JP6172484B1 - Active energy ray-curable printing ink and printed matter - Google Patents

Abstract

An object of the present invention is to provide an active energy ray-curable ink having good static fluidity and good continuous printability. An active energy ray-curable ink containing a compound represented by the following general formula (1), a (meth) acrylate compound, a resin and a pigment. General formula (1) Q-(-X-Y) n (wherein Q is an n-valent organic dye residue, n is an integer of 1 to 4, and X is a direct bond (Q becomes Y without involving X) -CONH-Y2-, -SO2NH-Y2- or -CH2NHCOCH2NH-Y2-, where Y2 is a direct bond (bonds to Y without Y2), or an alkylene group which may have a substituent, or Arylene group, Y is a group represented by the general formula (2)) [Selection] None

Description

  The present invention relates to an active energy ray-curable printing ink.

  In recent years, offset printing is capable of instantaneous drying (curing) of active energy ray-curable ink by instantaneous irradiation of active energy rays, so post-processing (booking, package cutting, folding, varnish coating) immediately after printing Etc.) can be implemented, and the delivery time can be shortened and the productivity can be greatly improved. Therefore, the substitution from the oxidation polymerization type ink that requires drying time of about one day is rapidly progressing.

  In offset printing inks, pigments exist in a finely dispersed state in the ink, and this is indispensable for obtaining good printing paper surface quality (color reproducibility, gloss, transparency, etc.). .

  On the other hand, offset printing forms an image of the ink layer by repelling ink and dampening water by supplying dampening water to the non-image area on the printing plate, and the obtained image is printed on the paper surface via a blanket. This is a printing method in which a printed matter is obtained by being transferred to a print. Therefore, during continuous printing, dampening water is usually mixed into the ink and the ink is emulsified. Further, in long-time printing with a large number of continuously printed sheets, dampening water is continuously supplied into the ink and emulsification proceeds. In the state where this emulsification proceeds, the offset printing ink is a printed matter with the same performance from the initial printing to the end (the change in the printing density between the printing paper surfaces from the initial printing to the end is small, the emulsified ink Smudges due to ink (no soiling) occur, and the emulsified ink stains the printing press (the emulsified ink adheres to the dampening water supply roller of the printing press and causes smudges). The contamination of the feed water supply roller destabilizes the supply amount of dampening water, so that the printer must be stopped and cleaning is reduced, resulting in reduced productivity.) Need to have continuous printability). In order to maintain these aptitudes, it is necessary to maintain the state in which the pigment is finely dispersed in an appropriate range even in the emulsified state.

  In addition, offset printing inks have finely dispersed pigments, so that the thixotropic property is high on the viscous surface, and the static fluidity of the ink is lowered. Ink with low static fluidity causes long-term printing to reduce the fluidity of the ink in the ink fountain that is the ink supply source in the printing press. Therefore, there is a problem that the ink supply to the printing press (to the printing plate) is delayed and the density of the printing paper surface is reduced, and the paper surface quality is impaired.

  Therefore, Patent Document 1 discloses an active energy ray-curable printing ink using trifunctional (meth) acrylate and polyester for pigment dispersion.

JP 2003-342514 A

  However, conventional active energy ray curable inks are remarkably inferior in continuous printing suitability and stationary fluidity as compared with oxidation polymerization type inks. Therefore, there is a problem that the initial print quality during continuous printing is difficult to maintain at the end, and the print quality tends to deteriorate. Furthermore, the dampening water supply roller is likely to be smeared with emulsified ink, resulting in a decrease in paper quality, resulting in a decrease in productivity due to an increase in the number of times the printing is stopped and the dampening water supply roller is washed. was there.

  An object of the present invention is to provide an active energy ray-curable ink having good static fluidity and good continuous printability.

The active energy ray-curable ink of the present invention contains a compound represented by the following general formula (1), a (meth) acrylate compound, a diallyl phthalate resin, and a pigment.
General formula (1)
Q-(-X-Y) n
(Wherein, Q is an n-valent organic pigment residue, n represents an integer of 1 to 4, X is a direct bond (what a Q-Y not via X), - CONH-Y2 - , - SO 2 NH- Y ₂ — or —CH ₂ NHCOCH ₂ NH—Y ₂ —, wherein Y 2 is a direct bond (bonds to Y without going through Y 2), or an alkylene group or an arylene group which may have a substituent, Y is represented by the following general formula Group represented by (2))
General formula (2)

(Wherein, Y3 is hydrogen atom, a halogen _atom, -NO 2, -NH ₂ or _-SO 3 H, k is an integer from 1 to 4, the case of k = 1 to 3, Y3 is a carboxyl group bound benzene ring Bonded at any position except the site, provided that when Y3 is a hydrogen atom, k is 4, and when k is 1 to 3, the remaining Y3 is a hydrogen atom, and m is an integer of 1 to 6. .)

  According to the present invention, by using the compound represented by the general formula (1), the stability of the fine dispersion state in the pigment is improved, so that the continuous printability is improved, and the ink Good static fluidity was obtained because the thixotropic property could be reduced.

  According to the present invention, it is possible to provide an active energy ray-curable ink having good static flowability and good continuous printability.

  First, terms used in the present invention are defined. The active energy ray in the present invention means an ultraviolet ray, an electron beam or the like having energy necessary for exciting the (meth) acryloyl group from the ground state to the transition state. The (meth) acrylate compound is a compound having an acryloyl group or a methacryloyl group. The monomer is an ethylenically unsaturated double bond-containing monomer.

The active energy ray-curable ink of the present invention contains a compound represented by the following general formula (1), a (meth) acrylate compound, and a resin.
General formula (1) Q-(-X-Y) n
(Wherein, Q is an n-valent organic pigment residue, n represents an integer of 1 to 4, X is a direct bond (what a Q-Y not via X), - CONH-Y2 - , - SO 2 NH- Y ₂ — or —CH ₂ NHCOCH ₂ NH—Y ₂ —, wherein Y 2 is a direct bond (bonds to Y without going through Y 2), or an alkylene group or an arylene group which may have a substituent, Y is represented by the following general formula Group represented by (2))
General formula (2)

(Wherein, Y3 is hydrogen atom, a halogen _atom, -NO 2, -NH ₂ or _-SO 3 H, k is an integer from 1 to 4, the case of k = 1 to 3, Y3 is a carboxyl group bound benzene ring Bonded at any position except the site, provided that when Y3 is a hydrogen atom, k is 4, and when k is 1 to 3, the remaining Y3 is a hydrogen atom, and m is an integer of 1 to 6. .)

  The active energy ray-curable ink (hereinafter also referred to as ink) of the present invention can be used as a printing ink. The printing ink is preferably offset printing because it can be used by known printing methods such as offset printing, gravure printing, flexographic printing, and screen printing.

  The ink of the present invention contains a (meth) acrylate compound, a resin, a pigment, and a compound represented by the general formula (1). When the ink is a photocurable ink, it may further contain a photopolymerization initiator. preferable. On the other hand, when the ink is an electron beam curable ink, it is not always necessary to include a photopolymerization initiator.

  In the present invention, the (meth) acrylate compound is a compound having one or more (meth) acrylolyl groups. As the (meth) acrylate compound, a compound usually used in an active energy ray-curable ink can be used. Therefore, as the (meth) acrylate compound, for example, a monofunctional monomer, a bifunctional monomer, a trifunctional monomer, or a tetrafunctional or higher monomer can be used, and in particular, the dryness of printed matter (also referred to as curable or polymerizable). From the viewpoint of the above, it is preferable to use a tri- or higher functional monomer in combination. If the drying property is sufficient, blocking (the ink of the lower printed product on the stacked print will adhere to the back side of the upper printed product), rubbing (the printed part may be scratched by rubbing with other paper), etc. A printed matter that does not occur and has a good quality can be produced.

  Examples of the tri- or higher functional monomer include the following.

  Examples of the trifunctional monomer include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolhexanetri (meth) ) Acrylate, trimethylol octane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and the like.

  Examples of tetra- or higher functional monomers include pentaerythritol tetra (meth) acrylate, pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and ditrimethylolpropane tetra. Caprolactonate tetra (meth) acrylate, ditrimethylolethanetetra (meth) acrylate, ditrimethylolbutanetetra (meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acryl Chromatography, tri pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate.

  As the tri- or higher functional monomer, a modified product of (meth) acrylate obtained by reacting an alkylene oxide adduct of an aliphatic alcohol compound with these monomers is also preferable. The alkylene oxide adduct (meth) acrylate monomer of the aliphatic alcohol compound is preferably a mono- or poly (eg, 2-20 unit adduct of alkylene oxide) alkylene (2-20 carbon atoms) oxide adduct of the aliphatic alcohol compound. . The alkylene oxide is preferably, for example, ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide or the like.

  Among the modified products, trifunctional monomers include, for example, glycerin poly (2 to 20) alkylene (2 to 20 carbon atoms) oxide adduct tri (meth) acrylate, trimethylolpropane poly (C2 to 20) alkylene (2 to 2 carbon atoms). 20) Oxide adduct tri (meth) acrylate, trimethylolethane poly (2-20) alkylene (2-20 carbon atoms) oxide adduct tri (meth) acrylate, trimethylolhexane poly (2-20) alkylene (carbon number) 2-20) Oxide adduct tri (meth) acrylate, trimethyloloctane poly (2-20) alkylene (2-20 carbon atoms) oxide adduct tri (meth) acrylate, pentaerythritol poly (2-20) alkylene (carbon) Number 2 to 20) Oxide adduct tri (meth) acryl Over doors and the like.

  Moreover, the tetrafunctional or higher-functional monomer in the modified body is, for example, pentaerythritol poly (2 to 20) alkylene (carbon number 2 to 20) oxide adduct tetra (meth) acrylate, ditrimethylolpropane poly (carbon number 2 to 20). ) Alkylene (2-20 carbons) oxide adduct tetra (meth) acrylate, ditrimethylolpropane poly (2-20 carbons) alkylene oxide tetra (meth) acrylate, ditrimethylolpropane tetracaprolactonate tetra (meth) acrylate Ditrimethylolethane poly (2-20 carbons) alkylene (2-20 carbons) oxide adduct tetra (meth) acrylate, ditrimethylolbutane poly (2-20 carbons) alkylene (2-20 carbons) oxide adduct Tetra (meth) a Lilate, ditrimethylolhexane poly (2-20 carbon atoms) alkylene (2-20 carbon atoms) oxide adduct tetra (meth) acrylate, ditrimethyloloctane poly (2-20 carbon atoms) alkylene (2-20 carbon atoms) oxide Adduct tetra (meth) acrylate, dipentaerythritol poly (5 to 20 carbon atoms) alkylene (2 to 20 carbon atoms) oxide adduct penta (meth) acrylate, dipentaerythritol poly (2 to 20 carbon atoms) alkylene (carbon Number 2-20) Oxide adduct hexa (meth) acrylate, dipentaerythritol hexacaprolactonate poly (2-20) alkylene (C2-20) oxide adduct hexa (meth) acrylate tripentaerythritol poly (carbon Number 2-20) Archile (C2-C20) oxide adduct hepta (meth) acrylate, tripentaerythritol poly (C2-C20) alkylene (C2-C20) oxide adduct octa (meth) acrylate, tripentaerythritol poly (carbon Number 2-20) alkylene (2-20 carbon atoms) oxide adduct hexa (meth) acrylate and the like.

  The (meth) acrylate compound can be used alone or in combination of two or more.

The (meth) acrylate compound can be used in the ink at any content as long as it can produce the ink. For example, it is preferable to use in the range of 10-60 mass% in printing ink. Thereby, sufficient drying property is obtained.

In the present invention, the resin is preferably a thermoplastic resin or a thermosetting resin. When the resin is contained, the viscosity of the ink is improved and the emulsification resistance is improved. The resin is preferably a resin that has good compatibility with the (meth) acrylate compound and is soluble. For solubility, 50 g of resin and 50 g of ditrimethylolpropane tetraacrylate or dipentaerythritol hexaacrylate are charged in a container and thermally dissolved at 100 ° C. Next, after leaving at 25 ° C. for one day, no new resin precipitation or turbidity of the solution occurs. In addition, after the heat dissolution, the solution may have turbidity that does not affect the quality of the printed matter.
Examples of the resin include polyester, polyvinyl chloride, poly (meth) acrylic acid ester, epoxy resin, polyurethane, petroleum (based) resin, cellulose derivatives (for example, ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymer , Synthetic rubber such as polyamide, polyvinyl acetal, diallyl phthalate resin, polyvinyl acetal resin, butadiene-acrylonitrile copolymer, and the like. Among these, diallyl phthalate resin is particularly preferable when used in combination with the compound represented by the general formula (1) because continuous printability and static fluidity are remarkably improved. As the diallyl phthalate resin, either an ortho diallyl phthalate resin or an isodiallyl phthalate resin can be used, and these can be used alone or in combination.
The resins can be used alone or in combination of two or more.

  The mass average molecular weight (Mw) of the resin is preferably 1,000 to 1,000,000, and more preferably 10,000 to 100,000.

  It is preferable to contain 5-25 mass parts of resin with respect to 100 mass parts of pigments. If it is this range, when it uses together with the compound shown by General formula (1), continuous printing aptitude and stationary fluidity will improve more.

In the present invention, the pigment is a known pigment, and an organic pigment and an inorganic pigment are preferable.
Organic pigments are soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, pyrazolone, etc .; β-naphthol, β-oxynaphthoic acid anilide Insoluble azo pigments such as azoacetate anilide monoazo, acetoacetate anilide disazo, and pyrazolone. Phthalocyanine pigments such as copper phthalocyanine blue, halogenated (eg chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal free phthalocyanine. Quinacridone, dioxazine, sulene (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, di As the polycyclic pigment such as ketopyrrolopyrrole, heterocyclic pigment, and inorganic pigment, various known and publicly known pigments such as carbon black can be used.

When the organic pigment is represented by the CI color index, for example, Pigment Yellow (hereinafter abbreviated as PY) 1, PY3, PY12, PY13, PY14, PY17, PY18, PY24, PY74, PY83, PY93, PY94, PY95, PY100, PY108, PY104, PY138, PY139, PY174, PY150, PY151, PY154, PY155, PY167, PY180, PY185, etc., pigment red (hereinafter abbreviated as PR) 1, PR3, PR5, PR21, PR114, PR48, PR49, PR50, PR52 PR57, PR57: 1, PR81, PR83, PR90, PR122, PR144, PR146, PR147, PR148, PR150, PR166, PR170, PR176, PR177, PR168, R169, PR172, PR173, PR174, PR184, PR185, PR187, PR193, PR202, PR214, PR242, PR254, PR255, PR264, PR266, PR269, etc., pigment blue (hereinafter abbreviated as PB) 1, PB2, PB14, PB15, PB15 : 1, PB15: 2, PB15: 3, PB15: 4, PB15: 6, PB60, PB62, etc., Pigment Violet (hereinafter abbreviated as PV) 1, PV2, PV3, PV4, PV12, PV23, PV39, Pigment Green (hereinafter referred to as “Pigment Green”) (Abbreviated as PG) 1, PG2, PG3, PG4, PG7, PG36, PG45, PG58, etc., Pigment Brown 25, Pigment Orange (hereinafter abbreviated as PO) 5, PO13, PO34, PO36, PO38, PO39 PO51, PO74, and the like,
Inorganic pigments represented by CI color index include, for example, pigment black (hereinafter abbreviated as PBL) PBL7.

  The pigment can be used in the ink at any content as long as the desired concentration can be reproduced on the surface of the printing paper. For example, it is common to contain 5-30 mass% in ink.

  In the present invention, the compound represented by the general formula (1) is preferably used for dispersing the pigment in combination with a resin. When the ink contains the compound represented by the general formula (1), the affinity between the resin and the pigment is greatly improved, and the fine dispersion state of the pigment can be stably maintained. This can similarly maintain a stable fine dispersion state of the pigment even in the ink emulsified during printing, so that continuous printing is improved. At the same time, the stability of the ink is improved because the thixotropic property of the ink is lowered.

The compound represented by the general formula (1) is Q-(-X-Y) n.
However, where, Q is an n-valent organic pigment residue, n is an integer from 1 to 4, X is a direct bond (what a Q-Y not via X), - CONH-Y2 - , - SO 2 NH -Y2- or _{-CH 2} NHCOCH 2 NH-Y2-, although Y2 is (binds to Y without the intervention of the Y2) direct bond, or an optionally substituted alkylene group or an arylene group, Y is represented by the following general It is a group represented by the formula (2), and the general formula (2) is represented by the following chemical formula.

General formula (2)

However Shikichu, Y3 is a hydrogen atom, a halogen _atom, -NO 2, -NH ₂ or _-SO 3 H, k is an integer from 1 to 4, the case of k = 1 to 3, Y3 is a carboxyl group bound benzene ring Bonded at any position except the site, provided that when Y3 is a hydrogen atom, k = 4, and in other cases when k = 1-3, the remaining Y3 is a hydrogen atom, and m is an integer of 1-6. .

  Here, Q in the compound represented by the general formula (1) is an n-valent organic dye residue. Such an organic pigment residue is preferably derived from an organic pigment that is a dispersion. Thereby, in the compound represented by the general formula (1), Q becomes a pigment affinity site, and the-(-XY) n site becomes a dispersion stabilization site, so that the fine dispersion state of the pigment can be stably stabilized in the ink. Easy to maintain.

  The compound represented by the general formula (1) can use any structure, and the — (— X—Y) n moiety is a phthalimidomethyl group (X is a direct bond, Y (phthalimide group) is m = 1, Y3 is preferably a hydrogen atom, k = 4). When it has a phthalimidomethyl group, since affinity with resin improves more, the continuous printing ability of ink and stationary fluidity improve more.

  When copper phthalocyanine is used as a pigment in the ink, Q is preferably a copper phthalocyanine residue, and a compound represented by the following chemical formula (1) and a compound represented by the chemical formula (2) are preferred. Note that a phthalimidomethyl group (also referred to as a phthalimidomethylene group) was introduced into the copper phthalocyanine residue as a substituent.

Chemical formula (1)

Chemical formula (2)

In both chemical formula (1) and chemical formula (2), Cu-pc is a copper phthalocyanine residue.

  When quinacridone is used as the pigment, Q is preferably a quinacridone residue, and a compound represented by the following chemical formula (3) is preferable. A phthalimidomethyl group was introduced as a substituent on the quinacridone residue.

Chemical formula (3)

However, QRN is a quinacridone residue

  When pigment yellow 12 is used as the pigment, Q is preferably a pigment yellow residue, and a compound represented by the following chemical formula (4) is preferable. In addition, a phthalimidomethyl group was introduced as a substituent in Pigment Yellow 12 residue.

Chemical formula (4)

However, PY12 is Pigment Yellow 12 residues

When pigment yellow 13 is used as a pigment, Q is preferably a pigment yellow 13 residue, and a compound represented by the following chemical formula (5) is preferable. In addition, a phthalimidomethyl group was introduced as a substituent in Pigment Yellow 13 residue.
Chemical formula (5)

However, PY13 is Pigment Yellow 13 residues

  Needless to say, the pigment used in the present invention and the compound represented by the general formula (1) are not limited to the above combinations.

The compound represented by the general formula (1) can be prepared by a known synthesis method. For example, it can be produced by a method of modifying an organic pigment or a method of introducing a substituent into a raw material in advance and then synthesizing it. Moreover, for example, the method described in JP2007-191699A is also exemplified. In the case of a cyan pigment, for example, it can be synthesized by modifying a phthalocyanine pigment. In the case of a yellow pigment, for example, PY12 can be used as a raw material to introduce a substituent and synthesize it.
Examples of the substituent to be introduced include an acidic substituent, a basic substituent, and a neutral substituent.

  The compounds represented by the general formula (1) can be used alone or in combination of two or more.

  The compound represented by the general formula (1) preferably contains, for example, 0.01 to 10% by mass in the ink, more preferably 0.1 to 3% by mass, and further 0.2 to 2% by mass. preferable. Within this range, the continuous printability and the stationary fluidity are further improved, and the ink hue can be maintained well.

  When the ink is a photocurable ink, a photopolymerization initiator can be included. The photopolymerization initiator is preferably a general photocleavable initiator or a hydrogen abstraction initiator. Examples of the photocleavable initiator include acylphosphine oxide compounds and acetophenone compounds. Examples of the hydrogen abstraction type initiator include benzophenone compounds and thioxanthone compounds.

  Acylphosphine oxide compounds include, for example, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or 2,4,6-trimethylbenzoyl-diphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl A phosphine oxide etc. are mentioned.

  The acetophenone compound is, for example, 2- (dimethylamino) -1- (4-morpholinophenyl) -2-benzyl-1-butanone or 2-dimethylamino) -2- (4 methylbenzyl) -1 ^ -4 morpholinophenyl) Butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl) -Propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one or oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone].

  Examples of benzophenone compounds include 4,4′-bis- (dimethylamino) benzophenone, 4,4′-dialkylaminobenzophenones such as 4,4′-bis- (diethylamino) benzophenone, 4-benzoyl-4′-methyldiphenyl, and the like. And sulfides.

  Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- Dichlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy-N, N, N-trimethyl-1 -Propanamine hydrochloride etc. are mentioned.

  Other examples include 2,2-dimethoxy-1,2-diphenylethane-1-one.

As for a photoinitiator, it is common to mix | blend 3-20 mass% in ink.
A photoinitiator can be individual or can use 2 or more types together.

  When the ink contains a photopolymerization initiator, a catalyst can be blended. The catalyst is preferably a tertiary amine compound. The tertiary amine compound is a compound other than the α- (dimethyl) aminoalkylphenone compound, the α-morpholinoalkylphenone compound, and the dialkylaminobenzophenone compound.

  Tertiary amine compounds include, for example, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, ethyl 4- (dimethylamino) benzoate, N, N-dihydroxyethylaniline. , Triethylamine, N, N-dimethylhexylamine and the like.

The tertiary amine compound can be blended in the ink with any content as long as the catalytic effect of the target photopolymerization initiator is obtained. The tertiary amine compound is generally blended in an amount of 0.3 to 5% by mass in the ink.
Tertiary amine compounds can be used alone or in combination of two or more.

  The ink can further contain additives and extender pigments. Examples of the additive include a wax, a polymerization inhibitor, an ultraviolet absorber, an infrared absorber, and an antibacterial agent. These additives can be used alone or in combination of two or more.

  The wax can impart printed matter with friction resistance, anti-blocking, slipperiness and anti-scratch properties. Waxes include natural waxes and synthetic waxes. Examples of natural waxes include carnauba wax, wax, lanolin, montan wax, paraffin wax, and microcrystalline wax. Examples of the synthetic wax include Fischer-Trops wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, and polyamide wax silicone compound.

  The polymerization inhibitor can impart storage stability to the printing ink. Examples of polymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitro _Sobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1 , 3-Dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime, etc. It is.

  The extender pigment can impart viscosity to the ink. Examples of extender pigments include calcium carbonate, magnesium carbonate, magnesium nitrate, talc, and silica. The extender pigments can be used alone or in combination of two or more.

  The amount of the extender pigment is about 0.1 to 10% by mass in the ink. The compounding quantity of an additive is about 0.1-10 mass% in ink, respectively.

The ink can be produced by mixing together a (meth) acrylate compound, a resin, a pigment, and a compound represented by the general formula (1) in a kneader and stirring and mixing. In the case of using a photopolymerization initiator, a photopolymerization initiator catalyst, an additive, an extender pigment, and the like, it can be produced by adding it to a kneader together with the previous pigment and the like and stirring and mixing.
It is also preferable to prepare each ink, such as pigments, in advance and add preliminary stirring to the kneading machine before feeding into the kneading machine and then into the kneading machine to produce ink. Moreover, it is also preferable that components other than the pigment are previously dissolved in the (meth) acrylate compound and added as a varnish. The ink can also be produced using a flushing method.

  When producing a varnish, a (meth) acrylate compound is used as a solvent component for dissolving components other than the pigment. Thereby, the fluidity | liquidity of resin improves and the mixability of components, such as a pigment, improves. The (meth) acrylate compound described above can be used as the usable (meth) acrylate compound. These (meth) acrylate compounds can be used alone or in combination of two or more.

  In the case of the stirring and mixing, if the temperature is appropriately cooled and the temperature is kept at about 20 to 120 ° C., a good quality ink can be easily obtained. Examples of the kneader include kneader mixing apparatuses such as a kneader, three rolls, an attritor, a sand mill, a gate mixer, and a kneader.

  As the ink, each color of cyan, magenta, yellow, and black is a basic color, and an ink having a color obtained from the above-described pigment can be arbitrarily produced.

The printed matter of the present invention includes a base material and an ink layer formed from an active energy ray-curable ink.
The ink layer can be formed by a known printing method such as offset printing, gravure printing, flexographic printing or screen printing, and offset printing is preferred. In addition, offset printing is also called lithographic printing. The thickness of the ink layer is usually about 0.5 to 4 μm.

  As the base material, a known material used for printed matter can be used. The substrate is, for example, non-coated paper such as fine paper, fine coated paper, art paper, coated paper, lightweight coated paper, coated paper such as cast coated paper, white paperboard, paperboard such as ball coat, synthetic paper, Examples include aluminum vapor-deposited paper and plastic sheets such as polypropylene, polyethylene, polyethylene terephthalate, and polyvinyl chloride.

  The ink is cured by irradiating an active energy ray to an ink layer formed by printing and drying (curing) the ink layer. The active energy ray is, for example, ionizing radiation such as ultraviolet ray, electron beam, X-ray, α ray, β ray, γ ray, microwave, high frequency, etc. Any energy ray that can generate radical active species. However, visible light, infrared light, or laser light may be used. Ultraviolet light source is, for example, ultra high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, helium cadmium laser, YAG laser, excimer laser, argon laser, LED lamp Etc. Any light source may be used as long as it is used for photocurable ink such as offset printing. Specifically, for example, a light source of about 40 W to 240 W is preferable for a metal halide lamp, a mercury lamp, or the like, and a light source of about 2 W to 20 W is preferable for an LED lamp. It should be noted that the number of light sources and the like can be appropriately adjusted according to the printing speed, the distance between the printed matter and the lamp on the apparatus configuration, and the dry state of the ink layer.

The printed matter of the present invention is, for example, printed matter for forms, printed matter for various books, printed matter for packaging such as carton paper, various printed matter for plastics, printed matter for seal / label, printed matter for art, printed matter for metal (printed matter for art, printed beverage can, canned product, etc. Food prints), advertisements, flyers, pamphlet prints, etc.

  Hereinafter, the present invention will be described specifically by way of examples. In this embodiment, “part” represents “part by mass” and “%” represents “% by mass”. Moreover, the compounding quantity in a table | surface is a mass part.

1. Production of resin varnish First, a resin varnish was produced. The varnish was prepared by charging diallyl phthalate resin / ditrimethylolpropane tetraacrylate / hydroquinone at a mass ratio of 30 / 69.9 / 0.1 and stirring and mixing at 100 ° C. in an air stream.

2. Production of active energy ray-curable printing ink (Example 1)
Pigment Blue 15: 3 18.0 parts, 0.9 part of the compound represented by the chemical formula (1), 42.0 parts of resin varnish, 10.0 parts of dipentaerythritol hexaacrylate, 12.0 parts of ditrimethylolpropane tetraacrylate, 7.05 parts of ethylene oxide-modified trimethylolpropane tetraacrylate, 3.0 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 4,4-bis (diethylamino) 2.0 parts benzophenone, 1.0 part 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 1.0 part 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, Aluminum N-nitrosophenylhydroxylamine 0.05 part, magnesium carbonate 3.0 After measuring and stirring a part, it disperse | distributed with the 3 roll mill, and ink was obtained by performing filtration.

(Examples 2 to 6)
Except having changed the mixing | blending of Example 1 as described in Table 1, it carried out by the method similar to Example 1, and obtained the ink of Examples 2-9, respectively.

(Comparative Examples 1-2)
Except having changed the mixing | blending of Example 1 as described in Table 1, it carried out by the method similar to Example 1, and obtained the ink of Comparative Examples 1-2, respectively.

  The following tests were conducted on the obtained ink.

1. Continuous printing suitability (density between printing paper surfaces, background stains)
About the obtained ink, a continuous printing test was performed using the following printing machine,
Sampling was performed every 00 sheets, 8000 sheets, 12000 sheets, and 16000 sheets, and the density stability of the printed matter and visual observation of the presence or absence of soiling (background stain) of the printed matter were performed. The evaluation criteria are as follows.
<Soil dirt>
A: The ink layer non-formation part was free from stains and a good printed matter was obtained.
Δ: A practically printed matter was obtained although the ink layer non-formed part was slightly stained.
X: The ink layer non-formation part had a stain | pollution | contamination, and the printed matter which cannot be used was obtained.

<Concentration stability>
A continuous printing test was performed in the same manner as described above, and the density value of the solid portion of the printed material was measured with respect to the density value of the 200th printed material after the start of printing. The closer the value is to 1, the better the concentration is maintained. X-riteEXACT (D50, 2 degree visual field, ISOStatusE) (manufactured by Videojet X-Rite) was used for the measurement of the density of the printed matter.

2. Continuous printing suitability (dirt of dampening water supply roller)
About the obtained ink, a continuous printing test is performed in the same manner as described above, the printing machine is stopped at 5000 sheets, 15000 sheets, and 30000 sheets, respectively, and the state of the fountain solution supply roller is visually checked, and if necessary, The dampening water supply roller was washed. The evaluation standard is described as the number of washings required for printing up to each number of sheets.
(Printing conditions)
・ Offset printing machine: LITHRONE26 (manufactured by Komori Corporation)
-PS (presensitized plate) version: XP-F (manufactured by FFGS)
・ Paper: Pearl Court N (Mitsubishi Paper)
・ Dampening water: tap water / ASTRO MARK 3 (manufactured by Nikken Chemical Laboratories) / Isopropyl alcohol = mixed at a ratio of 95 wt% / 2 wt% / 3 wt% Printing conditions: temperature 25 ± 1 ° C., printing Speed: 8000 sheets / hour / printing operation conditions: The scale of the dampening water supply device was set to the minimum value at which the printed matter was not stained.

2. Evaluation of static fluidity 3 g of the obtained ink was dropped on a brass inclined plate inclined at 60 ° in an atmosphere of 25 ° C, and the distance that flowed from the ink landing point for 10 minutes was measured and evaluated as static fluidity. did. Note that the evaluation standard was better as the length of ink flow was longer. The unit is expressed in mm.

From the results of Table 1, Examples 1 to 6 have good static fluidity. Further, since there is little background contamination when continuous printing is performed, there is little paper loss and the productivity of printed matter is improved. In addition, since the change in the density of the ink layer can be suppressed when continuous printing is performed, the productivity of printed matter is improved in that the number of times of cleaning by temporarily stopping the printing press can be reduced.
On the other hand, since Comparative Examples 1 and 2 did not contain the compound represented by the chemical formula (1), the static fluidity of the ink was the same as before. Moreover, since the pigment cannot be kept in a finely dispersed state in the ink during continuous printing, the above-described effects cannot be obtained and productivity cannot be improved.

Claims (4)

An active energy ray-curable ink containing a compound represented by the following general formula (1), a (meth) acrylate compound, a resin and a pigment ,
An active energy ray-curable ink in which the resin is diallyl phthalate resin.
General formula (1)
Q-(-X-Y) n
(Wherein, Q is an n-valent organic pigment residue, n represents an integer of 1 to 4, X is a direct bond (what a Q-Y not via X), - CONH-Y2 - , - SO 2 NH- Y ₂ — or —CH ₂ NHCOCH ₂ NH—Y ₂ —, wherein Y 2 is a direct bond (bonds to Y without going through Y 2), or an alkylene group or an arylene group which may have a substituent, Y is represented by the following general formula Group represented by (2))
General formula (2)

(In the formula, Y3 is a hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ or —SO ₃ H, k is an integer of 1 to 4, and when k = 1 to 3, Y3 is a carboxyl group bond of a benzene ring. Bonded at any position except the site, provided that when Y3 is a hydrogen atom, k is 4, and when k is 1 to 3, the remaining Y3 is a hydrogen atom, and m is an integer of 1 to 6. .)   The active energy ray-curable ink according to claim 1, comprising 0.01 to 10% by mass of the compound represented by the general formula (1) in the active energy ray-curable ink. Characterized in that an offset printing ink, according to claim 1 or 2 active energy beam-curable ink according. A printed matter comprising a substrate and an ink layer that is a cured product of the active energy ray-curable ink according to claim 1.