JP2020045394A - Active energy-ray curable resin composition, ink and printed matter - Google Patents

Abstract

To provide active energy-ray curable ink which has curability by active energy rays, solves ink bottle release trouble during printing, and improves a dot gain of a printed matter.SOLUTION: A resin composition contains a diallyl phthalate resin modified product (A) and a monomer having a radical polymerizable double bond, in which the diallyl phthalate resin modified product (A) is a reactant of a thiol compound having an organic acid structure and a diallyl phthalate resin, and an acid value of the diallyl phthalate resin modified product (A) is 2.5 to 50.0 (mgKOH/g).SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable resin composition containing an allyl-based polymer, and an active energy ray-curable ink containing the resin composition, and further uses the active energy ray-curable ink. The present invention relates to a method for manufacturing a printed matter and a printed matter.

Conventionally, printed matter for forms, printed matter for various books, printed matter for packaging such as carton paper, printed matter for various plastics, sticker, label printed matter, art printed matter, metal printed matter (art printed matter, beverage can printed matter, food printed matter such as canned food) In order to obtain various printed materials, various printing methods such as lithographic printing (normal lithographic printing using fountain solution and lithographic printing plate without using fountain solution), letterpress printing, intaglio printing, stencil printing are adopted. Uses an ink suitable for each printing method. Active energy ray-curable inks are known as one of such inks.

In recent years, the demand for shorter delivery times and environmentally friendly printing has increased, and the use of active energy ray-curable inks that are quick-drying and do not use solvents have been expanding in place of oil-based inks that have been conventionally used.

However, compared to oil-based inks, active energy ray-curable inks have poor fluidity of the ink, so that the ink cannot be scraped from the ink fountain to the roller during printing (ink foal escape), and the dot gain of the printed matter is low. There is a problem that the print reproducibility is lowered.

Patent Document 1 discloses an acid value of 5 to improve the fluidity of an active energy ray-curable ink.
An ink composition containing 0 to 600 (mg KOH / g) of a polymer has been proposed. However, in offset printing in which an ink image is formed on the plate surface by repulsion of water and oil, if a high acid value polymer is mixed with a hydrophobic ink, the ink becomes hydrophilic, and the ink is printed on the non-image area of the printed matter. It adheres and causes dirt.

Further, it is known that the active energy ray-curable ink contains diallyl phthalate resin, which is an allyl polymer, to improve the stability during printing and the curing speed of the ink coating film. Although diallyl phthalate resin is commercially available, the acid value of the commercially available diallyl phthalate resin is about 2 (mg KOH / g). On the other hand, Patent Literature 2 describes a diallyl phthalate resin having an acid value of 2 (mg KOH / g) or more, but does not mention any use of the diallyl phthalate resin in a resin composition and ink.

Further, in recent years, while the use of active energy ray-curable inks has been expanding in place of conventional oil-based inks, there has been a demand for improvements in ink fluidity and print reproducibility, which are disadvantages.

JP 2010-159343 A Japanese Patent Publication No. 40-026715

An object of the present invention is to provide an active energy ray-curable ink that eliminates the problem of ink fountain escape during printing and improves the dot gain of printed matter, and to provide a resin composition used for the ink.

As a result of intensive research to solve the above-mentioned problems, active energy ray-curable inks composed of a resin composition containing a specific diallyl phthalate resin modified product have excellent ink fluidity and eliminate ink fountain escape problems. Then, they found that the dot gain could be further improved, and completed the present invention.

That is, a first invention of the present invention is a resin composition comprising a modified diallyl phthalate resin (A) and a monomer having a radical polymerizable double bond,
The modified diallyl phthalate resin (A) is a reaction product of a thiol compound having an organic acid structure and a diallyl phthalate resin,
The modified diallyl phthalate resin (A) has an acid value of 2.5 to 50.0 (mg KOH /
g) A resin composition characterized in that:

Further, the second invention of the present invention relates to an active energy ray-curable ink containing the resin composition according to the first invention.

Further, a third invention of the present invention relates to a printed material obtained by printing on a base material using the active energy ray-curable ink according to the second invention and curing the active energy ray.

According to the present invention, an ink is obtained by using an active energy ray-curable ink comprising a resin composition containing a modified diallyl phthalate resin (A) obtained by reacting a thiol compound having an organic acid structure with a diallyl phthalate resin. In addition to eliminating bottle escape problems, it has become possible to improve the dot gain of printed matter.

The resin composition of the present invention containing the modified diallyl phthalate resin (A) and a monomer having a radical polymerizable double bond will be described.

The modified diallyl phthalate resin (A) is obtained by an acid modification reaction between a thiol compound having an organic acid structure and a diallyl phthalate resin. More specifically, the organic acid structure can be introduced into the diallyl phthalate resin by an ene-thiol reaction between the thiol group of the thiol compound having the organic acid structure and the allyl group of the diallyl phthalate resin.

The compounding amount of the diallyl phthalate resin and the thiol compound having an organic acid structure for obtaining the diallyl phthalate resin modified product (A) is based on 100 parts by mass of the diallyl phthalate resin.
The thiol compound having an organic acid structure is preferably 0.1 to 10 parts by mass.

The ene-thiol reaction of the present invention proceeds by mixing a diallyl phthalate resin and a thiol compound having an organic acid structure and heating the mixture at a temperature of 30 to 100 ° C. for about 1 to 10 hours. Is selected as appropriate. In the above reaction, if necessary, a diluting solvent described below and a catalyst such as a thermal radical initiator described below can be added. Further, the above reaction is preferably performed in a nitrogen atmosphere.

As a method for confirming the progress of the ene-thiol reaction, for example, confirming the disappearance amount of the thiol group by infrared absorption spectrum measurement, confirming the disappearance amount of the double bond of the diallyl phthalate resin by measuring the iodine value, liquid Examples include confirmation of the disappearance of the thiol compound by chromatography or gas chromatography, and structural analysis of the thiol compound and diallyl phthalate resin by nuclear magnetic resonance spectroscopy.

The acid value of the modified diallyl phthalate resin (A) is from 2.5 to 50.0 mgKOH / g, and preferably from 2.5 to 25 mgKOH / g. When the acid value of the modified diallyl phthalate resin (A) is 2.5 mg KOH / g or more, the effect of the present invention is sufficiently exhibited,
When the acid value is 50.0 mgKOH / g or less, hydrophilicity can be suppressed, and printing trouble hardly occurs.

The weight average molecular weight of the modified diallyl phthalate resin (A) is not particularly limited, but the weight average molecular weight (in terms of polystyrene) determined by gel permeation chromatography (GPC) is preferably from 5,000 to 100,000, more preferably from 10,000. 000 to 50,000
0. When it is 5,000 or more, the viscosity of the ink becomes high, misting or the like hardly occurs, and when it is less than 100,000, gelation is easily suppressed when producing a resin, and production becomes easy.

The thiol compound having an organic acid structure in the present invention is a compound having an organic acid group and a mercapto group. Examples of the organic acid group include a carboxylic acid and a sulfonic acid, and among them, a compound having a carboxylic acid is preferable.

Examples of the thiol compound having an organic acid structure include mercaptoacetic acid, mercaptopropionic acid, 2-mercaptopropionic acid, mercaptobutyric acid, 3-mercaptoisobutyric acid,
Mercaptoaliphatic carboxylic acids such as mercaptosuccinic acid and dimercaptosuccinic acid; mercaptoaromatic carboxylic acids such as 2-mercaptobenzoic acid, 3-mercaptobenzoic acid and 4-mercaptobenzoic acid; 2-mercaptoethanesulfonic acid; Mercapto aliphatic sulfonic acids such as mercaptopropanesulfonic acid, mercaptoaromatic sulfonic acids such as 2-mercaptobenzenesulfonic acid, 3-mercaptobenzenesulfonic acid, and 4-mercaptobenzenesulfonic acid; and compounds having a hydroxyl group and an organic acid. Examples thereof include mercapto organic acids obtained by esterification of a compound having a carboxylic acid and a mercapto group. These thiol compounds having an organic acid structure may be used alone or in combination of two or more.

The diallyl phthalate resin before modification is not particularly limited, but is preferably a diallyl orthophthalate resin. As the diallyl orthophthalate resin, for example, Daiso Dap A (manufactured by Osaka Soda Co., Ltd.) can be used as a commercially available diallyl orthophthalate resin.

Examples of the diluting solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol;
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl Ketones such as -n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone,
Esters such as methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, -n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, and butyl lactate;
Ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene Glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol dipropyl ether, glycol and glycol ethers such as tripropylene glycol monomethyl ether,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Glycol acetates such as monobutyl ether acetate and dipropylene glycol monomethyl ether acetate;
saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, isododecane,
Unsaturated hydrocarbons such as 1-hexene, 1-heptene and 1-octene;
Cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, and decalin;
cyclic esters such as γ-butyrolactone and δ-valerolactone;
Nitrogen-containing heterocycles such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone;
Cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene;
Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene.
These organic solvents may be used alone or as a mixture of two or more.
When a diluting solvent is used, it is preferably used in a range of 80% by mass or less based on the total amount of the reaction solution.

As the thermal radical initiator, for example, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-
Azo compounds such as 2,4-dimethylvaleronitrile) and dimethyl-2,2'-azobis (2-methylpropionate), benzoyl peroxide, t-butyl (2-ethylhexanoyl)
Organic peroxides such as peroxide, t-hexyl (2-ethylhexanoyl) peroxide, dilauroyl peroxide, hydrogen peroxide and the like. These thermal radical initiators may be used alone or in combination of two or more. When a thermal radical initiator is used, it is preferably used in a range of 10% by mass or less based on the total amount of the reaction solution.

Examples of the monomer having a radical polymerizable double bond of the present invention include the following.

Monofunctional monomers include carbons such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate. (Alkyl) (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane monomethylol (meth) acrylate, 2-hydroxyethyl (meth) acrylate having a number of 1 to 18 , 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, hydroxypentyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, diethylene glycol mono (Meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (
(Meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, acryloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 2- (meth) acryloyloxypropyl Phthalate, β-carboxyethyl (meth) acrylate, (meth) acrylic acid dimer, ω-carboxy-polycaprolactone mono (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylformamide, (meth) acryloylmorpholine,
Examples thereof include alkylphenol (meth) acrylates such as butylphenol, octylphenol, nonylphenol, and dodecylphenol.

Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl Hydroxypivalate di (meth) acrylate (commonly known as Manda), hydroxypivalyl hydroxypivalate dicaprolactonate di (meth) ac Rate, 1,6-hexanediol di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexanediol di (
(Meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1
1,12-dodecanediol di (meth) acrylate, 1,2-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16 -Hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-
2,4-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2, 4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2
, 4-Trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2, 5-hexanediol di (meth) acrylate, 2-
Methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-
1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-hexanediol di ( (Meth) acrylate, 2,5-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, 1,2-decanediol di (meth)
Acrylate, 1,10-decanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1
, 2-dodecanediol di (meth) acrylate, 1,14-tetradecanediol di (
(Meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16
-Hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanedi (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate , 2-methyl-2-propyl-1,
3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2 , 4-Trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2, 5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate tricyclode Candimethylol di (meth) acrylate, tricyclodecane dimethylol dicaprolactonate di (meth) a Relate, bisphenol A tetraethylene oxide adduct di (meth) acrylate, bisphenol F tetraethylene oxide adduct di (meth) acrylate, bisphenol S tetraethylene oxide adduct di (meth) acrylate, water-added bisphenol A tetraethylene oxide adduct Di (meth) acrylate, water-added bisphenol F tetraethylene oxide adduct di (meth) acrylate,
Water-added bisphenol A di (meth) acrylate, water-added bisphenol F di (meth) acrylate, bisphenol A tetraethylene oxide adduct dicaprolactonate di (
Examples thereof include (meth) acrylate, bisphenol F tetraethylene oxide adduct dicaprolactonate di (meth) acrylate, and the like.

As trifunctional monomers, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tricaprolactonate tri (
Examples thereof include (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolhexanetri (meth) acrylate, trimethyloloctanetri (meth) acrylate, and pentaerythritol tri (meth) acrylate.

Pentaerythritol tetra (meth) acrylate as a tetra- or higher functional monomer,
Pentaerythritol tetracaprolactonate tetra (meth) acrylate, diglycerin tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, ditrimethylolpropanetetracaprolactonate tetra (meth) acrylate,
Ditrimethylolethanetetra (meth) acrylate, ditrimethylolbutanetetra (
(Meth) acrylate, ditrimethylolhexanetetra (meth) acrylate, ditrimethyloloctanetetra (meth) acrylate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate, etc. Is exemplified.

Further, as a compound containing a (meth) acryl group, there is an alkylene oxide adduct (meth) acrylate of an aliphatic alcohol compound.
Examples of the alkylene oxide adduct (meth) acrylate monomer of an aliphatic alcohol compound include mono- or poly (1-20) alkylene (C2-C2) of an aliphatic alcohol compound.
20) Mono- or poly (1-10) (meth) acrylates of oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, etc.).

Examples of the monofunctional monomer include an alkylene oxide adduct (meth) acrylate having 2 to 20 carbon atoms, such as methanol mono- or poly (1-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide as the alkylene oxide). , Butylene oxide) (meth) acrylate, ethanol mono- or poly (1
To 20) alkylene (C2 to C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) (meth) acrylate, butanol mono- or poly (1 to 20) alkylene (C2 to C20) oxide adducts ( As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, hexanol mono or poly (1-20)
) Alkylene (C2 to C20) oxide adducts (for example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, octanol mono- or poly (1 to 20) alkylene (C2 to C20) oxide adducts (alkylene oxides) For example, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate, dodecanol mono- or poly (1-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) (Meth) acrylate, stearyl mono- or poly (1-20) alkylene (C2-C20) oxide adduct (example as alkylene oxide If ethylene oxide, propylene oxide) (meth)
Acrylate,
Examples thereof include poly (1-20) alkylene (C2-C20) oxide adducts of butylphenol, octylphenol, nonylphenol, and dodecylphenol (eg, ethylene oxide, propylene oxide, butylene oxide) (meth) acrylate as the alkylene oxide.

Examples of the bifunctional monomer include ethylene glycol mono- or poly (1-20) alkylene (C2-C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, diethylene glycol mono- or poly ( 2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, triethylene glycol poly (2-20) alkylene (C2-C20) oxide addition as alkylene oxide (Alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate;
Polyethylene glycol poly (2-20) alkylene (C2-C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, propylene glycol poly (2-20) alkylene (C2-C20) ) Oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, dipropylene glycol poly (2-20) alkylene (C2-C20) oxide adduct (
As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, tripropylene glycol poly (2-20) alkylene (C2-C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) ) Di (meth) acrylate,
Polypropylene glycol poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, butylene glycol poly (2-20) alkylene (C2-C20) ) Oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, pentyl glycol poly (2-20) alkylene (C2 to C20) oxide adducts (eg, ethylene oxide, propylene as alkylene oxide) Oxide, butylene oxide) di (methaneopentyl glycol poly (2-20) (for example, ethylene oxide, propylene oxide, Adylene di (meth) acrylate, hydroxypivalyl hydroxypivalate poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide) di (meth ) Acrylate (commonly known as Manda), hydroxypivalyl hydroxypivalate dicaprolactonate poly (2-20) alkylene (C2-
C20) Oxide adduct (for example, as an alkylene oxide, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,6 hexanediol poly (2-20) alkylene (C2-C20) oxide adduct (for example, as an alkylene oxide Ethylene oxide, propylene oxide, butylene oxide)
Di (meth) acrylate, 1,6 hexanediol poly (2-20) alkylene oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide, etc.)
Di (meth) acrylate, 1,2-hexanediol di (meth) acrylate, 1,5-
Hexanediol poly (2-20) alkylene (C2-C20) oxide adducts (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-hexanediol poly (2-20) alkylene (C2-C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 1,
7-heptanediol poly (2-20) alkylene (C2-C20) oxide adduct (
As alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,8-octanediol poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide as alkylene oxide) , Butylene oxide) di (meth) acrylate,
1,2-octanediol poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate di (meth) acrylate, 1,9- Nonanediol poly (2-20) alkylene (C2-C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide)
Di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (C2-
C20) Oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 1,10-decanediol poly (2-20) alkylene (C2-C20) oxide adduct (as alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-decanediol poly (2-20) alkylene (C2
To C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 1,12-dodecanediol poly (2-20) alkylene (C2-C20) oxide adduct (alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-dodecanediol mono or poly (1-20
) Alkylene (C2 to C20) oxide adducts (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate and 1,14-tetradecanediol poly (2 to 20) alkylene (C2 to C20) oxide addition (Alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,2-tetradecanediol poly (2-20) alkylene (C2-C20) oxide adduct (alkylene oxide such as ethylene oxide, Propylene oxide, butylene oxide) di (meth) acrylate, 1,16-hexadecanediol mono- or poly (2-20) alkylene (C2-C20) oxa De adducts (e.g. ethylene oxide as alkylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 1,
2-hexadecanediol poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2-methyl-2,4-pentanediol poly (2-20) alkylene (C2-C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide) as alkylene oxide di (meth) acrylate, 3-methyl-1,5-pentanediol poly (2-20) Alkylene (
C2-C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate as alkylene oxide, 2-methyl-2-propyl-1,3-propanediol poly (2-20) alkylene (C2 ~ C20
) Oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2,4-dimethyl-2,
4-pentanediol poly (2-20) alkylene (C2-C20) oxide adduct (
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,2-diethyl-1,3-propanediol mono or poly (2-20) alkylene (C2-C20) oxide adduct ( As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol mono- or poly (2-20) alkylene (C2-C20) oxide adduct (For example, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide)
Di (meth) acrylate, dimethyloloctane poly (2-20) alkylene (C2-C
20) Oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2-ethyl-1,3
-Hexanediol poly (2 to 20) alkylene (C2 to C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol Poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2-methyl-1,8-octanediol poly (2-20 ) Alkylene (
C2-C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol poly (2-20) alkylene (C2 To C20)
Oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) di (meth) acrylate, 2,4-diethyl-1,5
-Pentanediol poly (2-20) alkylene (C2-C20) oxide adduct (
Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide) di (meth) acrylate.

Examples of the trifunctional monomer include glycerin poly (2-20) alkylene (C2 to C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tri (meth) acrylate, trimethylolpropane poly (2-20 ) Alkylene (C2 to C20) oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide) tri (meth) acrylate, trimethylolethanepoly (2 to 20) alkylene (C2 to C20)
Oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tri (meth) acrylate, trimethylolhexane poly (2-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene as alkylene oxide) Oxide, butylene oxide) tri (
(Meth) acrylate, trimethyloloctanepoly (2-20) alkylene (C2-C2
0) Oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tri (meth) acrylate, trimethyloloctane poly (3-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide as alkylene oxide) , Propylene oxide, butylene oxide) tri (meth) acrylate, pentaerythritol poly (2-20) alkylene (C2-C
20) Oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tri (meth) acrylate and the like.

Examples of tetrafunctional or higher-functional monomers include pentaerythritol poly (2-20) alkylene (
C2 to C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide) as tetraalkyl (alkylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2 to 20) alkylene (C2 to C20) oxide adducts (eg, as alkylene oxides) Ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolpropane poly (2-20)
Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylolpropanetetracaprolactonate, tetra (meth) acrylate, ditrimethylolethanepoly (2-20) alkylene (C2-C20) Oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) tetra (meth) acrylate, ditrimethylolethanepoly (2-20) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) Acrylate,
Ditrimethylol butane poly (2-20) alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethylol hexane poly (2-20) alkylene (C2-C20) oxide adduct (alkylene oxide) For example, ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethylolhexanepoly (2 to 2)
0) Alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide, etc.) tetra (meth) acrylate, ditrimethyloloctane (2-20)
Alkylene (C2-C20) oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide) tetra (meth) acrylate, ditrimethyloloctane poly (4-200) alkylene oxides (eg, ethylene oxide, propylene oxide, butylene oxide) Etc.) Tetra (meth) acrylate, dipentaerythritol poly (5-20) alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) penta (meth) acrylate, dipentaerythritol poly (
2-20) alkylene (C2 to C20) oxide adducts (alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide) hexa (meth) acrylate, propylene oxide, butylene oxide, etc. hexa (meth) acrylate, dipentaerythritol hexa Caprolactonate poly (2-20) alkylene (C2-C20) oxide adduct (for example, ethylene oxide, propylene oxide, butylene oxide) hexa (meth) acrylate, tripentaerythritol poly (2-20) alkylene (as alkylene oxide) C2-C20) oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) hepta (meth ) Acrylate, tripentaerythritol poly (2-2
0) Alkylene (C2-C20) oxide adduct (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) octa (meth) acrylate, tripentaerythritol poly (2-20) alkylene (C2-C20)
Oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide as alkylene oxide) hexa (meth) acrylate, tripentaerythritol polyalkylene oxide hepta (meth) acrylate, tripentaerythritol poly (2-20) alkylene (C2-C20) Oxide adducts (eg, ethylene oxide, propylene oxide, butylene oxide) octa (meth) acrylate as an alkylene oxide are exemplified, but not limited thereto.

Further, as a compound containing a (meth) acrylate group, an active energy ray-curable (
A (meth) acrylic oligomer, urethane (meth) acrylate, epoxy (meth) acrylate, or polyester (meth) acrylate can be used as appropriate.

Examples of the (meth) acrylic oligomer include polyols, esterified products of polybasic acids and (meth) acrylic acids, and epoxy acrylates. Examples of the polyol include ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol. Examples of the polybasic acid include phthalic anhydride, isophthalic acid, (anhydrous) succinic acid, (anhydrous) maleic acid, adipic acid, and sebacic acid. You. The ester reaction of the polyol, polybasic acid and (meth) acrylic acid is carried out by a conventional method.

Examples of the urethane (meth) acrylate include general aromatic or aliphatic urethane (meth) acrylates. As an example, (meth) acrylates such as tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate may be mentioned.

As the epoxy (meth) acrylate, a general aromatic or aliphatic epoxy (
(Meth) acrylates. As an example, (meth) acrylates such as bisphenol A epoxy, bisphenol F epoxy, novolak epoxy, and phosphoric acid epoxy may be used.

Examples of the polyester (meth) acrylate include a general polyester (meth) acrylate, a fatty acid-modified type, and a chlorinated polyester.

As a method for obtaining the resin composition, a modified diallyl phthalate resin (A) and a monomer having a radical polymerizable double bond are mixed, and the mixture is mixed at a temperature of 80 to 120 ° C. under an air atmosphere for 0.5 minute.
It is obtained by dissolving in ~ 2 hours.

The content of the modified diallyl phthalate resin (A) in the resin composition is 10 to
70 mass%, preferably 20 to 60 mass%. The content of the monomer having a radical polymerizable double bond is 30 to 90% by mass, and preferably 40 to 80% by mass. The resin composition preferably contains a radical polymerization inhibitor, and the content of the radical polymerization inhibitor is 0 to 5% by mass, and preferably 0.1 to 1% by mass.

Examples of the radical polymerization inhibitor include alkylphenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, nitrosobenzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperon, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- (3-oxyanilino-1,3- Dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, cyclohexanone oxime And the like.

Next, the usage form as the active energy ray-curable ink in the present invention will be described.

The active energy ray-curable ink in the present invention comprises 0 to 30% by mass of a pigment, 5 to 30% by mass of a binder resin, 20 to 70% by mass of the monomer having a radical polymerizable double bond, and 0 to 1% by mass of a radical polymerization inhibitor. %, A photopolymerization initiator and / or a sensitizer in an amount of 0 to 20% by mass, and other additives in an amount of 0 to 10% by mass.

Here, the modified diallyl phthalate resin (A) in the present invention is a binder resin and is used in the form of the resin composition of the present invention.

The active energy ray in the present invention is energy that is required to excite a starting material of a curing reaction from a ground state to a transition state. Examples of the active energy ray in the present invention include an ultraviolet ray and an electron beam. .

In the photocuring method of the active energy ray-curable ink composition, a light source that emits ultraviolet light such as a metal halide lamp, a high-pressure mercury lamp, and an LED is generally used.

The active energy ray-curable ink of the present invention does not contain a pigment as a colorant, and if it has a transparent structure, it will be an OP varnish, and if it contains the pigment shown below, it will be a color printing ink. .

Examples of the pigment include an inorganic pigment and an organic pigment. As an inorganic pigment, graphite,
Zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder,
Bengala etc.
As organic pigments, soluble azo pigments such as β-naphthol-based, β-oxynaphthoic-acid-based, β-oxynaphthoic-acid-based anilide-based, acetoacetic-anilide-based, and pyrazolone-based, β-naphthol-based, and β-oxynaphthoic-acid-based Insoluble azo pigments such as anilide-based, acetoacetate-anilide-based monoazo, acetoacetate-anilide-based disazo, and pyrazolone-based, copper phthalocyanine blue,
Phthalocyanine pigments such as halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine; Various publicly known pigments such as polycyclic pigments such as thioindigo, anthraquinone, perinone, and perylene), isoindolinone, metal complex, and quinophthalone, and heterocyclic pigments can be used.

The content of the modified diallyl phthalate resin (A) in the ink is preferably from 5 to 30% by mass, more preferably from 5 to 20% by mass. If the amount is less than 5% by mass, the effect of the present invention cannot be sufficiently exerted.

In the active energy ray-curable ink of the present invention, a binder resin other than the diallyl phthalate resin modified product (A) can be used, if necessary.

As the binder resin other than the diallyl phthalate resin modified product (A), diallyl phthalate resins other than the diallyl phthalate resin modified product (A) (diallyl ortho phthalate resin,
Diallyl isophthalate resin, diallyl terephthalate resin, etc.), polyester, polyvinyl chloride, poly (meth) acrylate, epoxy resin, polyurethane resin, petroleum (based) resin, cellulose derivative (eg, ethyl cellulose, cellulose acetate, nitrocellulose) And a synthetic rubber such as a vinyl chloride-vinyl acetate copolymer, a polyamide resin, a polyvinyl acetal resin, a polyamide resin, a polyvinyl acetal resin, and a butadiene-acrylonitrile copolymer.
One or more of these resins can be used.

Examples of the photopolymerization initiator include a photocleavable type initiator and a hydrogen abstraction type polymerization initiator.

Examples of the photocleavable initiator include an α-dimethylaminoalkylphenone compound, an α-morpholinoalkylphenone compound, an acylphosphine oxide compound, and the like.

More specifically, as the α-dimethylaminoalkylphenone compound, 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 or 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane -1-one and the like,
Examples of the α-morpholinoalkylphenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one,
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Further, examples of the hydrogen abstraction type polymerization initiator include a dialkylbenzophenone compound and a thioxanthone compound.

More specifically, as a dialkylaminobenzophenone compound, 4,4′-bis- (
Examples thereof include 4,4′-dialkylaminobenzophenones such as dimethylamino) benzophenone and 4,4′-bis- (diethylamino) benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2-chlorothioxanthone, and 1-chlorothioxanthone. Chloro-4-propoxythioxanthone, 2-hydroxy-3- (
3,4-dimethyl-9-oxo-9H thioxanthon-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride.
One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.

Examples of the sensitizer include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 2,3,4-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, and (1,3-acryloyl-
1,4,7,10,13-pentaoxotridecyl) benzophenone, methyl-o-benzoylbenzoate, [4- (methylphenylthio) phenyl] phenylmethanone, (4
-Benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, benzoin methyl ether, Examples include benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether and the like. These may be used alone or in combination of two or more.

Further, the active energy ray-curable ink of the present invention may contain other additives as necessary.

For example, the above-mentioned radical polymerization inhibitor can be exemplified as an additive for imparting the storage stability of the ink. Examples of additives that impart abrasion resistance, anti-blocking properties, slipperiness, and anti-scratch properties include carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, and other natural waxes, and Fischer-Trops wax. And synthetic waxes such as polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compound.

In addition, additives such as an ultraviolet absorber, an infrared absorber, and an antibacterial agent can be added according to the required performance.

The method for producing the active energy ray-curable ink of the present invention may be performed by a method similar to that of a conventional active energy ray-curable ink.
The resin composition of the present invention, a monomer having a radical polymerizable double bond, a polymerization inhibitor, a photopolymerization initiator and a sensitizer, and other ink composition components such as additives, a kneader, a three-roll, an attritor, and a sand mill It is manufactured using a meat mixer, a mixing and adjusting machine such as a gate mixer.

Examples of the printing method include lithographic printing (normal lithographic printing using dampening solution and waterless lithographic printing without using dampening solution), letterpress printing, intaglio printing, stencil printing, etc., and preferably lithographic printing. .

The substrate of the printed matter is not particularly limited, and includes printing on any material such as paper, plastic, seal, label, and metal, and preferably printing on paper.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples do not limit the scope of the present invention. In the present invention, “parts” represents “parts by mass”, and “%” represents “% by mass”.

The weight average molecular weight is determined by gel permeation chromatography (HL, manufactured by Tosoh Corporation).
C-8320). A calibration curve was created using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used for the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.
Further, in the present invention, unless otherwise specified, “molecular weight” indicates a weight average molecular weight.

  The hydroxyl value and the acid value were determined by neutralization titration according to JIS K0070.

The diallyl phthalate resin before denaturation includes a diallyl orthophthalate resin “Daiso Dap A” manufactured by Osaka Soda Co., Ltd. (hydroxyl value: 12 mg KOH / g, acid value: 2.1 mg KOH / g)
, Weight average molecular weight: 30,000).

Production of modified resin (modified resin A-1)
99.59 parts of diallyl orthophthalate resin is placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube, and mixed with MEK so as to become a 67% methyl ethyl ketone (MEK) solution of the diallyl orthophthalate resin. The mixture was heated to 60 ° C. while stirring under a nitrogen atmosphere. Then, after adding 0.41 part of mercaptoacetic acid and heating and stirring for 8 hours,
The iodine value was measured according to IS K0070, and it was confirmed that the disappearance of the double bond of the diallyl orthophthalate resin was the same as that of the compounded thiol compound, and the reaction was terminated by cooling to room temperature. After 1160 parts of methanol was added to the solution after the reaction to precipitate the polymer, the polymer was taken out and washed three times with methanol. The washed polymer was vacuum-dried at 25 ° C. to obtain a diallyl phthalate resin modified product (A-1).

(Resin modified products A-2 to 9)
After reacting the diallyl orthophthalate resin with a thiol compound having an organic acid structure in the same manner as in the modified resin A-1 according to the composition in Table 1, the resin is modified by washing and vacuum drying in the same manner as in the modified resin A-1. Products (A-2 to 9) were obtained.

(Modified resin B-1 to 3)
After reacting the diallyl orthophthalate resin with a thiol compound having an organic acid structure in the same manner as in the modified resin A-1 according to the composition in Table 1, the resin is modified by washing and vacuum drying in the same manner as in the modified resin A-1. A product (B-1, 2, 3) was obtained.

(Modified resin B-4)
230 parts of acetone was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube, and 69.44 parts of diallyl orthophthalate resin was added with stirring.
After heating and stirring for 3 minutes to dissolve, 30.56 parts of dodecanethiol was further added and stirred for 10 minutes to dissolve. Next, the reaction was performed by irradiating light with a mercury xenon lamp while stirring at 25 ° C. After adding 1160 parts of methanol to the solution after the reaction to precipitate the polymer,
The polymer was removed and washed three times with methanol. The washed polymer was vacuum-dried at 25 ° C. to obtain a modified resin (B-4).

(Examples 1 to 10, Comparative Examples 1 to 4)
Production of resin composition (resin composition A'-1)
30 parts of the resin-modified product (A-1), 69.8 parts of dipentaerythritol hexaacrylate, and 0.2 part of t-butylhydroquinone were mixed and dissolved at 100 ° C., and then cooled to room temperature. '-1) was obtained.

(Resin composition A′-2 to 10)
According to the composition of Table 2, in the same manner as the resin composition (A'-1), the resin composition (A'-2 to 10)
) Got.

(Resin composition B'-1 to 4-2)
According to the composition in Table 2, in the same manner as the resin composition (A'-1), the resin composition for comparative example (B'-
1, 2, 3-2, 4-2) were obtained.
Since the modified resins B-3 and B-4 had poor solubility in DPHA, comparative resin compositions (B'-3-1) and (B'-4-1) could be obtained. Did not.

Samples of Examples 1 to 10 and Comparative Examples 1 to 4 were obtained by mixing the resin composition and the initiator according to the composition shown in Table 3. The adhesion of the obtained sample to the PET substrate was evaluated, and the results are shown in Table 3.

<Adhesion test>
The adhesion was measured by applying a sample for adhesion to a corona-treated PET substrate (A-PET sheet Novaclear A2012 manufactured by Mitsubishi Chemical Corporation, thickness: 0.25 mm) using an RI tester (simple color developing machine). Then, it was cured using a metal halide lamp (output: 160 W / cm ² , lamp distance: 10 cm, conveyor speed: 30 m / min, number of passes: 2). A cellophane tape (manufactured by Nichiban Co., width 18 mm) is attached to the cured coating film, rubbed 10 times from the upper surface with a thumb, and the cellophane tape is sufficiently adhered to the coated surface, and then the cellophane tape is peeled off at 90 °. Judgment was made based on the degree of adhesion of the coating film to the substrate when the coating was performed.
(Evaluation criteria)
◎: The cured film is not peeled off at all. ○: The cured film remains at 75% or more and less than 100%. Δ: The cured film remains at 50% or more and less than 75%. X: The cured film remains at less than 50%.

  From Examples 1 to 10, it was found that the resin composition of the present invention was excellent in adhesion.

(Examples 11 to 20, Comparative Examples 5 to 8)
According to the compositions in Table 4, the active energy ray-curable inks of Examples 11 to 20 and Comparative Examples 5 to 8 were obtained by kneading with a three-roll mill. The "viscosity" and "fluidity" of the obtained active energy ray-curable ink composition were measured, and the "dot gain" of the printed matter and the "ink fountain escape" on a printing machine were examined. Table 4 also shows the results.

<Measurement method of viscosity>
The viscosity was measured using a viscoelasticity measuring device (H
AAKE RheoStress 6000) was used at a measurement temperature of 25 ° C. and a cone plate (diameter: 20 mm, tilt angle: 0.5 °).

<Method of measuring fluidity>
After placing 2.1 cc of the ink in a metal plate having a hemispherical dent and allowing it to stand for 2 minutes, the length of the ink flowing at an angle of 60 ° for 10 minutes was measured, and the evaluation was performed based on the following evaluation criteria. Was. The higher the value, the less tightness of the ink and the better the fluidity.
(Evaluation criteria)
◎: 70 mm or more ○: 50 mm or more to less than 70 mm ×: less than 50 mm

Next, printing was performed at a speed of 10,000 sheets / hour (curing conditions: metal halide lamp, 160) by an actual offset sheet-fed printing press LITHRONE L426 (Komori Corporation).
W / cm ² ), and it was confirmed that the ink on the printed matter was sufficiently cured.
<Dot gain evaluation method for printed matter>

Printing was performed under the printing conditions described above, and how much 50% halftone dots on the plate surface had expanded (dot gain) in the printed material at the end of printing 5000 sheets was determined by Spectr manufactured by GretagMacbeth.
It was measured using oEye.
(Evaluation criteria)
：: dot gain of 10% or more ×: dot gain of less than 10%

<Method for measuring ink fountain escape>
Printing was performed under the above printing conditions, and it was observed whether or not an ink fountain escaped in which the ink was not scraped off by the supply roller in the ink fountain during printing.
(Evaluation criteria)
：: Not generated for 20 minutes or more ：: Not generated for 10 minutes to less than 20 minutes ×: Generated for less than 10 minutes

The inks of Examples 11 to 20 of the present invention are superior to the inks of Comparative Examples 5 to 8 in any evaluation of the fluidity of the ink, the escape of the ink fountain during printing, and the dot gain of the printed matter,
It was found that an active energy ray-curable ink capable of solving problems during printing can be obtained.

In the resin composition of the present invention, the carboxylic acid of the resin can be effectively adsorbed on the surface of an organic pigment, inorganic fine particles, or the like, and a stable dispersion can be formed. Therefore, various printing inks, paints,
Useful for coatings, photoresists, etc.

Claims (3)

A resin composition comprising a modified diallyl phthalate resin (A) and a monomer having a radical polymerizable double bond,
The modified diallyl phthalate resin (A) is a reaction product of a thiol compound having an organic acid structure and a diallyl phthalate resin,
The modified diallyl phthalate resin (A) has an acid value of 2.5 to 50.0 (mg KOH /
g) a resin composition,   An active energy ray-curable ink comprising the resin composition according to claim 1. A printed material obtained by printing the active energy ray-curable ink according to claim 2 on a base material and curing with the active energy ray.