WO2019017270A1 - Composition and printing ink - Google Patents

Abstract

The present invention is a composition comprising an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B), the acid group-containing urethane (meth) acrylate resin (A), A composition comprising the resin composition (C) in addition to the metal complex (B), a printing ink comprising the composition, and a printed matter obtained by printing the printing ink. The composition described above can form a printing ink having high flowability and excellent gloss on the printing surface by being blended with the printing ink.

Description

Composition and printing ink

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

Active energy ray-curable printing inks are excellent in workability because they can be instantaneously cured by irradiation with energy rays such as ultraviolet rays, and basically they are used without a solvent, so they have advantages such as relatively low environmental impact. Besides paper printing, it is used for various applications such as plastic packaging materials. However, on the other hand, the leveling property of the printing surface is low due to the above-mentioned immediate curing property so that the gloss is difficult to appear, and the adhesion to the printing surface is low compared to oil-based ink. There is also a need for effective solutions to these issues.

Examples of binder resins for active energy ray-curable printing inks include diallyl phthalate resins which are excellent in compatibility with reactive diluents such as dipentaerythritol polyacrylate, and rosin-modified (meth) acrylate resins which are excellent in substrate adhesion. Although known, issues with print surface gloss remained in any of the techniques.

Japanese Patent Laid-Open No. 2010-100821

Therefore, the problem to be solved by the present invention is to provide a printing ink excellent in printed surface gloss.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, by blending a composition containing an acid group-containing urethane (meth) acrylate resin and a metal complex into a printing ink, the flowability of the printing ink becomes As a result, it has been found that an improved, high-gloss printed surface can be obtained, and the present invention has been completed.

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

The invention further relates to a printing ink comprising the composition.

The present invention further relates to a printed material obtained by printing the printing ink.

ADVANTAGE OF THE INVENTION According to this invention, the printing ink which is excellent in printing surface gloss, the printed matter using this, and a composition useful as said printing ink raw material can be provided.

The composition of the present invention contains an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B). The acid group-containing urethane (meth) acrylate resin (A) may have a urethane bond site in the molecular structure and an acid group such as a carboxy group, and the other specific structure is not particularly limited. . In the present invention, the (meth) acrylate resin refers to a resin having an acryloyl group, a methacryloyl group, or both in the molecule. Moreover, a (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group, and a (meth) acrylate is a general term for an acrylate and a methacrylate.

As an example of the said urethane (meth) acrylate resin (A), what uses a polyisocyanate compound (a1), a hydroxy (meth) acrylate compound (a2), and an acid group containing hydroxy compound (a3) as an essential reaction raw material is mentioned. Etc.

Examples of the polyisocyanate compound (a1) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone Alicyclic diisocyanate compounds such as diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, aromatic diisocyanate compounds such as 1,5-naphthalene diisocyanate; Polyisocyanate having a repeating structure represented by the following structural formula (1) Compound; these isocyanurate modified product, a biuret modified product, and allophanate modified compounds and the like. These may be used alone or in combination of two or more.

［式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ^２はそれぞれ独立に炭素原子数１～４のアルキル基、又は構造式（１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｌは０又は１～３の整数であり、ｍは１以上の整数である。］

[Wherein, each R ¹ independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² each independently represents an alkyl group having 1 to 4 carbon atoms, or a bonding point which is linked to the structural moiety represented by the structural formula (1) via a methylene group marked with an asterisk (*). l is an integer of 0 or 1 to 3, and m is an integer of 1 or more. ]

Among the above-mentioned polyisocyanate compounds (a1), it is possible to obtain a printing ink which is excellent in fluidity and gloss of the printing surface, and is also excellent in general printability such as misting resistance and emulsification suitability. It is preferable to essentially use a polyisocyanate compound having a molecular structure represented by the above, or a polyisocyanate compound having an average functional group number of 3 or more, such as isocyanurate-modified products of various diisocyanate compounds. In particular, the proportion of the polyisocyanate compound having an average functional group number of 3 or more in the polyisocyanate compound (a1) is preferably 70% by mass or more, and more preferably 90% by mass or more. 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 preferable.

Examples of the hydroxy (meth) acrylate compound (a2) include aliphatic hydroxy mono (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl acrylate; glycerin di (meth) acrylate, Aliphatic hydroxy poly (meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate , 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3- Aromatic hydroxy mono (meth) acrylate compounds such as phenoxypropyl acrylate; various hydroxy (meth) acrylate compounds as described above, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether And polyoxyalkylene-modified monohydroxy (meth) acrylate compounds obtained by ring-opening polymerization with various cyclic ether compounds such as allyl glycidyl ether; weight of the monohydroxy (meth) acrylate compound and lactone compounds such as ε-caprolactone The lactone modified | denatured hydroxy (meth) acrylate compound etc. which are obtained by condensation are mentioned. These may be used alone or in combination of two or more.

Among the hydroxy (meth) acrylate compounds (a2), the above-mentioned fat is excellent because it is excellent in fluidity and gloss on the printing surface, and is also excellent in general printability such as misting resistance and emulsification suitability. Group hydroxy mono (meth) acrylate compounds, the above-mentioned aliphatic hydroxy poly (meth) acrylate compounds, and polyoxyalkylene modified products or lactone modifications thereof are preferable, lactone modified aliphatic hydroxy (meth) acrylate compounds are more preferable, and lactone modified Particular preference is given to aliphatic hydroxy mono (meth) acrylate compounds. Furthermore, it is preferable that the ratio of the said lactone modified | denatured aliphatic hydroxy mono (meth) acrylate compound to the said hydroxy (meth) acrylate compound (a2) is 70 mass% or more, and it is more preferable that it is 90 mass% or more.

As long as the acid group-containing hydroxy compound (a3) has an acid group such as a carboxy group and a hydroxy group in its molecular structure, the number of carboxy groups and hydroxy groups and other specific structures are not particularly limited. The acid group-containing hydroxy compounds (a3) may be used alone or in combination of two or more. Among them, an aliphatic compound is preferable because a printing ink having excellent fluidity and print surface gloss can be obtained, and an aliphatic hydrocarbon having 2 to 20 carbon atoms having 1 to 3 carboxy groups, hydroxy Compounds having 1 to 3 groups are more preferred. Specific examples of such compounds include, for example, glycolic acid, lactic acid, hydroxybutanoic acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxydodecanoic acid, hydroxy Monohydroxy compounds such as tetradecanoic acid, hydroxyhexadecanoic acid, hydroxyheptadecanoic acid, hydroxyoctadecanoic acid (hydroxystearic acid), ricinoleic acid, etc. Glyceric acid, 2- (hydroxymethyl) -3-hydroxypropionic acid, 2- (dihydroxymethyl) Dihydroxy compounds such as propionic acid, dimethylol propionic acid, 3, 3-dimethylol propionic acid; trihydroxy compounds such as 3-hydroxy-2, 2-bis (hydroxymethyl) propionic acid Compounds, and the like.

The acid group-containing urethane (meth) acrylate resin (A) is a reaction raw material other than the polyisocyanate compound (a1), the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3) May be used in combination. As another reaction raw material, polyol compounds other than the said hydroxy (meth) acrylate compound (a2) and the said acid group containing hydroxy compound (a3) etc. are mentioned, for example. Examples of the polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol and dipentaerythritol; and aromatics such as biphenol and bisphenol Polyol compounds; (Poly) oxyalkylene chains in which (poly) oxyethylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains are introduced into the molecular structures of the various polyol compounds Modified products; lactone modified products in which a (poly) lactone structure is introduced into the molecular structure of the various polyol compounds, and the like.

When the other reaction raw material is used, the effect exerted by the present invention is sufficiently exhibited. Therefore, the polyisocyanate compound (a1) in the reaction raw material of the acid group-containing urethane (meth) acrylate resin (A) The ratio of the total mass of the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3) is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the acid group-containing urethane (meth) acrylate resin (A) is not particularly limited, and in general, it can be produced by the same method as a general urethane (meth) acrylate resin. The reaction ratio of each component, the reaction order, and the like are appropriately adjusted according to the desired resin design and resin performance, and are not particularly limited. As an example of the reaction conditions, each reaction raw material is heated to a temperature of 20 to 120 ° C. at a ratio that the hydroxyl group in the reaction raw material is in the range of 0.9 to 1.1 mol with respect to 1 mol of isocyanate group in the reaction raw material. Methods are included. In the reaction, if necessary, known and conventional urethanization catalysts such as zinc octylate, various antioxidants, polymerization inhibitors and the like may be used.

The acid value of the acid group-containing urethane (meth) acrylate resin (A) is preferably in the range of 1 to 50 mg KOH / g, since a printing ink having more excellent fluidity and gloss on the printed surface can be obtained. The range of 40 mg KOH / g is more preferable, and the range of 3 to 35 mg KOH / g is particularly preferable. In the present invention, the acid value of the resin is a value measured by the neutralization titration method of JIS K 0070 (1992).

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

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

Measuring device; Tosoh Corp. HLC-8220GPC
Column; Tosoh Corp. TSK-GUARDCOLUMN SuperHZ-L
+ Tosoh Corporation TSK-GEL SuperHZM-M × 4
Detector; RI (differential refractometer)
Data processing; Tosoh Corp. multi station GPC-8020 model II
Measurement condition: Column temperature 40 ° C
Solvent: Tetrahydrofuran Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene sample: 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)

The metal complex (B) is, for example, aluminum trialkylate such as aluminum triethylate aluminum tripropylate, aluminum dipropylate monobutyrate, aluminum tributyrate etc; aluminum acetyl acetate dipropylate, aluminum acetyl acetate dibutyrate, Aluminum alkyl acetoacetates such as aluminum triacetyl acetate, aluminum ethyl acetoacetate dipropylate, aluminum tris ethyl acetoacetate, aluminum octadecyl acetoacetate dipropylate; titanium tetraalkylates such as titanium tetrapropylate, titanium tetrabutyrate; titanium bis Titanium alkylacetoacetates such as (acetyl acetate) dipropylate; Zirconium tetra alkylate such as benzalkonium tetrabutylate and the like. As specific commercial products of these, for example, aluminum organic compound series (“AMD”, “ASBD”, “AIPD”, “PADM”, “aluminum ethoxide”, “ALCH”, manufactured by Kawaken Fine Chemical Co., Ltd., "ALCH-TR", "Aluminum Chelate M", "Aluminum Chelate D", "Aluminum Chelate A, A (W)", Ajinomoto Fine Techno Co., Ltd. "Prenact" series ("AL-M", "TTS" ) “Orgatics” series (“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- 5 "," ZA-65 "," AC-150 "," ZC-540 "), and the like. The said metal complex (B) may be used individually by 1 type, and may use 2 or more types together.

Although the compounding quantity of the said metal complex (B) can be suitably adjusted according to the desired ink performance etc., in particular, it is highly fluid, it is excellent in the glossiness of a printing surface, and other performances, such as misting resistance and emulsification suitability. Since the printing ink is sufficiently high, it is preferably in the range of 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, per 100 parts by mass of the acid group-containing urethane (meth) acrylate resin (A). The range is particularly preferred.

The composition of the present invention may contain other components such as other resin component (C) in addition to the acid group-containing urethane (meth) acrylate resin (A) and the metal complex (B). Examples of the other resin component (C) include various (meth) acrylate monomers (C1), urethane (meth) acrylate resins (C2) other than the component (A), and epoxy (meth) acrylate resins (C3) And polyester (meth) acrylate resin (C4), ketone resin (C5), diallyl phthalate (DAP) resin (C6) and the like. The effect of the present invention, that is, by using a composition containing an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B) for printing ink applications, the flowability is high and the gloss of the printing surface is excellent The effect of becoming a printing ink is sufficiently exhibited regardless of which resin component (C) is used. Therefore, the other resin component (C) may be any of various resin materials that can be used for printing ink, and is not particularly limited, but some 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; cyclohexyl (meth) acrylate ) Alicyclic mono (meth) acrylate compounds such as acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl Aromatic mono (meth) acrylate compounds such as (meth) acrylates and phenoxy (meth) acrylates; hydroxyl group-containing mono (hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, etc. A) Acrylate compounds; polyoxyalkylene modified mono (meth) having a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxy tetramethylene chain introduced into the molecular structure of the various mono (meth) acrylate compounds Acrylate compounds; Lactone-modified mono (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structures of the various mono (meth) acrylate compounds;

Aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol 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, tricyclodecane dimethanol di (meth) acrylate; biphenol Aromatic di (meth) acrylate compounds such as di (meth) acrylates and bisphenol di (meth) acrylates; polyoxyethylene chains, polyoxyprosts in the molecular structures of the various di (meth) acrylate compounds Polyoxyalkylene-modified di (meth) acrylate compounds into which a polyoxyalkylene chain such as a ren chain or a polyoxytetramethylene chain is introduced; (poly) lactone structures are introduced into the molecular structures of the various di (meth) acrylate compounds A lactone modified di (meth) acrylate compound;

Aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) A hydroxyl group-containing tri (meth) acrylate compound such as acrylate; a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain introduced into the molecular structure of each of the various tri (meth) acrylate compounds Polyoxyalkylene-modified tri (meth) acrylate compounds; Lactone-modified tri (meth) acrylate compounds in which a (poly) lactone structure is introduced into the molecular structures of the various tri (meth) acrylate compounds;

Tetrafunctional or higher aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; dipentaerythritol tetra (meth) acrylate, dipentaerythritol And tetrafunctional or higher hydroxyl group-containing poly (meth) acrylate compounds such as pentaerythritol penta (meth) acrylate; polyoxyethylene chains, polyoxypropylene chains, polyoxytetramethylenes in the molecular structures of the various poly (meth) acrylate compounds; And the like. A tetrafunctional or higher polyoxyalkylene-modified poly (meth) acrylate compound into which a polyoxyalkylene chain such as a chain is introduced; (poly) lactone structure in the molecular structures of the various poly (meth) acrylate compounds Off to tetra- or higher-functional lactone-modified poly (meth) acrylate compounds, and the like.

Examples of the urethane (meth) acrylate resin (C2) include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as needed. Specific examples of these reaction raw materials include those exemplified in the explanation of the acid group-containing urethane (meth) acrylate resin (A).

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

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

In the composition of the present invention, the compounding amount of the other resin component (C) can be appropriately adjusted according to the desired ink performance etc., but the effect of the present invention can be exhibited more effectively. Acid group-containing urethane (meth) acrylate resin (A) and metal complex (B) with respect to the total of the metal complex (B) and the other resin component (C) Is preferably in the range of 0.5 to 20% by mass, and more preferably in the range of 1 to 10% by mass.

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

Commercially available products of the photopolymerization initiator include, for example, “IRGACURE” series (“IRGACURE 127”, “IRGACURE 184”, “IRGACURE 250”, “IRGACURE 270”, “IRGACURE 290”, “IRGACURE 369 E”, “IRGACURE 379 EG”, manufactured by BASF Corporation), IRGACURE 500 "," IRGACURE 651 "," IRGACURE 754 "," IRGACURE 819 "," IRGACURE 907 "," IRGACURE 1173 "," IRGACURE 2959 "," IRGACURE MBF "," IRGACURE TPO "," IRGACURE OXE 01 "," IRGACURE OXE 02 " "OMNIRAD" manufactured by IGM RESINS (“OMNIRAD 184”, “OMNIRAD 250”, “OMNIRAD 369”, “OMNIRAD 369E”, “OMNIRAD 651”, “OMNIRAD 907FF”, “OMNIRAD 1173”), “DAIDO UV-CURE” series manufactured by Daido Chemical Industries, Ltd. “BENZOPHENONE”, PHOTOCURE 50 "," PHOTOCURE 550 "," EAB-SS "etc. are mentioned. These photopolymerization initiators are preferably used in a range of about 0.05 to 20 parts by mass in 100 parts by mass of the total of the composition.

The composition of the present invention may contain a photosensitizer in combination with the above-mentioned polymerization initiator. Examples of the photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, and sulfur compounds such as sodium diethyl dithiophosphate and s-benzylisothyuronium-p-toluenesulfonate. . These photosensitizers are preferably used in the range of about 0.1 to 10 parts by mass in 100 parts by mass of the total of the composition.

The composition of the present invention may further comprise a pigment, a dye, an extender, an organic or inorganic filler, an organic solvent, an antistatic agent, an antifoamer, a viscosity modifier, a polymerization inhibitor, a light stabilizer, a weathering stabilizer, and a heat resistant stabilizer. You may contain various additives which normal printing ink contains, such as an agent, an ultraviolet absorber, an antioxidant, a leveling agent, a pigment dispersant, and a wax.

Examples of the pigment include publicly known and publicly used organic pigments for coloring, such as, for example, organic pigments for printing ink disclosed in "organic pigment handbook (author: Hashimoto Isao, publishing office: color office, 2006 first edition)" Soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone Based pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, and other polycyclic pigments can be used. The addition amount of the pigment varies in optimum value depending on the kind of the pigment and the like, but is preferably in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the total of the composition.

Examples of the extender pigment include titanium oxide, claphyte, zinc, lime carbonate powder, precipitated calcium carbonate, gypsum, clay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, Barite powder, glass beads, etc. are raised. The addition amount of these extender pigments varies in optimum value depending on the kind of pigment and the like, but is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the composition.

In the composition and printing ink of the present invention, the blending ratio and the like of each component are not particularly limited, and the blending and the blending ratio can be appropriately adjusted according to the target printing application, performance and the like. Each of the components may be blended all at once, or may be split such as blending a part with the other components after preparing a premix first. The mixing method is not particularly limited, and examples thereof include a method of stirring and mixing with a mixer or the like, a method of using a three-roll mill, and a method of using a dispersing machine such as a bead mill.

The printing ink of the present invention can be cured by irradiation with active energy rays. Examples of the active energy ray include ionizing radiation such as ultraviolet ray, electron beam, alpha ray, beta ray, and gamma ray. Examples of light sources include germicidal lamps, fluorescent lamps for ultraviolet light, UV-LEDs, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, super high pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light etc. UV rays, electron beams by a scanning or curtain type electron beam accelerator, and the like can be mentioned.

The printing ink of the present invention can be printed on various substrates such as paper and various plastic films. Specifically, paper substrates used for catalogs, posters, flyers, CD jackets, direct mails, brochures, cosmetics and beverages, pharmaceuticals, toys, equipment packages etc .; polypropylene films, polyethylene terephthalate films etc., food and beverages, Plastic film substrates for packaging materials such as cosmetics; aluminum foil, synthetic paper, and various other substrates conventionally used as printing substrates can be used as printing objects.

The printing method of the printing ink of the present invention is not particularly limited, and for example, it can be printed by lithographic offset printing, letterpress printing, gravure printing, gravure offset printing, flexographic printing, screen printing and the like. Among these, it can be suitably used particularly in lithographic offset printing in which water is continuously supplied to the printing plate. Offset printing presses that continuously supply water are manufactured and sold by a number of printing press manufacturers, and include, for example, Heidelberg, Komori Corporation, Ryobi MHI Graphic Technology, Man Roland, KBA, etc. The present invention can be suitably used in a sheet-fed offset printing press using printing sheets in a sheet form, an offset rotary printing press using printing sheets in a reel form, and any sheet feeding method. More specifically, offset printing machines such as Heidelberg's Speedmaster series, Komori Corporation's Lithlon series, Ryobi MHI Graphic Technology's diamond series, etc. can be mentioned.

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

Measurement 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 showing an isocyanate group.

Measurement of mass average molecular weight (Mw) It measured by gel permeation chromatography (GPC) of the following conditions.
Measuring device; Tosoh Corp. HLC-8220GPC
Column; Tosoh Corp. TSK-GUARDCOLUMN SuperHZ-L
+ Tosoh Corporation TSK-GEL SuperHZM-M × 4
Detector; RI (differential refractometer)
Data processing; Tosoh Corp. multi station GPC-8020 model II
Measurement condition: Column temperature 40 ° C
Solvent: Tetrahydrofuran Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene sample: 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)

Measurement conditions of acid value It measured by the neutralization titration method of JISK 0070 (1992).

Production Example 1 Production of Urethane (Meth) Acrylate Resin (A-1) In a flask equipped with a stirrer, a gas introduction pipe, a condenser and a thermometer, lactone modified hydroxyethyl acrylate ("Placcel FA2D" manufactured by Daicel Corporation) 187.1 Parts by weight, 16.1 parts by weight of 12-hydroxystearic acid, 0.17 parts by weight of aluminum N-nitroso-N-phenylhydroxylamine were added, and the mixture was heated to 65 ° C. 108.6 parts by mass of isocyanurate-modified hexamethylene diisocyanate (Sumidur N3300 manufactured by Sumika Covestrourethane Co., Ltd.) was dropped over 1 hour. After completion of the dropwise addition, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum at 2250 cm.sup.- ¹ showing the isocyanate group had disappeared, and the intended urethane (meth) acrylate resin (A-1) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-1) was 4,477, and the acid value was 11.2 mg KOH / g.

Production Example 2 Production of Urethane (Meth) Acrylate Resin (A-2) In a flask equipped with a stirrer, a gas introduction pipe, a condenser and a thermometer, lactone modified hydroxyethyl acrylate ("Placcel FA2D" manufactured by Daicel Corporation) 143.3 The parts by mass, 6.0 parts by mass of 12-hydroxystearic acid, 0.12 parts by mass of N-nitroso-N-phenylhydroxylamine aluminum were added, and the mixture was heated to 65 ° C. 79.8 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Kobesutorurethane Co., Ltd.) was dropped over 1 hour. After completion of the dropwise addition, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum at 2250 cm.sup.- ¹ showing the isocyanate group had disappeared, and the intended urethane (meth) acrylate resin (A-2) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-2) was 4,275, and the acid value was 6.0 mg KOH / g.

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

Production Example 4 Production of Urethane (Meth) Acrylate Resin (A-4) In a flask equipped with a stirrer, a gas introduction pipe, a condenser and a thermometer, lactone modified hydroxyethyl acrylate ("Placcel FA2D" manufactured by Daicel Corporation) 201.4 Parts by weight, 3.8 parts by weight of glycolic acid, and 0.17 parts by weight 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 Kobesutorurethane Co., Ltd.) was dropped over 1 hour. After completion of the dropwise addition, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum at 2250 cm.sup.- ¹ indicating the isocyanate group had disappeared, and the intended urethane (meth) acrylate resin (A-4) was obtained. The mass average molecular weight (Mw) of the urethane (meth) acrylate resin (A-4) was 4,135, and the acid value was 8.9 mg KOH / g.

Production Example 5 Production of Urethane (Meth) Acrylate Resin (A-5) In a flask equipped with a stirrer, a gas introduction pipe, a condenser and a thermometer, lactone modified hydroxyethyl acrylate ("Placcel FA2D" manufactured by Daicel Corporation) 167.9 A mass part, 3.4 mass parts of dimethylol propionic acid, and 0.17 mass part of N-nitroso-N-phenylhydroxylamine aluminum were added, and the mixture was heated to 65 ° C. 116.9 parts by mass of isocyanurate-modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) was dropped over 1 hour. After completion of the dropwise addition, the mixture was heated to 95 ° C. and reacted for 2 hours. It was confirmed that the infrared absorption spectrum at 2250 cm.sup.- ¹ showing the isocyanate group had disappeared, and the intended urethane (meth) acrylate resin (A-5) was obtained. The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (A-5) was 4,389, and the acid value was 5.5 mg KOH / g.

Examples 1 to 7 Preparation of Compositions (1) to (8) The components were blended in the proportions 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: "OTA 480" manufactured by Daicel Ornex Co., Ltd., propylene oxide modified glycerin triacrylate, average number of propylene oxide adducts per molecule 3
Metal complex (B-1): "ALCH-TR" manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum tris (ethyl acetoacetate)
Metal complex (B-2): “Plenact AL-M” manufactured by Ajinomoto Fine Techno Co., Ltd., aluminum alkyl acetoacetate diisopropylate

Examples 9 to 21 and Comparative Example 1 Production of Printing Ink Each component is compounded in the proportions shown in Tables 3 to 5 below, stirred by a mixer (single-axis dissolver), and then drawn using a three-roll mill to print I got the ink. About Example 14, after mix | blending components other than a composition (1) and stirring by a mixer (single-screw dissolver) and using 3 roll mills, it mixes and adds a composition (1), after mixing , Obtained printing ink.
The resulting printing ink was subjected to various evaluations in the following manner. The results are shown in Tables 3 to 5.

Production Example 6 Production of Urethane (Meth) Acrylate Resin In a four-necked flask equipped with a stirrer, a gas introduction pipe, a condenser, and a thermometer, polymeric diphenylmethane diisocyanate ("Milliate MR-400" manufactured by Nippon Polyurethane Industry Co., Ltd.) 60. 3 parts by mass, 0.1 parts by mass of tertiarybutylhydroxytoluene, 0.02 parts by mass of methoxyhydroquinone, and 0.02 parts by mass of zinc octylate were added, and the mixture was heated to 75 ° C. While the flask was being stirred, 35.7 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was further allowed to proceed at 75 ° C. for 3 hours. 4.0 parts by mass of glycerin was added, the reaction was continued at 75 ° C., and it was confirmed that the infrared absorption spectrum at 2250 cm ⁻¹ showing an isocyanate group disappeared, to obtain a urethane (meth) acrylate resin.

Evaluation of Fluidity In a room conditioned to 25 ° C., 1.0 ml of printing ink was placed on the top of a glass plate at an angle of 70 ° with the ground plane, and the distance of flow after one day was measured. The larger the value, the better the fluidity.

Method of Producing Displayed Color Material 0.10 ml of printing ink was uniformly stretched on a rubber roll and a metal roll of RI tester using a simple display color machine (“RI tester” manufactured by Toyoei Seiko Co., Ltd.). The surface of art paper ("OK Kinto One Side" made by Oji Paper Co., Ltd.) is spread uniformly over a 200 cm ² area with a yellow density of 1.4 (measured with "SpectroEye densitometer" made by X-Rite). The color was made to make a display. The RI tester is a tester that develops ink on paper or film, and can adjust the amount of ink transfer and printing pressure.

Method of curing with ultraviolet (UV) lamp light source The previously obtained color product was irradiated with ultraviolet (UV) light to cure the printing ink. Specifically, using a water-cooled metal halide lamp (power 120 W / cm1 lamp) and an ultraviolet (UV) irradiator (made by Eye Graphics Co., Ltd., attached with a cold mirror) equipped with a belt conveyor, the display color is placed on the conveyor The printing ink was cured by passing immediately under the lamp (irradiation distance 11 cm) at a speed of 40 meters per minute.

Gloss of Printed Surface The gloss value of the printed surface of the developed product after curing was measured with a 60 ° gloss meter (manufactured by BYK Garder GmbH) and evaluated in the following three steps. The higher the number, the better the gloss.
(Evaluation criteria)
A: Gloss 55 or more B: Gloss 45 or more 55 or less C C: Gloss 45 or less

Claims (9)

A composition comprising an acid group-containing urethane (meth) acrylate resin (A) and a metal complex (B). The composition according to claim 1, wherein the acid value of the acid group-containing urethane (meth) acrylate resin (A) is in the range of 1 to 50 mg KOH / g. 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. The acid group-containing urethane (meth) acrylate resin (A) contains the polyisocyanate compound (a1), the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3) as essential reaction raw materials The composition of claim 1. The composition according to claim 1, wherein the central metal of the metal complex (B) is any of aluminum, titanium and zirconium. The composition according to claim 1, wherein the content of the metal complex (B) is in the range of 0.5 to 20 parts by mass with respect to 100 parts by mass of the acid group-containing urethane (meth) acrylate resin (A). The acid group-containing urethane (meth) acrylate resin (A) contains, in addition to the metal complex (B), another resin component (C), and the acid group-containing urethane (meth) acrylate resin (A) relative to the total of these The composition according to claim 1, wherein the total mass of the metal complex (B) and the metal complex (B) is in the range of 0.5 to 20% by mass. A printing ink comprising the composition according to any one of claims 1 to 7. A printed matter formed by printing the printing ink according to claim 8.