Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • 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
• • 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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
• • 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
• • 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
• • 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

Definitions

• the present invention relates to a functional material having a coating layer excellent in water repellency, oil resistance, water vapor barrier property, heat sealing property, and blocking resistance, and a method for producing the same.
• paper and film have been used as base materials for functional materials.
• food packaging materials which are a type of functional material
• water and oil components contained in food are prevented from seeping out of the packaging material, and deterioration and discoloration of the contents, growth of bacteria and mold growth are suppressed. Therefore, the food packaging material is required to have water repellency, oil resistance, and water vapor barrier property. Further, blocking resistance is required when the packaging material is stored, and heat sealability is required during the molding process.
• food packaging materials but also general wrapping paper and release paper, many of the functional materials based on paper have been laminated paper laminated with plastic such as polyethylene in order to satisfy these various properties. Has been used. It was
• laminated paper generally lacks recyclability as used paper, in recent years, instead of laminating, a resin that exhibits the desired function as a functional material and is easily removed when the used paper is reused is applied. Paper has been considered. It was
• Patent Document 1 is obtained by applying a paint containing an acrylic resin aqueous emulsion to paper and drying it to form an oil-resistant resin layer, and the glass transition temperature (Tg) of the oil-resistant resin layer is different.
• Oil-resistant paper for foods having good oil resistance at 40 to 70 ° C. has been proposed. It was
• Patent Document 2 a detergent or a food container is manufactured in which a resin layer composed of two layers, an undercoat layer and a topcoat layer, is provided on at least one surface of a paper substrate, and the topcoat layer contains a water and oil resistant agent.
• Water and oil resistant papers suitable for this have been proposed. It was
• Patent Document 3 describes, as an alternative technique for a fluorine-based oil-resistant agent that imparts oil resistance to paper, a food-grade oil-resistant paper in which an acrylic synthetic resin emulsion is applied to a paper substrate to form an oil-resistant synthetic resin layer.
• the oil-resistant synthetic resin layer has an undercoat layer formed on the surface of the paper substrate and an overcoat layer to be the surface layer, and the glass transition temperature Tg 1 of the undercoat layer resin is ⁇ 30 to 0 ° C.
• An oil-resistant paper for foods which has a glass transition temperature Tg 2 of an overcoat layer resin of 0 to 30 ° C. and is used as a material for confectionery cartons, fast food containers, and the like, has been proposed.
• Patent Document 4 applies an emulsion having at least two or more oil-resistant layers on one side on a base paper and the oil-resistant component of the oil-resistant layer is mainly acrylic resin.
• the obtained paper an oil-resistant paper for food packaging having a glass transition temperature of the acrylic resin of 30 ° C. or higher has been proposed. It was
• Japanese Unexamined Patent Publication No. 2001-303475 Japanese Unexamined Patent Publication No. 9-87994 Japanese Unexamined Patent Publication No. 2006-28697 Japanese Unexamined Patent Publication No. 2006-316637
• a functional material having a coating layer exhibiting water repellency, oil resistance, water vapor barrier property, heat sealability, and blocking resistance which are the performances required for a functional material, and a method for producing the functional material are described.
• the purpose is to provide.
• the present inventors apply a specific synthetic resin on a substrate such as paper or film in two or more layers, so that the coated layer has water repellency, oil resistance, water vapor barrier property, heat seal property, and blocking resistance. We have found that all of the sex is expressed at a satisfactory level. It was
• the present invention is (1) a functional material having two or more continuous coating layers on the surface of at least one base material, and the coating layer (X) in direct contact with the base material has an acid value of 35.
• the synthetic resin (A) of ⁇ 65 mgKOH / g is contained, the outermost coating layer (Y) contains the synthetic resin (B) having a glass transition temperature of ⁇ 35 to 65 ° C., and the synthetic resin is contained in the entire coating layer.
• the functional material according to (1) above wherein is a styrene acrylic resin and / or an acrylic resin, and (3) the constituent monomers of the synthetic resin (A) and the synthetic resin (B) have a carboxy group.
• the function according to (1) or (2) above, wherein the vinyl monomer / (meth) acrylic acid ester / styrenes 4.5 to 10/40 to 95.5 / 0 to 51% by mass.
• the coating amount of the synthetic resin (A) is 6.0 to 30 g / m 2
• the coating amount of the synthetic resin (B) is 3.0 to 6.0 g.
• the functional material obtained in the present invention exhibits water repellency, oil resistance, water vapor barrier property, heat sealability, and blocking resistance at a satisfactory level, it is expected to be used as a food packaging material. It can also be applied to other packaging materials that require these physical properties, release paper, wallpaper for building materials, paper containers, and the like.
• the functional material of the present invention has two or more continuous coating layers on the surface of at least one substrate, and the coating layer (X) in direct contact with the substrate has an acid value of 35 to 65 mgKOH / g.
• a synthetic resin (B) containing a synthetic resin (A) hereinafter, may be simply abbreviated as "synthetic resin (A)" and having a coating layer (Y) on the outermost surface having a glass transition temperature of ⁇ 35 to 65 ° C. ) (Hereinafter, it may be simply abbreviated as "synthetic resin (B)"), and 0.5 to 10% by mass of the wax component is contained in the total coating layer with respect to the total mass of the synthetic resin. It was
• the base material that can be used for the functional material of the present invention is not limited, and examples of the base material used as a food packaging material include paper, cloth, plastic film, and aluminum foil. Paper and plastic films are preferable, and neutral woodfree papers, PET films and polylactic acid films are more preferable. It was
• the coating layer (X) is a coating that is in direct contact with the substrate among two or more coating layers that are continuous with the surface of at least one substrate. It is a work layer and contains a synthetic resin (A). It was
• the synthetic resin (A) used in the present invention must have an acid value in the range of 35 to 65 mgKOH / g from the viewpoint of oil resistance and water vapor barrier property. If the acid value is less than 35 mgKOH / g, the water vapor barrier property deteriorates, and if it exceeds 65 mgKOH / g, the oil resistance deteriorates.
• the acid value of the synthetic resin is a value measured according to the neutralization titration method of JIS K0070-1992.
• styrene acrylic resin and / or an acrylic resin is a copolymer of a vinyl monomer having a corresponding carboxy group, a (meth) acrylic acid ester, and styrenes used as necessary. It was
• the vinyl monomer having a carboxy group may be any vinyl monomer having one or more carboxy groups, and examples thereof include (meth) acrylic acid.
• examples of the (meth) acrylic acid ester include (meth) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate. ) Acrylic acid esters; (meth) acrylic acid esters having a hydroxyl group such as (meth) 2-hydroxyethyl acrylate; (meth) glycidyl acrylate and the like can be mentioned.
• the styrenes may be any monomer having a styrene skeleton, and examples thereof include styrene and ⁇ -methylstyrene. These are used alone or in admixture of two or more. It was
• the coating layer (Y) is a coating located on the outermost surface of at least two or more coating layers continuous with the surface of one of the base materials. It is a layer and contains a synthetic resin (B). It was
• the synthetic resin (B) used in the present invention must have a glass transition temperature in the range of ⁇ 35 to 65 ° C. from the viewpoint of water repellency, heat sealability, and blocking resistance. If the glass transition temperature is less than ⁇ 35 ° C., the water repellency and blocking resistance deteriorate, and if it exceeds 65 ° C., the heat sealability deteriorates. From the viewpoint of blocking resistance, the temperature is preferably in the range of -18 to 65 ° C.
• the synthetic resin (A) is preferably a styrene acrylic resin and / or an acrylic resin, and is composed of the monomers listed as the constituent monomers of the synthetic resin (A). It was
• the synthetic resin (B) may be the same as the synthetic resin (A) as long as the conditions of the present invention are satisfied. It was
• the mass fraction of each monomer constituting the total synthetic resin component contained in the emulsion composition is based on the charging ratio when the charging amount of the monomer is known. When the amount to be charged is unknown, the emulsion composition is obtained by mass spectrometry from the dried and solidified one. It was
• the synthetic resin (A) and the synthetic resin (B) may be in any form as long as they satisfy the respective conditions specified in the present invention, but are coated and dried on the base material and other coating layers. Since a film is formed to form a coating layer, an emulsion is preferable as a raw material form used for producing a functional material. If at least one emulsion containing either the synthetic resin (A) or the synthetic resin (B) contains a wax component described later, the trouble of dispersing the wax before coating can be saved and a uniform coating can be applied. It is more preferable because it is easy to form a work layer.
• Examples of commercially available products include XP8812 (acid value 61, glass transition temperature -9 ° C, paraffin wax contained), XP8829 (acid value 57, glass transition temperature -8 ° C, paraffin wax contained), NE-2260 (acid value 53). , Glass transition temperature ⁇ 10 ° C.), PE-2273 (acid value 38, glass transition temperature -11 ° C.) (all manufactured by Starlight PMC Co., Ltd.) and the like.
• the synthetic resin (A) and the synthetic resin (B) can be obtained by a known method.
• a mixture of monomers constituting the synthetic resin (A) or the synthetic resin (B) is emulsified in the presence of water, an emulsifier (including a polymer emulsifier), and if necessary, a wax component. Obtained by polymerization. It was
• the total mass of the total synthetic resin containing the synthetic resin (A) and the synthetic resin (B) in the total coating layer is necessary to contain 0.5 to 10% by mass of a wax component. If the content of the wax component is less than 0.5% by mass, sufficient water vapor barrier property cannot be obtained, and if it exceeds 10% by mass, the heat sealability deteriorates, and depending on the amount of coating, a coating layer is formed by repellent. Can not.
• the wax component may be contained in at least one coating layer among all the coating layers. It was
• the wax component used in the present invention is preferably a mixture of normal paraffin having 20 or more carbon atoms, which is solid (wax-like) and insoluble in water at room temperature.
• the wax component for example, the trade name "Paraffin WAX” series manufactured by Nippon Seiro Co., Ltd. (135 (melting point 59 ° C.), 140 (61 ° C.), 145 (63 ° C.), 150 (66 ° C.), 155 (69 ° C.)) and the like. It was
• the functional material of the present invention includes the coating layer (X) and the coating layer (Y) as long as the effects of the present invention are not impaired.
• the coating layer on the surface of the functional material preferably has a three-layer structure or less from the viewpoint of coating efficiency and the like.
• the intermediate coating layer preferably contains a synthetic resin (A) and / or a synthetic resin (B).
• the functional material of the present invention may contain a filler in addition to the above-mentioned components in the coating layer.
• the filler is not particularly limited as long as it is usually used for paper coating.
• kaolinite, talc, titanium oxide, calcium carbonate, clay, silica and the like can be mentioned, and calcium carbonate, clay and the like can be mentioned as preferable ones. It was
• an emulsion containing a synthetic resin (A) having an acid value of 35 to 65 mgKOH / g is applied to the surface of a substrate to coat the coating layer (X).
• any of known flexo, gravure, curtain coater, size press coater, roll coater, air knife coater, blade coater, and rod coater can be adopted, and one type is appropriately used. Or apply in combination of two or more.
• the amount of each emulsion forming the coating layer (X) and the coating layer (Y) is not particularly limited as long as the effect of the present invention can be obtained, but pinholes and cracks in the coating film do not occur.
• the coating amount of the synthetic resin (A) is 6.0 to 30 g / m 2
• the coating amount of the synthetic resin (B) is 3.0 to 6.0 g / m 2, respectively, from the viewpoint of performance. It is preferable to adjust the coating amount so as to be m 2 .
• the wax component may be contained in at least one coating layer among all the coating layers, and the method of adding the wax component and the coating layer to be added are not particularly limited. It is preferable to use a water-dispersible wax emulsion containing wax and mix and disperse it in a coating liquid containing a synthetic resin for coating. As described above, either the synthetic resin (A) or the synthetic resin (B) is used. It is more preferable to apply an emulsion containing wax in at least one of the emulsions, because it saves the trouble of dispersing the wax before coating and makes it easy to form a uniform coating layer. It was
• drying after coating is not particularly limited as long as the effect of the present invention can be obtained, but it is preferable to dry at 50 to 90 ° C. for 30 to 60 seconds.
• Example 1 ⁇ Manufacturing of functional material using neutral woodfree paper as a base material> As a base material, 21.0 cm ⁇ 29.7 cm (A4 size) neutral woodfree paper (basis weight 65 g / m 2 ) was used.
• An emulsion 7 containing a synthetic resin 7 as a synthetic resin (A) is applied to one side of a base material using a wire bar # 6, and placed in a dryer at 80 ° C. for 30 seconds to obtain the synthetic resin (A).
• a coating layer (X) having a coating amount of 6.0 g / m 2 was formed.
• the emulsion 1 containing the synthetic resin 1 as the synthetic resin (B) is coated on the coating layer (X) using the wire bar # 4, and placed in a dryer at 80 ° C. for 30 seconds to obtain the synthetic resin (B).
• a coating layer (Y) having a coating amount of 4.0 g / m 2 was formed to obtain a functional material 1.
• Example 2 (Examples 2, 3, 6 to 9, Comparative Examples 1, 2, 4 to 13)
• the functional material 2 is the same as in Example 1 except that the emulsions used are replaced with those shown in Tables 2 and 3. , 3, 6-9, and comparative functional materials 1, 2, 4-13 were obtained. It was
• Emulsion 1 containing the synthetic resin 1 as the synthetic resin (A) is coated on one side of the base material using a wire bar # 6, placed in a dryer at 80 ° C. for 30 seconds, and the synthetic resin (A) is applied.
• a coating layer (X) having a coating amount of 6.0 g / m 2 was formed.
• the emulsion 7 containing the synthetic resin 7 is coated on the coating layer (X) using the wire bar # 6, placed in a dryer at 80 ° C. for 30 seconds, and the coating amount is 6.0 g / m 2 .
• An intermediate layer was formed.
• an emulsion 1 containing the synthetic resin 1 as the synthetic resin (B) is applied onto the intermediate layer using a wire bar # 4, and the mixture is placed in a dryer at 80 ° C. for 30 seconds to increase the amount of the synthetic resin (B) applied.
• a coating layer (Y) of 4.0 g / m 2 was formed to obtain a functional material 4.
• Example 5 Functional materials 5 and 13 were obtained in the same manner as in Example 4 except that the emulsion used was replaced with that shown in Table 2. It was
• Example 10 The same as in Example 1 except that the wire bar at the time of forming the coating layer (X) was replaced with # 15 and the coating amount of the coating layer (X) was 15.0 g / m 2 .
• the functional material 10 was obtained.
• Example 11 The same as in Example 1 except that the wire bar at the time of forming the coating layer (X) was replaced with # 30 and the coating amount of the coating layer (X) was set to 30.0 g / m 2 .
• the functional material 11 was obtained.
• Example 12 The same as in Example 1 except that the wire bar at the time of forming the coating layer (Y) was replaced with # 6 and the coating amount of the coating layer (Y) was 6.0 g / m 2 .
• the functional material 12 was obtained.
• Example 3 (Comparative Example 3) The emersion used is replaced with the one shown in Table 3, the wire bar at the time of forming the coating layer (X) is replaced with # 10, and the coating amount of the coating layer (X) is 10.0 g / m 2 .
• a comparative functional material 3 was obtained in the same manner as in Example 1 except that the coating layer (Y) was not formed.
• Table 2 shows the types and acid values of the synthetic resin forming the coating layer (X), the types of the synthetic resin forming the intermediate layer, the types and Tg of the synthetic resin forming the coating layer (Y), and all coatings. Shows the amount of wax in the layer. It was
• the oil resistance was evaluated in accordance with the Kit value: JAPAN TAPPI No41.
• the Kit value is in the range of 6 to 12 at a practical level. It was
• the water vapor barrier property was evaluated in accordance with JIS Z0208 (cup method, 40 ° C., humidity 90% RH, 24 hours). The smaller the moisture permeability value, the better the water vapor barrier property. In the present invention, the moisture permeability is 100 g / m 2.24 h or less for neutral woodfree paper, 15 g / m 2.24 h or less for PET film, and 30 g / m 2.24 h or less for polylactic acid film.
• Heat sealability Prepare two coating samples cut into 2 cm x 15 cm, and after overlapping the coated surfaces, pressurize pressure 1 kgf / cm 2 , pressurization time 0.5 seconds, pressurization temperature. Heat sealing was performed at 90 to 200 ° C.
• the pressurization temperature when the coated substrate is broken is defined as the heat seal temperature, and 120 ° C. or lower is a practical level.
• Tables 4 to 6 show the results of performance evaluation of each functional material and comparative functional material. It was

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

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• 2021
  • 2021-09-30 WO PCT/JP2021/036190 patent/WO2022137707A1/ja not_active Ceased
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