Anchor agent, printed material and packaging material

Abstract

To provide an anchor agent that allows overprinting with any kind of ink, whether UV offset ink or gravure ink, and that can also improve adhesion.SOLUTION: An anchor agent comprising a binder resin, the binder resin comprising both a urethane resin and a polyester resin, or comprising a urethane-modified polyester resin; a printed material having a layer formed by the anchor agent; and a packaging material using the printed material having the anchor agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an anchoring agent, a printed matter having a layer formed by the anchoring agent, and a packaging material using the printed matter. [Background technology]

[0002] When printing an ink layer on a metal surface, such as a metal or metal foil, or a substrate with aluminum foil attached via an adhesive, or a vapor-deposited film, an anchoring agent is printed to enhance the ink's adhesion, and then another ink layer is printed on top of it. Anchor agents used include vinyl chloride-vinyl acetate copolymers, acrylic resins, and polyester resins (see Patent Document 1).

[0003] Various anchor agents for printing inks are used depending on the type of printing ink to be applied thereon, such as those for gravure ink and those for offset ink.

[0004] However, there is no anchor agent that can be used for two different types of ink, such as gravure ink and offset ink, and the need to use different agents for different types of inks has led to problems that hinder work efficiency at the printing site.In addition, current anchor agents sometimes have poor adhesion to the substrate, so there is a demand for improved adhesion.

[0005] Furthermore, vinyl chloride-vinyl acetate copolymers are widely used as anchoring agents, but they are also a source of environmentally hazardous substances. Demand for recyclable packaging materials has been increasing in recent years, but vinyl chloride-vinyl acetate copolymers are feared to be substances that hinder the recycling of packaging for the following reasons (a) and (b).

[0006] (a) Chlorine-based resins such as vinyl chloride can cause corrosion of equipment or piping by releasing hydrogen chloride and generating hydrochloric acid during the thermal decomposition process of recycling.

[0007] (b) In thermal recycling, which reuses the energy generated when waste is incinerated, the incineration of chlorine-based resins can result in the release of environmental hormones such as dioxins.

[0008] Therefore, there is a need to develop environmentally friendly anchoring agents that do not contain chlorine-based resins. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-267819 Summary of the Invention [Problem to be solved by the invention]

[0010] An object of the present invention is to solve the problems of the conventional technology, to provide an anchoring agent that can be used for overprinting with either UV offset ink or gravure ink, regardless of the type of ink used for overprinting, and that can also improve adhesion.

[0011] Another object of the present invention is to provide an anchoring agent that does not contain a chlorine-based resin, and therefore does not generate substances that are of concern to the environment, and has excellent recyclability. [Means for solving the problem]

[0012] As a result of extensive research to solve the above problems, the present inventors discovered that an anchor agent containing both a urethane resin and a polyester resin, or a urethane-modified polyester resin, can be used with any type of ink and has excellent adhesive properties even without containing a chlorine-based resin, thereby completing the present invention.

[0013] That is, the present invention is an anchoring agent that contains a binder resin, and the binder resin contains both a urethane resin and a polyester resin, or a urethane-modified polyester resin.

[0014] The present invention also relates to a printed matter having a substrate having a metal foil or a metal vapor-deposited film on its surface, an anchor layer provided on the substrate, and a printed layer provided on the anchor layer, wherein the anchor layer is a layer formed from an anchor agent containing both a urethane resin and a polyester resin, or a urethane-modified polyester resin.

[0015] The present invention also provides a packaging material using a printed matter that has a substrate having metal foil or a metal vapor-deposited film on its surface, an anchor layer provided on the substrate, and a printed layer provided on the anchor layer, wherein the anchor layer is a layer formed from an anchor agent containing both a urethane resin and a polyester resin, or a urethane-modified polyester resin. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide an anchoring agent that can be used for overprinting with either UV offset ink or gravure ink, regardless of the type of ink to be overprinted, and that can also improve adhesion.Since there are no restrictions on the type of ink to be overprinted, overprinting with a variety of inks becomes possible.

[0017] Furthermore, according to the present invention, an anchoring agent can be provided that does not contain a chlorine-based resin, does not generate substances that cause an environmental load, and is highly recyclable.

[0018] According to the present invention, it is possible to provide printed matter and packaging materials that use such anchoring agents and have good adhesion to the substrate and the printed layer. DETAILED DESCRIPTION OF THE INVENTION

[0019] The anchoring agent, printed matter, and packaging material of the present invention will be described in detail below with reference to exemplary embodiments. <Definition> In this specification, all "parts" refer to "parts by mass," "total amount of anchoring agent" refers to the total amount of anchoring agent including all volatile components such as solvents, and "total amount of ink solids" refers to the total amount of only non-volatile components, excluding volatile components.

[0020] <Anchor agent> The anchor agent of this embodiment contains a binder resin, which is provided between the metal and the printing layer and has the effect of improving the adhesion between them. In this specification, the term "binder resin" refers to a resin that has a binding effect, and does not include wax, which will be described later.

[0021] (First Configuration) In a first configuration of the anchoring agent of the present invention, the binder resin contains both a polyurethane resin and a polyester resin. --Polyurethane resin-- The polyurethane resin is not particularly limited as long as it is a polyurethane resin obtained by reacting a polyol with a polyisocyanate.

[0022] As the polyol, for example, various known polyols generally used in the production of polyurethane resins can be used, and one or more of them may be used in combination. Specific examples of the polyol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, and the like. Saturated or unsaturated low molecular weight polyols (1), such as ethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, and pentaerythritol; and mixtures of these low molecular weight polyols (1) with sebacic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, thiazolinone ... Examples of the polyester polyols include (2) polyester polyols obtained by dehydration condensation or polymerization of polycarboxylic acids such as trimellitic acid and pyromellitic acid, or anhydrides thereof; (3) polyester polyols obtained by ring-opening polymerization of cyclic ester compounds, such as lactones such as polycaprolactone, polyvalerolactone, and poly(β-methyl-γ-valerolactone); (4) polycarbonate polyols obtained by reacting the low molecular weight polyols (1) or the like with, for example, dimethyl carbonate, diphenyl carbonate, ethylene carbonate, or phosgene; (5) polybutadiene glycols; (6) glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A; and (7) acrylic polyols obtained by copolymerizing, in one molecule, one or more hydroxyethyl groups, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like, or the corresponding methacrylic acid derivatives, with, for example, acrylic acid, methacrylic acid, or an ester thereof.

[0023] In addition, various known polyether polyols commonly used in the production of polyurethane resins can be used, and one or more of them may be used in combination. For example, polyether polyols of polymers or copolymers of methylene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, etc. can be used. Specifically, known general-purpose polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can be used.

[0024] In the polyurethane resin of the present invention, it is preferable to use a polyester polyol as the polyol, and it is more preferable to use the polyester polyols (2) and polyether polyols.

[0025] Examples of the polyisocyanate include various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are generally used in the production of polyurethane resins. Specific examples of the polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3, 5-Diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5-triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 1-methyl-naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate aromatic polyisocyanates such as 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and diphenylmethane-2,4-diisocyanate;Aliphatic or alicyclic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclopentylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-di(isocyanatomethyl)cyclohexane, 1,4-di(isocyanatomethyl)cyclohexane, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more.

[0026] A chain extender can also be used for the polyurethane resin. Examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, and dicyclohexylmethane-4,4'-diamine, as well as amines having a hydroxyl group in the molecule, such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. These chain extenders can be used alone or in combination of two or more.

[0027] In addition, a monovalent active hydrogen compound can be used as a terminal blocking agent for the polyurethane resin to terminate the reaction. Examples of such compounds include dialkylamines such as di-n-butylamine, and alcohols such as ethanol and isopropyl alcohol. Furthermore, when it is particularly desired to introduce carboxyl groups into the polyurethane resin, amino acids such as glycine and L-alanine can be used as reaction terminators. These terminal blocking agents can be used alone or in combination of two or more.

[0028] The weight average molecular weight of the polyurethane resin is preferably 10,000 to 100,000, and more preferably in the range of 15,000 to 80,000.

[0029] In the present invention, the number-average and weight-average molecular weights are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0030] Measurement equipment: High-speed GPC equipment (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

[0031] "TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mmI.D. x 30cm) x 1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene. [Standard polystyrene] Tosoh Corporation's "TSKgel Standard Polystyrene A-500" Tosoh Corporation's "TSKgel Standard Polystyrene A-1000" Tosoh Corporation's "TSKgel Standard Polystyrene A-2500" Tosoh Corporation's "TSKgel Standard Polystyrene A-5000" "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation Tosoh Corporation's "TSKgel Standard Polystyrene F-2" Tosoh Corporation's "TSKgel Standard Polystyrene F-4" Tosoh Corporation's "TSKgel Standard Polystyrene F-10" Tosoh Corporation's "TSKgel Standard Polystyrene F-20" Tosoh Corporation's "TSKgel Standard Polystyrene F-40" Tosoh Corporation's "TSKgel Standard Polystyrene F-80" Tosoh Corporation's "TSKgel Standard Polystyrene F-128" Tosoh Corporation's "TSKgel Standard Polystyrene F-288" Tosoh Corporation's "TSKgel Standard Polystyrene F-550" The proportion of the polyurethane resin in the total amount of the binder resin is preferably 5% by mass or more, preferably 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more, from the viewpoint of improving adhesion to the metal surface. On the other hand, the proportion of the polyurethane resin in the total amount of the binder resin is preferably 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less, from the viewpoint of improving adhesion to both the metal surface and the printing layer. Here, this proportion refers to the proportion in solid content.

[0032] --Polyester resin-- The polyester resin is not particularly limited as long as it is a polyester resin obtained by reacting an alcohol with a carboxylic acid using a known esterification polymerization reaction. Examples of the alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,2-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butynediol, and 1,4-butylenediol. Examples of the alcohols include diol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, spiroglycol, and isosorbide. These may be used alone or in combination of two or more. Among these, polyfunctional alcohols are preferred.

[0033] Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and 1,4-cyclohexanedicarboxylic acid. These may be used alone or in combination of two or more. Among these, polyfunctional carboxylic acids are preferred.

[0034] The polyester resin preferably has a weight average molecular weight of 3,000 to 45,000, more preferably 20,000 to 30,000.

[0035] The proportion of the polyester resin in the total amount of the binder resin is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more, from the viewpoint of improving adhesion to the printing layer. On the other hand, the proportion of the polyester resin in the total amount of the binder resin is preferably 50% by mass or less, more preferably 45% by mass or less, and more preferably 40% by mass or less, from the viewpoint of improving adhesion to both the metal surface and the printing layer. Here, this proportion refers to the proportion in solid content.

[0036] The mass ratio of the polyurethane resin to the polyester resin in solid content is preferably polyurethane resin:polyester resin=1:4 to 4:1, and more preferably 2:3 to 3:2.

[0037] The total mass of the polyurethane resin and the polyester resin in the total mass of the binder resin is preferably in the range of 30% by mass to 90% by mass, more preferably 40% by mass to 80% by mass, and even more preferably 50% by mass to 70% by mass, where the ratio refers to the ratio in terms of solid content. -Other binder resins- Examples of binder resins other than the polyurethane resin and polyester resin include cellulose resin, urethane-modified polyester resin, ketone resin, rosin resin, and acrylic resin. Examples of other binder resins include polyamide resin, chlorinated polypropylene resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, and vinyl chloride resin such as polyvinyl chloride resin, alkyd resin, cyclized rubber, chlorinated rubber, polyvinyl butyral resin, and petroleum resin. Among these, preferred binder resins are cellulose resin, urethane-modified polyester resin, ketone resin, rosin resin, acrylic resin, and polyvinyl butyral resin. The inclusion of a urethane-modified polyester resin, as described below, can further improve the adhesion between the metal surface and the printing layer. Furthermore, it is preferable that the binder resin does not contain a chlorine-based resin (a resin containing chlorine), such as a vinyl chloride-vinyl acetate copolymer. The absence of a chlorine-based resin can reduce the generation of environmentally harmful substances and improve recyclability. --Cellulose resin-- Examples of the cellulose resin (cellulose-based resin) include cellulose ester resins such as cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), soluble cellulose resins, hydroxyalkyl cellulose, and carboxyalkyl cellulose. The cellulose ester resin preferably has an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, and a hexyl group, and the alkyl group may further have a substituent. The cellulose resin is preferably soluble cellulose resin.

[0038] The cellulose resin preferably has a weight-average molecular weight of 5,000 to 200,000, more preferably 10,000 to 50,000. The cellulose resin preferably has a glass transition temperature of 120° C. to 180° C. Use of the cellulose resin is expected to improve the blocking resistance, scratch resistance, and other physical properties of the ink film.

[0039] --Nitrified cotton resin-- The soluble nitrocellulose resin is preferably obtained as a nitric acid ester by reacting natural cellulose with nitric acid to replace three hydroxyl groups in the six-membered ring of the anhydroglucopyranose group in the natural cellulose with nitric acid groups. The use of nitrocellulose (nitrocellulose solubles) provides high dispersibility in pigments, making it particularly suitable for use as a surface printing coating agent, as it can improve the strength of the printing ink film. The nitrocellulose solubles preferably have a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 30 to 500, and more preferably have a nitrogen content of 10 to 13% by mass and an average degree of polymerization of 45 to 290.

[0040] The proportion of the soluble nitrocellulose resin in the total amount of the binder resin is preferably in the range of 10% to 60% by mass, more preferably 20% to 50% by mass, and even more preferably 25% to 45% by mass, since a higher proportion is advantageous in terms of preventing blocking, but a higher proportion leads to poorer adhesion to the original substrate and poorer adhesion to the overprinted ink.

[0041] The total mass of the polyurethane resin, polyester resin, and soluble nitrocellulose resin in the total amount of the binder resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, where the ratio refers to the ratio in terms of solid content. --Ketone-based resins-- Examples of the ketone resin include known resins, and for example, formaldehyde resin, cyclohexanone-formaldehyde resin, ketone aldehyde condensation resin, etc. can be suitably used. --Rosin-based resin-- The rosin resin is not particularly limited as long as it is a resin having a rosin skeleton, but preferred are rosin-modified maleic acid resin, rosin ester, rosin phenol, polymerized rosin, etc. The rosin resin preferably has a softening point (measured by the ring and ball method) of 90 to 200°C. --Acrylic resin-- The acrylic resin is not particularly limited as long as it is a copolymer of polymerizable monomers whose main component is a (meth)acrylic acid ester. Examples of polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, iso-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Here, "(meth)acrylate" refers to both acrylate and methacrylate. The polymerization method is not particularly limited, and those obtained by known methods such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

[0042] The acrylic resin preferably has a weight average molecular weight of 5,000 to 200,000, more preferably in the range of 10,000 to 100,000. --Polyvinyl butyral resin-- The polyvinyl butyral resin is not particularly limited and any known polyvinyl butyral resin can be used. In general, a reaction product obtained by acetalizing polyvinyl alcohol with butyraldehyde by a known reaction can be used as the polyvinyl butyral resin.

[0043] The polyvinyl butyral resin preferably has a weight-average molecular weight of 5,000 to 150,000, more preferably 5,000 to 60,000. The polyvinyl butyral resin preferably has a glass transition temperature (hereinafter sometimes referred to as Tg) in the range of 50°C to 120°C, more preferably 55°C to 115°C, and even more preferably 60°C to 110°C. In this specification, the glass transition temperature is determined by measurement using a differential scanning calorimeter.

[0044] The polyvinyl butyral resin preferably has a hydroxyl group content of 10% by mass to 40% by mass, more preferably 15% by mass to 30% by mass, and preferably has an acetyl group content of 8% by mass or less, more preferably 5% by mass or less.

[0045] (wax) The anchoring agent of the present embodiment preferably contains wax. An anchoring agent containing wax can prevent blocking during winding and is easy to process. The wax is preferably a polyolefin wax or a fatty acid amide wax known in the fields of anchor agents and liquid inks. Examples of the polyolefin wax include oxidized polyethylene wax and oxidized polypropylene wax. Examples of the fatty acid amide wax include saturated fatty acid amides such as stearic acid amide and palmitic acid amide, unsaturated fatty acid amides such as erucic acid amide, substituted amides, and aromatic amides.

[0046] The content of the wax is not particularly limited and may be in a known range, but is usually preferably in the range of 0.1 to 20% by mass based on the total solid content of the anchor agent.

[0047] (solvent) The anchoring agent of this embodiment may contain a solvent (preferably an organic solvent), and preferably contains at least one solvent selected from the group consisting of aromatic solvents, ketone solvents, ester solvents, and alcohol solvents. Aromatic solvents, ketone solvents, ester solvents, and alcohol solvents have good solubility for the polyurethane resins, polyester resins, and other binder resins described above. The content of the solvent in the anchoring agent is preferably in the range of 10 to 90% by mass.

[0048] Examples of the aromatic solvents include toluene, xylene, Solvesso #100, and Solvesso #150. Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ester solvents include methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, and propylene glycol monomethyl ether acetate. Examples of the alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, and propylene glycol monomethyl ether. These can be used alone or in a mixture of two or more. In recent years, from the perspective of the working environment, it has been more preferable to avoid the use of aromatic solvents such as toluene and xylene, and ketone solvents.

[0049] (others) The anchor agent of the present embodiment may further contain, as necessary, an extender pigment, a pigment dispersant, a leveling agent, an antifoaming agent, a plasticizer, an infrared absorbing agent, an ultraviolet absorbing agent, an aromatic agent, a flame retardant, and the like. In the anchor agent of this embodiment, the content of polyurethane resin and polyester resin in the total amount of the anchor agent is preferably 5 to 30 mass %, the content of other binder resins (auxiliary resins) is preferably 1 to 20 mass %, the content of solvents is preferably 10 to 90 mass %, and the content of other additives (wax, etc.) is preferably 0 to 10 mass %.

[0050] (Second Configuration) In a second configuration of the anchoring agent of the present invention, the binder resin in the anchoring agent contains a urethane-modified polyester resin.

[0051] --Urethane-modified polyester resin-- The urethane-modified polyester resin can be obtained, for example, by reacting a polyester resin having two or more functional groups such as hydroxyl groups in one molecule with a polyisocyanate compound. The polyester resin may be the same as that used in the first configuration. The polyisocyanate compound may be any of various known aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates that are commonly used in the production of polyurethane resins, and the same polyisocyanates as those used in the polyurethane resin of the first configuration may be used.

[0052] From the viewpoint of imparting excellent adhesiveness, the urethane-modified polyester resin preferably has a glass transition temperature of −55 to 110°C, more preferably −30 to 80°C, particularly preferably 0 to 50°C, and most preferably 10 to 30°C. The molecular weight of the urethane-modified polyester resin is preferably 10,000 to 40,000.

[0053] The proportion of the urethane-modified polyester resin in the total amount of the binder resin is preferably 30% by mass or more, preferably 40% by mass or more, and preferably 50% by mass or more, from the viewpoint of improving adhesion to the metal surface and the printing layer. On the other hand, there is no particular upper limit, but from the viewpoint of improving blocking properties, it is preferably 90% by mass or less, preferably 80% by mass or less, and preferably 70% by mass or less. Here, this proportion refers to the proportion in solid content.

[0054] -Other binder resins- As the binder resin other than the urethane-modified polyester resin, the same binder resins as those used in the first configuration can be used. Among these, preferred binder resins are cellulose resins, ketone resins, rosin resins, acrylic resins, and polyvinyl butyral resins. It is also preferred to contain the polyurethane resin and polyester resin used in the first configuration. By containing a polyurethane resin or a polyester resin, the adhesion between the metal surface and the printing layer can be further improved. It is also preferred that the binder resin does not contain a chlorine-based resin (a resin containing chlorine), such as a vinyl chloride-vinyl acetate copolymer. By not containing a chlorine-based resin, the generation of environmentally hazardous substances can be reduced and recyclability can be improved.

[0055] In the second configuration, the proportion of the soluble nitrocellulose resin in the total amount of the binder resin is preferably in the range of 10% by mass to 60% by mass in order to obtain an anti-blocking effect, where the proportion refers to the proportion in terms of solid content.

[0056] The total mass of the urethane-modified polyester resin and the soluble nitrocellulose resin in the total amount of the binder resin is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, where the ratio refers to the ratio in terms of solid content.

[0057] In the second configuration, the configuration other than the binder resin is the same as in the first configuration.

[0058] (hardening agent) The anchor agent of this embodiment may contain a curing agent. Examples of the curing agent include curing agents commonly used in organic solvent-based gravure inks, such as isocyanate-based curing agents. From the perspective of curing efficiency, the amount of the curing agent added is preferably in the range of 0.3% to 10.0% by mass, and more preferably 1.0% to 7.0% by mass, based on the total solids content of the liquid ink composition.

[0059] On the other hand, the anchor agent of the present embodiment is preferably used as a one-component type because it can exhibit excellent adhesion to each printed layer even in a one-component form and has excellent workability in printing.

[0060] (Application) The anchoring agent of this embodiment can be applied to printing on various objects, but is useful as an anchoring agent for a printed layer when applied to a metal surface. Specifically, since it has high adhesion to metal foils and metal vapor deposition films and excellent adhesion to various printed layers, it is particularly useful as an anchoring agent for a printed layer of metal foils or metal vapor deposition films. <Printed material> The printed matter of this embodiment is characterized by the use of the anchoring agent of this embodiment on a substrate having a metal surface. Because the printed matter of this embodiment uses the anchoring agent of this embodiment, the adhesion of the printed layer can be improved regardless of the type of printed layer provided thereon.

[0061] Examples of the printed matter include a substrate having a metal surface, a layer (anchor layer) made of the anchor agent, and a printed layer provided on the anchor layer. The substrate can be appropriately selected depending on the application, and examples include metal plates, metal sheets, metal foils, metal foil-containing substrates in which metal foil is provided on resin films or paper via an adhesive, and metal-deposited films.

[0062] Examples of metal foils include aluminum foil. Examples of resin films include those made from PET (polyethylene terephthalate), A-PET (amorphous polyethylene terephthalate), PBT (polybutylene terephthalate), BOPP (biaxially oriented polypropylene), PE (polyethylene), PVC (polyvinyl chloride), PS (polystyrene), Ny (nylon), and EVOH (ethylene-vinyl alcohol copolymer). Examples of paper include those produced using natural fibers for papermaking, such as wood pulp, on a known papermaking machine. Examples of natural fibers for papermaking include wood pulp (e.g., softwood pulp, hardwood pulp), non-wood pulp (e.g., Manila hemp pulp, sisal hemp pulp, and flax pulp), and chemically modified versions of these pulps. Examples of pulp that can be used include chemical pulp produced by sulfate cooking, acidic, neutral, or alkaline sulfite cooking, and soda cooking, as well as ground pulp, chemi-ground pulp, and thermomechanical pulp. More specifically, examples include uncoated papers such as various types of printing paper, gravure paper, kraft paper, Kent paper, copy paper, bleached paper, and newspaper; lightly coated papers; coated papers such as art paper, one-sided art paper, coated paper, one-sided coated paper, and lightweight coated paper; high-quality paper; double-glazed kraft papers for heavy-duty, general-purpose, and special purposes; unbleached wrapping papers such as ribbed kraft paper and one-sided glossy kraft paper; pure white roll paper; bleached kraft papers such as double-glazed bleached kraft paper and one-sided glossy bleached kraft paper; other bleached wrapping papers; resin-impregnated papers such as paraffin paper, cardboard, and cardboard; metal-deposited papers in which metals such as aluminum are vapor-deposited onto these papers; and laminated papers in which these papers are laminated with metal foil such as aluminum foil.

[0063] The metallized film may be the above-mentioned resin film on which a metal layer such as aluminum is deposited. Metallized paper may also be used, in which a metal such as aluminum is deposited on the above-mentioned paper.

[0064] The anchor layer can be formed on the substrate by a general printing method that has been conventionally used for printing the anchor agent on substrates, for example, by applying a coating liquid. The anchor layer is provided on the metal surface of the substrate where a printing layer is to be provided.

[0065] The average thickness of the anchor layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 μm to 10 μm, and more preferably 1 μm to 5 μm.

[0066] The printing layer provided on the anchor layer is a layer on which characters, figures, symbols, and other desired designs are printed. The anchor layer using the anchor agent of this embodiment has excellent adhesion regardless of the type of printing ink, and can be used with various printing inks. Therefore, the printing method and printing ink used in the printing layer are not particularly limited, and known printing methods and printing inks can be used. Specific examples include printing inks using gravure printing, flexographic printing, lithographic offset printing, inkjet recording printing, etc. Printing inks that combine these printing methods with methods of curing using active energy rays such as ultraviolet (UV), LED, and electron beam (EB), or methods of curing using heat, are also used. More specific examples include gravure printing ink, flexographic printing ink, ultraviolet-curable ink for lithographic offset printing, electron beam-curable ink for lithographic offset printing, ultraviolet-curable ink for inkjet recording printing, and electron beam-curable ink for inkjet recording printing.

[0067] The printed matter of the present invention may have a removable primer layer between the metal foil and the anchor layer, or between the metal vapor deposition layer and the anchor layer. The removable primer layer makes it easier to peel off the printed layer or multiple films, improves the recyclability of the film used as the substrate, and also improves the quality of recycled plastics made from recovered films.

[0068] The primer layer is preferably a film that can be detached from the substrate by treatment with an alkaline solution, for example. A known layer that can be detached from the substrate by treatment with an alkaline solution can be used, and for example, it can be dissolved or swelled by hydrolysis in the alkaline solution, thereby being detached from the substrate. As long as a film that can be detached from the substrate by treatment with an alkaline solution can be formed, the type of primer layer-forming composition that forms the primer layer is not particularly limited. For example, a composition containing a urethane resin or polyvinyl alcohol is preferred, or a composition containing a resin having an acidic group is also preferred.

[0069] Examples of the resin having an acid group include a polyurethane resin having an acid value, a resin having an acid value such as a rosin-modified maleic acid resin or a rosin-modified fumaric acid resin; a resin which is a radical copolymer such as a (meth)acrylic resin, a styrene-(meth)acrylic resin, a styrene-maleic (anhydride) resin, or a terpene-maleic (anhydride) resin, which is copolymerized with a polymerizable monomer having an acid group, such as a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, or an acid anhydride thereof, a polymerizable monomer having a sulfonic acid group such as sulfonated styrene, or a polymerizable monomer having a sulfonamide group such as vinylbenzenesulfonamide; and an acid-modified polyolefin resin, and these may be used singly or in combination.

[0070] In addition to the resin described above, the composition for forming a primer layer may contain a solvent such as an organic solvent or an aqueous solvent, an additive, etc. Examples of the additive include the same auxiliaries and acidic additives that can be added to the composition for forming an ink layer described above. <Label or packaging> The printed matter of this embodiment can be used for various purposes, but is preferably used, for example, as labels or packaging materials. Examples of labels or packaging materials include boxes for cosmetics or alcohol, beverage containers, and labels for these. They can also be used for packaging boxes for pharmaceuticals, lids for press-through packs, household goods, industrial goods, etc. [Example]

[0071] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. Hereinafter, "parts" and "%" are all based on mass unless otherwise specified.

[0072] The weight average molecular weight (polystyrene equivalent) was measured by GPC using an HLC8220 system manufactured by Tosoh Corporation under the following conditions.

[0073] Separation column: Four TSKgel GMHHR-N columns manufactured by Tosoh Corporation were used. Column temperature: 40℃ Mobile phase: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. Flow rate: 1.0mL / min Sample concentration: 1.0% by weight Sample injection volume: 100 microliters Detector: differential refractometer <Preparation of anchoring agent> The components were mixed according to the formulation shown in Table 1 to prepare anchoring agents for the Examples and Comparative Examples.

[0074] [Table 1]

[0075] In Table 1, nitrocellulose is industrial nitrocellulose L1 / 4 (nitrocellulose, solid content 70%, JIS 62.5 parts of a mixture of isopropyl alcohol / ethyl acetate / toluene (20 / 30 / 50 mass ratio) was added to 37.5 parts of K-6703 (viscosity 9.0-14.9% at 25.0% solution concentration, manufactured by Taihei Chemical Products Co., Ltd.) and mixed thoroughly to prepare a soluble nitrocellulose resin solution. This soluble nitrocellulose resin solution was used to prepare an anchoring agent. Table 1 shows the solid content.

[0076] The urethane-modified polyester resin used was Vylon (registered trademark) manufactured by Toyobo Co., Ltd. Table 1 shows the content as solid content.

[0077] The polyurethane resin was prepared by adding 233.38 parts of neopentyl glycol adipate diol (hydroxyl value: 37.4 mg KOH / g), 2.36 parts of polyethylene glycol (hydroxyl value: 280.5 mg KOH / g), and 31.58 parts of isophorone diisocyanate to a four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, and reacting at 90 ° C for 10 hours under a nitrogen stream to produce a urethane prepolymer with an isocyanate group content of 1.77% by mass. 66.8 parts of ethyl acetate was then added to this to form a homogeneous solution of the urethane prepolymer. The urethane prepolymer solution was then added to a mixture of 10.59 parts of isophorone diamine, 0.28 parts of cyclohexylamine, 387.6 parts of ethyl acetate, and 194.7 parts of isopropyl alcohol, and the mixture was stirred and reacted at 45 ° C for 5 hours to obtain a polyurethane resin solution. The obtained polyurethane resin solution had a resin solid concentration of 30.3% by mass and a weight average molecular weight (Mw) of the resin solid content of 58,000. This polyurethane resin solution was used to prepare an anchoring agent. Table 1 shows the content as solid content.

[0078] To prepare the polyester resin, 500.0 parts by mass of neopentyl glycol, 663.1 parts by mass of adipic acid, and 0.07 parts by mass of tetraisopropyl titanate as a catalyst were added to a reaction vessel equipped with a stirrer, condenser, and thermometer. The mixture was allowed to react for 20 hours at 200-220°C with stirring under a nitrogen stream, yielding a polyester resin with a number-average molecular weight (Mn) of 3,200 and a hydroxyl value of 30 mgKOH / g. This polyester resin solution was used to prepare an anchoring agent. Table 1 shows the solid content.

[0079] The solvent is the total amount of solvent in the anchor agent, and includes methyl ethyl ketone / normal propyl acetate=1 / 1 (mass ratio) in addition to the solvent used to dissolve the binder resin and the like.

[0080] The wax used was commercially available shellac wax, and the solid content is shown in Table 1.

[0081] The vinyl chloride vinyl acetate copolymer solution used to prepare the anchoring agent was Solvine (registered trademark) manufactured by Nissin Chemical Industry Co., Ltd., dissolved in methyl ethyl ketone. Table 1 shows the solid content.

[0082] The acrylic resin used was a commercially available polymer of methyl (meth)acrylate. Table 1 shows the content as solid content.

[0083] <Anchor agent evaluation 1> The resulting anchoring agent was evaluated for transferability, adhesion and blocking properties of various gravure inks or offset inks as follows.

[0084] (metastatic) A soft aluminum foil was used as the aluminum foil layer, and each anchor agent was applied to the entire surface of the soft aluminum foil. Surface printing gravure ink A, surface printing gravure ink B, reverse printing gravure ink C, paper gravure ink D, UV offset ink E, and oil-based offset ink F were printed thereon, and all inks except UV offset ink F were dried at room temperature. The curing conditions for UV offset ink F were an air-cooled metal halide lamp with an intensity of 120 W / cm and a speed of 40 m / min, and drying was performed using one lamp to obtain a printed matter.

[0085] The degree of ink transfer (degree of blurring) to the printed portion of the resulting print was evaluated.

[0086] (evaluation) 5: No smear at all 4.5: Approximately 5% of the image is blurred 4: Approximately 10% of the image is blurred 3.5: Approximately 20% of the image is blurred 3: Approximately 30% of the image is blurred 2.5: Approximately 50% of the image is blurred 2: Approximately 70% of the image is blurred 1.5: Approximately 80% of the image is blurred 1: Almost all surfaces are blurred (approximately 100%) The results are shown in Table 2.

[0087] [Table 2]

[0088] Ink A is surface printing gravure ink A (containing toluene), Brighton D: nitrocellulose / polyamide system (manufactured by DIC Graphics Corporation) Ink B is a surface gravure ink B (non-toluene, Ultima NT: nitrocellulose / polyamide type (manufactured by DIC Graphics Co., Ltd.) Ink C is a reverse printing gravure ink C: vinyl chloride / urethane type (containing toluene), Univia A (manufactured by DIC Graphics Co., Ltd.) Ink D is reverse printing gravure ink D (non-toluene, Univia NT: vinyl chloride acetate / urethane type (manufactured by DIC Graphics Co., Ltd.) Ink E is gravure ink E for paper (containing toluene, XOS-1200: vinyl chloride / acrylic (manufactured by DIC Graphics Corporation) Ink F is UV offset ink F (DC MAS (DIC Graphics Corporation) As ink G, oil-based offset ink G (NCP Naturalis (manufactured by DIC Graphics Corporation)) was used.

[0089] (adhesion) For each printed matter obtained in the same manner as in the transferability test, Nichiban cellophane tape (18 mm wide) was applied to the surface printed layer (layer of various inks), and the cellophane tape was peeled off at a 90° angle. Peeling of the printed layer was visually judged and rated on a scale of 1 to 5. The rating was in increments of 0.5, with 1 representing poor and 5 representing good, and a higher rating indicates better adhesion of the printed layer to the anchor layer.

[0090] 5: No peeling at all 4.5: Approximately 5% peeling 4: Approximately 10% peeling 3.5: Approximately 20% peeling 3: Approximately 30% peeling 2.5: Approximately 50% peeling 2: Approximately 70% peeled off 1.5: Approximately 80% peeled 1: Complete peeling (approximately 100% peeling) The results are shown in Table 3.

[0091] [Table 3]

[0092] (Blocking property) For each printed material obtained in the same manner as in the transferability test, the printed layer and the non-printed layer were overlapped so that they were in contact to prepare a measurement sample, which was then left to stand for 24 hours in a thermostatic chamber at 50°C and 0% humidity under a load of 0.1 N. After 24 hours, the measurement sample was removed, returned to room temperature, and then peeled off, and the surface condition was visually evaluated.

[0093] (Evaluation criteria) 5: No peeling at all 4: Approximately 25% peeled off 3: Approximately 50% peeled off 2: Approximately 75% peeled 1: Complete peeling (approximately 100% peeling) The results are shown in Table 4.

[0094] [Table 4]

[0095] <Anchor agent evaluation 2> Next, the adhesiveness of the resulting anchoring agent was compared with that of the original material as follows.

[0096] The anchor agent of the Example or Comparative Example was applied to the entire surface of soft aluminum foil, and then all the inks except for UV offset ink F were dried at room temperature. The curing conditions for UV offset ink F were an air-cooled metal halide lamp with an intensity of 120 W / cm and a speed of 40 m / min, using one lamp, to obtain a printed matter.

[0097] Similarly, the anchor agent of the Example or Comparative Example was applied to the entire surface of hard aluminum foil, and then all the inks except for UV offset ink F were dried at room temperature. The curing conditions for UV offset ink F were an air-cooled metal halide lamp with an intensity of 120 W / cm and a speed of 40 m / min, using one lamp, to obtain a printed matter.

[0098] Similarly, the anchor agent of the Example or Comparative Example was applied to the entire vapor-deposited surface of the vapor-deposited PET film, and then the inks other than UV offset ink F were dried at room temperature. The UV offset ink F was cured using an air-cooled metal halide lamp with an intensity of 120 W / cm and a speed of 40 m / min, using one lamp, to obtain a printed matter.

[0099] Nichiban cellophane tape (18 mm wide) was applied to the printed area of ​​the resulting print, and the cellophane tape was peeled off at a 90° angle. Peeling of the ink film was visually evaluated and rated on a scale of 1 to 5. The ratings were in increments of 0.5, with 1 being poor and 5 being good, and the higher the rating, the better the adhesion of the ink film to the hard aluminum substrate. Details of the ratings are shown below.

[0100] 5: No peeling at all 4.5: Approximately 5% peeling 4: Approximately 10% peeling 3.5: Approximately 20% peeling 3: Approximately 30% peeling 2.5: Approximately 50% peeling 2: Approximately 70% peeled off 1.5: Approximately 80% peeled 1: Complete peeling (approximately 100% peeling) The results are shown in Table 5.

[0101] [Table 5]

[0102] [Table 6]

[0103] In the table, * for Comparative Example 2 and Example 1 for vapor-deposited PET indicates that peeling occurred between the oil offset and the AC agent.

[0104] From the above results, the anchor agents of Examples 1 and 2 showed excellent adhesion to all of the various gravure inks, UV offset ink F, and oil-based offset ink G, and also had excellent blocking and transfer properties.

[0105] On the other hand, Comparative Example 1 was inferior to UV offset ink G and oil-based offset ink F, and Comparative Example 2 was inferior to various gravure inks.

Claims

1. Contains a binder resin, The binder resin is an anchoring agent containing both a urethane resin and a polyester resin, or a urethane-modified polyester resin.

2. It also contains nitrocellulose resin The anchoring agent according to claim 1 .

3. The molecular weight of the urethane-modified polyester resin is 10,000 to 40,000. The anchoring agent according to claim 1 or 2.

4. The urethane resin, polyester resin, and urethane-modified polyester resin are contained The anchoring agent according to claim 1 or 2.

5. Further, it contains wax The anchoring agent according to claim 1 or 2.

6. Further, the ink contains at least one solvent selected from the group consisting of aromatic solvents, ketone solvents, ester solvents, and alcohol solvents. The anchoring agent according to claim 1 or 2.

7. Contains no chlorine-based resin The anchoring agent according to claim 1 or 2.

8. Used for metal foil or metal vapor deposition film The anchoring agent according to claim 1 or 2.

9. A substrate having a metal foil or a metal vapor-deposited film on its surface, an anchor layer provided on the substrate, and a printing layer provided on the anchor layer, The printed matter, wherein the anchor layer is a layer formed by the anchor agent according to claim 1 or 2.

10. A label or packaging material using the printed matter according to claim 9.

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