JP2021195502A - Active energy ray-curable ink for lithographic offset printing, method for producing ink cured product and printed matter - Google Patents

Abstract

To provide active energy ray-curable ink for lithographic offset printing which has good adhesion to a plastic film, and has flexibility, printability, blocking resistance and low migration property.SOLUTION: There are provided active energy ray-curable ink for lithographic offset printing which contains (1) a monomer that is an ethylene oxide-modified trimethylol propane tri(meth)acrylate having an average addition molar number of an ethylene oxide of 4-9 moles per one molecule and has an ethylenically unsaturated double bond, and (2) a varnish that is a polyester resin containing a polyethylene terephthalate resin, rosin and a polyol compound as essential reaction raw materials; a method for producing an ink cured product; a printed matter; and a varnish for active energy ray-curable ink for lithographic offset printing.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable ink for flat plate offset printing and a printed matter that can be adhered to a plastic film or the like often used for food packaging materials.

Conventionally, various printed matter for foam, various book printed matter, various packaging printed matter such as carton paper, various plastic printed matter, stickers, label printed matter, art printed matter, metal printed matter (art printed matter, beverage can printed matter, food printed matter such as canned food), etc. In order to obtain various printed matter, various printing methods such as flat plate (normal flat plate using dampening water and waterless flat plate not using dampening water), letterpress, concave plate, stencil printing, etc. are adopted, and these printing methods are used. Uses ink suitable for each printing method. An active energy ray-curable ink is known as one of such inks.

Among these, since the plastic film has flexibility for the plastic film (also referred to as flexible packaging material) which is often used for food packaging materials, the printed matter has adhesiveness (adhesion) to the film. It is required to have the ability to follow the film. However, since active energy ray-curable ink is instantaneously activated energy ray-cured and three-dimensionally crosslinked, it tends to be a printed matter having high hardness but inferior flexibility, and its adhesiveness to a plastic substrate shrinks in volume. This tends to be inferior in adhesiveness and followability as compared with non-curable inks such as solvent-based gravure printing inks.

Japanese Unexamined Patent Publication No. 2018-16688

The subject of the present invention is to provide a printed matter having good adhesiveness to a plastic film and having flexibility that can follow the bending of the film, and has printability and blocking resistance equivalent to those of a conventional active energy ray-curable offset ink. Further, it is an object of the present invention to provide an active energy ray-curable ink for flat plate offset printing, which has a low migration property.

The present inventors have found that an active energy ray-curable ink for flat plate offset printing using a polyester resin containing a polyethylene terephthalate resin, a rosin, and a polyol compound as essential reaction raw materials as a varnish solves the above-mentioned problems. rice field.

As a varnish, a composition for an active energy ray-curable ink using a rosin-modified unsaturated polyester resin is known (see, for example, Patent Document 1). However, although Patent Document 1 evaluates the gloss value, wear resistance, etc. after changing jobs to art paper, it does not describe the evaluation of the plastic film at all.

That is, the present invention is an active energy ray-curable ink for flat plate offset printing containing a monomer having an ethylenically unsaturated double bond and a varnish.
(1) The monomer having an ethylenically unsaturated double bond is ethylene oxide-modified trimethylolpropane tri (meth) acrylate in which the average number of moles of ethylene oxide added is 4 to 9 mol per molecule.
(2) The varnish provides an active energy ray-curable ink for flat plate offset printing, which is a polyester resin containing a polyethylene terephthalate resin, a rosin, and a polyol compound as essential reaction raw materials.

The present invention also provides a method for producing an ink-cured product, which is offset-printed using the above-mentioned active energy ray-curable ink for flat plate offset printing and the printed ink is cured by using the active energy ray.

The present invention also provides a printed matter obtained by the method for producing a cured ink product described above.

The present invention also provides a varnish for active energy ray-curable ink for flat plate offset printing, which contains a polyethylene terephthalate resin, a rosin, and a polyester resin containing a polyol compound as an essential reaction raw material.

INDUSTRIAL APPLICABILITY According to the present invention, a printed matter having good adhesiveness to a plastic film and having flexibility that can follow the bending of the film is provided, and has printability and blocking resistance equivalent to those of a conventional active energy ray-curable offset ink. Further, an active energy ray-curable ink for flat plate offset printing having low migration property can be obtained.

(Monomer with ethylenically unsaturated double bond)
The monomer having an ethylenically unsaturated double bond used in the present invention contains ethylene oxide-modified trimethylolpropane tri (meth) acrylate in which the average number of moles of ethylene oxide added is 4 to 9 mol per molecule.

(Ethylene oxide-modified trimethylolpropane triacrylate)
Ethylene oxide-modified trimethylolpropane tri (meth) acrylates, which have an average number of moles of ethylene oxide (hereinafter sometimes referred to as EO) added of 4 to 9 mol per molecule, are specifically the ethylene oxide in the monomer. Ethylene oxide-modified trimethylolpropane triacrylate having an additional molar number of 4 mol or more and 9 mol or less. (Hereinafter referred to as monomer (B))
Specific examples of the monomer (B) include EO6 mol-added trimethylolpropane triacrylate such as Miwon's Miramer M3160 and Arkema Saltmer's SR499NS, Miwon's Miramer M3190, and Arkema Saltomer's SR502N. Examples thereof include methylolpropane triacrylate.
The monomer (B) preferably contains 5% by mass or more and 15% by mass or less, more preferably 5% by mass or more and 10% by mass or less, based on the total amount of the active energy ray-curable offset ink.

The monomer (B) is particularly polyethylene terephthalate (hereinafter sometimes referred to as PET) by combining it with a polyethylene terephthalate resin used as a varnish, a rosin, and a polyester resin using a polyol compound as an essential reaction raw material, which will be described later. It is possible to increase the peeling strength of the laminate in which the base materials are combined, and at the same time, it is possible to suppress excessive emulsification of the ink when offset printing is performed using dampening water, and during printing. It is possible to suitably suppress the fluctuation of the color density.

(Other monomers with ethylenically unsaturated double bonds)
The active energy ray-curable monomer and / or oligomer other than the monomer (B) can be used without particular limitation as long as it is a monomer and / or oligomer used in the active energy ray-curable technical field. In particular, those having a (meth) acryloyl group, a vinyl ether group, or the like as a functional group are preferable. Further, the number of functional groups and the molecular weight are not particularly limited, and those having a large number of functional groups tend to have higher reactivity but higher viscosity and crystallinity, and those having a higher molecular weight tend to have a higher viscosity. It can be used in combination as appropriate according to the desired physical properties. For example, in terms of being suitably cured by low energy irradiation such as UV-LED, a more reactive active energy ray-curable monomer having trifunctionality or higher is combined, and adhesiveness to a printing substrate and a film are used depending on the application. In order to obtain the necessary physical properties such as flexibility, monofunctional and bifunctional monomers can be used alone or in combination as appropriate, but bifunctional or less-functional monomers tend to swell rubber rollers of offset printing machines and the like. Therefore, when used as a diluent for offset printing ink as in the present invention, it is preferable to use a monomer having trifunctionality or higher.

Specifically, for example, monofunctional (meth) acrylates, polyfunctional (meth) acrylates, polymerizable oligomers, etc., which have a proven track record in the lamp method, can be used as they are in the ultraviolet light emitting diode method described in the present invention. It is possible.

Examples of the monofunctional (meth) acrylate include ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and hexadecyl. (Meta) acrylate, octadecyl (meth) acrylate, isoamyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxy Ethyl (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 Examples thereof include meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate.

Examples of the bifunctional or higher (meth) acrylate include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. ) Acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tricyclodecandy Methanol 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 dihydric alcohol, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 mol per mol of neopentyl glycol Di (meth) acrylate of diol obtained by adding the above ethylene oxide or propylene oxide, di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane Tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, etc. 3 Poly (meth) acrylate of polyhydric alcohol above valence, tri (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of glycerin, 3 mol of ethylene to 1 mol of trimethylolpropane Di or tri (meth) acrylate of triol obtained by adding oxide, di or tri (meth) acrylate of triol obtained by adding 3 mol or more of propylene oxide to 1 mol of trimethylolpropane, tri (meth) of triol. ) Polyacrylate, bisphenol Poly such as di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of A Examples thereof include poly (meth) acrylates of oxyalkylene polyols.

Examples of the polymerizable oligomer 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, thiol-modified polyester acrylates, and thiol (meth) acrylates. Thiol-modified acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polyolefin (meth) acrylate, polystyrene (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like can be mentioned.

(varnish)
The varnish used in the present invention contains a polyethylene terephthalate resin, a rosin, and a polyester resin containing a polyol compound as an essential reaction raw material. (Hereafter referred to as polyester resin (A))

(Polyester resin (A) Polyethylene terephthalate resin)
The polyethylene terephthalate resin used in the present invention is obtained by polycondensation of terephthalic acid or dimethyl terephthalate and ethylene glycol, and further, isophthalic acid, phthalic acid anhydride, adipic acid, cyclohexanedicarboxylic acid, 1,3- Those modified with substances such as butanediol and cyclohexanedimethanol can also be used. Further, commercially available unused PET bottles, PET films, crushed leftovers from other PET products during production, recycled PET collected from waste and washed, and the like can be used. Above all, it is preferable to use recycled PET. These are washed and pelletized and are available on the market.

The intrinsic viscosity (IV) of PET is preferably 0.50-0.80 dL / g. Within this range, the polycondensation reaction between PET and other raw materials can be performed at 250 ° C. or lower. Further, this range is also preferable from the viewpoint of developing the adhesive strength, durability and heat resistance of the reactive adhesive containing the PET-containing polyester polyol.

(Polyester resin (A) rosin)
The rosin used in the present invention is not particularly limited, and rosin used in the ink technology field can be used.
For example, natural rosin, which is a natural resin containing a resin acid as a main component, can be mentioned. The resin acid is a compound having a carboxyl group derived from a tree, and specifically, a resin acid having a conjugated double bond such as avietinic acid, palastolic acid, neoavietic acid, and levopimalic acid, for example, dehydroavietic acid. , Dihydroavietic acid, tetrahydroavietic acid and other resin acids that do not have a conjugated double bond.
More specifically, examples of natural rosin include tall oil rosin, gum rosin, and wood rosin. These natural rosins can be used alone or in combination of two or more. Preferred natural rosins include gum rosins.

Further, it may be a rosin derivative such as a hydrogenated rosin, a polymerized rosin, a disproportionated rosin, a reinforced rosin, or a rosin ester obtained by subjecting the natural rosin to a hydrogenation treatment, a disproportionation treatment, a polymerization treatment, or the like. These may be used alone or in combination of two or more.
Among these, the use of hydrogenated rosin is particularly preferable because it can suppress gelation of the active energy ray-curable ink for lithographic offset printing of the present invention and improve the pot life of the product.

(Polyester resin (A) polyol compound)
The polyol compound used in the present invention is not particularly limited, and known polyhydric alcohols can be used.
For example, 1,2-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,3-butanediol, 2, Aromatic diols such as 2,4-trimethyl-1,3-pentanediol; 1,3-bis (2-hydroxypropyl) cyclopentane, 1,3-bis (2-hydroxybutyl) cyclopentane, 1,4- Aromatic diols such as bis (2-hydroxypropyl) cyclohexane, 1,4-bis (2-hydroxybutyl) cyclohexane; 1,4-bis (2-hydroxypropyl) benzene, 1,4-bis (2-hydroxy) Butyl) Aromatic diols such as benzene;

2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol A"), 2,2-bis (4-hydroxyphenyl) butane (hereinafter abbreviated as "bisphenol B"), bis (4- 1,2-propylene oxide and 1,2-butylene are added to bisphenols such as hydroxyphenyl) methane (hereinafter abbreviated as "bisphenol F") and bis (4-hydroxyphenyl) sulfone (hereinafter abbreviated as "bisphenol S"). Bisphenol alkylene oxide adduct obtained by adding an alkylene oxide having a secondary hydroxyl group such as oxide; ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3 -Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylol Aliphatic polyols such as ethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol; ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

Modifications obtained by ring-opening polymerization of the aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyether polyols; lactone-based polyester polyols obtained by polycondensation reaction between the aliphatic polyols and various lactones such as ε-caprolactone; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; bisphenol A, bisphenol F, etc. Examples thereof include an ethylene oxide adduct of bisphenol obtained by adding ethylene oxide to bisphenol.

Each of these may be used alone or in combination of two or more. Among them, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, neopentylglycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, etc. An aliphatic polyol is preferable, and 1,6-hexanediol is preferable.
Among them, it is preferable to use a glycol having a highly linear and flexible structure such as polyethylene glycol having a number average molecular weight of 300 to 600 in order to bring out the effect of the present invention, and diethylene glycol is particularly preferable.
In addition, glycerin can also be preferably used when the resin is branched to the extent that the effect of the present invention is not impaired.

(Polyester resin (A) polybasic acid)
The polybasic acid used in the present invention is not particularly limited, and known polybasic acids can be used.
For example, aromatic dicarboxylic acids such as phthalic acid, anhydrous phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydro. Aliphatic dicarboxylic acids such as phthalic acid and 1,4-cyclohexanedicarboxylic acid; maleic acid, maleic anhydride, citraconic acid, dimethylmaleic acid, cyclopentene-1,2-dicarboxylic acid, 1-cyclohexene-1,2- An aliphatic unsaturated dicarboxylic acid such as dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid, mesaconic acid, itaconic acid, glutaconic acid; 1,2,5-hexanetricarboxylic acid, 1,2, Examples thereof include aliphatic tricarboxylic acids such as 4-cyclohexanetricarboxylic acid; aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and dimeric acid. Each of these may be used alone or in combination of two or more. Of these, dimer acid is preferable.

(Polyester resin (A) fatty acid)
The fatty acid used in the present invention is a saturated or unsaturated fatty acid obtained by hydrolysis of vegetable oil, such as acetic acid, propionic acid, butyric acid, caproic acid, capric acid, pelargonic acid, capric acid, lauric acid, oleic acid, and eridine. Acids, linoleic acid, linolenic acid, arachidonic acid, eikosanoic acid, erucic acid, docosahexaenoic acid, ricinoleic acid and the like can be exemplified, and coconut oil fatty acid, hydrogenated coconut oil fatty acid, palm oil fatty acid, rapeseed oil fatty acid, soybean oil. Examples thereof include fatty acids, hydrogenated soybean oil fatty acids, flaxseed oil fatty acids, tung oil fatty acids, tall oil fatty acids, dehydrated castor oil fatty acids, rice bran fatty acids, and fractionated fatty acids produced by fractional distillation thereof.
These may be used alone or in combination of two or more.
Among these, the use of tall oil fatty acid, hydrogenated coconut oil fatty acid, and rice bran fatty acid can preferably improve the flexibility of the coating film.

(Polyester resin (A) manufacturing method)
The method for producing the polyester resin (A) using the polyethylene terephthalate resin, the rosin, and the polyol compound as essential reaction raw materials is not particularly limited and may be carried out by a known method. For example, the polyethylene terephthalate resin, the rosin, and the polyol compound are once decomposed by a reaction with a low molecular weight polyol and then a condensation reaction between the decomposition product and a polybasic acid, or together with an esterification catalyst. Examples thereof include a method of mixing with and reacting with the above.
The ratio of the preferable charge amount of an acid such as rosin to the PET resin is 0.70 to 3.0 in terms of the substance amount ratio (the substance amount of the acids / the substance amount of the PET resin). More preferably, it is in the range of 1.1 to 2.0.
The range of the ratio of the total amount of substances of the hydroxyl groups of polyhydric alcohols (the amount of substance of OH groups / the amount of substances of COOH groups) to the total amount of substances of acid groups of acids at the time of preparation is 1.00 to 1.30. It is preferably in the range of 1.05 to 1.20.
The heating conditions are preferably 150 to 280 ° C, more preferably 200 to 250 ° C.

As the esterification catalyst, known and publicly available esterification catalysts such as titanium-based catalysts such as tetraisopropyl titanate (TiPT) and tetrabutyl titanate and tin-based catalysts such as dibutyltin oxide can be used.
The preferred range of the amount of the esterification catalyst used is preferably 0.001 to 0.1 parts by mass, more preferably 0.003 to 0.006, based on 100 parts by mass of the total amount of the constituent raw materials of the resin (A). It is in the range of parts by mass.

(Acid value of polyester resin (A))
The acid value of the polyester resin (A) is 0 in order to suppress over-emulsification of the ink in offset printing using dampening water, prevent stains on non-image areas, and stabilize the density of each color. The range is preferably in the range of 1 to 15 mgKOH / g, and particularly preferably in the range of 0.1 to 5 mgKOH / g.
In the present invention, the acid value of the resin is a value measured by the neutralization titration method of JIS K 0070 (1992).

The polyester resin (A) can be used in the range of 10 to 50% by mass with respect to the total amount of the active energy ray-curable ink for flat plate offset printing of the present invention, and can be used for the specific gravity of the pigment and the desired viscosity of the ink. It is also possible to adjust the blending amount as appropriate.

(Varnish and other resins)
The active energy ray-curable ink for flat plate offset printing of the present invention may be used in combination with a non-reactive resin other than the polyester resin (A) that is not cured by the active energy ray. For example, examples of the non-reactive resin include ketone resin, diallyl phthalate resin, epoxy resin, epoxy ester resin, polyurethane resin, polyester resin, petroleum resin, poly (meth) acrylic acid ester, cellulose derivative, vinyl chloride-vinyl acetate copolymer. , Polyamide resin, polyvinyl acetal resin, butadiene-acrylic nitrile copolymer and the like, and epoxy acrylate compound having at least one polymerizable group in the molecule, urethane, as long as the effect of the present invention is not impaired. An acrylate compound, a polyester acrylate compound, or the like can also be used, and these binder resins may be used alone or in combination of any one or more.

[Photopolymerization initiator]
In the present invention, when ultraviolet rays are used as active energy rays, they are appropriately general-purpose in consideration of the type of ultraviolet light source to be used, the irradiation intensity of the ultraviolet light source, the integrated amount of ultraviolet irradiation, the color, the printing film thickness, the hygiene, and the like. Photopolymerization initiator can be used. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- On, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, phenylglycoxyacid methyl ester, oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester Mix of oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4 -(4-Morphorinyl) phenyl] -1-butanone and other compounds can be mentioned.

In addition, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphinoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl- Examples thereof include acylphosphine oxide compounds such as pentylphosphine oxide.

In addition, 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-iroxy-N, N, N-trimethyl-1-propaneamine) Examples thereof include thioxanthone compounds such as hydrochloride.

Further, 4,4'-dialkylaminobenzophenones such as 4,4'-bis- (dimethylamino) benzophenone, 4,4'-bis- (diethylamino) benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like. Examples include benzophenone compounds.

Other than that, for example, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4 -(1,3-Acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, methyl-o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethanone, diethoxyacetophenone, Examples thereof include dibutoxyacetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether and the like.

In the present invention, the general-purpose photopolymerization initiator may be used alone or in combination of several kinds. Above all, it is preferable to use a photopolymerization initiator having a number average molecular weight of 300 or more in order to suppress the migration of the photopolymerization initiator from the printed matter, and for black and chromatic color inks other than white, the molecular weight is 300 or more. Bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2- [ It is particularly preferable to use an aminoacetophenone-based photopolymerization initiator represented by (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone in combination.
The mixing ratio of the bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the aminoacetophenone-based photopolymerization initiator is preferably 1: 0.1 to 1: 0.5 in terms of mass ratio. Further, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide should be contained in the ink composition in an amount of 0.5% by mass or more and 5% by mass or less with respect to the reactivity of the ink and the ink binder of the initiator. It is preferable from the viewpoint of maintaining solubility.

[Sensitizer / Photostart aid]
In the present invention, in addition to the above-mentioned general-purpose photopolymerization initiator, a photoinitiator such as a photosensitizer or a tertiary amine may be used in combination. The photosensitizer is not particularly limited, and examples thereof include thioxanthone-based, benzophenone-based such as 4,4'-bis (diethylamino) benzophenone, anthraquinone-based, and coumarin-based.
Among these, thioxanthone compounds such as 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and the like , Michler ketone, 4,4'-bis- (diethylamino) benzophenone, etc. 4,4'-dialkylaminobenzophenone, etc. are preferable, and 2,4-diethylthioxanthone, 2- Isopropylthioxanthone, 4,4'-bis- (diethylamino) benzophenone is particularly preferred.
When a sensitizer or a photoinitiator is used in combination, it is preferably 0.05 to 10% by mass, more preferably 0.1 to 7.0% by mass, based on the total amount of solid ink. If it is less than 0.05% by mass, a sufficient effect of improving the curability cannot be obtained, and if it exceeds 10% by mass, the hue of the cured coating film becomes unacceptably yellowish or a sensitizer is used. Precipitation may occur or the fluidity of the composition may be significantly reduced.

On the other hand, the tertiary amine is not particularly limited, but is limited to ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline. , N, N-dimethyl-p-toluidine, N, N-dihydroxyethylaniline, triethylamine and N, N-dimethylhexylamine, etc., and thioxanthones which reduce polymerization inhibition by oxygen or are activated by ultraviolet rays. , 4,4'-Reacts with dialkylaminobenzophenones to become an active radical donor and improve the curing performance of the ink. The tertiary amine is preferably used in combination as long as the printing performance of the active energy ray-curable ink of the present invention is not impaired, preferably 0.1 to 10% by mass, and 0.1 to 5.0% by mass with respect to the total amount of solid ink. It is more preferable to use it in the range of mass%.

Further, in applications where high hygiene is required, a high molecular weight compound obtained by branching a plurality of photopolymerization initiators, photosensitizers and tertiary amines in one molecule with a polyhydric alcohol or the like can be appropriately used. For example, Speedcure7005, Speedcure7010, Speedcure7040 (manufactured by Rambson), EsacureONE, Omnipol910, OmnipolTX, OmnipolBP (manufactured by IGM) GenopolBP-1, GenoPolBP-1, GenopolyRA (manufactured by IGM), GenopolBP-1, Genopol

(Blocking resistant agent)
The active energy ray-curable offset ink composition of the present invention preferably contains inorganic or organic fine particles having an average particle size of 3 to 6 μm measured by laser scattered light. Specifically, as the inorganic or organic fine particles, porous silica particles having an average particle diameter of 3 to 6 μm, benzoguanamine beads, or spherical silicon beads are preferable. These act as blocking agents.
Within the range of the average particle size, printing can be performed without the particles accumulating on the image line portion of the plate during offset printing, and when the film is wound and stored after printing, the temperature is 30 ° C. to When stored in a room exposed to a humidity of 50 RH% or more at 50 ° C., it is possible to prevent a phenomenon called blocking in which the films stick to each other.
Further, it is preferable that these blocking resistant agents are blended in the ink composition in the range of 1 to 5% by mass. If it is 1% by mass or more, the blocking resistance effect can be sufficiently exhibited. On the other hand, if the amount does not exceed 5% by mass, the rheological property of the ink can be maintained.

In addition, the active energy ray-curable ink for lithographic offset printing of the present invention can be used in combination with a resin, a pigment, and various additives as long as the effects of the present invention are not impaired.

(Pigment)
Examples of the pigment used in the present invention include publicly known and publicly available organic pigments for coloring, for example, for printing inks published in "Organic Pigments Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)". Examples thereof include soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindolin pigments, dioxazine pigments, and thioindigo. Pigments, anthracinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments and the like can be used.

Further, in the active energy ray-curable ink for lithographic offset printing of the present invention, inorganic fine particles may be used as the extender pigment. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, and zinc flower; lime carbonate powder, precipitated calcium carbonate, plaster, ChinaClay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, and stear. Inorganic pigments such as aluminum acetate, magnesium carbonate, barite powder, abrasive powder; and other inorganic pigments, silicones, glass beads, and the like can be mentioned. By using these inorganic fine particles in the range of 0.1 to 60% by weight in the ink, it is possible to adjust the coloring and the rheological characteristics of the ink.

(Pigment dispersant)
The pigment dispersant used in the present invention is preferably a polar group-containing dispersant because it can further improve the dispersity and ink fluidity of the pigment. Examples of the polar group include an acidic group, a basic group, and other functional groups.
Examples of the acidic group include a carboxyl group, a sulfo group, and a phosphoric acid group. Examples of the basic group include an amino group and the like. Examples of other functional groups include a hydroxyl group, a nitro group, a cyano group and the like. The polar group-containing dispersant may also have two or more types of polar groups. The polar group-containing dispersant does not contain a diallyl phthalate resin, a photopolymerization initiator containing a polar group, or a catalyst for the photopolymerization initiator. In particular, it is preferable to use a basic group-containing dispersant.

Examples of the acidic group-containing dispersant include Solsparse series (manufactured by Lubrizol) having an acid value such as Solsparse 26000.
Examples of the commercially available basic-containing dispersant include an azispar series having an amine value such as azispar PB821, a sparse sparse series having an amine value such as sol sparse 24000 and sol sparse 32000 (manufactured by Lubrizol). Examples of other functional group-containing dispersants include copolymers of vinyl alcohol and the like.

The polar group-containing dispersant is preferably contained in an amount of 0.25 to 10 parts by mass with respect to 100 parts by mass of the pigment. If it is contained in this range, the static fluidity and continuous printing performance are further improved. If it exceeds this range, the emulsification rate of the printing ink becomes excessive due to the influence of the polar functional group, and the continuous printing performance is impaired. The content is more preferably 0.25 to 6 parts by mass. When used in this range, the long-term storage stability of the printing ink is further improved. The polar group-containing dispersant can be used alone or in combination of two or more.

(Other additives)
Other additives include, for example, natural additives such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, and microcrystallin wax, which impart abrasion resistance, blocking prevention, slipperiness, and scratch prevention. Examples thereof include waxes, Fishertropus waxes, polyethylene waxes, polypropylene waxes, polytetrafluoroethylene waxes, polyamide waxes, and synthetic waxes such as silicone compounds.

For example, as additives that impart storage stability to the ink, (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picryl. Hydradil, Phenothiadin, p-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyldisulfide, picric acid, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl , N- (3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guayacol, o-isopropylphenol, butyraldoxime, methylethylketoxim, cyclohexanone oxime and the like are exemplified.

In addition, additives such as fluorescent whitening agents, ultraviolet absorbers, infrared absorbers, and antibacterial agents can be added depending on the required performance, but the effects of the present application are appropriately adjusted so as not to be impaired.

The active energy ray-curable ink of the present invention can be used without a solvent, or an appropriate solvent can be used if necessary. The solvent is not particularly limited as long as it does not react with each of the above components, and can be used alone or in combination of two or more.

The active energy ray-curable ink of the present invention may be carried out by the same method as before, for example, the pigment, resin, acrylic monomer or oligomer, polymerization inhibitor, initiator and amine at room temperature to 100 ° C. Ink composition components such as sensitizers such as compounds and other additives are produced by using a kneader, a three-roll, an attritor, a sand mill, a gate mixer, or the like, a kneading machine, a mixing machine, and an adjusting machine.

(Manufacturing method of cured ink, printed matter)
The second aspect of the present invention is to form a layer of the active energy ray-curable ink on a substrate or a printing ink layer printed on the substrate and irradiate the active energy rays. It is a printed matter characterized by being obtained. When ultraviolet rays are used as the active energy rays, it is preferable to irradiate the ultraviolet rays with an ultraviolet light emitting diode light source having a peak wavelength of 350 to 420 nm because the deformation of the plastic substrate due to heat can be suppressed. Further, in order to suppress polymerization inhibition due to oxygen in the air, it is preferable to irradiate ultraviolet rays in a nitrogen atmosphere. The integrated light amount value of the ultraviolet rays emitted from the ultraviolet light emitting diode light source to the UV curable composition cannot be strictly specified because it differs depending on the type of the UV curable composition on the printing substrate, the thickness of the printing layer, and the like. Although preferable conditions are appropriately selected, for example, the total amount of integrated light is about 5 to 200 mJ / cm2, and more preferably about 10 to 100 mJ / cm2. It is difficult to obtain sufficient curability under the condition that the integrated light amount value is less than 5 mJ / cm2, while the condition that the integrated light amount value exceeds 200 mJ / cm2 is unnecessary in the printing method described in the present invention and is an ultraviolet light emitting diode. Excessive energy irradiation is not performed for the purpose of maintaining the energy saving characteristic of the light source.

^{Regarding the irradiation intensity (mW / cm 2} ) of the ultraviolet rays emitted from the ultraviolet light emitting diode light source to the UV curable composition on the printing substrate, the number of ultraviolet light emitting diode light sources arranged in the printing direction and the irradiation from the light source to the composition. Since the appropriate irradiation intensity range varies depending on various conditions such as distance, it is not particularly specified, but the moving speed of the printing substrate in the printing method described in the present invention is 60 to 400 m / min. Therefore, it is preferable that the irradiation intensity is such that the integrated light amount value is about the above-mentioned degree with respect to the UV curable composition on the printing substrate moving at the printing speed.

On the other hand, when an electron beam is used as the active energy ray, the acceleration voltage is preferably in the range of 80 kV to 170 kV, and further, the range of 80 kV to 110 kV can suitably suppress the penetration of the electron beam into the substrate, and the base. Damage to the material can be minimized. Further, when the irradiation dose is in the range of 20 to 40 kGy, the printed matter can be suitably cured, and poor adhesion of the ink to the substrate due to excessive curing can be suitably suppressed.

The printing substrate used in the printed matter of the present invention is not particularly limited, but for example, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, and vinyl acetate co-weight. Examples include coalesced, ethylene vinyl alcohol copolymers, ethylene methacrylate copolymers, films or sheets such as nylon, polylactic acid, and polycarbonate, cellophane, aluminum foil, and various other substrates that have been conventionally used as printing substrates. Can be done. Further, these plastic substrates may be discharged by a general-purpose corona treatment device immediately before printing.

When an ultraviolet light emitting diode is used for producing the printed matter of the present invention, the emission wavelength of the ultraviolet rays emitted from the light source is preferably, for example, a emission peak wavelength of about 350 to 420 nm.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(Resin synthesis example 1)
Synthesis of polyester resin A-1
66.75 g of glycerin, 492.87 g of disproportionated rosin, 140.02 g of recycled PET pellets and esterification in a glass 1 liter four-necked flask equipped with a stirring blade, temperature sensor, nitrogen gas inlet tube and rectification tower. 0.36 g of tetraisoppiltitanate was charged as a catalyst, and the temperature was gradually raised to 240 ° C. with stirring under a normal pressure nitrogen stream to continuously remove the generated water. Heating was continued at 240 ° C. until the acid value became 10 or less to obtain a polyester resin A-1. The acid value of the polyester resin A-1 was 7.9.

(Resin synthesis example 2)
Synthesis of polyester resin A-2
81.13 g of diethylene glycol, 433.24 g of hydrogenated rosin, 185.31 g of recycled PET pellets and esterification catalyst in a glass 1 liter four-necked flask equipped with a stirring blade, temperature sensor, nitrogen gas introduction tube and rectification tower. As a result, 0.32 g of tetraisoppil titanate was charged, and the temperature was gradually raised to 240 ° C. while stirring under a normal pressure nitrogen stream to continuously remove the generated water. Heating was continued at 240 ° C. until the acid value became 10 or less to obtain a polyester resin A-2. The acid value of the polyester resin A-2 was 9.9.

(Resin synthesis example 3)
Synthesis of polyester resin A-3
Diethylene glycol 405.66 g, hydrogenated rosin 2166.22 g, recycled PET pellets 926.54 g and esterification catalyst in a glass 5 liter four-necked flask equipped with a stirring blade, temperature sensor, nitrogen gas inlet tube and rectification tower. 1.59 g of tetraisoppil titanate was charged as a catalyst, and the temperature was gradually raised to 250 ° C. with stirring under a normal pressure nitrogen stream to continuously remove the generated water. Heating was continued at 250 ° C. until the acid value became 2.5 or less to obtain a polyester resin A-3. The acid value of the polyester resin A-3 was 2.2.

(Resin synthesis example 4)
Synthesis of polyester resin A-4
66.75 g of glycerin, 492.87 g of gumrosin, 140.02 g of recycled PET pellets and tetra as an esterification catalyst in a 1 liter glass four-necked flask equipped with a stirring blade, temperature sensor, nitrogen gas inlet tube and rectification tower. 0.36 g of isoppil titanate was charged, and the temperature was gradually raised to 240 ° C. with stirring under a normal pressure nitrogen stream to continuously remove the generated water. Heating was continued at 240 ° C. until the acid value became 10 or less to obtain a polyester resin A-4. The acid value of the polyester resin A-4 was 9.5.

(Varnishing of polyester resin)
Polyester resins A-1 to A-4 were placed in 1-liter glass four-necked flasks equipped with a stirring blade, a temperature sensor, an air introduction tube, and a rectification tower, and the temperature was raised to 160 ° C. After raising the temperature, Miramer M-300 or Miramer M-3160 was added so that the resin / monomer ratio was 82.5 / 17.5, and the mixture was stirred and mixed under normal pressure air flow for 1 hour or more to obtain a varnish. ..

(Manufacturing method of active energy ray-curable ink for lithographic offset printing)
Inks were obtained by kneading the compositions of Examples 1 to 13 and Comparative Examples 1 to 9 with a three-roll mill according to the compositions of Tables 1 to 2.

(How to make a color-developed cured product)
On the Toyobo ester film E5102 having a thickness of 12 μm, 0.13 ml of the inks of Examples and Comparative Examples were color-developed using a simple color developer (RI tester, manufactured by Hoei Seiko Co., Ltd.). This color-developed object is placed on a conveyor 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) equipped with a belt conveyor. It is placed on a conveyor belt at a conveyor speed of 40 m / min and passed directly under the LED (irradiation distance 9 cm). ) The ink film was cured and dried by irradiation.

(How to make a color-cured product for measuring laminate strength)
0.13 ml of the inks of Examples and Comparative Examples were color-developed on a 12 μm-thick Toyobo ester film E5102 using a simple color developer (RI tester, manufactured by Hoei Seiko Co., Ltd.). This color-developed object is placed on a conveyor 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) equipped with a belt conveyor. It is placed on a conveyor belt at a conveyor speed of 40 m / min and passed directly under the LED (irradiation distance 9 cm). ) The ink film was cured and dried by irradiation.

(Measuring method of laminate strength)
The dry laminate adhesive Dick Dry LX-500 / KR-90S (manufactured by DIC) was adjusted to a non-volatile content of 35% with ethyl acetate, and the bar coater No. No. 8 was used, and an adhesive was applied onto the above-mentioned color-developed material for measuring the strength of the laminate, and then dried with hot air. The dry weight of the coated adhesive was 3.5 g / cm ² . Linear low-density polyethylene (Mitsui Tocello TUX HC # 60) was laminated on a color-developed product coated with the above adhesive by a calendar roll (manufactured by Matsumoto Machinery Co., Ltd.) and aged at 40 ° C. for 3 days. , Obtained a laminate. The laminate obtained above is cut out to a width of 15 mm, and a 180-degree peel test is performed with a tensile tester (RTG-1210 manufactured by A & D Co., Ltd.) under the condition of a tensile speed of 50 mm / min, and the above-mentioned laminate strength is measured. The laminating strength of the color-developed cured product was measured. The obtained laminate strength was evaluated according to the following criteria.
〇: 3N / 15mm or more Δ: 1-2N / 15mm
×: 0 to 1N / 15mm

(Film bending test)
The color-developed cured product was rubbed back and forth 10 times, and the degree to which the cured coating film was destroyed such as cracks and pinholes in the cured ink coating film was visually confirmed and evaluated according to the following criteria.
◯: There are no cracks or pinholes on the cured ink coating film.
Δ: Cracks and pinholes are observed on the cured coating film, but the cured coating film does not separate from the substrate.
X: The cured coating film is detached from the base material at a plurality of places and becomes shattered.

(How to check printability)
[Evaluation method of active energy ray-curable ink for lithographic offset printing: Offset printing suitability]
As a method for evaluating the printability of active energy ray-curable ink for flat plate offset printing, first set the water supply dial of the printing machine to 40 (standard water volume), and the printed matter density is the standard process indigo density 1.6 (X-Rite). The ink supply key was fixed so that it would be (measured with a VectoroEye densitometer manufactured by the company). After that, under the condition that the ink supply key was fixed, the ink density of the printed matter after 300 sheets was measured. After that, under the condition that the ink supply key was fixed, the water supply dial was changed from 40 to 55, and 300 sheets were printed under the condition that the water supply amount was increased, and the ink density of the printed matter after 300 sheets was measured. Even when the amount of water supplied is increased, the smaller the decrease in the density of the printed matter, the better the emulsification suitability and the better the printability. The printability of the active energy ray-curable ink for lithographic offset printing was evaluated according to the following criteria.
〇: The black density of the printed matter is 1.6 or more, and the offset printing suitability is good.
Δ: The black density of the printed matter is 1.5 or more and less than 1.6, and the offset printing suitability is medium.
X: The black density of the printed matter is less than 1.5, and the offset printing suitability is poor.

(How to check blocking resistance)
0.13 ml of the inks of Examples and Comparative Examples were color-developed on a 12 μm-thick Toyobo ester film E5102 using a simple color developer (RI tester, manufactured by Hoei Seiko Co., Ltd.). This color-developed object is placed on a conveyor 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) equipped with a belt conveyor. It is placed on a conveyor belt at a conveyor speed of 40 m / min and passed directly under the LED (irradiation distance 9 cm). ) The ink film was cured and dried by irradiation.
The color-developed material obtained above was cut into a length of 5 cm and a width of 5 cm, and the untreated surface of E5102 was superposed on the color-developed surface. Three sets were stacked for each ink, and 5 cm x 5 cm coated cardboard was placed on the top and bottom. This laminate was subjected to a load of 5 kg / cm2 for 24 hours under the conditions of 40 ° C. and 80% RH with a blocking tester.
After 24 hours, the laminate was taken out from the constant temperature bath, left to stand at room temperature, and then the laminated films were peeled off to evaluate the blocking property according to the following criteria.
〇: The stacked films can be peeled off without resistance.
Δ: Although there is resistance when peeling off, the cured ink coating film does not transfer to the non-treated surface of the film.
X: It is difficult to peel off, and the cured ink coating film is transferred to the non-treated surface of the film.

〔migration〕
After each amount of indigo ink printed surface was molded printed material so as to 60mg, and a sealant film inside, in volume 1000 cm ³ so that all the printed surface is in contact with the liquid surface, and the contents of 1000 cm ³ solution A liquid container having a total area of 600 cm ^{2 on the inner surface of the liquid container in contact with the liquid container was prepared, and 1000 cm 3} of an aqueous ethanol solution (a mixed solution of 50% by mass of ethanol and 50% by mass of pure water) was poured and sealed. Subsequently, the sealed liquid container was allowed to stand in an atmosphere of 40 ° C. for 10 days, then the aqueous ethanol solution was taken out from the liquid container, and the adhesive layer provided on the ultraviolet curable offset ink layer by liquid chromatograph mass analysis and the adhesive layer thereof. The amount of the photopolymerizable initiator component eluted from the offset ink layer into the aqueous ethanol solution through the sealant film laminated on top was evaluated according to the following three criteria.
◯: less than 500 ppb Δ: 500 ppb or more and less than 1000 ppb ×: 1000 ppb or more

In the table, blanks are abbreviations for unblended. The molecular weights of the monomers shown in the table are calculated from the values described in the catalogs of each monomer manufacturer or the structures described in the catalogs. However, the molecular weight distribution is not taken into consideration.

Details of the raw materials used are as follows.
Heliogen Blue D7079: PB15: 3
Neolite SA300: Colloidal Calcium Carbonate 24000 GR: Lubrizol Basic Dispersant Magnesium Carbonate TT: Magnesium Carbonate S-381-N1: Shamlock Wax KTL4N Kitamura Co., Ltd. PTFE wax steerer TBH: tert-butylhydroquinone Omnirad 819 manufactured by Seiko Kagaku Co., Ltd .: bis (2,4,6-trimethylbenzoylphenylphosphine oxide Omnirad 369: 2-benzyl-2- (dimethylamino) -4 manufactured by IGM Co., Ltd. '-Morphorinobutyrophenone Omnirad 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one TINOPAR OB CO: Fluorescent whitening agent manufactured by BASF.

Epoxy ester resin: A varnish in which the epoxy ester resin used in DIC's Luxidia V-3221 is dissolved in trimethylolpropane triacrylate.

SR355NS: Arkema Sartomer dimethylolpropane tetraacrylate Miramer M-300: Miwon trimethylolpropane triacrylate Miramer M-3130: Miwon EO3 trimethylolpropane triacrylate Miramer M-3160: Miwon EOtri. Triacrylate Miramer M-3190: Miwon's EO9 trimethylolpropane triacrylate SR9035: Arkema Sartomer's EO15 trimethylolpropane triacrylate

Siricia 350D: Fuji Silicia Chemical Co., Ltd. Particle diameter 3.9 μm Colloidal silica Siricia 740: Fuji Silicia Chemical Co., Ltd. Particle diameter 5.0 μm Colloidal silica Cyricia 310P: Fuji Silicia Chemical Co., Ltd. Particle diameter 2.6 μm Colloidal silica Epostal M05: Nippon Catalyst Co., Ltd. particle diameter 5.2 μm benzoguanamine / formaldehyde condensate Epostal L15: Nippon Catalyst Co., Ltd. particle diameter 9 μm benzoguanamine / formaldehyde condensate Tospearl 130: Momentive Co., Ltd. particle diameter 3 μm true spherical silicone fine particles Tospearl 145 : Momentive particle diameter 4.5 μm spherical silicone fine particles Tospearl 1100: Momentive particle diameter 10 μm spherical silicone fine particles

The abbreviations are as follows.
Average number of moles of EO added: Average number of moles of ethylene oxide added EO-modified TMPTA: Ethylene oxide-modified trimethylolpropane triacrylate

As a result, it is clear that the active energy ray-curable ink for lithographic offset printing of the present invention shown in Examples is excellent in various physical properties.

Claims (8)

An active energy ray-curable ink for flat plate offset printing containing a monomer having an ethylenically unsaturated double bond and a varnish.
(1) The monomer having an ethylenically unsaturated double bond is ethylene oxide-modified trimethylolpropane tri (meth) acrylate in which the average number of moles of ethylene oxide added is 4 to 9 mol per molecule.
(2) An active energy ray-curable ink for flat plate offset printing, wherein the varnish is a polyester resin containing a polyethylene terephthalate resin, a rosin, and a polyol compound as essential reaction raw materials. The ink composition contains 5 to 15% by mass of ethylene oxide-modified trimethylolpropane tri (meth) acrylate having an average number of moles of ethylene oxide added of 4 to 9 mol per molecule, and the polyester resin is used in the ink composition. The active energy ray-curable ink for flat plate offset printing according to claim 1, which contains 10 to 50% by mass of the medium. The active energy ray-curable ink for lithographic offset printing according to claim 1 or 2, wherein the polyester resin has an acid value of 1 to 15 mgKOH / g. The active energy ray curing for flat plate offset printing according to any one of claims 1 to 3, wherein the ink composition contains 1 to 5% by mass of inorganic or organic fine particles having an average particle diameter of 3 to 6 μm measured by laser scattered light. Mold ink. The active energy ray-curable ink for lithographic offset printing according to any one of claims 1 to 4, wherein the ink composition contains 2 to 10% by mass of a photopolymerization initiator having a number average molecular weight of 300 or more. An ink-cured product characterized by offset printing using the active energy ray-curable ink for flat plate offset printing according to any one of claims 1 to 5, and curing the printed ink using the active energy ray. Production method. A printed matter obtained by the method for producing a cured ink product according to claim 6. A varnish for active energy ray-curable ink for flat plate offset printing, which contains a polyester resin containing a polyethylene terephthalate resin, a rosin, and a polyol compound as essential reaction raw materials.