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
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
• • 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
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/16—Sizing or water-repelling agents
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

Definitions

• the present invention relates to water resistant paper and a wrapping paper or container using the water resistant paper.
• Paper packaging materials such as paper bags, paper boxes, and paper cups have been used conventionally according to various uses and purposes.
• plastic materials as one of the materials with functions such as “reusable” and “biodegradable”.
• paper made from “wood”, which is a possible resource.
• paper cups used as containers for beverages, ice cream, yogurt, etc.
• paper cups are paper
• water resistance is imparted by using a polyethylene film as a part of the raw material.
• Such paper cups are obtained by bonding a polyethylene film, a polypropylene film, or the like obtained by extruding a polyethylene resin, a polypropylene resin, or the like melted by heat into a film shape to a paper base material.
• the polyethylene film is molded into a paper cup, it acts as an adhesive by heat melting under indirect heating such as a burner or hot air, and since the polyethylene film exists inside the paper cup, the paper base material does not come into direct contact with the contents and is waterproof. Properties, moisture resistance and strength are imparted.
• the bonded polyethylene film does not dissolve in the alkaline solution used in the paper recycling process during paper recycling, so it must be physically removed, leading to a decrease in recycling efficiency.
• marine pollution caused by the outflow of plastic waste into the ocean has become a global problem.
• the target of the Sustainable Development Goals (SDGs) is "By 2025, prevent and significantly reduce all types of marine pollution, including marine debris and eutrophication, especially pollution from land activities.” It has become an important global theme, as it has been raised and it has been agreed to strengthen efforts at the summit (summit of major countries). Therefore, there is a demand for a polyethylene film substitute that can be applied to these applications and does not reduce the paper recycling efficiency.
• a water-based heat sealant is known as an adhesive that acts as an adhesive when molding bags, boxes, paper cups, and the like.
• an ethylene-based resin aqueous dispersion in which an olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer neutralized with ammonia or an amine and an olefin-based thermoplastic resin other than the above are mixed and dispersed in a specific ratio. It is disclosed that the liquid can be applied as a heat sealant.
• an aqueous dispersion containing a polyolefin resin composed of an unsaturated carboxylic acid unit, an ethylene-based hydrocarbon, and an acrylic acid ester or a methacrylic acid ester, a natural wax, and an aqueous medium in a specific ratio Is disclosed that it can be applied as a heat sealant.
• the problem to be solved by the present invention is that it has a water-resistant coat layer capable of imparting excellent water resistance and moisture resistance to paper only by coating, and is an alternative to paper laminated with a plastic film. It is an object of the present invention to provide a water resistant paper capable of improving the recyclability of the paper, and a wrapping paper or a container using the water resistant paper. Further, since the coated paper of the present invention has a heat-sealing coat layer, a water-resistant paper having a heat-sealing function in addition to water resistance and moisture resistance, and a wrapping paper or a container using the water-resistant paper are provided. To do.
• the present invention uses a paper substrate and A water resistant coat layer provided on at least a part of the paper substrate, and Provided is a water resistant paper having a heat-sealable coat layer provided in a portion different from the portion having the water resistant coat layer.
• the present invention provides a package or a container using the above-mentioned water resistant paper.
• the water resistant paper of the present invention has a water resistant coat layer capable of imparting excellent water resistance and moisture resistance to the paper only by coating, it is excellent in water resistance and moisture resistance and improves recyclability. be able to. Further, since the coated paper of the present invention has a heat-sealing coating layer, it is possible to realize a water-resistant paper having a heat-sealing function in addition to water resistance and moisture resistance.
• the water-resistant layer and the heat-sealing coat layer provided on the water-resistant paper of the present invention can be formed of a material having high safety to the environment and the human body.
• the coated paper of the present invention is useful as a substitute for paper laminated with a plastic film, and the coated paper can be used for packaging and containers.
• the coated paper of the present invention has a water-resistant coat layer provided on at least a part of the paper base material and a heat-sealable coat layer provided on a portion different from the portion having the water-resistant coat layer.
• (meth) acrylate represents a general term for acrylate and methacrylate
• (meth) acrylic acid represents a general term for acrylic acid and methacrylic acid.
• Heat-sealing coat layer In the water-resistant paper, the heat-sealable coat layer is provided on an appropriate portion on the paper base material depending on the shape and application of the final packaging material or container. For example, in the paper base material, the water-resistant coat layer is provided. It is more preferable to provide a heat-sealing coat layer on the surface opposite to the surface to be coated.
• the water-resistant paper of the present invention has a heat-sealing function and has improved water resistance by having a heat-sealing coat layer. Further, by laminating the heat-sealed portion, various packaging materials such as bags and boxes can be manufactured according to the application, and the workability is improved.
• a known heat-sealing coating agent can be used for the heat-sealing coating layer, but in order to improve the water resistance, an aqueous solvent, an olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer and a wax ( It is preferable to use an aqueous heat sealant (HS) containing W1).
• the water-based heat sealant (HS) can be used as a heat sealant when manufacturing a paper container or the like, and the coated portion other than the seal (adhesive) portion is a coating agent that imparts waterproofness to the paper. Also works as.
• the aqueous heat sealant (HS) contains at least an aqueous solvent, an olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer and a wax (W1).
• aqueous solvent As the aqueous solvent used for the aqueous heat sealant HS, water, a water-soluble organic solvent soluble in water, or the like can be used. As the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled water, or ultrapure water can be used.
• water using water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide prevents the growth of mold or bacteria when the aqueous pigment dispersion or the ink using the aqueous pigment dispersion is stored for a long period of time. It is suitable because it can be used.
• water-soluble organic solvent examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; diols such as butanediol, pentandiol and hexanediol; propylene laurate.
• glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol
• diols such as butanediol, pentandiol and hexanediol
• propylene laurate examples of the water-soluble organic solvent
• Glycol esters such as glycols; diethylene glycol ethers such as diethylene glycol monoethyl, diethylene glycol monobutyl, diethylene glycol monohexyl, carbitol; glycol ethers such as cellosolves containing propylene glycol ethers, dipropylene glycol ethers, and triethylene glycol ethers; methanol , Ethanol, isopropyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, butyl alcohol, pentyl alcohol and other alcohols; sulfolane, ester, ketone, ⁇ -butyrolactone and other lactones, N- (2) -Hydroxyethyl) Lactates such as pyrrolidone, various other solvents known as aqueous organic solvents such as glycerin and its polyalkylene oxide adducts and the like can be mentioned.
• aqueous organic solvents can be used alone or in combination of two or more. Of these, water is the most preferable.
• olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer examples include olefins, ⁇ , ⁇ -unsaturated carboxylic acids, metal salts of ⁇ , ⁇ -unsaturated carboxylic acids, and ⁇ .
• it is a metal salt of ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ -unsaturated carboxylic acid or a copolymer of ⁇ , ⁇ -unsaturated carboxylic acid ester and olefin, and is olefin- ⁇ , ⁇ .
• Unsaturated carboxylic acid copolymer ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid-maleic anhydride copolymer, ethylene-acrylic acid
• examples thereof include an ester-maleic anhydride copolymer, an ethylene-methacrylic acid-maleic anhydride copolymer, an ethylene-methacrylic acid ester-maleic anhydride copolymer, and a metal salt thereof.
• These copolymers may be used alone or as a mixture of two or more kinds.
• olefin- ⁇ and ⁇ unsaturated carboxylic acid copolymers are preferable.
• examples of the olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer include a random copolymer or a block copolymer of ethylene- and ⁇ , ⁇ -unsaturated carboxylic acid.
• Examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, butadiene, dicyclopentadiene and 5-ethylidene-2-. Norbornene and the like can be mentioned. Of these, ethylene is preferable.
• Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and the like. Among these, acrylic acid and methacrylic acid are preferably used. These ⁇ , ⁇ -unsaturated carboxylic acids may be used alone or in combination of two or more.
• ⁇ , ⁇ -unsaturated carboxylic acid ester known acrylic acid or methacrylic acid alkyl esters, hydroxyalkyl esters, alkoxyalkyl esters and the like can be used without particular limitation.
• the olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer it can be obtained by a known method, for example, radical copolymerization under high temperature and high pressure.
• the content of the ⁇ , ⁇ -unsaturated carboxylic acid in the olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer is preferably 8 to 24% by weight, preferably 18 to 23% by weight.
• content of ⁇ , ⁇ -unsaturated carboxylic acid is less than 8% by weight, dispersibility in an aqueous dispersion medium is poor due to the non-polar property derived from ethylene-unit, and excellent olefin- ⁇ , ⁇ unsaturated It may be difficult to obtain an aqueous dispersion of a carboxylic acid copolymer resin.
• the olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer used in the aqueous heat sealant HS is used as an aqueous dispersion dispersed in an aqueous solvent.
• the method of dispersing in an aqueous solvent is not particularly limited, and a known method may be used.
• a method of emulsifying with a surfactant and dispersing in an aqueous solvent a method of neutralizing an olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer with a basic compound and then dispersing in an aqueous solvent can be mentioned.
• surfactant used for emulsification various known anionic, cationic, nonionic surfactants, or various water-soluble polymers can be used in combination as appropriate.
• the basic compound used for neutralization examples include organic amines such as ammonia, methylamine, ethylamine, diethylamine, dimethylethanolamine, diethanolamine and triethanolamine, sodium hydroxide, potassium hydroxide and lithium hydroxide. Alkali metal hydroxides such as. These basic compounds may be used alone or in combination of two or more.
• the degree of neutralization with the basic compound may be any degree as long as the degree of neutralization in which the olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer is stably present in the aqueous solvent. For example, it may be 30 to 100 mol% of the carboxyl group of the copolymer, and more preferably 40 to 90 mol%.
• a known method for example, as a dispersion device using a medium, a paint shaker, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, an agitator mill and the like can be used. It can be used and can be dispersed by an ultrasonic homogenizer, a high-pressure homogenizer, a nanomizer, a resolver, a disper, a high-speed impeller disperser, or the like without using a medium.
• the solid content of the aqueous dispersion of the olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer used in the present invention is not particularly limited, and has a desired viscosity when applied as a heat sealant and after application of the heat sealant. It may be appropriately determined depending on the drying conditions, the film thickness, and the like. Generally, it is often applied in the range of solid content concentration of 10 to 40% by mass. (Wax (W1) used for water-based heat sealant (HS)) Blocking resistance can be maintained by adding wax (W1) to the aqueous heat sealant (HS).
• wax (W1) examples include fatty acid amide wax, carbana wax, polyolefin wax, paraffin wax, Fisher Tropsch wax, honey wax, microcrystallin wax, polyethylene oxide-wax, amido wax and other waxes, coconut oil fatty acid and soybean oil. Fatty acids and the like can be mentioned. These may be used alone or in combination.
• fatty acid amide wax carbana wax, and Fisher Tropsch wax
• fatty acid amide wax and carbana wax it is preferable to use fatty acid amide wax, carbana wax, and Fisher Tropsch wax.
• fatty acid amide wax examples include pelargonic acid amide, capric acid amide, undecyl acid amide, lauric acid amide, tridecyl acid amide, myristic acid amide, pentadecyl acid amide, palmitic acid amide, heptadecyl acid amide, and stearic acid amide.
• carnauba wax include MICROKLEAR 418 (manufactured by Micro Powders, Inc.), purified carnauba wax No. 1 powder (Nippon Wax Co., Ltd.) and the like.
• the blending amount of the wax (W1) is preferably 1.5 to 20% by mass with respect to the total amount of the wax (W1) of 100% by mass of the solid content of the aqueous heat sealant (HS). If the total amount of the wax (W1) is 3% by mass or more with respect to the total solid content of the aqueous heat sealant (HS), the blocking resistance tends to be maintained, and the total amount of the wax (W1) is the aqueous heat sealant. If the solid content of (HS) is 15% by mass or less with respect to the total amount of 100%, the heat sealability tends to be maintained.
• the wax (W1) may be directly added to the aqueous dispersion of the olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer and mixed and dispersed, or the olefin- ⁇ , ⁇ -unsaturated carboxylic acid copolymer may be mixed and dispersed. It may be added at the same time as the dispersion in the aqueous solvent and mixed and dispersed.
• the dispersion method the method used in the above-mentioned method for dispersing the olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer in an aqueous solvent can be appropriately used.
• a plurality of types of waxes (W1) may be added at the same time, or may be added in a plurality of steps. For example, after adding the first wax (W1) when dispersing the olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer in the aqueous solvent, the second wax (W1) is added to the obtained first wax.
• An aqueous heat sealant (HS) can be obtained by a method of further adding (W1) to the aqueous dispersion of the olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer.
• the aqueous heat sealant (HS) includes silica, alumina, a defoaming agent, a viscosity modifier, a leveling agent, a tackifier, a preservative, and an antibacterial agent, as long as the object of the present invention is not impaired. Additives such as rust preventives, antioxidants, and silicone oils may be blended. Further, in the aqueous heat sealant (HS), a polymer-based defoaming agent, a silicon-based defoaming agent, and a fluorine-based defoaming agent are preferably used in order to prevent foaming when coating with various coaters. ..
• defoaming agents both emulsified dispersion type and solubilized type can be used. Of these, a polymer-based defoaming agent is preferable.
• the amount of the defoaming agent added is preferably 0.005% by weight to 0.1% by weight of the total amount of the aqueous heat sealant.
• the water-based heat sealant (HS) can be used as a heat sealant when manufacturing paper packaging materials such as bags and boxes and paper containers, and the coated part other than the seal (adhesive) part is on paper. It functions as a coating agent that imparts waterproofness.
• HS heat seal coating agent
• the coat layer of the heat seal is provided, for example, by applying a known heat seal coating agent or heat seal agent (HS) to a paper substrate. A known method can be used as the coating method for coating.
• a drying step may be provided in an oven or the like after coating.
• HS aqueous heat sealant
• the film thickness of the solid content after coating may be a desired film thickness, and when used for a paper container for food, for example, the film thickness is in the range of 2 to 12 g / m 2 . If there is, sufficient water resistance and heat sealability can be obtained. Above all, it is more preferably in the range of 5 to 10 g / m 2 .
• the water-based heat sealant has a function as an adhesive that adheres two parts coated with the water-based heat sealant on a paper substrate in a superposed state.
• the aqueous heat sealant of the present invention is applied to at least one portion (which may be both portions) of the two portions of the paper substrate, and then softened by heating.
• the water-based heat sealant can be easily softened by heating with a burner or hot air to bond the papers or paper to other materials, and then cooled to solidify the bonded part and to the papers or paper to other materials. Can be firmly sealed.
• a heat source such as a burner, hot air, electric heat, infrared rays, electron beams, or other conventionally known means can be used. Specifically, depending on the method of heating with a burner or hot air, or the form of molding. A heat welding sealing method, an ultrasonic sealing method, or a high frequency sealing method is preferable.
• the heating temperature at this time is preferably 200 to 500 ° C., and the heating time is preferably 0.1 to 3 seconds.
• the aqueous heat sealant can be easily heated and softened even by non-contact heating, and even if it is separated from the heat source, other than the method of directly contacting the heat seal bar or the like to melt it.
• the heat seal function lasts for a certain period of time.
• the base material is paper
• the paper may be burnt if it is brought into direct contact with a heat source. It is particularly useful as a heat sealant for industrial production of paper containers that require line speed.
• a heat sealant can be used as a heat sealant by applying a water-based heat sealant (HS), heating and softening the coated portion, and then pressure-bonding the coated portion and another portion in a superposed state. ..
• the crimping method is not particularly limited, and a hot plate method, an ultrasonic sealing method, or a high frequency sealing method can be used.
• the aqueous heat-sealing agent (HS) may be used as a coating agent for paper without heat-sealing.
• the film may be coated to a desired film thickness by the above-mentioned coating method, and then dried by a drying method such as heat drying or room temperature drying.
• the water resistant paper of the present invention has a water resistant coat layer on a paper base material.
• the water-resistant coat layer is provided on an appropriate portion on the paper substrate depending on the shape and application of the final packaging material or container, and as described above, the heat-sealable coat layer is provided on the paper substrate. It is preferable that the coating layer is provided in a portion different from the provided portion, and it is more preferable to have the water resistant coating layer on the surface opposite to the surface on which the heat-sealing coating layer is provided.
• the water resistant coat layer is preferably formed by a water resistant overcoating composition (OCM) for paper containing an aqueous solvent, a styrene acrylic copolymer (A) and a wax (W2).
• OCM water resistant overcoat composition
• the water resistant overcoating composition (OCM) contains at least an aqueous solvent, a styrene acrylic copolymer (A) and a wax (W2).
• Aqueous solvent As the aqueous solvent, the same aqueous solvent as that used for the above-mentioned aqueous heat sealant (HS) can be used.
• the styrene acrylic copolymer (A) preferably has a core-shell structure formed by a copolymer of styrenes and (meth) acrylates, and a copolymer of styrenes and (meth) acrylates and styrenes. It is more preferable that the copolymer of (meth) acrylate and (meth) acrylic acid forms a core-shell structure.
• the styrenes used as constituents of the styrene-acrylic copolymer (A) are styrene, ⁇ -methylstyrene (any or a mixture of o-methylstyrene, m-methylstyrene, p-methylstyrene), styrene dimer, and styrene trimmer.
• Styrene derivative p-dimethylsilylsticistyrene, p-tert-butyldimethylsiloxystyrene, p-tert-butylstyrene
• Styrene derivative p-dimethylsilylsticistyrene, p-tert-butyldimethylsiloxystyrene, p-tert-butylstyrene
• Styrene derivative p-dimethylsilylsticistyrene, p-tert-butyldimethyls
• the styrenes may be one type or two or more types. Among them, it is preferable to use styrene, and when two or more kinds of styrenes are used, it is preferable to use styrene as a main component, for example, the mass ratio of styrene is the largest among all styrenes.
• the (meth) acrylate used as a constituent component of the styrene acrylic copolymer (A) is not particularly limited, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, and the like.
• a homopolymer having an acrylate is preferable because it exhibits a lower glass transition temperature
• an acrylate having an alkyl group having 1 to 20 carbon atoms is preferable as a main component
• an alkyl group having 1 to 12 carbon atoms is preferable. It is preferable to use the acrylate as the main component.
• the acrylate having an alkyl group having 1 to 12 carbon atoms include methyl acrylate, ethyl acrylate, iso-propyl acrylate, allyl acrylate, n-butyl acrylate, and iso-butyl acrylate.
• the (meth) acrylate used as a constituent component of the styrene-acrylic copolymer (A) of the present invention may be one kind or two or more kinds.
• styrene-acrylic copolymer (A) As a constituent component of the styrene-acrylic copolymer (A), other known polymerizable compounds other than styrenes, (meth) acrylate, and (meth) acrylic acid may be contained.
• the core-shell structure of the styrene-acrylic copolymer (A) includes a region in which a large amount of "polymer of styrenes and (meth) acrylate” exists, and "styrenes, (meth) acrylate and (meth) acrylic acid.
• a core-shell structure is formed in the core-shell structure.
• a copolymer of styrenes, (meth) acrylate and (meth) acrylic acid exists in a region where "a copolymer of styrenes and (meth) acrylate" is abundant.
• copolymers may be polymerized with each other.
• a copolymer of styrenes, (meth) acrylate and (meth) acrylic acid having an acidic group is a shell component, but “styrenes”. And a part of "copolymer of (meth) acrylate and (meth) acrylic acid” may be present in the core portion.
• the wax (W2) described later may be contained in the styrene-acrylic copolymer (A). By containing the wax (W2) in the styrene-acrylic copolymer (A), the water resistance can be further improved.
• the wax (W2) may be present in the core portion or the shell portion. It may be present on the surface of the styrene-acrylic copolymer (A).
• the ratio of "polymer of styrenes and (meth) acrylate” and “copolymer of styrenes and (meth) acrylate and (meth) acrylic acid” is The mass ratio is preferably in the range of 20:80 to 95: 5, more preferably in the range of 30:70 to 92: 8, and most preferably in the range of 40:60 to 90:10.
• the ratio of styrenes and (meth) acrylate is preferably in the range of 20:80 to 80:20 by mass ratio, and in the range of 30:70 to 70:30. More preferably, the range of 40:60 to 60:40 is most preferable.
• the proportion of styrenes is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 30 to 80% by mass. Most preferably, it is 70% by mass.
• the ratio of (meth) acrylate is preferably 10 to 80% by mass, more preferably 15 to 70% by mass. It is preferably 20 to 60% by mass, most preferably 20 to 60% by mass.
• the ratio of (meth) acrylic acid is preferably 10 to 70% by mass, preferably 15 to 60% by mass. It is more preferably 20 to 50% by mass, and most preferably 20 to 50% by mass.
• the styrene-acrylic copolymer (A) contains other known polymerizable compounds other than styrenes, (meth) acrylate, and (meth) acrylic acid, other polymerization in the styrene-acrylic copolymer (A).
• the proportion of the sex compound is preferably 10% by mass or less, and preferably 5% by mass or less.
• the glass transition temperature (hereinafter sometimes referred to as Tg) of the styrene-acrylic copolymer (A) is in the range of ⁇ 30 ° C. to 10 ° C., preferably in the range of ⁇ 25 ° C. to 5 ° C., and more preferably. It is in the range of -20 ° C to 0 ° C.
• the glass transition temperature is obtained by measurement with a differential scanning calorimeter.
• the styrene-acrylic copolymer (A) can be produced by a known method. For example, a step (i) of supplying a monomer mixture forming a shell polymer and polymerizing the monomer mixture to form a shell polymer in the presence of an initiator, and a step (i) of forming a core polymer. It is obtained by the step (ii) of feeding the shell polymer of the above and polymerizing this monomer mixture in the presence of an initiator to form a shell on the core polymer. Further, a step (1) of supplying a monomer mixture forming a core polymer and polymerizing the monomer mixture to form a core polymer in the presence of an initiator, and a step (1) of forming a shell polymer. It is obtained by the step (2) of feeding the core polymer of the above and polymerizing this monomer mixture in the presence of an initiator to form a shell on the core polymer.
• the initiator is not particularly limited, and a peroxide, a persulfate, an azo compound, a redox type, or a mixture thereof used in an emulsion polymerization method or the like may be used.
• Peroxides include, for example, hydrogen peroxide, ammonium peroxide, sodium peroxide, or potassium peroxide, t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and benzene peroxide.
• the persulfate include ammonium persulfate, sodium persulfate, and potassium persulfate.
• azo compound examples include 2,2-azobisisobutyronitrile and 4,4'-(4-cyanovaleric acid).
• the redox system is composed of an oxidizing agent and a reducing agent, and the oxidizing agent is, for example, one of the above-mentioned peroxides, persulfates, or azo compounds, or sodium chloride or potassium chloride, or sodium bromide. Examples include potassium bromide.
• reducing agent examples include ascorbic acid, glucose, ammonium, sodium hydrogensulfate or potassium hydrogensulfate, sodium hydrogensulfite or potassium hydrogensulfite, sodium thiosulfate or potassium thiosulfate, or sodium sulfide or potassium sulfide, or iron (II). ) Ammonium sulfate can be mentioned.
• persulfate more preferably ammonium persulfate, is preferable.
• the polymerization of the monomer mixture can be carried out, for example, in the presence of additives such as a surfactant, a chain transfer agent and a chelating agent, for example, in the presence of a surfactant and a chain transfer agent.
• additives such as a surfactant, a chain transfer agent and a chelating agent, for example, in the presence of a surfactant and a chain transfer agent.
• additives may be added in advance to the aqueous medium used in step (i) and / or step (ii), step (1) and / or step (2), or step (i) and / Or may be mixed with the monomer mixture supplied in step (ii), step (1) and / or step (2).
• the wax (W2) may be added in advance to the aqueous medium used in step (i) and / or step (ii), step (1) and / or step (2), or step (i) and / Or a state in which the wax (W2) is incorporated into the styrene acrylic copolymer (A) by mixing with the monomer mixture supplied in the step (ii), the step (1) and / or the step (2).
• Core shell structure can be formed.
• the surfactant is not particularly limited, and examples thereof include disodium dodecyldiphenyl oxide and disulfonate.
• the chain transfer agent is also not particularly limited, and examples thereof include ⁇ -methylstyrene dimer, thioglycolic acid, sodium hydrogenphosphite, 2-mercaptoethanol, N-dodecyl mercaptan, and t-dodecyl mercaptan.
• the chelating agent is not particularly limited, and examples thereof include ethylenediaminetetraacetic acid.
• the water resistant overcoat composition (OCM) can further improve the water resistance by containing the wax (W2).
• the wax (W2) is preferably at least one wax selected from paraffin wax, microcrystalline wax, polyethylene oxide-wax, and amido wax, and paraffin wax or microcrystalline wax is more preferable. These may be used alone or in combination.
• the melting point of the wax (W2) is preferably in the range of 30 ° C to 130 ° C, more preferably in the range of 50 ° C to 100 ° C.
• the blending amount of the wax (W2) is preferably 0.5 to 20% by mass, preferably 1 to 15% by mass, based on 100% by mass of the styrene-acrylic copolymer (A).
• the wax (W2) may be dispersed in the water-resistant coat layer and may be present. However, as described above, the wax (W2) is present in the core portion and / or the shell portion of the styrene acrylic copolymer (A), whereby styrene is present. It is preferable that it exists integrally with the acrylic copolymer (A). In the water-resistant coat layer, wax (W2) is present in a form contained in the styrene-acrylic copolymer (A) and is not contained in the styrene-acrylic copolymer (A). May be.
• the wax (W2) may be directly added to the emulsion containing the styrene-acrylic copolymer (A) and mixed and dispersed, or the dispersion of the wax (W2) may be prepared and then mixed with the emulsion.
• a dispersion method a known method, for example, a paint shaker, a ball mill, an attritor, a basket mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a spike mill, an agitator mill or the like is used as a dispersion device using a medium. It can be dispersed by an ultrasonic homogenizer, a high-pressure homogenizer, a nanomizer, a resolver, a disper, a high-speed impeller disperser, or the like without using a medium.
• the kneading method can be carried out by a known method.
• the plurality of types of waxes may be added at the same time, or may be added separately in a plurality of steps.
• the polymerization of the monomer mixture constituting the styrene-acrylic copolymer (A) is carried out in the presence of the wax (W2) as described above. Can be done with.
• the water-resistant overcoating composition (OCM) further comprises silica, alumina, wax, defoaming agent, leveling agent, tackifier, preservative, and antibacterial agent as long as the object of the present invention is not impaired. Additives such as agents and rust preventives may be blended.
• a resin other than the styrene-acrylic copolymer (A) may be blended.
• a leveling agent and / or a wax is further blended.
• the wax further blended is a wax (W3) further added separately from the above wax (W2).
• wax (W3) examples include waxes such as fatty acid amide wax, carnauba wax, polyolefin wax, paraffin wax, Fisher Tropsch wax, honey wax, microcrystallin wax, polyethylene oxide-wax, and amido wax, which are used alone. It may be used in or used in combination. Among them, fatty acid amide wax, carnauba wax, Fisher Tropsch wax, polyolefin wax, and paraffin wax are preferably used, and carnauba wax, polyolefin wax, and paraffin wax are particularly preferable.
• fatty acid amide wax examples include pelargonic acid amide, capric acid amide, undecyl acid amide, lauric acid amide, tridecyl acid amide, myristic acid amide, pentadecyl acid amide, palmitic acid amide, heptadecyl acid amide, and stearic acid amide.
• carnauba wax include MICROKLEAR 418 (manufactured by Micro Powders, Inc.), purified carnauba wax No. 1 powder (Nippon Wax Co., Ltd.) and the like.
• olefin wax examples include polyethylene wax and polypropylene wax, and examples thereof include MPP-635VF (MicroPowerers, Inc.), MP-620VFXF (MicroPowerers, Inc), and Chemipearl W-400 (Mitsui Chemicals, Inc.). Made) and the like.
• the total amount of the wax (W3) is 0.3 to 10% by mass with respect to the total amount of 100% by mass of the solid content in the composition of the present invention.
• the blocking resistance tends to be maintained, and more preferably 0.5% by mass or more. be.
• the total amount of wax (W3) is 10% by mass or less with respect to the total amount of 100% solid content of the aqueous heat sealant, the sliding angle does not become too large, so that the workability tends to be kept good. It is preferably 5% by mass or less, and more preferably 3% by mass or less.
• the melting point of the wax (W3) is preferably in the range of 80 ° C to 130 ° C from the viewpoint of oil resistance and heat resistance.
• the wax (W3) may be directly added to the emulsion of the resin containing the styrene-acrylic copolymer (A) and mixed and dispersed, or the wax dispersion may be prepared and then mixed with the emulsion.
• the wax (W3) is not present in the styrene acrylic copolymer (A) but is dispersed so as to be present near the surface of the water resistant coat layer. Is preferable.
• the type of leveling agent is not particularly limited, but it is preferable to use an acetylene-based surfactant.
• an acetylene-based surfactant 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9 -Tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol Examples thereof include all, 3-hexyne-2,5-diol, 2-butyne-1,4-diol and the like.
• alkylene oxide-non-modified acetylene glycol-based surfactants such as Surfinol 61, 82, 104 (all manufactured by Air Products and Chemicals), and [0037] Surfinol 420, 440, 465, 485.
• TG 2502, Dynol 604, 607 (all manufactured by Air Products), Surfinol SE, MD-20, Orfin E1004, E1010, PD-004, EXP4300, PD-501, PD-502, SPC (all)
• alkylene oxide-modified acetylene glycol-based surfactants such as acetylenol EH, E40, E60, E81, E100, and E200 (all manufactured by Kawaken Fine Chemicals Co., Ltd.), Nisshin Kagaku Kogyo Co., Ltd.
• the amount of the leveling agent added is preferably 0.01% by weight to 0.1% by weight of the total amount of the overcoating composition for paper.
• the blocking property can be improved while maintaining the leveling property.
• the water-resistant coat layer of the present invention is a polymer-based defoaming agent or a silicon-based defoaming agent in order to prevent the composition from foaming when the composition is coated on paper using the water-resistant overcoating composition (OCM).
• OCM water-resistant overcoating composition
• a fluorine-based defoaming agent is blended.
• these defoaming agents both emulsified dispersion type and solubilized type can be used.
• a polymer-based defoaming agent is preferable.
• the amount of the defoaming agent added is preferably 0.005% by weight to 0.1% by weight based on the total amount of the overcoating composition for paper.
• the water resistant coat layer of the present invention is preferably formed by using a water resistant overcoating composition containing at least a styrene acrylic copolymer (A), a wax (W2) and an aqueous solvent.
• the water resistant coat layer is provided on the paper substrate, for example, by coating the paper substrate.
• a known method can be used as a method for applying the water resistant overcoating composition (OCM) on a paper substrate.
• OCM water resistant overcoating composition
• comma coater, roll coater, reverse roll coater, direct gravure coater, reverse gravure coater, offset gravure coater, roll kiss coater, reverse kiss coater, kiss gravure coater, reverse kiss gravure coater, air doctor coater, knife coater, bar coater Use one or a combination of two or more coating methods such as wire bar coater, die coater, lip coater, dip coater, blade coater, brush coater, curtain coater, die slot coater, offset printing machine, screen printing machine, etc. Can be done.
• the water resistant coat layer may be provided on the paper substrate by impregnating the water resistant overcoating composition of the present invention with the paper substrate. Further, a drying step may be provided in an oven or the like after coating.
• the film thickness of the water resistant overcoating composition (OCM) at the time of coating depends on the application, but when used for a food paper container, for example, if it is in the range of 1 to 10 g / m 2 , the effect of the present invention can be obtained. You can get enough. Above all, the range of 2 to 6 g / m 2 is more preferable.
• the water resistant coat layer formed as described above has excellent water resistance and can maintain water resistance.
• the water-resistant coat layer of the present invention maintains a contact angle of 70 degrees or more 30 minutes after dropping water, preferably 75 degrees or more, and more preferably 80 degrees or more. Further, the water resistant coat layer of the present invention maintains a contact angle of 50 degrees or more 40 minutes after dropping water, preferably 60 degrees or more, preferably 70 degrees or more, and more preferably 75 degrees or more. Is preferable.
• the contact angle can be easily measured using a known contact angle measuring device (for example, an automatic contact angle measuring device manufactured by Kyowa Surface Chemistry Co., Ltd.).
• the water-resistant coat layer formed as described above has excellent moisture-proof properties and can maintain the moisture-proof properties.
• the water-resistant coat layer of the present invention preferably has a water vapor permeation amount of 500 g / m2 ⁇ day or less, preferably 300 g / m2 ⁇ day or less when held for 7 days under the conditions of a temperature of 25 ° C. and a relative humidity of 50% RH. It is preferably 250 g / m2 ⁇ day or less, and preferably 200 g / m2 ⁇ day or less. Further, the water vapor permeation amount when maintained at a temperature of 40 ° C.
• for 7 days is preferably 1000 g / m2 ⁇ day or less, preferably 600 g / m2 ⁇ day or less, and 500 g / m2 ⁇ day or less. It is preferably 400 g / m2 ⁇ day or less.
• the water resistant coat layer of the present invention has excellent abrasion resistance.
• the water-resistant paper of the present invention has at least the above-mentioned water-resistant coat layer and heat-sealable coat layer on a paper base material, and can be recycled as it is after use.
• the paper base material is manufactured by a known paper machine using natural fibers for paper making such as wood pulp, but the paper making conditions are not particularly specified.
• natural fibers for papermaking include wood pulp such as coniferous tree pulp and broadleaf tree pulp, non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps.
• wood pulp such as coniferous tree pulp and broadleaf tree pulp
• non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp
• pulp obtained by chemically modifying these pulps As the type of pulp, chemical pulp, gland pulp, chemi-grand pulp, thermomechanical pulp or the like obtained by a sulfate cooking method, an acidic / neutral / alkaline sulfite cooking method, a soda salt cooking method or the like can be used.
• various commercially available high-quality papers, coated papers, backing papers, impregnated papers, cardboards, paperboards and the like can also be used.
• the type, thickness, and the like of the paper can be sequentially selected according to the purpose.
• the paper substrate For example, for burger wrap, it is about 20 g / m 2 for paper density, for paper cups it is 200 to 300 g / m 2 , and for paper plates, paper spoons, paper madler, etc., it is 50 to 500 for paper density.
• Food base paper such as gram / m 2 cup base paper is preferred. From the viewpoint of recycling efficiency and cost reduction, it is preferable that these papers are not laminated with polyethylene-film, aluminum or the like.
• the paper substrate may have a printing layer.
• the water resistant paper of the present invention is excellent in water resistance and moisture resistance, it can be used as a water resistant paper and / or a moisture resistant paper. Further, the water resistant paper of the present invention can be used as various packages or containers. Further, by heat-sealing using the heat-sealing coat layer portion, it can be processed into a box, a bag, or a container.
• Examples of the package include a packaging bag, a paper bag, a paper box, a corrugated cardboard, a wrapping paper, an envelope, a cup sleeve, a lid, and the like.
• Examples of the container include a paper container, a paper plate, a tray, a cup holder, and the like.
• the water resistant paper of the present invention can be used for foods, miscellaneous goods, daily necessities, etc. that require water resistance and moisture resistance, and is also used for packaging foods, miscellaneous goods, daily necessities containing liquid or moisture. be able to.
• Bags or boxes for sanitary goods such as detergents and sanitary goods.
• a water resistant coat layer may be provided on the inner side surface of the packaging material or the container, may be provided on the outer surface surface, or may be provided on both sides.
• water resistant paper of the present invention for labels of bottles and cans, paper tapes such as curing paper tapes and paper gum tapes, books such as books and magazines, posters, calendars and the like.
• the water resistant coat layer functions as an overcoat layer of the paper substrate having the print layer.
• a water resistant paper having both a water resistant coat layer and a heat sealable coat layer to seal the heat sealable coat layer portion, it is possible to form a bag, a box, and a wrapping paper.
• a pillow-shaped bag for wrapping confectionery an envelope-shaped bag, a department store bag, a cosmetic box, a take-out bag or box for pizza and donuts, and a heat-sealed part for wrapping hamburgers and hot docks.
• examples thereof include an open wrapping paper, a tube-shaped container, and the like.
• the water-soluble resin obtained above was charged with 2 parts by mass of paraffin wax (paraffin wax 155, manufactured by Nippon Seiro Co., Ltd.) as waxes (W2) and stirred to prepare a wax dispersion. Subsequently, 10 parts of ion-exchanged water was added to the wax dispersion in a reaction flask, the temperature was raised to 80 ° C. to 82 ° C., 2 parts of potassium persulfate was added, and 30 parts of styrene and 24 parts of 2-ethylhexyl acrylate were added. The mixture was added dropwise over 2 hours. After completion of the dropping, 0.2 part of potassium persulfate was added and reacted for 2 hours. The solid content of the aqueous dispersion (A-1) of the styrene-acrylic copolymer thus obtained was 35%, and the glass transition point was ⁇ 10 ° C.
• paraffin wax paraffin wax 155, manufactured by Nippon Seiro Co
• styrene-acrylic copolymer (A) a copolymer of styrenes and (meth) acrylate and a copolymer of styrenes, (meth) acrylate and (meth) acrylic acid form a core-shell structure.
• the solid content of the aqueous dispersion (A-3) was 40%, and the glass transition point was -21 ° C.
• Comparative Example 2 Comparative Example 2 in the same manner as in Reference Examples 1 to 4 except that a comparative solvent-based varnish containing 13 parts of industrial nitrocellulose, 55 parts of isopropyl alcohol, and 32 parts of ethyl acetate was used in the overcoating composition for paper. A laminate was obtained.
• Comparative Example 3 Comparative Example 3 in the same manner as in Reference Examples 1 to 4 except that a comparative aqueous varnish containing 28% of styrene acrylic resin, 4 parts of isopropyl alcohol, and 68 parts of ion-exchanged water was used in the overcoating composition for paper. A laminate was obtained.
• ⁇ Evaluation items> (water resistant) Tap water is collected in a dropper, and 0.1 ml is dropped on the surface of the coated paper test piece for evaluation provided with the water resistant coat layer. After dripping tap water, wipe off the tap water at 25 ° C for 1 hour, 4 hours, 5 hours, and 8 hours, and visually evaluate the front and back surfaces according to the following evaluation criteria. do. ⁇ : There is no trace of dripping on the front surface, no swelling due to water, and no penetration into the back surface. ⁇ : There are traces of dripping on the front surface and water permeates, but does not permeate the back surface. X: There are traces of dripping on the front surface and swelling due to water, and there is penetration into the back surface.
• the contact angles after 0 minutes and 40 minutes were measured.
• An automatic contact angle meter manufactured by Kyowa Surface Chemistry Co., Ltd. was used to measure the contact angle.
• the coated surface of the produced waterproof paper was superposed so as to be in contact with each other, and the inclination angle at which the coated paper started to slide was measured as the sliding angle by the inclination method.
• the sliding angle was measured using a sliding angle inclination measuring device (manufactured by HEIDON). If the value of the sliding angle is too small, the load is likely to collapse when stacked. If it is too large, the coating material may get stuck. Therefore, if the coated paper has an appropriate sliding angle, it becomes easy to handle such as taking out the coated paper one by one from the laminated coated paper, and the workability is improved.
• the laminated body of Reference Example 1 As the water resistant paper used for the evaluation of water vapor permeability, the laminated body of Reference Example 1, the kraft paper of Comparative Example 1, and the laminated body of Comparative Example 4 were used.
• an aqueous dispersion (solid content 30%) containing a commercially available styrene-acrylic copolymer having a core-shell structure was used instead of the composition (OC-1) in Example 1.
• it is a laminated body produced in the same manner as in Reference Example 1.
• ⁇ Method for producing olefin- ⁇ , ⁇ unsaturated carboxylic acid copolymer for heat sealant> (Manufacturing Example 4) 77.8 parts of ethylene, 11.1 parts of ethyl acrylate, and 11.2 parts of acrylic acid were synthesized by a conventional method to obtain an ethyl acrylate-acrylic acid copolymer. Twenty-five parts of the obtained copolymer, ammonia having a neutralization rate of 100% with respect to the acid value of the copolymer, water as an aqueous solvent, and 1.5 parts of a fatty acid amide wax as a wax were charged and stirred to form an olefin. An aqueous dispersion (H1) of a - ⁇ , ⁇ unsaturated carboxylic acid copolymer and a fatty acid amide wax was obtained.
• aqueous heat sealant was prepared by mixing 67 parts of water and 3 parts of isopropyl alcohol with 30 parts of the aqueous dispersion (H1) obtained in Production Example 3 or Production Example 4.
• Examples 1 to 12 The paper substrates shown in Tables 4 to 7 are prepared, and the water-resistant overcoating composition used in Reference Example 1 is applied to one surface of the paper substrate so that the film thickness is 2 g / m 2 . Then, it was dried at 150 ° C. for 20 seconds using a dryer. Subsequently, the aqueous heat sealant was applied to the other surface of the paper substrate so that the film thickness was 2 g / m 2 , and dried at 100 ° C. for 30 seconds using a dryer. A laminated body of ⁇ 10 was prepared.
• the overcoating composition for paper and the aqueous heat sealant were applied so as to have a film thickness of 5 g / m 2 , and the laminates of Examples 11 to 18 were prepared.
• Tables 4 and 5 show the results of applying the water resistant overcoating composition (2 g / m 2 ) and the heat sealant (2 g / m 2 ).
• Tables 6 and 7 show the water resistant overcoating composition (5 g / m 2 ) and heat seal. This is the result of applying the agent (5 g / m 2 ).

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