JP7173781B2 - Actinic energy ray-curable offset ink and printed matter - Google Patents

Description

The present invention relates to an active energy ray-curable offset ink characterized by maintaining excellent curability, printability and print quality under active energy ray conditions for use in offset printing on thin paper and packaging applications. Furthermore, it relates to a printed matter using the offset printing ink.

Ultraviolet curable offset inks that cure under active energy ray conditions are used for commercial printing, fine art printing, sticker/label printing, business form printing, package printing for food packaging such as toys and paper containers, due to the convenience of instant drying characteristics. It is widely used in fields such as

And due to the convenience of instant drying characteristics, especially in commercial printing, the switch from conventional oxidative polymerization type oil-based ink to UV-curable ink is progressing. performance equivalent to that of oil-based ink is required.
However, in recent years, as a detrimental effect of the shift to UV, there have been occasional phenomena in which ink components tend to polymerize due to the mechanical structure of some printing presses, causing the ink to spew powder. Once the ink begins to spout, it leads to problems such as hickeys and pinholes on the paper surface, so there is a demand for an ink that is improved in spouting of powder.

For example, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (DPHA), which are acrylic monomers useful in terms of curability, are widely used, and urethane acrylate varnish and diallyl phthalate varnish (DAP varnish) are used in combination. Patent document 1 can be cited as an example of an active energy ray-curable offset ink composition, but it cannot be said that quality deterioration such as hickeys caused by ink powder ejection on a printing press has been overcome.

JP 2016-079211

An object of the present invention is to provide an active energy ray-curable offset ink that has a standard curability, does not cause the ink to squirt on a printing press, and can suppress the occurrence of misting. It is in.

As a result of extensive research to solve the above problems, the inventors of the present invention have achieved the phenomenon of powder ejection of active energy ray-curable offset ink under specific conditions using an ink kneader. , found that there is a correlation with the powder blowing phenomenon on the printing press, and completed the present invention.

That is, in the present invention, an active energy ray-curable offset ink having a viscosity adjusted to a range of 5 to 50 pascal seconds (Pa.s.) at a temperature of 25° C. is placed on a roll mill, which is an ink kneader, and the roll mill and rolls are used. After the temperature was adjusted so that the surface temperature of the active energy ray-curable offset ink placed on the top was 35° C., pressure was applied between the rolls. ) relates to the above active energy ray-curable offset ink.

Further, the present invention relates to an active energy ray-curable offset ink containing a binder (A) and a (meth)acrylate monomer (B).

Further, in the present invention, the binder (A) comprises urethane resin, diallyl phthalate resin, diallyl isophthalate resin, ureaaldehyde resin, ketone aldehyde resin, epoxy (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate. It relates to an active energy ray-curable offset ink which is one or more selected from the group.

Further, in the present invention, the urethane resin comprises an alkyl monoalcohol compound (d1), a polyol compound (d2), and a polyisocyanate compound (d3) as essential reaction raw materials, and the (meth)acrylate monomer (B ) relates to an active energy ray-curable offset ink containing a (meth)acrylic compound (b1) having three or more (meth)acryloyl groups in one molecule.

Further, the present invention relates to an active energy ray-curable offset ink in which the (meth)acrylate monomer (B) is dipentaerythritol hexa(meth)acrylate or dipentaerythritol penta(meth)acrylate (DPHA).

Further, the present invention relates to active energy ray-curable offset inks containing talc, magnesium carbonate, or calcium carbonate as extender pigments.

Furthermore, the present invention relates to a printed matter comprising a cured product of the active energy ray-curable offset ink on a substrate.

The active energy ray-curable offset ink of the present invention has standard curability, does not cause the ink to splatter on a printing press, and is capable of suppressing the occurrence of misting. Offset ink can be obtained.

The active energy ray-curable offset ink of the present invention is "an active energy ray-curable offset ink having a viscosity adjusted to a range of 5 to 50 pascal seconds (Pa.s.) at a temperature of 25°C. After adjusting the temperature so that the surface temperature of the active energy ray-curable offset ink placed on the roll mill and on the rolls is 35°C, when the rolls are pressurized, ink powder spraying occurs. When the applied pressure is 3 megapascals (MPa) or more, the powder ejection phenomenon is suppressed even on an actual printing press.

When active energy ray-curable offset ink is used on the ink fountain of an offset printing press, a powder ejection phenomenon is observed due to its polymerization activity if the gap between the ink fountain and the supply roller is narrow. This powder blowing phenomenon is considered to be due to the polymerization of active radicals called mechanoradicals, which are mainly generated when the molecular structure of the binder resin is sheared by mechanical shearing. Since this active radical is short-lived but strong, it instantly reacts to form a polymer even if there is no photopolymerization initiator. Accumulation of this polymer can cause hickeys and pinholes that degrade the quality of printed paper. The active energy ray-curable offset ink of the present invention can be made by checking the degree of ink powder ejection under specific conditions on an ink kneader equipped with a steel roll mill. To provide the ink excellent in mechanical stability, which is difficult to be cured.
The polymer is a value obtained by subtracting the mass of the active energy ray-curable composition before roll pressure from 50 g of the active energy ray curable composition containing the residue after roll pressure of the kneader, If it is 5 mg or more, it is determined that "a polymer is generated". If the insoluble polymer is generated on the roll, it can be visually confirmed. In that case, 5 mg or more of residue is generated without exception, so the occurrence of powder spraying must be visually determined. can be done.

The mechanical stability of the active energy ray-curable offset ink of the present invention can be evaluated by measuring the pressure at the time when powder blowing is observed on the roll of the kneader according to the following method/procedure. . Specifically, the rolls of the kneader are heated, and the temperature on the rolls is confirmed to be 35° C. with a non-contact thermometer. Next, an active energy ray-curable offset ink having a viscosity in the range of 5 to 50 pascal seconds (Pa.s.) at 25° C. was placed between the two rolls, and the clearance between the rolls was made zero. After rotating at 4 MPa, the pressure was increased stepwise by 0.2 MPa every 2 minutes, and the pressure was recorded when even a slight amount of powder caused by the polymer was visible on the roll.
As a result, by setting the conditions at which ink powder ejection occurs to 3 megapascals (MPa) or more, active energy ray-curable offsets with excellent mechanical stability that are difficult to develop powder ejection even on a printing machine. It can be confirmed that it is ink.

Next, the active energy ray-curable offset ink of the present invention preferably contains a binder (A) and a (meth)acrylate monomer (B). Containing is more preferable. In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acrylic compound" refers to one or both of acrylic compound and methacrylic compound.

The binder (A) used in the active energy ray-curable offset ink of the present invention includes urethane resin, diallyl phthalate resin, diallyl isophthalate resin, urea aldehyde resin, ketone aldehyde resin, epoxy (meth)acrylate, urethane (meth) Any one or more of acrylates and polyester (meth)acrylates can be used, and each may be used alone or in combination of any one or more.
Epoxy resins, petroleum resins, rosin ester resins, poly(meth)acrylic acid esters, cellulose derivatives, etc., as long as they have suitable pigment affinity and dispersibility and rheological properties required for printing inks, etc. , vinyl chloride-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, butadiene-acrylonitrile copolymers, polyester (meth)acrylate compounds, etc. can also be used. Any one or more of them may be used in combination. Among them, urethane resin is more preferable.

Among the urethane resins, those containing an alkyl monoalcohol compound (a1), a polyol compound (a2), and a polyisocyanate compound (a3) as essential reaction raw materials are preferred.

Examples of the alkyl monoalcohol compound (a1) include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 2,2-dimethyl-1-propanol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 3- methyl-1-butanol, 3,3-dimethyl-2-butanol, 2-methyl-1-butanol, 3-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-butanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2-ethyl-1-butanol, n-pentyl alcohol, 2-pentanol, 2-methyl-1-pentanol, 3,3 -dimethyl-1-butanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 3-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3- methyl-3-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-ethylhexanol, nonyl alcohol and its isomers, decyl alcohol and its isomers, undecyl alcohol and its isomers, dodecyl alcohol and its isomers, and the like. Among these, alkyl monoalcohols having 3 to 8 carbon atoms are preferred because they give an active energy ray-curable offset ink having excellent curability and printability.

The amount of the alkyl monoalcohol compound (a1) used is the reaction raw material for the urethane resin (A), since an active energy ray-curable offset ink having excellent curability, mechanical stability and printability can be obtained. It is preferably in the range of 10 to 40% by mass based on the total amount of the alkyl monoalcohol compound (a1), the polyol compound (a2) and the polyisocyanate compound (a3).

The polyol compound (a2) is not particularly limited, for example, as long as it is a compound having a plurality of hydroxyl groups in the molecule. It is preferable from the viewpoint of aptitude. Examples of such polyol compounds include bifunctional polyols such as neopentyl glycol, 1,3-butanediol, 1,4-butanediol and tripropylene glycol; trifunctional polyols such as glycerin and trimethylolpropane; Tetrafunctional polyols such as erythritol and ditrimethylolpropane; hexafunctional polyols such as dipentaerythritol; Propylene oxide adduct of (average 1 to 4 mol addition per molecule), 1,3-butanediol adduct of the trifunctional polyol (average addition of 1 to 2 mol per molecule), ethylene of the tetrafunctional polyol Oxide adducts (addition of 1 to 3 mol on average per molecule), ethylene oxide adducts of the above hexafunctional polyols (addition of 1 to 3 mol on average per molecule), and the like can be mentioned. These polyol compounds can be used alone or in combination of two or more. Among these, since an active energy ray-curable offset ink having excellent curability, mechanical stability and printability can be obtained, trifunctional polyols such as glycerin and trimethylolpropane, neopentyl glycol, 1 ,6-hexanediol and tripropylene glycol are preferred, and trifunctional polyols such as glycerin and trimethylolpropane are more preferred.

Since an active energy ray-curable offset ink having excellent curability, mechanical stability and printability can be obtained, the amount of the polyol compound (a2) used is the reaction raw material of the urethane resin (A). The total amount of the alkyl monoalcohol compound (a1), the polyol compound (a2), and the polyisocyanate compound (a3) is preferably in the range of 30 to 80% by mass.

Examples of the polyisocyanate compound (a3) include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and trimethylhexamethylene diisocyanate; polyisocyanates having an alicyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, 1,5-naphthalene diisocyanate, aromatic polyisocyanate such as polymethylene polyphenyl polyisocyanate and isocyanate. In addition, nurate modified products, adduct modified products, biuret modified products, allophanate modified products, etc. of these polyisocyanates can also be used. These polyisocyanate compounds can be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred because they give active energy ray-curable offset inks with excellent curability, mechanical stability and printability.

Among the aromatic polyisocyanates, in particular, polyfunctional polyisocyanate compounds containing a component having three or more isocyanate groups per molecule (trifunctional or higher component) have excellent curability, mechanical stability and printing. It is preferable because a suitable active energy ray-curable offset ink can be obtained, more preferably containing 30% by mass or more of trifunctional or higher functional components, and particularly preferably polymethylene polyphenyl polyisocyanate.

More preferably, the polymethylene polyphenyl polyisocyanate has a viscosity of 100 to 700 mPa·s. In addition, the viscosity here is the value measured with the E-type viscometer (25 degreeC).

The amount of the polyisocyanate compound (a3) used is the raw material for the reaction of the urethane resin (A) because an active energy ray-curable offset ink having excellent curability, mechanical stability and printability can be obtained. The total amount of the alkyl monoalcohol compound (a1), the polyol compound (a2), and the polyisocyanate compound (a3) is preferably in the range of 30 to 80% by mass.

The method for producing the urethane resin (A) is not particularly limited, and any method may be used. For example, the alkyl monoalcohol compound (a1), the polyol compound (a2), and the polyisocyanate compound (a3) may be produced by a method of reacting all reaction raw materials as essential, or the polyol compound A method of reacting (a2) with the polyisocyanate compound (a3) and then reacting the alkyl monoalcohol compound (a1); A method of reacting a part of the monoalcohol compound (a1) and then adding the remaining alkyl monoalcohol compound (a1) to further react may be used. Among them, the molecular weight of the urethane resin (A) to be obtained is easy to control, and gelation or the like is unlikely to occur. A method of reacting an alkyl monoalcohol compound (a1) is preferred.

As a method of reacting the polyol compound (a2) with the polyisocyanate compound (a3), for example, the polyisocyanate compound (a3) and, if necessary, a known and commonly used urethanization catalyst are added, and the °C, and a predetermined amount of the polyol compound (a2) is continuously or intermittently added to the reaction system for reaction.

The reaction between the polyol compound (a2) and the polyisocyanate compound (a3) is the equivalent ratio of the hydroxyl groups of the polyol compound (a2) to the isocyanate groups of the polyisocyanate compound (a3) [isocyanate group/ hydroxyl group] is preferably in the range of 40/60 to 90/10, more preferably in the range of 60/40 to 80/20.

As a method of reacting the alkyl monoalcohol compound (a1) after reacting the polyol compound (a2) and the polyisocyanate compound (a3), for example, the polyol compound (a2) and the polyisocyanate compound ( The alkyl monoalcohol compound (a1) is added to the reaction product obtained by the reaction with a3) and heated to 20 to 120° C., and the infrared absorption spectrum at 2250 cm ⁻¹ indicating the isocyanate group disappears. A method of reacting up to

The weight-average molecular weight (Mw) of the urethane resin (A) is in the range of 3,000 to 30,000 so that an active energy ray-curable offset ink having excellent curability, mechanical stability and printability can be obtained. is preferred, the range of 6,000 to 20,000 is more preferred, and the range of 10,000 to 20,000 is particularly preferred.

In addition, in this invention, a weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.

The diallyl phthalate resin has three isomers, ortho, iso, and tere. can be used.
Examples of the diallyl isophthalate resin include a composition containing a polybasic acid such as phthalic acid as a main agent, allyl alcohol as a curing agent, a cross-linking agent, and the like. Examples of the cross-linking agent include styrene and vinyl acetate.
Diallyl phthalate resin and diallyl isophthalate resin are particularly useful for imparting excellent paper peeling properties, emulsification resistance, and long-run printability.
As the diallyl phthalate resin, specifically, Daiso Dap A (manufactured by Daiso Co., Ltd.),
Examples of the diallyl isophthalate resin include Daiso Isodap (manufactured by Daiso Corporation).

Moreover, resins, such as urea aldehyde resin and ketone aldehyde resin, can be used as a binder (A). The urea aldehyde resin is characterized by its wide solubility and compatibility, and commercially available products include Laropal A81 (manufactured by BASF).
The ketone aldehyde resin is characterized by its high pigment binding property and low solution viscosity, and commercially available products include the VariPlus series from Ebonix.

Moreover, photopolymerizable oligomers such as epoxy (meth)acrylate, urethane (meth)acrylate, and polyester (meth)acrylate can be used as the binder (A). The epoxy (meth)acrylate is synthesized by reacting an epoxy group with acrylic acid or methacrylic acid. Epoxy (meth)acrylate is preferable because of its excellent flexibility, adhesiveness, appropriate hardness, heat resistance, chemical resistance, and high curing speed.

The main raw materials of the urethane (meth)acrylate are diisocyanate, polyol, and hydroxy (meth)acrylate, and molecular design can be performed by appropriately changing the combination thereof. One of the features of urethane (meth)acrylate is that it is relatively easy to design molecules, and is excellent in toughness, moderate hardness, chemical resistance, flexibility, adhesion, light resistance, oxygen resistance, and low temperature suitability. preferable from the point of view.

The polyester (meth)acrylate is obtained by condensing the OH group remaining in the polyester skeleton synthesized from various diols, polyols and dibasic acids with acrylic acid. An advantage of polyester (meth)acrylates is that they tend to have lower viscosities than other oligomers and are also useful as reactive diluents.

These binders (A) may be used alone or in combination.
In the active energy ray-curable offset ink composition of the present invention, the binder (A) is preferably 5 to 20% by mass, more preferably 5 to 15% by mass, of the total amount of the ink composition.
If the content of the binder (A) is less than 5% by mass, sufficient ink viscosity cannot be obtained, and problems such as dot gain and staining tend to occur in printing. On the other hand, when the content exceeds 20% by mass, the fluidity of the ink is significantly impaired, and sufficient printability may not be imparted.

The (meth)acrylate monomer (B) preferably contains a (meth)acryloyl compound (b1) having three or more (meth)acryloyl groups in one molecule as an essential component.

In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acrylic compound" refers to one or both of acrylic compound and methacrylic compound.

Examples of the (meth)acryloyl compound (b1) having three or more (meth)acryloyl groups in one molecule include glycerin tri(meth)acrylate, diglycerin tri(meth)acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di Pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylol Propane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, tris-2-hydroxyethyl isocyanurate tri(meth)acrylate and the like. . These (meth)acryloyl compounds having three or more (meth)acryloyl groups in one molecule can be used alone or in combination of two or more. Among these, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, trimethylolpropane tri(meth)acrylate, Ethoxylated trimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate are preferred, and dipentaerythritol hexa(meth)acrylate and dipentaerythritol penta(meth)acrylate are particularly preferred.

As the (meth)acrylate monomer (B), in addition to the (meth)acryloyl compound (b1) having three or more (meth)acryloyl groups in one molecule, other (meth)acryloyl Combinations of compounds can also be used.

Examples of the other (meth)acryloyl compounds include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate ) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3- Methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphoric acid (meth)acrylate, ethylene oxide-modified phosphoric acid (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide-modified phenoxy (meth)acrylate, propylene oxide-modified Phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, propylene oxide-modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate ) acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, 2-(meth)acryloyloxypropyl tetrahydrophthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, Hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, adamantyl mono(meth)acrylate b) acrylates and other mono (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, neopentyl glycol ethoxylated di(meth) acrylate, neopentyl glycol di(meth) hydroxypivalate Di(meth)acrylates such as acrylates and the like are included.

The content of the (meth)acrylate monomer (B) is It is preferably in the range of 75 to 3400 parts by mass.

When using the photopolymerization initiator, for example, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl] -2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl (2,4,6-trimethoxy benzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and the like. These photopolymerization initiators can be used alone or in combination of two or more.

Commercially available products of the photopolymerization initiator include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", " Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad- 754”, “Omnirad-784”, “Omnirad-500”, “Omnirad-81” (manufactured by IGM), “Kayacure-DETX”, “Kayacure-MBP”, “Kayacure-DMBI”, “Kayacure-EPA”, "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stouffer Chemical), "Trigonal P1" (manufactured by Akzo), "Sunray 1000" (Sandos) ), “Deep” (manufactured by Upjohn), “Quantacure-PDO”, “Quantacure-ITX”, “Quantacure-EPD” (manufactured by Ward Blenkinsop), “Runtecure-1104” (manufactured by Runtec ) and the like.

When the photopolymerization initiator is contained, the amount added is preferably in the range of 1 to 20% by mass in terms of solid content in the active energy ray-curable offset ink of the present invention, and is preferably in the range of 5 to 15% by mass. more preferred. That is, when the total amount of the photopolymerization initiator used is 1% by mass or more, good curability can be obtained, and when it is 20% by mass or less, unreacted polymerization initiators remain in the cured product. Insufficient curing can also be suppressed. However, in principle, the use of these photopolymerization initiators is not essential when electron beams are used as active energy rays.

In addition, since the active energy ray-curable offset ink can improve the curability of the cured coating film of the composition, a photosensitizer can be further added to improve the curability as necessary. .

Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, and sulfur compounds such as s-benzylisothiuronium-p-toluenesulfonate. compound and the like. The amount of these photosensitizers used is from 1 to 1 as the total amount used with respect to 100% by mass of non-volatile components in the active energy ray-curable offset ink of the present invention, since the effect of improving curability is good. It is preferably in the range of 20% by mass.

The active energy ray-curable offset ink of the present invention comprises, in addition to the binder (A), (meth)acrylate monomer (B), and photopolymerization initiator, an organic solvent, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, and silicon. system additives, fluorine-based additives, silane coupling agents, phosphate ester compounds, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, coloring agents, waxes, pigments, dyes, etc. good.

Furthermore, when preparing the active energy ray-curable offset ink of the present invention, it is preferable to add an extender (C) in consideration of printability (misting). Examples of the extender pigment (C) include inorganic fine particles.
Examples of the inorganic fine particles include calcium carbonate, magnesium carbonate, talc, silica, alumina, zirconia, titania, barium titanate, antimony trioxide, titanium oxide, graphite, zinc white, lime carbonate powder, precipitated calcium carbonate, gypsum, In addition to fine particles such as clay (ChinaClay), diatomaceous earth, kaolin, barium sulfate, aluminum stearate, barite powder, abrasive powder, silicon, glass beads and the like can be used. These inorganic fine particles can be used alone or in combination of two or more.
In particular, when preparing the active energy ray-curable offset ink of the present invention, it is preferable to add calcium carbonate, magnesium carbonate, and talc because their addition has the effect of suppressing misting. Among them, talc is more preferable because it has a greater effect of suppressing misting.
By using the inorganic fine particles in a range of 0.1 to 20% by mass based on the total amount of the active energy ray-curable offset ink, misting can be suppressed.

Wax can be added to the active energy ray-curable offset ink of the present invention for the purpose of improving curability. Examples of the wax include waxes such as paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene wax, polyethylene oxide wax, polytetrafluoroethylene wax, and amide wax; Fatty acids in the range can be mentioned.

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.

Examples of the inorganic pigment include iron oxide and carbon black produced by a known method such as a contact method, a furnace method, a thermal method, and the like.
For example, Raven 14, Raven 450, Raven 860 Ultra, Raven 1035, Raven 1040, Raven 1060 Ultra, Raven 1080 Ultra, Raven 1180, Raven 1255 (manufactured by Birla), Regal 400R, Regal 330R, Regal 660R, Mogul L (above, Cabot Corporation), MA7, MA8, MA11 (manufactured by Mitsubishi Chemical Corporation), etc., and these may be used alone or in combination of two or more.

Examples of the organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, Examples include quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These pigments can be used alone or in combination of two or more.

Specific examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.

Specific examples of pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, etc. C. I. Pigment Violet 19 and the like.

Specific examples of pigments used in cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15, 15:3, 15:4, 16, 22, 60, 63, 66 and the like.

Further dyes include, for example, azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, and naphthoquinone. dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane dyes, and the like; These dyes can be used alone or in combination of two or more.

After printing on a substrate, the active energy ray-curable offset ink of the present invention can be irradiated with an active energy ray to form a cured coating film and produce a printed matter.

Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.

As the source of the ultraviolet rays, an ultraviolet lamp is generally used from the viewpoint of practicality and economy. Specifically, germicidal lamps, fluorescent lamps for ultraviolet rays, high-pressure mercury lamps for copying, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, carbon arcs, xenon lamps, gallium lamps, and metal halides. Lamps, sunlight, ultraviolet light emitting diodes (UV-LEDs) and the like can be mentioned.

Examples of printing methods using the active energy ray-curable offset ink of the present invention include wet offset printing, waterless offset printing, resin letterpress printing, dry offset printing, screen printing and the like.

The printing substrate for printing the active energy ray-curable offset ink of the present invention is not particularly limited. High-quality paper used for printing, coated paper, art paper, imitation paper, thin paper, thick paper, various synthetic papers, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, Films or sheets of polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate, etc., cellophane, aluminum foil, and other conventionally used printing substrates. Various substrates can be mentioned.
Other base materials include, for example, metal base materials, glass base materials, paper base materials, wood base materials, fiber base materials, and the like.

In the production of the active energy ray-curable offset ink described in the present invention, the pigment, (meth)acrylate monomer, binder, photopolymerization initiator, extender pigment, and other additives are used in the same manner as in conventional active energy ray-curable offset inks. It is produced by blending agents and the like, stirring and mixing them with a mixer or the like, and kneading them with a dispersing machine such as a three-roll mill or a bead mill.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples.

In addition, in the present Examples, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; guard column _HXL -H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard; Polystyrene Sample; A tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered through a microfilter (100 μl)

(Synthesis Example 1: Synthesis of urethane resin (1))
A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer was charged with 136.05 parts by mass of polymethylene polyphenyl polyisocyanate (“Lupranate M-20S” manufactured by BASF INOAC Polyurethane Co., Ltd., 2,6-di 0.99 parts by mass of t-butyl-4-methylphenol, 0.10 parts by mass of hydroquinone monomethyl ether, and 0.04 parts by mass of zinc 2-ethylhexanoate were added, the temperature was raised to 40°C, and 52.5 parts by mass of n-butanol was added. 24 parts by mass was added dropwise over 1 hour, followed by reaction for 5 hours at 80° C. Then, 9.06 parts by mass of glycerin was added, and furthermore, an infrared absorption spectrum at 2250 cm ⁻¹ indicating an isocyanate group at 90° C. was added. The reaction was carried out until the was disappeared to obtain urethane resin (1), which had a weight average molecular weight (Mw) of 17,000.

(Synthesis Example 2: Synthesis of urethane resin (2))
A 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser and a thermometer was charged with 136.05 parts by mass of polymethylene polyphenyl polyisocyanate (“Lupranate M-20S” manufactured by BASF INOAC Polyurethane Co., Ltd., 2,6-di - 0.99 parts by mass of t-butyl-4-methylphenol, 0.10 parts by mass of hydroquinone monomethyl ether, and 0.04 parts by mass of zinc 2-ethylhexanoate were added, heated to 40°C, and 58.5 parts by mass of n-butanol. 6 parts by mass was added dropwise over 1 hour, followed by reaction for 5 hours at 80° C. Next, 13.2 parts by mass of trimethylolpropane was added, and furthermore, an infrared ray of 2250 cm ⁻¹ indicating an isocyanate group at 90° C. was added. The reaction was continued until the absorption spectrum disappeared to obtain Urethane Resin (2), which had a weight average molecular weight (Mw) of 14,000.

Table 1 shows the compositions of the obtained urethane resins (1) and (2).

(Example 1: Preparation of active energy ray-curable offset black ink (1))
The urethane resin (1) obtained in Synthesis Example 1 was diluted at 100° C. with dipentaerythritol hexaacrylate (“MIRAMER M600” manufactured by MIWON) at a resin ratio of 40% to prepare a varnish. Subsequently, 5 parts by mass of the varnish, 65 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-1-one (IGM "Omnirad 907") 10 parts by mass, 4,4'-bisdiethylaminobenzophenone (Omnirad EMKIGM) 5 parts by mass at 60 ° C. for 3 hours After mixing to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added, and after stirring using a mixer (single-axis dissolver), three bottles of the formulation were added. It was kneaded with a roll mill to obtain an active energy ray-curable offset ink (1). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Example 2: Preparation of active energy ray-curable offset black ink (2))
Using the same varnish as in Example 1, 35 parts by weight of varnish, 35 parts by weight of dipentaerythritol hexaacrylate (“MIRAMER M600” manufactured by MIWON), and α-aminoalkylphenone-based initiator as a photopolymerization initiator, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight at 60 ° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla) is added, and after stirring using a mixer (single shaft dissolver) , the formulation was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (2). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Example 3-4: Preparation of active energy ray-curable offset black ink (3-4))
It was produced in the same manner as in Examples 1 and 2, except that the urethane resin (1) was replaced with the urethane resin (2).

(Example 5: Preparation of active energy ray-curable offset black ink (5))
At 100° C., Variplus AP (manufactured by Evonik) was diluted with dipentaerythritol hexaacrylate (“MIRAMER M600” manufactured by MIWON) to a resin ratio of 40% to prepare a varnish. Subsequently, 15 parts by mass of the varnish, 60 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-1-one (IGM "Omnirad 907") 10 parts by mass, 4,4'-bisdiethylaminobenzophenone (Omnirad EMKIGM) 5 parts by mass at 60 ° C. for 3 hours After mixing to obtain an active energy ray-curable ink composition), 10 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added, and after stirring using a mixer (single-axis dissolver), three bottles of the formulation were added. It was kneaded with a roll mill to obtain an active energy ray-curable offset ink (5). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Example 6: Preparation of active energy ray-curable offset black ink (6))
Using the same varnish as in Example 5, 40 parts by weight of varnish, 30 parts by weight of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), α-aminoalkylphenone initiator, 2-methyl as a photopolymerization initiator -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight at 60 ° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla) is added, and after stirring using a mixer (single shaft dissolver) , the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (6). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Example 7-8: Preparation of active energy ray-curable offset black ink (7-8))
Examples 5 and 6 were prepared in the same manner, except that Variplus AP (manufactured by Evonik) was replaced with Laropal A81 (manufactured by BASF).

(Example 9: Preparation of active energy ray-curable offset black ink (9))
PE210: 15 parts by mass of bisphenol A epoxy acrylate (manufactured by MIWON), 60 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" by MIWON), α-aminoalkylphenone-based initiator as a photopolymerization initiator, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight After mixing the parts at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 10 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added and stirred using a mixer (single shaft dissolver). After that, the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (9). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Example 10: Preparation of active energy ray-curable offset black ink (10))
PE210: 40 parts by mass of bisphenol A type epoxy acrylate (manufactured by MIWON), 30 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), α-aminoalkylphenone-based initiator as a photopolymerization initiator, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight After mixing the parts at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added and stirred using a mixer (single shaft dissolver). After that, the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (10). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Example 11-12: Preparation of active energy ray-curable offset black ink (11-12))
From Examples 9 and 10, PE210: bisphenol A type epoxy acrylate (manufactured by MIWON) and Ebecryl436: a mixture of chlorinated polyester and trimethylolpropane triacrylate (TMPTA) in a mass ratio of 6:4 (manufactured by Daicel Allnex) was prepared in the same manner except that it was substituted with

(Example 13-14: Preparation of active energy ray-curable offset black ink (13-14))
Examples 9 and 10 were prepared in the same manner, except that PE210: bisphenol A type epoxy acrylate (manufactured by MIWON) was replaced with Ebecryl220: aromatic urethane acrylate (manufactured by Daicel Allnex).

(Example 15: Preparation of active energy ray-curable offset black ink (15))
At 100 ° C., DAP A: diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd.) was mixed with trimethylolpropane ethylene oxide (hereinafter abbreviated as EO) modified triacrylate (TMP (EO) 3TA) Miramer M3130 ( (manufactured by MIWON) to prepare a varnish. Subsequently, 15 parts by mass of the varnish, 55 parts by mass of trimethylolpropane EO-modified triacrylate (TMP (EO) 3TA) Miramer M3130 (manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight After mixing the parts at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added and stirred using a mixer (single shaft dissolver). After that, the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (15). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Example 16: Preparation of active energy ray-curable offset black ink (16))
Using the same varnish as in Example 15, 31 parts by mass of varnish, trimethylolpropane EO-modified triacrylate (TMP (EO) 3TA) Miramer M3130 (manufactured by MIWON) 39 parts by mass, α-aminoalkylphenone as a photopolymerization initiator system initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by mass, 4,4'-bisdiethylaminobenzophenone ( After mixing 5 parts by mass of Omnirad EMKIGM at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added, and a mixer (single-axis dissolver ), the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (16). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Example 17: Preparation of active energy ray-curable offset black ink (17))
At 100°C, ISO DAP: diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd.) was diluted with trimethylolpropane EO-modified triacrylate (TMP (EO) 3TA) Miramer M3130 (manufactured by MIWON) so that the resin ratio was 40%. , produced a varnish. Subsequently, 20 parts by mass of the varnish, 50 parts by mass of trimethylolpropane EO-modified triacrylate (TMP (EO) 3TA) Miramer M3130 (manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight After mixing the parts at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added and stirred using a mixer (single shaft dissolver). After that, the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (17). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Example 18: Preparation of active energy ray-curable offset black ink (18))
Using the same varnish as in Example 17, 36 parts by mass of varnish, trimethylolpropane EO-modified triacrylate (TMP (EO) 3TA) Miramer M3130 (manufactured by MIWON) 34 parts by mass, α-aminoalkylphenone as a photopolymerization initiator system initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by mass, 4,4'-bisdiethylaminobenzophenone ( After mixing 5 parts by mass of Omnirad EMKIGM at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added, and a mixer (single-axis dissolver ), the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (18). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Example 19: Preparation of active energy ray-curable offset black ink (19))
A varnish was prepared by diluting DAP A: diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd.) with dipropylene glycol diacrylate (DPGDA) Miramer M222 (manufactured by MIWON) at a resin ratio of 40% at 100°C. Subsequently, 27 parts by mass of the varnish, 43 parts by mass of dipropylene glycol diacrylate (DPGDA) Miramer M222 (manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight at 60 ° C. After mixing for a period of time to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added and stirred using a mixer (single-axis dissolver). It was kneaded with this roll mill to obtain an active energy ray-curable offset ink (19). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Example 20: Preparation of active energy ray-curable offset black ink (20))
Using the same varnish as in Example 19, 39 parts by weight of varnish, dipropylene glycol diacrylate (DPGDA) Miramer M222 (manufactured by MIWON) 34 parts by weight, α-aminoalkylphenone initiator as a photopolymerization initiator, 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight After mixing the parts at 60° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added and stirred using a mixer (single shaft dissolver). After that, the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (20). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Examples 21-26: Preparation of active energy ray-curable offset black ink (21-26))
In contrast to Examples 1 and 2, the extender pigment (C) was replaced with 5 parts by mass of each of calcium carbonate, magnesium carbonate and talc, and ink pigment Raven 1060 Ultra (manufactured by Birla).

(Comparative Example 1: Preparation of active energy ray-curable offset black ink (H1))
A varnish was prepared by diluting DAP A: diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd.) with dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON) at a resin ratio of 40% at 100°C. Subsequently, 10 parts by mass of the varnish and 85 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON) were mixed at 60°C for 3 hours to obtain an active energy ray-curable ink composition). After adding 5 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla) and stirring using a mixer (single-shaft dissolver), the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (H1). rice field. The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Comparative Example 2: Preparation of active energy ray-curable offset black ink (H2))
Using the same varnish as in Comparative Example 1, 30 parts by mass of varnish and 55 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON) were mixed at 60°C for 3 hours to give an active energy ray-curable ink composition. ), add 15 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla), stir using a mixer (single-shaft dissolver), then knead the formulation with a three-roll mill to obtain an active energy ray-curable offset An ink (H2) was obtained. The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Comparative Example 3: Preparation of active energy ray-curable offset black ink (H3))
Using the same varnish as in Comparative Example 1, 5 parts by mass of varnish, 75 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight at 60 ° C. for 3 hours to obtain an active energy ray-curable ink composition), 5 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla) is added, and after stirring using a mixer (single shaft dissolver) , the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (H3). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Comparative Example 4: Preparation of active energy ray-curable offset black ink (H4))
Using the same varnish as in Comparative Example 1, 25 parts by mass of varnish, 45 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), and an α-aminoalkylphenone-based initiator as a photopolymerization initiator, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight at 60 ° C. for 3 hours to obtain an active energy ray-curable ink composition), 5 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla) is added, and after stirring using a mixer (single shaft dissolver) , the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (H4). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Comparative Example 5-8: Preparation of active energy ray-curable offset black ink (H5-8))
From Examples 3 and 4, the photoinitiator α-aminoalkylphenone initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM "Omnirad 907 ”) 10 parts by mass, 5 parts by mass of 4,4′-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM), and in Comparative Examples 5 and 6, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM “Omnirad TPO ”) 10 parts by mass, 5 parts by mass of 4,4′-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM), and in Comparative Examples 7 and 8, an α-aminoalkylphenone initiator, 2-methyl-1-[4-( methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 7 parts by mass, α-aminoalkylphenone initiator, 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)-butanone-1 ("Omnirad 369" manufactured by IGM) was substituted with 3 parts by weight and 5 parts by weight of 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM).

(Comparative Example 9: Preparation of active energy ray-curable offset black ink (H9))
ISO DAP: diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd.) was diluted with dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON) at 100° C. to a resin ratio of 40% to prepare a varnish. Subsequently, 8 parts by mass of the varnish, 72 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), an α-aminoalkylphenone initiator as a photopolymerization initiator, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-1-one (IGM "Omnirad 907") 10 parts by mass, 4,4'-bisdiethylaminobenzophenone (Omnirad EMKIGM) 5 parts by mass at 60 ° C. for 3 hours After mixing to obtain an active energy ray-curable ink composition), 5 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added, and after stirring using a mixer (single-axis dissolver), three bottles of the formulation were added. It was kneaded with a roll mill to obtain an active energy ray-curable offset ink (H9). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Comparative Example 10: Preparation of active energy ray-curable offset black ink (H10))
Using the same varnish as in Comparative Example 9, 28 parts by mass of varnish, 42 parts by mass of dipentaerythritol hexaacrylate ("MIRAMER M600" manufactured by MIWON), and α-aminoalkylphenone initiator, 2-methyl as a photopolymerization initiator. -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("Omnirad 907" manufactured by IGM) 10 parts by weight, 4,4'-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) 5 parts by weight at 60 ° C. for 3 hours to obtain an active energy ray-curable ink composition), 15 parts by mass of black pigment Raven 1060 Ultra (manufactured by Birla) is added, and after stirring using a mixer (single shaft dissolver) , the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (H10). The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Comparative Example 11: Preparation of active energy ray-curable offset black ink (H11))
ISO DAP: diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd.) was diluted with ditrimethylolpropane tetraacrylate (DTMPTA) Miramer M410 (manufactured by MIWON) at a resin ratio of 40% at 100 ° C. to prepare a varnish. . Subsequently, 5 parts by mass of the varnish, 65 parts by mass of ditrimethylolpropane tetraacrylate (DTMPTA) Miramer M410 (manufactured by MIWON), and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by IGM) as a photopolymerization initiator. Omnirad TPO”) 10 parts by mass and 5 parts by mass of 4,4′-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) were mixed at 60° C. for 3 hours to obtain an active energy ray-curable ink composition). After adding 15 parts by mass of Raven 1060 Ultra (manufactured by Birla) and stirring using a mixer (single-shaft dissolver), the mixture was kneaded with a three-roll mill to obtain an active energy ray-curable offset ink (H11). The viscosity of the produced ink at 25° C. was 5 Pa.s. was s.

(Comparative Example 12: Preparation of active energy ray-curable offset black ink (H12))
Using the same varnish as in Comparative Example 11, 30 parts by mass of varnish, ditrimethylolpropane tetraacrylate (DTMPTA) Miramer M410 (manufactured by MIWON) 40 parts by mass, and 2,4,6-trimethylbenzoyldiphenylphosphine as a photopolymerization initiator. 10 parts by mass of oxide (“Omnirad TPO” manufactured by IGM) and 5 parts by mass of 4,4′-bisdiethylaminobenzophenone (manufactured by Omnirad EMKIGM) were mixed at 60° C. for 3 hours to form an active energy ray-curable ink composition). After obtaining, 15 parts by mass of ink pigment Raven 1060 Ultra (manufactured by Birla) was added, and after stirring using a mixer (single-axis dissolver), the formulation was kneaded with a three-roll mill to give an active energy ray-curable offset ink ( H10) was obtained. The viscosity of the produced ink at 25° C. was 50 Pa.s. was s.

(Comparative Examples 13 to 20: Adjustment of active energy ray-curable offset black inks (H13) to (H20))
Various binders, (meth)acrylate monomers, and photopolymerization initiators were prepared in the same manner as in Comparative Examples 13 and 14 with the formulations shown in Tables 6 and 7. and an example in which the temperature was adjusted so that the surface temperature of the active energy ray-curable offset ink placed on the roll was 32° C. or 38° C.”, “The viscosity at a temperature of 25° C. was 5 to 50 pascal seconds (Pa.s. ) outside the range of 3 pascal seconds (Pa.s.) or 55 pascal seconds (Pa.s.)” were prepared.

Using the active energy ray-curable offset black inks obtained in Examples 1 to 26 and Comparative Examples 1 to 20, the following evaluations were performed.

[Evaluation item 1: Powder injection by a meat grinder]
Mechanical stability was evaluated by measuring the pressure at the time when powder blowing was observed on the roll by the following method. Specifically, three rolls manufactured by Buehler (SDY-200: roll diameter 150 mm, width 200 mm) were heated, and the temperature of the active energy ray-curable offset ink on the rolls reached 35°C with a non-contact thermometer. After confirming that the base ink has a viscosity of 5 to 50 Pa.s at 25°C. Each UV curable offset ink shown in the examples and comparative examples in the range of s was placed between the feeder roll and the middle roll, the clearance between the two rolls was set to zero, and the feeder roll was rotated at a speed of 37 rmp. After the middle roll was rotated at 110 rpm and a pressure of 1.4 MPa, the pressure was increased stepwise by 0.2 MPa every 2 minutes, and the pressure at the time when even a slight amount of powder due to polymerization on the roll could be visually confirmed. was recorded. In addition, the powder spraying due to the polymerization was obtained by dissolving 50 g of the active energy ray-curable offset ink containing the residue after roll pressing in 100 g of tetrahydrofuran (THF) solvent and passing it through a 25 μm filter. Based on the case where the value obtained by subtracting the mass of the residue of the active energy ray-curable offset ink before pressurization with the roll obtained in the same manner from the amount of residue obtained is 5 mg or more, "powder, that is, polymer occurred,” he concluded. As for the mechanical stability, when the generation of the polymer, which is the insoluble matter, could be visually confirmed on the roll, 5 mg or more of residue was generated without exception, so powder spraying occurred. judged visually.
In addition, since the pressure between the feeder roll and the middle roll cannot be set to 4 MPa or more due to the mechanical mechanism, the one that does not cause powder blowing at 4 MPa is the most excellent in mechanical stability.

[Evaluation item 2: Powder spraying by printing machine]
For powder spraying on the printing press, Lithrone G40 manufactured by Komori Corporation was used to adjust the clearance between the ink fountain and the roller to 2-3 μm. The temperature was set at 32° C. and the urn was rotated for 1 week, and the amount of powder remaining in the urn was visually confirmed according to the following 5-grade evaluation.
(Evaluation criteria)
5: No powder spraying at all.
4: Slight dusting is observed.
3: Powder spraying is observed, but at a printable level.
2: A lot of powder spraying is observed.
1: Remarkable powder spraying is observed.

[Evaluation Item 3: Ink Curability]
Using an RI tester (manufactured by IHI), 0.125 ml of the active energy ray-curable offset ink was spread on OK Top Coat Plus (57.5 kg, A size) manufactured by Oji Paper Co., Ltd. to a predetermined density. Next, a water-cooled metal halide lamp (output 160 W / cm, 1 lamp used) manufactured by Eye Graphics Co., Ltd. is used as an ultraviolet irradiation device to cure with ultraviolet rays at 120 m/min, and the paper surface after curing is rubbed with OK Top Coat Plus, and printed with the rubbed paper. Curability was evaluated by visually confirming both surfaces according to the following five grades.
(Evaluation criteria)
5: Neither the rubbed paper nor the printed matter is rubbed at all.
4: The rubbed paper is slightly colored, but the print is not rubbed.
3: The rubbed paper is colored, and the printed matter is also rubbed, but printing is possible in terms of quality.
2: Coloring of the rubbed paper is strong, and the printed matter is greatly rubbed.
1: The ink peels off from the surface of the printed matter due to insufficient curability.

[Evaluation item 4: misting]
1.35 ml of active energy ray-curable offset ink was applied on an incometer manufactured by Toyo Seiki, and OK Top Coat Plus (57.5 kg, A size) manufactured by Oji Paper Co., Ltd. was installed at the bottom and rear of the machine, and the speed was 1200 rpm. and rotated for 3 minutes. After that, misting was visually evaluated in the following 5 grades based on the amount of ink splashed onto the placed paper.

(Evaluation criteria)
5: Not flying at all.
4: Flying, but less.
3: Although it is flying, printing is possible in terms of quality.
2: Large amount of flying 1: Remarkably flying

The formulations, viscosities, and evaluation results of the active energy ray-curable offset black inks are shown below.

表２～７の数値は質量％である。各表に示す諸原料及び略を以下に示す。
・Ｒａｖｅｎ １０６０Ｕｌｔｒａ：ビルラ社製カーボンブラック
・Ｏｍｎｉｒａｄ ９０７：α－アミノアルキルフェノン系開始剤、２－メチル－１－[４－（メチルチオ）フェニル]－２－モルフォリノプロパン－１－オン、ＩＧＭ社製
・ＯｍｎｉｒａｄＴＰＯ：２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、数平均分子量４１８．５、ＩＧＭ社製
・Ｏｍｎｉｒａｄ３６９：α－アミノアルキルフェノン系開始剤、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、ＩＧＭ社製
・ＯｍｎｉｒａｄＥＭＫ：４，４’-ビス(ジエチルアミノ)ベンゾフェノン、数平均分子量３２４．５、ＩＧＭ社製
・ＤＡＰ Ａ：ジアリルフタレート樹脂、平均重量分子量５．５万：（株）大阪ソーダ社製
・ＩＳＯ ＤＡＰ：ジアリルフタレート樹脂、平均重量分子量５万：（株）大阪ソーダ社製
・Ｖａｒｉｐｌｕｓ ＡＰ：ケトンアルデヒド樹脂、Ｅｖｏｎｉｋ社製
・Ｌａｒｏｐａｌ Ａ８１：尿素アルデヒド樹脂、ＢＡＳＦ社製
・ＰＥ２１０：ビスフェノールＡ型エポキシアクリレート、ＭＩＷＯＮ社製
・Ｅｂｅｃｒｙｌ４３６：塩素化ポリエステル対トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）が質量比で６：４の混合物、平均重量分子量５０００、ダイセル・オルネクス（株）製
・Ｅｂｅｃｒｙｌ２２０：芳香族ウレタンアクリレート、平均重量分子量１０００、ダイセル・オルネクス（株）製
・Ｍｉｒａｍｅｒ Ｍ６００：ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート混合物（ＤＰＨＡ）、ＭＩＷＯＮ社製
・Ｍｉｒａｍｅｒ Ｍ４１０：ジトリメチロールプロパンテトラアクリレート（ＤＴＭＰＴＡ）、ＭＩＷＯＮ社製
・Ｍｉｒａｍｅｒ Ｍ３１３０：トリメチロールプロパンＥＯ変性トリアクリレート（ＴＭＰ（ＥＯ）３ＴＡ）、ＭＩＷＯＮ社製
・Ｍｉｒａｍｅｒ Ｍ２２２：ジプロピレングリコールジアクリレート（ＤＰＧＤＡ）

The numerical values in Tables 2 to 7 are mass %. Raw materials and abbreviations shown in each table are shown below.
・Raven 1060 Ultra: carbon black manufactured by Birla ・Omnirad 907: α-aminoalkylphenone initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, manufactured by IGM · Omnirad TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, number average molecular weight 418.5, manufactured by IGM · Omnirad 369: α-aminoalkylphenone initiator, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1, manufactured by IGM ・Omnirad EMK: 4,4'-bis(diethylamino)benzophenone, number average molecular weight 324.5, manufactured by IGM ・DAP A: diallyl phthalate resin, average weight molecular weight 5 50,000: manufactured by Osaka Soda Co., Ltd. ・ISO DAP: diallyl phthalate resin, average weight molecular weight of 50,000: manufactured by Osaka Soda Co., Ltd. ・Variplus AP: ketone aldehyde resin, manufactured by Evonik ・Laropal A81: urea aldehyde resin , manufactured by BASF ・PE210: Bisphenol A type epoxy acrylate, manufactured by MIWON ・Ebecryl436: a mixture of chlorinated polyester and trimethylolpropane triacrylate (TMPTA) in a mass ratio of 6:4, average weight molecular weight of 5000, Daicel Allnex ( Co., Ltd. Ebecryl220: aromatic urethane acrylate, average weight molecular weight 1000, Daicel Ornex Co., Ltd. Miramer M600: dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate mixture (DPHA), MIWON Miramer M410: Ditrimethylolpropane tetraacrylate (DTMPTA), manufactured by MIWON Miramer M3130: trimethylolpropane EO-modified triacrylate (TMP (EO) 3TA), manufactured by MIWON Miramer M222: dipropylene glycol diacrylate (DPGDA)

In the example, the pressure between the rolls at which powder spraying starts to occur on the rolls of the kneading machine is higher than in the comparative example, resulting in difficulty in powder spraying in the printing machine, ink curability, and misting. became. On the other hand, the comparative examples lacked any of powder jetting, ink curability, and misting.
Comparative Examples 16 and 18 could not be evaluated because the viscosity of the ink was extremely hard and it was difficult to sufficiently knead the ink.

The active energy ray-curable offset printing ink of the present invention and printed matter printed with the ink can be used for packaging paper containers such as food, beverages, sanitary, cosmetics, toys, equipment, pharmaceuticals, books, leaflets, posters, catalogs, etc. It can be widely used in commercial printing applications such as cards, direct mail, pamphlets, CD jackets, and seal labels.

Claims (5)

An active energy ray-curable offset ink with a viscosity adjusted to a range of 5 to 50 pascal seconds (Pa.s.) at a temperature of 25°C is placed on a roll mill, which is an ink kneader, and activated energy is placed on the roll mill and rolls. After adjusting the surface temperature of the line-curing offset ink to 35°C, pressurize between the rolls, and confirm that the pressure at which ink powder is ejected is 3 megapascals (MPa) or more. An active energy ray-curable offset ink.
However, (1) the active energy ray-curable offset ink contains a binder (A) and a (meth)acrylate monomer (B).
(2) The binder (A) contains a urethane resin containing an alkyl monoalcohol compound (d1), a polyol compound (d2), and a polyisocyanate compound (d3) as essential reaction raw materials.
(3) The content of the urethane resin is 2 to 14 mass % of the total amount of the ink.
The active energy ray curing according to claim 1 , wherein the (meth)acrylate monomer (B) contains a (meth)acrylic compound (b1) having three or more (meth)acryloyl groups in one molecule. offset ink.
3. The active energy ray-curable offset ink according to claim 1, wherein the (meth)acrylate monomer (B) is dipentaerythritol hexa(meth)acrylate or dipentaerythritol penta(meth)acrylate.
4. The active energy ray-curable offset ink according to any one of claims 1 to 3 , further comprising talc, magnesium carbonate, or calcium carbonate as an extender (C).
A printed matter comprising a cured product of the active energy ray-curable offset ink according to any one of claims 1 to 4 on a substrate.