Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
  • C09D109/06—Copolymers with styrene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/10—Copolymers of styrene with conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
  • C09D125/02—Homopolymers or copolymers of hydrocarbons
  • C09D125/04—Homopolymers or copolymers of styrene
  • C09D125/08—Copolymers of styrene
  • C09D125/14—Copolymers of styrene with unsaturated esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols

Definitions

• the present invention relates to an anchor coating agent for a base paper of a paper barrier material, a composition set of a paper barrier material, an anchor coat layer, a laminate, and a paper barrier material.
• the paper barrier material is a material in which at least a gas barrier layer having a gas barrier property is provided on a base paper (paper base material), and is widely used as a packaging material.
• a gas barrier layer described above, for example, Patent Documents 1 to 5 disclose a gas barrier layer containing a water-soluble polymer and a pigment.
• these documents also disclose that a water vapor barrier layer is provided between the base paper and the gas barrier layer.
• the water vapor barrier layer specifically disclosed in these contains a synthetic adhesive such as styrene-butadiene and an inorganic pigment such as kaolin, and the inorganic pigment is 50% by mass or more in the solid content of the barrier layer. Is what.
• the anchor coating agent forming the anchor coating layer as described above has good printability (leveling property), and when actual use is taken into consideration, no coagulant is generated in the coating agent. Mechanical stability is required.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an anchor coating agent for a base paper of a paper barrier material having leveling property and mechanical stability.
• the present invention is an anchor coating agent for a base paper of a paper barrier material, which contains a styrene-butadiene resin emulsion, a styrene-acrylic resin emulsion, an alkali-soluble resin, and an aqueous medium, and is a solid of the anchor coating agent.
• the proportion of the resin in the styrene-butadiene resin emulsion is 50% by mass or more and 80% by mass or less, and the proportion of the resin in the styrene-acrylic resin emulsion is 3% by mass or more and 25% by mass or less.
• the present invention relates to an anchor coating agent for a base paper of a paper barrier material in which the proportion of the alkali-soluble resin is 3% by mass or more and 25% by mass or less.
• the present invention also relates to a composition set of a paper barrier material having an anchor coating agent for a base paper of the paper barrier material and a gas barrier agent containing a water-soluble polymer and a pigment.
• the present invention also relates to an anchor coat layer formed from an anchor coat agent for a base paper of the paper barrier material.
• the present invention also relates to a base paper and a laminate having the anchor coat layer.
• the present invention relates to a paper barrier material having a gas barrier layer formed from the laminate and a gas barrier agent containing a water-soluble polymer and a pigment.
• the anchor coating agent for the base paper of the paper barrier material of the present invention contains a styrene-butadiene resin emulsion, a styrene-acrylic resin emulsion, an alkali-soluble resin, and an aqueous medium, and the solid content of the anchor coating agent is described as described above.
• the ratio of the resin in the styrene-butadiene resin emulsion is 50% by mass or more and 80% by mass or less
• the ratio of the resin in the styrene-acrylic resin emulsion is 3% by mass or more and 25% by mass or less
• the ratio of the alkali-soluble resin is The ratio is 3% by mass or more and 25% by mass or less.
• the base paper anchor coating agent contains a specific amount of the above three components in an aqueous medium, it has a good balance of leveling property and mechanical stability, and is formed from the base paper anchor coating agent.
• a gas barrier layer can be provided on the anchor coat layer surface.
• the styrene-butadiene resin emulsion can be expected to have an effect of imparting a water vapor barrier property as disclosed in the above patent document.
• the anchor coating agent for the base paper of the paper barrier material of the present invention includes a styrene-butadiene resin emulsion, a styrene-acrylic resin emulsion, an alkali-soluble resin, and an aqueous medium.
• the styrene-butadiene resin emulsion of the present invention is a monomer composition containing a styrene-based monomer, butadiene, and, if necessary, a styrene-based monomer and another monomer copolymerizable with butadiene.
• a resin emulsion obtained by emulsion polymerization At least one type of the styrene-butadiene resin emulsion may be used, and two or more types may be used in combination.
• styrene-based monomer examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, ⁇ -ethylstyrene, ⁇ -butylstyrene, 4-methoxystyrene, vinyltoluene and the like. Be done.
• Examples of the styrene-based monomer and other monomers copolymerizable with butadiene include (meth) acrylic acid alkyl ester monomers such as methyl (meth) acrylate and butyl (meth) acrylate; acrylonitrile. , Vinyl cyanide monomer such as methacrylonitrile; amide group-containing monomer such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide; 2-hydroxyethyl (meth) acrylic acid, (meth) acrylic acid Examples include (meth) acrylic acid hydroxyalkyl ester monomers such as 2-hydroxypropyl; carboxyl group-containing monomers such as itaconic acid, maleic acid, and (meth) acrylic acid.
• a carboxy group-containing monomer is preferable from the viewpoint of emulsion stability, and the styrene-butadiene resin emulsion is preferably a carboxy (carboxy group) modified styrene-butadiene resin emulsion.
• the styrene-butadiene resin emulsion preferably has a glass transition temperature of the resin of ⁇ 20 ° C. or higher, more preferably ⁇ 10 ° C. or higher, and more preferably ⁇ 10 ° C. or higher, from the viewpoint of improving blocking property and leveling property. From the viewpoint of improving the barrier property, the temperature is preferably 20 ° C. or lower, and more preferably 10 ° C. or lower.
• the glass transition temperature is determined by differential scanning calorimetry (DSC) and is usually calculated at the midpoint of the temperature range where the glass transition occurs.
• styrene-butadiene resin emulsion examples include "Nippor SX1105A”, “Nippor LX407S12”, and “Nippor LX435" (all manufactured by Nippon Zeon Corporation).
• the styrene-acrylic resin emulsion of the present invention comprises the styrene-based monomer, the (meth) acrylic acid alkyl ester monomer, and, if necessary, the styrene-based monomer and the (meth) acrylic acid alkyl ester simple substance. It is a resin emulsion obtained by emulsion polymerization of a monomer composition containing a styrene and another monomer copolymerizable. At least one type of the styrene-acrylic resin emulsion may be used, and two or more types may be used in combination.
• Examples of other monomers copolymerizable with the styrene-based monomer and the (meth) acrylic acid ester monomer include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; (meth) acrylamide and N. , N-dimethyl (meth) acrylamide and other amide group-containing monomers; (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl and other (meth) acrylic acid hydroxyalkyl ester monomers; Examples thereof include carboxyl group-containing monomers such as itaconic acid, maleic acid, and (meth) acrylic acid. Among these, a carboxy group-containing monomer is preferable from the viewpoint of improving water resistance.
• the styrene-acrylic resin emulsion preferably has an acid value of 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 160 mgKOH / g or less. It is preferably 120 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
• the acid value of the resin can be calculated based on the potentiometric titration method (JIS-K-0070).
• the styrene-acrylic resin emulsion preferably has a glass transition temperature of the resin of 100 ° C. or higher, more preferably 110 ° C. or higher, and base paper fixability. From the viewpoint of the above, it is preferably 140 ° C. or lower, and more preferably 130 ° C. or lower.
• the glass transition temperature is determined by differential scanning calorimetry (DSC) and is usually calculated at the midpoint of the temperature range where the glass transition occurs.
• the alkali-soluble resin of the present invention is an alkali-soluble resin that can be used for pigment dispersion of ordinary inks and paints and as a binder, and is not particularly limited as long as it can be dissolved in an aqueous medium in the presence of a basic compound.
• At least one type of the alkali-soluble resin may be used, and two or more types may be used in combination.
• the alkali-soluble resin further has a hydrophobic portion in the molecule mainly for improving water resistance.
• hydrophobic moiety introduced into the molecule include hydrophobic groups such as long-chain alkyl groups, alicyclic groups, and aromatic cyclic hydrocarbon groups.
• the acid value of the alkali-soluble resin is preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, and more preferably 200 mgKOH / g, from the viewpoint of increasing the solubility in an aqueous medium and improving the storage stability. It is more preferably g or more, and from the viewpoint of improving the water resistance of the printed matter, it is preferably 300 mgKOH / g or less, and more preferably 280 mgKOH / g or less.
• the acid value was calculated mathematically by the number of mg of potassium hydroxide theoretically required to neutralize 1 g of the alkali-soluble resin based on the composition of the monomer used for synthesizing the alkali-soluble resin. It is the theoretical acid value.
• the glass transition temperature of the alkali-soluble resin is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, from the viewpoint of improving the blocking resistance of the printed matter.
• the glass transition temperature of the alkali-soluble resin is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, from the viewpoint of improving the bending resistance of the printed matter.
• the glass transition temperature of the alkali-soluble resin is the theoretical glass transition temperature obtained by the following wood formula.
• Wood's formula: 1 / Tg W1 / Tg1 + W2 / Tg2 + W3 / Tg3 + ... + Wx / Tgx
• Tg1 to Tgx are the monomers 1, 2, 3 ... x constituting the alkali-soluble resin.
• the glass transition temperature of each homopolymer, W1 to Wx represent the polymerization fractions of the monomers 1, 2, 3 ... X, and Tg represents the theoretical glass transition temperature.
• the glass transition temperature in the wood equation is an absolute temperature.
• the glass transition temperature of the alkali-soluble resin is the theoretical glass transition temperature obtained by thermal analysis when the alkali-soluble resin is other than the acrylic copolymer resin.
• a method of thermal analysis according to JIS K7121 (method for measuring transition temperature of plastic), as an example, using Pyris1 DSC manufactured by PerkinElmer Co., Ltd., a heating rate of 20 ° C./min and a nitrogen gas flow velocity of 20 ml / min.
• the glass transition temperature can be measured below.
• the weight average molecular weight of the alkali-soluble resin is preferably 5,000 or more, and more preferably 10,000 or more, from the viewpoint of improving the water resistance of the printed matter.
• the weight average molecular weight of the alkali-soluble resin is preferably 100,000 or less, and more preferably 50,000 or less, from the viewpoint of increasing the solubility in an aqueous medium.
• the weight average molecular weight can be measured by a gel permeation chromatography (GPC) method.
• GPC gel permeation chromatography
• Water2690 manufactured by Waters
• PLgel 5 ⁇ as a column
• MIXED-D manufactured by Polymer Laboratories
• Chromatography can be performed under the conditions of a detector, a sample injection concentration of 10 mg / ml, and an injection amount of 100 microliters, and the weight average molecular weight in terms of polystyrene can be obtained.
• the alkali-soluble resin examples include an acrylic copolymer resin, a maleic acid copolymer resin, a polyester resin obtained by a polycondensation reaction, and a polyurethane resin.
• a material for synthesizing such an alkali-soluble resin is disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-94825, and an acrylic copolymer resin obtained by using the material described in the publication.
• Maleic acid-based copolymer resins, polyester-based resins, polyurethane-based resins and the like can be used. Furthermore, resins obtained by using other materials other than these can also be used.
• the alkali-soluble resin can be used alone or in combination of two or more.
• acrylic copolymer resin for example, a mixture of an anionic group-containing monomer and another copolymerizable monomer is used as an ordinary radical generator (for example, benzoyl peroxide, tertiary butyl peroxybenzoate, etc.). Those obtained by polymerization in a solvent in the presence of (azobisisobutyronitrile, etc.) can be used.
• an ordinary radical generator for example, benzoyl peroxide, tertiary butyl peroxybenzoate, etc.
• anionic group-containing monomer examples include a monomer having at least one anionic group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphonic acid group, and among these, carboxyl.
• a monomer having a group is particularly preferable.
• Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and anhydrous. Maleic acid, maleic anhydride, maleic acid half ester and the like can be mentioned. Examples of the monomer having a sulfonic acid group include sulfoethyl methacrylate and the like. Examples of the monomer having a phosphonic acid group include phosphonoethyl methacrylate.
• the other monomer copolymerizable with the anion group-containing monomer preferably contains a hydrophobic group-containing monomer from the viewpoint of improving water resistance.
• the hydrophobic group-containing monomer is, for example, an alkyl ester having 8 or more carbon atoms of a radically polymerizable unsaturated carboxylic acid such as (meth) acrylic acid as a monomer having a long-chain alkyl group (for example).
• the monomer having an aromatic hydrocarbon group include styrene-based monomers such as benzyl (meth) acrylate, styrene, ⁇ -methylstyrene and vinyltoluene.
• the hydrophobic group-containing single amount can be used alone or in combination
• a hydrophilic group-containing monomer can be included from the viewpoint of suppressing aggregation of the alkali-soluble resin in an aqueous medium.
• hydrophilic group-containing monomer examples include methoxypolyethylene glycol, methoxypolyethylene polypropylene glycol, ethoxypolyethylene glycol, ethoxypolyethylene polypropylene glycol, propoxypolyethylene glycol, and propoxypolyethylene as monomers having a (poly) oxyalkylene chain.
• Esterates of one-terminal alkyl-blocking (poly) alkylene glycols such as polypropylene glycol and radically polymerizable unsaturated carboxylic acids such as (meth) acrylic acid, and radically polymerizable unsaturated carboxylic acids such as (meth) acrylic acid.
• hydroxyalkyl esters of (meth) acrylic acid such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate
• hydroxypropyl (meth) acrylate as a monomer having an epoxy group, for example, glycidyl.
• examples include (meth) acrylate.
• the hydrophilic group-containing monomer can be used alone or in combination of two or more.
• Examples of the copolymerizable monomer other than the hydrophobic group-containing monomer and the hydrophilic group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth). Examples thereof include alkyl esters having less than 8 carbon atoms of (meth) acrylic acid such as propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate.
• the above-mentioned hydrophobic group-containing monomer and other copolymerizable monomers other than the hydrophilic group-containing monomer can be used alone or in combination of two or more.
• the alkali-soluble resin is preferably neutralized with a basic compound from the viewpoint of being dissolved in an aqueous medium.
• the amount of the basic compound used may be any amount as long as the alkali-soluble resin is dissolved in an aqueous medium, but is usually used in the range of 40 to 100% of the amount capable of neutralizing the alkali-soluble resin.
• Examples of the basic compound include inorganic basic compounds such as sodium hydroxide and potassium hydroxide; ammonia, methylamine, ethylamine, monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, and the like.
• Examples thereof include organic basic compounds such as N, N-dibutylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, morpholin, N-methylmorpholin, and N-ethylmorpholin.
• the basic compound can be used alone or in combination of two or more.
• the aqueous medium of the present invention is a medium containing water as a main component, such as ion-exchanged water, distilled water, and industrial water, but may be, for example, an aqueous medium containing an organic solvent.
• the organic solvent may be any one that is miscible with water, and examples thereof include alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and ketone-based solvents. At least one type of the aqueous medium may be used, and two or more types may be used in combination.
• the ratio of the resin of the styrene-butadiene resin emulsion to the solid content (nonvolatile content) in the base paper anchor coating agent of the paper barrier material is 50% by mass or more and 80% by mass or less.
• the ratio of the resin of the styrene-butadiene resin emulsion to the solid content (nonvolatile content) in the base paper anchor coating agent of the paper barrier material shall be 55% by mass or more from the viewpoint of improving the barrier property. Is preferable, and it is more preferably 60% by mass or more, and from the viewpoint of improving mechanical stability, it is preferably 75% by mass or less.
• the resin of the styrene-butadiene resin emulsion also contains a resin component such as a polymer emulsifier contained in the emulsion.
• the ratio of the resin of the styrene-acrylic resin emulsion to the solid content (nonvolatile content) in the base paper anchor coating agent of the paper barrier material is 3% by mass or more and 25% by mass or less.
• the ratio of the resin of the styrene-acrylic resin emulsion to the solid content (nonvolatile content) in the base paper anchor coating agent of the paper barrier material shall be 5% by mass or more from the viewpoint of improving the barrier property. Is preferable, and it is more preferably 10% by mass or more, and more preferably 20% by mass or less.
• the resin of the styrene-acrylic resin emulsion also contains a resin component such as a polymer emulsifier contained in the emulsion.
• the proportion of the alkali-soluble resin in the solid content (nonvolatile content) in the base paper anchor coating agent of the paper barrier material is 3% by mass or more and 25% by mass or less.
• the proportion of the alkali-soluble resin in the solid content (nonvolatile content) of the base paper anchor coating agent of the paper barrier material is preferably 5% by mass or more, preferably 8% by mass, from the viewpoint of improving the blocking property. It is more preferably 20% by mass or less, and more preferably 15% by mass or less from the viewpoint of reducing the viscosity.
• the total ratio of the resin of the styrene-butadiene resin emulsion, the resin of the styrene-acrylic resin emulsion, and the alkali-soluble resin in the solid content (nonvolatile content) in the anchor coating agent for the base paper of the paper barrier material is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more, from the viewpoint of improving leveling property and mechanical stability.
• the proportion of the aqueous medium is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, in the anchor coating agent for the base paper of the paper barrier material.
• the mass ratio of the resin of the styrene-butadiene resin emulsion to the resin of the styrene-acrylic resin emulsion is a viewpoint of improving gas barrier properties. Therefore, it is preferably 3 or more, more preferably 4 or more, and further preferably 5 or more.
• additives other than the above components can be used as the anchor coating agent for the base paper of the paper barrier material, if necessary.
• various additives include extender pigments such as calcium carbonate, kaolin, barium sulfate, aluminum hydroxide, clay and talc; inorganic fine particles; adhesive resins such as acrylic resin and vinyl acetate resin; acetylene glycol-based surfactants.
• Silicone-based surfactants Silicone-based surfactants, fluorine-based surfactants and other surfactants; polyamide-based rheology control agents, urethane-based rheology control agents, polycarboxylic acid-based rheology control agents and other rheology control agents; slip agents; antifoaming agents; Examples include basic compounds such as rheological soda; waxes; cross-linking agents; and the like.
• the anchor coating agent for the base paper of the paper barrier material preferably has a pH of 6.5 to 8.5, and more preferably 7 to 8 from the viewpoint of preventing deterioration of the base paper. ..
• the base paper anchor coating agent for the paper barrier material preferably has a viscosity (initial viscosity after production) of 50 to 500 mPa ⁇ s, and preferably 80 to 230 mPa ⁇ s. Is more preferable, and 100 to 200 mPa ⁇ s is even more preferable.
• the method for preparing the anchor coating agent for the base paper of the paper barrier material of the present invention is not particularly limited, and for example, the above components are added in order or at the same time to a normal stirring device (for example, a dispenser). Etc.) can be mixed and prepared.
• the anchor coat layer of the present invention is a dry film formed from the anchor coat agent for the base paper of the paper barrier material. Further, a laminate obtained by applying an anchor coating agent for a base paper, which is a barrier material made of paper, to a base paper is called a laminate.
• the coating method of the anchor coating agent is not particularly limited, and for example, various coating methods such as a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, a curtain coater, a die coater, and a spray coater. A coating method using an apparatus can be mentioned.
• the coating amount (dry film thickness) of the anchor coat layer is usually preferably 10 g / m 2 or more, more preferably 15 g / m 2 or more, and 25 g / m 2 or less. Is preferable, and 20 g / m 2 or less is more preferable.
• Examples of the base paper include sheets containing pulp, fillers, and various auxiliaries.
• Examples of the pulp include chemical pulps such as broadleaf bleached kraft pulp (LBKP), coniferous bleached kraft pulp (NBKP), broadleaf unbleached kraft pulp (LUKP), coniferous unbleached kraft pulp (NUKP), and sulfite pulp; Mechanical pulp such as pulp and thermomechanical pulp; wood fiber such as deinked pulp and used paper pulp, non-wood fiber obtained from kenaf, bamboo, hemp, etc. can be used, and can be appropriately mixed and used. is there.
• filler for example, 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.
• various auxiliary agents include, for example, yield improver, drainage improver, paper strength enhancer, internal sizing agent, dye, fluorescent whitening agent, pH adjuster, defoaming agent, pitch control agent, slime control. Examples include agents.
• the method for producing the base paper is not particularly limited, and an acidic papermaking method, a neutral papermaking method, or an alkaline papermaking method can be used using a known long net former, on-top hybrid former, gap former machine, or the like. It can be manufactured by papermaking. Further, the base paper may have one layer or may be composed of two or more layers. Further, the surface of the base paper may be treated with various chemicals.
• the paper barrier material of the present invention has the laminate and a gas barrier layer.
• the gas barrier layer is a layer formed from a gas barrier agent.
• a gas barrier agent a conventional gas barrier layer can be applied, and usually contains a water-soluble polymer and a pigment.
• the composition set of the paper barrier material of the present invention has the anchor coating agent for the base paper of the paper barrier material and the gas barrier agent.
• water-soluble polymer examples include polyvinyl alcohols such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, and ethylene copolymerized polyvinyl alcohol; proteins such as casein, soybean protein, and synthetic protein; oxidized starch, and cationization. Starches such as starch, urea phosphate esterified starch and hydroxyethyl etherified starch; cellulose derivatives such as carboxymethyl cellulose, hydroxymethyl cellulose and hydroxyethyl cellulose; polyvinylpyrrolidone, sodium alginate and the like. Among these, polyvinyl alcohols and cellulose derivatives are preferable, and polyvinyl alcohols are more preferable, from the viewpoint of improving gas barrier properties. At least one type of the water-soluble polymer may be used, and two or more types may be used in combination.
• the pigment examples include kaolin, clay, bentonite, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, mica, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, and silicic acid.
• Inorganic pigments such as salt, colloidal silica, and satin white; organic pigments such as solid, hollow, or core-shell type. Among these, it is preferable to use an inorganic pigment from the viewpoint of improving the gas barrier property. At least one of the pigments may be used, and two or more of the pigments may be used in combination.
• the mass ratio of the pigment to the water-soluble polymer is preferably 1/100 to 1000/100.
• the gas barrier agent may contain a cross-linking agent from the viewpoint of improving the gas barrier property.
• the cross-linking agent may be any cross-linking agent that can be dispersed, emulsified or dissolved in the aqueous medium and can proceed with the cross-linking reaction in the aqueous medium.
• cross-linking agent examples include polyvalent metal salts (polyvalent metals such as copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium and titanium, and carbonate ions, sulfate ions and nitrates.
• polyvalent metal salts polyvalent metals such as copper, zinc, silver, iron, potassium, sodium, zirconium, aluminum, calcium, barium, magnesium and titanium
• carbonate ions, sulfate ions and nitrates examples include compounds in which ionic substances such as ions, phosphate ions, silicate ions, nitrogen oxides and boron oxides are bonded), amine compounds, amide compounds and aldehyde compounds.
• the amide compound examples include hydrazide compounds.
• the hydrazide compound is preferably a dihydrazide compound, and is, for example, dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide succinic acid, dihydrazide adipic acid, dihydrazide adipic acid, dihydrazide dihydrazide, dihydrazide maleate, dihydrazide humalic acid, and dihydrazide adipic acid. Examples include dihydrazide.
• the proportion of the cross-linking agent in the solid content (nonvolatile content) in the gas barrier agent is usually about 1% by mass or more and 10% by mass or less, and 3% by mass or more and 6% by mass or less. Is preferable.
• gas barrier agent various commonly used auxiliaries such as surfactants, thickeners, water retention agents, antifoaming agents, water resistant agents, dyes, and fluorescent dyes can be used.
• the gas barrier layer for example, a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, and a rod so that the amount of the gas barrier agent applied (dry film thickness) is 0.2 to 20 g / m 2. It can be obtained by applying and drying using various coating devices such as a blade coater, a lip coater, a curtain coater, a die coater, and a spray coater.
• the gas barrier layer may be composed of one layer or two or more layers.
• styrene-butadiene resin emulsions carboxy-modified styrene-butadiene emulsions ("Nipol SX1105A", manufactured by Nippon Zeon Co., Ltd., solid content 45.5% by mass, resin glass transition temperature -4 ° C) and styrene- As an acrylic resin emulsion, the following styrene-acrylic resin emulsion, and as an alkali-soluble resin, an alkali-soluble resin neutralized with a basic compound ("John Krill 70J", manufactured by BASF Japan Co., Ltd., solid content of 30 mass) %, Glass transition temperature is 102 ° C., acid value is 240 mgKOH / g), ethanol, surfactant ("Aceticol E00", manufactured by Kawaken Fine Chemicals Co., Ltd.), and r
• the above styrene-acrylic resin emulsion was produced as follows. An aqueous solution of dimethylethanolamine, an alkali-soluble resin obtained by a conventional method with 20 parts by mass of acrylic acid and 35 parts by mass of ⁇ -methylstyrene, was prepared as a polymer emulsifier. 70 parts by mass of methyl methacrylate and 30 parts by mass of styrene were added to 55 parts by mass of the resin solid content of this polymer emulsifier, and emulsion polymerization was carried out by a conventional method to obtain an acid value of 97 mgKOH / g, a glass transition temperature of 117 ° C., and a solid content. An emulsion having a concentration of 45.5% by weight was obtained.
• Anchor coating agent for base paper which is a paper barrier material, is applied onto the base paper (kraft paper, manufactured by Chuetsu Pulp & Paper Co., Ltd.) using a 1.0 mm bar coater (coating amount is about 16 g / m 2 ), and then in an oven.
• a laminate having an anchor coat layer was prepared under the conditions of a temperature of 100 ° C. and a drying time of 1 minute, and the state of the coated surface was visually evaluated according to the following three criteria. ⁇ The above was the acceptance criteria. ⁇ : No unpainted streaks can be seen. ⁇ : Some unpainted streaks can be seen. ⁇ : Many unpainted streaks are seen.
• ⁇ Preparation of gas barrier agent> As a pigment, 0.53 parts by mass of bentnite (layered filler, "Kripia F”, manufactured by Kunimine Kogyo Co., Ltd.), and as a water-soluble polymer, polyvinyl alcohol resin ("OKS-1009", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). 3.82 parts by mass, 0.95 parts by mass of crosslinkable polyvinyl alcohol resin ("DF-10", Japan Vam & Poval Co., Ltd.), 0.24 parts by mass of adipic acid dihydrazide as a cross-linking agent, and 74 parts of water for the rest A gas barrier agent having a mass of .34 parts was prepared.
• Japanese Patent Application Laid-Open No. 2019-65132 can be mentioned.
• the anchor coating agent for the base paper of the paper barrier materials of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above was applied to the base paper ( kraft paper having a paper density of 75 g / m 2 and manufactured by Chuetsu Pulp & Paper Co., Ltd.). ) was developed with a No. 40 bar coater and dried in a dryer wind at 110 ° C. to form an anchor coat layer (coating amount of about 16 g / m 2 ) on the base paper. Subsequently, the above gas barrier agent was colored on the anchor coat layer surface with a No. 12 bar coater and dried in a dryer wind at 110 ° C. to form a gas barrier layer (coating amount of about 5 g / m 2 ). A test piece of a paper barrier material was prepared.
• Oxygen permeability (OTR value) (unit: (cm 3 / m 2 ⁇ day ⁇ kPa)) was measured. The measurement was carried out at 25 ° C. in an atmosphere of 0 to 10% RH. The acceptance criteria were 200 (cm 3 / m 2 , day, kPa) or less.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Paper (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=75166063

Family Applications (1)

Country Status (3)

Cited By (1)

Citations (6)

• 2019
  • 2019-09-27 JP JP2019177095A patent/JP2021054897A/ja active Pending
• 2020
  • 2020-08-21 WO PCT/JP2020/031621 patent/WO2021059815A1/ja active Application Filing
  • 2020-09-07 TW TW109130574A patent/TW202116940A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events