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
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
  • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/26—Printing on other surfaces than ordinary paper
  • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

Definitions

• the present invention relates to a printed matter and a laminate printed with printing ink on at least one surface of a polyolefin film by a printing method using a plate.
• product packaging has a simple structure in which printing ink is printed on the front side of the plastic film that is the base material for decoration and surface protection, and not on the back side that comes into contact with the product (front printing method). (It is said) printed matter is used. In this way, since the front printing ink is printed on the front side of the plastic film as the base material, the ink film is directly exposed to the outside, and tough film physical properties are required when handling the product. To.
• the material of the plastic film used as the base material is diverse. Specifically, polyamide resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, and poly. Polyester resins such as butylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate), polypropylene, polyethylene and the like.
• PET polyethylene terephthalate
• polyester resins such as butylene naphthalate, polyhydroxycarboxylic acids such as polylactic acid, biodegradable resins such as aliphatic polyester resins such as poly (ethylene succinate) and poly (butylene succinate), polypropylene, polyethylene and the like.
• Examples thereof include a film made of a thermoplastic resin such as a polyolefin resin, a polyimide resin, a polyarylate resin, or a mixture thereof, and a laminate thereof.
• a thermoplastic resin such as a polyolefin resin, a polyimide resin, a polyarylate resin, or a mixture thereof, and a laminate thereof.
• base films both unstretched films and stretched films are used, and the printed surface of the base film may be subjected to corona discharge treatment to facilitate printing, and silica, alumina, etc. are used. It may be vapor-deposited.
• an ink using an organic solvent has been used as a printing ink for front printing using a plate, which can be applied to these various plastic films. Since the organic solvent has solubility in plastic, some degree of adhesion can be expected.
• environment-friendly inks have been demanded, and water-based printing inks for front printing have been required as environment-friendly inks. Since the water-based printing ink for front printing does not use an organic solvent, it is effective in reducing the emission of carbon dioxide and VOC generated during printing.
• the obtained printed matter has a reduced adhesiveness to the plastic film, and the resulting deterioration in the physical characteristics of the coating film has been regarded as a problem.
• polyolefin films such as polypropylene and polyethylene, it has been difficult to obtain printed matter having the same adhesion as ink using an organic solvent.
• Patent Document 1 describes an acid group-containing resin emulsion in which a part or all is neutralized with a volatile basic compound, and a hydrazine type having at least two or more hydrazine residues in the molecule.
• Aqueous flexo printing for surface printing containing 0.1 to 1 equivalent of a compound and an aqueous polycarbodiimide compound with respect to 1 equivalent of an acid group in an acid group-containing resin emulsion, a pigment, a surfactant, and an aqueous solvent. It is disclosed that the ink composition is excellent in pot life, substrate adhesion, water resistance, abrasion resistance, and blocking resistance.
• the material of the target base material is not described in Cited Document 1, and it is not clear what base material has excellent adhesion to the base material.
• polyethylene terephthalate is an aqueous flexo ink containing a pigment, water, a urethane resin having a graft chain, and a wax, wherein the acid value of the urethane resin is 25 to 100 mgKOH / g.
• PET polyethylene terephthalate
• (PET) film base material exhibits excellent coating material properties (base material adhesion, water friction resistance, water blocking resistance, low odor).
• base material adhesion base material adhesion, water friction resistance, water blocking resistance, low odor
• Patent Document 3 an ink composition containing a self-crosslinked acrylic polymer having a glass transition temperature exceeding 0 ° C., a silicon emulsion, and water is described as polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP). On the other hand, it is disclosed that it is excellent in low temperature friction fastness and wet friction fastness (see table 10).
• An object to be solved by the present invention is to provide a printed matter and a laminate, which are formed on a polyolefin film by a printing method using a plate and have excellent coating film physical characteristics, particularly scratch resistance and adhesion.
• the present invention is a printed matter printed with a printing ink on at least one surface of a polyolefin film by a printing method using a plate, and the content concentration of the polyolefin film on a mass basis of an organic lubricant is 1200 ppm or less.
• the printing ink contains 5 to 60% by mass of the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) and the radical polymerizable monomer 40 to 95 copolymerizable with the carboxyl group-containing radical polymerizable monomer.
• a printed matter which is a printing ink containing a copolymer obtained by copolymerizing with mass%.
• R 1 is a hydrogen atom or a methyl group
• R 2 is a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms
• n is an integer of 1 to 10.
• the present invention is a laminate having at least one surface of a polyolefin film having a printed matter printed with a printing ink by a printing method using a plate, and the content concentration of the polyolefin film on a mass basis of an organic lubricant is 1200 ppm.
• the printing ink is a radical polymerizable simple copolymer capable of copolymerizing with 5 to 60% by mass of a carboxyl group-containing radical polymerizable monomer represented by the general formula (1) and the carboxyl group-containing radical polymerizable monomer.
• a laminate which is a printing ink containing a copolymer obtained by copolymerizing 40 to 95% by mass of a weight.
• R 1 is a hydrogen atom or a methyl group
• R 2 is a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms
• n is an integer of 1 to 10.
• Polyolefin film examples of the polyolefin film used in the present invention include polyethylene-based films and polypropylene-based films.
• the polyethylene-based film used in the present invention is a polyethylene-based film having a content concentration of a slip agent, particularly an organic lubricant, contained in the film on a mass basis of 1200 ppm or less.
• a slip agent particularly an organic lubricant
• the content concentration of the slip agent is preferably 200 to 1000 ppm, more preferably 300 to 900 ppm.
• the slip agent may be any one added to the resin forming the film surface to improve the slipperiness (external lubricity) of the film surface, and various lubricants such as fatty acid amides, fatty acid metals, fatty acids and waxes. Etc. can be used, but among them, fatty acid amide is preferable.
• fatty acid amide include behenic acid amide, stearic acid amide, palmitic acid amide, lauric acid amide, erucic acid amide, oleic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, methylene bistreic acid amide, and ethylene.
• Examples thereof include bisoleic acid amide, methylene bisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisoleic acid amide, octamethylene biserucic acid amide, and among them, erucic acid amide, oleic acid amide, and bechenic acid amide. Is preferable, and erucic acid amide is particularly preferable.
• the polyethylene-based film used in the present invention is a film containing an ethylene-based resin as a main resin component.
• the content of the ethylene-based resin in the resin component contained in the polyethylene-based film is preferably 80% by mass or more, more preferably 90% by mass or more, and all of the resin components may be ethylene-based resin.
• the polyethylene-based film may have a single-layer structure or a multi-layer structure, but in the case of the multi-layer structure, the content of the ethylene-based resin in the resin component contained in the layer on which the printing ink is printed is 80% by mass or more. It is preferable, it is more preferably 90% by mass or more, and all of the resin components may be an ethylene-based resin.
• the ethylene resin used for the polyethylene film is not particularly limited, but for example, linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) and the like.
• Polyethylene resin can be used.
• low-density polyethylene (LDPE) can be preferably used because it is easy to obtain suitable ink adhesion.
• the density of the ethylene resin is preferably 0.910 to 0.970 [g / cm 3 ], more preferably 0.915 to 0.965 [g / cm 3 ].
• a resin other than the ethylene resin is used in combination with the polyethylene film
• another olefin resin such as a propylene resin
• the propylene-based resin include a propylene homopolymer, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, a propylene-ethylene-butene-1 copolymer, a metallocene-catalyzed polypropylene, and the like.
• the ethylene-methyl methacrylate copolymer (EMMA), the ethylene-ethyl acrylate copolymer (EEA), and the ethylene-methyl acrylate (EMA) common weight are used.
• ethylene-based copolymers such as ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA);
• E-EA-MAH ethylene-ethyl acrylate-maleic anhydride copolymer
• EAA ethylene-acrylic acid copolymer
• EAA ethylene-methacrylic acid copolymer
• an ethylene-acrylic acid copolymer ionomer, an ethylene-methacrylic acid copolymer ionomer, and the like can be used.
• the content of the resin other than the ethylene resin is preferably 20% by mass or less of the resin component contained in the polyethylene film. It is more preferable to use it in an amount of mass% or less.
• additives may be added to the polyethylene film as long as the effects of the present invention are not impaired.
• examples of the additive include antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, nucleating agents, pigments and the like.
• the thickness of the polyethylene-based film may be appropriately preferably one depending on the intended use, but the thickness of the film is preferably 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m, still more preferably 30 to 50 ⁇ m. is there.
• the polyethylene-based film used in the present invention preferably has a static friction coefficient and a dynamic friction coefficient of 0.1 to 1.0, and more preferably 0.2 to 0.6, on the surface of the printing surface on which the printing ink is printed. This is more preferably 0.3 to 0.5.
• the surface of the printed surface is preferably treated so that the wetting tension of the surface is in the range of 36 mN / m or more, and more preferably 38 mN / m or more. When the wetting tension is within this range, the print adhesion can be further improved.
• the surface treatment method include corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona discharge treatment is preferred.
• the polypropylene-based film used in the present invention is a polypropylene-based film having a content concentration of a slip agent, particularly an organic lubricant, contained in the film on a mass basis of 1200 ppm or less.
• a slip agent particularly an organic lubricant
• the content concentration of the slip agent is preferably 200 to 1000 ppm, more preferably 300 to 900 ppm.
• the slip agent may be any one added to the resin forming the film surface to improve the slipperiness (external lubricity) of the film surface, and various lubricants such as fatty acid amides, fatty acid metals, fatty acids and waxes. Etc. can be used, but among them, fatty acid amide is preferable.
• fatty acid amide include behenic acid amide, stearic acid amide, palmitic acid amide, lauric acid amide, erucic acid amide, oleic acid amide, methylene bisstearic acid amide, ethylene bisstearic acid amide, methylene bistreic acid amide, and ethylene.
• Examples thereof include bisoleic acid amide, methylene bisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisoleic acid amide, octamethylene biserucic acid amide, and among them, erucic acid amide, oleic acid amide, and bechenic acid amide. Is preferable, and erucic acid amide is particularly preferable.
• the polypropylene-based film used in the present invention is a film containing a propylene-based resin as a main resin component.
• the content of the propylene-based resin in the resin component contained in the polypropylene-based film is preferably 80% by mass or more, more preferably 90% by mass or more, and all of the resin components may be propylene-based resin. preferable.
• the polypropylene-based film may have a single-layer structure or a multi-layer structure, but in the case of the multi-layer structure, the content of the propylene-based resin in the resin component contained in the layer on which the printing ink is printed is 80% by mass or more. It is preferably 90% by mass or more, and all of the resin components may be propylene-based resins.
• the propylene resin used for the polypropylene film is not particularly limited, but other olefin resins such as propylene resin can be preferably used.
• the propylene-based resin include a propylene homopolymer, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, a propylene-ethylene-butene-1 copolymer, a metallocene-catalyzed polypropylene, and the like.
• the polypropylene-based film may be a non-stretched polypropylene-based film (CPP) or a stretched polypropylene-based film (OPP), and a suitable film can be appropriately used depending on the intended use.
• CPP non-stretched polypropylene-based film
• OPP stretched polypropylene-based film
• the density of the propylene-based resin is preferably 0.880 to 0.910 [g / cm 3 ], more preferably 0.885 to 0.905 [g / cm 3 ].
• ethylene-based resin examples include linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).
• LLDPE linear low-density polyethylene
• LDPE low-density polyethylene
• MDPE medium-density polyethylene
• HDPE high-density polyethylene
• the ethylene-methyl methacrylate copolymer (EMMA), the ethylene-ethyl acrylate copolymer (EEA), and the ethylene-methyl acrylate (EMA) common weight are used.
• ethylene-based copolymers such as ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMAA);
• E-EA-MAH ethylene-ethyl acrylate-maleic anhydride copolymer
• EAA ethylene-acrylic acid copolymer
• EAA ethylene-methacrylic acid copolymer
• an ethylene-acrylic acid copolymer ionomer, an ethylene-methacrylic acid copolymer ionomer, and the like can be used.
• the content of the resin other than the propylene resin is preferably 20% by mass or less of the resin component contained in the polypropylene film. It is more preferable to use it in an amount of mass% or less.
• additives may be added to the polypropylene film as long as the effects of the present invention are not impaired.
• examples of the additive include antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, nucleating agents, pigments and the like.
• the thickness of the polypropylene-based film may be appropriately preferably one depending on the intended use, but the thickness of the film is preferably 10 to 100 ⁇ m, more preferably 20 to 60 ⁇ m, still more preferably 30 to 50 ⁇ m. is there.
• the polypropylene film used in the present invention preferably has a static friction coefficient and a dynamic friction coefficient of 0.1 to 1.0, and more preferably 0.2 to 0.6, on the surface of the printing surface on which the printing ink is printed. This is more preferably 0.3 to 0.5.
• the surface of the printed surface is preferably treated so that the wetting tension of the surface is in the range of 36 mN / m or more, and more preferably 38 mN / m or more.
• the surface treatment method include corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, surface oxidation treatment such as ozone / ultraviolet treatment, and surface unevenness treatment such as sandblasting. Corona discharge treatment is preferred.
• the method for producing the polyolefin film is not particularly limited, but is a coextrusion laminated molding method, for example, a known coextrusion method such as a coextrusion multilayer die method or a feed block method in which melt extrusion is performed using two or more extruders. After laminating in a molten state, a method of processing into a long roll film by a method such as inflation or a T-die / chill roll method is preferable, and a coextrusion method using a T-die is more preferable.
• the printing ink forming the printing layer of the present invention is a printing ink printed by a printing method using a plate, and the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) is 5 to 60% by mass and the carboxyl. It is a printing ink containing a copolymer obtained by copolymerizing a group-containing radical polymerizable monomer and a radically polymerizable monomer copolymerizable in an amount of 40 to 95% by mass.
• the printing ink used in the present invention is a printing ink printed by a printing method using a plate, and among them, a liquid ink applied to a printing method using a printing plate such as a gravure printing ink or a flexo printing ink is used.
• a printing plate such as a gravure printing ink or a flexo printing ink
• liquid inks are collectively referred to as liquid printing inks.
• a gravure printing ink using a gravure plate or a flexographic printing ink using a flexographic plate is preferable.
• the gravure printing ink using the gravure plate is called the water-based gravure printing ink
• the flexo printing ink using the flexo plate is called the water-based flexo printing ink.
• it is a liquid ink
• high-viscosity inks such as lithographic offset inks are not included in the liquid printing inks defined in the present invention.
• it is a printing ink in which the viscosity of the ink is 7 to 25 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigo Co., Ltd., and the surface tension of the ink at 25 ° C. is 25 to 50 mN / m.
• the liquid printing ink of the present invention does not contain an active energy curable component, that is, is a liquid ink that is non-reactive with active energy rays.
• the "inks" used in the following description all refer to "printing inks”.
• the printing ink used in the present invention is copolymerized with 5 to 60% by mass of the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) and the carboxyl group-containing radical polymerizable monomer.
• R 1 is a hydrogen atom or a methyl group
• R 2 is a substituted or unsubstituted alkylene group having 2 to 18 carbon atoms
• n is an integer of 1 to 10.
• the carboxyl group-containing radically polymerizable monomer represented by the general formula (1) is (meth) acrylic acid, for example, acrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalate.
• Carboxyl group-containing acrylates such as acid and 2-acryloyloxyethyl hexahydrophthalic acid
• carboxyl group-containing methacrylates such as methacrylic acid, 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxyethyl hexahydrophthalic acid can be mentioned.
• “(meth) acrylate” refers to either or both of acrylate and methacrylate
• “(meth) acrylic” refers to either or both of acrylic and methacrylic.
• the radical polymerizable monomer copolymerizable with the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) is known without particular limitation as long as the effect of the present invention is not impaired without interfering with the reaction.
• the radically polymerizable monomer of the above can be used.
• Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylate and isobonyl (meth) acrylate;
• Fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
• Polyethylene oxide group-containing ethylenically unsaturated monomer such as polyethylene glycol mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, and methoxypolyethylene glycol mono (meth) acrylate;
• the copolymer can be produced, for example, by polymerizing various monomers in a temperature range of 50 ° C. to 180 ° C. in the presence of a polymerization initiator, and more preferably in a temperature range of 80 ° C. to 150 ° C. ..
• Examples of the polymerization method include a massive polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
• examples of the polymerization mode include random copolymers, block copolymers, and graft copolymers.
• an emulsion obtained by polymerizing the copolymer in an aqueous medium in the coexistence of an emulsifier or the like, or polymerizing the copolymer in an organic solvent medium and then neutralizing with an alkali may be an aqueous dispersion which has been subjected to phase inversion emulsification.
• the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) and the radical polymerizable monomer copolymerizable with the carboxyl group-containing radical polymerizable monomer are represented by the general formula (1).
• the above-mentioned carboxyl group-containing radical polymerizable monomer is 5 to 60% by mass
• the radical polymerizable monomer copolymerizable with the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) is 40 to 60 to 60%. It may be in the range of 95% by mass.
• the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) is 15 to 40% by mass, and is copolymerized with the carboxyl group-containing radical polymerizable monomer represented by the general formula (1). It is preferable that the possible radically polymerizable monomer is in the range of 50 to 80% by mass.
• the copolymer may be a core-shell type.
• the core-shell type resin refers to a state in which the polymer (a2) is dispersed in an aqueous medium by the polymer (a1), and usually, the polymer (a1) is present on the outermost side of the resin particles to form a shell. In many cases, a portion is formed and a part or all of the polymer (a2) forms a core portion.
• the resin forming the shell portion will be referred to as a polymer (a1)
• the resin forming the core portion will be referred to as a polymer (a2).
• the core-shell type resin used in the present invention is one or more hydrophilic groups selected from the group consisting of a carboxyl group and a carboxylate group formed by neutralizing the carboxyl group of the polymer (a1) constituting the shell portion. It is preferable that the polymer contains an acrylic resin having the above, and the carboxyl group-containing radical polymerizable monomer represented by the general formula (1) is 5 to 60% by mass and the carboxyl group-containing radical polymerizable monomer. It may be a copolymer obtained by copolymerizing 40 to 95% by mass of a radically polymerizable monomer copolymerizable.
• the acid value of the shell portion of the core-shell type resin is preferably in the range of 40 mgKOH / g or more and 250 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
• the carboxyl group of the polymer (a1) constituting the shell portion is neutralized with a basic compound to form a carboxylate group.
• ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine and the like can be used, and ammonia and triethylamine can be used to withstand the temperature of the coating film. It is preferable for further improving the property, corrosion resistance and chemical resistance.
• the weight average molecular weight of the core portion is preferably in the range of 200,000 to 3,000,000, and more preferably 800,000 or more.
• Tg is preferably in the range of ⁇ 30 ° C. to 30 ° C.
• a copolymer such as an acrylic monomer similar to the above-mentioned acrylic resin can be used, but among them, it is preferably produced in an aqueous medium. Specifically, it can be produced by collectively supplying or sequentially supplying the monomer and the polymerization initiator or the like to a reaction vessel containing an aqueous medium for polymerization. At that time, a pre-emulsion is produced by mixing the monomer, an aqueous medium, and a reactive surfactant or the like in advance, and the polymerization initiator or the like is supplied to a reaction vessel containing the aqueous medium. It may be polymerized.
• Examples of the polymerization initiator that can be used in producing the polymer (a2) include radical polymerization initiators such as persulfate, organic peroxide, and hydrogen peroxide, and 4,4'-azobis (4-4'-azobis). Azo initiators such as cyanovaleric acid) and 2,2'-azobis (2-amidinopropane) dihydrochloride can be used. Further, the radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent described later.
• persulfate for example, potassium persulfate, sodium persulfate, ammonium persulfate and the like can be used.
• organic peroxide include benzoyl peroxide, lauroyl peroxide, decanoyle peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxylaurate, and t-butyl peroxybenzoate.
• Kumen hydroperoxide, paramentan hydroperoxide, t-butyl hydroperoxide and the like can be used.
• reducing agent examples include ascorbic acid and its salt, erythorbic acid and its salt (sodium salt, etc.), tartrate acid and its salt, citric acid and its salt, formaldehyde sulfoxylate metal salt, sodium thiosulfate, and the like.
• Sodium bicarbonate, ferric chloride, etc. can be used.
• the amount of the polymerization initiator used may be an amount that allows the polymerization to proceed smoothly, but from the viewpoint of maintaining the excellent corrosion resistance of the obtained coating film, a smaller amount is preferable, and it is preferable for the production of the vinyl polymer (a2). It is preferably 0.01% by mass to 0.5% by mass with respect to the total amount of the monomers used.
• the total amount of the polymerization initiator used is preferably within the above range.
• a reactive surfactant anionic surfactant, nonionic surfactant, cationic surfactant, zwitterionic surfactant and the like are used. May be good.
• the acid value of the copolymer is preferably 20 mgKOH / g or more, 120 mgKOH / g or less, and more preferably 25 mgKOH or more.
• the acid value referred to here indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin.
• the weight average molecular weight of the copolymer is preferably in the range of 5,000 to 100,000.
• the weight average molecular weight is 5,000 or more, the heat resistance of the resin film does not decrease, and the friction resistance and the water friction resistance of the laminate tend to be maintained. If it is 100,000 or less, the laminate tends to have both substrate adhesion and scratch resistance.
• the glass transition temperature (Tg) of the copolymer is preferably in the range of 0 ° C. to 55 ° C.
• Tg glass transition temperature
• the glass transition temperature (Tg1) refers to a so-called calculated glass transition temperature, and refers to a value calculated by the following method.
• Tg (° C.) Tg (K) -273 W1, W2, ... Wn in the formula 1 represent the mass% of each monomer with respect to the total mass of the monomers used for producing the polymer, and T1, T2, ... Tn are the homopolymers of each monomer. Represents the glass transition temperature (K).
• T1, T2, ... Tn the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immunogut, EA Grulke) are used.
• the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and an extended straight line of each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
• the liquid printing ink used in the present invention may appropriately contain a binder resin other than the copolymer as long as the effects of the present invention are not impaired.
• the binder resin is not particularly limited, and is used in general water-based liquid printing inks: urethane resin, polyvinyl alcohols, polyvinylpyrrolidones, styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene-acrylic acid copolymer; vinyl.
• Naphthalene-maleic acid copolymer vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid
• Vinyl acetate-based copolymers such as copolymers and salts thereof can be used. These can also be used in combination as appropriate depending on the desired physical characteristics.
• urethane resin as the binder resin because it is easily available.
• the urethane resin has, for example, a polyol such as a polyether polyol, a polyester polyol, or a polycarbonate polyol, and a hydrophilic group such as an anionic group, a cationic group, a polyoxyethylene group, or a polyoxyethylene-polyoxypropylene group.
• a polyol such as a polyether polyol, a polyester polyol, or a polycarbonate polyol
• a hydrophilic group such as an anionic group, a cationic group, a polyoxyethylene group, or a polyoxyethylene-polyoxypropylene group.
• examples thereof include a urethane resin obtained by reacting a polyol with a polyisocyanate.
• the weight average molecular weight of the urethane resin is not particularly limited, but is generally 5,000 to 200,000, and more preferably 20,000 to 150,000.
• polyether polyol examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol.
• Glycerin Trimethylol Ethan, Trimethylol Propane, Sorbitol, Sucrose, Aconit Sugar, Femimeric Acid, Phosphoric Acid, Ethylene Diamine, Diethylene Triamine, Triisopropanolamine, Pyrogalol, Dihydroxybenzoic Acid, Hydroxyphthalic Acid, 1,2,3-Propane
• a compound having two or more active hydrogen groups such as trithiol and an addition polymerization of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclophenylene, or the cyclic ether compound.
• a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclophenylene, or the cyclic ether compound.
• the polyester polyol is obtained by a dehydration condensation reaction of a diol compound, a dicarboxylic acid, a hydroxycarboxylic acid compound or the like, a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone, and a copolymerization of the polyester obtained by these reactions. Be done.
• the diol compound used as a raw material for this polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane.
• dicarboxylic acid used as a raw material for the polyester polyol examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4.
• hydroxycarboxylic acid used as a raw material for the polyester polyol examples include p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid.
• polycarbonate polyol for example, one obtained by reacting a carbonic acid ester with a low molecular weight polyol, preferably a linear aliphatic diol, can be used.
• carbonic acid ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.
• Examples of the low molecular weight polyol capable of reacting with the carbonic acid ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, and 1 , 3-Butandiol, 1,2-Butandiol, 2,3-Butandiol, 1,5-Pentanediol, 1,5-Hexanediol, 2,5-Hexanediol, 1,6-Hexanediol, 1, 7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4 -Relatively low molecular weight dihydroxy compounds such as cycl
• the polycarbonate structure is preferably used in the range of 10% by mass to 90% by mass with respect to the total mass of the polyol used for producing the polycarbonate-based urethane resin and the polyisocyanate.
• the urethane resin has a hydrophilic group in order to impart dispersion stability in the water-based liquid printing ink.
• a hydrophilic group an anionic group, a cationic group, or a nonionic group can be generally used, but it is preferable to use an anionic group or a cationic group.
• anionic group for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used, and among them, a carboxylate group partially or wholly neutralized with a basic compound or the like can be used. It is preferable to use a sulfonate group in order to maintain good water dispersibility.
• Examples of the basic compound that can be used to neutralize the carboxyl group and the sulfonic acid group as the anionic group include organic amines such as ammonia, triethylamine, pyridine and morpholine, alkanolamines such as monoethanolamine, and Na. Examples thereof include metal base compounds containing K, Li, Ca and the like.
• a tertiary amino group or the like can be used as the cationic group.
• the acid that can be used to neutralize a part or all of the tertiary amino group formic acid, acetic acid and the like can be used, for example.
• the quaternizing agent that can be used when partially or all of the tertiary amino group is quaternized for example, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate can be used.
• the nonionic group includes, for example, a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group.
• a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group.
• a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group.
• the presence of 0.5% by mass to 30% by mass of the hydrophilic group with respect to the entire urethane resin imparts even better water dispersibility, and is in the range of 1% by mass to 20% by mass. More preferred.
• cross-linking agent described later can be used depending on the desired physical properties.
• the cross-linking agent it is preferable to use the urethane resin having a functional group capable of cross-linking with the functional group of the cross-linking agent.
• Examples of the functional group include a carboxyl group and a carboxylate group that can be used as the hydrophilic group.
• the carboxyl groups and the like contribute to the water dispersion stability of the urethane resin in an aqueous medium, and when they undergo a cross-linking reaction, they also act as the functional groups and can partially carry out a cross-linking reaction of the cross-linking agent.
• the urethane resin When a carboxyl group or the like is used as the functional group, the urethane resin preferably has an acid value of 2 to 55, and it is preferable to use a urethane resin having an acid value of 15 to 50. It is preferable to improve the above.
• the acid value referred to in the present invention is a theoretical value calculated based on the amount of the acid group-containing compound such as the carboxyl group-containing polyol used in the production of the urethane resin.
• the urethane resin can be produced, for example, by reacting a polyol, a polyisocyanate, and a chain extender, if necessary.
• chain extender polyamines, other active hydrogen atom-containing compounds, and the like can be used.
• polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 3,3'-.
• Diamines such as dimethyl-4,4'-dicyclohexamethylenediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; dihydrazide succinate, dihydrazide adipate, dihydrazide glutarate, sebacic acid Dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide propionate hydrazide, 3-semicarbazid-propyl-carbazic acid ester, semicarbazid-3-semicarbazidemethyl-3
• Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and neo.
• Glycos such as pentyl glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone Diols such as, water, etc. can be used.
• the equivalent of the amino group and the active hydrogen atom-containing group of the chain extender is the equivalent of the isocyanate group of the urethane prepolymer obtained by reacting the polyol with polyisocyanate. It is preferably used in the range of 1.9 or less (equivalent ratio), more preferably in the range of 0.0 to 1.0 (equivalent ratio), and more preferably 0.5% by mass.
• the chain extender can be used when reacting the polyol with polyisocyanate or after the reaction. Further, the chain extender can also be used when the urethane resin obtained above is dispersed in an aqueous medium to make it aqueous.
• polyols other than the above include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1, , 6-Hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol , Bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol and other relatively low molecular weight polyols. These polyols can be used alone or in combination
• polyisocyanate that reacts with the polyol to form a urethane resin examples include aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexanediisocyanate, isophorone diisocyanate, and dicyclohexylmethane.
• aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexanediisocyanate, isophorone diisocyanate, and dicyclohexylmethane.
• Aliphatic or aliphatic cyclic structure-containing diisocyanates such as diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used alone or in combination of two or more.
• the copolymer functions as a binder resin.
• the binder resin is preferably 5 to 50% by mass in terms of solid content of the water-based liquid printing ink of the present invention. When it is 5% by mass or more, the strength of the ink coating film does not decrease, and good substrate adhesion, water friction resistance, and the like are maintained. On the contrary, when it is 50% by mass or less, the decrease in coloring power can be suppressed, the high viscosity can be avoided, and the workability does not decrease. Of these, 10 to 40% by mass is still more preferable, and 15 to 35% by mass is most preferable. Further, the copolymer is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, in terms of solid content in the total binder resin.
• the liquid printing ink used in the present invention contains a colorant.
• the colorant include dyes, inorganic pigments, and organic pigments used in general inks, paints, recording agents, and the like. Of these, pigments such as inorganic pigments and organic pigments are preferable.
• Organic pigments include soluble azo, insoluble azo, azo, phthalocyanine, halogenated phthalocyanine, anthraquinone, anthraquinone, dianthraquinone, anthrapyrimidine, perylene, perinone, and quinacridone.
• Pigments such as thioindigo-based, dioxazine-based, isoindolinone-based, quinophthalone-based, azomethine-azo-based, flavanthlon-based, diketopyrrolopyrrole-based, isoindoline-based, indanslon-based, and carbon black-based pigments can be mentioned.
• Carmin 6B Lake Red C, Permanent Red 2B, Disazo Yellow, Pyrazolone Orange
• Carmin FB Chromophtal Yellow, Chromophtal Red, Phthalocyanine Blue, Phthalocyanine Green, Dioxazine Violet, Quinacridone Magenta, Quinacridone Red, Indance.
• Examples thereof include lonblue, pyrimidine yellow, thioindigo bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, and daylight fluorescent pigment. Further, both unacidified treated pigments and acidic treated pigments can be used. Specific examples of preferable organic pigments are given below.
• black pigments examples include C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7, C.I. I. Pigment Black 9, C.I. I. Pigment Black 20 and the like.
• Examples of the indigo pigment include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 5, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17: 1, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 24: 1, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 61, C.I. I.
• Pigment Blue 62 C.I. I. Pigment Blue 63, C.I. I. Pigment Blue 64, C.I. I. Pigment Blue 75, C.I. I. Pigment Blue 79, C.I. I. Pigment Blue 80 and the like.
• green pigments examples include C.I. I. Pigment Green 1, C.I. I. Pigment Green 4, C.I. I. Pigment Green 7, C.I. I. Pigment Green 8, C.I. I. Pigment Green 10, C.I. I. Pigment Green 36 and the like.
• red pigment examples include C.I. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 10, C.I. I. Pigment Red 11, C.I. I. Pigment Red 12, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 18, C.I. I. Pigment Red 19, C.I. I. Pigment Red 20, C.I. I.
• Pigment Red 112 C.I. I. Pigment Red 114, C.I. I. Pigment Red 119, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 136, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 149, C.I. I. Pigment Red 150, C.I. I. Pigment Red 164, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 169, C.I. I. Pigment Red 170, C.I. I.
• Pigment Red 220 C.I. I. Pigment Red 221 and C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I. I. Pigment Red 226, C.I. I. Pigment Red 237, C.I. I. Pigment Red 238, C.I. I. Pigment Red 239, C.I. I. Pigment Red 240, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 247, C.I. I. Pigment Red 248, C.I. I. Pigment Red 251 and C.I. I. Pigment Red 253, C.I. I. Pigment Red 254, C.I. I.
• Examples of purple pigments include C.I. I. Pigment Violet 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3: 1, C.I. I. Pigment Violet 3: 3, C.I. I. Pigment Violet 5: 1, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 19 ( ⁇ type, ⁇ type), C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 31, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 38, C.I. I. Pigment Violet 42, C.I. I. Pigment Violet 50 and the like.
• yellow pigment examples include C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, Pigment Yellow 17, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 42, C.I. I. Pigment Yellow 55, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 65, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I.
• Pigment Yellow 109 C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 120, Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 137, C.I. I. Pigment, Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I.
• Pigment Yellow 155 C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 213 and the like.
• orange pigment examples include C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 37, C.I. I. Pigment O Orange 38, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment range 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 71, or C.I. I. Pigment Orange 74 and the like.
• brown pigments examples include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, or C.I. I. Pigment Brown 26 and the like.
• C.I. I. Pigment Black 7 As an indigo pigment, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, As a green pigment, C.I. I. Pigment Green 7, As a red pigment, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 146, C.I.
• inorganic pigments examples include white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum.
• white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, silica, lithobon, antimony white, and gypsum.
• titanium oxide has a white color and is preferable from the viewpoints of coloring power, hiding power, chemical resistance and weather resistance, and from the viewpoint of printing performance, the titanium oxide is preferably treated with silica and / or alumina.
• non-white inorganic pigments examples include aluminum particles, mica (mica), bronze powder, chrome vermilion, chrome yellow, cadmium yellow, cadmium red, ultramarine, dark blue, red iron oxide, yellow iron oxide, iron black, and zircon.
• aluminum is in the form of powder or paste, it is preferably used in the form of paste from the viewpoint of handleability and safety, and whether chrome yellow or non-leafing is used is appropriately selected from the viewpoint of brightness and density.
• the average particle size of the pigment is preferably in the range of 10 to 200 nm, more preferably about 50 to 150 nm.
• the pigment is contained in the ink in an amount sufficient to secure the concentration and coloring power of the liquid printing ink used in the present invention, that is, 1 to 60% by weight based on the total weight of the liquid printing ink used in the present invention. In terms of solid content weight ratio, it is preferably contained in a ratio of 10 to 90% by weight.
• these pigments can be used alone or in combination of two or more. Further, the pigment can be dispersed in advance with a commercially available pigment dispersant and used as a high-concentration pigment dispersion for adjusting the ink.
• a surfactant in the liquid printing ink used in the present invention, a surfactant can be added depending on the desired physical characteristics.
• a general-purpose surfactant can be used in the present technical field without particular limitation, and among them, an acetylene-based surfactant and an alcohol alkoxylate-based surfactant are preferable.
• acetylene-based surfactant used in the present invention 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2, 4,7,9-Tetramethyl-5-decine-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1 -Pentyne-3-ol, 3-hexyne-2,5-diol, 2-butyne-1,4-diol and the like can be mentioned.
• Commercially available products include alkylene oxide-non-modified acetylene glycol-based surfactants such as Surfinol 61, 82, 104 (all manufactured by Air Products & Chemicals).
• 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 manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol EH, E40, E60, E81, E100, E200 (all manufactured by Kawaken Fine Chemical Co., Ltd.) and other alkylene oxide-modified acetylenes. Glycol-based surfactants and the like can be mentioned.
• an alkylene oxide-modified acetylene glycol-based surfactant is preferable.
• the alcohol alkoxylate-based surfactant used in the present invention DYNWET800 (manufactured by Big Chemie Japan) can be mentioned.
• These acetylene-based surfactants and alcohol alkoxylate-based surfactants may be used alone or in combination of two or more.
• the total amount of these acetylene-based surfactants and / or alcohol alkoxylate-based surfactants added is preferably 0.1 to 1% by mass of the total amount of the ink.
• acetylene-based surfactants may be used alone or in combination of two or more, and the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is the total amount. When it is 0.1% by mass or more of the total amount of ink, the coatability with the base material is improved and the adhesion with the base material can be maintained. If the total amount of the acetylene-based surfactant and / or the alcohol alkoxylate-based surfactant added is 1% by mass or less of the total amount of the ink, the abrasion resistance, the water abrasion resistance, and the scratch resistance may decrease. Absent.
• the total amount of the surfactant used is preferably 0.1 to 1% by mass of the total amount of the ink.
• wax in the present invention, wax can be added according to desired physical properties.
• the wax is preferably a carbon-based wax, and the carbon wax is liquid paraffin, natural paraffin, synthetic paraffin, microcrystallin wax, polyethylene wax, fluorocarbon wax, ethylene-propylene copolymer wax, tetrafluoroethylene resin wax, Fisher. Examples include tropsch wax. These waxes may be used alone or in combination of two or more, and the total amount of these waxes added is preferably 0.5 to 5% by mass of the total amount of the ink. When the total amount of wax added is 0.5% by mass or more of the total amount of ink, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained. When the total amount of wax added is 5% by mass or less of the total amount of ink, adhesion to the substrate, abrasion resistance, water abrasion resistance, and scratch resistance can be maintained.
• a curing agent can be added according to desired physical properties.
• the curing agent capable of reacting with the acid used in the present invention is not particularly limited, and a known curing agent capable of reacting with an acid group that can be used in an aqueous medium can be used.
• a known curing agent capable of reacting with an acid group that can be used in an aqueous medium can be used.
• an epoxy-based curing agent, a carbodiimide-based curing agent, an oxazoline-based curing agent, and the like can be mentioned.
• the epoxy-based curing agent is not particularly limited as long as it is a compound having at least one epoxy group.
• examples of the epoxy-based curing agent include epoxy resins such as bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolak glycidyl ether, glycerin polyglycidyl ether, and polyglycerin polyglycidyl ether.
• a polycarbodiimide compound having at least two or more carbodiimide groups is preferable.
• the oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
• Specific examples of the oxazoline-based curing agent include the Epocross series manufactured by Nippon Shokubai Co., Ltd.
• Examples of the epoxy compound include bisphenol A diglycidyl ether and its oligomer, hydride bisphenol A diglycidyl ether and its oligomer, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid.
• Diglycidyl ester tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipate diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , 1,4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol diglycidyl ethers, trimeric acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, Examples thereof include diglycidyl propylene urea, glycerol triglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl
• the amount of the curing agent added in the present invention is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 9.0% by mass in terms of solid content of the total amount of ink. If the amount added is 0.1% by mass or more, the effect as a curing agent can be obtained, while if it is 10.0% by mass or less, the substrate adhesion, abrasion resistance, and water friction resistance tend to be maintained. Become.
• the present invention may also include extender pigments, pigment dispersants, leveling agents, defoamers, plasticizers, infrared absorbers, ultraviolet absorbers, fragrances, flame retardants and the like.
• extender pigments such as oleic acid amide, stearic acid amide, and erucic acid amide for imparting abrasion resistance and slipperiness
• silicon-based and non-silicon-based defoamers and pigments for suppressing foaming during printing.
• Various dispersants and the like that improve the wetting of oleic acid are useful.
• a mixture to which a pigment, an aqueous medium, a dispersant, an antifoaming agent and the like are added in advance is dispersed by a disperser to obtain a pigment dispersion. It can be obtained by adding an additive such as the copolymer, an aqueous medium, and if necessary, a leveling agent to the obtained pigment dispersion, and stirring and mixing the mixture.
• a disperser it is manufactured by using a bead mill, an Eiger mill, a sand mill, a gamma mill, an attritor or the like which are generally used for manufacturing gravure and flexographic printing inks.
• liquid printing ink of the present invention When the liquid printing ink of the present invention is used as a water-based flexographic printing ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 4 manufactured by Rigo Co., Ltd., more preferably 10 to 20 seconds. Is.
• the surface tension of the obtained flexographic ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m. The lower the surface tension of the ink, the better the wettability of the ink to the substrate such as a film. However, when the surface tension is less than 25 mN / m, the ink spreads and the halftone dots adjacent to each other are adjacent to each other.
• the liquid printing ink used in the present invention When the liquid printing ink used in the present invention is used as a water-based gravure printing ink, its viscosity may be 7 to 25 seconds at 25 ° C. using Zahn Cup # 3 manufactured by Rigo Co., Ltd., more preferably 10 to 10 to 20 seconds.
• the surface tension of the obtained gravure ink at 25 ° C. is preferably 25 to 50 mN / m, more preferably 33 to 43 mN / m, as in flexographic ink.
• the lower the surface tension of the ink the better the wettability of the ink to the substrate such as a film. However, when the surface tension is less than 25 mN / m, the ink spreads and the halftone dots are adjacent to each other.
• the liquid printing ink is printed on the polyolefin film, and a printed matter is obtained by providing a printing layer.
• a printing layer is obtained by applying ink to a base material using a gravure method or a flexographic printing method, drying the ink by drying in an oven, and fixing the ink.
• the drying temperature is usually about 40 to 60 ° C.
• Flexographic printing is a type of letterpress printing, in which a rubber plate is mainly used as a printing plate (letter plate), and a fine mesh engraving roll called anilox roll is used for a portion that supplies ink to the printing plate.
• the anilox roll receives ink from the chamber type doctor and applies ink on the printing plate, and has an advantage that the ink can be uniformly transferred to the printing plate through the anilox roll.
• ink is applied to the surface of the bulkhead and the anilox roll having many openings surrounded by the bulkhead, and the doctor is pressed against the surface of the anilox roll to scrape off the ink existing on the top surface of the bulkhead of the anilox roll. , Fill the recesses, which are the openings, with ink. Subsequently, the flexographic plate is pressed against the anilox roll to transfer the ink existing in the concave portion of the anilox roll to the convex portion (pattern portion) of the printing plate, and then the plate is brought into contact with the base material and exists in the pattern portion of the plate. The ink to be used is transferred to a substrate to obtain a printed matter.
• a rotary printing method may be combined. For example, in a method for manufacturing a plastic film rotary printed matter, rotary printing is performed on the surface of a wound plastic film using a water-based liquid printing ink. After printing, processes such as laminating, slitting (cutting unnecessary parts in the width portion), and bag making (cutting and heat-sealing to make a bag) can be performed. High-speed printing is possible and productivity is excellent by winding the liquid printing ink and rotating it on a plastic film.
• the rotary printing includes gravure rotary printing and flexographic rotary printing, and either method may be used. However, in the present application, it is preferable to print the water-based liquid printing ink by using the flexographic printing method as described above. Rotational printing will be described in detail. In the present specification, the rotary printing means gravure rotary printing and flexographic rotary printing, and does not include ink jet printing and silk screen printing, which are other printing methods.
• ink is supplied directly from a container for storing liquid printing ink or via an ink supply pump or the like to an Anilox roller having an uneven shape on the surface, and the ink supplied to the Anilox roller is used on the plate surface.
• the contact with the convex portion transfers to the plate surface, and the contact between the plate surface and the plastic film finally transfers to the plastic film to form a pattern and / or characters.
• the ink drying property is slightly inferior to that of the solvent-based flexographic printing ink, so that the ink film thickness is preferably as thin as possible. From this point of view, it is preferable that the amount of ink supplied to the Aronix roller is as small as possible.
• the print density tends to decrease as the film thickness decreases, so the pigment density of the water-based flexographic printing ink used may be appropriately controlled. Specifically, when the pigment concentration of the water-based flexographic printing ink is 1 to 5% by weight more than the concentration of the solvent-type flexographic printing ink, an appropriate printing density can be obtained.
• the take-up plastic film is a roll-shaped plastic film having a predetermined width, and is a film for rotary printing, which is different from a sheet of paper in which each sheet is separated in advance.
• the width of the film is appropriately selected based on the plate width of the rotary printing press to be used and the width of the image (picture) portion of the gravure plate.
• the printing order thereof is not particularly limited.
• the base material is white, that is, for example, a paper base material and a plastic film kneaded with a white pigment, printing with only color ink is possible if necessary.
• the color ink When performing back printing, it is common to print the color ink on the take-up plastic film first, and then print the white ink.
• the color ink has a plurality of colors, for example, black, cyan, magenta, and yellow can be printed in this order, but the printing is not particularly limited.
• special colors and the like can be used in addition to the basic colors. That is, the large-sized printing machine has a plurality of printing units corresponding to 5 to 10 colors, and one printing unit is provided with one color of ink and can perform overprinting of 5 to 10 colors at a time.
• the laminated laminate can be obtained by applying an anchor coating agent, an adhesive or the like to the printed surface of the rotary printed matter obtained by the above method, drying it if necessary, and then laminating it with a film or the like.
• the printed matter of the present invention is suitable for a so-called front print printed matter in which the printed layer is the outermost layer because the printed matter has high scratching property and adhesion, but there is no particular limitation on the method of use, and the printing is described above.
• the printed layer may be located on the outermost layer of the laminated body (so-called front printing), and printing is performed between the plurality of base materials. It may be a laminated body in which layers are located (so-called back printing).
• the water-based liquid printing ink of the present invention is an ink that can be applied to either configuration. Further, the structure may be such that a transparent overprint varnish is provided on the print layer.
• the laminate of the present invention may be a laminate that includes a printed matter printed with the printing ink used in the present invention on at least one surface of the polyolefin film used in the present invention by a printing method using a plate.
• a laminate in which the polyolefin film used in the present invention and another base material are bonded with an adhesive or the like can be mentioned.
• Examples of other base materials include paper, synthetic paper, thermoplastic resin film, steel plate, aluminum foil, wood, woven cloth, knitted cloth, non-woven fabric, gypsum board, wood board and the like. Of these, paper, synthetic paper, thermoplastic resin film and the like are preferable.
• thermoplastic resin film examples include general-purpose polyethylene films (LLDPE: low-density polyethylene film, MDPE: medium-density polyethylene, HDPE: high-density polyethylene film) and polypropylene films (CPP) other than the polyolefin film used in the present invention.
• LLDPE low-density polyethylene film
• MDPE medium-density polyethylene
• HDPE high-density polyethylene film
• CPP polypropylene films
• Non-stretched polypropylene film Non-stretched polypropylene film
• OPP Biaxially stretched polypropylene film
• PET polyethylene terephthalate
• PET polystyrene film
• polyamide film polyacrylonitrile film
• polyvinyl alcohol film ethylene-vinyl alcohol copolymer film
• etc. Can be mentioned. These may be stretched.
• a stretching treatment method it is common to melt-extrude the resin by an extrusion film forming method or the like to form a sheet, and then perform simultaneous biaxial stretching or sequential biaxial stretching. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching treatment and then lateral stretching. Specifically, a method of combining longitudinal stretching using the speed difference between rolls and transverse stretching using a tenter is often used. Further, a film obtained by laminating a vapor-deposited layer of a metal such as aluminum or stainless steel or a metal oxide such as silica or alumina may be used on the film for laminating.
• polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cyclic olefin resin, and polyimide which are widely used for industrial purposes.
• examples thereof include a film made of a resin, a polyvinyl fluoride resin, a vinylidene fluoride resin, an ethylene-vinyl acetate copolymer and the like.
• the thickness of the base film is not particularly limited, but usually it may be in the range of 1 to 500 ⁇ m.
• the adhesive is not particularly limited, and a general-purpose one-component adhesive, two-component adhesive, or the like can be used.
• printing layer A the printing layer used in the present invention
• polyolefin film A the polyolefin film used in the present invention
• Printing layer A / polyolefin film A / adhesive layer 1 / sealant film (2) Printing layer A / polyolefin film A / adhesive layer 1 / metal-deposited unstretched film (3) Printing layer A / polyolefin film A / adhesive layer 1 / Metal vapor deposition stretched film (4) Printing layer A / Polyethylene film A / Transparent vapor deposition stretching film / Adhesive layer 1 / Sealant film (5) Printing layer A / Polyethylene film A / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Sealant film (6) Printing layer A / Polyethylene film A / Adhesive layer 1 / Metal vapor deposition stretched film / Adhesive layer 2 / Sealant film (7) Printing layer A / Polyethylene film A / Adhesive layer 1 / Transparent vapor deposition stretched film / Adhesive layer 2 / sealant film (8) Printing layer A / polyolefin film A
• the sealant film examples include CPP film and LLDPE film.
• a metal-deposited unstretched film a VM-CPP film in which a metal such as aluminum is vapor-deposited on a CPP film is used, and as a metal-deposited stretched film, a VM-OPP film in which a metal such as aluminum is vapor-deposited on an OPP film is used.
• the transparent vapor-deposited stretched film include a film obtained by subjecting silica or alumina vapor deposition to an OPP film, PET film, nylon film or the like. A film coated on the vapor-deposited layer may be used for the purpose of protecting the inorganic vapor-deposited layer of silica or alumina.
• Examples of the base film 2 include a nylon film, a PET film, a polyvinylidene fluoride film, and the like.
• Examples of the metal layer include aluminum foil.
• a general-purpose coating agent may be applied on the print layer A.
• thermoplastic resin film is subjected to a corona discharge treatment.
• Silica, alumina, etc. may be vapor-deposited, or a gas barrier coat layer such as an oxygen gas barrier layer may be laminated.
• the base material When paper is used as the base material, it can be used as moisture-proof paper.
• the base paper include kraft paper, liner paper, art paper, coated paper, carton paper and the like.
• the structure of the synthetic paper is not particularly limited. Therefore, it may have a single-layer structure or a multi-layer structure.
• the multi-layer structure include a two-layer structure consisting of a base material layer and a surface layer, a three-layer structure in which the base material layer and the front and back surfaces are present, and another resin film layer between the base material layer and the surface layer.
• a multi-layer structure can be exemplified. Further, each layer may or may not contain an inorganic or organic filler. Further, a microporous synthetic paper having a large number of fine voids can also be used.
• LLDPE Linear low-density polyethylene film
• MDPE Medium density polyethylene film
• HDPE High-density polyethylene film
• CPP Non-stretched polypropylene film
• CPP is a non-stretched polypropylene film
• OPP is a biaxially stretched polypropylene film
• LLDPE is a low density polyethylene film
• MDPE is a medium density polyethylene film
• HDPE is a high density polyethylene film
• VMCPP is a film in which a metal such as aluminum is vapor-deposited on a CPP film.
• VMPET is a PET film on which a metal such as aluminum is vapor-deposited.
• EVA is ethylene vinyl alcohol
• AL represents aluminum foil.
• the printed matter or laminate of the present invention is mainly used as a packaging material.
• the (12) printing layer A / polyolefin film having the simplest structure such as a linear low-density polyethylene film (LLDPE) having a content concentration of the printing layer A / organic lubricant on a mass basis of 1200 ppm or less.
• LLDPE linear low-density polyethylene film
• the laminate having the configuration A is expected to be product-identifiable and lightweight, it can be used as various exterior materials such as foods, sanitary products, cosmetics, and industrial products such as electronic parts. In particular, it can be suitably used as an exterior packaging material for sanitary applications.
• its layer structure may change depending on the contents, usage environment, and usage pattern.
• the package of the present invention may be appropriately provided with an easy-opening process or a resealable means.
• the peripheral end portions thereof can be heat-sealed to form a bag shape to obtain a packaging material.
• the laminate of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type.
• the packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. Free-standing packaging materials (standing pouches), etc. are also possible.
• a heat sealing method a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
• the opening After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
• foods include rice confectionery, bean confectionery, nuts, biscuits / cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles.
• Non-food items include tobacco, disposable body warmers, medicines such as infusion packs, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, liquid conditioners, cosmetics such as lotions and emulsions, and vacuum. It can also be used as various packaging materials such as heat insulating materials and batteries.
• the weight average molecular weight (in terms of polystyrene) was measured by GPC (gel permeation chromatography) in the present invention using the HLC8220 system manufactured by Toso Co., Ltd. under the following conditions. Separation column: Uses 4 TSKgelGMH HR-N manufactured by Tosoh Corporation. Column temperature: 40 ° C. Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow velocity: 1.0 ml / min. Sample concentration: 1.0% by mass. Sample injection volume: 100 microliters. Detector: Differential refractometer.
• the acid value of the acrylic resin indicates the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin, and each dried water-soluble resin is titrated according to JIS K2501. It was calculated from potentiometric titration with a potassium / ethanol solution.
• the glass transition temperature (Tg) refers to the so-called calculated glass transition temperature, and refers to a value calculated by the following method.
• Equation 1 / Tg (K) (W1 / T1) + (W2 / T2) + ... (Wn / Tn)
• Tn the values described in Polymer Handbook (Fourth Edition, J. Brandrup, E.H. Immunogut, EA Grulke) are used.
• the glass transition temperature of the homopolymer of each monomer is not described in the Polymer Hand Book, the glass transition temperature is based on JIS K7121 using a differential scanning calorimeter "DSC Q-100" (manufactured by TA Instrument). It was measured by the method described above. Specifically, the polymer from which the solvent has been completely removed by vacuum suction is measured for a change in calorific value in the range of -100 ° C to + 200 ° C at a heating rate of 20 ° C./min, and an extended straight line of each baseline. The point where the straight line equidistant from the vertical axis direction and the curve of the stepwise change portion of the glass transition intersect was defined as the glass transition temperature.
• the mixture was cooled and neutralized by adding 3.6 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of acrylic resin A having a solid content of 50%.
• the acid value was 39 mgKOH / g, Tg was 70 ° C., and the weight average molecular weight was 8,200.
• the mixture was cooled and neutralized by adding 18.0 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of acrylic resin B having a solid content of 50%.
• the acid value was 195 mgKOH / g, Tg was 74 ° C., and the weight average molecular weight was 11,800.
• the mixture was cooled and neutralized by adding 43.2 parts of 30% aqueous ammonia to the obtained acrylic resin solution. Further, ion-exchanged water was added and solvent substitution was carried out while heating to obtain an aqueous solution of acrylic resin C having a solid content of 50%.
• the acid value was 467 mgKOH / g, Tg was 72 ° C., and the weight average molecular weight was 11,800.
• A1 aqueous solution having a solid content of 40%.
• the acid value was 20 mgKOH / g
• Tg was 20 ° C.
• the weight average molecular weight was 1,200,000.
• PIGMENT BLUE 15 3 indigo pigment (manufactured by Sunchemical) 45 parts, alkali-soluble pigment dispersion water-soluble resin (ammonia neutralization, solid content 30%) 19 parts, pigment dispersant 2 parts, propylene glycol 2 parts, and water After stirring and mixing 32 parts of the mixture, the mixture was kneaded with a bead mill to prepare an indigo pigment dispersion.
• Adjustment example 3 Manufacture of acrylic indigo ink 2
• Acrylic indigo ink 2 was prepared by the same procedure. It was confirmed that the viscosity of the obtained acrylic indigo ink 2 was 20 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
• Adjustment example 4 Manufacture of acrylic indigo ink 3
• Acrylic indigo ink 3 was prepared by the same procedure. It was confirmed that the viscosity of the obtained acrylic indigo ink 3 was 19 seconds (25 ° C.) with Zahn Cup # 4 (manufactured by Rigosha).
• Table 1 shows an example of adjusting each ink.
• Evaluation film As a film for printing the liquid printing ink, a non-stretched polypropylene film (CPP1-3) and a low density polyethylene film (LDPE1-3) were used. Table 2 below shows the thickness of each film, the mass-based content concentration of the organic lubricant (erucic acid amide) in the film, the wetting index of the printed surface surface, and the friction coefficient of the printed surface surface.
• CPP1-3 non-stretched polypropylene film
• LDPE1-3 low density polyethylene film
• the ink using the composition of the present invention is excellent in printability (transferability) and adhesion to a polyolefin film. Further, the polyolefin film having a friction coefficient limited in the present invention has processing suitability for sanitary use packaging.

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