CN110945044B - Composition and printing ink - Google Patents

Abstract

The present invention provides: a composition characterized by containing an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B), a composition characterized by containing a resin component (C) in addition to the acid group-containing urethane (meth) acrylate resin (A) and the metal complex (B), a printing ink obtained by using the composition, and a printed matter obtained by printing the printing ink. By blending the composition in a printing ink, a printing ink having high fluidity and excellent gloss of a printed surface can be formed.

Description

Composition and printing ink

Technical Field

The present invention relates to a composition that can be suitably used for printing ink applications, a printing ink using the composition, and a printed article obtained by printing the printing ink.

Background Art

Active energy ray-curable printing inks are easy to handle because they can be cured instantly by irradiation with energy rays such as ultraviolet rays. They are basically used without solvents, so they have a relatively low environmental impact. Due to the above advantages, they are used for paper printing and plastic packaging materials. However, on the other hand, due to the aforementioned instant curing property, there are also the following problems: low leveling of the printed surface, difficulty in producing gloss, and low adhesion to the printed surface compared to oil-based inks, which are unique to active energy ray-curable printing inks. Effective solutions to these problems are sought.

As binder resins for active energy ray-curable printing inks, diallyl phthalate resins having excellent compatibility with reactive diluents such as dipentaerythritol polyacrylate and rosin-modified (meth)acrylate resins having excellent substrate adhesion are known. However, any of these technologies still have issues related to the gloss of the printed surface.

Prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Publication No. 2010-100821

Summary of the invention

Problem that the invention aims to solve

Therefore, an object of the present invention is to provide a printing ink having excellent printing surface gloss.

Solutions for solving problems

The inventors have conducted intensive studies to solve the above problems and have found that by blending a composition containing an acid group-containing urethane (meth)acrylate resin and a metal complex into a printing ink, the fluidity of the printing ink is improved, resulting in a high-gloss printed surface, thereby completing the present invention.

That is, the present invention relates to a composition comprising: an acid group-containing urethane (meth)acrylate resin (A); and a metal complex (B).

The present invention also relates to a printing ink prepared using the above composition.

The present invention also relates to a printed matter obtained by printing the above-mentioned printing ink.

Effects of the Invention

According to the present invention, it is possible to provide a printing ink having excellent printed surface gloss, a printed article using the same, and a composition useful as a raw material for the printing ink.

DETAILED DESCRIPTION

The composition of the present invention contains an acid group-containing urethane (meth)acrylate resin (A) and a metal complex (B). The aforementioned acid group-containing urethane (meth)acrylate resin (A) has a urethane bonding site in the molecular structure and has an acid group such as a carboxyl group, and other specific structures are not particularly limited. In addition, in the present invention, (meth)acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule. In addition, (meth)acryloyl refers to one or both of acryloyl and methacryloyl, and (meth)acrylate refers to the general term for acrylate and methacrylate.

Examples of the urethane (meth)acrylate resin (A) include a polyisocyanate compound (a1), a hydroxy (meth)acrylate compound (a2), and an acid group-containing hydroxy compound (a3) as essential reaction raw materials.

The polyisocyanate compound (a1) includes, for example, aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as toluene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate; polyisocyanate compounds having a repeating structure represented by the following structural formula (1); isocyanurate-modified products, biuret-modified products, and allophanate-modified products thereof. Each of these may be used alone or in combination of two or more.

[In the formula, ^R1 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. ^R2 is independently an alkyl group having 1 to 4 carbon atoms or a bonding point connected to the structural part represented by the structural formula (1) via a methylene group marked with an *. l is 0 or an integer of 1 to 3, and m is an integer greater than 1.]

Among the polyisocyanate compounds (a1), it is preferred to use polyisocyanate compounds having an average functional group number of 3 or more, such as polyisocyanate compounds having a molecular structure represented by the structural formula (1) and isocyanurate modified products of various diisocyanate compounds, in order to obtain a printing ink having excellent fluidity and gloss of the printed surface, and also excellent general printing adaptability such as ink splash resistance and emulsification adaptability. In particular, the ratio of the polyisocyanate compounds having an average functional group number of 3 or more in the polyisocyanate compound (a1) is preferably 70% by mass or more, more preferably 90% by mass or more. In addition, when the polyisocyanate compound is an isocyanurate modified product, the raw material diisocyanate compound is preferably an aliphatic or alicyclic diisocyanate compound, and an aliphatic diisocyanate compound is particularly preferred.

Examples of the hydroxy(meth)acrylate compound (a2) include: aliphatic hydroxymono(meth)acrylate compounds such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and hydroxybutyl acrylate; aliphatic hydroxypoly(meth)acrylate compounds such as glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenylethyl acrylate, 4-hydroxyphenylethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetyl acrylate; Aromatic hydroxy mono(meth)acrylate compounds such as phenyl ester and 2-hydroxy-3-phenoxypropyl acrylate; polyoxyalkylene-modified monohydroxy(meth)acrylate compounds obtained by ring-opening polymerization of the aforementioned various hydroxy(meth)acrylate compounds and various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether; lactone-modified hydroxy(meth)acrylate compounds obtained by polycondensation of the aforementioned monohydroxy(meth)acrylate compounds and lactone compounds such as ε-caprolactone, etc. These may be used alone or in combination of two or more.

Among the hydroxy(meth)acrylate compounds (a2), the aliphatic hydroxymono(meth)acrylate compounds, the aliphatic hydroxypoly(meth)acrylate compounds, and their polyoxyalkylene modified or lactone-modified forms are preferred, and lactone-modified aliphatic hydroxy(meth)acrylate compounds are more preferred, and lactone-modified aliphatic hydroxymono(meth)acrylate compounds are particularly preferred, from the perspective of being able to obtain a printing ink having excellent fluidity and gloss on the printed surface, and also excellent general printing adaptability such as ink splash resistance and emulsification adaptability. Furthermore, the ratio of the lactone-modified aliphatic hydroxymono(meth)acrylate compounds in the hydroxy(meth)acrylate compound (a2) is preferably 70% by mass or more, and more preferably 90% by mass or more.

The aforementioned acid group-containing hydroxy compound (a3) only needs to have an acid group such as a carboxyl group and a hydroxyl group in the molecular structure, and the number of carboxyl groups and hydroxyl groups and other specific structures are not particularly limited. In addition, the acid group-containing hydroxy compound (a3) can be used alone or in combination of two or more. Among them, from the aspect of being able to obtain a printing ink with better fluidity and gloss on the printed surface, an aliphatic compound is preferred, and a compound having 1 to 3 carboxyl groups and 1 to 3 hydroxyl groups on an aliphatic hydrocarbon having 2 to 20 carbon atoms is more preferred. Specific examples of such compounds include monohydroxy compounds such as glycolic acid, lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxydodecanoic acid, hydroxytetradecanoic acid, hydroxyhexadecanoic acid, hydroxyheptadecanoic acid, hydroxyoctadecanoic acid (hydroxystearic acid), and ricinoleic acid; dihydroxy compounds such as glyceric acid, 2-(hydroxymethyl)-3-hydroxypropionic acid, 2-(dihydroxymethyl)propionic acid, dihydroxymethylpropionic acid, and 3,3-dihydroxymethylpropionic acid; and trihydroxy compounds such as 3-hydroxy-2,2-bis(hydroxymethyl)propionic acid.

The acid group-containing urethane (meth) acrylate resin (A) may be used in combination with the polyisocyanate compound (a1), the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3), and other reaction raw materials. Examples of other reaction raw materials include polyol compounds other than the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3). Examples of the aforementioned polyol compounds include: aliphatic polyol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified products obtained by introducing (poly)oxyethylene chains such as (poly)oxypropylene chains and (poly)oxytetramethylene chains into the molecular structures of the aforementioned various polyol compounds; lactone modified products obtained by introducing (poly)lactone structures into the molecular structures of the aforementioned various polyol compounds, etc.

When the aforementioned other reaction raw materials are used, from the aspect of being able to fully exert the effects of the present invention, the ratio of the total mass of the aforementioned polyisocyanate compound (a1), the aforementioned hydroxy (meth) acrylate compound (a2) and the aforementioned acid group-containing hydroxy compound (a3) in the reaction raw materials of the aforementioned acid group-containing urethane (meth) acrylate resin (A) is preferably 70% by mass or more, more preferably 90% by mass or more.

The method for manufacturing the acid group-containing urethane (meth) acrylate resin (A) is not particularly limited, and it can usually be manufactured using the same method as a general urethane (meth) acrylate resin. The reaction ratio of each component, the reaction order, etc. can be appropriately adjusted according to the desired resin design and resin performance, and are not particularly limited. As an example of the reaction conditions, the following method can be cited: each reaction raw material is used in a ratio of 0.9 to 1.1 moles of hydroxyl groups in the reaction raw materials relative to 1 mole of isocyanate groups in the reaction raw materials, and heated at 20 to 120°C. In the reaction, known and commonly used urethane catalysts such as zinc octylate, various antioxidants, inhibitors, etc. can be used as desired.

The acid value of the acid group-containing urethane (meth)acrylate resin (A) is preferably in the range of 1 to 50 mgKOH/g, more preferably in the range of 3 to 40 mgKOH/g, and particularly preferably in the range of 3 to 35 mgKOH/g, from the viewpoint of obtaining a printing ink having better fluidity and gloss on the printed surface. In the present invention, the acid value of the resin is a value measured by the neutralization titration method of JIS K0070 (1992).

The mass average molecular weight (Mw) of the acid group-containing urethane (meth)acrylate resin (A) is preferably in the range of 1,000 to 25,000, more preferably in the range of 1,000 to 10,000, from the viewpoint of obtaining a printing ink having better fluidity and gloss of the printed surface when used for printing ink.

In the present invention, the molecular weight of a resin is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation

Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation

+ TSK-GEL SuperHZM-M×4 made by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: Multi station GPC-8020modelII manufactured by Tosoh Corporation

Determination conditions: column temperature 40°C

Solvent Tetrahydrofuran

Flow rate 0.35ml/min

Standard; monodisperse polystyrene

Sample: A substance obtained by filtering a tetrahydrofuran solution having a resin solid content of 0.2% by mass using a microfilter (100 μl)

Examples of the metal complex (B) include: aluminum trialkanolates such as aluminum triethoxide, aluminum tripropoxide, aluminum dipropoxide monobutyrate, and aluminum tributoxide; alkyl aluminum acetoacetates such as aluminum dipropyl acetoacetate, aluminum dibutyl acetoacetate, aluminum triacetoacetate, ethyl aluminum dipropyl acetoacetate, tris(ethylacetoacetoxy)aluminum, and aluminum octadecyl aluminum dipropyl acetoacetate; titanium tetraalkoxides such as titanium tetrapropoxide and titanium tetrabutoxide; titanium alkyl acetoacetates such as bis(acetoacetoxy)titanium dipropyl ester; zirconium tetraalkoxides such as zirconium tetrabutoxide, and the like. Specific commercial products thereof include, for example, aluminum organic compound series manufactured by Kawaken Fine Chemicals Co., Ltd. ("AMD", "ASBD", "AIPD", "PADM", "Aluminum ethoxide", "ALCH", "ALCH-TR", "Aluminum Chelate M", "Aluminum Chelate D", "Aluminum Chelate A, A(W)"), "Plenact" series manufactured by Ajinomoto Fine-Techno Co., Inc. ("AL-M", "TTS"), and "ORGATIX" series manufactured by Matsumoto Fine Chemical Co., Ltd. ("AL-3001", "AL-3100", "AL-3200", "AL-3215", "TA-8", "TA-21", "TA-23", "TA-30", "TC-100", "TC-401", "TC-710", "TC-750", "ZA-45", "ZA-65", "AC-150", "ZC-540"), etc. The metal complex (B) may be used alone or in combination of two or more.

The amount of the metal complex (B) compounded can be appropriately adjusted according to the desired ink properties, etc., and is preferably in the range of 0.5 to 20 parts by mass, and particularly preferably in the range of 1 to 15 parts by mass, relative to 100 parts by mass of the acid group-containing urethane (meth)acrylate resin (A), from the perspective of forming a printing ink having high fluidity, excellent gloss on the printed surface, and sufficiently high other properties such as ink splash resistance and emulsification adaptability.

In addition to the aforementioned acid-containing urethane (meth) acrylate resin (A) and metal complex (B), the composition of the present invention may also contain other components such as other resin components (C). As an example of the aforementioned other resin components (C), various (meth) acrylate monomers (C1), urethane (meth) acrylate resins (C2) other than the aforementioned (A) component, epoxy (meth) acrylate resins (C3), polyester (meth) acrylate resins (C4), ketone resins (C5), diallyl phthalate (DAP) resins (C6), etc. can be cited. The effect of the present invention, that is, the effect of forming a printing ink with high fluidity and excellent gloss on the printed surface by using the composition containing the acid-containing urethane (meth) acrylate resin (A) and the metal complex (B) for printing ink purposes, can be fully exerted regardless of the resin of the other resin component (C). Therefore, the aforementioned other resin component (C) can use any various resin materials that can be used for printing inks without special restrictions, and a part of the specific examples are listed below.

Examples of the (meth)acrylate monomer (C1) include: aliphatic mono(meth)acrylate compounds such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, and butyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; benzyl(meth)acrylate, Aromatic mono(meth)acrylate compounds such as phenoxy esters; hydroxyl-containing mono(meth)acrylate compounds such as hydroxyethyl(meth)acrylate and hydroxypropyl(meth)acrylate; polyoxyalkylene-modified mono(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains into the molecular structures of the aforementioned various mono(meth)acrylate compounds; lactone-modified mono(meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structures of the aforementioned various mono(meth)acrylate compounds;

Aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains into the molecular structures of the aforementioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structures of the aforementioned various di(meth)acrylate compounds;

Aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerol tri(meth)acrylate; hydroxyl-containing tri(meth)acrylate compounds such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate and dipentaerythritol tri(meth)acrylate; polyoxyalkylene-modified tri(meth)acrylate compounds obtained by introducing polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains and polyoxytetramethylene chains into the molecular structures of the aforementioned various tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds obtained by introducing (poly)lactone structures into the molecular structures of the aforementioned various tri(meth)acrylate compounds;

Aliphatic poly(meth)acrylate compounds having four or more functional groups, such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; poly(meth)acrylate compounds having four or more functional groups, such as dipentaerythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate; poly(meth)acrylate compounds having four or more functional groups, such as polyoxyalkylene chains, such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains, which are introduced into the molecular structures of the aforementioned poly(meth)acrylate compounds; lactone-modified poly(meth)acrylate compounds having four or more functional groups, which are introduced into the molecular structures of the aforementioned various poly(meth)acrylate compounds, and the like.

The urethane (meth) acrylate resin (C2) includes, for example, those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as required. Specific examples of these respective reaction raw materials include those exemplified in the description of the urethane (meth) acrylate resin (A) containing an acid group.

Examples of the epoxy (meth)acrylate compound (C3) include (meth)acrylates of epoxy group-containing compounds such as bisphenol epoxy resins and trimethylolpropane triglycidyl ether. The epoxy (meth)acrylate compound (C3) may have a polyoxyalkylene chain in its molecular structure.

The polyester (meth)acrylate resin (C4) may be any (meth)acrylate resin having a polyester structure in its molecular structure, and may be an alkyd resin type in which a part of the reaction raw materials includes oils and fats or fatty acids, or a urethane-modified type in which a part of the reaction raw materials includes polyisocyanate.

In the composition of the present invention, the amount of the aforementioned other resin component (C) compounded can be appropriately adjusted according to the desired ink performance, etc. From the perspective of being able to more effectively exert the effects of the present invention, the total mass of the aforementioned acid group-containing urethane (meth) acrylate resin (A) and the aforementioned metal complex (B) is preferably in the range of 0.5 to 20 mass %, and more preferably in the range of 1 to 10 mass %, relative to the total of the aforementioned acid group-containing urethane (meth) acrylate resin (A), the aforementioned metal complex (B) and the other resin components (C).

The composition of the present invention can be suitably used mainly for active energy ray-curable printing inks, and preferably contains a photopolymerization initiator corresponding to the irradiated active energy ray. As the photopolymerization initiator, for example, alkyl phenyl ketone-based photopolymerization initiators such as 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; intramolecular hydrogen abstraction-type photopolymerization initiators such as benzophenone compounds, etc. They can be used alone or in combination of two or more. In addition, the selection of the photopolymerization initiator can be selected according to the type of active energy ray irradiated, etc.

Examples of commercially available photopolymerization initiators include the "IRGACURE" series manufactured by BASF ("IRGACURE 127", "IRGACURE 184", "IRGACURE 250", "IRGACURE 270", "IRGACURE 290", "IRGACURE 369E", "IRGACURE 379EG", "IRGACURE 500", "IRGACURE 651", "IRGACURE 754", "IRGACURE 819", "IRGACURE 907", "IRGACURE 1173", "IRGACURE 2959", "IRGACURE MBF", "IRGACURE TPO", "IRGACURE OXE01", "IRGACURE "OXE02"), "OMNIRAD" series ("OMNIRAD184", "OMNIRAD250", "OMNIRAD369", "OMNIRAD369E", "OMNIRAD651", "OMNIRAD907FF", "OMNIRAD1173") manufactured by IGMRESINS, "DAIDOUV-CURE" series, "BENZOPHENONE", "PHOTOCURE50", "PHOTOCURE550", "E AB-SS" manufactured by Daido Chemical Industry Co., Ltd. These photopolymerization initiators are preferably used in an amount of about 0.05 to 20 parts by mass in a total of 100 parts by mass of the composition.

The composition of the present invention may contain a photosensitizer together with the polymerization initiator. Examples of the photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, sulfur compounds such as S-benzylisothiouronium p-toluenesulfonate, etc. These photosensitizers are preferably used in an amount of about 0.1 to 10 parts by mass in a total of 100 parts by mass of the composition.

The composition of the present invention may also contain various additives contained in conventional printing inks, such as pigments, dyes, extender pigments, organic or inorganic fillers, organic solvents, antistatic agents, defoaming agents, viscosity modifiers, polymerization inhibitors, light stabilizers, weather stabilizers, heat stabilizers, ultraviolet absorbers, antioxidants, leveling agents, pigment dispersants, waxes, etc.

The pigments include known and commonly used organic pigments for coloring, such as organic pigments for printing inks described in "Handbook of Organic Pigments (author: Hashimoto Isao, publisher: Color Office, first edition in 2006)", soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrene pigments, isoindolinone pigments, isoindolinone pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments, etc. The addition amount of these pigments varies depending on the type of pigment, and preferably ranges from 5 to 30 parts by mass relative to 100 parts by mass of the total composition.

Examples of the extender pigment include titanium oxide, graphite, zinc, carbonated lime powder, precipitated calcium carbonate, gypsum, clay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, glass microspheres, etc. The amount of these extenders added varies depending on the type of pigment, and is preferably in the range of 0.1 to 20 parts by mass relative to a total of 100 parts by mass of the composition.

In the composition and printing ink of the present invention, the blending ratio of each component is not particularly limited, and the compounding material and blending ratio can be appropriately adjusted according to the target printing application, performance, etc. All components can be mixed at once, or mixed in batches such as mixing a part to make a premix and then mixing with other components. The mixing method is not particularly limited, and examples include a method of stirring and mixing with a mixer, a method using a three-roll mill, a method using a disperser such as a bead mill, etc.

The printing ink of the present invention can be cured by irradiation with active energy rays. Examples of the active energy rays include ultraviolet rays, electron rays, ionizing radiation such as α rays, β rays, and γ rays. Examples of light sources include germicidal lamps, fluorescent lamps for ultraviolet rays, UV-LEDs, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultrahigh-pressure mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as a light source, and electron rays generated by scanning or curtain-type electron beam accelerators.

The printing ink of the present invention can be printed on various substrates such as paper and various plastic films. Specifically, the following substrates can be used as printing objects: paper substrates used for packaging of catalogs, posters, flyers, CD sleeves, direct mail advertisements, brochures, cosmetics, beverages, pharmaceuticals, toys, machines, etc.; plastic film substrates such as polypropylene films and polyethylene terephthalate films, and packaging materials for food, beverages, cosmetics, etc.; aluminum foil, synthetic paper, and other various substrates that have been used as printing substrates.

The printing method of the printing ink of the present invention is not particularly limited, for example, printing can be performed by lithographic offset printing, relief printing, gravure printing, gravure offset printing, flexographic printing, screen printing, etc. Among them, it is particularly suitable for lithographic offset printing in which water is continuously supplied to the plate surface. The offset printing machine for continuously supplying water is manufactured and sold by multiple printing machine manufacturers. As an example, Heidelberg Company, KOMORI Corporation, RYOBI MHI Graphic Technology Ltd., manroland AG, KBA Company, etc. can be cited. In addition, the present invention can be suitably utilized in a sheet-fed offset printing machine using printing paper in sheet form, an offset rotary printing machine using printing paper in reel form, and any paper supply method. More specifically, offset printing machines such as the Speedmaster series made by Heidelberg Company, the RISURON series made by KOMORI Corporation, and the Diamond series made by RYOBI MHI Graphic Technology Ltd. can be cited.

Example

Hereinafter, the present invention will be described in more detail by way of examples. It should be noted that the present invention is not limited to these examples.

Determination of infrared absorption spectrum

[Model] FT/IR-4100 manufactured by JASCO Corporation

[Measurement Conditions] The completion of the reaction was confirmed by confirming the infrared absorption spectrum at 2250 cm ^-1 indicating an isocyanate group.

Determination of mass average molecular weight (Mw)

The measurement was performed by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220GPC manufactured by Tosoh Corporation

Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation

+ TSK-GEL SuperHZM-M×4 made by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: Multi station GPC-8020modelII manufactured by Tosoh Corporation

Determination conditions: column temperature 40°C

Solvent Tetrahydrofuran

Flow rate 0.35ml/min

Standard; monodisperse polystyrene

Sample: A substance obtained by filtering a tetrahydrofuran solution having a resin solid content of 0.2% by mass using a microfilter (100 μl)

Acid value determination conditions

The measurement was carried out by the neutralization titration method of JIS K0070 (1992).

Production Example 1 Production of urethane (meth)acrylate resin (A-1)

In a flask equipped with a stirrer, a gas inlet pipe, a condenser and a thermometer, 187.1 parts by mass of lactone-modified hydroxyethyl acrylate ("PLACCEL FA2D" manufactured by Daicel Corporation), 16.1 parts by mass of 12-hydroxystearic acid, and 0.17 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65°C. 108.6 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 95°C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250cm ^-1 representing the isocyanate group disappeared, and the target urethane (meth) acrylate resin (A-1) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-1) is 4,477 and the acid value is 11.2 mgKOH/g.

Production Example 2 Production of urethane (meth) acrylate resin (A-2)

In a flask equipped with a stirrer, a gas inlet pipe, a condenser and a thermometer, 143.3 parts by mass of lactone-modified hydroxyethyl acrylate ("PLACCEL FA2D" manufactured by Daicel Corporation), 6.0 parts by mass of 12-hydroxystearic acid, and 0.12 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65°C. 79.8 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) were added dropwise over 1 hour. After the addition was completed, it was heated to 95°C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250cm ^-1 representing the isocyanate group disappeared, and the target urethane (meth) acrylate resin (A-2) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-2) is 4,275 and the acid value is 6.0 mgKOH/g.

Production Example 3 Production of urethane (meth)acrylate resin (A-3)

In a flask equipped with a stirrer, a gas inlet pipe, a condenser and a thermometer, 116.4 parts by mass of lactone-modified hydroxyethyl acrylate ("PLACCEL FA2D" manufactured by Daicel Corporation), 31.3 parts by mass of 12-hydroxystearic acid, and 0.12 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65°C. 79.1 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 95°C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250cm ^-1 representing the isocyanate group disappeared, and the target urethane (meth) acrylate resin (A-3) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-3) is 4,663 and the acid value is 27.3 mgKOH/g.

Production Example 4 Production of urethane (meth)acrylate resin (A-4)

In a flask equipped with a stirrer, a gas inlet pipe, a condenser and a thermometer, 201.4 parts by mass of lactone-modified hydroxyethyl acrylate ("PLACCEL FA2D" manufactured by Daicel Corporation), 3.8 parts by mass of glycolic acid, and 0.17 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65°C. 116.7 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) were added dropwise over 1 hour. After the addition was completed, the mixture was heated to 95°C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250cm ^-1 representing the isocyanate group disappeared, and the target urethane (meth) acrylate resin (A-4) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-4) is 4,135 and the acid value is 8.9 mgKOH/g.

Production Example 5 Production of urethane (meth)acrylate resin (A-5)

In a flask equipped with a stirrer, a gas inlet pipe, a condenser and a thermometer, 167.9 parts by mass of lactone-modified hydroxyethyl acrylate ("PLACCEL FA2D" manufactured by Daicel Corporation), 3.4 parts by mass of dimethylol propionic acid, and 0.17 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added and heated to 65°C. 116.9 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) were added dropwise over 1 hour. After the addition was completed, it was heated to 95°C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250cm ^-1 representing the isocyanate group disappeared, and the target urethane (meth) acrylate resin (A-5) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-5) is 4,389 and the acid value is 5.5 mgKOH/g.

Examples 1 to 7 Preparation of Compositions (1) to (8)

The components were blended in the ratio shown in Table 1 below, and stirred for 1 hour to obtain compositions (1) to (8). The details of the metal complex are as follows.

·(Meth)acrylate monomer: DAICEL-ALLNEX LTD. "OTA480", propylene oxide-modified glyceryl triacrylate, average number of propylene oxide additions per molecule 3

Metal complex (B-1): "ALCH-TR" manufactured by Kawaken Fine Chemicals Co., Ltd., tris(ethylacetoacetoxy)aluminum

Metal complex (B-2): "plenact AL-M" manufactured by Ajinomoto Fine-Techno Co., Inc., alkylaluminum diisopropyl acetoacetate

[Table 1]

Preparation of Printing Ink in Examples 9 to 21 and Comparative Example 1

The components were mixed in the ratios shown in Tables 3 to 5 below, stirred with a mixer (single-axis dissolver), and then ground with a three-roll mill to obtain a printing ink. Regarding Example 14, the components other than the composition (1) were mixed, stirred with a mixer (single-axis dissolver), ground with a three-roll mill, and then the composition (1) was added and mixed to obtain a printing ink.

The obtained printing ink was subjected to various evaluations in the following manner. The results are shown in Tables 3 to 5.

[Table 2]

Preparation Example 6 Preparation of urethane (meth) acrylate resin

In a four-necked flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, 60.3 parts by mass of polymerized diphenylmethane diisocyanate ("Millionate MR-400" manufactured by Nippon Polyurethane Industry Co., Ltd.), 0.1 parts by mass of tert-butylhydroxytoluene, 0.02 parts by mass of methoxyhydroquinone, and 0.02 parts by mass of zinc octanoate were added and heated to 75°C. While stirring the flask, 35.7 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After the addition was completed, the mixture was further reacted at 75°C for 3 hours. 4.0 parts by mass of glycerol was added, and the reaction was continued at 75°C. It was confirmed that the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group disappeared, and a urethane (meth) acrylate resin was obtained.

Liquidity Evaluation

In a room with air conditioned to 25°C, place 1.0 ml of printing ink on the top of a glass plate at an angle of 70° to the ground, and measure the flow distance after 1 day. The larger the value, the better the fluidity.

Method for making color display objects

Using a simple color development machine ("RI tester" manufactured by Toyoei Seiko Co., Ltd.), 0.10 ml of printing ink was evenly stretched on the rubber roller and metal roller of RI tester. The color was developed so that the surface of art paper ("OK Kinteng Single-sided" manufactured by Prince Paper Co., Ltd.) was evenly coated with a yellow concentration of 1.4 (measured by "SpectroEye Densitometer" manufactured by X-Rite Co., Ltd.) over an area of 200 ^cm2 to produce a color development object. It should be noted that RI tester is a test machine for developing ink on paper and film, and the transfer amount of ink and printing pressure can be adjusted.

Curing method using ultraviolet (UV) light source

The color development material obtained previously was irradiated with ultraviolet light (UV) to cure the printing ink. Specifically, an ultraviolet light (UV) irradiation device (manufactured by EYE GRAPHICS CO., LTD., with a cold mirror) equipped with a water-cooled metal halide lamp (lamp output 120W/cm1) and a belt conveyor was used, and the color development material was placed on the conveyor and passed directly under the lamp at a speed of 40 meters per minute (irradiation distance 11 cm), thereby curing the printing ink.

Gloss of printed surface

The gloss value of the printed surface of the cured color development material was measured using a 60° gloss meter (manufactured by BYK Garder GmbH) and evaluated according to the following three levels. The higher the value, the better the gloss.

(Evaluation Criteria)

A: Gloss 55 or above

B: Gloss 45 or above and below 55

C: Gloss less than 45

[Table 3]

[Table 4]

[Table 5]

Claims (7)

1. A composition comprising: an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B), wherein the central metal of the metal complex (B) is any one of aluminum, titanium and zirconium, and the acid value of the acid group-containing urethane (meth) acrylate resin (A) is in the range of 5.5 to 50 mgKOH/g. 2 . The composition according to claim 1 , wherein the mass average molecular weight (Mw) of the acid group-containing urethane (meth)acrylate resin (A) is in the range of 1,000 to 25,000. 3. The composition according to claim 1, wherein the acid group-containing urethane (meth) acrylate resin (A) has a polyisocyanate compound (a1), a hydroxy (meth) acrylate compound (a2) and an acid group-containing hydroxy compound (a3) as necessary reaction raw materials. 4 . The composition according to claim 1 , wherein the amount of the metal complex (B) is in the range of 0.5 to 20 parts by mass based on 100 parts by mass of the acid group-containing urethane (meth)acrylate resin (A). 5. The composition according to claim 1, further comprising other resin components (C) in addition to the acid group-containing urethane (meth)acrylate resin (A) and the metal complex (B), wherein the total mass of the acid group-containing urethane (meth)acrylate resin (A) and the metal complex (B) is in the range of 0.5 to 20 mass % relative to the total mass of the acid group-containing urethane (meth)acrylate resin (A) and the metal complex (B). 6 . A printing ink comprising the composition according to claim 1 . 7. A printed matter obtained by printing the printing ink according to claim 6.