TW201908423A - 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 another resin component (C) in addition to the acid group-containing urethane (meth)acrylate resin (A) and the metal complex (B); a printing ink using same; and a printed article obtained by printing with the printing ink. When mixed with a printing ink, the compositions make it possible to form a printing ink that has high fluidity and that exhibits excellent glossiness in a printed surface.

Description

   Composition and printing ink   

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

Due to the advantages of instantaneous curing due to irradiation with energy rays such as ultraviolet rays, it has excellent workability and is basically used without solvents, so the environmental load is relatively low. Active energy ray curing printing inks, in addition to paper printing, It is also used in various applications such as plastic packaging materials. However, on the other hand, there are active energy ray-curable printing prints that are due to the aforementioned curability, the leveling of the printed surface is low and it is difficult to emit gloss, and the adhesion to the printed surface is low compared to oil-based inks Mexico ’s unique issues, and effective solutions to these issues are needed.

As binder resins for active energy ray-curable printing inks, diallyl phthalate resins excellent in compatibility with reactive diluents such as dipentaerythritol polyacrylate, or substrate adhesion are known. Excellent rosin modified (meth) acrylate resin, etc., but in any technology, there is still a problem about the gloss of the printed surface.

    [Prior Technical Literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 2010-100821

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

The inventors of the present case have repeated careful research in order to solve the above-mentioned problems. By blending a composition containing an acid group-containing urethane (meth) acrylate resin and a metal complex compound into the printing ink, The fluidity of the printing ink was improved, and as a result, it was found that a high-gloss printing surface was obtained, and the present invention was 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 made using the aforementioned composition.

The invention further relates to a printed matter printed by the printing ink.

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

    [Forms for carrying out the invention]    

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) may be any one as long as it has a urethane bond site in the molecular structure and has an acid group such as a carboxyl group. The specific structure is not particularly limited. In addition, in the present invention, the (meth) acrylate resin refers to a resin having an acryl group, a methacryl group, or both of them in the molecule. In addition, (meth) acryloyl refers to one or both of acryloyl and methacryloyl, and (meth) acrylate is a general term for acrylate and methacrylate.

As an example of the aforementioned urethane (meth) acrylate resin (A), for example, a polyisocyanate compound (a1), a hydroxy (meth) acrylate compound (a2) and an acid group-containing hydroxyl group Compound (a3) is a necessary reaction raw material, etc.

Examples of the polyisocyanate compound (a1) include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethyl Aliphatic diisocyanate compounds such as hexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; toluene diisocyanate Aromatic diisocyanate compounds such as isocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; have the following structural formula (1) Polyisocyanate compounds with a repeating structure; isocyanurate modified products, biuret modified products, allophanate modified products, etc. These can be used individually or in combination of two or more.

[In the formula, R ^{1 is} independently any one of a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms. R ^{2 is} each independently an alkyl group having 1 to 4 carbon atoms, or any one of the bonding points connected through the structural part represented by the structural formula (1) and the methylene group marked with a *. l is an integer of 0 or 1 to 3, and m is an integer of 1 or more. ]

Among the aforementioned polyisocyanate compounds (a1), from the viewpoint of obtaining a printing ink that is excellent in fluidity and gloss on the printing surface, and also has general printing suitability such as misting resistance and emulsification suitability, It is preferable to use a polyisocyanate compound having an average functional group number of 3 or more, such as a polyisocyanate compound having the molecular structure represented by the aforementioned structural formula (1), or an isocyanurate modified product of various diisocyanate compounds. In particular, the ratio of the polyisocyanate compound having an average number of functional groups 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 particularly preferably an aliphatic diisocyanate compound.

Examples of the hydroxy (meth) acrylate compound (a2) include aliphatic hydroxy mono (meth) acrylic acid such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl acrylate. Ester compounds; glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylic acid Aliphatic hydroxy poly (meth) acrylate compounds such as esters; 4-hydroxyphenyl acrylate, β-hydroxyphenyl acrylate, 4-hydroxyphenyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, acrylic acid Aromatic hydroxy mono (meth) acrylate compounds such as 3-hydroxy-4-ethoxyphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate; by the aforementioned various hydroxy (meth) acrylate compounds and rings Various cyclic forms such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc. Polyoxyalkylene obtained by ring-opening polymerization of ether compound modified mono (meth) acrylate hydroxyester compound; by the aforementioned mono (meth) acrylate hydroxyester compound and ε-hexane Lactones obtained by polycondensation of lactone compounds such as lactones are modified hydroxy (meth) acrylate compounds. These can be used individually or in combination of two or more.

From the viewpoint of obtaining a printing ink that is excellent in fluidity and gloss on the printing surface, and also has general printing suitability such as anti-fogging property and emulsification suitability, among the aforementioned hydroxy (meth) acrylate compounds (a2) , Preferably the aliphatic hydroxy mono (meth) acrylate compound, the aliphatic hydroxy poly (meth) acrylate compound, and polyoxyalkylene modified products or lactone modified compounds of these, more preferably lactone Modified aliphatic hydroxy (meth) acrylate compounds, especially lactone modified aliphatic hydroxy mono (meth) acrylate compounds. Furthermore, the ratio of the lactone-modified aliphatic hydroxy mono (meth) acrylate compound to the hydroxy (meth) acrylate compound (a2) is preferably 70% by mass or more, more preferably 90 Mass% or more.

As long as the acid group-containing hydroxy compound (a3) has an acid group such as a carboxyl group and a hydroxyl group in the molecular structure, the number of carboxyl groups and hydroxyl groups or other specific structures are not particularly limited. Moreover, the hydroxy compound (a3) containing an acid group may be used independently, or may use 2 or more types together. From the viewpoint of obtaining a printing ink with more excellent fluidity and gloss on the printing surface, among them, aliphatic compounds are preferred, and it is more preferred to have 1 to 3 carboxyl groups on an aliphatic hydrocarbon having 2 to 20 carbon atoms. 1 to 3 hydroxyl compounds. Specific examples of the aforementioned compounds include, for example, glycolic acid, lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxydodecanoic acid , Hydroxy myristic acid, hydroxy hexadecanoic acid, hydroxy heptadecanoic acid, hydroxy octadecanoic acid (hydroxystearic acid), grate oleic acid and other monohydroxy compounds; glycerol acid, 2- (hydroxymethyl) -3- Dihydroxy compounds such as hydroxypropionic acid, 2- (dimethylol) propionic acid, dimethylol propionic acid, 3,3-dimethylol propionic acid; 3-hydroxy-2,2-bis (hydroxymethyl) ) Trihydroxy compounds such as propionic acid.

The acid group-containing urethane (meth) acrylate resin (A), except the polyisocyanate compound (a1), the hydroxy (meth) acrylate compound (a2), and the acid group-containing hydroxy compound In addition to (a3), other reaction raw materials may be used in combination. Examples of other reaction raw materials include polyol compounds other than the hydroxy (meth) acrylate compound (a2) or the acid group-containing hydroxy compound (a3). Examples of the aforementioned polyol compound include ethylene glycol, propylene glycol, butylene glycol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, neopentyltetraol, and dineopentyl. Aliphatic polyol compounds such as alcohol; aromatic polyol compounds such as bisphenol and bisphenol; introducing (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) tetrahydrofuran into the molecular structures of the aforementioned various polyol compounds (Poly) oxyalkylene chain-modified (poly) oxyalkylene chain; lactone-modified product containing a (poly) lactone structure introduced into the molecular structure of the aforementioned various polyol compounds.

When using the above-mentioned other reaction raw materials, from the viewpoint of fully exerting the effects exerted by the present invention, it is preferable that the reaction raw materials of the acid group-containing urethane (meth) acrylate resin (A) account for The ratio of the total mass of the polyisocyanate compound (a1), the hydroxy (meth) acrylate compound (a2) and the acid group-containing hydroxy compound (a3) is 70% by mass or more, 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 can generally be produced by the same method as the general urethane (meth) acrylate resin. The reaction ratio or reaction order of each component is appropriately adjusted according to the required resin design or resin performance, and is not particularly limited. As an example of the reaction conditions, the ratio of the hydroxyl group in the reaction raw material to the range of 0.9 to 1.1 moles relative to 1 mole of the isocyanate group in the reaction raw material can be used, and each reaction raw material is heated to 20 to 120 ° Methods. For this reaction, well-known and commonly used carbamate catalysts such as zinc octoate, various antioxidants, polymerization inhibitors, etc. may be used as needed.

The acid value of the acid group-containing urethane (meth) acrylate resin (A) is preferably 1 to 50 mgKOH / from the viewpoint of obtaining a printing ink with better fluidity and gloss on the printing surface. The range of g is more preferably 3 to 40 mgKOH / g, and particularly preferably 3 to 35 mgKOH / g. In the present invention, the acid value of the resin is a value measured by the neutralization titration method of JIS K 0070 (1992).

From the viewpoint of obtaining a printing ink with better fluidity and gloss on the printing surface when used in printing ink applications, the acid group-containing urethane (meth) acrylate resin (A) The mass average molecular weight (Mw) is preferably in the range of 1,000 to 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: HLC-8220GPC manufactured by Tosoh Corporation

Column: TSK-GUARDCO LUMN SuperHZ-L manufactured by Tosoh Corporation + TSK-GEL SuperHZM-M × 4 manufactured by Tosoh Corporation

Detector: RI (Differential Refractometer)

Data processing: MultistationGPC-8020modelII manufactured by Tosoh Corporation

Measurement conditions: column temperature 40 ℃ solvent tetrahydrofuran flow rate 0.35ml / min

Standard: Monodisperse polystyrene

Sample: A tetrahydrofuran solution converted into 0.2% by mass of resin solid content was filtered through a microfilter (100 μl)

Examples of the aforementioned metal complex (B) include aluminum triethylate (aluminum triethylate), aluminum tripropylate (aluminum tripropylate), aluminum dipropylate monobutyrate (aluminum dipropylate monobutyrate), aluminum tributyrate (aluminum tributyrate ) Etc. aluminum trialkylate (aluminum trialkylate); acetyl acetate dipropyl alcohol (aluminum acetylacetate dipropylate), acetyl acetate aluminum dibutoxide (aluminum acetylacetate dibutyrate), triethyl acetyl acetate (aluminum triacetylacetate) , Aluminum ethyl acetoacetate dipropylate, aluminum tris-ethyl acetoacetate, aluminum octadecyl acetoacetate dipropylate, etc. aluminum alkyl acetoacetate; titanium tetrapropoxide, titanium tetrabutoxide and other titanium tetraalkylate (titanium tetraalkylate); bis (acetyl acetate) titanium dipropoxide (titanium bis (titanium bis acetylacetate) dipropylate) and other titanium alkyl acetoacetate; zirconium tetraalkylate and other zirconium tetraalkylate. As such specific commercially available products, for example, aluminum organic compound series ("AMD", "ASBD", "AIPD", "PADM", "aluminum oxide" manufactured by Kawaken Fine Chemicals Co., Ltd., "ALCH", "ALCH-TR", "Aluminum chelating agent M", "Aluminum chelating agent D", "Aluminum chelating agent A, A (W)"), "PLENACT" series manufactured by Ajinomoto Fine-Techno Co., Ltd. ( "AL-M", "TTS"), Matsumoto Fine Chemical Co., Ltd. "ORGATIX" 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-45 '' , "ZA-65", "AC-150", "ZC-540"), etc. The aforementioned metal complex (B) may be used alone or in combination of two or more.

The blending amount of the aforementioned metal complex compound (B) can be appropriately adjusted according to the required ink performance, etc., in particular, it becomes high in fluidity and excellent in gloss of the printed surface, and also has other properties such as anti-fogging or emulsification suitability From the viewpoint of very high printing ink, it is preferably in the range of 0.5 to 20 parts by mass relative to 100 parts by mass of the aforementioned acid group-containing urethane (meth) acrylate resin (A). It is preferably in the range of 1 to 15 parts by mass.

The composition of the present invention may contain other resin components (C) in addition to the aforementioned acid group-containing urethane (meth) acrylate resin (A) and metal complex (B) Ingredients. As an example of the aforementioned other resin component (C), various (meth) acrylate monomers (C1) and urethane (meth) acrylate resins (C2) other than the aforementioned (A) component can be given. ), Epoxy (meth) acrylate resin (C3), polyester (meth) acrylate resin (C4), ketone resin (C5), diallyl phthalate (DAP) resin (C6), etc. 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, becomes The effect of printing ink with high fluidity and excellent gloss on the printing surface can be fully exerted regardless of the other resin component (C). Therefore, for the aforementioned other resin component (C), various resin materials that can be used for printing ink can be used arbitrarily, and are not particularly limited, but a part of the specific examples is described below.

Examples of the (meth) acrylate monomer (C1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Aliphatic mono (meth) acrylate compounds; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl mono (meth) acrylate, etc. ; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate, tetrahydrofuran methyl acrylate; aromatic mono (meth) acrylate, phenoxy (meth) acrylate, etc. Meth) acrylate compounds; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and other hydroxyl group-containing mono (meth) acrylate compounds; among the aforementioned various mono (meth) acrylate compounds Polyoxyalkylene modified mono (meth) acrylate compounds with polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polytetrahydrofuran chains, etc. introduced into the molecular structure; A lactone modified mono (meth) acrylate compound with a (poly) lactone structure introduced into the molecular structure; Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate Aliphatic di (meth) acrylate compounds such as acrylates; norbornanyl di (meth) acrylate, norbornanyl dimethanol di (meth) acrylate, dicyclopentyl di (meth) acrylate, tris Alicyclic di (meth) acrylate compounds such as cyclodecane dimethanol di (meth) acrylate; aromatic di (meth) acrylates such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate Group) Acrylate compound; polyoxyalkylene modified di (methacrylate) with polyoxyalkylene chain such as polyoxyethylene chain, polyoxypropylene chain, polytetrahydrofuran chain introduced into the molecular structure of the aforementioned various di (meth) acrylate compounds Group) acrylate compound; lactone modified di (meth) acrylate compound with (poly) lactone structure introduced into the molecular structure of the aforementioned various di (meth) acrylate compounds; trimethylolpropane tri ( Aliphatic tri (meth) acrylate compounds such as meth) acrylate and glycerin tri (meth) acrylate ; Neopentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate and other hydroxyl-containing tri (meth) acrylates Compounds; polyoxyalkylene modified tri (meth) acrylates that incorporate polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polytetrahydrofuran chains, etc. into the molecular structure of the aforementioned various tri (meth) acrylate compounds Compounds; lactone-modified tri (meth) acrylate compounds with (poly) lactone structure introduced into the molecular structure of the aforementioned various tri (meth) acrylate compounds; neopentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, di neopentaerythritol hexa (meth) acrylate and other aliphatic poly (meth) acrylate compounds with more than 4 functions; di neopentaerythritol tetra ( Methacrylate), dipentaerythritol penta (meth) acrylate and other 4 functional hydroxyl-containing poly (meth) acrylate compounds; the molecular structure of the aforementioned various poly (meth) acrylate compounds Introduce polyoxyethylene chains such as polyoxyethylene chains, polyoxypropylene chains, polytetrahydrofuran chains, etc. 4 Modified poly (oxyalkylene) poly (meth) acrylate compounds with higher functionalities; modified poly (meth) acrylate compounds with 4 or more functionalized lactones with (poly) lactone structure introduced into the molecular structure of the aforementioned various poly (meth) acrylate compounds (Meth) acrylate compounds, etc.

Examples of the urethane (meth) acrylate resin (C2) include, for example, various polyisocyanate compounds, hydroxyl-containing (meth) acrylate compounds, and, if necessary, various polyhydric alcohol compounds. Winner. Specific examples of these reaction raw materials include those exemplified in the description of the acid group-containing urethane (meth) acrylate resin (A).

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

The polyester (meth) acrylate resin (C4) may be a (meth) acrylate resin having a polyester structure part in the molecular structure, or may be an alcohol containing fat or fatty acid in a part of the reaction raw materials The acid type (alkyd) or the urethane modified type containing polyisocyanate in a part of the reaction raw materials.

In the composition of the present invention, the blending amount of the aforementioned other resin component (C) can be appropriately adjusted according to the required ink performance, etc., from the viewpoint of further effectively exerting the effects of the present invention, it is preferably The above-mentioned acid group-containing urethane is added to the total of the acid group-containing urethane (meth) acrylate resin (A), the metal complex (B) and other resin components (C) The total mass of the ester (meth) acrylate resin (A) and the metal complex (B) is in the range of 0.5 to 20% by mass, 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 it is preferably a photopolymerization initiator containing active energy rays to be irradiated. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-benzophenone and 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1, 2- (dimethylamino) -2-[(4-tolyl) methyl] -1- [4- (4- Phenyl) phenyl] -1-butanone and other alkylphenone series photopolymerization initiators; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide and other acyl group oxidation Phosphine photopolymerization initiators; intramolecular dehydrogenation photopolymerization initiators such as benzophenone compounds. These can be used individually or in combination of two or more. In addition, the selection of the photopolymerization initiator may be selected according to the type of active energy ray to be irradiated, etc., and used appropriately.

Examples of the commercially available products of the photopolymerization initiator include "IRGACURE" series ("IRGACURE 127", "IRGACURE 184", "IRGACURE 250", "IRGACURE 270", "IRGACURE 290", manufactured by BASF Corporation, `` IRGACURE 369E '', `` IRGACURE 379EG '', `` 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 '' series made by IGM RESINS (`` OMNIRAD184 '', `` OMNIRAD250 '', `` OMNIRAD369 '', `` OMNIRAD369E '', `` OMNIRAD651 '', `` OMNIRAD907FF "," OMNIRAD1173 ")," DAIDO UV-CURE "series manufactured by Datong Chemical Industry Co., Ltd.," BENZOPHENONE "," PHOTOCURE 50 "," PHOTOCURE 550 "," EAB-SS ", etc. These photopolymerization initiators are preferably used in a range of about 0.05 to 20 parts by mass out of a total of 100 parts by mass of the composition.

The composition of the present invention may contain the polymerization initiator and the photosensitizer together. Examples of the photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, and s-benzylisoureonium-p-toluenesulfonate. Sulfur compounds such as acid salts. These light sensitizers are preferably used in a range of about 0.1 to 10 parts by mass out of a total of 100 parts by mass of the composition.

The composition of the present invention may further contain pigments, dyes, filler pigments, organic or inorganic fillers, organic solvents, antistatic agents, defoamers, viscosity modifiers, polymerization inhibitors, light stabilizers, weather stabilizers, heat resistance Stabilizers, ultraviolet absorbers, antioxidants, leveling agents, pigment dispersants, waxes, and other additives containing common printing inks.

Examples of the aforementioned pigments include organic pigments for coloring, which are publicly known, and examples include organic pigments for printing inks published in the "Organic Pigment Handbook (Author: Hashimoto Ae, Publishing House: COLOR OFFICE, early 2006 edition)". , And can use soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perylene ketone pigments, isoindolinone pigments , Isoindoline pigments, two Pigments, sulfur indigo 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 the pigment and the like, but it is preferably in the range of 5 to 30 parts by mass relative to 100 parts by mass of the total composition.

Examples of the filler pigment include titanium oxide, graphite, zinc, lime carbonate powder, precipitated calcium carbonate, gypsum, clay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, and hard Aluminum fatty acid, magnesium carbonate, barium oxide powder, glass beads, etc. The addition amount of these filler pigments differs depending on the type of pigment and the like, but it is preferably in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of the total 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 or blending ratio can be appropriately adjusted according to the intended printing application, performance, and the like. Each component can be blended all at once, or a part can be blended first. After making the premix, it can be blended separately with other components. The mixing method is not particularly limited, and examples thereof include a method of stirring and mixing with a mixer, a method of using a three-roll mill, a method of using a disperser such as a bead mill, and the like.

The printing ink of the present invention can be hardened by irradiating active energy rays. Examples of the aforementioned active energy rays include free radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of the light source include sterilization lamps, ultraviolet fluorescent lamps, UV-LEDs, carbon arc lamps, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, and electrodeless lamps. , Metal halide lamps, natural light and other ultraviolet rays as light sources, electron beams using scanning or curtain type electron beam accelerators, etc.

The printing ink of the present invention can print on various substrates such as paper or various plastic films. Specifically, paper substrates that can be used for packaging such as catalogs, posters, leaflets, CD covers, direct mail, brochures, cosmetics or beverages, pharmaceuticals, toys, equipment, etc .; polypropylene film , Polyethylene terephthalate film and other plastic film substrates for packaging materials such as food or beverages, cosmetics, etc .; aluminum foil paper, synthetic paper, and other various substrates that have been used as printing substrates in the past are set as printing objects.

The printing method of the printing ink of the present invention is not particularly limited. For example, lithography offset printing, relief printing, gravure printing, gravure offset printing, flexographic printing, screen printing, etc. can be used for printing. Among these, especially in lithographic offset printing in which water is continuously supplied to the plate surface, it can be suitably used. Offset printing machines that continuously supply water are manufactured and sold by most printing machine manufacturers. Examples include Heidelberg, KOMORI Corporation, RYOBI MHI Graphic Technology, Manroland, KBA, etc. The present invention can also be suitably used in a sheet-type offset printing machine using sheet-shaped printing paper, a blanket printing machine using roll-shaped printing paper, or any paper supply method. More specifically, there may be mentioned offset printing machines such as Speedmaster series manufactured by Heidelberg, Lithrone series manufactured by KOMORI Corporation, and DIAMOND series manufactured by RYOBI MHI Graphic Technology.

    [Example]    

The present invention will be described in more detail below based on examples. Furthermore, the invention is not limited to these embodiments.

Determination of infrared absorption spectrum

[Model] FT / IR-4100 manufactured by Japan Spectroscopy Co., Ltd.

[Measurement conditions] By confirming the infrared absorption spectrum of 2250 cm ^-1 representing the isocyanate group, the completion of the reaction was confirmed.

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 manufactured by Tosoh Corporation

Detector: RI (Differential Refractometer)

Data processing: MultistationGPC-8020modelII manufactured by Tosoh Corporation

Measurement conditions: column temperature 40 ℃ solvent tetrahydrofuran flow rate 0.35ml / min

Standard: Monodisperse polystyrene

Sample: The resin solid content was converted into 0.2% by mass of tetrahydrofuran solution and filtered with a microfilter (100 μl)

Measurement conditions of acid value

The measurement was carried out according to JIS K 0070 (1992) neutralization titration method.

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

In a flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, add 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, N -Nitroso-N-phenylhydroxylamine aluminum 0.17 parts by mass, heated to 65 ° C. It took 1 hour to add 108.6 parts by mass of isocyanurate modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.). After the dropwise addition, it was heated to 95 ° C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group 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) 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 introduction tube, a condenser, and a thermometer, add 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, N -Nitroso-N-phenylhydroxylamine aluminum 0.12 parts by mass, heated to 65 ° C. 79.8 parts by mass of isocyanurate modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After the dropwise addition, it was heated to 95 ° C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group 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) 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 introduction tube, a condenser and a thermometer, add 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, N -Nitroso-N-phenylhydroxylamine aluminum 0.12 parts by mass, heated to 65 ° C. 79.1 parts by mass of isocyanurate modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After the dropwise addition, it was heated to 95 ° C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group 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 mgKOH / g.

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

In a flask equipped with a stirrer, a gas introduction tube, a condenser, and a thermometer, add 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 N-nitroso -0.17 parts by mass of aluminum N-phenylhydroxylamine, heated to 65 ° C. 116.7 parts by mass of isocyanurate modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After the dropwise addition, it was heated to 95 ° C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group 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) 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 introduction tube, a condenser and a thermometer, add 167.9 parts by mass of lactone-modified hydroxyethyl acrylate ("PLACCEL FA2D" manufactured by Daicel Corporation), 3.4 parts by mass of dimethylolpropionic acid, N -Nitroso-N-phenylhydroxylamine aluminum 0.17 parts by mass, heated to 65 ° C. 116.9 parts by mass of isocyanurate modified hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) was added dropwise over 1 hour. After the dropwise addition, it was heated to 95 ° C and reacted for 2 hours. It was confirmed that the infrared absorption spectrum of 2250 cm ^-1 indicating the isocyanate group disappeared, and the intended 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 Manufacture of compositions (1) to (8)

Each component was 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: "OTA 480" manufactured by Daicel-Allnex Co., Ltd., propylene oxide-modified glycerin triacrylate, and the average number of additions per molecule of propylene oxide is 3

‧Metal complex (B-1): "ALCH-TR" manufactured by Kawaken Fine Chemicals Co., Ltd., aluminum ginseng (ethyl acetoacetate)

‧Metal complex (B-2): "PLENACT AL-M" manufactured by Ajinomoto Fine-Techno Co., Ltd., aluminum diacetate aluminum acetyl acetate

Examples 9 to 21 and Comparative Example 1 Manufacturing of printing ink

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

With respect to the obtained printing ink, various evaluations were conducted in the following manner. The results are shown in Tables 3 to 5.

Production Example 6 Production of urethane (meth) acrylate resin

Into a four-necked flask equipped with a stirrer, a gas introduction tube, a capacitor, and a thermometer, polymerized diphenylmethane diisocyanate ("MILLIONATE MR-400" manufactured by Japan Polyurethane Industry Co., Ltd.) 60.3 parts by mass, tertiary butyl 0.1 parts by mass of hydroxytoluene, 0.02 parts by mass of methoxyhydroquinone, and 0.02 parts by mass of zinc octoate were heated to 75 ° C. While stirring the inside of the flask, 35.7 parts by mass of 2-hydroxyethyl acrylate was added dropwise over 1 hour. After the dropwise addition, the reaction was further carried out at 75 ° C for 3 hours. 4.0 parts by mass of glycerin 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.

Evaluation of liquidity

In a room with an air conditioner of 25 ° C, place 1.0 ml of printing ink on the upper end of a glass plate that forms an angle of 70 ° with the ground plane, and measure the flow distance one day later. The larger the value, the better the fluidity.

How to make color display

Using a simple color development machine ("RI test machine" manufactured by Feng Rong Seiko Co., Ltd.), 0.10 ml of printing ink is evenly spread on the rubber roller and metal roller of the RI test machine. On the surface of coated paper ("OK Golden Rattan" manufactured by Oji Paper Co., Ltd.), through an area of 200 cm ^2, it is evenly coated with a yellow density of 1.4 (measured by "SpectroEye Densitometer" manufactured by X-Rite Corporation) to develop a color. Color. Furthermore, the RI testing machine is a testing machine that develops the printing ink on paper or film, and can adjust the transfer amount or printing pressure of the printing ink.

Hardening method using ultraviolet (UV) light source

Ultraviolet (UV) light is irradiated to the previously developed color development object to harden the printing ink. Specifically, using an ultraviolet (UV) irradiation device (manufactured by EYE GRAPHICS, with additional cold light mirror) equipped with a water-cooled metal halogen lamp (120W / cm1 output lamp) and a conveyor belt, the color developing object is placed on the conveyor belt to The speed of 40 meters per minute passes directly under the lamp (the irradiation distance is 11 cm), so that the printing ink is hardened.

Printing surface gloss

The gloss value of the printed surface in the cured color development was measured with a 60 ° gloss meter (manufactured by BYK Garder GmbH), and the following three stages were evaluated. The higher the value, the better the gloss.

(Evaluation criteria)

A: Gloss above 55

B: Gloss 45 or more, less than 55

C: Gloss is less than 45

Claims (9)

    A composition containing 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 mgKOH / g.         The composition of 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 composition according to claim 1, wherein the acid group-containing urethane (meth) acrylate resin (A) is a polyisocyanate compound (a1), a hydroxy (meth) acrylate compound (a2) and An acid group-containing hydroxy compound (a3) is required as a reaction raw material.         The composition of claim 1, wherein the central metal of the metal complex (B) is any one of aluminum, titanium, and zirconium.         The composition according to claim 1, wherein the blending amount of the metal complex (B) with respect to 100 parts by mass of the acid group-containing urethane (meth) acrylate resin (A) is 0.5 ~ The range of 20 parts by mass.         The composition of claim 1, which contains the resin group (A) and the metal complex (B) in addition to the acid group-containing urethane (meth) acrylate resin (B), also contains other resin components ( C), and the total mass of the acid group-containing urethane (meth) acrylate resin (A) and the metal complex (B) relative to the total of these is 0.5 to 20% by mass range.         A printing ink made of the composition according to any one of claims 1 to 7.         A printed matter printed by printing ink as in claim 8.