WO2015056591A1 - Coating liquid, article using same, and printed matter - Google Patents

Abstract

The present invention provides: a coating liquid having superior storage stability and that obtains a metallic coating film that is uniform and has no grainy sensation; an article coated using the coating liquid; and printed matter that has been printed by means of a printing method that has plates or is plateless using the coating liquid. The coating liquid is characterized by containing a polythiophene represented by general formula (1). (In the formula, R¹ represents a hydrogen atom, an alkoxy group, an amino group, or a hydroxyl group, R² represents an alkoxy group, an amino group, or a hydroxyl group, and n represents an integer from 3 to 100.)

Description

Coating liquid, articles and printed matter using the same

The present invention provides a coating solution having a uniform metallic-tone coating film without graininess using an organic compound and having excellent storage stability, an article coated with the coating solution, and the coating The present invention relates to a printed matter that is printed using a liquid in a plate or non-plate printing system.

In recent years, metallic pigments such as aluminum flakes, bronze flakes, mica flakes, mica-like iron oxides, mica-like iron oxides coated with metal oxides, mica flakes coated with metal oxides have been blended to improve the design of articles. Using the metallic paint, the appearance of the article is painted metallic. Since the metallic pigment used for producing the metallic tone is a particle, a metallic tone design can be obtained, but there is a problem that it is difficult to obtain a non-granular material such as metal plating. In addition, since the metallic pigment settles due to the difference in specific gravity with other components in the metallic paint, there is a problem in storage stability, and the metallic pigment aggregates in the metallic paint and the metallic feeling is lowered.

In addition, metallic gravure ink is used for gravure printing of metallic characters and patterns on packages such as food packaging (see, for example, Patent Document 1). This metallic gravure ink also has the same problems as the metallic paint because it contains a metallic pigment.

On the other hand, metallic ink-jet ink and ink-jet printing are used to print metallic characters and designs (for example, see Patent Document 2). However, since ink jet printing is a method in which ink is ejected from nozzles and adheres to a printing material, when metallic pigments aggregate in the ink, there is a problem that causes nozzle clogging.

Accordingly, there has been a demand for a coating liquid that can provide a uniform metallic-tone coating film without graininess, has excellent storage stability, and can be used for metallic paints, metallic gravure inks, metallic inkjet inks, and the like.

Japanese Patent Laid-Open No. 2-8268 JP 2007-46034 A

The problem to be solved by the present invention is that a uniform metallic-tone coating film without graininess is obtained, and an excellent coating stability, an article coated with the coating liquid, and the coating An object of the present invention is to provide a printed matter printed by a plate or non-plate printing method using a working liquid.

As a result of diligent research to solve the above problems, the present inventors have used a polythiophene having a specific substituent on the thiophene ring as a coloring material that exhibits a metallic luster, thereby providing a coating solution having excellent storage stability. The obtained article coated with the coating liquid and the printed matter printed with the coating liquid using the plate or non-plate printing method can obtain a uniform metallic tone coating film without graininess. As a result, the present invention has been completed.

That is, this invention uses the coating liquid characterized by containing the polythiophene represented by following General formula (1), the article coated using this coating liquid, and this coating liquid. The present invention provides a printed matter printed with a plate or non-plate printing method.

(Wherein R ¹ represents a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, R ² represents an alkoxy group, an amino group or a hydroxyl group. N represents an integer of 3 to 100)

Since the coating liquid of the present invention uses polythiophene, which is an organic compound, without using a metallic pigment as a material that develops a metallic tone, it is included in paints when used in paints, gravure inks, inkjet inks, etc. Since the specific gravity difference with other components is smaller than that of metallic pigments, it has excellent storage stability without settling. In addition, since the polythiophene used in the present invention is in a dissolved state regardless of whether it is solvent-based or water-based, it is not a metallic tone having a granular feeling like a metallic pigment, but is uniform such as metal plating. A metallic paint film can be obtained. Furthermore, since it does not agglomerate like a metallic pigment, the metallic tone of the resulting coating film does not deteriorate over time, and when used as an inkjet ink for inkjet printing, nozzle clogging may occur. Absent.

Since it has the above features, the coating liquid of the present invention can be suitably used as metallic paint, metallic gravure ink, metallic inkjet ink and the like.

The coating liquid of the present invention contains a polythiophene represented by the following general formula (1) (hereinafter abbreviated as “substituted polythiophene (1)”).

(Wherein R ¹ represents a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, R ² represents an alkoxy group, an amino group or a hydroxyl group. N represents an integer of 3 to 100)

Incidentally, ^{R 1} and ^{R 2} in the general formula (1) are in relation interchanged when the repeating units to rotate 180 degrees included in the general formula (1), substituted polythiophenes (1), ^{R 1} and R ² may include a repeating unit having an arrangement in which the arrangement shown in the formula (1) is replaced with each other. That is, the substituted polythiophene (1) may have the same positional relationship between R ¹ and R ² in all the repeating units, or in the general formula (1) in at least one repeating unit appropriately selected. The positions of R ¹ and R ² shown may be reversed.

The substituted polythiophene is a polymer in which two or more molecules of a substituted thiophene compound represented by the following general formula (2) (hereinafter abbreviated as “substituted thiophene compound (2)”) are bonded to each other.

(In the formula, R ¹ represents a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, and R ² represents an alkoxy group, an amino group or a hydroxyl group.)

In the substituted thiophene compound (2), R ¹ is a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, and R ² is an alkoxy group, an amino group or a hydroxyl group, but R ¹ is preferably a hydrogen atom. , R ² is preferably an alkoxy group. In synthesizing the substituted polythiophene (1), the substituted thiophene compound (2) as a raw material thereof can be used alone or in combination of two or more.

In the substituted thiophene compound (2), when either R ¹ or R ² or both are alkoxy groups, the alkyl chain preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of the substituted thiophene compound (2) having an alkoxy group include 3-methoxythiophene, 3-ethoxythiophene, 3-propoxythiophene, 3-isopropoxythiophene, 3-butoxythiophene, 3,4-dimethoxythiophene, 3 , 4-diethoxythiophene, 3-methoxy-4-ethoxythiophene, 3,4-dipropoxythiophene and the like.

In the substituted thiophene compound (2), when either R ¹ or R ² or both are amino groups, specific examples of the substituted thiophene compound (2) include 3-aminothiophene, 3,4-diaminothiophene, 3- (N-methylamino) thiophene, 3- (N, N-dimethylamino) thiophene, 3- (N-ethylamino) thiophene, 3- (N, N-diethylamino) thiophene, 3- (N, N- Propylamino) thiophene, 3- (N, N-dibutylamino) thiophene, 3,4-bis (N, N-dimethylamino) thiophene, 3,4-bis (N, N-diethylamino) thiophene and the like.

In the substituted thiophene compound (2), when R ¹ is other than a hydrogen atom and the types of substituents of R ¹ and R ² are different, specific examples of the substituted thiophene compound (2) include 3-amino-4-methyl Examples include thiophene, 3-amino-4-hydroxythiophene, 3-methyl-4-hydroxythiophene, 3-methoxy-4-aminothiophene, 3-methoxy-4-methylthiophene, 3-methoxy-4-hydroxythiophene, etc. .

N in the general formula (1) representing the substituted polythiophene (1) represents the number of repeating units having the substituted thiophene compound (2) as a unit, and the range thereof is 3 to 100. In order to obtain a more excellent metallic-tone coating film, the number of repeating units n is preferably in the range of 3-40.

The substituted polythiophene (1) can be produced by a chemical polymerization method or an electrolytic polymerization method using the substituted thiophene compound (2) as a raw material. The “chemical polymerization method” in the present invention is a method in which a substituted thiophene compound (2) and an oxidizing agent are added in the presence of a solvent, and polymerization is carried out in the liquid phase, the solid phase, the interface between the liquid phase and the solid phase, or both phases. Say the method. The “electrolytic polymerization method” is a method in which a substituted thiophene compound (2) and an electrolyte are added in the presence of a solvent, platinum, gold, or the like is used as an anode, platinum, nickel, or the like is used as a cathode. It is a method in which polymerization is performed on an electrode by inserting it into the electrode and applying a voltage to the electrolyte.

The oxidant used in the chemical polymerization method and the electrolyte used in the electrolytic polymerization method can be the same, and various metal salts can be used. Examples of the metal salt include titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, tantalum, Tungsten, rhenium, osmium, iridium, platinum, cerium, neodymium and other metal fluoride salts, chloride salts, bromide salts, iodide salts, ammonium salts, sulfates, hypochlorites, chlorates, perchlorates Acid salt, permanganate, chromate, dichromate, phosphate, citrate, tartrate, oxalate, paratoluenesulfonate, hexafluorophosphate, tetrafluoroborate, etc. Can be mentioned. Among these, iron (III) perchlorate and iron (III) chloride are preferable.

In the production of the substituted polythiophene (1), an oxidizing agent used in the chemical polymerization method or an anion derived from the electrolyte used in the electrolytic polymerization method may be introduced into the polythiophene skeleton as a dopant. This dopant interacts and stabilizes with a cation site in the polythiophene skeleton, and when the coating liquid of the present invention is applied and printed, the molecular orientation of the substituted polythiophene (1) is promoted on the coating film surface, It becomes easier to obtain a metallic paint film. Thus, it is preferable that the coating liquid of this invention is what doped the anion with respect to substituted polythiophene (1).

The solvent used in the chemical polymerization method is preferably one in which the substituted thiophene compound (2) is sufficiently dissolved, and the solvent used in the electrolytic polymerization method is preferably one in which the substituted thiophene compound (2) and the electrolyte are sufficiently dissolved. Further, since the polymerization reaction proceeds on the surface of the oxidant even in a state where the oxidant is not sufficiently dissolved, the solvent used in the chemical polymerization method may not be a solvent in which the oxidant is sufficiently dissolved. Those that are sufficiently soluble are preferred. Specific examples of the solvent used in the chemical polymerization method and the electrolytic polymerization method include methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate, normal propyl acetate, hexane, heptane, toluene, xylene, cyclohexanone, dichloromethane, chloroform, carbon tetrachloride, Examples include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, acetonitrile, nitromethane, γ-butyrolactone, and propylene carbonate. These solvents can be used alone or in combination of two or more.

In addition, the amount of the substituted thiophene compound (2) and the oxidizing agent used in the chemical polymerization method and the amount of the substituted thiophene compound (2) and the electrolyte used in the electrolytic polymerization method are further promoted in the molecular orientation of the substituted polythiophene (1). Since it becomes easier to obtain a metallic-tone coating film, the oxidizing agent or the electrolyte is preferably in the range of 0.25 to 15 mol, more preferably in the range of 0.5 to 10 mol, relative to 1 mol of the substituted thiophene compound (2). preferable.

The substituted polythiophene (1) obtained by the above chemical polymerization method or electrolytic polymerization method is obtained by precipitation in the reaction solution as a colored solid. The precipitated substituted polythiophene (1) is obtained by filtration and washing, and then recovered through a drying process such as drying under reduced pressure. The obtained substituted polythiophene (1) is dissolved in a solvent according to the characteristics (for example, drying speed, environment / toxicity to human body) required for each application such as paint, gravure ink, inkjet ink, etc. A coating solution is obtained.

The coating liquid of the present invention preferably contains 0.05 to 15% by mass of the substituted polythiophene (1). Although the coating liquid of this invention is suitably prepared according to the characteristic calculated | required for every use, the effect of this invention is fully acquired in said range.

When the coating liquid of the present invention is used as a metallic paint, the composition of each component in the metallic paint is, for example, 0.25 to 15 parts by weight of substituted polythiophene (1), 10 to 50 parts by weight of vehicle, and 50 to 90 parts of solvent. What consists of 5 mass parts or less of other mass parts and other additives is mentioned.

Examples of the vehicle include acrylic resin, epoxy resin, polysiloxane resin, maleic acid resin, vinyl resin, polyamide resin, nitrocellulose, cellulose acetate, ethyl cellulose, ethylene-vinyl acetate copolymer, urethane resin, polyester resin, alkyd. Examples thereof include resins. These vehicles can be used alone or in combination of two or more. Here, the coating liquid of the present invention uses a substituted polythiophene (1) having no self-film forming property instead of using a metallic pigment that requires a vehicle to form a coating film in order to obtain a metallic coating film. The vehicle is not always necessary. When no vehicle is used, the composition of each component in the metallic paint is, for example, 0.25 to 10 parts by weight of substituted polythiophene (1), 90 to 99.5 parts by weight of solvent, and 5 parts by weight or less of other additives. What is done.

Examples of the solvent include water; alcohol solvents such as ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert-butanol; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; methyl acetate, acetic acid Ethyl, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, methyl 2-methoxypropionate, 2 -Ester solvents such as ethyl methoxypropionate, propyl 2-methoxypropionate and butyl 2-methoxypropionate; aprotic such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, acetonitrile Polar solvents; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol-n-propyl ether, propylene glycol-n-butyl ether, propylene glycol monomethyl ether acetate Propylene glycol such as propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate and ester compounds thereof; diglyme solvents such as diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether; halogen solvents such as trichloroethane and chloroform; cyclics such as tetrahydrofuran and dioxane Ether solvent; Zen, toluene, aromatic solvents xylene. These solvents can be used alone or in combination of two or more.

Examples of the other additives include pigment dispersants, antifoaming agents, thickeners, leveling agents, ultraviolet absorbers, light stabilizers, antibacterial agents, antifungal agents, preservatives, and waxes. These additives can be used alone or in combination of two or more.

Examples of the coating method when the coating liquid of the present invention is used as a metallic paint include a roll coater, a comma coater, a knife coater, a curtain coater, a shower coater, a spin coater, dipping, screen printing, a spray, an applicator, and a bar coater. Etc. The coating liquid of the present invention is preferably diluted with the solvent in order to obtain an appropriate viscosity corresponding to these coating methods.

The article of the present invention has a coating film formed from the coating liquid of the present invention on a base material, but the base material of the article when the coating liquid of the present invention is used as a metallic paint is a plastic. A base material, a metal base material, a glass base material, various building materials, a rubber base material, etc. are mentioned.

The resin used as the material for the plastic substrate may be a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer, polymethyl methacrylate, polyvinyl alcohol, polyvinylidene chloride, General-purpose plastics such as polyethylene terephthalate; Engineering plastics such as polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultrahigh molecular weight polyethylene (U-PE), polyvinylidene fluoride; polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate , Polyamideimide, polyetherimide, polyetheretherketone, polyimide, liquid crystal polymer, Such as super engineering plastics such as Li and polytetrafluoroethylene. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, unsaturated polyester, epoxy resin, silicone resin, polyurethane resin, and the like. The shape of the plastic base material made of these resins may be a molded one, a film or a sheet.

Examples of the metal substrate include rolled steel, hot rolled mild steel, cold rolled steel, hot dip galvanized steel, tinplate, electrogalvanized steel, chrome molybdenum steel, cold rolled stainless steel, carbon tool steel. High carbon chromium bearing steel, copper plate, phosphor bronze plate, aluminum alloy plate, magnesium alloy plate, nickel alloy plate, titanium alloy plate and the like.

Examples of the glass substrate include float plate glass. Moreover, as said various building materials, a slate board, a calcium silicate board, a slag gypsum board, a mortar board etc. are mentioned, for example.

Examples of the material of the rubber base include butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene, ethylene / propylene diene rubber, fluoro rubber, butyl rubber, natural rubber, silicone rubber, urethane rubber, and the like. The shape of these rubber substrates may be a molded one or a film or a sheet.

When the substrate of the article of the present invention is a plastic substrate or a metal substrate, in order to improve the adhesion of the coating film of the coating liquid of the present invention to the substrate, a primer is previously applied to the substrate surface. You may keep it. Examples of the primer include a primer using a two-component curable urethane resin, a fluororesin, an epoxy resin, an aqueous urethane resin, and the like.

Moreover, in order to improve the durability of the coating film of the coating liquid of the present invention, a top coat layer may be provided on the coating film. Examples of the resin used for the coating agent for the top coat layer include petroleum resins, chlorinated ethylene-vinyl acetate copolymer resins, fluororesins, ethylene-vinyl acetate copolymer resins, polyester resins, cellulose resins, polyamide resins. , Nitrified cotton, vinyl resin, acrylic resin and the like.

The article of the present invention may be a printed matter. As one aspect of the printed matter of the present invention, one obtained by printing the coating liquid of the present invention on a substrate by gravure printing can be mentioned. When the coating liquid of the present invention is used as a metallic gravure ink, the composition of each component in the metallic gravure ink is, for example, substituted polythiophene (1) 0.25 to 10 parts by weight, vehicle 5 to 40 parts by weight, solvent 50 Examples include those composed of ˜90 parts by mass and other additives of 5 parts by mass or less.

Examples of the vehicle include tall oil rosin, gum rosin, wood rosin, lime rosin, rosin ester, maleic acid resin, vinyl resin, polyamide resin, nitrocellulose, cellulose acetate, ethyl cellulose, ethylene-vinyl acetate copolymer, urethane resin, polyester. Resins, alkyd resins, acrylic resins and the like can be mentioned. As these vehicles, those dissolved in a solvent and those dispersed in a solvent can be used. These vehicles can be used alone or in combination of two or more. Here, as in the case where the coating liquid of the present invention is used as a metallic paint, a vehicle is not necessarily required. Therefore, when a vehicle is not used, the composition of each component in the metallic gravure ink is, for example, a substituted polythiophene. (1) 0.25 to 10 parts by mass, 90 to 99.5 parts by mass of solvent, and 3 parts by mass or less of other additives may be mentioned.

As the solvent and other additives used when the coating liquid of the present invention is used as a metallic gravure ink, the same solvents as those used as the metallic paint can be used.

Among the printed materials of the present invention, those by gravure printing are those obtained by gravure printing on a substrate to be printed using the coating liquid of the present invention as a metallic gravure ink. Examples of the substrate to be printed include a plastic film substrate and a paper substrate. Examples of the plastic film substrate include polyethylene film, ethylene-vinyl acetate copolymer film, polypropylene film, polyethylene terephthalate film, nylon film, polyvinyl chloride film, polyvinylidene chloride film, and ethylene-vinyl alcohol copolymer film. , Polystyrene film, polyacrylonitrile copolymer film; film obtained by co-extruding a plurality of resins used in these films; film coated with a resin such as polyvinylidene chloride to provide barrier properties based on these films A film on which a metal such as aluminum or an inorganic compound such as silica or alumina is vapor-deposited.

Examples of the paper substrate include art paper, coated paper, matte paper, high-quality paper, and medium-quality paper. Among these, art paper and coated paper having a smooth surface are those of the present invention. By printing the coating liquid, it is preferable because a more excellent metallic-tone printed matter can be obtained.

When using the coating liquid of the present invention as a metallic gravure ink and performing gravure printing on a plastic film substrate, a primer is previously applied to the surface of the substrate in the same manner as in the case of using the metallic coating as described above. May be. Moreover, you may provide a topcoat layer similarly on the coating film obtained by carrying out the gravure printing of the coating liquid of this invention.

As one aspect of the printed matter of the present invention, one obtained by printing the coating liquid of the present invention on a substrate by inkjet printing can be mentioned. When the coating liquid of the present invention is used as a metallic inkjet ink, the composition of each component in the metallic inkjet ink is, for example, substituted polythiophene (1) 0.05 to 7.5 parts by mass, vehicle 1 to 10 parts by mass, Examples thereof include 85 to 98 parts by mass of a solvent and 5 parts by mass or less of other additives. When the composition of each component is within this range, a coating film having a more excellent metallic feeling can be obtained, and the ejection stability of ink from the nozzle head of the inkjet printer can be further stabilized.

As the vehicle, the same vehicle as in the case where the coating liquid of the present invention is used as a metallic gravure ink can be used. Further, as in the case of using the coating liquid of the present invention as a metallic paint and a metallic gravure ink, a vehicle is not necessarily required, and when a vehicle is not used, the composition of each component in the metallic inkjet ink is, for example, , Substituted polythiophene (1) 0.05 to 7.5 parts by mass, solvent 90 to 99.5 parts by mass, and other additives 5 parts by mass or less. When the composition of each component is within this range, a coating film having a more excellent metallic feeling can be obtained, and the ejection stability of ink from the nozzle head of an ink jet printer can be further stabilized.

As a solvent used when the coating liquid of the present invention is used as a metallic inkjet ink, it is preferable to use a solvent having wettability for the purpose of preventing drying of the ink in addition to water. As the wettable solvent, those which are miscible with water and can prevent clogging of the head of an ink jet printer are preferable. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less , Propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples include mesoerythritol and pentaerythritol. These solvents can be used alone or in combination of two or more. The content of the wet solvent in the metallic inkjet ink is preferably in the range of 3 to 50% by mass.

Furthermore, it is preferable to add a solvent having a function of improving permeability to a substrate to be printed and a function of adjusting a dot diameter on the substrate to be printed. Examples of such solvents include lower alcohols such as ethanol and isopropyl alcohol; ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether; and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether. It is done. Similarly, these solvents can be used alone or in combination of two or more. The content of such a solvent in the metallic inkjet ink is preferably in the range of 0.01 to 10% by mass.

Examples of other additives used when the coating liquid of the present invention is used as a metallic inkjet ink include surfactants added to adjust ink characteristics such as surface tension. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Among these, anionic surfactants and nonionic surfactants are preferable.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, higher alcohol. Examples include sulfates and sulfonates of ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, etc. Specific examples of these include dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, dibutylphenylphenol dis Acid salts, and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid. Esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol And polyethylene glycol polypropylene glycol block copolymer. Among these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkyl Roll amide, acetylene glycol, oxyethylene adduct of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymer are preferred.

As surfactants other than the above, silicone surfactants such as polysiloxane oxyethylene adducts; fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers Agents: Biosurfactants such as spicrispolic acid, rhamnolipid, and lysolecithin can also be used.

The above surfactants can be used alone or in combination of two or more. Further, since the dissolution stability of the surfactant is improved, the HLB (Hydrophile-Lipophile Balance) value is preferably in the range of 7-20. Further, when the surfactant is added, the addition amount is preferably in the range of 0.001 to 2% by mass, more preferably in the range of 0.001 to 1.5% by mass, and 0.01 to 1% in the total amount of the ink. A range of mass% is more preferred.

Further, as other additives other than the above-mentioned surfactants, preservatives, viscosity modifiers, pH adjusters, chelating agents, plasticizers, antioxidants, ultraviolet absorbers, etc. may be added as necessary. it can.

The surface tension of the above metallic inkjet ink is preferably in the range of 20 to 60 mN / m, more preferably in the range of 20 to 45 mN / m, and more preferably in the range of 20 to 40 mN / m because the printability in the inkjet printer is further improved. A range is more preferred.

The viscosity of the metallic inkjet ink is preferably in the range of 1.2 to 20 mPa · s, and more preferably in the range of 2 to 15 mPa · s, since the ejection stability in the inkjet printer is further improved. The surface tension and viscosity of the metallic ink-jet ink can be set within the above-mentioned preferred ranges by adjusting the type and addition amount of the surfactant and water-soluble solvent to be blended.

Among the printed matter of the present invention, those by inkjet printing are those obtained by inkjet printing on a substrate to be printed using the coating liquid of the present invention as a metallic inkjet ink. Examples of the substrate to be printed include plain paper (including recycled paper), coated paper, porous particulate glossy paper, film-based polymeric glossy paper, paper-based porous particulate glossy paper, polyethylene film, and ethylene-acetic acid. Vinyl copolymer film, polypropylene film, polyethylene terephthalate film, nylon film, polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl alcohol copolymer film, polystyrene film, polyacrylonitrile copolymer film; used for these films Films obtained by co-extrusion of a plurality of resins; films coated with resins such as polyvinylidene chloride to provide barrier properties based on these films; metals such as aluminum, and inorganic compounds such as silica and alumina are deposited. Film and the like.

When using the coating liquid of the present invention as a metallic inkjet ink and performing inkjet printing on a plastic film substrate, a primer is previously applied to the surface of the substrate in the same manner as in the case of using the metallic paint and the metallic gravure ink. A primer layer may be provided by processing. Examples of the primer layer include a coating film or a cured coating film such as a two-component curable urethane resin, a water-based urethane resin, a water-based acrylic resin, and an active energy ray-curable vinyl monomer. Moreover, you may provide a topcoat layer similarly on the coating film obtained by inkjet-printing the coating liquid of this invention.

Hereinafter, the present invention will be described in more detail with reference to specific examples. In addition, the weight average molecular weight (Mw) of a polymer is measured on condition of the following by gel permeation chromatography (GPC).

[GPC measurement conditions]
Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: N-methylpyrrolidone Flow rate: 1.0 mL / min Injection volume: 100 μL (sample concentration 4 mg / mL tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

<Synthesis Example 1>
To an Erlenmeyer flask having a volume of 50 ml, 6.5 g of iron (III) perchlorate and 7.3 g of acetonitrile were added as oxidizing agents, and stirred to prepare a 1 M concentration solution. Next, 1.0 g of 3-methoxythiophene and 12.8 g of acetonitrile were added to a 100 ml three-necked flask equipped with a nitrogen introduction tube and an Allen cooling tube, and the flask was immersed in an ice bath while introducing nitrogen gas into the liquid. The solution was stirred for 30 minutes to prepare a 0.5M concentration solution. Thereafter, the ice bath was removed and the temperature of the solution was raised to 20 ° C., and then the aforementioned 1M iron (III) perchlorate acetonitrile solution was poured into a three-necked flask and reacted at 20 ° C. for 4 hours. After completion of the reaction, the resulting solution was filtered through a Kiriyama funnel, and the residue was washed with methanol to remove the oxidizing agent. The residue obtained after washing was vacuum-dried to obtain a blue-violet solid of polythiophene compound (S-1) exhibiting metallic luster in a yield of 80%. The weight average molecular weight Mw of the polythiophene compound (S-1) was 1,600.

<Synthesis Example 2>
To an Erlenmeyer flask with a capacity of 50 ml, 9.5 g of iron (III) chloride and 4.3 g of acetonitrile were added as oxidizing agents, and stirred to prepare a 2M concentration solution. Next, 1.0 g of 3-methoxythiophene and 12.8 g of acetonitrile were added to a 100 ml three-necked flask equipped with a nitrogen introduction tube and an Allen cooling tube, and the flask was immersed in an ice bath while introducing nitrogen gas into the liquid. The solution was stirred for 30 minutes to prepare a 0.5M concentration solution. Thereafter, the ice bath was removed and the temperature of the solution was raised to 50 ° C., and then the 2M-iron (III) chloride chloride solution was poured into a three-necked flask and reacted at 50 ° C. for 4 hours. After completion of the reaction, the resulting solution was filtered through a Kiriyama funnel, and the residue was washed with methanol to remove the oxidizing agent. The residue obtained after washing was vacuum-dried to obtain a blue-violet solid of polythiophene compound (S-2) exhibiting metallic luster with a yield of 75%. The weight average molecular weight Mw of the polythiophene compound (S-2) was 1,400.

<Example 1>
1 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 is dissolved in a mixed solvent composed of 70 g of acetonitrile and 29.6 g of methyl ethyl ketone, and the rheology control agent (manufactured by Big Chemie Japan Co., Ltd.) is stirred while the solution is stirred. 0.1 g of “BYK-410”) and 0.3 g of an antifoaming agent (“Dappo SN-368” manufactured by San Nopco Co., Ltd.) were added to obtain a metallic gravure ink composition (A-1). A gravure ink printed matter (AP-1) was obtained by coating and printing this by the method specified in each evaluation method as a gravure ink described later.

<Example 2>
Primer (“Univia NT K1 Medium” manufactured by DIC Graphics Co., Ltd.) was added to Zahn Cup No. 3 using a diluent solvent (“Reducer No. 3K” manufactured by DIC Graphics Co., Ltd.). Dilute to a viscosity of 3-15 seconds. This diluted primer solution was applied / printed in the same manner as the gravure ink coating / printing method specified in each evaluation method as a gravure ink described later, and obtained in Example 1 after drying the primer coating film. The metallic gravure ink composition (A-1) was coated and printed by the method specified in each evaluation method as a gravure ink described later. As a result, a gravure ink print (AP-2) comprising two layers of primer / gravure ink was obtained.

<Example 3>
Primer (“Univia NT K1 Medium” manufactured by DIC Graphics Co., Ltd.) was added to Zahn Cup No. 3 using a diluent solvent (“Reducer No. 3K” manufactured by DIC Graphics Co., Ltd.). Dilute to a viscosity of 3-15 seconds. This diluted primer solution was applied / printed in the same manner as the gravure ink coating / printing method specified in each evaluation method as a gravure ink described later, and obtained in Example 1 after drying the primer coating film. The metallic gravure ink composition (A-1) was applied and printed. Next, the top coat ("ULTIMA Z OP varnish" manufactured by DIC Graphics Co., Ltd.) was added to the Zahn Cup No. 3 using a diluting solvent ("Reducer No. 3K" manufactured by DIC Graphics Co., Ltd.). Dilute to a viscosity of 3-15 seconds. This diluted topcoat solution was coated / printed on the aforementioned (A-1) layer in the same manner as the gravure ink coating / printing method specified in each evaluation method as a gravure ink described later, A gravure ink print (AP-3) consisting of three layers of primer / gravure ink / topcoat was obtained.

<Example 4>
1. 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved in 99.2 g of water, and the rheology control agent (“BYK-420” manufactured by Big Chemie Japan Co., Ltd.) was stirred while the solution was stirred. 1 g, 0.2 g of antifoaming agent (“SN deformer 777” manufactured by San Nopco Co., Ltd.) and 0.5 g of leveling agent (“BYK-348” manufactured by Big Chemie Japan Ltd.) are added, and a metallic gravure ink composition (A-4) ) This was coated and printed by the method specified in each evaluation method as a gravure ink described later, to obtain a gravure ink printed matter (AP-4).

<Example 5>
The primer (“SF Primer No. 930” manufactured by DIC Graphics Co., Ltd.) was added to the Zahn Cup No. 3 using a diluent solvent (“Reducer No. 3K” manufactured by DIC Graphics Co., Ltd.). Dilute to a viscosity of 3-15 seconds. The diluted primer solution was applied and printed in the same manner as the gravure ink coating and printing method specified in each evaluation method as a gravure ink described later, and obtained in Example 4 after drying the primer coating film. The metallic gravure ink composition (A-2) was applied and printed. As a result, a gravure ink print (AP-5) comprising two layers of primer / gravure ink was obtained.

<Comparative Example 1>
Solvent-based back-printed gravure ink ("Univia LT Silver K1" manufactured by DIC Graphics Co., Ltd.) is referred to as metallic gravure ink (B-1) and diluted solvent ("Reducer No. 3K" manufactured by DIC Graphics Co., Ltd.) Zahn cup no. Dilute to a viscosity of 3-15 seconds. This solution was applied and printed by the method specified in each evaluation method as a gravure ink described later to obtain a gravure ink printed matter (BP-1).

<Comparative example 2>
Water-based back-printed gravure ink (“Marine Plus G Silver (K3)” manufactured by DIC Graphics Co., Ltd.) is referred to as metallic gravure ink (B-2), and diluted solvent (“Reducer for water based No. No. 3 "). Dilute to a viscosity of 3-18 seconds. This solution was applied and printed by the method specified in each evaluation method as a gravure ink described later to obtain a gravure ink printed matter (BP-2).

The following evaluation was performed on the metallic gravure inks obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and printed materials using them.

<Evaluation method as gravure ink>
[Gloss value]
The gravure ink composition is applied to a corona surface-treated surface of a biaxially stretched polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd., 12 μm thick) using a bar coater, and dried at 80 ° C. It was. After drying the coating film at 80 ° C., the gloss at an incident angle of 60 degrees and a reflection angle of 60 degrees was measured at an arbitrary 5 points with a gloss meter (micro-TRI-gloss manufactured by BYK Gardner), and the average value was recorded.

[Appearance of coating film]
The gravure ink composition is applied to a corona surface-treated surface of a biaxially stretched polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd., 12 μm thick) using a bar coater, and dried at 80 ° C. It was. The appearance of the coated film after drying was visually evaluated according to the following criteria.
(Background concealment)
○: The base is completely hidden.
Δ: The base is slightly transparent.
X: The base is clearly transparent and the base material type can be visually discriminated.
(Specular reflection of coating film)
○: Recognize even the details of mirror images without image distortion and blurring.
Δ: Although the image is slightly distorted and blurred, the shape of the mirror image can be recognized.
X: The image is severely distorted and blurred, and the mirror image cannot be recognized.
(Coating grain feeling)
○: There is no graininess like the plated surface.
Δ: A very fine granular pattern is visible.
×: Clearly grainy.

[Sedimentation stability]
The gravure ink composition was put in a glass sample bottle, the lid was closed, allowed to stand at room temperature, allowed to stand for 6 hours, and the degree of sedimentation of the pigment after standing for 24 hours was visually observed.
○: No pigment precipitation was observed after 24 hours.
Δ: Pigment sedimentation was not observed after 6 hours, but pigment sedimentation was confirmed after 24 hours.
X: Pigment sedimentation was confirmed after 6 hours.

[Storage stability]
After measuring the viscosity of the gravure ink composition with an E-type viscometer (“TV-20 type” manufactured by Toki Sangyo Co., Ltd.), the gravure ink composition was placed in a glass sample bottle and sealed with the lid closed. It was left in a thermostatic bath. After 30 days, the sample bottle was taken out from the thermostat and the viscosity of the ink was measured. Evaluation was judged as follows.
○: Change rate of viscosity is less than 10%.
Δ: Viscosity change rate is 10% or more and less than 20%.
X: Viscosity change rate is 20% or more, or ink separation occurs.

[Adhesion to film substrate]
Using a bar coater, the gravure ink composition was converted into a biaxially stretched polypropylene film (“Pyrene P2161” manufactured by Toyobo Co., Ltd., thickness 20 μm, abbreviated as “OPP” in Table 1 below), biaxially stretched polyethylene terephthalate film (Toyobo) “E5100” manufactured by Co., Ltd., thickness 12 μm, abbreviated as “PET” in Table 1 below), biaxially stretched nylon film (“Emblem ON” manufactured by Unitika Ltd., thickness 15 μm, abbreviated as “ONy” in Table 1 below) ) And a corona surface-treated surface with a film thickness of 1 μm and dried at 80 ° C. Next, a cellophane tape (“Cello Tape” (registered trademark), manufactured by Nichiban Co., Ltd., 18 mm width) manufactured by Nichiban Co., Ltd. is applied to the coated surface, and the tape is peeled off in a 180 ° direction at a speed of 10 mm per second 10 seconds after the application. A test was conducted. The surface of the coated material after the test was converted into electronic data with a scanner having a resolution of 300 dpi, and the peeled area / cello tape area = the coating film peeling ratio (%) was calculated. The smaller this value, the stronger the adhesion between the ink coating film and the film. This value is preferably 30% or less and more preferably 15% or less in each film.

[Plate fog]
Corona of biaxially stretched polypropylene film (“Pyrene P2161” manufactured by Toyobo Co., Ltd., 20 μm thick) using a gravure ink composition at two levels of printing speeds of 100 meters and 150 meters per minute using a Helio 175 line gradation plate Printed on the discharge-treated surface. The phenomenon that ink was printed in spite of the non-image area, that is, the plate fog occurred even a little, and the printing speed transferred to the printed matter was evaluated according to the following criteria.
○: No plate fog occurs even at a printing speed of 150 meters per minute.
Δ: When printing speed at which plate fog occurs is 150 meters per minute.
X: When the printing speed at which plate fogging occurred was 100 meters per minute.

[Highlight transition]
Corona discharge of a biaxially stretched polypropylene film (“Pyrene P2161” manufactured by Toyobo Co., Ltd., thickness 20 μm) using a gravure ink composition at two levels of printing speed of 100 meters per minute and 150 meters per minute using a Helio 175 wire tone plate. Printed on the treated surface. Observe the gradation part of the printed matter, and the lightest part (density 20%, 15%, 10%, 7%, 5%, 3%, 1%) is the thinnest highlight on which 98% or more of the printed area is printed The light value was recorded. The lower this value is, the better the highlight transferability is, and even a light-colored portion can be clearly printed, and 5% or less is particularly preferable.

[Blocking resistance]
The gravure ink composition was applied to a corona discharge-treated surface of a biaxially stretched polypropylene film (“Pyrene P2161” manufactured by Toyobo Co., Ltd., thickness 20 μm) using a bar coater at a film thickness of 1 μm, and dried at 80 ° C. . Next, another untreated surface of the biaxially stretched polypropylene film was adhered to the coated surface of the gravure ink composition. A pressure of 0.5 MPa was applied to the two-layered film test piece and left for 24 hours in an environment of a temperature of 50 ° C. and a relative humidity of 80%. After the film was air-cooled to room temperature, the two test pieces were peeled off. The surface of the coated material after the test was converted into electronic data using a scanner with a resolution of 300 dpi, and the peeled area / pressurized area = coating film peeling ratio [%] was calculated. It means that it is excellent in blocking resistance, so that this value is small. This value is preferably 20% or less in each film, and more preferably 10% or less.

[Laminate adhesive strength]
The gravure ink composition was applied to a corona discharge-treated surface of a biaxially stretched polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd., thickness: 12 μm) with a film thickness of 1 μm and dried at 80 ° C. Next, an adhesive for laminating (15 parts by mass of “Dick Dry LX-703VL” manufactured by DIC Graphics, 1 part by mass of “KR-90” manufactured by DIC Graphics Co., Ltd.) is applied to the coated surface. The coating was performed at 0.0 g / m ² . A linear low-density polyethylene film (“TUX-HC” manufactured by Mitsui Chemicals, Inc., thickness 60 μm) as a sealant was layered on this adhesive-coated film and laminated. The laminate laminate was left in a constant temperature bath at 40 ° C. for 72 hours, and after aging, the film was air-cooled to room temperature, and the laminate laminate was cut into a tape having a width of 15 mm. Using a tensile tester ("Tensilon RTM-25" manufactured by Orientec Co., Ltd.), a peel test in a state where the sealant was bent 180 degrees was performed at a tensile speed of 300 mm / min, and the strength was recorded. The laminate strength is preferably 1.0 N / 15 mm or more, and more preferably 2.0 N / 15 mm or more.

Table 1 shows a summary of the composition of gravure ink prints and the results of evaluation when the coating liquid of the present invention is used as gravure ink.

<Example 6>
A mixed solvent of 5 g of propylene glycol, 3 g of 1,3-butanediol and 89.8 g of water was prepared, and 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved therein. While stirring this solution, 1.2 g of a leveling agent (“Surfinol 485” manufactured by Nissin Chemical Industry Co., Ltd.) was added to obtain a metallic ink (A-6) for water-based inkjet recording. This was coated and printed by the method specified in each evaluation method as an inkjet ink described later to obtain an inkjet print (AP-6).

<Example 7>
A mixed solvent consisting of 15 g of propylene glycol, 10 g of 1,3-butanediol and 64.9 g of water was prepared, and 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved therein. While stirring this solution, 8.6 g of an acrylic resin (“Boncoat WKA-565” manufactured by DIC Corporation) and 0.5 g of a leveling agent (“Surfinol 485” manufactured by Nissin Chemical Industry Co., Ltd.) were added, and an aqueous inkjet was added. A metallic ink for recording (A-7) was obtained. This was coated and printed by the method specified in each evaluation method as an ink-jet ink described later to obtain an ink-jet printed matter (AP-7).

<Example 8>
A mixed solvent consisting of 15 g of propylene glycol, 10 g of 1,3-butanediol and 63.5 g of water was prepared, and 1 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved therein. Further, while stirring this solution, 10 g of a polyolefin resin (“Hardlen NA-3002” manufactured by Toyobo Co., Ltd.) and 0.5 g of a leveling agent (“Surfinol 485 manufactured by Nissin Chemical Industry Co., Ltd.) are added, for aqueous inkjet recording. A metallic ink (A-8) was obtained. This was coated and printed by the method specified in each evaluation method as an inkjet ink described later to obtain an inkjet printed matter (AP-8).

<Comparative Example 3>
Vapor-deposited aluminum pigment ("Metaseen 41-0310" manufactured by BASF, 2-methoxy-1-methylethyl acetate dispersion with aluminum content of 10% by mass) is ultrasonic oscillator ("US-300T" manufactured by Nippon Seiki Seisakusho Co., Ltd.) ) To obtain an aluminum pigment dispersion having an average particle diameter (D50) of 6.0 μm and an average thickness of 20 nm. To 20 g of this dispersion, 15 g of propylene glycol, 10 g of 1,3-butanediol, 45.9 g of water, 8.6 g of acrylic resin (“Boncoat WKA-565” manufactured by DIC Corporation) and a leveling agent (Nisshin Chemical Industry Co., Ltd.) 0.5 g of “Surfinol 485” manufactured by the company) was added to obtain a metallic ink (B-3) for aqueous inkjet recording. This was coated / printed by the method specified in each evaluation method as an inkjet ink described later to obtain an inkjet printed matter (BP-3).

The following evaluation was performed on the inkjet inks obtained in Examples 6 to 8 and Comparative Example 3 described above and printed matter using them.

<Evaluation method as inkjet ink>
[Gloss value]
An inkjet ink composition is an inkjet printer having a piezo head with a maximum driving frequency of 7.6 KHz and a resolution of 360 dpi (360 dots per 25.4 mm), a biaxially stretched polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd., thickness 12 μm). ) Was printed on the corona surface-treated surface. After drying the coating film at 80 ° C., the gloss at an incident angle of 60 degrees and a reflection angle of 60 degrees was measured at an arbitrary 5 points with a gloss meter (micro-TRI-gloss manufactured by BYK Gardner), and the average value was recorded.

[Appearance of coating film (film)]
An inkjet ink composition is an inkjet printer having a piezo head with a maximum driving frequency of 7.6 KHz and a resolution of 360 dpi (360 dots per 25.4 mm), a biaxially stretched polyethylene terephthalate film (“E5100” manufactured by Toyobo Co., Ltd., thickness 12 μm). ) Was printed on the corona surface-treated surface. After the coating film was dried at 80 ° C., the following items were visually evaluated with respect to the coating film appearance according to the following criteria.
(Background concealment)
○: The base is completely hidden.
Δ: The base is slightly transparent.
X: The base is clearly transparent and the base material type can be visually discriminated.
(Specular reflection of coating film)
○: Recognize even the details of mirror images without image distortion and blurring.
Δ: Although the image is slightly distorted and blurred, the shape of the mirror image can be recognized.
X: The image is severely distorted and blurred, and the mirror image cannot be recognized.
(Coating grain feeling)
○: There is no graininess like the plated surface.
Δ: A very fine granular pattern is visible.
×: Clearly grainy.

[Appearance of coated film (paper)]
An inkjet ink composition is an A4 size copy paper (Mitsubishi PPC paper manufactured by Mitsubishi Paper Industries Co., Ltd.) that is compatible with the Green Purchasing Law with an inkjet printer having a piezo head with a maximum drive frequency of 7.6 KHz and a resolution of 360 dpi (360 dots per 25.4 mm). RE-N FSC certification-MX ") was printed in full solid. About the external appearance after printing, the following items were visually evaluated according to the following criteria.
○: Metallic luster and brightness like gold leaf can be confirmed.
(Triangle | delta): Although the metal color is dull, it can confirm that there exists a glossiness.
X: There is no brightness feeling and it does not look like a metallic color.

[Sedimentation stability]
The ink-jet ink composition was put in a glass sample bottle, the lid was closed, and allowed to stand at room temperature. After settling for 6 hours and after standing for 24 hours, the degree of sedimentation of the pigment was visually observed.
○: No pigment precipitation was observed after 24 hours.
Δ: Pigment sedimentation was not observed after 6 hours, but pigment sedimentation was confirmed after 24 hours.
X: Pigment sedimentation was confirmed after 6 hours.

[Storage stability]
After measuring the viscosity of the ink-jet ink composition with an E-type viscometer (“TV-20 type” manufactured by Toki Sangyo Co., Ltd.), it was placed in a glass sample bottle and sealed with the lid closed. It was left in a thermostatic bath. After 30 days, the sample bottle was taken out from the thermostat and the viscosity of the ink was measured. Evaluation was judged as follows.
○: Change rate of viscosity is less than 10%.
Δ: Viscosity change rate is 10% or more and less than 20%.
X: Viscosity change rate is 20% or more, or ink separation occurs.

[Adhesion to film substrate]
An inkjet ink composition is an inkjet printer having a piezo head having a maximum driving frequency of 7.6 KHz and a resolution of 360 dpi (360 dots per 25.4 mm), a biaxially stretched polypropylene film (“Pylon P2161” manufactured by Toyobo Co., Ltd., thickness 20 μm). In Table 2, abbreviated as “OPP”) and printed on the corona surface-treated surfaces of biaxially stretched polyethylene terephthalate films (“E5100” manufactured by Toyobo Co., Ltd., thickness: 12 μm, abbreviated as “PET” in Table 2 below). . After the coating film is dried at 80 ° C., cellophane tape (“Cellotape” (registered trademark) manufactured by Nichiban Co., Ltd., 18 mm width) is applied to the coated surface, and after 10 seconds, the cellophane tape is peeled off at 180 ° direction at a speed of 10 mm per second. A peel test was conducted. The surface of the coated product after the test was converted into electronic data using a scanner with a resolution of 300 dpi, and the peeled area / cello tape area = coating film peeling ratio [%] was calculated. The smaller this value, the stronger the adhesion between the ink coating film and the film. This value is preferably 30% or less and more preferably 20% or less in each film.

[Discharge aptitude test]
An inkjet ink composition is an A4 solid 100 on a PET film (“Ester E-5100” manufactured by Toyobo Co., Ltd.) using an inkjet printer having a piezo head with a maximum driving frequency of 7.6 KHz and a resolution of 360 dpi (360 dots per 25.4 mm). After printing the equivalent of the sheet, a check pattern was printed and the non-ejection nozzle was evaluated. Evaluation was judged as follows.
A: Less than 1% of non-ejection nozzles
Δ: Non-ejection nozzle 1% or more and less than 5%.
X: 5% or more of non-discharge nozzles.

Table 2 shows a summary of the configuration of ink-jet printed matter and each evaluation result when the coating liquid of the present invention is used as an ink-jet ink.

<Example 9>
A primer is prepared by mixing 40 g of acrylic resin (“Acridic 56-1155” manufactured by DIC Corporation), 30 g of an aromatic organic solvent (“Solvesso 100” manufactured by TonenGeneral Sekiyu KK), and 30 g of butyl acetate. did. This was coated / printed by the same method as the coating / printing method of the metallic paint specified in each evaluation method as a metallic paint described later. Next, 1.5 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 is dissolved in a mixed solvent consisting of 18 g of acetonitrile and 80 g of N-methylpyrrolidone, and the leveling agent (BIC Chemie) is stirred while the solution is stirred. -0.5 g of "BYK-348" manufactured by Japan Co., Ltd.) was added to obtain a metallic paint (A-9). By coating and printing this on the above-mentioned primer coating layer by the method specified in each evaluation method as a metallic paint to be described later, a metallic coating material comprising two layers of primer layer / metallic coating layer ( AP-9) was obtained.

<Example 10>
A mixed solvent consisting of 47.5 g of N-methylpyrrolidone and 12.5 g of acetonitrile was prepared, and 1 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 was dissolved therein. Further, while stirring this solution, 40 g of acrylic resin (“ACRICID 56-1155” manufactured by DIC Corporation) was added to obtain a metallic paint (A-10). This was coated by the method specified in each evaluation method as a metallic paint described later, to obtain a metallic paint (AP-10).

<Example 11>
Aqueous acrylic resin (DIC Co., Ltd. “Boncoat EM-400”) 80 g, dipropylene glycol-n-butyl ether 19.7 g, and leveling agent (BIC Chemie Japan Co., Ltd. “BYK-348”) 0.5 g were mixed. And stirred to prepare a primer. This was coated / printed by the same method as the coating / printing method of the metallic paint specified in each evaluation method as a metallic paint described later. Next, 1.5 g of the polythiophene compound (S-2) obtained in Synthesis Example 2 was dissolved in 98.0 g of water, and a leveling agent (“BYK-348 manufactured by Big Chemie Japan Co., Ltd.” was further stirred. ]) 0.5 g was added to obtain a metallic paint (A-11). By coating and printing this on the above-mentioned primer coating layer by the method specified in each evaluation method as a metallic paint to be described later, a metallic coating material comprising two layers of primer layer / metallic coating layer ( AP-11) was obtained.

<Example 12>
A mixed solvent consisting of 10 g of dipropylene glycol-n-butyl ether and 48.5 g of water was prepared, and 1 g of the polythiophene compound (S-1) obtained in Synthesis Example 1 was dissolved therein. Further, while stirring this solution, 40 g of an aqueous acrylic resin (“Boncoat EM-400” manufactured by DIC Corporation) and 0.5 g of a leveling agent (“BYK-348” manufactured by Big Chemie Japan Co., Ltd.) were added. A-12) was obtained. This was coated by the method specified in each evaluation method as a metallic paint described later to obtain a coated product (AP-12).

<Comparative example 4>
Aluminum pigment (Toyo Aluminum Co., Ltd. “TCR-3040”) 0.79 g, Aluminum pigment (Showa Aluminum Powder Co., Ltd. “SAP 550N”) 3.88 g, Acrylic resin (DIC Corporation “Acridic 56-1155”) 33.6 g, 10 g of xylene, 20 g of an aromatic organic solvent (“Solvesso 100” manufactured by TonenGeneral Sekiyu KK) and 31.7 g of butyl acetate were mixed to obtain a metallic paint (B-4). This was coated and printed by the method specified in each evaluation method as a metallic paint described later to obtain a metallic paint (BP-4).

<Comparative Example 5>
Mix and knead 5.0 g of aluminum pigment (“STAPA Hydrolan 2194” manufactured by Eckert), 5.0 g of diethylene glycol dimethyl ether, and 0.5 g of pigment dispersant (“Disparlon AQ-330” manufactured by Enomoto Chemical Co., Ltd.) A paste was prepared. 10.0 g of this aluminum paste is 55.6 g of a water-based acrylic resin (“Bernock WD-551” manufactured by DIC Corporation), 0.2 g of a leveling agent (“BYK-348” manufactured by Big Chemie Japan Co., Ltd.), and a leveling agent (Nissin) Chemical Industry Co., Ltd. “Surfynol 104DPM” 0.6 g, Antifoaming agent (BYK-011 “BYK-011” 0.4 g), and Rheology Control Agent (BYK-Japan Japan “BYK-425”) ]) 0.3g was mixed and the main ingredient metallic paint was prepared. Further, 5.8 g of water-dispersed polyisocyanate (“Bernock DNW-5500” manufactured by DIC Corporation) and 10 g of water were added to 70 g of the main metallic coating material to obtain a two-component curable metallic coating material (B-5). This was coated and printed by the method specified in each evaluation method as a metallic paint described later, and dried at 23 ° C. for 7 days to obtain a metallic paint (BP-5).

The metallic paints obtained in Examples 9 to 12 and Comparative Examples 4 to 5 and their coated products were evaluated as follows.

<Evaluation method as metallic paint>
[Gloss value]
The coating composition was applied to a glass plate with an air spray with a film thickness of 10 μm, and dried at room temperature for 10 minutes and then at 80 ° C. for 10 minutes. With respect to the surface of the coating film after drying, the gloss at an incident angle of 60 degrees and a reflection angle of 60 degrees was measured at an arbitrary five points with a gloss meter (“micro-TRI-gloss” manufactured by BYK Gardner), and the average value was recorded. .

[Appearance of coating film]
The coating composition was applied to a PC (polycarbonate) plate and a PET (polyethylene terephthalate) plate with an air spray with a film thickness of 10 μm, and dried at room temperature for 10 minutes and then at 80 ° C. for 10 minutes. The appearance of the coated film after drying was visually evaluated according to the following criteria.
(Background concealment)
○: The base is completely hidden.
Δ: The base is slightly transparent.
X: The base is clearly transparent and the base material type can be visually discriminated.
(Specular reflection of coating film)
○: Recognize even the details of mirror images without image distortion and blurring.
Δ: Although the image is slightly distorted and blurred, the shape of the mirror image can be recognized.
X: The image is severely distorted and blurred, and the mirror image cannot be recognized.
(Coating grain feeling)
○: There is no graininess like the plated surface.
Δ: A very fine granular pattern is visible.
×: Clearly grainy.

[Sedimentation stability]
The coating composition was put in a glass sample bottle, the lid was closed, and the mixture was allowed to stand at room temperature, and the degree of sedimentation of the pigment after standing for 6 hours and after standing for 24 hours was visually observed.
○: No pigment precipitation was observed after 24 hours.
Δ: Pigment sedimentation was not observed after 6 hours, but pigment sedimentation was confirmed after 24 hours.
X: Pigment sedimentation was confirmed after 6 hours.

[Storage stability]
After the viscosity of the coating composition was measured with an E-type viscometer (“TV-20” manufactured by Toki Sangyo Co., Ltd.), it was placed in a glass sample bottle and sealed with a lid closed and sealed at 60 ° C. Left in the tank. After 30 days, the sample bottle was taken out from the thermostat and the viscosity of the ink was measured. Evaluation was judged as follows.
○: Change rate of viscosity is less than 10%.
Δ: Viscosity change rate is 10% or more and less than 20%.
X: Viscosity change rate is 20% or more, or ink separation occurs.

[Primary adhesion test]
The coating composition was applied to a PC (polycarbonate) plate and a PET (polyethylene terephthalate) plate with an air spray with a film thickness of 10 μm, and dried at room temperature for 10 minutes and then at 80 ° C. for 10 minutes. Next, 10 × 10 cuts are made with a cutter knife on the surface of the coating film, and a peel test is performed with a cellophane tape (“Cello Tape” (registered trademark), manufactured by Nichiban Co., Ltd., 18 mm width). Evaluation was made according to the following criteria.
○: 86 to 100 △: 60 to 85 ×: 59 or less

[Secondary adhesion test]
A coated substrate was prepared by the same means as in the primary adhesion test described above, and was immersed in warm water at 40 ° C. for 24 hours. Thereafter, a peel test using the same cellophane tape (“Cello Tape” (registered trademark), 18 mm width, manufactured by Nichiban Co., Ltd.) similar to the primary adhesion test was performed, and the remaining number of eyes was evaluated according to the following criteria.
○: 86 to 100 △: 60 to 85 ×: 59 or less

Table 3 shows a summary of the composition of the metallic paint and the evaluation results when the coating liquid of the present invention is used as a metallic paint.

From the evaluation results shown in Tables 1 to 3, it was confirmed that the coating liquid of the present invention can be sufficiently used as a metallic gravure ink, a metallic inkjet ink, and a metallic paint. It was also confirmed that by coating and printing these, a metallic coating film equivalent to uniform metal plating without graininess could be formed on the printing material and the coating material.

On the other hand, it was confirmed that the coating solution of the comparative example using the metallic pigment was inferior in sedimentation stability and storage stability. In addition, by applying and printing the coating liquid of the comparative example, a metallic tone design was obtained on the printing material and the coating material, but only a metallic tone with a graininess was obtained.

Claims (6)

1. The coating liquid characterized by containing the polythiophene represented by following General formula (1).
   

   

   (Wherein R ¹ represents a hydrogen atom, an alkoxy group, an amino group or a hydroxyl group, R ² represents an alkoxy group, an amino group or a hydroxyl group. N represents an integer of 3 to 100)
2. The coating solution according to claim 1, wherein the polythiophene is doped with an anion.
3. The coating solution according to claim 1 or 2, comprising 0.05 to 15% by mass of the polythiophene.
4. An article comprising a coating film formed from the coating liquid according to any one of claims 1 to 3 on a substrate.
5. A printed matter obtained by printing the coating liquid according to any one of claims 1 to 3 on a substrate by gravure printing.
6. A printed matter obtained by printing the coating liquid according to any one of claims 1 to 3 on a substrate by ink jet printing.