TW201510058A - Active energy ray-curable composition, active energy ray-curable printing ink comprising same, and printed matter - Google Patents

Abstract

Provided are: an active energy ray-curable composition which can exhibit high curability when used in a printing ink, and has excellent emulsion aptitude and offset printing aptitude; an active energy ray-curable printing ink which has all of excellent curability, emulsifying properties and offset printing aptitude; and a printed matter produced using the printing ink. Specifically, the active energy ray-curable composition contains, as essential components, (A) a resin containing a polymerizable unsaturated group and (B) a polymerization initiator, wherein the resin (A) is produced by reacting an epoxy resin with a monocarboxylic acid having a polymerizable unsaturated group, and wherein the ratio of the number of [alpha]-glycol groups relative to the total number of terminal structural moieties induced by or derived from a glycidyloxy group is 5 mol% or less as measured by 13C-NMR measurement.

Description

Active energy ray-curable composition, active energy ray-curable printing ink and printed matter using the same

The present invention relates to an active energy ray-curable composition which is useful as a raw material of an active energy ray-curable ink or the like. Further, it relates to an active energy ray-curable printing ink and a printed matter using the composition.

The active energy ray-curable composition is excellent in hardness and scratch resistance due to less heat history to the coated substrate, and is used for hard coating agents, papers, and the like for various plastic substrates such as home electric appliances and mobile phones. Protective layer agents, adhesives for printing inks, solder resists, and other fields. Among them, an epoxy acrylate resin obtained by adding an epoxy resin or acrylic acid or methacrylic acid is used as a material excellent in adhesion to a substrate and adhesion, and is used in various fields (for example, see Patent Document 1).

However, when the epoxy acrylate is used as a binder for printing inks, particularly when used as a lithographic ink, there is a disadvantage that emulsification suitability which is considered to be indispensable is poor. That is, the ink and water are simultaneously and continuously supplied to the layout, and the repulsion of the ink and the water is utilized, whereby the emulsification suitability for the ink is required in the lithography for image formation, but the above epoxy acrylate is used. The hydrophilicity is strong, and the characteristics of appropriately releasing the emulsified water are inferior. Therefore, there are many cases where the ink is excessively emulsified during printing, and printing failure such as a decrease in printing density occurs. On the other hand, as an active energy ray-curable UV (Ultraviolet) ink which is excellent in emulsification characteristics, a technique of using a rosin-modified phenol resin as a varnish and an active energy ray-curable monomer is known (for example, refer to the patent literature). 2). however, Since the rosin-modified phenol resin does not have polymerizability to the active energy ray, there is a problem that the hardenability of the ink itself is lowered.

As described above, as the active energy ray-curable printing ink, it has not been obtained that it exhibits high hardenability, and a high emulsifying suitability is obtained.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-218620

[Patent Document 2] Japanese Patent No. 4734490

Accordingly, an object of the present invention is to provide an active energy ray-curable composition which exhibits high hardenability in the case of printing ink and which has excellent emulsification suitability and lithographic suitability, and is excellent in both. An active energy ray-curable printing ink having curable, emulsifiable, and lithographic suitability, and a printed matter thereof.

In order to solve the above problems, the inventors of the present invention have made an effort to study the results, and have found that a polymerizable unsaturated group obtained by modifying an epoxy resin (A) with a monocarboxylic acid (B) having a polymerizable unsaturated group is used. The resin exhibits excellent hardening by adjusting the ratio of the α-diol group in the total number of terminal structural portions of the resin to a ratio of 5 mol% or less as a result of ¹³ C-NMR measurement. The emulsification characteristics of the printing ink itself are drastically improved, and good printing characteristics are obtained, thereby completing the present invention.

In other words, the present invention provides an active energy ray-curable composition which comprises an epoxy resin and a polymerizable unsaturated group-containing resin obtained by reacting a monocarboxylic acid having a polymerizable unsaturated group. Further, the ratio of the α-diol group to the total number of terminal structure sites derived from or derived from the glycidoxy group in the epoxy resin is a ratio of 5 mol% or less based on the result of ¹³ C-NMR measurement. The polymerizable unsaturated group-containing resin (A) and the polymerization initiator (B) are essential components.

The present invention further provides an active energy ray-curable printing ink comprising the active energy ray-curable composition.

The present invention further provides a printed matter which is printed using the above active energy ray-curable printing ink.

According to the present invention, it is possible to provide an active energy ray-curable composition which exhibits high hardenability in the case of printing ink, and which has excellent emulsification suitability and lithographic suitability, and has excellent hardenability and emulsification. Sexual, lithographically compatible active energy ray-curable printing inks, and printed matter thereof.

1‧‧‧Inner cylinder drive motor

2‧‧‧Inner tube

3‧‧‧Outer tube

4‧‧‧Constant water tank

5‧‧‧Outer cylinder drive motor

6‧‧‧Water supply

7‧‧‧Evaluation of adhesives

Fig. 1 is a cross-sectional view of a Ductet tester (manufactured by Kawamura Riken) for use in an emulsification suitability evaluation test.

The active energy ray-curable composition of the present invention is characterized in that it is an epoxy resin, a polymerizable unsaturated group-containing resin obtained by reacting a carboxylic acid having a polymerizable unsaturated group, and a terminal structural portion thereof. The α-diol structural moiety is present in a ratio of 5 mol% or less.

Here, in the resin containing a polymerizable unsaturated group, the terminal structure portion derived from or derived from the glycidoxy group in the epoxy resin means that the epoxy group in the raw material epoxy resin has Any terminal structure site generated by the reaction of a carboxylic acid of a polymerizable unsaturated group, or an epoxy group remaining in an unreacted state, specifically, the following structural formula (i) to (vi)

(In the structural formulae (i) to (iv), R ¹ and R ² are a hydrogen atom or a methyl group)

Various end structures are indicated.

In the present invention, the content of the α-diol structural moiety represented by the above structural formula (v) is adjusted to a ratio of 5 mol% or less in the total number of terminal structures which can be measured by ¹³ C-NMR. The printing ink using the polymerizable unsaturated group-containing resin has good hardenability and exhibits excellent emulsifying properties. In particular, when the content is 3 mol% or less, it is preferable in the case where lithographic printing is performed as a printing ink, and printing characteristics are particularly excellent.

Furthermore, in the present invention, it is not necessary to include all of the above various terminal structures (the above structural formulas (i) to (vi)), based on the total number of terminal structures selected from the above, as long as the above-mentioned α-diol structural moiety The content is preferably 5 mol% or less.

Here, the existence ratio of the above structural formulae (i) to (vi) can be measured by ¹³ C-NMR as described above, and specifically, the area ratio of each peak of a carbon atom represented by the following * can be used. Export. Further, in the case where each peak is repeated with other carbon atoms in other structures, the ratio of the other carbon atoms may be removed, and the ratio may be determined.

(In the structural formulae (i) to (iv), R ¹ and R ² are a hydrogen atom or a methyl group).

Here, the measurement method of ¹³ C-NMR can be carried out under the following conditions.

[Model] JNM-ECA500 manufactured by JEOL

[Measurement conditions]

Sample concentration: 30% (w/v)

Determination of solvent: DMSO-d6

Cumulative number: 4000 times

In the present invention, the ratio of the existence of each terminal structure portion of the above structural formulas (i) to (vi) is as described above, and the α-diol structure portion represented by the structural formula (v) may be 5 mol% or less. More preferably, it is 3 mol% or less, and in terms of hardenability and emulsifying property, it is preferable that the other terminal structural part is 70 mol% or more of the α addition structure part represented by the structural formula (i), for example. More specifically, the α addition structure site represented by the structural formula (i) is 70 mol% or more, and the α addition structure site represented by the structural formula (i) and the structural formula (ii) are represented. The total of the β addition structure sites is a ratio of 84% or more. In addition, it is preferable that the αβ addition structure portion represented by the above structural formula (iii) is 5 mol% or less in terms of emulsifiability, and it is preferable that the curability is good. The structure of the structure represented by the above formula (iv) in the α addition structure and the methic acid addition structure of the monocarboxylic acid having a polymerizable unsaturated group is a ratio of 8 mol% or less. In addition, the epoxy group represented by the above formula (vi) is an epoxy group remaining in an unreacted state, and the ratio of the epoxy group is preferably 2 mol% or less, and particularly preferably 1 mol% or less.

Further, the epoxy resin is preferably a compound having two or more epoxy groups in one molecule, and specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S. Epoxy resin, bisphenol AD epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, hydrogenated bisphenol S epoxy resin, hydrogenated bisphenol AD epoxy resin, four Bisphenol epoxy resin such as bromine bisphenol A epoxy resin; o-cresol novolac epoxy resin; phenol novolak epoxy resin, naphthol novolac epoxy resin, bisphenol A phenolic epoxy resin, bromine Phenolic epoxy resin such as phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, bisphenol S phenolic epoxy resin, methoxy-containing phenolic epoxy resin, brominated phenol novolac epoxy resin In addition, phenol aralkyl type epoxy resin (known as epoxide of ZYLOCK resin), diglycidyl ether of resorcinol, diglycidyl ether of hydroquinone, diglycidyl ether of catechol , biphenyl type epoxy resin, tetramethyl Bifunctional epoxy resin such as biphenyl type epoxy resin; triglycidyl isocyanurate, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition A reactive epoxy resin, a biphenyl-modified novolac type epoxy resin (epoxide of a polyphenol resin in which a bisphenol is bonded to a phenol core), a methoxy-containing phenol aralkyl resin, or the like. Further, the above epoxy resins may be used singly or in combination of two or more.

Among these, in terms of printability, a bisphenol type epoxy resin or a novolac type epoxy resin is preferred, and the emulsion property is excellent, and in the case of use as a printing ink, excellent printability is obtained. In particular, bisphenol type epoxy resins having an epoxy equivalent in the range of 170 to 500 g/eq, especially bisphenol A type epoxy resins, are preferred.

On the other hand, the monocarboxylic acid having a polymerizable unsaturated group which is reacted with the above epoxy resin may, for example, be acrylic acid, methacrylic acid or crotonic acid, and particularly preferably acrylic acid, in terms of printability. Methacrylic acid, especially acrylic acid.

The polymerizable unsaturated group-containing resin (A) used in the present invention can be produced by reacting an epoxy resin with the above-mentioned carboxylic acid having a polymerizable unsaturated group as described above, and specifically, it is easy to In the aspect where the amount of the α-diol is reduced to 5 mol% or less, it is preferred to carry out the reaction in the presence of a basic catalyst containing a nitrogen atom.

The above nitrogen atom-containing basic catalyst used herein is a basic compound having a nitrogen atom. Examples of the nitrogen atom-containing basic catalyst include primary amines such as n-butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, and benzylamine, and diethylamine and dipropyl groups. a cyclic secondary amine such as an amine, diisopropylamine or dibutylamine, aziridine, azetidine, pyrrolidine, piperidine, azepane, azacyclooctane, etc. Amines and secondary amines such as alkyl substituents, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylamine, 1,4-diaza Bicyclo[2.2.2]octane, quinine ring And an aliphatic tertiary amine such as 3-quinol, an aromatic tertiary amine such as dimethylaniline, and a heterocyclic tertiary amine such as isoquinoline, pyridine, trimethylpyridine or β-methylpyridine, or imidazole , hydrazine, triazole, hydrazine, etc. 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]nona-5-ene (DBN), etc. A basic catalyst containing a nitrogen atom such as a tertiary hydrazine. These basic nitrogen-containing catalysts may be used singly or in combination of two or more.

Among the basic catalysts containing a nitrogen atom, it is preferred to reduce the amount of the α-diol in the polymerizable unsaturated group-containing resin to 5% or less, preferably triethylamine or chlorine. Tetramethylammonium.

Here, in terms of reducing the amount of the α-diol in the polymerizable unsaturated group-containing resin and improving the emulsifying property, the amount of the above-mentioned nitrogen atom-containing basic catalyst is relative to the raw material component. The total mass is 100 parts by mass, preferably 0.01 to 0.6 parts by mass, more preferably 0.03 to 0.5 parts by mass, and even more preferably 0.05 to 0.3 parts by mass.

Moreover, the method of producing the above polymerizable unsaturated group-containing resin (A) is preferably as follows in terms of reducing the amount of the α-diol in the polymerizable unsaturated group-containing resin to 5% or less. : a range in which an epoxy resin and a carboxylic acid having a polymerizable unsaturated group are in the presence of a basic catalyst containing a nitrogen atom, and an epoxy group and a carboxyl group are in a range of 0.9/1.0 to 1.0/0.9 (mole ratio) In addition, the ratio is 0.01 to 0.6 parts by mass, preferably 0.03 to 0.5 parts by mass, and particularly 0.05 to 0.3 parts by mass, based on 100 parts by mass of the total weight of the raw material components. The reaction is carried out at a reaction temperature of 80 to 125 ° C, preferably 90 to 110 ° C until the epoxy equivalent becomes 8000 g/eq or more or the acid value becomes 2.0 or less.

Further, in the reaction of the above epoxy resin with a carboxylic acid having a polymerizable unsaturated group, a radical polymerizable monomer which does not contain a site where a carboxyl group and an epoxy group are reacted may be used as a reaction solvent in the reaction solvent. get on.

Examples of the radical polymerizable monomer which does not contain a moiety which reacts with a carboxyl group and an epoxy group include N-vinylpyrrolidone and propylene oxime. Porphyrin, dicyclopentadienyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, Phenyloxyethyl methacrylate, butoxyethyl (meth) acrylate, (meth) acrylate Mono(meth) acrylate such as monoester (meth) acrylate of phenol, bisphenol F, mono(meth) acrylate of alkylene oxide addition bisphenol F; ethylene glycol di(meth) acrylate, Dicyclopentenyl (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dimethylol tricyclodecane diacrylate, tripropylene glycol Di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, alkylene oxide addition 1,6-hexanediol Di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol Ester di(meth)acrylate, bis(meth)acrylate of bisphenol A, di(meth)acrylate of bisphenol F, di(meth)acrylate of alkylene oxide addition bisphenol A , an alkylene oxide addition bisphenol F bis(meth) acrylate such as di(meth) acrylate; trimethylolpropane tri (meth) acrylate, alkylene oxide addition trimethylolpropane three Tris(methyl)propene such as (meth) acrylate or pentaerythritol triacrylate Ethyl ester; hexaacrylate of dipentaerythritol.

As described above, the polymerizable unsaturated group-containing resin (A) obtained in this manner preferably has an epoxy equivalent of 8000 g/eq or more or an acid value of 2.0 or less. In addition, in the case of producing a printing ink, a resin containing a polymerizable unsaturated group (A) is excellent in the anti-flying property and the roll transfer property in the case of producing a printing ink. Preferably, the solution viscosity of the non-volatile 80% by mass solution in the case of being dissolved in butyl acetate is in the range of 0.5 to 30 Pa s, and particularly preferably in the range of 1.0 to 10.0 in terms of the effects becoming apparent. The range of Pa‧s.

Then, the polymerization initiator (B) used in the present invention may, for example, be an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzoin dimethyl ketal. , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) Ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]-phenyl}-2-methyl Base-propan-1-one, 2,2-di Acetophenone-based compound such as methoxy-1,2-diphenylethane-1-one or 2,2-diethoxy-1,2-diphenylethane-1-one; 1-[ 4-(phenylthio)-2-(O-benzylidenehydrazide)], 1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl An oxazole compound such as -1-(O-ethinyl hydrazine) or an oxazole compound such as 3,6-bis(2-methyl-2-morpholinopropanol)-9-butylcarbazole or benzoin a benzoin compound such as benzoin methyl ether or benzoin isopropyl ether;

2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl )-1-(4-morpholinylphenyl)butan-1-one, 2-methyl-2-morpholinyl ((4-methylthio)phenyl)propan-1-one, 2-benzyl Aminoalkylphenone compounds such as benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone; bis(2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-tri A mercaptophosphine oxide compound such as methyl-pentylphosphine oxide; benzophenone, methyl benzhydrazinecarboxylate or the like.

On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl phthalic acid benzoate-4-phenylbenzophenone, and 4,4'-dichloro bis. Benzophenone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra (peroxidation) a benzophenone compound such as a third butylcarbonyl)benzophenone or a 3,3'-dimethyl-4-methoxybenzophenone; a 2-isopropyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 9-oxosulfur a compound; an amine benzophenone compound such as 4,4'-bisdimethylaminobenzophenone or 4,4'-bisdiethylaminobenzophenone; in addition, 10- Butyl-2-chloroacridone, 2-ethylhydrazine, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators may be used singly or in combination of two or more. Among these, in particular, in terms of excellent hardenability, an aminoalkylphenone-based compound is preferable, and in particular, a UV-LED which generates ultraviolet rays having an emission peak wavelength of 350 to 420 nm is used. (Ultraviolet-Light Emitting Diode) When the light source is used as an active energy source, it is preferred to use an aminoalkylphenone compound and a mercaptophosphine in combination in terms of excellent hardenability. An organic compound and an aminobenzophenone-based compound.

The amount of the polymerization initiator (B) to be used is preferably in the range of 1 to 20 parts by mass based on the total amount of the non-volatile component in the active energy ray-curable composition of the present invention. . In other words, when the total amount of the polymerization initiator (B) used is 1 part by mass or more, good hardenability can be obtained, and in the case of 20 parts by mass or less, the initiation of unreacted polymerization can be avoided. The agent (B) has a problem that the physical properties such as migration, solvent resistance, and weather resistance caused by the residue in the cured product are lowered. In particular, it is more preferable that the total amount of the non-volatile component in the active energy ray-curable composition of the present invention is 3 to 15 parts by mass in terms of the better balance of performance of the active energy ray-curable composition of the present invention. The scope.

Further, when ultraviolet light is applied as an active energy ray to form a cured coating film, in addition to the above polymerization initiator (B), curability can be further improved by using a photosensitizer. Examples of the photosensitizer include an amine compound such as an aliphatic amine, a urea such as o-tolylthiourea, a sodium diethyl dithiophosphate, a sulfur compound such as s-benzylisothiourea-p-toluenesulfinate, and the like. . The amount of the photosensitizer to be used is preferably 100 parts by mass relative to the non-volatile component in the active energy ray-curable composition of the present invention in terms of the effect of improving the hardenability. It is calculated to be in the range of 1 to 20 parts by mass.

In the active energy ray-curable composition of the present invention, the polymerizable unsaturated group-containing resin (A) and the polymerization initiator (B) described above are essential components, and the present invention can be further used in combination with radical polymerizability. Monomer (C). Examples of the radical polymerizable monomer (C) include N-vinyl caprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, and N,N-dimethyl ( Methyl) acrylamide, acrylamide, propylene Porphyrin, 7-amino-3,7-dimethyloctyl (meth)acrylate, isobutoxymethyl (meth) acrylamide, trioctyl (meth) acrylamide, diacetone (Meth) acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyldiethyl Glycol (meth) acrylate, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylate Cyclopentenyl ester, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, tetrabromophenyl (meth) acrylate, ( 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxy (meth)acrylate Ethyl ethyl ester, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromyl (meth)acrylate, (methyl) acrylic acid Ester, methyl triethylene glycol (meth) acrylate, (meth) acrylate Monoester (meth) acrylate of ester, bisphenol F, mono(meth) acrylate of alkylene oxide addition bisphenol F; single {2-(methyl) propylene oxiranyl ethyl} acid phosphate Various vinyl-containing monomers containing a phosphate group; vinylsulfonic acid, allylsulfonic acid, 2-methylallylsulfonic acid, 4-vinylbenzenesulfonic acid, 2-(methyl)acryloxyloxy Various sulfonic acid group-containing vinyl monomers such as ethanesulfonic acid, 3-(meth)acryloxypropanesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid; and CH ₂ =CHCOO(CH) ₂ ) ₃ [Si(CH ₃ ) ₂ O]nSi(CH ₃ ) ₃ , CH ₂ =C(CH ₃ )COOC ₆ H ₄ [Si(CH ₃ ) ₂ O)]nSi(CH ₃ ) ₃ , CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ [Si(CH ₃ ) ₂ O]nSi(CH ₃ ) ₃ , CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ [Si(CH ₃ )(C ₆ H ₅ )O]nSi(CH ₃ ) ₃ , or CH ₂ =C(CH ₃ )COO(CH ₂ ) ₃ [Si(C ₆ H ₅ ) ₂ O]nSi(CH ₃ ) ₃ (wherein a medium containing n-oxyalkylene bonds represented by the general formula; n-(meth)acryloxypropyltrimethoxydecane, wherein n is set to 0 or an integer such as 1 to 130) Γ-(meth)acryloxypropyltriethoxydecane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-( Acryloxypropylmethyldiethoxydecane, γ-(meth)acryloxypropyltriisopropenyloxydecane, vinyltrimethoxydecane, vinyltriethoxydecane , vinyl (tri-β-methoxyethoxy) decane, vinyl triethoxy decane, vinyl trichloro decane or N-β-(N-vinylbenzylaminoethyl)-γ -Aminopropyltrimethoxydecane and its hydrochloride; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, poly a (meth) acrylate having a hydroxyl group such as propylene glycol mono(meth)acrylate, and an ε-caprolactone adduct of the monomers; 2-dimethylaminoethyl vinyl ether, 2-di Ethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether, 6-dimethylaminohexyl vinyl ether, etc. Various vinyl ethers of the amine; various vinyl ethers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether; or 2-hydroxyethoxyl Propyl ether, 4-hydroxybutoxy ally a monoether, or a di-allyl ether of trimethylolpropane, a mono- or penta-allyl ether, an allyl ether having a hydroxyl group, and an ε-hex of the monomers Lactone adduct; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclopentane Vinyl ether, vinyl ether such as cyclohexyl vinyl ether; ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, Tetraethylene glycol di(meth)acrylate, tricyclodecane di(meth)acrylate, dimethylol tricyclodecane diacrylate, tripropylene glycol di(meth)acrylate, 1,4- Butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl Di(meth)acrylate of diol di(meth)acrylate, neopentyl glycol hydroxypivalate, di(meth)acrylate of bisphenol A or F, alkylene oxide addition bisphenol A Or F bis (meth) acrylate; Bifunctional monomer such as divinyl esters of various dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, etc., such as divinyl methacrylate, trimethylolpropane tri(meth)acrylic acid Ester, alkylene oxide addition trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, alkylene oxide addition pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate Tris(meth)acrylate such as ester or alkylene oxide addition pentaerythritol tetra(meth)acrylate; penta(meth)acrylate of dipentaerythritol; penta(meth)acrylate of alkylene oxide addition dipentaerythritol And hexa(meth) acrylate of dipentaerythritol, hexa(meth) acrylate of alkylene oxide addition dipentaerythritol, and the ε-caprolactone adduct of the monomers.

Among these, in particular, in terms of excellent hardenability as printing ink, it is preferably five (meth) acrylate of dipentaerythritol and five ethylene oxide addition dipentaerythritol. (Meth) acrylate, hexa(meth) acrylate of dipentaerythritol, or hexa(meth) acrylate of alkylene oxide addition dipentaerythritol.

The active energy ray-curable composition of the present invention is particularly useful as an active energy ray-curable printing ink. In this case, a pigment, a dye, an extender pigment, an organic or inorganic filler, or an organic compound can be used as a formulation other than the above components. Solvents, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, weathering stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, pigment dispersants, waxes and other additives.

The active energy ray-curable composition of the present invention and the active energy ray-curable printing ink are printed on a substrate and then irradiated with an active energy ray to form a cured coating film. Examples of the active energy ray include free radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, especially in terms of hardenability, ultraviolet rays are preferred.

As the active energy ray for curing the active energy ray-curable composition of the present invention, as described above, it is an ultraviolet ray, an electron beam, an alpha ray, a beta ray, a gamma ray or the like, as a specific energy source or a curing device. For example, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a UV-LED, a carbon arc, a xenon lamp, a high pressure mercury lamp for photocopying, a medium or high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a metal halide lamp, and a natural light. Such as ultraviolet light from a light source, or an electron beam of a scanning type, a curtain type electron beam accelerator, or the like.

Further, as a pigment for the present invention the active energy ray curable printing inks, the known and include use of an organic coloring pigment, for example, "Organic Pigment Handbook (OF: Isao Hashimoto, Publisher: Color Office, 2006 year edition The organic pigment for printing ink disclosed in the above) may be a soluble azo pigment, an insoluble azo pigment, a condensed azo pigment, a metal phthalocyanine pigment, a metal-free phthalocyanine pigment, a quinacridone pigment, an anthraquinone pigment, or an anthracene. Pigment, isoindolinone pigment, isoporphyrin pigment, two Pigments, thioindigo pigments, lanthanide pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, carbon black pigments, other polycyclic pigments, and the like.

Further, in the active energy ray-curable printing ink of the present invention, inorganic may also be used. Microparticles are used as body pigments. Examples of the inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, and zinc white; calcium carbonate powder, precipitated calcium carbonate, gypsum, clay (porcelain), cerium oxide powder, diatomaceous earth, talc, kaolin, and aluminum white. An inorganic pigment such as an inorganic pigment such as barium sulfate, aluminum stearate, magnesium carbonate, barite powder or grindstone, or polyfluorene oxide or glass beads. These inorganic fine particles are used in an amount of 0.1 to 20 parts by mass in the ink, whereby an effect of adjusting the fluidity of the ink, preventing the ink mist, and preventing penetration into a printing substrate such as paper can be obtained.

Moreover, as a printing base material applied to the active energy ray-curable printing ink of the present invention, it can be used for catalogs, posters, advertisements, CD bags, direct mail, brochures, cosmetics or beverages, pharmaceuticals, toys, and machines. Paper substrates such as packaging materials such as polypropylene film and polyethylene terephthalate (PET) film, such as films for various food packaging materials, aluminum foil, synthetic paper, and other previously used as printing substrates. A variety of substrates.

Moreover, examples of the printing method of the active energy ray-curable printing ink of the present invention include lithographic offset printing, letterpress printing, gravure printing, gravure lithography, flexographic printing, and screen printing.

The present invention is preferably used in lithographic pattern printing in which water is continuously supplied to the printing plate in terms of improvement in emulsification characteristics of the ink. The lithographic printing machine that continuously supplies water is manufactured and sold by most printing machine manufacturers. For example, Heidelberg, KOMORI Corporation, Mitsubishi Heavy Industries Printing and Paper Machinery, Manroland, RYOBI, KBA, etc. The present invention can be preferably utilized in a single-plate lithographic printing machine for sheet-shaped printing paper, a lithographic rotary printing machine using a printing paper in a reel form, and any paper supply method. More specifically, a lithographic printing machine such as the Speedmaster series manufactured by Heidelberg Co., Ltd., the Lithrone series manufactured by KOMORI Corporation, and the DIAMOND series manufactured by Mitsubishi Heavy Industries Printing and Paper Machinery Co., Ltd. may be mentioned.

[Examples]

The invention is illustrated in more detail below by way of examples. Furthermore, the invention is not limited to the embodiments.

[Analysis method of epoxide end group amount of epoxy acrylate]

The amount of the diol terminal group of the polymerizable unsaturated group-containing resins (1) to (4) and (R1) to (R3) produced in Examples 1 to 4 and Comparative Examples 1 to 3 by ¹³ C-NMR. Analyze.

Specifically, an α addition structure, a β addition structure, an αβ addition structure, an α-diol, and the above α addition, which are represented by the following structural formulas of the terminal structure of each of the polymerizable unsaturated group-containing resins; The structure and the methic acid addition structure of the acryl-added acrylic acid, and the ratio of the existence of the carbon atom represented by the * mark of the residual epoxy group, and the molar ratio of each functional group is calculated from the peak area ratio of the ¹³ C-NMR chart. Ratio, and use the percentage of these to evaluate.

In the case where the chemical shift of each carbon atom represented by A to G in the following structural formulas (1) to (7) is set to 39.5 ppm as the peak of DMSO-d6 as the measurement solvent, the following is as follows. Said.

Chemical shift of carbon atom shown by A: 71.1 ppm

Chemical shift of carbon atom shown by B: 65.6 ppm

Chemical shift of carbon atom represented by C: 63.0 ppm

Chemical shift of carbon atom indicated by D: 62.5 ppm

Chemical shift of carbon atom represented by E: 59.7ppm

Chemical shift of carbon atom indicated by F: 60.0 ppm

Chemical shift of carbon atom represented by G: 43.9 ppm

Further, the peak of the carbon atom (indicated by B) attached to the * mark of the α addition structure of the following structural formula (1) and the structural part existing in the resin structure represented by the following structural formula (6) * The carbon atoms of the mark (the one shown by B) overlap, and the ratio of the existence of the α addition structure is obtained by subtracting the peak area of the carbon atom shown by A in the following structural formula (6) from the peak area of B. value.

(Measurement conditions of ¹³ C-NMR)

[Model] JNM-ECA500 manufactured by JEOL

[Measurement conditions]

Sample concentration: 30% (w/v)

Determination of solvent: DMSO-d6

Cumulative number: 4000 times

Example 1

In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, a liquid bisphenol A type epoxy resin ("Epiclon 850" manufactured by DIC Corporation, epoxide equivalent: 188 g/eq.); hereinafter referred to as "liquid BPA" 435.1 parts by mass, 163.6 parts by mass of acrylic acid, and 0.1 parts by mass of p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, triethylamine was added (touch Medium; the following is abbreviated as "TEA") 1.2 parts by mass. The reaction was carried out at 100 ° C for 15 hours to obtain an epoxy group having an epoxy equivalent of 18,000 g/eq., an acid value of 0.4 mgKOH/g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 1.8 Pa·s. Unsaturated resin (1). The ratio of the existence of each terminal structure portion based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (1) is shown in Table 1.

Example 2

In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, a liquid bisphenol A type epoxy resin ("Epiclon 850" manufactured by DIC Corporation, epoxide equivalent: 188 g/eq.); hereinafter referred to as "liquid BPA" 435.1 parts by mass, 163.6 parts by mass of acrylic acid, and 0.1 parts by mass of p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, tetramethylammonium chloride was added. (catalyst; hereinafter abbreviated as "TMAC") 1.2 parts by mass. The reaction was carried out at 100 ° C for 15 hours, thereby obtaining an epoxy equivalent of 14,000 g/eq., an acid value of 0.8 mgKOH/g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 1.3 Pa·s. Polymerizable unsaturated group resin (2). The ratio of the existence of each terminal structure portion based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (2) is shown in Table 1.

Example 3

In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, a liquid bisphenol A type epoxy resin ("Epiclon 850" manufactured by DIC Corporation, epoxide equivalent: 188 g/eq.); hereinafter referred to as "liquid BPA" 435.1 parts by mass, 163.6 parts by mass of acrylic acid, and 0.1 parts by mass of p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, 2-ethyl-4 was added. - Methylimidazole (catalyst; hereinafter abbreviated as "2E4MZ") 1.2 parts by mass. The reaction was carried out at 100 ° C for 15 hours, thereby obtaining an epoxy equivalent of 24,000 g / eq., an acid value of 0.3 mg KOH / g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 1.4 Pa ‧ Polymerizable unsaturated group resin (3). The ratio of the existence of each terminal structure portion based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (3) is shown in Table 1.

Example 4

A phenolic novolac epoxy resin ("EPICLON N-660" manufactured by DIC Corporation, epoxy equivalent 210 g/eq.) was added to a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube; Epoxy resin") 448.4 parts by mass, acrylic acid 150.9 parts by mass, and p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ") 0.1 parts by mass, and after heating to 100 ° C, triethylamine (catalyst added) ; The following is abbreviated as "TEA") 0.6 parts by mass. The reaction was carried out at 100 ° C for 15 hours, thereby obtaining an epoxy equivalent of 18,000 g/eq., an acid value of 0.4 mgKOH/g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 14.5 Pa·s. Polymerizable unsaturated group resin (4). The ratio of the existence of each terminal structure portion based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (4) is shown in Table 1.

Comparative example 1

In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, a liquid bisphenol A type epoxy resin ("EPICLON 850" manufactured by DIC Corporation, epoxide equivalent: 188 g/eq.); 435.1 parts by mass of BPA type epoxy resin), 163.6 parts by mass of acrylic acid, and 0.1 parts by mass of p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, triphenylphosphine ( Catalyst; the following is abbreviated as "TPP") 1.2 parts by mass. The reaction was carried out at 100 ° C for 15 hours, thereby obtaining an epoxy equivalent of 20,000 g / eq., an acid value of 0.5 mg KOH / g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 1.8 Pa ‧ Polymerizable unsaturated group resin (R1). The ratio of the existence of each terminal structure portion based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (R1) is shown in Table 2.

Comparative example 2

In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, a liquid bisphenol A type epoxy resin ("EPICLON 850" manufactured by DIC Corporation, epoxide equivalent: 188 g/eq.); 435.1 parts by mass of BPA type epoxy resin), 163.6 parts by mass of acrylic acid, and 0.1 parts by mass of p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 130 ° C, triethylamine was added ( Catalyst; the following is abbreviated as "TEA") 1.2 parts by mass. The reaction was carried out at 130 ° C for 15 hours, thereby obtaining an epoxy equivalent of 25,000 g / eq., an acid value of 0.2 mg KOH / g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 2.0 Pa ‧ Polymerizable unsaturated group resin (R2). The ratio of the existence of each terminal structure portion based on the ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (R2) is shown in Table 2.

Comparative example 3

In a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube, a liquid bisphenol A type epoxy resin ("Epiclon 850" manufactured by DIC Corporation, epoxide equivalent: 188 g/eq.); hereinafter referred to as "liquid BPA" 435.1 parts by mass, 163.6 parts by mass of acrylic acid, and 0.1 parts by mass of p-methoxyphenol (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, triethylamine was added (touch Medium; the following is abbreviated as "TEA") 6.0 parts by mass. The reaction was carried out at 100 ° C for 15 hours, thereby obtaining an epoxy equivalent of 20,000 g / eq., an acid value of 0.2 mg KOH / g, and a solution viscosity (butyl acetate nonvolatile matter 80 mass solution) of 1.2 Pa ‧ Polymerizable unsaturated group resin (R3). The ratio of the existence of each terminal structure portion based on ¹³ C-NMR of the obtained polymerizable unsaturated group-containing resin (R3) is shown in Table 2.

[Preparation of active energy ray-curable adhesive for evaluation of emulsification suitability]

In order to more clearly show the effect of improving the emulsifiability of the present invention, 83 parts by mass of each of the polymerizable unsaturated group-containing resins (1) to (4) and (R1) to (R3) is added as an active energy ray polymerization. 17 parts by mass of ethylene oxide-modified pentaerythritol tetraacrylate ("SR494" manufactured by Sartomer Co., Ltd.) of an acrylate monomer and mixed, thereby obtaining an active energy ray-curable adhesive (T1) for evaluation of emulsification suitability ~(T4) and (TR1)~(TR3).

[Evaluation method of emulsifying property of active energy ray-curable adhesive]

The emulsification suitability evaluation of the adjusted active energy ray-curable adhesives (T1) to (T4) and (TR1) to (TR3) was carried out using a Ductet tester (manufactured by Kawamura Riken).

A cross-sectional view of the Ductet tester is shown in Fig. 1. The outer cylinder 3 is a cylindrical metal having a bottom surface which is dug inside, and is configured to be internally filled with the evaluation adhesive 7. After the adhesive 7 (5 g) was put in, as shown in Fig. 1, the inner cylinder 2 as a cylindrical rod-shaped metal was inserted until it was close to a distance of 1 mm from the bottom surface of the outer cylinder 3. Thereafter, the inner cylinder was rotated clockwise at 2000 rpm, and the outer cylinder was rotated clockwise at 60 rpm, and a shear force was applied to the adhesive 7 by stirring the speed difference to stir. After stirring for 3 minutes, the distilled water was added dropwise directly above the binder 7 at a rate of 0.5 (g/min) while stirring, whereby the binder 7 was immediately stirred and mixed with the distilled water (emulsified). . The dropwise addition of distilled water was continued for 10 minutes, and the end of the time when the dropwise addition amount of distilled water reached a total of 5 g was completed.

The Ductet tester has a structure in which the outer cylinder 3 is rotated by the outer cylinder drive motor 5, the inner cylinder 2 is rotated by the inner cylinder drive motor 1, and the temperature of the adhesive 7 in the outer cylinder 3 is fixed. The constant temperature water tank 4 keeps the temperature of the tap water 6 at 30 °C.

After the agitation of the binder 7 (5 g) and distilled water (5 g) was completed, the weight (g) of the remaining distilled water (water remaining without being absorbed into the binder) inside the inner cylinder 2 was weighed. Thereby, the total weight Y of the distilled water absorbed into the binder 7 is

Y (g) = all distilled water (5 grams) - the weight of the remaining distilled water

As shown, the emulsification rate Z of the adhesive 7 is determined by

Z (%) = Y ÷ (adhesive 7 (5 grams) + Y) × 100

Shown.

(Here, for example, when 5 g of distilled water to be charged is all absorbed into the binder, and when the remaining distilled water is 0 g, Y = 5 (g), Z = 50 (%)) is calculated.

The lower the value of the binder emulsification rate Z (%), the more excellent the characteristics of the emulsified water are appropriately excluded, and the lithographic suitability of the ink described below is more excellent, and it is less likely to cause excessive emulsification or a decrease in concentration due to the like. malfunction. The emulsification suitability was evaluated according to the following criteria.

3: The emulsification rate Z (%) is less than 25%, and the emulsification suitability is good.

2: The emulsification rate Z (%) is 25% or more - less than 35%, and the emulsification is moderate.

1: The emulsification rate Z (%) is 35% or more, and the emulsification suitability is poor.

[Preparation of active energy ray-curable printing ink]

In an amount of 34.5 parts by mass of the polymerizable unsaturated group-containing resin (1) obtained in the above Example 1, and 19 parts by mass of a blue pigment ("HELIOGEN BLUE D7079" manufactured by BASF Corporation, Pigment Blue 15:3), 10 parts by mass of dipentaerythritol hexaacrylate ("DPHA" manufactured by Sartomer Co., Ltd.) of active energy ray-curable acrylate monomer, and di-trimethylolpropane tetraacrylate ("SR355NS" manufactured by Sartomer Co., Ltd.) 21.95 mass 5 parts by weight of trimethylolpropane triacrylate ("MIRAMER M-300" manufactured by MIWON Co., Ltd.), and as a body pigment ("Hi-Filler #5000PJ" hydrated magnesium citrate manufactured by Matsumura Industry Co., Ltd.) 2 Parts by mass and basic magnesium carbonate ("Magnesium Carbonate TT" manufactured by Naikai Salt Industries Co., Ltd.) 0.5 parts by mass as wax 1 part by mass ("S-381-N1" polyolefin wax) manufactured by SHAMROCK Co., Ltd. as a photopolymerization initiator ("Irgacure907" 2-methyl-1-[4-(methylthio) manufactured by BASF Corporation) ) phenyl]-2-morpholinol-1-one) 3.5 parts by mass as a photoinitiator ("EAB-SS" 4,4'-bis(diethylamino) manufactured by Datong Chemical Industry Co., Ltd. 2 parts by mass of benzophenone, as a polymerization inhibitor ("Q1301" N-nitrosophenylhydroxylamine aluminum manufactured by Wako Pure Chemical Co., Ltd.), 0.05 parts by mass of all the raw materials (total 100 parts by mass), The mixture was stirred using a mixer (uniaxial dispersion mixer), and thereafter, ink was pulverized using a three-roll mill, whereby an active energy ray-curable ink (I1) was obtained.

Hereinafter, in the same manner, the other polymerizable unsaturated group-containing resins (2) to (4) and (R1) to (R3) are also produced in the same manner using the same mass of the above-mentioned raw materials. Thereby, active energy ray-curable inks (I2) to (I4) and (IR1) to (IR3) are obtained.

[Manufacturing method of developing agent for evaluation of hardenability and solvent resistance]

The active energy ray-curable inks (I1) to (I4) and (IR1) to (IR4) obtained in this manner were used, and a simple color spreader (RI test machine, manufactured by Kyoei Seiko Co., Ltd.) was used, and 0.10 ml of ink was used. Uniformly stretched on the rubber roller and metal roller of the RI tester, on the surface of the coated paper ("OK Topcoat+57.5kg, A-open" manufactured by Oji Paper Co., Ltd.), covering an area of approximately 200cm ² in blue The concentration was 1.6 (measured by a SpectroEye concentration meter manufactured by X-Rite Co., Ltd.), and the color development was carried out by uniformly spreading the color developing agent. Furthermore, the so-called RI testing machine is a testing machine for developing ink on paper or film, and can adjust the amount of ink transfer or printing.

[Hardening method using UV light source]

Ultraviolet (UV) irradiation is applied to the toner after application of the ink to harden the ink film. Using a UV-irradiation device (manufactured by EYE GRAPHICS, Inc., with cold mirror) equipped with a water-cooled metal halide lamp (output 100W/cm1 lamp) and a belt conveyor, the toner is placed on the conveyor and made below Under the specific conditions described, it passes under the lamp (irradiation distance 11 cm). Ultraviolet radiation quantity system using ultraviolet light (Measured by UNIMETER UIT-150-A/Photoreceiver UVD-C365 manufactured by USHIO Electric Co., Ltd.).

[Evaluation method of active energy ray-curable ink: hardenability]

The curability is determined by the claw scratching method immediately after the irradiation to confirm the damage of the surface of the toner. The conveyor speed (m/min) at which the conveyor speed (m/min) of the UV irradiation device is changed to the surface toward the developer is irradiated with ultraviolet rays, and even if it is rubbed by the claws, the fastest conveyor speed (m/min) is not damaged. Therefore, the greater the value of the conveyor speed, the better the hardenability of the ink.

[Evaluation method of active energy ray-curable ink: solvent resistance]

The solvent resistance was confirmed by the solvent rubbing method immediately after the irradiation to confirm the damage of the surface of the printed matter. The toner was irradiated with ultraviolet rays at a conveyor speed of 50 (m/min) of the above-described UV irradiation device to harden the ink. After the hardening, the state change of the surface friction of the evaluation ink-cured coating film by the cotton swab containing ethanol was visually observed, and the solvent resistance was evaluated based on the following criteria.

3: No change

2: Residual scratches

1: The ink hardened coating film disappears, and the substrate (paper) can be confirmed.

[Living method of active energy ray-curable ink]

The lithographic suitability was evaluated for the active energy ray-curable inks (I1) to (I4) and (IR1) to (IR3). A lithographic printing machine (Roland R700 printing machine, width 40 ) machine) manufactured by Manroland Co., Ltd., which is equipped with a water-cooled metal halide lamp (output of 160 W/cm, 3 lamps) manufactured by EYE GRAPHICS, Inc., which is an ultraviolet irradiation device, is used. Lithographic printing was carried out at a printing speed of 9000 sheets per hour. For printing paper, OK Topcoat+ (57.5kg, A-book) manufactured by Oji Paper Co., Ltd. was used. The wetting liquid supplied to the plate was mixed with an aqueous solution containing 98 parts by mass of tap water and 2 parts by mass of an erosive liquid (FST-700, manufactured by DIC Corporation).

[Evaluation method of active energy ray-curable ink: printability]

As a method for evaluating the suitability of lithographic ink printing, first, the water supply dial of the printing press is set to 40 (standard water amount), and the printed matter concentration becomes a standard process blue density of 1.6 (measured by a SpectroEye concentration meter manufactured by X-Rite Co., Ltd.) The ink supply button is operated in such a manner that the ink supply button is fixed at a time point when the concentration is stabilized.

Then, under the condition that the ink supply button was fixed, 300 sheets were printed under the condition that the water supply dial was changed from 40 to 55, and the water supply amount was increased, and the blue density of the printed matter after 300 sheets was measured. In other words, in the state in which the amount of water supplied is increased, the decrease in the concentration of the printed matter is smaller, and it is possible to evaluate the ink which is excellent in emulsifiability and excellent in printability. The printability of the active energy ray-curable ink was evaluated in accordance with the following criteria.

3: The blue density of printed matter is 1.5 or more

2: The blue concentration of printed matter is 1.4 or more ~ less than 1.5

1: The blue density of printed matter is less than 1.4

Claims (7)

An active energy ray-curable composition characterized by comprising an epoxy resin, a polymerizable unsaturated group-containing resin obtained by reacting a monocarboxylic acid having a polymerizable unsaturated group, and α-II The ratio of the alcohol group to the total number of terminal structure sites derived from or derived from the glycidoxy group in the above epoxy resin is a polymerizable unsaturated ratio which is 5 mol% or less as a result of ¹³ C-NMR measurement. The base resin (A) and the polymerization initiator (B) are essential components. The active energy ray-curable composition according to claim 1, wherein the terminal structural moiety derived from or derived from the glycidyloxy group in the epoxy resin (A) is selected from the following structural formulae (i) to (vi) The group of people: (In the structural formulae (i) to (iv), R ¹ and R ² are a hydrogen atom or a methyl group). The active energy ray-curable composition of claim 1, wherein the epoxy resin (A) is a bisphenol type epoxy resin. The active energy ray-curable composition of claim 1, wherein the above polymerizable property is not The carboxylic acid of the saturated group is (meth)acrylic acid. An active energy ray-curable printing ink characterized by containing the active energy ray-curable composition according to any one of claims 1 to 4. An active energy ray-curable printing ink according to claim 5, wherein the active energy ray-curable printing ink is lithographic ink. A printed matter obtained by printing the active energy ray-curable printing ink of claim 5.