layer, a polyvalent metal salt (copper, zinc, Multivalent metals such as silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium and carbonate ions, sulfate ions, nitrate ions, phosphate ions, silicate ions, nitrogen oxides, boron oxides, etc.
  • a compound to which an ionic substance is bound) an amine compound, an amide compound, an aldehyde compound, a hydroxy acid, and the like can be appropriately selected and used.
  • a polyvalent metal salt from the viewpoint of expression of a crosslinking effect. More preferably, potassium alum is used.
  • the crosslinking agent is 1 to 10 parts by weight, more preferably 3 to 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, if the amount is more than 10 parts by weight, the viscosity of the coating solution is remarkably increased, and coating may be difficult.
  • the crosslinking agent when added to the coating solution for the water vapor barrier layer, it is preferable that the crosslinking agent is dissolved in a polar solvent such as ammonia and then added to the coating solution.
  • a polar solvent such as ammonia
  • a bond is formed between the cross-linking agent and the polar solvent, so that even when added to the coating solution, the cross-linking reaction with the water vapor barrier resin or water-soluble polymer does not occur immediately. The thickening of the liquid can be suppressed.
  • the polar solvent component volatilizes by drying after coating on the paper substrate, causing a cross-linking reaction with the water vapor barrier resin or water-soluble polymer, and a dense water vapor barrier layer is formed.
  • the water vapor barrier layer preferably contains a water repellent.
  • water repellents include paraffinic water repellents mainly composed of alkane compounds, natural oil and fat water repellents derived from animals and plants such as carnauba and lanoin, silicone-containing water repellents containing silicone or silicone compounds, and fluorine compounds. Examples thereof include a fluorine-containing water repellent.
  • These water repellents can be used alone or in combination of two or more.
  • the blending amount of the water repellent is not particularly limited, but the blending amount of the water repellent is 100 parts by weight in total of the water vapor barrier resin and the water-soluble polymer in dry weight.
  • the water repellent is preferably 1 part by weight or more and 100 parts by weight or less.
  • the amount of the water repellent is less than 1 part by weight, the effect of improving the water vapor barrier property may not be sufficiently obtained.
  • the amount exceeds 100 parts by weight the gas barrier layer may be difficult to form uniformly when the gas barrier layer is provided on the water vapor barrier layer, and the gas barrier property may be lowered.
  • the water vapor barrier layer coating solution preferably contains a water retention agent.
  • a water retention agent By including the water retaining agent, the film thickness after passing through the blade can be easily controlled to a desired value.
  • Water retention agents include hydrophilic polymers such as natural polymers such as polyvinyl alcohol, carboxymethyl cellulose, starch and gelatin, synthetic polymers such as polyethylene oxide, polyether compounds, polycarboxylic acid copolymers and polyacrylamide copolymers. Can be preferably used.
  • water retention agents such as synthetic polymers have a water retention mechanism in which the water retention property is expressed by adsorbing the water retention agent to pigments and binders to form a network, and in the polymer structure of the water retention agent.
  • An associative type in which the introduced hydrophobic group associates with the hydrophobic material in the coating liquid to create a network structure, and water retention is expressed, and the high molecular weight polymer of the water retention agent is entangled with each other to float the water retention Can be classified into types. Further, the form can be classified into a normal phase type (O / W type), a reverse phase type (W / O type), and the like. In the first invention, a floating reversed phase type water retention agent that exhibits good water retention even in a coating solution having a low solid content concentration and is easy to handle is preferable.
  • floating reversed-phase type water retention agent examples include Somalex 530 (polycarboxylic acid copolymer) manufactured by Somaal, Bistur 300 (polyacrylamide copolymer) manufactured by San Nopco, and the like. Moreover, as a specific example of the adsorption normal phase type water retention agent, Somalex 680K (acrylic ester-based copolymer) manufactured by Somaru Corporation can be exemplified.
  • the amount of the water retention agent is not particularly limited as long as the high shear viscosity is within the range of the first invention, but it is 0.01 to 1.5 parts by weight with respect to 100 parts by weight of the pigment contained in the water vapor barrier layer. preferable. Since the water retention agent is basically a hydrophilic polymer, the blending amount is preferably small from the viewpoint of maintaining the water vapor barrier property, specifically, it is more preferably 1.2 parts by weight or less. More preferably, it is 0 part by weight or less.
  • the coating liquid for the water vapor barrier layer includes the above water vapor barrier resin, water-soluble polymer, pigment, cross-linking agent, water repellent, water retention agent, dispersant, antifoaming agent, water resistant agent, and dye.
  • Various commonly used auxiliaries such as fluorescent dyes can be blended.
  • the coating solution for the water vapor barrier layer of the second invention is a coating solution mainly containing water in which at least a water vapor barrier resin and a pigment are dissolved and dispersed, and further, a floating type water retention agent or adsorption It contains a mold water retention agent.
  • the coating solution for water vapor barrier layer used in the second invention preferably has a solid content concentration of 32% by weight and a B-type viscosity at a temperature of 30 ° C. of 1500 mPa ⁇ s or less.
  • the B-type viscosity is more preferably 1000 mPa ⁇ s or less.
  • the B-type viscosity of the coating solution was measured using a Brookfield viscometer (B-type viscometer). It is a value measured at a rotational speed of 60 rpm using 3 rotors.
  • the water vapor barrier layer coating solution used in the second invention preferably has a solid content concentration of 32% by weight and a high shear viscosity at a temperature of 30 ° C. of 11.5 mPa ⁇ s to 20 mPa ⁇ s.
  • a high shear viscosity of the coating solution for the water vapor barrier layer within the above range, it is possible to obtain a coating layer having a very uniform appearance with little streak-like unevenness. If this high shear viscosity is less than 11.5 mPa ⁇ s, there may be a coating layer with a lot of streaky irregularities and a non-uniform surface appearance.
  • the high shear viscosity of the water vapor barrier layer coating solution is preferably 12 mPa ⁇ s or more, and more preferably 13 mPa ⁇ s or more. Moreover, it is preferable that it is 19 mPa * s or less, and it is more preferable that it is 18 mPa * s or less.
  • streaky unevenness is not a streaky coating defect having a width of 1 mm or less caused by foreign matter sandwiched between an applicator and a blade, but water in the coating liquid pressurized by the blade. It is a stripe-shaped unevenness having a width of about 1 cm, which is presumed to be caused by permeating into the base material and shrinking of the paper base material by subsequent drying.
  • the high shear viscosity is a value measured at a rotational speed of 8800 rpm using an E bob using a high shear viscometer. As the high shear viscometer, DV-10 manufactured by Kaltec Scientific can be used.
  • the coating solution for water vapor barrier layer used in the second invention preferably has a solid content concentration of 32% by weight and a pH at a temperature of 30 ° C. of 8.0 to 13.0. Moreover, it is more preferable that it is 8.5 or more, and it is still more preferable that it is 9.0 or more. Further, it is more preferably 12.0 or less, further preferably 11.0 or less, and particularly preferably 10.0 or less. It is preferable that the pH of the coating solution for the water vapor barrier layer is in the above range because the performance of the water retention agent is easily exhibited and it is easy to apply a water vapor barrier layer having a desired coating amount.
  • the water vapor barrier layer coating solution used in the second invention preferably has a solid content concentration in the range of 25 wt% to 44 wt%. Moreover, it is more preferable that it is 30 weight% or more, and it is more preferable that it is 40 weight% or less. It is preferable that the solid content concentration of the coating solution for the water vapor barrier layer is in the above range because desired water vapor barrier properties can be easily obtained and the coating solution can be easily prepared.
  • Water vapor barrier resins include styrene / butadiene, styrene / acrylic, ethylene / vinyl acetate, paraffin (WAX), butadiene / methyl methacrylate, vinyl acetate / butyl acrylate, and other copolymers, anhydrous maleic Synthetic adhesives such as acid copolymers, acrylic acid / methyl methacrylate copolymers, or their paraffin (WAX) blended synthetic adhesives can be used alone or in admixture of two or more.
  • WAX paraffin
  • the styrene / butadiene based synthetic adhesive is obtained by emulsion polymerization by combining styrene and butadiene as main constituent monomers and various comonomers intended for modification.
  • comonomers include methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, unsaturated carboxylic acids such as itaconic acid, maleic acid, and acrylic acid.
  • anionic surfactants such as sodium oleate, rosin acid soap, sodium alkylallylsulfonate, sodium dialkylsulfosuccinate and the like can be used alone or in combination with a nonionic surfactant.
  • amphoteric or cationic surfactants can also be used.
  • the styrene / acrylic synthetic adhesive is obtained by emulsion polymerization by combining styrene and acrylic as main constituent monomers and various comonomers intended for modification.
  • polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, proteins such as casein, soy protein, and synthetic protein, oxidation Starch, cationized starch, urea phosphated starch, starch such as hydroxyethyl etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, water-soluble polymers such as polyvinylpyrrolidone, sodium alginate, etc. It can also be used in combination with a water vapor barrier resin.
  • the pigment enhances the water vapor barrier property of the water vapor barrier layer, and can improve the adhesion between the water vapor barrier layer and the gas barrier layer when a gas barrier layer is applied on the water vapor barrier layer.
  • kaolin, clay, engineered kaolin, delaminated clay heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin
  • An inorganic pigment such as white and an organic pigment such as a solid type, a hollow type, or a core-shell type can be used alone or in admixture of two or more.
  • inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferred. preferable.
  • inorganic pigments having an aspect ratio of 10 or more are preferably used alone or in combination of two or more. The aspect ratio is more preferably 100 or more, and even more preferably 200 or more. Further, it is more preferable to use an inorganic pigment having a volume 50% average particle diameter (D50) (hereinafter also referred to as “average particle diameter”) of 5 ⁇ m or more singly or in combination.
  • D50 volume 50% average particle diameter
  • the water vapor barrier layer containing an inorganic pigment having an average particle size of 5 ⁇ m or more further contains a pigment having an average particle size of 5 ⁇ m or less. You may let them.
  • a pigment having an average particle diameter of 5 ⁇ m or less in combination, voids in the water vapor barrier layer formed of an inorganic pigment having an average particle diameter of 5 ⁇ m or more can be reduced, so that further excellent water vapor barrier properties are exhibited. .
  • the void formed by the inorganic pigment having a large average particle size in the water vapor barrier layer is filled with the pigment having a small average particle size. Since it bypasses the pigment, it is presumed that it has a higher water vapor barrier property than a water vapor barrier layer that does not contain a pigment having a different average particle size.
  • an inorganic pigment having an average particle size of 5 ⁇ m or more and a pigment having an average particle size of 5 ⁇ m or less are used in combination, an inorganic pigment having an average particle size of 5 ⁇ m or more and a pigment having an average particle size of 5 ⁇ m or less
  • the ratio is preferably 50/50 to 99/1 by dry weight. If the blending ratio of the inorganic pigment having an average particle size of 5 ⁇ m or more is less than the above range, the number of times that the water vapor bypasses the water vapor barrier layer is reduced, and the moving distance is shortened. Sometimes.
  • the void formed by the inorganic pigment having a large average particle diameter in the water vapor barrier layer cannot be sufficiently filled with the pigment having an average particle diameter of 5 ⁇ m or less, and therefore further improvement of the water vapor barrier property is observed. I can't.
  • the pigment having an average particle diameter of 5 ⁇ m or less used in combination with an inorganic pigment having an average particle diameter of 5 ⁇ m or more includes kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, Inorganic pigments such as talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, or core-shell type, alone or 2 A mixture of more than one type can be used. Among these pigments, it is preferable to use heavy calcium carbonate.
  • the blending amount of the pigment is within a range of 5 parts by weight or more and 200 parts by weight or less in total of the water vapor barrier resin and the water-soluble polymer with respect to 100 parts by weight of the dry pigment. It is preferably used, and more preferably 10 parts by weight or more and 150 parts by weight or less in total of the water vapor barrier resin and the water-soluble polymer.
  • the coating solution for a water vapor barrier layer of the second invention contains a floating water retention agent or an adsorption water retention agent.
  • Floating water retention agent is a water retention agent that expresses water retention when high molecular weight polymers of water retention agent are entangled with each other.
  • Adsorption type water retention agent is a water retention agent that adsorbs to pigments and binders to form a network. Refers to a water retention agent that exhibits water retention.
  • the water retention is expressed by creating a network structure by associating the hydrophobic group introduced into the polymer structure of the water retention agent and the hydrophobic material in the coating liquid. There are meeting types.
  • hydrophilic polymers such as synthetic polymers such as polyethylene oxide, polyether compounds, polycarboxylic acid copolymers and polyacrylamide copolymers can be preferably used. .
  • the water retention agent used in the second invention is preferably a reverse phase type.
  • the reverse phase type means a W / O type emulsion in which water-soluble components are dispersed in oil as particles. Since the reversed-phase type water retention agent exists in a state where the hydrophilic polymer is confined in the aqueous phase that is the dispersed phase, the molecular chain does not spread and the molecular chains are less entangled. For this reason, even if the molecular weight of the hydrophilic polymer is very high, the viscosity of the reversed-phase water-retaining agent itself that is an emulsion is not too high, and the handleability is excellent.
  • a reversed-phase type water retention agent When a reversed-phase type water retention agent is mixed with water to form a coating liquid, a phase inversion in which the aqueous phase that was the dispersed phase becomes a continuous phase occurs, and the molecular chains of the hydrophilic polymer spread, causing entanglement. It has a water retention effect.
  • the floating reversed-phase type water retention agent include Somalex 530 (polycarboxylic acid copolymer) manufactured by Somaal, Bistur 300 (polyacrylamide copolymer) manufactured by San Nopco, and the like. .
  • Somalex 680K acrylic ester-based copolymer manufactured by Somaru Corporation can be exemplified.
  • the blending amount of the water retention agent is preferably 0.01 parts by weight or more and 1.5 parts by weight or less with respect to 100 parts by weight of the pigment contained in the water vapor barrier layer. Since the water retention agent is basically a hydrophilic polymer, the blending amount is preferably small from the viewpoint of maintaining the water vapor barrier property, specifically, it is more preferably 1.2 parts by weight or less. More preferably, it is 0 part by weight or less.
  • a crosslinking agent represented by a polyvalent metal salt or the like can be added to the water vapor barrier layer. Since the crosslinking agent causes a crosslinking reaction with the water vapor barrier resin or the water-soluble polymer contained in the water vapor barrier layer, the number of bonds (crosslinking points) in the water vapor barrier layer increases. That is, the water vapor barrier layer has a dense structure and can exhibit good water vapor barrier properties.
  • the type of the crosslinking agent is not particularly limited, and in accordance with the type of the water vapor barrier resin or water-soluble polymer contained in the water vapor barrier layer, a polyvalent metal salt (copper, zinc, Multivalent metals such as silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium and carbonate ions, sulfate ions, nitrate ions, phosphate ions, silicate ions, nitrogen oxides, boron oxides, etc.
  • a compound to which an ionic substance is bound) an amine compound, an amide compound, an aldehyde compound, a hydroxy acid, and the like can be appropriately selected and used.
  • a polyvalent metal salt from the viewpoint of expression of a crosslinking effect. More preferably, potassium alum is used.
  • the crosslinking agent is 1 to 10 parts by weight, more preferably 3 to 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, if the amount is more than 10 parts by weight, the viscosity of the coating solution is remarkably increased, and coating may be difficult.
  • the crosslinking agent when added to the coating solution for the water vapor barrier layer, it is preferable that the crosslinking agent is dissolved in a polar solvent such as ammonia and then added to the coating solution.
  • a polar solvent such as ammonia
  • a bond is formed between the cross-linking agent and the polar solvent, so that even when added to the coating solution, the cross-linking reaction with the water vapor barrier resin or water-soluble polymer does not occur immediately. The thickening of the liquid can be suppressed.
  • the polar solvent component volatilizes by drying after coating on the paper substrate, causing a cross-linking reaction with the water vapor barrier resin or water-soluble polymer, and a dense water vapor barrier layer is formed.
  • the water vapor barrier layer preferably contains a water repellent.
  • water repellents include paraffinic water repellents mainly composed of alkane compounds, natural oil and fat water repellents derived from animals and plants such as carnauba and lanoin, silicone-containing water repellents containing silicone or silicone compounds, and fluorine compounds. Examples thereof include a fluorine-containing water repellent.
  • These water repellents can be used alone or in combination of two or more.
  • the blending amount of the water repellent is not particularly limited, but the blending amount of the water repellent is 100 parts by weight in total of the water vapor barrier resin and the water-soluble polymer in dry weight.
  • the water repellent is preferably 1 part by weight or more and 100 parts by weight or less.
  • the amount of the water repellent is less than 1 part by weight, the effect of improving the water vapor barrier property may not be sufficiently obtained.
  • the amount exceeds 100 parts by weight the gas barrier layer may be difficult to form uniformly when the gas barrier layer is provided on the water vapor barrier layer, and the gas barrier property may be lowered.
  • the coating liquid for the water vapor barrier layer includes a water vapor barrier resin, a water-soluble polymer, a pigment, a water retention agent, a crosslinking agent, a water repellent, a dispersant, an antifoaming agent, a water resistance agent, and a dye.
  • a water vapor barrier resin e.g., a polystyrene resin
  • a water-soluble polymer e.g., polystyrenethacrylate
  • a pigment e.g., polyethylene glycol dimethacrylate
  • a water retention agent e.g., poly(ethylene glycol)
  • a crosslinking agent e.g., 1,3-dioxanethacrylate
  • a water repellent e.g., 1, 6-butanethacrylate, 1, 6-butanethacrylate, 1, 6-butanethacrylate, 1, 6-butanethacrylate, 1, 6-butanethacrylate, 1, 6-butanethacrylate,
  • the coating amount of the water vapor barrier layer is preferably 3 g / m 2 or more and 50 g / m 2 or less by dry weight, and preferably 5 g / m 2 or more and 40 g / m 2 or less. it is more preferable, and even more preferably to a 7 g / m 2 or more 30 g / m 2 or less.
  • the coating amount of the water vapor barrier layer is less than 3 g / m 2 , it becomes difficult to completely coat the paper substrate with the coating liquid, and sufficient water vapor barrier properties cannot be obtained.
  • the gas barrier layer coating solution may penetrate into the paper substrate, and sufficient gas barrier properties may not be obtained.
  • the water vapor barrier layer may be a single layer or a multilayer of two or more layers.
  • the water vapor barrier layer is composed of two or more layers, at least the water vapor barrier layer in contact with the paper substrate is applied by the blade coating method, and the total coating amount of all the water vapor barrier layers is within the above range. Is preferred.
  • the paper substrate used in the first and second inventions is a sheet made of pulp, filler, various auxiliaries and the like.
  • Pulp includes chemical pulp such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP), softwood unbleached kraft pulp (NUKP), sulfite pulp, stone grind pulp, thermo Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and waste paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp and the like can be used, and can be used by appropriately blending.
  • LLKP hardwood bleached kraft pulp
  • NKP softwood bleached kraft pulp
  • LKP hardwood unbleached kraft pulp
  • NUKP softwood unbleached kraft pulp
  • sulfite pulp stone grind pulp
  • thermo Mechanical pulp such as mechanical pulp, wood fiber such as deinked pulp and waste paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp and
  • filler known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, and synthetic resin filler can be used.
  • sulfuric acid bands and various anionic, cationic, nonionic or amphoteric yield improvers, drainage improvers, paper strength enhancers and internal additive sizing agents, etc. Can be used.
  • dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
  • the production method (paper making) of the paper substrate is not particularly limited, and it is possible to use an acid paper making method, a neutral paper making method, or an alkaline paper making method using a known long web former, on-top hybrid former, gap former machine, etc. Papermaking can be used to produce a paper substrate. Further, the paper substrate may be a single layer or may be composed of two or more layers. Furthermore, it is possible to treat the surface of the paper substrate with various chemicals. Examples of the drug used include oxidized starch, hydroxyethyl etherified starch, enzyme-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agent, water-resistant agent, water retention agent, thickener, lubricant, etc.
  • pigments kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin
  • An inorganic pigment such as white and an organic pigment such as a solid type, a hollow type, or a core-shell type can be used alone or in admixture of two or more.
  • the surface treatment method of the paper substrate is not particularly limited, but a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • a known coating device such as a rod metalling size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, or a curtain coater should be used.
  • Paper bases obtained in this way include fine paper, medium paper, coated paper, glossy paper, kraft paper, glossy kraft paper, bleached kraft paper, glassine paper, paperboard, white paperboard, liners, etc.
  • the basis weight of the paper base material can be appropriately selected depending on various qualities desired for the paper barrier base material, handleability, and the like, but usually about 20 g / m 2 or more and 500 g / m 2 or less is preferable. .
  • paper barrier packaging materials used for packaging applications such as packaging materials for foods, containers, cups, etc.
  • those of 25 g / m 2 or more and 400 g / m 2 or less are more preferable, especially for soft packaging materials described later.
  • those of 30 g / m 2 or more and 110 g / m 2 or less are more preferable.
  • a gas barrier layer in the method for producing a paper barrier substrate according to the first invention and the second invention, a gas barrier layer can be formed by coating a gas barrier layer coating solution on a water vapor barrier layer.
  • the gas barrier layer coating liquid is preferably a coating liquid mainly composed of water in which a polymer such as a water-soluble polymer or a water-dispersible polymer is dissolved and dispersed.
  • the paper barrier substrate according to the first and second inventions having a gas barrier layer containing a polymer such as a water-soluble polymer or a water-dispersible polymer has both excellent water vapor barrier properties and gas barrier properties.
  • the water-soluble polymer used in the gas barrier layer includes polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, casein, soybean protein, Proteins such as synthetic proteins, starches such as oxidized starch, cationized starch, urea phosphate esterified starch, hydroxyethyl etherified starch, cellulose derivatives such as carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, sodium alginate, etc. Can be illustrated.
  • polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol, casein, soybean protein, Proteins such as synthetic proteins, starches such as oxidized starch, cationized starch, urea phosphate esterified starch, hydroxyethyl etherified starch, cellulose
  • polyvinyl alcohols and cellulose derivatives are preferable, and polyvinyl alcohols are more preferable.
  • the water dispersible polymer used in the gas barrier layer include polyvinylidene chloride, ethylene vinyl acetate resin, and modified polyolefin resin.
  • the gas barrier layer contains a pigment from the viewpoint of improving the gas barrier property.
  • a pigment used in the gas barrier layer, kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, Inorganic pigments such as silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, and core-shell type can be used alone or in combination of two or more.
  • inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferable.
  • inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferable.
  • the gas barrier layer contains a pigment
  • the blending ratio of the pigment, the water-soluble polymer and the water-dispersible polymer is dry weight, and the pigment / (water-soluble polymer and water-dispersible).
  • the sum of the polymers) is preferably 1/100 to 1000/100. If the ratio of the pigment is out of the above range, the gas barrier property improving effect may be reduced.
  • the pigment when the pigment is blended in the water-soluble polymer or the water-dispersible polymer, it is preferable to add and mix the slurry of the pigment.
  • a crosslinking agent typified by a polyvalent metal salt or the like can be added to the gas barrier layer. Since the crosslinking agent causes a crosslinking reaction with a polymer such as a water-soluble polymer or a water-dispersible polymer contained in the gas barrier layer, the number of bonds (crosslinking points) in the gas barrier layer increases. That is, the gas barrier layer has a dense structure and can exhibit good gas barrier properties.
  • the type of the crosslinking agent is not particularly limited, and may be selected according to the type of polymer such as a water-soluble polymer or water-dispersible polymer contained in the gas barrier layer.
  • Valent metal salts (copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium, titanium and other polyvalent metals, carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen
  • an amine compound, an amide compound, an aldehyde compound, or a hydroxy acid can be appropriately selected and used.
  • it is preferable to use a polyvalent metal salt from a viewpoint of expression of a crosslinking effect and it is more preferable to use potassium alum.
  • the blending amount of the crosslinking agent it can be blended without particular limitation as long as it is within the range of the coating liquid concentration and coating liquid viscosity that can be coated, but preferably with respect to 100 parts by weight of the pigment,
  • the crosslinking agent is 1 to 10 parts by weight, more preferably 3 to 5 parts by weight. If the amount is less than 1 part by weight, the effect of adding the crosslinking agent may not be sufficiently obtained. On the other hand, if the amount is more than 10 parts by weight, the viscosity of the coating solution is remarkably increased, and coating may be difficult.
  • a surfactant in the first invention and the second invention, it is preferable to contain a surfactant in the gas barrier layer from the viewpoint of adhesion to the water vapor barrier layer.
  • a surfactant there is no limitation on the ionicity of the surfactant, and any one of anionic surfactant, cationic surfactant, amphoteric surfactant and nonionic surfactant can be used alone or in combination of two or more. Can be used in combination. Specific types include silicone surfactants, fluorine surfactants, alcohol surfactants, acetylene surfactants having an acetylene group, and acetylenic diol surfactants having an acetylene group and two hydroxyl groups.
  • alkyl sulfonic acid type surfactant having alkyl group and sulfonic acid group
  • ester type surfactant amide type surfactant
  • amine type surfactant alkyl ether type surfactant
  • phenyl ether type surfactant examples thereof include sulfate ester surfactants and phenol surfactants.
  • the leveling property of the coating liquid is improved, the uniformity of the gas barrier layer is improved, so that the gas barrier property is improved.
  • the gas barrier layer coating solution includes a water-soluble polymer, a water-dispersible polymer, a pigment, a crosslinking agent, a surfactant, a dispersant, a thickener, and a water retention agent.
  • Various commonly used auxiliaries such as agents, antifoaming agents, water-proofing agents, dyes, fluorescent dyes and the like can be blended.
  • the coating amount of the gas barrier layer is preferably 0.2 g / m 2 or more and 20 g / m 2 or less by dry weight. If the coating amount of the gas barrier layer is less than 0.2 / m 2 , it may be difficult to form a uniform gas barrier layer, and sufficient gas barrier properties may not be obtained. On the other hand, when it is more than 20 g / m 2 , the drying load during coating increases.
  • the gas barrier layer may be a single layer or a multilayer of two or more layers. When the gas barrier layer is composed of two or more layers, the total coating amount of all the gas barrier layers is preferably within the above range.
  • the method of applying the gas barrier layer is not particularly limited, and the curtain coater, blade coater, bar coater, roll coater, air knife coater, reverse roll coater, spray coater, size Examples include press coaters and gate roll coaters.
  • these coating methods there is little streak-like unevenness, and the effect of the present invention that a water vapor barrier layer having a very uniform and beautiful appearance and / or a very homogeneous coating layer can be formed is impaired.
  • the gas barrier layer is preferably applied by the air knife coating method or the curtain coating method, and the curtain coating method is more preferable because the appearance with excellent smoothness and uniformity can be maintained.
  • the surface tension of the gas barrier layer coating solution is preferably adjusted to 10 mN / m or more and 60 mN / m or less, preferably 15 mN / m or more. It is more preferable to adjust to 50 mN / m or less. In the case of curtain coating of the gas barrier layer, it is preferably adjusted to 45 mN / m or less.
  • the paper barrier substrate produced in the first invention and the second invention is produced through a normal drying process after coating at least a water vapor barrier layer coating solution on the paper substrate by a blade coating method. .
  • the coated paper moisture after production is adjusted to be 3% by weight to 10% by weight, more preferably 4% by weight to 8% by weight.
  • a method for drying the water vapor barrier layer and the gas barrier layer for example, usual methods such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, a cylinder dryer, and the like are used.
  • a smoothing processing device such as a normal super calendar, gloss calendar, soft calendar, thermal calendar, shoe calendar, or the like can be used.
  • the smoothing apparatus is appropriately used on-machine or off-machine, and the form of the pressure device, the number of pressure nips, heating, and the like are also adjusted as appropriate.
  • the paper barrier substrate produced in the first invention and the second invention is a paper barrier substrate, or laminated with various resins, etc.
  • a laminate used for packaging materials such as foods, paper barrier packaging materials used for packaging applications such as containers and cups, or industrial materials.
  • it can be suitably used as a paper barrier packaging material used for packaging materials such as foods, packaging materials such as containers and cups, and can be particularly suitably used as a soft packaging material such as foods.
  • the soft packaging material is a packaging material composed of a material rich in flexibility. Generally, a thin flexible material such as paper, film, aluminum foil, etc. is used alone or bonded. Refers to packaging material.
  • the packaging material which maintains a solid shape by putting the contents, such as a bag, is pointed out.
  • the paper barrier substrate produced in the first invention and the second invention is used as a packaging material for foods, in particular, as a flexible packaging material, it is hermetically sealed as a packaging material by laminating with a heat-sealable resin. It is possible to increase the storage period by protecting the contents from oxidation due to oxygen or deterioration due to moisture.
  • it when used as a laminate used for industrial materials, etc., it can prevent decay and deterioration by suppressing the intrusion of oxygen and moisture, and flavor barrier properties to prevent the odor of solvent from leaking out. The effect is expected.
  • the first and second inventions of the present invention will be described in detail with reference to examples. However, the first and second inventions are of course not limited to these examples.
  • the part and% in an example show a weight part and weight%, respectively.
  • the obtained paper barrier substrate was tested based on the following evaluation method.
  • ⁇ High shear viscosity> Using the high shear viscometer (manufactured by Kaltec Scientific, DV-10), the viscosity when the solid content concentration of the obtained coating solution for water vapor barrier layer is 32% by weight and the temperature is 30 ° C., using E Bob, The measurement was performed at a rotational speed of 8800 rpm.
  • ⁇ B type viscosity> Using the Brookfield viscometer (manufactured by Tokyo Keiki Co., Ltd., BII type viscometer), the viscosity when the solid content concentration of the obtained coating solution for water vapor barrier layer was 32% by weight and the temperature was 30 ° C. was used.
  • a water vapor barrier layer coated product with a coating width of 2100 mm is divided into 700 mm widths in the width direction, and each of them is front (vent blade coater operation side), middle (center portion), back (vent blade coater drive side) To do.
  • each of front, middle and back The coating amount (g / m 2 ) of the water vapor barrier layer was calculated. Furthermore, the average coating amount (g / m 2 ) was calculated for the second invention.
  • Example of the first invention (Preparation of paper substrate) Canadian standard freeness (CSF) 500 ml of hardwood kraft pulp (LBKP) and CSF 530 ml of softwood kraft pulp (NBKP) were blended at a weight ratio of 80/20 to obtain raw pulp.
  • CSF Canadian standard freeness
  • LKP hardwood kraft pulp
  • NKP softwood kraft pulp
  • Polyacrylamide (PAM) with a molecular weight of 2.5 million as a dry paper strength enhancer is 0.1% per dry pulp weight
  • alkyl ketene dimer (AKD) as a sizing agent is 0.35 per dry pulp weight.
  • gas barrier layer coating solution B1 An aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117) was prepared so as to have a solid content concentration of 12% to obtain a gas barrier layer coating liquid B1.
  • the surface tension of the gas barrier layer coating solution B1 was 35 mN / m.
  • Example 2 Preparation of water vapor barrier layer coating liquid A2
  • a water retention agent Somarex 530, floating reverse phase water retention agent
  • solid content was added to the water retention agent (San Nopco, Vistur 300, floating).
  • a water vapor barrier layer coating solution A2 having a solid content concentration of 32% was obtained in the same manner as in the water vapor barrier layer coating solution A1 except that the amount was changed to 0.7 parts (solid phase water retentive agent).
  • a paper barrier substrate was obtained in the same manner as in Example 1 except that the water vapor barrier layer coating liquid A2 was used instead of the water vapor barrier layer coating liquid A1.
  • Example 3 Preparation of water vapor barrier layer coating liquid A3
  • a water retention agent Somarex 530, floating reversed phase type water retention agent
  • solid content water retention agent
  • Somarex, Somalex 680K, order of adsorption water retention agent
  • a water vapor barrier layer coating liquid A3 having a solid content concentration of 32% was obtained in the same manner as in the water vapor barrier layer coating liquid A1 except that the phase type water retention agent) was changed to 0.4 part (solid content).
  • a paper barrier substrate was obtained in the same manner as in Example 1 except that the water vapor barrier layer coating liquid A3 was used instead of the water vapor barrier layer coating liquid A1.
  • a paper barrier substrate was obtained in the same manner as in Example 1 except that the water vapor barrier layer coating liquid A4 was used instead of the water vapor barrier layer coating liquid A1.
  • a paper barrier substrate was obtained in the same manner as in Example 1 except that the water vapor barrier layer coating liquid A5 was used instead of the water vapor barrier layer coating liquid A1.
  • Examples 1 to 3 in which the coating solution for the water vapor barrier layer of the first invention having a solid content concentration of 32% by weight and a high shear viscosity at a temperature of 30 ° C. of 11.5 mPa ⁇ s to 20 mPa ⁇ s are applied to the coated surface.
  • the arithmetic average roughness was small, the surface appearance of the non-coated surface was excellent, and the appearance was uniform and beautiful.
  • the coating amount in the width direction was uniform, and a paper barrier substrate with little variation could be produced.
  • Comparative Examples 1 and 2 in which a coating solution for a water vapor barrier layer having a solid content concentration of 32% by weight and a high shear viscosity at a temperature of 30 ° C. of less than 11.5 mPa ⁇ s has an arithmetic average roughness of the coated surface. It was as large as 20 ⁇ m or more, and the non-coated surface was visually non-uniform. Moreover, the variation of the coating amount in the width direction was large.
  • Example 4 (Preparation of paper substrate) Canadian standard freeness (CSF) 500 ml of hardwood kraft pulp (LBKP) and CSF 530 ml of softwood kraft pulp (NBKP) were blended at a weight ratio of 80/20 to obtain raw pulp.
  • CSF Canadian standard freeness
  • LKP hardwood kraft pulp
  • NNKP softwood kraft pulp
  • Polyacrylamide (PAM) with a molecular weight of 2.5 million as a dry paper strength enhancer is 0.1% per dry pulp weight
  • alkyl ketene dimer (AKD) as a sizing agent is 0.35 per dry pulp weight.
  • gas barrier layer coating solution b1 An aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117) was prepared so as to have a solid content concentration of 12% to obtain a gas barrier layer coating solution b1.
  • the surface tension of the gas barrier layer coating solution b1 was 35 mN / m.
  • Example 5 Preparation of water vapor barrier layer coating solution a2
  • a water retention agent Somarex 530, floating reverse phase type water retention agent
  • solid content was added to the water retention agent (San Nopco, bistur 300, floating).
  • a water vapor barrier layer coating liquid a2 having a solid content concentration of 32% was obtained in the same manner as in the water vapor barrier layer coating liquid a1, except that 0.7 parts (solid content) of the reverse phase type water retention agent was changed.
  • a paper barrier substrate was obtained in the same manner as in Example 4 except that the water vapor barrier layer coating liquid a2 was used instead of the water vapor barrier layer coating liquid a1.
  • Example 6 Preparation of water vapor barrier layer coating solution a3)
  • a water retention agent Somarex 530, floating reversed phase type water retention agent
  • solid content water retention agent
  • Somarex, Somalex 680K, order of adsorption water retention agent
  • a water vapor barrier layer coating liquid a3 having a solid content concentration of 32% was obtained in the same manner as in the water vapor barrier layer coating liquid a1 except that the phase type water retention agent) was changed to 0.4 part (solid content).
  • a paper barrier substrate was obtained in the same manner as in Example 4 except that the water vapor barrier layer coating liquid a3 was used instead of the water vapor barrier layer coating liquid a1.
  • a paper barrier substrate was obtained in the same manner as in Example 4 except that the water vapor barrier layer coating liquid a4 was used instead of the water vapor barrier layer coating liquid a1.
  • a paper barrier substrate was obtained in the same manner as in Example 4 except that the water vapor barrier layer coating liquid a5 was used instead of the water vapor barrier layer coating liquid a1.
  • Examples 4 to 6 in which the coating solution for the water vapor barrier layer containing the floating water retention agent and the adsorption water retention agent of the second invention was applied the coating amount was large and the coating amount in the width direction was also large. It was possible to produce a paper barrier substrate having a uniform coating layer that was uniform and had little variation. Further, the arithmetic average roughness of the coated surface was small, the surface feeling of the non-coated surface was excellent, and the appearance was uniform and beautiful.
  • Examples 4 and 5 in which a coating solution for a water vapor barrier layer containing a floating reverse phase type water retaining agent was applied had no very streak-like unevenness and had a very beautiful appearance.
  • steam barrier layers containing water retention agents other than a floating type water retention agent and an adsorption type water retention agent were applied.
  • Comparative Example 4 although the coating was performed under the same conditions, the coating amount was smaller than in Examples 4 to 6. Moreover, the variation of the coating amount in the width direction was large. In particular, although Comparative Example 4 contained 3.0 parts by weight of an associative water retention agent with respect to 100 parts by weight of the pigment, the coating amount was small. Moreover, since a large amount of a water retention agent which is a hydrophilic polymer was contained, the water vapor barrier property tended to decrease. Further, in Comparative Examples 3 and 4, the arithmetic average roughness of the coated surface was as large as 20 ⁇ m or more, and unevenness could be visually recognized on the non-coated surface.

Abstract

La présente invention aborde le problème de l'obtention d'un procédé de fabrication d'un substrat barrière pour la fabrication de papier, le substrat ayant un aspect extérieur exceptionnellement uniforme et/ou une couche de couchage exceptionnellement homogène. L'invention concerne en outre un procédé de fabrication d'un substrat barrière pour la fabrication de papier, le procédé comprenant une étape consistant à coucher, au moyen d'un procédé de couchage à la lame, un substrat de papier avec un liquide de couchage de couche barrière à la vapeur d'eau contenant au moins une résine barrière à la vapeur d'eau et un pigment pour former une couche barrière à la vapeur d'eau, le procédé satisfaisant les conditions (1) et/ou (2). (1) À une concentration en contenu solide de 32 % en poids pour le liquide de couchage de couche barrière à la vapeur d'eau et à une température de 30 °C, une viscosité de cisaillement élevée va de 11,5 mPa•s à 20 mPa•s inclus. (2) Le liquide de couchage de couche barrière à la vapeur d'eau contient un agent de rétention d'eau à suspension ou un agent de rétention d'eau à adsorption.
PCT/JP2019/005019 2018-03-29 2019-02-13 Procédé de fabrication d'un substrat barrière pour la fabrication de papier WO2019187717A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN114381971A (zh) * 2021-12-15 2022-04-22 金华盛纸业（苏州工业园区）有限公司 一种纸袋的制备方法及环保型纸袋

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