JP7236578B1 - Actinic energy ray-curable offset printing ink, printed matter using the same, and method for producing printed matter - Google Patents

Abstract

An object of the present invention is to provide an active energy beam having excellent curability and stability not only for conventional metal halide lamps and high-pressure mercury lamps, but also for ozone-free metal halide lamps, light-emitting diodes, and UV-LED lamps that do not generate ozone. To provide a curable offset ink.
(1) a photopolymerization initiator (1) which is an α-aminoalkylphenone compound and/or an acylphosphine oxide compound;
(2) a photoinitiator (2) that is a benzophenone compound, a thioxanthone compound, and/or a ketocoumarin compound;
(3) a photopolymerization initiator (3) which is a hydroxyacetophenone compound and/or a benzyldimethylketal compound;
(4) An active energy ray-curable offset printing ink characterized by containing a compound having an ethylenic double bond.
[Selection figure] None

Description

The present invention uses an ultraviolet irradiation device that does not generate ozone using a light source that uses an ozone cut or an infrared filter for a metal halide lamp, a high-pressure mercury lamp, an electrodeless metal halide lamp, or the like, a light-emitting diode, or a UV-LED lamp. The present invention relates to an active energy ray-curable offset printing ink characterized by excellent curability and stability even with an ultraviolet irradiation device. Furthermore, it relates to a printed matter using the ink and a method for producing the printed matter.

Active energy ray-curable inks are solvent-free and instantaneously cured with active energy rays. Lithographic printing that does not use dampening water or waterless lithographic printing that does not use dampening water), letterpress printing, intaglio printing, stencil printing, and after transferring the ink attached to these plates to an intermediate transfer body such as a blanket It is used as an ink in various printing methods that combine the transfer (offset) method for printing, such as printed materials for forms, various printed materials for books, various printed materials for packaging such as carton paper, various printed materials for plastics, stickers, printed materials for labels, It is applied to various printed materials such as art prints and metal prints (art prints, beverage can prints, food prints such as canned food). In particular, active energy ray-curable offset printing ink, which combines lithographic printing with offset printing, is widely used in various fields such as book printing, art printing, seal/label printing, business form printing, and package printing for food packaging such as toys and paper containers. It is used.
Active energy ray-curable inks can be applied to light sources such as conventionally used high-pressure mercury lamps and metal halide lamps, as well as light sources that generate ultraviolet rays of 230 to 420 nm using ozone-less metal halide lamps that do not generate ozone, and light sources that emit light. Various types of light sources such as UV-LED, a light-emitting diode that emits ultraviolet light with a peak wavelength of 350 to 420 nm, have been used in recent years. Inventions combining a plurality of methods have been made (Patent Documents 1 to 3).
However, at present, it cannot be said that the ink itself has sufficient stability over time while obtaining sufficient curability for all light sources.

WO2009/008226 JP 2011-94117 A JP 2012-214782 A

An object of the present invention is to provide excellent curability and stability not only to conventional metal halide lamps and high-pressure mercury lamps, but also to ozone-less metal halide lamps that do not generate ozone, light-emitting diodes, and UV-LED lamps. An object of the present invention is to provide an active energy ray-curable offset printing ink. Another object of the present invention is to provide a printed matter using the ink and a method for producing the printed matter.

The present inventors have conducted intensive research to solve the above problems, and found that by using three types of specific photopolymerization initiators in combination with a compound having an ethylenic double bond, excellent curability and The inventors have found that an active energy ray-curable offset printing ink having stability can be obtained, and have completed the present invention.

That is, the present invention
(1) a photopolymerization initiator (1) which is an α-aminoalkylphenone compound and/or an acylphosphine oxide compound;
(2) a photoinitiator (2) that is a benzophenone compound, a thioxanthone compound, and/or a ketocoumarin compound;
(3) a photopolymerization initiator (3) which is a hydroxyacetophenone compound and/or a benzyldimethylketal compound;
(4) To provide an active energy ray-curable offset printing ink containing a compound having an ethylenic double bond.

Further, in the present invention, the α-aminoalkylphenone compound is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl )-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2- benzyl-2-dimethylamino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, 1-(4 -methoxyphenyl)-2-methyl-2-morpholin-4-yl-propan-1-one, polyethylene glycol (200) di(β-4[4-(2-dimethylamino-2-benzyl)butanonylphenyl ] To provide an active energy ray-curable offset printing ink which is piperazine propionate.

The present invention also provides an active energy ray-curable offset printing ink, wherein the acylphosphine oxide compound is a compound represented by general formula (1).

In general formula (1),
Y ₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a structural moiety represented by general formula (2);
Y ₂ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a (poly)alkoxyalkyl group having 1 to 6 carbon atoms (the alkoxyalkyl group portion is a alkoxyalkyl group), a phenyl group, or a structural moiety represented by general formula (3),
Y ₃ represents a phenyl group or a group represented by general formula (2),

In general formula (3), Y ₁₁ each independently represents the same group as Y ₁ in general formula (1),
Y ₃₃ in general formula (3) each independently represents the same group as Y ₃ in general formula (1),
R ₁₄ and R ₁₅ in general formula (3) each independently represents an alkylene group having 1 to 6 carbon atoms or a (poly)oxyalkylene group having 1 to 6 carbon atoms,
R ₁ to R ₁₃ in general formula (1), general formula (2) and general formula (3) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Further, in the present invention, the benzophenone compound is 4,4'-bis-(dimethylamino)benzophenone, 4,4'-bis-(diethylamino)benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4-methylbenzophenone. To provide an active energy ray-curable offset printing ink which is at least one selected from the group consisting of

The present invention also provides an active energy ray-curable offset printing ink, wherein the compound having an ethylenic double bond is a compound having two or more ethylenic double bonds.

The present invention also provides a method for producing a printed matter, comprising the steps of printing the active energy ray-curable offset printing ink on a substrate to be printed, and curing the ink printed with the active energy ray. do.

According to the present invention, not only conventional metal halide lamps and high-pressure mercury lamps, but also ozone-less metal halide lamps that do not generate ozone, light-emitting diodes, and UV-LED lamps have excellent curability and stability. A line-curable offset printing ink can be provided. Furthermore, it is possible to provide a printed matter using the ink and a method for producing the printed matter.

The active energy ray-curable offset printing ink of the present invention is
(1) a photopolymerization initiator (1) which is an α-aminoalkylphenone compound and/or an acylphosphine oxide compound;
(2) a photoinitiator (2) that is a benzophenone compound, a thioxanthone compound, and/or a ketocoumarin compound;
(3) a photopolymerization initiator (3) which is a hydroxyacetophenone compound and/or a benzyldimethylketal compound;
(4) By containing a compound having an ethylenic double bond, the intended effect of the present invention is exhibited.

As the photopolymerization initiator (1) used in the active energy ray-curable offset printing ink of the present invention, an α-aminoalkylphenone compound and/or an acylphosphine oxide compound is used.

Examples of the α-aminoalkylphenone compounds include 2-(dimethylamino)-2-methyl-1-[4-(4-morpholinyl)phenyl]-3-phenyl-1-propanone, 1-butanone, 2-(dimethyl amino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylmethyl)-, (2S)-, 2-(dimethylamino)-2-methyl-3-(4-methylphenyl)-1 -[4-(4-morpholinyl)phenyl]-1-propanone, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylmethyl)-1-pentanone, 2-( dimethylamino)-2-[(4-ethylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-hydroxyphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-[(4-butylphenyl)methyl]-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl] -1-butanone, 1-butanone, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-[(4-propylphenyl)methyl]-, 2-(dimethylamino)-1 -[4-(4-morpholinyl)phenyl]-2-phenyl-1-butanone, 3-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-3-(phenylmethyl)-2-pentanone , 2-(dimethylamino)-2-ethyl-1-[4-(4-morpholinyl)phenyl]-4-phenyl-1-butanone, 3-(dimethylamino)-1-[4-(4-morpholinyl) Phenyl]-3-phenyl-2-butanone, 1-(4-mercaptophenyl)-2-methyl-2-(4-morpholinyl)-1-propanone, 1-[4-(ethylthio)phenyl]-2-methyl -2-(4-morpholinyl)-1-propanone, dimethyl[4-[2-methyl-2-(4-morpholinyl)-1-oxopropyl]phenyl]sulfonium, 2-methyl-1-[4-[( 1-methylethyl)thio]phenyl]-2-(4-morpholinyl)-1-propanone, ethylmethyl[4-[2-methyl-2-(4-morpholinyl)-1-oxopropyl]phenyl]sulfonium, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino- 2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopro pan-1-one, 2-benzyl-2-dimethylamino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropane- 1-one, 1-(4-methoxyphenyl)-2-methyl-2-morpholin-4-yl-propan-1-one, polyethylene glycol (200) di(β-4[4-(2-dimethylamino -2-benzyl)butanonylphenyl]piperazine propionate and the like.
In particular, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4- yl-phenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, 1-(4-methoxyphenyl)-2-methyl-2-morpho Phosphorus-4-yl-propan-1-one, polyethylene glycol (200) di(β-4[4-(2-dimethylamino-2-benzyl)butanonylphenyl]piperazinepropionate is preferred.

The acylphosphine oxide compound is preferably a compound represented by general formula (1).

In general formula (1),
Y ₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a structural moiety represented by general formula (2);
Y ₂ is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a (poly)alkoxyalkyl group having 1 to 6 carbon atoms (the alkoxyalkyl group portion is a alkoxyalkyl group), a phenyl group, or a structural moiety represented by general formula (3),
Y ₃ represents a phenyl group or a group represented by general formula (2),

In general formula (3), Y ₁₁ each independently represents the same group as Y ₁ in general formula (1),
Y ₃₃ in general formula (3) each independently represents the same group as Y ₃ in general formula (1),
R ₁₄ and R ₁₅ in general formula (3) each independently represents an alkylene group having 1 to 6 carbon atoms or a (poly)oxyalkylene group having 1 to 6 carbon atoms,
R ₁ to R ₁₃ in general formula (1), general formula (2) and general formula (3) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
Further, the alkylene group having 1 to 6 carbon atoms is specifically exemplified by a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and the like.

In _{particular , in} general formula (1 _{) , ethylphenyl} ( _2,4,6- Trimethylbenzoyl)phosphinate is preferred, and TPO-L (#CAS 84434-11-7, manufactured by SARTOMER) can be mentioned as a commercial product.

In general formula (1), R ₁ , R ₂ and R ₄ are methyl groups, R ₃ is a hydrogen atom, Y ₂ is a polyalkoxymethyl group having 2 carbon atoms, and Y ₃ is represented by general formula (2). It is preferable that R ₆ , R ₇ and R ₉ are methyl groups and R ₅ and R ₈ are hydrogen. I can mention

Further, in general formula (1), R ₁ , R ₂ and R ₄ are methyl groups, R ₃ is a hydrogen atom, Y ₁ is a structural moiety represented by general formula (2), and R ₅ to R ₉ is a hydrogen atom, Y ₂ is an ethyl group, and Y ₃ is a phenyl group. 1539267-56-5, manufactured by SARTOMER).

In general formula (1), R ₁ , R ₂ and R ₄ are methyl groups, R ₃ and Y ₁ are hydrogen atoms, Y ₃ is a phenyl group, and Y 2 is represented by general formula (3). R ₁₀ , R ₁₁ , and R ₁₃ are methyl groups, R ₁₂ and Y ₁₁ are hydrogen atoms, Y ₃₃ is a phenyl group, and R ₁₄ and R ₁₅ are (poly)oxyalkylene groups having 2 carbon atoms. A commercially available product is Omnipol TP (#CAS 1834525-17-5, manufactured by IGM Resins B.V.).
These acylphosphine oxide compounds may be used alone or in combination of two or more.

A benzophenone compound, a thioxanthone compound, and/or a ketocoumarin compound is used as the photopolymerization initiator (2) used in the active energy ray-curable offset printing ink of the present invention.

Examples of the benzophenone compound include 4,4'-dialkylaminobenzophenones such as 4,4'-bis-(dimethylamino)benzophenone, 4,4'-bis-(diethylamino)benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 4-methylbenzophenone and the like. Among these, 4,4'-bis-(diethylamino)benzophenone is preferred from the viewpoint of safety. These benzophenone compounds may be used alone or in combination of two or more.

The thioxanthone compounds 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-9H thioxanthone-2-yloxy-N,N,N-trimethyl- 1-propanamine hydrochloride and the like, preferably 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2 -isopropylthioxanthone These thioxanthone compounds may be used alone or in combination of two or more.

Examples of the ketocoumarin compounds include 3-benzoylcoumarin, 3-(4-methoxybenzoyl)coumarin, 3-benzoyl-7-methoxycoumarin, 3-(4-methoxybenzoyl)7-methoxy-3-coumarin, 3-acetyl- 7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3,3′-coumarinoketone, 3,3′-bis(7-diethylaminocoumarinino)ketone and the like. These ketocoumarin compounds may be used alone or in combination of two or more.

Examples of the photopolymerization initiator (3) used in the active energy ray-curable offset printing ink of the present invention include hydroxyacetophenone compounds and benzyldimethylketal compounds.

Examples of the hydroxyacetophenone compounds include ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1- one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like. These hydroxyacetophenone compounds may be used alone or in combination of two or more.

A benzyl dimethyl ketal compound may also be used as the photopolymerization initiator (3). Examples of the benzyl dimethyl ketal compound include 2,2-dimethoxy-2-phenylacetophenone (Omnirad 651, manufactured by IGM Resins B.V.).

The content of the photopolymerization initiator based on the α-aminoalkylphenone compound is preferably in the range of 2 to 10 mass % of the total amount of each ink. If it is 2% by mass or more, curability can be obtained, and if it is 10% by mass or more, the precipitation of the initiator and the odor of the cured product become noticeable. Moreover, the content of the photopolymerization initiator based on the acylphosphine oxide compound is preferably in the range of 4 to 12% by mass based on the total amount of the ink. If it is 4% by mass or more, curability can be obtained, and if it is 12% by mass or more, it will be saturated with the acrylate monomer and will impair fluidity.
The content of the benzophenone compound, the thioxanthone compound, and the ketocoumarin compound as photopolymerization initiators is preferably in the range of 2 to 8 mass % of the total amount of the ink. If it is 2% by mass or more, curability can be obtained, and if it is 8% by mass or more, it will be saturated with the acrylate monomer and will impair fluidity.
The content of the photopolymerization initiator of the hydroxyacetophenone compound and the benzyldimethylketal compound is preferably in the range of 2 to 8 mass % of the total amount of the ink. If it is 2% by mass or more, curability can be obtained, and if it is 8% by mass or more, it will be saturated with the acrylate monomer and will impair fluidity.
Moreover, from the viewpoint of achieving both excellent curability and excellent fluidity associated with the combined use of various compounds, the amount of both added is preferably within this range.

Furthermore, the active energy ray-curable offset printing ink of the present invention must contain (4) a compound having an ethylenic double bond.

Examples of the compound having an ethylenic double bond include (meth)acrylic group-containing compounds and additives.
Monofunctional monomers that are (meth)acrylic group-containing compounds include, for example, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, and lauryl (meth)acrylate. , tridecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, isoamyl (meth)acrylate, isodecyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, nonylphenoxyethyl tetrahydrofurfuryl (meth) ) acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and the like.

Bifunctional or higher monomers include, for example, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecanedimethanol 2 such as di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc.) Di(meth)acrylate of a hydric alcohol, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, 4 mol or more per 1 mol of neopentyl glycol di(meth)acrylate of a diol obtained by adding ethylene oxide or propylene oxide to 1 mol of bisphenol A, di(meth)acrylate of a diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane tri Poly(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, etc. (Meth)acrylate, triol tri(meth)acrylate obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of glycerin, adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane Poly(meth)acrylate of polyoxyalkylene polyol such as di- or tri(meth)acrylate of triol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A acrylates and the like.

Furthermore, the (meth)acrylic group-containing compound may be a polymerizable oligomer. Polymerizable oligomers include amine-modified polyether acrylates, amine-modified epoxy acrylates, amine-modified aliphatic acrylates, amine-modified polyester acrylates, amine-modified acrylates such as amino (meth)acrylates, polyester (meth)acrylates, and polyether (meth)acrylates. Acrylate, polyolefin (meth)acrylate, polystyrene (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate and the like.

The total amount of compounds having an ethylenic double bond is preferably in the range of 10 to 60% by mass, more preferably 10 to 40% by mass, and even more preferably 10 to 25% by mass of the total amount of the ink composition. . Moreover, from the viewpoint of achieving both excellent curability and excellent fluidity associated with the combined use of various compounds, the amount of both added is preferably within this range.

Further, an extender pigment may be used in the active energy ray-curable offset printing ink of the present invention. Inorganic fine particles can be used as the extender pigment. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, and zinc white; Inorganic pigments such as barium sulfate, aluminum stearate, calcium stearate, magnesium carbonate, barite powder, abrasive powder; These inorganic fine particles control the fluidity of the ink, prevent misting, and prevent penetration into printing substrates such as paper. You can add an effect that
Especially when the base material is a paper material, among these, talc, magnesium carbonate and silica are preferable from the viewpoint of suppressing "paper peeling", and talc and magnesium carbonate are particularly preferable from the viewpoint of maintaining fluidity of the composition.

The talc, magnesium carbonate, and silica may be used alone or in combination of two or more. When talc is used, its content is preferably in the range of 1 to 6% by mass of the total amount of ink, and when magnesium carbonate is used, its content is preferably in the range of 1 to 10% by mass of the total amount of ink, and silica is added. When used, its content is preferably 0.1 to 5% by mass of the total amount of ink.

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

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 to be used is preferably in the range of 1 to 20% by mass of the total amount of the active energy ray-curable ink of the present invention, since the effect of improving curability is good.

The active energy ray-curable offset printing ink of the present invention may further contain antioxidants, polymerization inhibitors, silicone additives, waxes, pigments, dyes, and the like, if necessary.

Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, and the like. These antioxidants can be used alone or in combination of two or more.

Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified Dimethylpolysiloxane copolymer, polyorganosiloxane having an alkyl group or a phenyl group such as an amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having a polyether-modified acrylic group, polydimethylsiloxane having a polyester-modified acrylic group, etc. mentioned. These silicon additives can be used alone or in combination of two or more.

Wax can be added to the active energy ray-curable offset printing 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 of about 18 can be mentioned.

In the active energy ray-curable offset printing ink of the present invention, 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 250R, Regal 400R, Regal 330R, Regal 660R, Mogul L (manufactured by Cabot Corporation), MA7, MA8, MA11 (manufactured by Mitsubishi Chemical Corporation) and the like, and these may be used alone or in combination of two or more. good.

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.

(resin)
As the resin, various known binder resins can be used. The binder resin mentioned here refers to resins in general that have appropriate pigment affinity and dispersibility and rheological properties required for printing inks. Resins, polyurethane resins, polyester resins, petroleum resins, rosin ester resins, poly(meth)acrylic acid esters, cellulose derivatives, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, butadiene-acrylonitrile copolymers, etc. Epoxy acrylate compounds, urethane acrylate compounds, polyester acrylate compounds, etc. having at least one or more polymerizable groups in the molecule can also be used, and these binder resins can be used alone. , any one or more of which may be used in combination.

The active energy ray-curable offset printing ink of the present invention can be made into a cured coating film by irradiating an active energy ray after printing on a substrate.

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.

In particular, in the active energy ray-curable offset printing ink of the present invention, by appropriately using the photopolymerization initiators (1) to (3) and (4) a compound having an ethylenic double bond, conventional metal halide lamps and Excellent curability, excellent surface curability, internal curability and adhesion can be maintained not only with high-pressure mercury lamps, but also with ozone-less metal halide lamps that do not generate ozone, light-emitting diodes, and UV-LED lamps.

The printing substrate used in the active energy ray-curable offset printing ink of the present invention is not particularly limited. It can be used for high-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper, and various synthetic papers used for printing on packages, etc. Polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl Alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate film or sheet, cellophane, aluminum foil, and other conventional It can be used for various substrates used as printing substrates.
Moreover, you may use for other base materials, such as a metal base material, a glass base material, a paper base material, a wood base material, and a fibrous base material.

In the production of the active energy ray-curable offset printing ink described in the present invention, the compound having an ethylenic double bond, the photopolymerization initiator, other additives, etc. are added in the same manner as the conventional active energy ray-curable offset printing ink. It is produced by blending, stirring and mixing with a mixer or the like, and kneading 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.

[Manufacturing method of DAP-A varnish]
Diallyl phthalate resin (Daiso Dap A, manufactured by Osaka Soda Co., Ltd.) solid content 33.33% by mass and MIRAMER M600 dipentaerythritol hexaacrylate (manufactured by MIWON) 66.67% by mass are sufficiently dissolved at 90 ° C. and stirred to form DAP varnish. was made.

[Method for producing active energy ray-curable offset printing ink]
Active energy ray-curable offset printing by kneading the active energy ray-curable offset printing inks of Examples 1 to 6 and Comparative Examples 1 to 7 according to the formulations shown in Tables 1 to 3 with a three-roll mill. Got ink. A blank column in the table means unblended, and the numerical value in the table is % by mass.

Curability and stability of the active energy ray-curable offset printing ink thus prepared were evaluated.

(Evaluation item 1: curability)
0.13 mL of the inks of Examples and Comparative Examples were applied on top of OK Topcoat+ (basis weight: 57.5 kg) manufactured by Oji Paper Co., Ltd. using a simple color development machine (RI tester, manufactured by Hoei Seiko Co., Ltd.). Using a water-cooled UV-LED (center emission wavelength 385 nm ± 5 nm UV-LED output 100%) and a UV irradiation device (manufactured by Eye Graphics Co., Ltd.) equipped with a belt conveyor, the printed matter is placed on the conveyor. Placed, passed directly under the LED (irradiation distance 9 cm) at a conveyor speed of 100 m / min, and applied with the active energy ray curable ink for lithographic offset printing obtained by the above method. The ink film was cured and dried by irradiation.
Immediately after irradiation with ultraviolet rays, the degree of damage to the solid surface of the produced printed matter was confirmed by the nail scratch method, and visually evaluated in the following three stages. With a composition that causes damage to the cured ink film when rubbed with a fingernail, the printed matter is likely to be damaged in each step of cutting, boxing, and transportation of the printed matter.
(Evaluation criteria)
◯: Curability is good, with no flaws caused by fingernail scratches or only a few fine flaws.
Δ: Nail scratches are observed.
x: Scratches easily caused by fingernail scratches, and the curability is insufficient.

(Evaluation item 2: stability)
40 g of each of the indigo inks of Examples 1 to 6 and Comparative Examples 1 to 7 was placed in a metal can having a content of 50 mL, and after the lid was closed, it was stored in an oven at 60° C. for 1 month. It was dissolved in tetrahydrofuran and filtered through a wire mesh. After filtration, it was visually confirmed whether an insoluble gel substance was present on the wire mesh.
◯: No gel was observed on the wire mesh.
x: A gel substance was confirmed on the wire mesh.

Tables 1 to 3 show the formulations of the active energy ray-curable offset printing inks and the evaluation results.

The raw materials shown in the table are as follows.
FASTOGEN BLUE FA5375: Pigment Blue 15:3 (manufactured by DIC Corporation)
Neolite SA300: calcium carbonate (manufactured by Takehara Chemical Industry Co., Ltd.)
High Filler 5000PJ: Talc (manufactured by Matsumura Sangyo Co., Ltd.)
S-381-N1: polyethylene wax (manufactured by Shamrock)
DAP-A varnish: Diallyl phthalate resin Daiso Dapp A, a mixture of 33.33% by mass manufactured by Osaka Soda Co., Ltd. and 66.67% by mass of MIRAMER M600 (manufactured by MIWON) Miramer M600: Dipentaerythritol hexaacrylate (manufactured by Miwon)
SR355NS: Ditrimethylolpropane tetraacrylate (manufactured by Arkema Sartomer)
Miramer M3130: EO3mol trimethylolpropane triacrylate (manufactured by Miwon)
Omnirad 379: 2-dimethylamino-2-(4-methyl-benzoyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (manufactured by IGM Resins B.V.)
Omnipol 907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins B.V.)
Omnirad TPO-L: Ethylphenyl (2,4,6-trimethylbenzoyl) phosphinate (manufactured by IGM Resins B.V.)
SpeedCure XKm: Ethyl (3-benzoyl-2,4,6-trimethylbenzoyl) (phenyl) phosphinate (#CAS 1539267-56-5, manufactured by SARTOMER)
Omnirad EMK: 4,4′-bis-(diethylamino)benzophenone (manufactured by IGM Resins B.V.)
Omnirad DETX: 2,4-diethyl-9H-thioxanthen-9-one (manufactured by IGM Resins B.V.)
Omnirad 184: 1-hydroxycyclohexylphenyl ketone (manufactured by IGM Resins B.V.)
Omnirad 651: 2,2-dimethoxy-2-phenylacetophenone (manufactured by IGM Resins B.V.)
Irgacure OXE01: oxime ester photopolymerizing agent 1,2-octanedione, 1-[4-(phenitrio]phenyl]-2,(o-benzoyloxime)
Suncellar TT-CU: Copper dimethyldithiocarbamate (manufactured by Sanshin Chemical Industry Co., Ltd.)
ADEKA STAB 7RD: 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TMPOL) (manufactured by ADEKA Co., Ltd.)
Metoquinone: p-methoxyphenol (manufactured by Seiko Chemical Co., Ltd.)

As a result, it is clear that the active energy ray-curable offset printing ink of the present invention has both excellent curability and stability.

Claims (5)

(1) a photopolymerization initiator (1) which is an α-aminoalkylphenone compound and an acylphosphine oxide compound;
(2) a photoinitiator (2) that is a benzophenone compound, a thioxanthone compound, and/or a ketocoumarin compound;
(3) a photopolymerization initiator (3) which is a hydroxyacetophenone compound and/or a benzyldimethylketal compound;
(4) An active energy ray-curable offset printing ink containing a compound having an ethylenic double bond.

However, the acylphosphine oxide compound is a compound represented by the general formula (1).

In general formula (1),
Ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate in which R ₁ , R ₂ and R ₄ are methyl groups, R ₃ and Y ₁ are hydrogen, Y ₂ is ethyl group and Y ₃ is phenyl group .

Alternatively, in general formula (1), R ₁ , R ₂ and R ₄ are methyl groups, R ₃ is a hydrogen atom, Y ₂ is a polyalkoxymethyl group having 2 carbon atoms, and Y ₃ is represented by general formula (2). wherein R6 _, R7 _and R9 _are methyl groups and R5 _and R8 _are hydrogen.

Alternatively, in general formula (1), R ₁ , R ₂ and R ₄ are methyl groups, R ₃ is a hydrogen atom, Y ₁ is a structural moiety represented by general formula (2), and R ₅ to R ₉ is a hydrogen atom, Y2 _is an ethyl group, and Y3 _is an ethyl (3-benzoyl-2,4,6-trimethylbenzoyl)(phenyl)phosphinate.

Alternatively, in general formula (1), R ₁ , R ₂ and R ₄ are methyl groups, R ₃ and Y ₁ are hydrogen atoms, Y ₃ is a phenyl group, and Y2 is represented by general formula (3) R ₁₀ , R ₁₁ , and R ₁₃ are methyl groups, R ₁₂ and Y ₁₁ are hydrogen atoms, Y ₃₃ is a phenyl group, and R ₁₄ and R ₁₅ are (poly)oxyalkylene groups having 2 carbon atoms. .

In general formula (3), Y ₁₁ each independently represents the same group as Y ₁ in general formula (1) ,
Y ₃₃ in general formula (3) each independently represents the same group as Y ₃ in general formula (1) ,
R ₁₄ and R ₁₅ in general formula (3) each independently represents an alkylene group having 1 to 6 carbon atoms or a (poly)oxyalkylene group having 1 to 6 carbon atoms,
R ₁ to R ₁₃ in general formula (1), general formula (2) and general formula (3) each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The α-aminoalkylphenone compound is 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-dimethylamino-2-(4-methyl-benzyl)-1-( 4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl amino-1-(4-piperidinylphenyl)-1-butanone, 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, 1-(4-methoxyphenyl)- 2-methyl-2-morpholin-4-yl-propan-1-one, polyethylene glycol (200) di(β-4[4-(2-dimethylamino-2-benzyl)butanonylphenyl]piperazinepropionate The active energy ray-curable offset printing ink according to claim 1. the benzophenone compound is selected from the group consisting of 4,4'-bis-(dimethylamino)benzophenone, 4,4'-bis-(diethylamino)benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, and 4-methylbenzophenone; The active energy ray-curable offset printing ink according to claim 1, which is at least one kind of active energy ray-curable offset printing ink. The active energy ray-curable offset printing ink according to claim 1, wherein the compound having an ethylenic double bond is a compound having two or more ethylenic double bonds. A method for producing a printed matter, comprising the steps of: printing the active energy ray-curable offset printing ink according to claim 1 on a printed material; and curing the ink printed with the active energy ray.