WO2019187717A1 - Method for manufacturing paper-making barrier substrate - Google Patents

Method for manufacturing paper-making barrier substrate 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
Application number
PCT/JP2019/005019
Other languages
French (fr)
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 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/en
Publication of WO2019187717A1 publication Critical patent/WO2019187717A1/en

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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

This invention addresses the problem of providing a method for manufacturing a paper-making barrier substrate having an exceptionally uniform outward appearance and/or an exceptionally homogeneous coating layer. Provided as a solution is a method for manufacturing a paper-making barrier substrate having a step of coating, via a blade coating method, a paper substrate with a water vapor barrier layer coating liquid containing at least a water vapor barrier resin and a pigment to form a water vapor barrier layer, the method satisfying the following conditions (1) and/or (2). (1) At a solid content concentration of 32 wt% for the water vapor barrier layer coating liquid and a temperature of 30°C, high shear viscosity is 11.5 mPa•s to 20 mPa•s inclusive. (2) The water vapor barrier layer coating liquid contains a suspension-type water retention agent or an adsorption-type water retention agent.

Description

紙製バリア基材の製造方法Method for producing paper barrier substrate
　本発明は、極めて均一な外観及び／又は極めて均質な塗工層を有する紙製バリア基材の製造方法に関する。 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.
　紙製の包装材料に水蒸気バリア性、ガスバリア性（特に、酸素バリア性）を付与することは、包装される各種製品を水蒸気やガス（特に酸素）による劣化等から守るために重要である。 Giving water vapor barrier properties and gas barrier properties (especially oxygen barrier properties) to paper packaging materials is important for protecting various products to be packaged from deterioration due to water vapor and gas (especially oxygen).
　従来から、紙基材に金属箔や金属蒸着フィルム、セラミック蒸着フィルム等を積層した紙製の包装材料や、紙基材にガスバリア性を有する樹脂と水蒸気バリア性を有する樹脂をラミネートした包装材料が知られている。また、特許文献１には、紙基材上に、塗工により水蒸気バリア層とガスバリア層とを設けた紙製バリア包装材料が提案されている。 Conventionally, a paper packaging material in which a metal foil, a metal vapor deposition film, a ceramic vapor deposition film, etc. are laminated on a paper substrate, or 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 substrate. Are known. 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.
　塗工層の製造方法の一種として、接触式の塗工方式であるブレード式塗工方法（以下、ブレード塗工法ともいう）が用いられている。
　ブレード塗工法は、水を主体とする塗工液を原紙に塗工した後、ブレードにより過剰な塗工液を掻き落して所望の塗工量に仕上げる塗工法（平滑化塗工法）であり、塗工層表面の平滑性は良好となる。 As one type of manufacturing method for the coating layer, 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.
　ブレード塗工法は、塗工液がブレードを通過する際、塗工液がブレードで加圧されて塗工液中の水分が紙に浸透し、この水分が乾燥する際に紙が収縮して、スジ状のムラが発生し、塗工面の面感に劣る場合がある。また、ブレードを通過する際に塗工液には非常に強いせん断応力がかかるため、想定より多くの塗工液が掻き落とされてしまい、所望の膜厚の塗工層や幅方向で均一な塗工量を得るために調整が必要となる場合がある。 In the blade coating method, 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. In addition, since 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.
特許第５３３１２６５号公報Japanese Patent No. 533265
　本発明は、極めて均一な外観を有する紙製バリア基材の製造方法、及び／又は、塗工量の調整が容易であり、極めて均質な塗工層を有する紙製バリア基材の製造方法を提供することを目的とする。 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.
　本発明は、以下の〔１〕～〔１２〕を提供するものである。
〔１〕紙基材上に、少なくとも水蒸気バリア性樹脂と顔料とを含有する水蒸気バリア層用塗工液を、ブレード塗工法により塗工して水蒸気バリア層を形成する工程を有し、
　下記条件（１）及び／又は（２）を満足することを特徴とする紙製バリア基材の製造方法。
（１）前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下である。
（２）前記水蒸気バリア層用塗工液が、保水剤として浮遊型保水剤または吸着型保水剤を含有する。
〔２〕前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下であることを特徴とする〔１〕に記載の紙製バリア基材の製造方法。
〔３〕前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるＢ型粘度が１５００ｍＰａ・ｓ以下であることを特徴とする〔２〕に記載の紙製バリア基材の製造方法。
〔４〕前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるｐＨが８．０以上１３．０以下であることを特徴とする〔２〕または〔３〕のいずれかに記載の紙製バリア基材の製造方法。
〔５〕前記水蒸気バリア層用塗工液の固形分濃度が、２５重量％以上４４重量％以下であることを特徴とする〔２〕～〔４〕のいずれかに記載の紙製バリア基材の製造方法。
〔６〕前記水蒸気バリア層上に、ガスバリア層用塗工液を塗工して、ガスバリア層を形成する工程、を含むことを特徴とする〔２〕～〔５〕のいずれかに記載の紙製バリア基材の製造方法。
〔７〕前記水蒸気バリア層用塗工液が、保水剤として浮遊型保水剤または吸着型保水剤を含有することを特徴とする〔１〕に記載の紙製バリア基材の製造方法。
〔８〕前記保水剤が、浮遊逆相型保水剤であることを特徴とする〔７〕に記載の紙製バリア基材の製造方法。
〔９〕前記保水剤の含有量が、顔料１００重量部に対し０．０１重量部以上１．５重量部以下であることを特徴とする〔７〕または〔８〕に記載の紙製バリア基材の製造方法。
〔１０〕前記水蒸気バリア層用塗工液のｐＨが、８．０以上１３．０以下であることを特徴とする〔７〕～〔９〕のいずれかに記載の紙製バリア基材の製造方法。
〔１１〕前記水蒸気バリア層用塗工液の固形分濃度が、２５重量％以上４４重量％以下であることを特徴とする〔７〕～〔１０〕のいずれかに記載の紙製バリア基材の製造方法。
〔１２〕前記水蒸気バリア層上に、ガスバリア層用塗工液を塗工して、ガスバリア層を形成する工程、を含むことを特徴とする〔７〕～〔１１〕のいずれかに記載の紙製バリア基材の製造方法。
　以下、条件（１）を満足する製造方法を第一発明、条件（２）を満足する製造方法を第二発明とする。 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;
A method for producing a paper barrier substrate, which satisfies the following conditions (1) and / or (2):
(1) 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.
(2) The water vapor barrier layer coating solution contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
[2] The paper according to [1], wherein the water vapor barrier layer coating liquid 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 method for producing a barrier substrate.
[3] The paper barrier substrate according to [2], wherein the water vapor barrier layer coating solution 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. Production method.
[4] The water vapor barrier layer coating solution has a solid content concentration of 32% by weight and a pH at a temperature of 30 ° C. of 8.0 to 13.0, either [2] or [3] A method for producing a paper barrier substrate as described in 1.
[5] The paper barrier substrate according to any one of [2] to [4], wherein the solid content concentration of the coating liquid for the water vapor barrier layer is 25 wt% or more and 44 wt% or less. Manufacturing method.
[6] The paper according to any one of [2] to [5], further comprising a step of coating a gas barrier layer coating liquid on the water vapor barrier layer to form a gas barrier layer. A method for producing a barrier substrate.
[7] The method for producing a paper barrier base material according to [1], wherein the water vapor barrier layer coating liquid contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
[8] The method for producing a paper barrier base material according to [7], wherein the water retention agent is a floating reversed phase type water retention agent.
[9] The paper barrier group according to [7] or [8], wherein the content of the water retention agent is 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. A method of manufacturing the material
[10] The production of the paper barrier substrate according to any one of [7] to [9], wherein the pH of the coating solution for the water vapor barrier layer is 8.0 or more and 13.0 or less. Method.
[11] The paper barrier substrate according to any one of [7] to [10], wherein the solid content concentration of the coating solution for the water vapor barrier layer is 25% by weight or more and 44% by weight or less. Manufacturing method.
[12] The paper according to any one of [7] to [11], comprising a step of coating a gas barrier layer coating solution on the water vapor barrier layer to form a gas barrier layer. A method for producing a barrier substrate.
Hereinafter, the manufacturing method that satisfies the condition (1) is the first invention, and the manufacturing method that satisfies the condition (2) is the second invention.
・第一発明
　第一発明である製造方法は、接触式のブレード塗工法により水蒸気バリア層用塗工液を塗工するが、塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度を１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下とすることにより、スジ状のムラが少なく、極めて均一で美麗な外観を有する水蒸気バリア層を形成することができる。第一発明である製造方法で塗工した水蒸気バリア層は、面の均一性が極めて優れているため、この水蒸気バリア層上にガスバリア層等を塗工した場合も、平滑性、均一性に優れた外観を維持することができる。
　さらに、第一発明の水蒸気バリア層用塗工液を用いることにより、塗工幅全体に亘って均一な塗工量で塗工することができ、端部、中央部とで性能のバラツキが少なく、塗工面全面を利用することができるため、歩留まりを高めることができる。 -1st invention The manufacturing method which is 1st invention coats the coating liquid for water vapor | steam barrier layers with a contact-type blade coating method, However, The solid content density | concentration of coating liquid is 32 weight%, High shear viscosity in 30 degreeC of temperature By setting the ratio 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. Since 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.
Furthermore, by using 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.
　固形分濃度３２重量％、温度３０℃におけるＢ型粘度が１５００ｍＰａ・ｓ以下である水蒸気バリア層用塗工液は、塗工液の送液性や取扱い性に優れ、安定した塗工を行うことができる。
　固形分濃度３２重量％、温度３０℃におけるｐＨが８．０以上１３．０以下である水蒸気バリア層用塗工液は、ハイシェア粘度が高い状態で塗工することができ、均一な外観の紙製バリア基材を得ることができる。
　固形分濃度が、２５重量％以上４４重量％以下である水蒸気バリア層用塗工液は、所望する水蒸気バリア性が得られやくなると共に、塗工液の調製が容易となる。 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.
・第二発明
　第二発明である製造方法は、接触式のブレード塗工法により水蒸気バリア層用塗工液を塗工するが、水蒸気バリア層用塗工液が、浮遊型保水剤または吸着型保水剤を含有することにより、所望の塗工量に調整することが容易となる。この水蒸気バリア層用塗工液を用いることにより、塗工幅全体に亘って均一な塗工量で塗工することができ、極めて均質な塗工層を得ることができる。そのため、第二発明である製造方法で塗工した水蒸気バリア層は、端部、中央部とで性能のバラツキが少なく、塗工面全面を利用することができ、歩留まりを高めることができる。
　さらに、第二発明である製造方法で塗工した水蒸気バリア層は、スジ状のムラが少なく、美麗な外観を有し、極めて均一な外観を有する。特に、浮遊逆相型保水剤を含有する水蒸気バリア層用塗工液を塗工した第二発明の水蒸気バリア層は、スジ状のムラが非常に少なく、非常に美麗な外観を有している。第二発明である製造方法で塗工した水蒸気バリア層は、面の均一性が極めて優れているため、この水蒸気バリア層上にガスバリア層等を塗工した場合も、平滑性、均一性に優れた外観を維持することができる。 -2nd invention The manufacturing method which is 2nd invention applies the coating liquid for water vapor | steam barrier layers with a contact-type blade coating method, but the coating liquid for water vapor | steam barrier layers is a floating type water retention agent or adsorption type water retention. By containing an agent, it becomes easy to adjust to a desired coating amount. By using this water vapor barrier layer coating solution, 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.
Furthermore, 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. In particular, 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. . Since 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.
　保水剤は基本的には親水性であるが、保水剤が顔料１００重量部に対し０．０１重量部以上１．５重量部以下である水蒸気バリア層用塗工液は、得られる水蒸気バリア層の水蒸気バリア性を高く保つことができる。
　ｐＨが８．０以上１３．０以下である水蒸気バリア層用塗工液は、保水剤の性能が発揮されやすく、所望の塗工量の水蒸気バリア層を塗工することが容易である。
　固形分濃度が、２５重量％以上４４重量％以下である水蒸気バリア層用塗工液は、所望する水蒸気バリア性が得られやくなると共に、塗工液の調製が容易となる。 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.
　本発明は、紙製バリア基材の製造方法に関し、紙基材上に、少なくとも水蒸気バリア性樹脂と顔料とを含有する水蒸気バリア層用塗工液を、ブレード塗工法により塗工して水蒸気バリア層を形成する工程を有し、
　下記条件（１）及び／又は（２）を満足することを特徴とする。
（１）前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下である。
（２）前記水蒸気バリア層用塗工液が、保水剤として浮遊型保水剤または吸着型保水剤を含有する。 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. Forming a layer,
The following condition (1) and / or (2) is satisfied.
(1) 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.
(2) The water vapor barrier layer coating solution contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
　本発明の第一発明は、紙製バリア基材の製造方法に関し、紙基材上に、少なくとも水蒸気バリア性樹脂と顔料とを含有する水蒸気バリア層用塗工液を、ブレード塗工法により塗工して水蒸気バリア層を形成する工程を有し、この水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下であることを特徴とする。 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. Features.
　本発明の第二発明は、紙製バリア基材の製造方法に関し、紙基材上に、少なくとも水蒸気バリア性樹脂と顔料とを含有する水蒸気バリア層用塗工液を、ブレード塗工法により塗工して水蒸気バリア層を形成する工程を有し、この水蒸気バリア層用塗工液が、浮遊型保水剤または吸着型保水剤を含有することを特徴とする。 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.
「紙製バリア基材の製造方法」
　第一発明、第二発明において、紙製バリア基材は、紙基材上に、少なくとも水蒸気バリア性樹脂と顔料とを含有する水蒸気バリア層用塗工液を、ブレード塗工法により塗工して水蒸気バリア層を形成することにより製造される。 "Production method of paper barrier substrate"
1st invention, 2nd invention WHEREIN: The paper barrier base material apply | coats the coating liquid for water vapor | steam barrier layers containing a water vapor | steam barrier resin and a pigment on a paper base material with a blade coating method. It is manufactured by forming a water vapor barrier layer.
　ブレード塗工を行なう際は、ブレード塗工に用いられる公知の装置を使用することができる。例えば、べベルブレードコーター、ベントブレードコーター、バーブレードコーターなどが挙げられる。 When performing blade coating, a known apparatus used for blade coating can be used. For example, a bevel blade coater, a vent blade coater, a bar blade coater and the like can be mentioned.
（第一発明の水蒸気バリア層用塗工液）
　第一発明の水蒸気バリア層用塗工液は、少なくとも水蒸気バリア性樹脂と顔料とを含有し、これらが溶解、分散した水を主体とする塗工液であり、固形分濃度３２重量％、温度３０℃においてハイシェア粘度（以下、単にハイシェア粘度という）が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下であることを特徴とする。
　水蒸気バリア層用塗工液のハイシェア粘度を上記範囲内とすることにより、スジ状のムラが少なく、表面が非常に均一な外観の塗工層を得ることができる。また、水蒸気バリア層用塗工液のハイシェア粘度を上記範囲内とすることにより、ブレード通過後の膜厚を維持することができ、所望の膜厚の塗工層を容易に得ることができる。このハイシェア粘度が１１．５ｍＰａ・ｓ未満であると、スジ状のムラが多く、表面の外観が不均一な塗工層となる。また、このハイシェア粘度が２０ｍＰａ・ｓより大きいと、ブレードによる過剰な塗工液の掻き落しが不安定になり、塗工幅全体で塗工量を均一に制御することが困難となる。そのため、端部、中央部とで性能のバラツキが大きくなり、歩留まりが低くなる。
　第一発明において、水蒸気バリア層用塗工液のハイシェア粘度は、１２ｍＰａ・ｓ以上であることが好ましく、１３ｍＰａ・ｓ以上であることがより好ましい。また、１９ｍＰａ・ｓ以下であることが好ましく、１８ｍＰａ・ｓ以下であることがより好ましい。なお、本明細書において、スジ状のムラとは、アプリケーターやブレードに異物が挟まって生じる幅１ｍｍ以下のスジ状の塗工欠陥ではなく、ブレードで加圧された塗工液中の水分が紙基材に浸透し、その後の乾燥により紙基材が収縮することにより生じると推測される、幅２ｃｍ程度のスジ状のムラである。なお、ハイシェア粘度は、ハイシェア粘度計を使用し、Ｅボブを用いて、８８００ｒｐｍの回転速度で測定される値である。ハイシェア粘度計としては、Ｋａｌｔｅｃ　Ｓｃｉｅｎｔｉｆｉｃ社製のＤＶ－１０などが使用可能である。 (Coating liquid for water vapor barrier layer of the first invention)
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.
By setting the 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. In addition, by setting the high shear viscosity of the water vapor barrier layer coating liquid within the above range, the film thickness after passing through the blade can be maintained, and a coating layer having a desired film thickness can be easily obtained. When 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. On the other hand, when 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.
In the first invention, 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. In the present specification, 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 2 cm, which is presumed to be caused by penetration of the base material and subsequent shrinkage of the paper base material. 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.
　また、第一発明に用いる水蒸気バリア層用塗工液は、固形分濃度３２重量％、温度３０℃におけるＢ型粘度が１５００ｍＰａ・ｓ以下であることが好ましい。Ｂ型粘度が１５００ｍＰａ・ｓより高いと、塗工液の送液性や取扱い性が劣る等の操業上の問題が発生しやすくなる。Ｂ型粘度は１０００ｍＰａ・ｓ以下であることがより好ましい。また、２００ｍＰａ・ｓ以上であることがより好ましい。なお、塗工液のＢ型粘度は、ブルックフィールド粘度計（Ｂ型粘度計）を使用し、Ｎｏ．３のローターを用いて、６０ｒｐｍの回転速度で測定される値である。 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. When the B-type viscosity is higher than 1500 mPa · s, operational problems such as inferior liquid feeding property and handling property of the coating liquid tend to occur. The B-type viscosity is more preferably 1000 mPa · s or less. Moreover, it is more preferable that it is 200 mPa * s or more. 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.
　また、第一発明に用いる水蒸気バリア層用塗工液は、固形分濃度３２重量％、温度３０℃におけるｐＨが８．０以上１３．０以下の範囲であることが好ましい。また、８．５以上であることがより好ましく、９．０以上であることがさらに好ましい。また、１２．０以下であることがより好ましく、１１．０以下であることがさらに好ましく、１０．０以下であることが特に好ましい。水蒸気バリア層用塗工液のｐＨが上記範囲であると、ハイシェア粘度を所定の範囲内とすることが容易となるため好ましい。 In addition, 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.
　また、第一発明に用いる水蒸気バリア層用塗工液は、固形分濃度が２５重量％以上４４重量％以下の範囲であることが好ましい。また、３０重量％以上であることがより好ましく、４０重量％以下であることがより好ましい。水蒸気バリア層用塗工液の固形分濃度が上記範囲であると、所望する水蒸気バリア性が得られやくなると共に、塗工液の調製が容易となるため好ましい。 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.
（水蒸気バリア性樹脂）
　水蒸気バリア性樹脂としては、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、パラフィン（ＷＡＸ）系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系等の各種共重合体、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等の合成接着剤、またはそれらのパラフィン（ＷＡＸ）配合合成接着剤等を単独あるいは２種類以上混合して使用することができる。これらの中では、水蒸気バリア性の点からスチレン・ブタジエン系合成接着剤、スチレン・アクリル系合成接着剤を使用することが好ましい。
　第一発明においてスチレン・ブタジエン系合成接着剤とは、スチレンとブタジエンを主構成モノマーとし、これに変性を目的とする各種のコモノマーを組み合わせ、乳化重合したものである。コモノマーの例として、メチルメタクリルレート、アクリロニトリル、アクリルアミド、ヒドロキシエチルアクリレートや、イタコン酸、マレイン酸、アクリル酸などの不飽和カルボン酸などが挙げられる。また、乳化剤としては、オレイン酸ナトリウム、ロジン酸石鹸、アルキルアリルスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウムなどのアニオン性界面活性剤を単独、またはノニオン性界面活性剤と組み合わせて用いることができる。目的によっては、両性またはカチオン性界面活性剤を用いることもできる。また、スチレン・アクリル系合成接着剤とは、スチレンとアクリルを主構成モノマーとし、これに変性を目的とする各種のコモノマーを組み合わせ、乳化重合したものである。 (Water vapor barrier resin)
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. Among these, it is preferable to use a styrene / butadiene synthetic adhesive or a styrene / acrylic synthetic adhesive from the viewpoint of water vapor barrier properties.
In the first invention, 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. Examples of comonomers include methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, unsaturated carboxylic acids such as itaconic acid, maleic acid, and acrylic acid. In addition, as the emulsifier, 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. Depending on the purpose, 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.
（水溶性高分子）
　なお、水蒸気バリア性に問題がない程度であれば、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、エチレン共重合ポリビニルアルコールなどのポリビニルアルコール類、カゼイン、大豆タンパク、合成タンパクなどのタンパク質類、酸化澱粉、カチオン化澱粉、尿素リン酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉などの澱粉類、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、ポリビニルピロリドン、アルギン酸ナトリウムなどの水溶性高分子を、上記水蒸気バリア性樹脂と併用することも可能である。 (Water-soluble polymer)
As long as there is no problem with water vapor barrier properties, 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.
（顔料）
　顔料は、水蒸気バリア層の水蒸気バリア性を高め、また、水蒸気バリア層の上にガスバリア層を塗工する場合に、水蒸気バリア層とガスバリア層の密着性を向上させることができる。
　顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、マイカ、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコア－シェル型などの有機顔料などを単独または２種類以上混合して使用することができる。
　これらの顔料の中でも、水蒸気バリア性の向上と、ガスバリア層形成用塗工液の浸透抑制の両方の観点から、形状が扁平なカオリン、マイカ、タルクなどの無機顔料が好ましく、カオリン、マイカがより好ましい。これらの中で、アスペクト比が１０以上の無機顔料を単独または２種類以上混合して使用することが好ましい。アスペクト比は１００以上がより好ましく、２００以上がさらに好ましい。また、体積５０％平均粒子径（Ｄ５０）（以下、「平均粒子径」とも言う。）が５μｍ以上の無機顔料を単独または２種類以上混合して使用することがより好ましい。使用する無機顔料の平均粒子径またはアスペクト比が上記範囲より小さいと、水蒸気バリア性の向上効果が小さくなる。 (Pigment)
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.
As 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.
Among these pigments, from the viewpoints of improving the water vapor barrier property and suppressing the penetration of the gas barrier layer forming coating solution, inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferred. preferable. Of these, 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 μm or more singly or in combination. When the average particle diameter or aspect ratio of the inorganic pigment used is smaller than the above range, the effect of improving the water vapor barrier property is reduced.
　第一発明において、水蒸気バリア性の向上、およびガスバリア層との密着性向上のため、平均粒子径が５μｍ以上の無機顔料を含有する水蒸気バリア層に、さらに平均粒子径が５μｍ以下の顔料を含有させてもよい。平均粒子径が５μｍ以下の顔料を併用することにより、平均粒子径が５μｍ以上の無機顔料により形成された水蒸気バリア層中の空隙を減少させることができるため、さらに優れた水蒸気バリア性が発現する。つまり、水蒸気バリア層に平均粒子径の異なる顔料を含有させた場合、水蒸気バリア層中で大きな平均粒子径の無機顔料により形成される空隙に小さな平均粒子径の顔料が充填された状態となり、水蒸気は顔料を迂回して通過するため、異なる平均粒子径の顔料を含有していない水蒸気バリア層と比較して、高い水蒸気バリア性を有するものと推測される。
　第一発明において、平均粒子径が５μｍ以上の無機顔料と、平均粒子径が５μｍ以下の顔料を併用する場合、平均粒子径が５μｍ以上の無機顔料と、平均粒子径が５μｍ以下の顔料の配合比率は、乾燥重量で、５０／５０～９９／１であることが好ましい。平均粒子径が５μｍ以上の無機顔料の配合比率が上記範囲より少ないと、水蒸気が水蒸気バリア層中を迂回する回数が減少し、移動する距離が短くなるため、水蒸気バリア性の改善効果が小さくなることがある。一方、上記範囲より多いと、水蒸気バリア層中の大きな平均粒子径の無機顔料が形成する空隙を平均粒子径が５μｍ以下の顔料で十分に埋めることができないため、水蒸気バリア性のさらなる向上は見られない。 In the first invention, in order to improve water vapor barrier properties and adhesion to the gas barrier layer, the water vapor barrier layer containing an inorganic pigment having an average particle size of 5 μm or more further contains a pigment having an average particle size of 5 μm or less. You may let them. By using a pigment having an average particle diameter of 5 μm or less in combination, voids in the water vapor barrier layer formed of an inorganic pigment having an average particle diameter of 5 μm or more can be reduced, so that further excellent water vapor barrier properties are exhibited. . That is, when a pigment having a different average particle size is contained in the water vapor barrier layer, 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.
In the first invention, when an inorganic pigment having an average particle size of 5 μm or more and a pigment having an average particle size of 5 μm or less are used in combination, an inorganic pigment having an average particle size of 5 μm or more and a pigment having an average particle size of 5 μm 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 μm 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. On the other hand, if it exceeds the above range, 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 μm or less, and therefore further improvement of the water vapor barrier property is observed. I can't.
　第一発明において、平均粒子径が５μｍ以上の無機顔料と併用する平均粒子径が５μｍ以下の顔料としては、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコア－シェル型などの有機顔料などを単独または２種類以上混合して使用することができる。これらの顔料の中では、重質炭酸カルシウムを使用することが好ましい。 In the first invention, the pigment having an average particle size of 5 μm or less used in combination with an inorganic pigment having an average particle size of 5 μm 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.
　水蒸気バリア層に顔料を含有させる場合、顔料の配合量は、乾燥重量で顔料１００重量部に対して、水蒸気バリア性樹脂と水溶性高分子の合計で５重量部以上２００重量部以下の範囲で使用されることが好ましく、より好ましくは水蒸気バリア性樹脂と水溶性高分子の合計で１０重量部以上１５０重量部以下である。 When the water vapor barrier layer contains a pigment, 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.
（架橋剤）
　第一発明において、水蒸気バリア層に多価金属塩などに代表される架橋剤を添加することができる。架橋剤は水蒸気バリア層に含有される水蒸気バリア性樹脂や水溶性高分子と架橋反応を起こすため、水蒸気バリア層内の結合の数（架橋点）が増加する。つまり、水蒸気バリア層が緻密な構造となり、良好な水蒸気バリア性を発現することができる。
　第一発明において、架橋剤の種類としては特に限定されるものではなく、水蒸気バリア層に含有される水蒸気バリア性樹脂や水溶性高分子の種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタンなどの多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物などのイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸など適宜選択して使用することが可能である。
　水蒸気バリア性に優れた効果を発現するスチレン・ブタジエン系、スチレン・アクリル系などのスチレン系の水蒸気バリア性樹脂を用いた場合、架橋効果発現の観点から、多価金属塩を使用することが好ましく、カリウムミョウバンを使用することがより好ましい。
　架橋剤の配合量については、塗工可能な塗工液濃度や塗工液粘度の範囲内であれば特に限定されることなく配合することができるが、好ましくは顔料１００重量部に対して、架橋剤が１重量部以上１０重量部以下であり、より好ましくは３重量部以上５重量部以下である。１重量部未満であると架橋剤の添加効果が十分に得られないことがある。また、１０重量部より多いと塗工液の粘度上昇が著しくなり、塗工が困難となることがある。 (Crosslinking agent)
In the first invention, 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.
In the first invention, 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.
In the case of using a styrene-based water vapor barrier resin such as styrene / butadiene, styrene / acrylic or the like that exhibits an excellent effect on water vapor barrier properties, it is preferable to use a polyvalent metal salt from the viewpoint of expression of a crosslinking effect. More preferably, potassium alum is used.
Regarding 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.
　第一発明において、水蒸気バリア層用塗工液に架橋剤を添加する場合、アンモニアなどの極性溶媒に架橋剤を溶解させてから塗工液へ添加することが好ましい。架橋剤を極性溶媒に溶解させると架橋剤と極性溶媒で結合を作るため、塗工液へ添加しても直ちには水蒸気バリア性樹脂や水溶性高分子との架橋反応が起こらないため、塗工液の増粘を抑制することができる。その場合、紙基材への塗工後に乾燥することにより極性溶媒成分が揮発し、水蒸気バリア性樹脂や水溶性高分子との架橋反応が起こり、緻密な水蒸気バリア層が形成されると推測される。 In the first invention, when the crosslinking agent is 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. When the cross-linking agent is dissolved in a polar solvent, 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. In that case, it is speculated that 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
（撥水剤）
　第一発明において、水蒸気バリア性向上の観点から、水蒸気バリア層に撥水剤を含有させることが好ましい。撥水剤としては、アルカン化合物を主体とするパラフィン系撥水剤、カルナバやラノインなどの動植物由来の天然油脂系撥水剤、シリコーンまたはシリコーン化合物を含有するシリコーン含有系撥水剤、フッ素化合物を含有するフッ素含有系撥水剤など例示することができる。これらの中では、水蒸気バリア性能発現の観点からパラフィン系撥水剤を使用することが好ましい。また、これらの撥水剤を単独あるいは２種類以上混合して使用することができる。 (Water repellent)
In the first invention, from the viewpoint of improving the water vapor barrier property, the water vapor barrier layer preferably contains a water repellent. Examples of 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. In these, it is preferable to use a paraffin type water repellent from a viewpoint of water vapor | steam barrier performance expression. These water repellents can be used alone or in combination of two or more.
　第一発明において、撥水剤の配合量は特に限定されるものではないが、撥水剤の配合量は、乾燥重量で水蒸気バリア性樹脂と水溶性高分子の合計１００重量部に対して、撥水剤が１重量部以上１００重量部以下であることが好ましい。撥水剤の配合量が１重量部未満であると、水蒸気バリア性の向上効果が十分に得られない場合がある。一方、１００重量部を超えた場合には、水蒸気バリア層上にガスバリア層を設ける場合にガスバリア層が均一に形成し難くなるため、ガスバリア性が低下する場合がある。 In the first invention, 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. When the blending 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. On the other hand, if 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.
（保水剤）
　第一発明において、水蒸気バリア層用塗工液は保水剤を含むことが好ましい。保水剤を含むことにより、ブレード通過後の膜厚を所望の値に制御しやすくなる。保水剤としては、ポリビニルアルコール、カルボキシメチルセルロース、デンプン、ゼラチン等の天然高分子、ポリエチレンオキサイド、ポリエーテル系化合物、ポリカルボン酸系共重合物、ポリアクリルアミド系共重合物等の合成高分子等の親水性高分子等を好ましく用いることができる。
　また、合成高分子等の保水剤は、保水性の発現機構では、保水剤が顔料やバインダーに吸着してネットワークを形成することにより保水性が発現する吸着型、保水剤の高分子構造中に導入された疎水基と塗工液中の疎水性材料が会合して、網目構造を作ることにより保水性が発現する会合型、保水剤の高分子量ポリマー同士が絡み合うことにより保水性が発現する浮遊型等に分類できる。また、形態では、順相型（Ｏ／Ｗ型）、逆相型（Ｗ／Ｏ型）等に分類できる。
　第一発明では、固形分濃度が低い塗工液においても保水性の発現が良好であり、取り扱いも容易である浮遊逆相型保水剤が好ましい。浮遊逆相型保水剤の具体例としては、ソマール社製ソマレックス５３０（ポリカルボン酸系共重合物）、サンノプコ社製ビストゥール３００（ポリアクリルアミド系共重合物）等を例示することが可能である。また、吸着順相型保水剤の具体例としては、ソマール社製ソマレックス６８０Ｋ（アクリルエステル系共重合物）等を例示することが可能である。 (Water retention agent)
In the first invention, the water vapor barrier layer coating solution preferably contains 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.
In addition, 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. Specific examples of 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. . 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.
　保水剤の配合量は、ハイシェア粘度が第一発明の範囲内であれば特に限定されないが、水蒸気バリア層が含有する顔料１００重量部に対し、０．０１～１．５重量部であることが好ましい。保水剤は、基本的に親水性高分子であるため、水蒸気バリア性維持の点から、配合量は少ないほうが好ましく、具体的には、１．２重量部以下であることがより好ましく、１．０重量部以下であることがさらに好ましい。 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.
　また、水蒸気バリア層用塗工液には、上記した水蒸気バリア性樹脂、水溶性高分子、顔料、架橋剤、撥水剤、保水剤の他、分散剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を配合することができる。 In addition, 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.
（第二発明の水蒸気バリア層用塗工液）
　第二発明の水蒸気バリア層用塗工液は、少なくとも水蒸気バリア性樹脂と顔料とを含有し、これらが溶解、分散した水を主体とする塗工液であり、さらに、浮遊型保水剤または吸着型保水剤を含有することを特徴とする。 (Coating solution for water vapor barrier layer of the second invention)
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.
　第二発明に用いる水蒸気バリア層用塗工液は、固形分濃度３２重量％、温度３０℃におけるＢ型粘度が１５００ｍＰａ・ｓ以下であることが好ましい。Ｂ型粘度が１５００ｍＰａ・ｓより高いと、塗工液の送液性や取扱い性が劣る等の操業上の問題が発生しやすくなる。Ｂ型粘度は１０００ｍＰａ・ｓ以下であることがより好ましい。また、２００ｍＰａ・ｓ以上であることがより好ましい。なお、塗工液のＢ型粘度は、ブルックフィールド粘度計（Ｂ型粘度計）を使用し、Ｎｏ．３のローターを用いて、６０ｒｐｍの回転速度で測定される値である。 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. When the B-type viscosity is higher than 1500 mPa · s, operational problems such as inferior liquid feeding property and handling property of the coating liquid tend to occur. The B-type viscosity is more preferably 1000 mPa · s or less. Moreover, it is more preferable that it is 200 mPa * s or more. 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.
　第二発明に用いる水蒸気バリア層用塗工液は、固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が、１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下であることが好ましい。水蒸気バリア層用塗工液のハイシェア粘度を上記範囲内とすることにより、スジ状のムラが少なく、表面が非常に均一な外観の塗工層を得ることができる。このハイシェア粘度が１１．５ｍＰａ・ｓ未満であると、スジ状のムラが多く、表面の外観が不均一な塗工層となる場合がある。また、このハイシェア粘度が２０ｍＰａ・ｓより大きいと、ブレードによる過剰な塗工液の掻き落しが不安定になり、端部、中央部とで性能のバラツキが大きくなる場合がある。
　第二発明において、水蒸気バリア層用塗工液のハイシェア粘度は、１２ｍＰａ・ｓ以上であることが好ましく、１３ｍＰａ・ｓ以上であることがより好ましい。また、１９ｍＰａ・ｓ以下であることが好ましく、１８ｍＰａ・ｓ以下であることがより好ましい。なお、本明細書において、スジ状のムラとは、アプリケーターやブレードに異物が挟まって生じる幅１ｍｍ以下のスジ状の塗工欠陥ではなく、ブレードで加圧された塗工液中の水分が紙基材に浸透し、その後の乾燥により紙基材が収縮することにより生じると推測される、幅１ｃｍ程度のスジ状のムラである。なお、ハイシェア粘度は、ハイシェア粘度計を使用し、Ｅボブを用いて、８８００ｒｐｍの回転速度で測定される値である。ハイシェア粘度計としては、Ｋａｌｔｅｃ　Ｓｃｉｅｎｔｉｆｉｃ社製のＤＶ－１０などが使用可能である。 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. By setting the 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. On the other hand, when the high shear viscosity is larger than 20 mPa · s, scraping off of the excessive coating liquid by the blade becomes unstable, and there may be a large variation in performance between the end portion and the central portion.
In the second invention, 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. In the present specification, 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.
　第二発明に用いる水蒸気バリア層用塗工液は、固形分濃度３２重量％、温度３０℃におけるｐＨが８．０以上１３．０以下の範囲であることが好ましい。また、８．５以上であることがより好ましく、９．０以上であることがさらに好ましい。また、１２．０以下であることがより好ましく、１１．０以下であることがさらに好ましく、１０．０以下であることが特に好ましい。水蒸気バリア層用塗工液のｐＨが上記範囲であると、保水剤の性能が発揮されやすく、所望の塗工量の水蒸気バリア層を塗工することが容易であるため好ましい。 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.
　第二発明に用いる水蒸気バリア層用塗工液は、固形分濃度が２５重量％以上４４重量％以下の範囲であることが好ましい。また、３０重量％以上であることがより好ましく、４０重量％以下であることがより好ましい。水蒸気バリア層用塗工液の固形分濃度が上記範囲であると、所望する水蒸気バリア性が得られやくなると共に、塗工液の調製が容易となるため好ましい。 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.
（水蒸気バリア性樹脂）
　水蒸気バリア性樹脂としては、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、パラフィン（ＷＡＸ）系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系等の各種共重合体、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等の合成接着剤、またはそれらのパラフィン（ＷＡＸ）配合合成接着剤等を単独あるいは２種類以上混合して使用することができる。これらの中では、水蒸気バリア性の点からスチレン・ブタジエン系合成接着剤、スチレン・アクリル系合成接着剤を使用することが好ましい。
　第二発明においてスチレン・ブタジエン系合成接着剤とは、スチレンとブタジエンを主構成モノマーとし、これに変性を目的とする各種のコモノマーを組み合わせ、乳化重合したものである。コモノマーの例として、メチルメタクリルレート、アクリロニトリル、アクリルアミド、ヒドロキシエチルアクリレートや、イタコン酸、マレイン酸、アクリル酸などの不飽和カルボン酸などが挙げられる。また、乳化剤としては、オレイン酸ナトリウム、ロジン酸石鹸、アルキルアリルスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウムなどのアニオン性界面活性剤を単独、またはノニオン性界面活性剤と組み合わせて用いることができる。目的によっては、両性またはカチオン性界面活性剤を用いることもできる。また、スチレン・アクリル系合成接着剤とは、スチレンとアクリルを主構成モノマーとし、これに変性を目的とする各種のコモノマーを組み合わせ、乳化重合したものである。 (Water vapor barrier resin)
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. Among these, it is preferable to use a styrene / butadiene synthetic adhesive or a styrene / acrylic synthetic adhesive from the viewpoint of water vapor barrier properties.
In the second invention, 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. Examples of comonomers include methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, unsaturated carboxylic acids such as itaconic acid, maleic acid, and acrylic acid. In addition, as the emulsifier, 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. Depending on the purpose, 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.
（水溶性高分子）
　なお、水蒸気バリア性に問題がない程度であれば、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、エチレン共重合ポリビニルアルコールなどのポリビニルアルコール類、カゼイン、大豆タンパク、合成タンパクなどのタンパク質類、酸化澱粉、カチオン化澱粉、尿素リン酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉などの澱粉類、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、ポリビニルピロリドン、アルギン酸ナトリウムなどの水溶性高分子を、上記水蒸気バリア性樹脂と併用することも可能である。 (Water-soluble polymer)
As long as there is no problem with water vapor barrier properties, 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.
（顔料）
　顔料は、水蒸気バリア層の水蒸気バリア性を高め、また、水蒸気バリア層の上にガスバリア層を塗工する場合に、水蒸気バリア層とガスバリア層の密着性を向上させることができる。
　顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、マイカ、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコア－シェル型などの有機顔料などを単独または２種類以上混合して使用することができる。
　これらの顔料の中でも、水蒸気バリア性の向上と、ガスバリア層形成用塗工液の浸透抑制の両方の観点から、形状が扁平なカオリン、マイカ、タルクなどの無機顔料が好ましく、カオリン、マイカがより好ましい。これらの中で、アスペクト比が１０以上の無機顔料を単独または２種類以上混合して使用することが好ましい。アスペクト比は１００以上がより好ましく、２００以上がさらに好ましい。また、体積５０％平均粒子径（Ｄ５０）（以下、「平均粒子径」とも言う。）が５μｍ以上の無機顔料を単独または２種類以上混合して使用することがより好ましい。使用する無機顔料の平均粒子径またはアスペクト比が上記範囲より小さいと、水蒸気バリア性の向上効果が小さくなる。 (Pigment)
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.
As 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.
Among these pigments, from the viewpoints of improving the water vapor barrier property and suppressing the penetration of the gas barrier layer forming coating solution, inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferred. preferable. Of these, 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 μm or more singly or in combination. When the average particle diameter or aspect ratio of the inorganic pigment used is smaller than the above range, the effect of improving the water vapor barrier property is reduced.
　第二発明において、水蒸気バリア性の向上、およびガスバリア層との密着性向上のため、平均粒子径が５μｍ以上の無機顔料を含有する水蒸気バリア層に、さらに平均粒子径が５μｍ以下の顔料を含有させてもよい。平均粒子径が５μｍ以下の顔料を併用することにより、平均粒子径が５μｍ以上の無機顔料により形成された水蒸気バリア層中の空隙を減少させることができるため、さらに優れた水蒸気バリア性が発現する。つまり、水蒸気バリア層に平均粒子径の異なる顔料を含有させた場合、水蒸気バリア層中で大きな平均粒子径の無機顔料により形成される空隙に小さな平均粒子径の顔料が充填された状態となり、水蒸気は顔料を迂回して通過するため、異なる平均粒子径の顔料を含有していない水蒸気バリア層と比較して、高い水蒸気バリア性を有するものと推測される。
　第二発明において、平均粒子径が５μｍ以上の無機顔料と、平均粒子径が５μｍ以下の顔料を併用する場合、平均粒子径が５μｍ以上の無機顔料と、平均粒子径が５μｍ以下の顔料の配合比率は、乾燥重量で、５０／５０～９９／１であることが好ましい。平均粒子径が５μｍ以上の無機顔料の配合比率が上記範囲より少ないと、水蒸気が水蒸気バリア層中を迂回する回数が減少し、移動する距離が短くなるため、水蒸気バリア性の改善効果が小さくなることがある。一方、上記範囲より多いと、水蒸気バリア層中の大きな平均粒子径の無機顔料が形成する空隙を平均粒子径が５μｍ以下の顔料で十分に埋めることができないため、水蒸気バリア性のさらなる向上は見られない。 In the second invention, in order to improve water vapor barrier properties and adhesion to the gas barrier layer, the water vapor barrier layer containing an inorganic pigment having an average particle size of 5 μm or more further contains a pigment having an average particle size of 5 μm or less. You may let them. By using a pigment having an average particle diameter of 5 μm or less in combination, voids in the water vapor barrier layer formed of an inorganic pigment having an average particle diameter of 5 μm or more can be reduced, so that further excellent water vapor barrier properties are exhibited. . That is, when a pigment having a different average particle size is contained in the water vapor barrier layer, 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.
In the second invention, when an inorganic pigment having an average particle size of 5 μm or more and a pigment having an average particle size of 5 μm or less are used in combination, an inorganic pigment having an average particle size of 5 μm or more and a pigment having an average particle size of 5 μm 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 μm 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. On the other hand, if it exceeds the above range, 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 μm or less, and therefore further improvement of the water vapor barrier property is observed. I can't.
　第二発明において、平均粒子径が５μｍ以上の無機顔料と併用する平均粒子径が５μｍ以下の顔料としては、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコア－シェル型などの有機顔料などを単独または２種類以上混合して使用することができる。これらの顔料の中では、重質炭酸カルシウムを使用することが好ましい。 In the second invention, the pigment having an average particle diameter of 5 μm or less used in combination with an inorganic pigment having an average particle diameter of 5 μm 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.
　水蒸気バリア層に顔料を含有させる場合、顔料の配合量は、乾燥重量で顔料１００重量部に対して、水蒸気バリア性樹脂と水溶性高分子の合計で５重量部以上２００重量部以下の範囲で使用されることが好ましく、より好ましくは水蒸気バリア性樹脂と水溶性高分子の合計で１０重量部以上１５０重量部以下である。 When the water vapor barrier layer contains a pigment, 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.
（保水剤）
　第二発明の水蒸気バリア層用塗工液は、浮遊型保水剤または吸着型保水剤を含有する。浮遊型保水剤とは、保水剤の高分子量ポリマー同士が絡み合うことにより保水性が発現する保水剤であり、吸着型保水剤とは、保水剤が顔料やバインダーに吸着してネットワークを形成することにより保水性が発現する保水剤をいう。なお、浮遊型、吸着型の他には、保水剤の高分子構造中に導入された疎水基と塗工液中の疎水性材料が会合して、網目構造を作ることにより保水性が発現する会合型等がある。
　保水剤を構成する高分子としては、ポリエチレンオキサイド、ポリエーテル系化合物、ポリカルボン酸系共重合物、ポリアクリルアミド系共重合物等の合成高分子等の親水性高分子等を好ましく用いることができる。 (Water retention agent)
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. In addition to the floating type and adsorption type, 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.
As the polymer constituting the water retention agent, hydrophilic polymers such as synthetic polymers such as polyethylene oxide, polyether compounds, polycarboxylic acid copolymers and polyacrylamide copolymers can be preferably used. .
　第二発明で使用する保水剤は、逆相型であることが好ましい。逆相型とは、油の中に水溶性成分が粒子となり分散したＷ／Ｏ型のエマルションを意味する。逆相型保水剤は、分散相である水相内に親水性高分子が閉じ込められた状態で存在するため、分子鎖が広がらず分子鎖同士の絡み合いが少ない。このため、親水性高分子の分子量が非常に高くても、エマルションである逆相型保水剤自体の粘性は高すぎず、取り扱い性に優れる。逆相型保水剤が水と混合されて塗工液とされると、分散相であった水相が連続相となる転相が生じ、親水性高分子の分子鎖が広がって絡み合いを起こすために保水効果を発現する。浮遊逆相型保水剤の具体例としては、ソマール社製ソマレックス５３０（ポリカルボン酸系共重合物）、サンノプコ社製ビストゥール３００（ポリアクリルアミド系共重合物）等を例示することが可能である。また、吸着順相型保水剤の具体例としては、ソマール社製ソマレックス６８０Ｋ（アクリルエステル系共重合物）等を例示することが可能である。 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. 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. Specific examples of 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. . 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.
　保水剤の配合量は、水蒸気バリア層が含有する顔料１００重量部に対し、０．０１重量部以上１．５重量部以下であることが好ましい。保水剤は、基本的に親水性高分子であるため、水蒸気バリア性維持の点から、配合量は少ないほうが好ましく、具体的には、１．２重量部以下であることがより好ましく、１．０重量部以下であることがさらに好ましい。 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.
（架橋剤）
　第二発明において、水蒸気バリア層に多価金属塩などに代表される架橋剤を添加することができる。架橋剤は水蒸気バリア層に含有される水蒸気バリア性樹脂や水溶性高分子と架橋反応を起こすため、水蒸気バリア層内の結合の数（架橋点）が増加する。つまり、水蒸気バリア層が緻密な構造となり、良好な水蒸気バリア性を発現することができる。
　第二発明において、架橋剤の種類としては特に限定されるものではなく、水蒸気バリア層に含有される水蒸気バリア性樹脂や水溶性高分子の種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタンなどの多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物などのイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸など適宜選択して使用することが可能である。
　水蒸気バリア性に優れた効果を発現するスチレン・ブタジエン系、スチレン・アクリル系などのスチレン系の水蒸気バリア性樹脂を用いた場合、架橋効果発現の観点から、多価金属塩を使用することが好ましく、カリウムミョウバンを使用することがより好ましい。　架橋剤の配合量については、塗工可能な塗工液濃度や塗工液粘度の範囲内であれば特に限定されることなく配合することができるが、好ましくは顔料１００重量部に対して、架橋剤が１重量部以上１０重量部以下であり、より好ましくは３重量部以上５重量部以下である。１重量部未満であると架橋剤の添加効果が十分に得られないことがある。また、１０重量部より多いと塗工液の粘度上昇が著しくなり、塗工が困難となることがある。 (Crosslinking agent)
In the second invention, 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.
In the second invention, 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.
In the case of using a styrene-based water vapor barrier resin such as styrene / butadiene, styrene / acrylic or the like that exhibits an excellent effect on water vapor barrier properties, it is preferable to use a polyvalent metal salt from the viewpoint of expression of a crosslinking effect. More preferably, potassium alum is used. Regarding 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.
　第二発明において、水蒸気バリア層用塗工液に架橋剤を添加する場合、アンモニアなどの極性溶媒に架橋剤を溶解させてから塗工液へ添加することが好ましい。架橋剤を極性溶媒に溶解させると架橋剤と極性溶媒で結合を作るため、塗工液へ添加しても直ちには水蒸気バリア性樹脂や水溶性高分子との架橋反応が起こらないため、塗工液の増粘を抑制することができる。その場合、紙基材への塗工後に乾燥することにより極性溶媒成分が揮発し、水蒸気バリア性樹脂や水溶性高分子との架橋反応が起こり、緻密な水蒸気バリア層が形成されると推測される。 In the second invention, when the crosslinking agent is 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. When the cross-linking agent is dissolved in a polar solvent, 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. In that case, it is speculated that 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
（撥水剤）
　第二発明において、水蒸気バリア性向上の観点から、水蒸気バリア層に撥水剤を含有させることが好ましい。撥水剤としては、アルカン化合物を主体とするパラフィン系撥水剤、カルナバやラノインなどの動植物由来の天然油脂系撥水剤、シリコーンまたはシリコーン化合物を含有するシリコーン含有系撥水剤、フッ素化合物を含有するフッ素含有系撥水剤など例示することができる。これらの中では、水蒸気バリア性能発現の観点からパラフィン系撥水剤を使用することが好ましい。また、これらの撥水剤を単独あるいは２種類以上混合して使用することができる。 (Water repellent)
In the second invention, from the viewpoint of improving the water vapor barrier property, the water vapor barrier layer preferably contains a water repellent. Examples of 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. In these, it is preferable to use a paraffin type water repellent from a viewpoint of water vapor | steam barrier performance expression. These water repellents can be used alone or in combination of two or more.
　第二発明において、撥水剤の配合量は特に限定されるものではないが、撥水剤の配合量は、乾燥重量で水蒸気バリア性樹脂と水溶性高分子の合計１００重量部に対して、撥水剤が１重量部以上１００重量部以下であることが好ましい。撥水剤の配合量が１重量部未満であると、水蒸気バリア性の向上効果が十分に得られない場合がある。一方、１００重量部を超えた場合には、水蒸気バリア層上にガスバリア層を設ける場合にガスバリア層が均一に形成し難くなるため、ガスバリア性が低下する場合がある。 In the second invention, 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. When the blending 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. On the other hand, if 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.
　また、水蒸気バリア層用塗工液には、上記した水蒸気バリア性樹脂、水溶性高分子、顔料、保水剤、架橋剤、撥水剤の他、分散剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を配合することができる。 In addition, 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. Various commonly used auxiliaries such as fluorescent dyes can be blended.
　第一発明、第二発明において、水蒸気バリア層の塗工量は、乾燥重量で３ｇ／ｍ２以上５０ｇ／ｍ２以下とすることが好ましく、５ｇ／ｍ２以上４０ｇ／ｍ２以下とすることがより好ましく、７ｇ／ｍ２以上３０ｇ／ｍ２以下とすることがさらに好ましい。水蒸気バリア層の塗工量が３ｇ／ｍ２未満であると、紙基材を塗工液が完全に被覆することが困難となり、十分な水蒸気バリア性が得られなくなることや、水蒸気バリア層上にガスバリア層を塗工する場合にガスバリア層用塗工液が紙基材にまで浸透して、十分なガスバリア性が得られなくなることがある。一方、５０ｇ／ｍ２より多いと、塗工時の乾燥負荷が大きくなる。
　なお、第一発明、第二発明において、水蒸気バリア層は１層であってもよく、２層以上の多層で構成してもよい。水蒸気バリア層を２層以上の多層で構成する場合は、少なくとも紙基材に接する水蒸気バリア層をブレード塗工法により塗工し、全ての水蒸気バリア層を合計した塗工量を上記範囲とすることが好ましい。 In the first invention and the second invention, 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. When 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. When a gas barrier layer is applied, the gas barrier layer coating solution may penetrate into the paper substrate, and sufficient gas barrier properties may not be obtained. On the other hand, when it is more than 50 g / m 2 , the drying load during coating increases.
In the first and second inventions, the water vapor barrier layer may be a single layer or a multilayer of two or more layers. When 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.
（紙基材）
　第一発明、第二発明において使用する紙基材は、パルプ、填料、各種助剤等からなるシートである。
　パルプとしては、広葉樹漂白クラフトパルプ（ＬＢＫＰ）、針葉樹漂白クラフトパルプ（ＮＢＫＰ）、広葉樹未漂白クラフトパルプ（ＬＵＫＰ）、針葉樹未漂白パルプ（ＮＵＫＰ）、サルファイトパルプなどの化学パルプ、ストーングラインドパルプ、サーモメカニカルパルプなどの機械パルプ、脱墨パルプ、古紙パルプなどの木材繊維、ケナフ、竹、麻などから得られた非木材繊維などを用いることができ、適宜配合して用いることが可能である。これらの中でも、原紙中への異物混入が発生し難いこと、使用後の紙容器を古紙原料に供してリサイクル使用する際に経時変色が発生し難いこと、高い白色度を有するため印刷時の面感が良好となり、特に包装材料として使用した場合の使用価値が高くなることなどの理由から、化学パルプ、機械パルプを用いることが好ましく、化学パルプを用いることがより好ましい。 (Paper substrate)
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. Among these, it is difficult for foreign matters to be mixed into the base paper, it is difficult to cause discoloration with time when the used paper container is recycled to the used paper raw material, and it has high whiteness, so the surface during printing It is preferable to use chemical pulp and mechanical pulp, and more preferable to use chemical pulp, for the reason that the feeling becomes good and the value in use particularly when used as a packaging material is increased.
　填料としては、ホワイトカーボン、タルク、カオリン、クレー、重質炭酸カルシウム、軽質炭酸カルシウム、酸化チタン、ゼオライト、合成樹脂填料等の公知の填料を使用することができる。また、硫酸バンドや各種のアニオン性、カチオン性、ノニオン性あるいは、両性の歩留まり向上剤、濾水性向上剤、紙力増強剤や内添サイズ剤等の抄紙用内添助剤を必要に応じて使用することができる。さらに、染料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等も必要に応じて添加することができる。 As the 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. In addition, 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. Furthermore, dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
　紙基材の製造（抄紙）方法は特に限定されるものではなく、公知の長網フォーマー、オントップハイブリッドフォーマー、ギャップフォーマーマシン等を用いて、酸性抄紙、中性抄紙、アルカリ性抄紙方式で抄紙して紙基材を製造することができる。また、紙基材は１層であってもよく、２層以上の多層で構成されていてもよい。
　さらに、紙基材の表面を各種薬剤で処理することが可能である。使用される薬剤としては、酸化澱粉、ヒドロキシエチルエーテル化澱粉、酵素変性澱粉、ポリアクリルアミド、ポリビニルアルコール、表面サイズ剤、耐水化剤、保水剤、増粘剤、滑剤などを例示することができ、これらを単独あるいは２種類以上を混合して用いることができる。さらに、これらの各種薬剤と顔料を併用してもよい。顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、マイカ、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコア－シェル型などの有機顔料などを単独または２種類以上混合して使用することができる。 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. These can be used alone or in admixture of two or more. Further, these various drugs and pigments may be used in combination. As 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.
　紙基材の表面処理の方法は特に限定されるものではないが、ロッドメタリングサイズプレス、ポンド式サイズプレス、ゲートロールコーター、スプレーコーター、ブレードコーター、カーテンコーターなど公知の塗工装置を用いることができる。
　この様にして得られる紙基材としては、上質紙、中質紙、塗工紙、片艶紙、クラフト紙、片艶クラフト紙、晒クラフト紙、グラシン紙、板紙、白板紙、ライナーなどの各種公知のものが例示可能である。
　また、紙基材の坪量は、紙製バリア基材に所望される各種品質や取り扱い性等により適宜選択可能であるが、通常は２０ｇ／ｍ２以上５００ｇ／ｍ２以下程度のものが好ましい。食品などの包装材、容器、カップなど、包装用途に使用する紙製バリア包装材料の場合は、２５ｇ／ｍ２以上４００ｇ／ｍ２以下のものがより好ましく、特に後述する軟包装材用途に使用する紙製バリア包装材料の場合は、３０ｇ／ｍ２以上１１０ｇ／ｍ２以下のものがより好ましい。 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. Can do.
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. Various well-known things can be illustrated.
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. . In the case of 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. In the case of the paper barrier packaging material to be used, those of 30 g / m 2 or more and 110 g / m 2 or less are more preferable.
（ガスバリア層）
　第一発明、第二発明である紙製バリア基材の製造方法は、水蒸気バリア層上に、ガスバリア層用塗工液を塗工して、ガスバリア層を形成することができる。ガスバリア層用塗工液は、水溶性高分子や水分散性高分子などの高分子が溶解、分散した水を主体とする塗工液であることが好ましい。水溶性高分子や水分散性高分子などの高分子を含有するガスバリア層を有する第一発明、第二発明である紙製バリア基材は、優れた水蒸気バリア性およびガスバリア性を併せ持つ。 (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.
（水溶性高分子・水分散性高分子）
　第一発明、第二発明において、ガスバリア層に使用される水溶性高分子としては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、エチレン共重合ポリビニルアルコールなどのポリビニルアルコール類、カゼイン、大豆タンパク、合成タンパクなどのタンパク質類、酸化澱粉、カチオン化澱粉、尿素リン酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉などの澱粉類、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース等のセルロース誘導体、ポリビニルピロリドン、アルギン酸ナトリウムなどを例示することができる。これらの中では、ガスバリア性の点から、ポリビニルアルコール類、セルロース誘導体が好ましく、ポリビニルアルコール類がさらに好ましい。
　また、ガスバリア層に使用される水分散性高分子としては、ポリ塩化ビニリデン、エチレン酢酸ビニル系樹脂、変性ポリオレフィン系樹脂などを例示することができる。 (Water-soluble polymer / water-dispersible polymer)
In the first invention and the second invention, 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. Among these, from the viewpoint of gas barrier properties, polyvinyl alcohols and cellulose derivatives are preferable, and polyvinyl alcohols are more preferable.
Examples of the water dispersible polymer used in the gas barrier layer include polyvinylidene chloride, ethylene vinyl acetate resin, and modified polyolefin resin.
（顔料）
　第一発明、第二発明において、ガスバリア層に顔料を含有させることは、ガスバリア性向上の観点から好ましい。ガスバリア層に使用される顔料としては、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、マイカ、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコア－シェル型などの有機顔料などを単独または２種類以上混合して使用することができる。
　これらの顔料の中でも、ガスバリア性向上の観点から、形状が扁平なカオリン、マイカ、タルクなどの無機顔料が好ましく、カオリン、マイカがより好ましい。また、平均粒子径が３μｍ以上の無機顔料を使用することがより好ましく、平均粒子径が５μｍ以上の無機顔料を使用することがさらに好ましい。また、アスペクト比が１０以上の無機顔料を使用することがより好ましく、アスペクト比が３０以上の無機顔料を使用することがさらに好ましい。 (Pigment)
In the first and second inventions, it is preferable that the gas barrier layer contains a pigment from the viewpoint of improving the gas barrier property. As pigments 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.
Among these pigments, from the viewpoint of improving gas barrier properties, inorganic pigments such as kaolin, mica and talc having a flat shape are preferable, and kaolin and mica are more preferable. Moreover, it is more preferable to use an inorganic pigment having an average particle diameter of 3 μm or more, and it is further preferable to use an inorganic pigment having an average particle diameter of 5 μm or more. Further, it is more preferable to use an inorganic pigment having an aspect ratio of 10 or more, and it is further preferable to use an inorganic pigment having an aspect ratio of 30 or more.
　ガスバリア層に顔料を含有させた場合、酸素などのガスは顔料を迂回して通過する。このため、顔料を含有していない水溶性高分子や水分散性高分子などの高分子からなるガスバリア層と比較して高湿度雰囲気下における優れたガスバリア性を有する。
　第一発明、第二発明において、ガスバリア層に顔料を含有させる場合、顔料と水溶性高分子および水分散性高分子の配合比率は、乾燥重量で、顔料／（水溶性高分子と水分散性高分子の合計）＝１／１００～１０００／１００であることが好ましい。顔料の比率が上記範囲外であると、ガスバリア性の改善効果が小さくなることがある。
　なお、第一発明、第二発明において、顔料を水溶性高分子、水分散性高分子中に配合する際に、顔料がスラリー化したものを添加し混合することが好ましい。 When a pigment is contained in the gas barrier layer, a gas such as oxygen passes around the pigment. For this reason, it has an excellent gas barrier property in a high humidity atmosphere as compared with a gas barrier layer made of a polymer such as a water-soluble polymer or a water-dispersible polymer that does not contain a pigment.
In the first invention and the second invention, when 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.
In the first invention and the second invention, 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.
（架橋剤）
　第一発明、第二発明において、ガスバリア層に多価金属塩などに代表される架橋剤を添加することができる。架橋剤はガスバリア層に含有される水溶性高分子や水分散性高分子などの高分子と架橋反応を起こすため、ガスバリア層内の結合の数（架橋点）が増加する。つまり、ガスバリア層が緻密な構造となり、良好なガスバリア性を発現することができる。
　第一発明、第二発明において、架橋剤の種類としては特に限定されるものではなく、ガスバリア層に含有される水溶性高分子や水分散性高分子などの高分子の種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタンなどの多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物などのイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸など適宜選択して使用することが可能である。なお、架橋効果発現の観点から、多価金属塩を使用することが好ましく、カリウムミョウバンを使用することがより好ましい。
　架橋剤の配合量については、塗工可能な塗工液濃度や塗工液粘度の範囲内であれば特に限定されることなく配合することができるが、好ましくは顔料１００重量部に対して、架橋剤が１重量部以上１０重量部以下であり、より好ましくは３重量部以上５重量部以下である。１重量部未満であると架橋剤の添加効果が十分に得られないことがある。また、１０重量部より多いと塗工液の粘度上昇が著しくなり、塗工が困難となることがある。 (Crosslinking agent)
In the first and second inventions, 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.
In the first and second inventions, 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 A compound in which an ionic substance such as an oxide or boron oxide is bound), an amine compound, an amide compound, an aldehyde compound, or a hydroxy acid can be appropriately selected and used. In addition, 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.
Regarding 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.
（界面活性剤）
　第一発明、第二発明において、水蒸気バリア層との密着性の観点より、ガスバリア層中に界面活性剤を含有することが好ましい。界面活性剤のイオン性は制限されるものはなく、陰イオン性界面活性剤、陽イオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤のいずれの種類でも単独もしくは２種類以上を組み合わせて使用することができる。また、具体的な種類としては、シリコーン系界面活性剤、フッ素系界面活性剤、アルコール系界面活性剤、アセチレン基を有するアセチレン系界面活性剤、アセチレン基と２つの水酸基を有するアセチレンジオール系界面活性剤、アルキル基とスルホン酸基を有するアルキルスルホン酸系界面活性剤、エステル系界面活性剤、アミド系界面活性剤、アミン系界面活性剤、アルキルエーテル系界面活性剤、フェニルエーテル系界面活性剤、硫酸エステル系界面活性剤、フェノール系界面活性剤などを例示することができる。これらの中では塗工液のレベリング性の向上効果が大きい、アセチレンジオール系界面活性剤を使用することが好ましい。なお、塗工液のレベリング性が向上すると、ガスバリア層の均一性が向上するため、ガスバリア性が向上する。 (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. 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. Agent, 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. Among these, it is preferable to use an acetylenic diol surfactant, which has a large effect of improving the leveling property of the coating liquid. In addition, when 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.
　第一発明、第二発明において、ガスバリア層用塗工液には、上記した水溶性高分子、水分散性高分子、顔料、架橋剤、界面活性剤の他、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を配合することができる。 In the first invention and the second invention, 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.
　第一発明、第二発明において、ガスバリア層の塗工量は、乾燥重量で０．２ｇ／ｍ２以上２０ｇ／ｍ２以下とすることが好ましい。ガスバリア層の塗工量が０．２／ｍ２未満であると、均一なガスバリア層を形成することが困難であるため、十分なガスバリア性が得られなくなることがある。一方、２０ｇ／ｍ２より多いと、塗工時の乾燥負荷が大きくなる。
　なお、第一発明、第二発明において、ガスバリア層は１層であってもよく、２層以上の多層で構成してもよい。ガスバリア層を２層以上の多層で構成する場合は、全てのガスバリア層を合計した塗工量を上記範囲とすることが好ましい。 In the first invention and the second invention, 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.
In the first and second inventions, 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.
　水蒸気バリア層上にガスバリア層を塗工する場合には、ガスバリア層の塗工方法は特に制限されず、カーテンコーター、ブレードコーター、バーコーター、ロールコーター、エアナイフコーター、リバースロールコーター、スプレーコーター、サイズプレスコーター、ゲートロールコーターなどが挙げられる。これらの塗工方法の中では、スジ状のムラが少なく、極めて均一で美麗な外観及び／又は極めて均質な塗工層を有する水蒸気バリア層を形成することができるという本発明の効果を損ねることがなく、平滑性、均一性に優れた外観を維持することができるため、エアナイフ塗工法またはカーテン塗工法によりガスバリア層を塗工することが好ましく、カーテン塗工法がより好ましい。 When the gas barrier layer is applied on the water vapor barrier layer, 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. Among 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.
　第一発明、第二発明において、水蒸気バリア層との密着性の観点から、ガスバリア層用塗工液の表面張力を、１０ｍＮ／ｍ以上６０ｍＮ／ｍ以下に調整することが好ましく、１５ｍＮ／ｍ以上５０ｍＮ／ｍ以下に調整することがより好ましい。ガスバリア層をカーテン塗工する場合は、４５ｍＮ／ｍ以下に調整することが好ましい。 In the first invention and the second invention, from the viewpoint of adhesion to the water vapor barrier layer, 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.
（紙製バリア基材）
　第一発明、第二発明で製造される紙製バリア基材は、紙基材上に少なくとも水蒸気バリア層用塗工液をブレード塗工法により塗工した後、通常の乾燥工程を経て製造される。好ましい態様において、製造後の塗工紙水分が３重量％以上１０重量％以下、より好ましくは４重量％以上８重量％以下程度となるように調整して仕上げられる。水蒸気バリア層、ガスバリア層を乾燥させる手法としては、例えば、蒸気加熱ヒーター、ガスヒーター、赤外線ヒーター、電気ヒーター、熱風加熱ヒーター、マイクロウェーブ、シリンダードライヤー等の通常の方法が用いられる。平滑化処理には、通常のスーパーキャレンダ、グロスキャレンダ、ソフトキャレンダ、熱キャレンダ、シューキャレンダ等の平滑化処理装置を用いることができる。平滑化処理装置は、オンマシンやオフマシンで適宜用いられ、加圧装置の形態、加圧ニップの数、加温等も適宜調整される。 (Paper barrier substrate)
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. . In a preferred embodiment, 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. As 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. For smoothing processing, 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.
　第一発明、第二発明で製造される紙製バリア基材は、紙製バリア基材のまま、または各種樹脂等と積層する、各種汎用フィルム、バリアフィルム、アルミ箔等と貼合するなどして、食品などの包装材、容器、カップ等の包装用途に用いられる紙製バリア包装材料、または産業用資材などに用いられる積層体とすることが可能である。
　これらの中で、食品などの包装材、容器、カップ等の包装用途に用いられる紙製バリア包装材料として好適に使用することができ、食品などの軟包装材として特に好適に使用することができる。なお、軟包装材とは、構成としては、柔軟性に富む材料で構成されている包装材であり、一般には紙、フィルム、アルミ箔等の薄く柔軟性のある材料を、単体あるいは貼り合せた包装材を指す。また、形状としては、袋など、内容物を入れることにより立体形状を保つような包装材を指す。
　第一発明、第二発明で製造される紙製バリア基材を食品などの包装材、特に軟包装材として用いる場合は、ヒートシール性を有する樹脂と積層することにより、包装材料としての密閉性を高め、内容物を酸素による酸化や湿気などによる劣化などから守り、保存期間の延長を可能にすることができる。
　また、産業用資材などに用いられる積層体として使用する場合においても、酸素や湿気の侵入を抑えることで、腐敗、劣化を防止できるほか、溶剤の臭気が漏れ出るのを防止するフレーバーバリア性などの効果が期待される。 The paper barrier substrate produced in the first invention and the second invention is a paper barrier substrate, or laminated with various resins, etc. Thus, it is possible to form 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.
Among them, 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. . In addition, 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. Moreover, as a shape, the packaging material which maintains a solid shape by putting the contents, such as a bag, is pointed out.
When 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.
In addition, 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.
　以下に実施例を挙げて、本発明の第一発明、第二発明を具体的に説明するが、第一発明、第二発明は、もちろんこれらの例に限定されるものではない。なお、特に断らない限り、例中の部および％は、それぞれ重量部、重量％を示す。なお、得られた紙製バリア基材について以下に示す様な評価方法に基づいて試験を行った。 Hereinafter, 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. In addition, unless otherwise indicated, 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.
　（評価方法）
＜水蒸気透過度（水蒸気バリア性）＞
　温度４０±０．５℃、相対湿度差９０±２％の条件下で、ＪＩＳ　Ｋ　７１２９：２００８　プラスチック－フィルム及びシート－水蒸気透過度の求め方（機器測定法）に準拠して、透湿度測定器（Ｄｒ．Ｌｙｓｓｙ社製、Ｌ８０－４０００）を用いて測定した。
＜酸素透過度（ガスバリア性）＞
　ＭＯＣＯＮ社製、ＯＸ－ＴＲＡＮ２／２１を使用し、２３℃－０％ＲＨ条件にて測定した。 (Evaluation methods)
<Water vapor permeability (water vapor barrier property)>
Measurement of moisture permeability under the conditions of a temperature of 40 ± 0.5 ° C and a relative humidity difference of 90 ± 2%, in accordance with JIS K 7129: 2008 Plastic-film and sheet-Method of measuring water vapor permeability (instrument measurement method) The measurement was carried out using a vessel (Dr. Lyssy, L80-4000).
<Oxygen permeability (gas barrier properties)>
Using OX-TRAN2 / 21 manufactured by MOCON, measurement was performed under the conditions of 23 ° C. and 0% RH.
＜ハイシェア粘度＞
　得られた水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃の時の粘度を、ハイシェア粘度計（Ｋａｌｔｅｃ　Ｓｃｉｅｎｔｉｆｉｃ社製、ＤＶ－１０）を使用し、Ｅボブを用いて、８８００ｒｐｍの回転速度で測定した。
＜Ｂ型粘度＞
　得られた水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃の時の粘度を、ブルックフィールド粘度計（東京計器社製、ＢＩＩ形粘度計）を使用し、Ｎｏ．３のローターを用いて、６０ｒｐｍの回転速度で測定した。
＜ｐＨ＞
　得られた水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃の時のｐＨを、ｐＨメーター（東亜ディーケーケー社製、ＨＭ－３０）を用いて測定した。 <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. Measurement was performed at a rotational speed of 60 rpm using a rotor No. 3.
<PH>
The pH 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 measured using a pH meter (manufactured by Toa DKK Corporation, HM-30).
＜面感（塗工面：Ｗａ）＞
　３Ｄマイクロスコープ（ＫＥＹＥＮＣＥ社製、ＶＲ－３０００）（ＩＳＯ４２８７準拠）を用いて、得られた紙製バリア基材の塗工面のうねりを幅方向で２００００μｍ（２ｃｍ）の範囲で検出した。得られたうねりデータからλｃ＝０．８ｍｍの波長をカットし、λｓ、λｆはカットせず、算術平均粗さ（Ｗａ）を算出した。
＜印刷面感（裏面：目視）＞
　得られた紙製バリア基材の非塗工面（裏面）に、ＲＩ印刷機を用いて下記条件でインキを印刷し乾燥させ、２３℃／５０％ＲＨの環境下で２４時間静置した後、印刷部の面感を目視により以下の基準で評価した。これは、紙の乾燥時の皺に由来すると考えられるスジ状のムラが、非塗工面（紙基材）にベタ印刷することにより視認しやすくなるためである。
（印刷条件）
　インキ種類：ＴＯＹＯインキ　ＴＫ　ＮＥＸ　ＭＺ　墨
　インキ量　：０．３ｍｌ
　使用ロール：ゴムロール
（評価基準）
　◎：全くムラが見られない 
　○：ほとんどムラが見られない 
　△：ややムラが見られる 
　×：ムラが見られる <Feeling (Coating surface: Wa)>
Using a 3D microscope (manufactured by KEYENCE, VR-3000) (ISO 4287 compliant), the waviness of the coated surface of the obtained paper barrier substrate was detected in the range of 20000 μm (2 cm) in the width direction. The wavelength of λc = 0.8 mm was cut from the obtained undulation data, λs and λf were not cut, and the arithmetic average roughness (Wa) was calculated.
<Print surface (reverse side: visual)>
On the non-coated surface (rear surface) of the obtained paper barrier substrate, ink was printed and dried under the following conditions using an RI printing machine, and allowed to stand in an environment of 23 ° C./50% RH for 24 hours. The printed surface was visually evaluated based on the following criteria. This is because streak-like unevenness that is considered to be derived from wrinkles at the time of paper drying becomes easy to visually recognize by solid printing on the non-coated surface (paper substrate).
(Printing conditions)
Ink type: TOYO ink TK NEX MZ black Ink amount: 0.3 ml
Roll used: Rubber roll (Evaluation criteria)
A: Unevenness is not seen at all
○: Unevenness is hardly seen
Δ: Slightly uneven
X: Unevenness is observed
＜塗工幅全体での塗工量の均一性と平均塗工量＞
　塗工幅２１００ｍｍの水蒸気バリア層塗工品を幅方向で７００ｍｍ幅に３分割し、それぞれを前（ベントブレードコーターの操作側）、中（中央部）、裏（ベントブレードコーターの駆動側）とする。
　水蒸気バリア層塗工品、および水蒸気バリア層塗工前の紙基材から、前、中、裏のそれぞれの中央部（幅３５０ｍｍ部分）を中心線としてＡ４判（幅２１０ｍｍ×高さ２９７ｍｍ）の測定用サンプルを１０枚ずつ切り出し、それぞれを絶乾状態として、（塗工品の重量（ｇ／ｍ２）－紙基材の重量（ｇ／ｍ２））から、前、中、裏のそれぞれの水蒸気バリア層の塗工量（ｇ／ｍ２）を算出した。さらに、第二発明について平均塗工量（ｇ／ｍ２）を算出した。 <Uniformity of coating amount over the entire coating width and average coating amount>
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.
A4 size (width 210 mm x height 297 mm) from the water vapor barrier layer coated product and the paper base material before the water vapor barrier layer coating, with the center of each of the front, middle, and back (width 350 mm) as the center line Cut out 10 samples for measurement, and let each be in an absolutely dry state. From (weight of coated product (g / m 2 ) −weight of paper substrate (g / m 2 )), 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.
・第一発明の実施例
　［実施例１］
（紙基材の作製）
　カナダ式標準ろ水度（ＣＳＦ）５００ｍｌの広葉樹クラフトパルプ（ＬＢＫＰ）とＣＳＦ５３０ｍｌの針葉樹クラフトパルプ（ＮＢＫＰ）を８０／２０の重量比で配合して、原料パルプとした。
　原料パルプに、乾燥紙力増強剤として分子量２５０万のポリアクリルアミド（ＰＡＭ）を対絶乾パルプ重量あたり０．１％、サイズ剤としてアルキルケテンダイマー（ＡＫＤ）を対絶乾パルプ重量あたり０．３５％、湿潤紙力増強剤としてポリアミドエピクロロヒドリン（ＰＡＥＨ）系樹脂を対絶乾パルプ重量あたり０．１５％、さらに歩留剤として分子量１０００万のポリアクリルアミド（ＰＡＭ）を対絶乾パルプ重量あたり０．０８％添加した後、長網抄紙機にて抄紙し、坪量５９ｇ／ｍ２の紙を得た。
　次いで、得られた紙に固形分濃度２％に調製したポリビニルアルコール（クラレ社製、ＰＶＡ１１７）をロッドメタリングサイズプレスで、両面合計で１．０ｇ／ｍ２塗工、乾燥し、坪量６０ｇ／ｍ２の原紙を得た。得られた原紙にチルドカレンダーを用いて、速度３００ｍｉｎ／ｍ、線圧５０ｋｇｆ／ｃｍ、１パスにて平滑化処理を行った。 Example of the first invention [Example 1]
(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.
Polyacrylamide (PAM) with a molecular weight of 2.5 million as a dry paper strength enhancer is 0.1% per dry pulp weight and alkyl ketene dimer (AKD) as a sizing agent is 0.35 per dry pulp weight. %, Polyamide epichlorohydrin (PAEH) resin as wet paper strength enhancer 0.15% per dry pulp weight, and polyacrylamide (PAM) with a molecular weight of 10 million as dry agent weight After adding 0.08% per unit, paper was made with a long net paper machine to obtain paper with a basis weight of 59 g / m 2 .
Next, polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) prepared to a solid content concentration of 2% was applied to the obtained paper with a rod metering size press, and 1.0 g / m 2 in total on both sides, dried, and a basis weight of 60 g. A base paper of / m 2 was obtained. The obtained base paper was smoothed using a chilled calendar at a speed of 300 min / m, a linear pressure of 50 kgf / cm, and one pass.
　（水蒸気バリア層用塗工液Ａ１の調製）
　エンジニアードカオリン（イメリス社製、バリサーフＨＸ、平均粒子径９．０μｍ、アスペクト比８０－１００）に分散剤としてポリアクリル酸ソーダを添加し（対顔料０．２％）、セリエミキサーで分散して固形分濃度６０％のカオリンスラリーを調製した。調製したカオリンスラリー９０部（固形分）に対しタルク（Ｓｐｅｃｉａｌｔｙ　ＭＩＮＥＲＡＬＳ社製、ＴＡＬＣＲＯＮ）１０部（固形分）を添加し、固形分濃度５０％の顔料スラリーを調製した。
　得られた顔料スラリー中に、顔料１００部（固形分）に対し水蒸気バリア性樹脂としてスチレン・アクリル系共重合体エマルション（サイデン化学社製、Ｘ－５１１－３７４Ｅ）を５０部（固形分）、アクリル系樹脂（三井化学社製、バリアスターＡＳＮ１００４）を５０部（固形分）、水酸化ナトリウムの１０％水溶液を１．５部（固形分）となるように配合し、さらに保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）を０．６部（固形分）となるように配合し、固形分濃度３２％の水蒸気バリア層用塗工液Ａ１を得た。 (Preparation of water vapor barrier layer coating liquid A1)
Polyacrylic acid soda was added as a dispersant to engineered kaolin (Imeris, Varisurf HX, average particle size 9.0 μm, aspect ratio 80-100) (with respect to pigment 0.2%), and dispersed with a serie mixer. A kaolin slurry having a solid content of 60% was prepared. To 90 parts (solid content) of the prepared kaolin slurry, 10 parts (solid content) of talc (Specialty Minerals Co., Ltd., TALCRON) was added to prepare a pigment slurry having a solid content concentration of 50%.
In the obtained pigment slurry, 50 parts (solid content) of styrene / acrylic copolymer emulsion (X-511-374E, manufactured by Seiden Chemical Co., Ltd.) as a water vapor barrier resin with respect to 100 parts (solid content) of the pigment, Acrylic resin (manufactured by Mitsui Chemicals, Barrier Star ASN1004) is blended to be 50 parts (solid content), a 10% aqueous solution of sodium hydroxide is 1.5 parts (solid content), and a water retention agent (Somar) Manufactured by Somalex 530, floating reversed-phase type water retention agent) so as to be 0.6 parts (solid content) to obtain a coating solution A1 for a water vapor barrier layer having a solid content concentration of 32%.
　（ガスバリア層用塗工液Ｂ１の調製）
　ポリビニルアルコール（クラレ社製、ＰＶＡ１１７）水溶液を固形分濃度１２％となるよう調製し、ガスバリア層用塗工液Ｂ１を得た。なお、このガスバリア層用塗工液Ｂ１の表面張力は３５ｍＮ／ｍであった。 (Preparation of 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.
（紙製バリア基材の作製）
　得られた原紙上に、水蒸気バリア層用塗工液Ａ１を乾燥重量で塗工量１０ｇ／ｍ２となるよう塗工速度３００ｍ／ｍｉｎでベントブレードコーターを用いて片面塗工、乾燥した後、その上にガスバリア層用塗工液Ｂ１を乾燥重量で塗工量５．０ｇ／ｍ２となるよう塗工速度３００ｍ／ｍｉｎでカーテンコーターを用いて片面塗工し、紙製バリア基材を得た。 (Preparation of paper barrier substrate)
On the obtained base paper, after one-side coating using a vent blade coater at a coating speed of 300 m / min and drying, the coating solution A1 for the water vapor barrier layer was dried at a coating weight of 10 g / m 2 . A gas barrier layer coating solution B1 is coated on one side using a curtain coater at a coating speed of 300 m / min so that the coating weight is 5.0 g / m 2 in terms of dry weight to obtain a paper barrier substrate. It was.
　［実施例２］
　（水蒸気バリア層用塗工液Ａ２の調製）
　水蒸気バリア層用塗工液Ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を保水剤（サンノプコ社製、ビストゥール３００、浮遊逆相型保水剤）０．７部（固形分）に替えた以外は水蒸気バリア層用塗工液Ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液Ａ２を得た。 [Example 2]
(Preparation of water vapor barrier layer coating liquid A2)
In preparation of the water vapor barrier layer coating liquid A1, 0.6 part (solid content) of 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).
　水蒸気バリア層用塗工液Ａ１に替えて水蒸気バリア層用塗工液Ａ２を使用した以外は、実施例１と同様にして紙製バリア基材を得た。 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.
　［実施例３］
　（水蒸気バリア層用塗工液Ａ３の調製）
　水蒸気バリア層用塗工液Ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を保水剤（ソマール社製、ソマレックス６８０Ｋ、吸着順相型保水剤）０．４部（固形分）に替えた以外は水蒸気バリア層用塗工液Ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液Ａ３を得た。 [Example 3]
(Preparation of water vapor barrier layer coating liquid A3)
In preparation of the coating solution A1 for the water vapor barrier layer, 0.6 part (solid content) of a water retention agent (Somarex 530, floating reversed phase type water retention agent) (solid content) was added to the water retention agent (Somarex, Somalex 680K, order of adsorption). 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).
　水蒸気バリア層用塗工液Ａ１に替えて水蒸気バリア層用塗工液Ａ３を使用した以外は、実施例１と同様にして紙製バリア基材を得た。 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.
　［比較例１］
　（水蒸気バリア層用塗工液Ａ４の調製）
　水蒸気バリア層用塗工液Ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を配合しない以外は水蒸気バリア層用塗工液Ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液Ａ４を得た。 [Comparative Example 1]
(Preparation of water vapor barrier layer coating liquid A4)
In preparation of the water vapor barrier layer coating liquid A1, the water vapor barrier layer coating liquid A1 except that 0.6 part (solid content) of a water retention agent (Somarex 530, floating reverse phase type water retention agent) is not blended. In the same manner as above, a water vapor barrier layer coating solution A4 having a solid content concentration of 32% was obtained.
　水蒸気バリア層用塗工液Ａ１に替えて水蒸気バリア層用塗工液Ａ４を使用した以外は、実施例１と同様にして紙製バリア基材を得た。 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.
　［比較例２］
　（水蒸気バリア層用塗工液Ａ５の調製）
　水蒸気バリア層用塗工液Ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を保水剤（サンノプコ社製、ＳＮシックナー６１２Ｎ、会合型保水剤）３．０部（固形分）に替えた以外は水蒸気バリア層用塗工液Ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液Ａ５を得た。 [Comparative Example 2]
(Preparation of water vapor barrier layer coating liquid A5)
In preparation of the water vapor barrier layer coating liquid A1, 0.6 part (solid content) of a water retention agent (Somalex 530, floating reversed phase type water retention agent) (solid content) was added to the water retention agent (San Nopco, SN thickener 612N). Except for changing to 3.0 parts (solid content) of the mold water retention agent), a water vapor barrier layer coating solution A5 having a solid content concentration of 32% was obtained in the same manner as the water vapor barrier layer coating solution A1.
　水蒸気バリア層用塗工液Ａ１に替えて水蒸気バリア層用塗工液Ａ５を使用した以外は、実施例１と同様にして紙製バリア基材を得た。 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下である第一発明の水蒸気バリア層用塗工液を塗工した実施例１～３は、塗工面の算術平均粗さが小さく、非塗工面の目視での面感にも優れており、均一で美麗な外観を有していた。また、幅方向での塗工量も均一であり、バラツキの少ない紙製バリア基材を製造することができた。
　一方、固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ未満である水蒸気バリア層用塗工液を塗工した比較例１、２は、塗工面の算術平均粗さが２０μｍ以上と大きく、非塗工面も目視でムラが視認できた。また、幅方向での塗工量のバラツキが大きかった。 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. Moreover, the coating amount in the width direction was uniform, and a paper barrier substrate with little variation could be produced.
On the other hand, 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 μm or more, and the non-coated surface was visually non-uniform. Moreover, the variation of the coating amount in the width direction was large.
・第二発明の実施例
　［実施例４］
（紙基材の作製）
　カナダ式標準ろ水度（ＣＳＦ）５００ｍｌの広葉樹クラフトパルプ（ＬＢＫＰ）とＣＳＦ５３０ｍｌの針葉樹クラフトパルプ（ＮＢＫＰ）を８０／２０の重量比で配合して、原料パルプとした。
　原料パルプに、乾燥紙力増強剤として分子量２５０万のポリアクリルアミド（ＰＡＭ）を対絶乾パルプ重量あたり０．１％、サイズ剤としてアルキルケテンダイマー（ＡＫＤ）を対絶乾パルプ重量あたり０．３５％、湿潤紙力増強剤としてポリアミドエピクロロヒドリン（ＰＡＥＨ）系樹脂を対絶乾パルプ重量あたり０．１５％、さらに歩留剤として分子量１０００万のポリアクリルアミド（ＰＡＭ）を対絶乾パルプ重量あたり０．０８％添加した後、長網抄紙機にて抄紙し、坪量５９ｇ／ｍ２の紙を得た。
　次いで、得られた紙に固形分濃度２％に調製したポリビニルアルコール（クラレ社製、ＰＶＡ１１７）をロッドメタリングサイズプレスで、両面合計で１．０ｇ／ｍ２塗工、乾燥し、坪量６０ｇ／ｍ２の原紙を得た。得られた原紙にチルドカレンダーを用いて、速度３００ｍｉｎ／ｍ、線圧５０ｋｇｆ／ｃｍ、１パスにて平滑化処理を行った。 -Example of the second invention [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.
Polyacrylamide (PAM) with a molecular weight of 2.5 million as a dry paper strength enhancer is 0.1% per dry pulp weight and alkyl ketene dimer (AKD) as a sizing agent is 0.35 per dry pulp weight. %, Polyamide epichlorohydrin (PAEH) resin as wet paper strength enhancer 0.15% per dry pulp weight, and polyacrylamide (PAM) with a molecular weight of 10 million as dry agent weight After adding 0.08% per unit, paper was made with a long net paper machine to obtain paper with a basis weight of 59 g / m 2 .
Next, polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.) prepared to a solid content concentration of 2% was applied to the obtained paper with a rod metering size press, and 1.0 g / m 2 in total on both sides, dried, and a basis weight of 60 g. A base paper of / m 2 was obtained. The obtained base paper was smoothed using a chilled calendar at a speed of 300 min / m, a linear pressure of 50 kgf / cm, and one pass.
　（水蒸気バリア層用塗工液ａ１の調製）
　エンジニアードカオリン（イメリス社製、バリサーフＨＸ、平均粒子径９．０μｍ、アスペクト比８０－１００）に分散剤としてポリアクリル酸ソーダを添加し（対顔料０．２％）、セリエミキサーで分散して固形分濃度６０％のカオリンスラリーを調製した。調製したカオリンスラリー９０部（固形分）に対しタルク（Ｓｐｅｃｉａｌｔｙ　ＭＩＮＥＲＡＬＳ社製、ＴＡＬＣＲＯＮ）１０部（固形分）を添加し、固形分濃度５０％の顔料スラリーを調製した。
　得られた顔料スラリー中に、顔料１００部（固形分）に対し水蒸気バリア性樹脂としてスチレン・アクリル系共重合体エマルション（サイデン化学社製、Ｘ－５１１－３７４Ｅ）を５０部（固形分）、アクリル系樹脂（三井化学社製、バリアスターＡＳＮ１００４）を５０部（固形分）、水酸化ナトリウムの１０％水溶液を１．５部（固形分）となるように配合し、さらに保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）を０．６部（固形分）となるように配合し、固形分濃度３２％の水蒸気バリア層用塗工液ａ１を得た。 (Preparation of water vapor barrier layer coating liquid a1)
Polyacrylic acid soda was added as a dispersant to engineered kaolin (Imeris, Varisurf HX, average particle size 9.0 μm, aspect ratio 80-100) (with respect to pigment 0.2%), and dispersed with a serie mixer. A kaolin slurry having a solid content of 60% was prepared. To 90 parts (solid content) of the prepared kaolin slurry, 10 parts (solid content) of talc (Specialty Minerals Co., Ltd., TALCRON) was added to prepare a pigment slurry having a solid content concentration of 50%.
In the obtained pigment slurry, 50 parts (solid content) of styrene / acrylic copolymer emulsion (X-511-374E, manufactured by Seiden Chemical Co., Ltd.) as a water vapor barrier resin with respect to 100 parts (solid content) of the pigment, Acrylic resin (manufactured by Mitsui Chemicals, Barrier Star ASN1004) is blended to be 50 parts (solid content), a 10% aqueous solution of sodium hydroxide is 1.5 parts (solid content), and a water retention agent (Somar) Manufactured by Somalex 530, floating reversed phase water retention agent) so as to be 0.6 parts (solid content) to obtain a coating solution a1 for a water vapor barrier layer having a solid content concentration of 32%.
　（ガスバリア層用塗工液ｂ１の調製）
　ポリビニルアルコール（クラレ社製、ＰＶＡ１１７）水溶液を固形分濃度１２％となるよう調製し、ガスバリア層用塗工液ｂ１を得た。なお、このガスバリア層用塗工液ｂ１の表面張力は３５ｍＮ／ｍであった。 (Preparation of 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.
（紙製バリア基材の作製）
　得られた原紙上に、水蒸気バリア層用塗工液ａ１を乾燥重量で塗工量１０ｇ／ｍ２となるよう塗工速度３００ｍ／ｍｉｎでベントブレードコーターを用いて片面塗工、乾燥した後、その上にガスバリア層用塗工液ｂ１を乾燥重量で塗工量５．０ｇ／ｍ２となるよう塗工速度３００ｍ／ｍｉｎでカーテンコーターを用いて片面塗工し、紙製バリア基材を得た。 (Preparation of paper barrier substrate)
On the obtained base paper, after one-side coating using a vent blade coater at a coating speed of 300 m / min and drying, the coating solution a1 for the water vapor barrier layer is dried at a coating weight of 10 g / m 2 . A gas barrier layer coating solution b1 is coated on one side using a curtain coater at a coating speed of 300 m / min so that the coating weight is 5.0 g / m 2 in terms of dry weight to obtain a paper barrier substrate. It was.
　［実施例５］
　（水蒸気バリア層用塗工液ａ２の調製）
　水蒸気バリア層用塗工液ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を保水剤（サンノプコ社製、ビストゥール３００、浮遊逆相型保水剤）０．７部（固形分）に替えた以外は水蒸気バリア層用塗工液ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液ａ２を得た。 [Example 5]
(Preparation of water vapor barrier layer coating solution a2)
In the preparation of the coating solution a1 for the water vapor barrier layer, 0.6 part (solid content) of 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.
　水蒸気バリア層用塗工液ａ１に替えて水蒸気バリア層用塗工液ａ２を使用した以外は、実施例４と同様にして紙製バリア基材を得た。 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.
　［実施例６］
　（水蒸気バリア層用塗工液ａ３の調製）
　水蒸気バリア層用塗工液ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を保水剤（ソマール社製、ソマレックス６８０Ｋ、吸着順相型保水剤）０．４部（固形分）に替えた以外は水蒸気バリア層用塗工液ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液ａ３を得た。 [Example 6]
(Preparation of water vapor barrier layer coating solution a3)
In preparation of the coating solution a1 for the water vapor barrier layer, 0.6 part (solid content) of a water retention agent (Somarex 530, floating reversed phase type water retention agent) (solid content) was added to the water retention agent (Somarex, Somalex 680K, order of adsorption). 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).
　水蒸気バリア層用塗工液ａ１に替えて水蒸気バリア層用塗工液ａ３を使用した以外は、実施例４と同様にして紙製バリア基材を得た。 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.
　［比較例３］
　（水蒸気バリア層用塗工液ａ４の調製）
　水蒸気バリア層用塗工液ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を配合しない以外は水蒸気バリア層用塗工液ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液ａ４を得た。 [Comparative Example 3]
(Preparation of water vapor barrier layer coating solution a4)
In preparing the water vapor barrier layer coating liquid a1, the water vapor barrier layer coating liquid a1 except that 0.6 part (solid content) of a water retention agent (Somarex 530, floating reversed phase water retention agent) was not blended. In the same manner as above, a water vapor barrier layer coating solution a4 having a solid content concentration of 32% was obtained.
　水蒸気バリア層用塗工液ａ１に替えて水蒸気バリア層用塗工液ａ４を使用した以外は、実施例４と同様にして紙製バリア基材を得た。 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.
　［比較例４］
　（水蒸気バリア層用塗工液ａ５の調製）
　水蒸気バリア層用塗工液ａ１の調製で、保水剤（ソマール社製、ソマレックス５３０、浮遊逆相型保水剤）０．６部（固形分）を保水剤（サンノプコ社製、ＳＮシックナー６１２Ｎ、会合型保水剤）３．０部（固形分）に替えた以外は水蒸気バリア層用塗工液ａ１と同様にして、固形分濃度３２％の水蒸気バリア層用塗工液ａ５を得た。 [Comparative Example 4]
(Preparation of water vapor barrier layer coating solution a5)
In preparation of the coating solution a1 for the water vapor barrier layer, 0.6 part (solid content) of a water retention agent (Somarex, 530, floating reversed phase type water retention agent) (solid content) was added to the water retention agent (San Nopco, SN thickener 612N). A water vapor barrier layer coating liquid a5 having a solid content concentration of 32% was obtained in the same manner as the water vapor barrier layer coating liquid a1 except that the water content was changed to 3.0 parts (solid content).
　水蒸気バリア層用塗工液ａ１に替えて水蒸気バリア層用塗工液ａ５を使用した以外は、実施例４と同様にして紙製バリア基材を得た。 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　第二発明の浮遊型保水剤、吸着型保水剤を含有する水蒸気バリア層用塗工液を塗工した実施例４～６は、塗工量が多く、また、幅方向での塗工量も均一であり、バラツキの少ない極めて均質な塗工層を有する紙製バリア基材を製造することができた。さらに、塗工面の算術平均粗さが小さく、非塗工面の目視での面感にも優れており、均一で美麗な外観を有していた。特に浮遊逆相型保水剤を含む水蒸気バリア層用塗工液を塗工した実施例４、５は、スジ状のムラが全く見えず、非常に美麗な外観を有していた。
　一方、保水剤を含有しない水蒸気バリア層用塗工液を塗工した比較例３、及び浮遊型保水剤、吸着型保水剤以外の保水剤を含有する水蒸気バリア層用塗工液を塗工した比較例４は、同様の条件で塗工したにも関わらず、実施例４～６と比較して塗工量が少なくなった。また、幅方向での塗工量のバラツキが大きかった。特に、比較例４は、顔料１００重量部に対して会合型保水剤を３．０重量部含有するにも関わらず、塗工量が少なかった。また、親水性高分子である保水剤を大量に含有させたため、水蒸気バリア性が低下する傾向が見られた。さらに、比較例３、４は、塗工面の算術平均粗さが２０μｍ以上と大きく、非塗工面も目視でムラが視認できた。 In 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. In particular, 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.
On the other hand, the comparative example 3 which applied the coating liquid for water vapor | steam barrier layers which does not contain a water retention agent, and the coating liquid for water vapor | steam barrier layers containing water retention agents other than a floating type water retention agent and an adsorption type water retention agent were applied. In 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 μm or more, and unevenness could be visually recognized on the non-coated surface.

Claims (12)

  1. 　紙基材上に、少なくとも水蒸気バリア性樹脂と顔料とを含有する水蒸気バリア層用塗工液を、ブレード塗工法により塗工して水蒸気バリア層を形成する工程を有し、
    　下記条件（１）及び／又は（２）を満足することを特徴とする紙製バリア基材の製造方法。
    （１）前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下である。
    （２）前記水蒸気バリア層用塗工液が、保水剤として浮遊型保水剤または吸着型保水剤を含有する。     On the paper base material, it has a step of 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 by a blade coating method,
    A method for producing a paper barrier substrate, which satisfies the following conditions (1) and / or (2):
    (1) 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.
    (2) The water vapor barrier layer coating solution contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
  2. 　前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるハイシェア粘度が１１．５ｍＰａ・ｓ以上２０ｍＰａ・ｓ以下であることを特徴とする請求項１に記載の紙製バリア基材の製造方法。 2. The paper barrier substrate according to claim 1, wherein the water vapor barrier layer coating solution 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 method of manufacturing the material.
  3. 　前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるＢ型粘度が１５００ｍＰａ・ｓ以下であることを特徴とする請求項２に記載の紙製バリア基材の製造方法。 The method for producing a paper barrier base material according to claim 2, wherein the water vapor barrier layer coating liquid 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.
  4. 　前記水蒸気バリア層用塗工液の固形分濃度３２重量％、温度３０℃におけるｐＨが８．０以上１３．０以下であることを特徴とする請求項２または３に記載の紙製バリア基材の製造方法。 The paper barrier substrate according to claim 2 or 3, wherein the water vapor barrier layer coating liquid has a solid content concentration of 32% by weight and a pH at a temperature of 30 ° C of from 8.0 to 13.0. Manufacturing method.
  5. 　前記水蒸気バリア層用塗工液の固形分濃度が、２５重量％以上４４重量％以下であることを特徴とする請求項２～４のいずれかに記載の紙製バリア基材の製造方法。 The method for producing a paper barrier substrate according to any one of claims 2 to 4, wherein a solid content concentration of the coating solution for the water vapor barrier layer is 25 wt% or more and 44 wt% or less.
  6. 　前記水蒸気バリア層上に、ガスバリア層用塗工液を塗工して、ガスバリア層を形成する工程、を含むことを特徴とする請求項２～５のいずれかに記載の紙製バリア基材の製造方法。 The paper barrier substrate according to any one of claims 2 to 5, further comprising a step of coating a gas barrier layer coating solution on the water vapor barrier layer to form a gas barrier layer. Production method.
  7. 　前記水蒸気バリア層用塗工液が、保水剤として浮遊型保水剤または吸着型保水剤を含有することを特徴とする請求項１に記載の紙製バリア基材の製造方法。 The method for producing a paper barrier substrate according to claim 1, wherein the coating liquid for the water vapor barrier layer contains a floating water retention agent or an adsorption water retention agent as a water retention agent.
  8. 　前記保水剤が、浮遊逆相型保水剤であることを特徴とする請求項７に記載の紙製バリア基材の製造方法。 The method for producing a paper barrier substrate according to claim 7, wherein the water retention agent is a floating reversed phase type water retention agent.
  9. 　前記保水剤の含有量が、顔料１００重量部に対し０．０１重量部以上１．５重量部以下であることを特徴とする請求項７または８に記載の紙製バリア基材の製造方法。 The method for producing a paper barrier substrate according to claim 7 or 8, wherein the content of the water retention agent is 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.
  10. 　前記水蒸気バリア層用塗工液のｐＨが、８．０以上１３．０以下であることを特徴とする請求項７～９のいずれかに記載の紙製バリア基材の製造方法。 The method for producing a paper barrier substrate according to any one of claims 7 to 9, wherein the pH of the water vapor barrier layer coating solution is 8.0 or more and 13.0 or less.
  11. 　前記水蒸気バリア層用塗工液の固形分濃度が、２５重量％以上４４重量％以下であることを特徴とする請求項７～１０のいずれかに記載の紙製バリア基材の製造方法。 The method for producing a paper barrier substrate according to any one of claims 7 to 10, wherein a solid content concentration of the coating solution for the water vapor barrier layer is 25 wt% or more and 44 wt% or less.
  12. 　前記水蒸気バリア層上に、ガスバリア層用塗工液を塗工して、ガスバリア層を形成する工程、を含むことを特徴とする請求項７～１１のいずれかに記載の紙製バリア基材の製造方法。 The paper barrier substrate according to any one of claims 7 to 11, further comprising a step of coating a gas barrier layer coating liquid on the water vapor barrier layer to form a gas barrier layer. Production method.
PCT/JP2019/005019 2018-03-29 2019-02-13 Method for manufacturing paper-making barrier substrate WO2019187717A1 (en)

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