TW201516068A - Active-energy-ray-curable composition, active-energy-ray-curable printing ink using same, and printed matter - Google Patents

Abstract

Provided are: an active-energy-ray-curable composition that demonstrates high curability when used in printing ink and that has excellent suitability for emulsification and offset printing; an active-energy-ray-curable printing ink that combines excellent curability, emulsifiability, and suitability for offset printing; and printed matter that uses the active-energy-ray-curable printing ink. Specifically, an active-energy-ray-curable resin composition characterized in that said composition is obtained by reacting an epoxy resin (A), an acid anhydride (C), and a monocarboxylic acid (B) having a polymerizable unsaturated group, and has an acid value of 5.0 mg KOH/g or less and a hydroxyl value of 180 mg KOH/g or less, said composition being used as a resin component for printing ink.

Description

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

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

The active energy ray-curable resin composition is hard to be used for various plastic substrates such as home electric appliances and mobile phones because it has less heat history to the coated substrate and has excellent coating film hardness or scratch resistance. It is used in various fields such as overcoat agents such as paints and papers, adhesives for printing inks, and solder resists. Among them, an epoxy acrylate resin obtained by reacting acrylic acid or methacrylic acid with an epoxy resin is often used in various fields as a material excellent in adhesion to a substrate and adhesion (see, for example, Patent Literature) 1).

However, when such an epoxy acrylate resin is used as a binder for printing ink, particularly when used as a stencil printing ink, there is a disadvantage that the required emulsification property is poor. That is to say, in the rubber printing which simultaneously supplies the ink and the water to the layout while performing image formation by utilizing the repulsion of the ink and the water, the epoxy acrylate is required after the ink has high emulsifying suitability. Strong hydrophilicity but proper discharge of emulsified water Since the characteristics of the sub-division are inferior, there are many cases in which printing problems such as excessive emulsification of the printing ink and a decrease in printing density occur. On the other hand, in the active energy ray-curable UV ink having excellent emulsification properties, a technique of using a rosin-modified phenol resin and an active energy ray-curable monomer as a varnish is known (refer to, for example, Patent Document 2) ). However, since the phenol resin modified by the rosin 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 an active energy ray-curable printing ink, it is not possible to obtain a high emulsification property while exhibiting high hardenability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication 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 when printing an ink and which has excellent emulsification suitability and rubber printability; and an excellent hardenability, Emulsifying, rubber-printable, active energy ray-curable printing ink; and printed matter thereof.

The present inventors have intensively studied in order to solve the above problems, and as a result, found that a monocarboxylic acid (B) having a polymerizable unsaturated group is used. The acid anhydride-curable resin obtained by modifying the epoxy resin (A) with an acid anhydride (C) can exhibit excellent curing properties and can significantly improve the emulsifying properties of the printing ink itself, thereby obtaining good printing characteristics. The present invention has been completed.

In other words, the present invention relates to an active energy ray-curable resin composition characterized by comprising an epoxy resin (A) and a monocarboxylic acid (B) having a polymerizable unsaturated group and an acid anhydride (C). The value is 5 mgKOH/g or less, and the hydroxyl value is 180 mgKOH/g or less.

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

The present invention is further directed to a printed matter printed using the aforementioned 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 at the time of printing ink and exhibits excellent emulsification suitability and excellent rubber printability; and has excellent hardenability, Emulsifying, rubber-printable, active energy ray-curable printing ink; 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‧‧‧Assessing adhesives

Fig. 1 is a cross-sectional view showing a ducted tester (developed by Kawamura) for use in an emulsification suitability test.

[Formation of the Invention]

The active energy ray-curable resin composition of the present invention comprises an active energy ray-curable resin obtained by reacting an epoxy resin (A), a monocarboxylic acid (B) having a polymerizable unsaturated group, and an acid anhydride (C). The product is characterized by an acid value of 5 mgKOH/g or less and a hydroxyl value of 180 mgKOH/g or less. In the present invention, by reducing the amount of hydroxyl groups and the content of carboxyl groups in the active energy ray-curable resin composition (resin component which is a nonvolatile component), the emulsification characteristics for printing ink can be remarkably improved. . In addition, as a result of lowering the amount of the hydroxyl group and the carboxyl group content in the active energy ray-curable resin composition, the degree of branching of the resin itself is increased, and the concentration of the polymerizable unsaturated group per molecule is increased. Therefore, it becomes an active energy ray-curable resin composition excellent in hardenability.

Here, the hydroxyl value can be determined by titration using a KOH alkaline solution. Specifically, the sample was collected in a flask, and 10 mL of a mass ratio (anhydrous acetic acid: pyridine solution) of 1:9 anhydrous acetic acid-pyridine solution was added thereto, and after fully shaking, it was connected to a reflux condenser and placed in a heating to 100 ° C. In the bath, after 1 hour of treatment, it was cooled, and 10 mL of pure water was added. After cooling at room temperature, 10 mL of n-butanol was added so as to clean the wall surface of the flask (in the case where the sample was not dissolved, an appropriate amount of pyridine was added to dissolve it until it became transparent). Thereafter, about 10 drops of phenolphthalein were added and measured by titration using 0.5 mol of ‧ L of KOH alkali solution.

On the other hand, the acid value can also be determined by titration using a KOH alkaline solution. Specifically, the sample can be dissolved in 15 mL of a neutral solvent (methanol/toluene mass ratio of 3/7), phenolphthalein is used as an indicator, a few drops are added, and a 0.1 mol/L KOH alcohol solution is used for titration. When the reddish color does not disappear, the measurement is performed as the end point.

Further, from the viewpoint that the emulsification characteristics are optimized and the rmisting resistance is improved, the above hydroxyl value and acid value are in the range of 100 to 180 mgKOH/g and the acid value is 5 mgKOH/g. The following range is preferred.

Here, the epoxy resin (A) in the present invention is not particularly limited, but 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 epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, tetramethyl bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F Type epoxy resin, hydrogenated bisphenol S type epoxy resin, hydrogenated bisphenol AD type epoxy resin, tetrabromobisphenol A type epoxy resin and other bisphenol type epoxy resin; o-cresol novolac type epoxy resin; Phenolic novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol A novolak type epoxy resin, brominated phenol novolac type epoxy resin, alkylphenol novolak type epoxy resin, bisphenol S Novolak type epoxy resin, methoxy novolak type epoxy resin, phenolic phenol novolak type epoxy resin and other novolak type epoxy resin; di-epoxypropyl ether of resorcinol, p-benzene Divalent epoxy compound such as diepoxypropyl ether or catechol of diphenol; phenol aralkyl type epoxy tree (known as epoxide of ZYLOCK resin), biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, hexa-epoxy propyl ether resin such as 1,6-dihydroxynaphthalene type epoxy resin; Oxypropyl isopropyl isocyanurate, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, polyfunctional having a naphthalene skeleton Type epoxy resin, biphenyl modified novolac type epoxy resin (epoxide of polyphenol resin obtained by bis-methylene-linked phenol ring), containing An oxy phenol aralkyl resin or the like. Further, the epoxy resin may be used singly or in combination of two or more. Further, it is also possible to use a part of the epoxy resin described above which has been modified.

Among these, the bisphenol type epoxy resin, the above divalent epoxy compound, and the above diglycidyl ether are preferable in view of the fact that the viscosity at the time of making a printing ink is adjusted to be good. A bifunctional epoxy resin such as a resin is preferably a bisphenol epoxy resin having an aromatic ring from the viewpoint of printability. In particular, from the viewpoint of excellent emulsifying properties and excellent printability when used as a printing ink, a bisphenol epoxy resin having an epoxy equivalent in the range of 170 to 500 g/eq is preferred. Phenolic A type epoxy resin.

On the other hand, the monocarboxylic acid (B) having a polymerizable unsaturated group which is reacted with the above epoxy resin (A) may, for example, be acrylic acid, methacrylic acid or crotonic acid, especially from the viewpoint of printability. Preferably, it is acrylic acid or methacrylic acid, and particularly preferably acrylic acid.

Next, examples of the acid anhydride (C) include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and 5-norbornene-2,3-dicarboxylate. Nadic anhydride, methyl-5-norbornene-2,3-nacarboxylic anhydride, cyclic dibasic acid anhydride such as chloro-hydroxy anhydride; maleic anhydride, succinic anhydride, alkenyl amber Acyclic aliphatic dibasic acid anhydride such as acid anhydride; aromatic tribasic acid anhydride such as trimellitic anhydride; pyromellitic anhydride; diphenyl ketone tetracarboxylic anhydride; ethylene glycol bis(benzene trimellitic anhydride) and other aromatic tetracarboxylic dianhydride An aliphatic group such as methylcyclohexenetetracarboxylic anhydride or 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride Tetracarboxylic dianhydride, glycerol ginseng (benzene trimellitic anhydride), etc. A high molecular weight polybasic acid anhydride obtained by an intermolecular dehydration condensation reaction of an aliphatic dibasic acid, such as aromatic hexacarboxylic acid trianhydride, polyadipate anhydride, polysebacic anhydride, or polysebacic anhydride.

These acid anhydrides (C) may be used singly or in combination with a plurality of acid anhydrides. Among them, in particular, from the viewpoint of resistance to gelation, a dibasic acid anhydride is preferable, and in particular, it can be obtained from further improvement. The viewpoint of the hydrophobicity of the resin component is preferably a phthalic acid-based dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride.

The active energy ray-curable resin composition used in the present invention is obtained by reacting an epoxy resin (A) and a monocarboxylic acid (B) having a polymerizable unsaturated group with an acid anhydride (C), and is in the ring In the reaction of an epoxy group in the oxygen resin (A) with an acid group in the monocarboxylic acid (B) having a polymerizable unsaturated group or an acid anhydride group in the acid anhydride (C), the occurrence of a secondary hydroxyl group or a carboxyl group is inhibited. The method is such that the hydroxyl value and the acid value in the obtained polymerizable unsaturated group-containing resin are lowered.

Specifically, the reaction system for suppressing the occurrence of a secondary hydroxyl group or a carboxyl group as described above is exemplified by the following reactions 1 to 4.

Reaction 1: An acid anhydride (C) is reacted on a secondary hydroxyl group formed by a condensation reaction of an epoxy resin (A) with a monocarboxylic acid (B) having a polymerizable unsaturated group, followed by a carboxyl group formed by the reaction. The epoxy group in the other epoxy resin (A) reacts, and the epoxy group in the epoxy resin (A) is further condensed with the monocarboxylic acid (B) having a polymerizable unsaturated group.

For example, a bifunctional epoxy resin is used as the epoxy resin (A) or (meth)acrylic acid as the monocarboxylic acid (B) having a polymerizable unsaturated group. In the case of the following, it will become the following reaction.

(wherein A is a structural moiety other than a glycidoxy group in a bifunctional epoxy resin, Y is an acid anhydride residue, R is a methyl group or a hydrogen atom, and a broken line portion indicates another epoxy resin (A) The bond of the residue.)

Reaction 2: Epoxy Resin (A) and Polymerizable Unsaturated Group The terminal α-diol group formed during the condensation reaction of the monocarboxylic acid (B) Condensation of the terminal α-diol group in the epoxy resin (A) with phthalic anhydride The reaction. Also using a 2-functional epoxy resin as the epoxy resin (A) In the case of acrylic acid as the monocarboxylic acid (B) having a polymerizable unsaturated group , will become the following reaction.

(wherein A is a structural moiety other than the glycidoxy group in the bifunctional epoxy resin, Y is an acid anhydride residue, R is a methyl group or a hydrogen atom, and a broken line portion indicates bonding with another structural site. )

Reaction 3: The acid anhydride (C) is reacted in the epoxy resin (A) a 2-stage hydroxyl group, for example, a 2-stage hydroxyl group present in a bifunctional epoxy resin, and an epoxy group in the other epoxy resin (A) is further condensed with a monocarboxylic acid (B) having a polymerizable unsaturated group. reaction.

Similarly, when a bifunctional epoxy resin is used as the epoxy resin (A) and acrylic acid is used as the monocarboxylic acid (B) having a polymerizable unsaturated group, the following reaction will occur.

(wherein A is a structural moiety other than a glycidoxy group in a bifunctional epoxy resin, Y is an acid anhydride residue, and R is a methyl group or a hydrogen atom. Further, a line segment indicated by a broken line indicates a hydrogen atom. A covalent bond is formed or a bond of a covalent bond to a carbonyl carbon atom which is opened by an acid anhydride (C), and a dotted line indicates a bond with another structural moiety.

Reaction 4: Epoxy group and anhydride (C) in epoxy resin (A) The reaction is carried out in the presence of a catalyst, and then the resulting reactive site is reacted with an epoxy group in the other epoxy resin (A), and this operation is repeated in sequence, followed by the epoxy group remaining in the product and having polymerizability. The unsaturated group monocarboxylic acid (B) undergoes a condensation reaction.

In the case where a bifunctional epoxy resin is used as the epoxy resin (A) or (meth)acrylic acid as the monocarboxylic acid (B) having a polymerizable unsaturated group, the following reaction will occur.

(wherein A is a structural moiety other than a glycidoxy group in a bifunctional epoxy resin, Y is an acid anhydride residue, R is a methyl group or a hydrogen atom, and CAT is derived from a catalyst bonded to an acid anhydride. The structural part of the catalyst. Further, the line segment indicated by a broken line indicates a bond which forms a covalent bond with a hydrogen atom or a covalent bond with a carbonyl carbon atom which is opened by an acid anhydride (C).

Although each of the above reactions 1 to 4 can be carried out separately, it can also occur simultaneously in the same minute. Therefore, the aforementioned reactions 1 to 4 can be randomly generated between arbitrary molecules. Therefore, the active energy ray-curable resin composition (resin component as a non-volatile component) can be represented by the following formula 1 in the structural formula when the reaction 1 to 4 is combined.

Here, in the above formula 1, A is a structural moiety excluding a glycidoxy group in the bifunctional epoxy resin, Y is an acid anhydride residue, and Z is a (meth)acryl fluorenyl group or a hydrogen atom, n It is a repeating unit and is an integer of 0 to 3, and m is a repeating unit and is an integer of 0 to 100. Further, in the above formula 1, the line segment indicated by a broken line indicates that a covalent bond is formed with a hydrogen atom or a covalent bond is formed with a carbon atom represented by "*" in the following formula 2. In addition, X in the formula 1 is a hydrogen atom, a structural unit which forms a covalent bond with a carbon atom represented by "*" in the following formula 2, or a structural moiety represented by the following formula 3. Here, the line segment represented by A, Y, Z and the broken line in the formula 2 is synonymous with the formula 1, wherein Y in the formula 3 is an acid anhydride residue, a line segment indicated by a broken line is a linkage bond, and CAT is a catalyst. When it is bonded to an acid anhydride, it originates from the structural part of the catalyst.

The active energy ray-curable resin composition of the present invention described in detail above is a mixture of various molecular weights represented by the above formula 1 and formula 2. As described above, the second-order hydroxyl group, the terminal α-diol group, and the second-order hydroxyl group in the epoxy resin (A) produced by the reaction of the epoxy resin (A) with the polymerizable unsaturated monocarboxylic acid (B) Further, the condensation reaction between the epoxy group and the acid anhydride (C) in the epoxy resin (A) can reduce the amount of the hydrophilic OH group or the carboxyl group, and the emulsifying property and the printability can be remarkably improved. Further, as shown in the above formulas 1 and 2, since the hydrophilic OH group or the carboxyl group is reduced in amount and multi-branched and polyfunctionalized, the curability at the time of use as a printing ink can be improved.

The active energy ray-curable resin composition used in the present invention can be reacted with an acid anhydride (C) and a monocarboxylic acid (B) having a polymerizable unsaturated group by reacting an acid anhydride (C) as described above. The production, specifically, the point of the α-diol body of the hydrophilic terminal structure which is formed as a by-product during the reaction, and the sequential interaction (ester bond) of the epoxy group and the acid anhydride which do not generate a hydroxyl group In view of the point that the hydroxyl group can be lowered, it is preferred to carry out the reaction in the presence of a nitrogen-containing basic catalyst.

The aforementioned nitrogen-containing basic catalyst used herein is a basic compound having a nitrogen atom. Examples of the nitrogen-containing basic catalyst include a primary amine such as n-butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, and benzylamine, diethylamine, dipropylamine, and diisopropylamine. a cyclic second-grade amine such as a linear second-order amine such as dibutylamine, ethiethyleneimine, trimethyleneimine, pyrrolidine, piperidine, azepane, or azocane, and a secondary amine of such an alkyl substituent, such as trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, 1,4-dioxabicyclo[2.2.2]octane, Pyridine and 3- An aliphatic tertiary amine such as 3-quinuclidinol, an aromatic tertiary amine such as dimethylaniline, and a heterocyclic tertiary amine such as isoquinoline, pyridine, colin base, β-methylpyridine, or the like Grade 4 ammonium salt such as methylammonium, imidazole, hydrazine, triazole, hydrazine, etc. , 1,8-dioxinbicyclo[5.4.0]undec-7-ene (DBU) and 1,5-dioxabicyclo[4.3.0]non-5-ene (DBN), etc. An alkaline catalyst for nitrogen atoms. These nitrogen-containing alkaline catalysts may be used singly or in combination of two or more.

Among these basic catalysts containing a nitrogen atom, an aliphatic tertiary amine, particularly triethylamine, is used from the viewpoint of more easily reducing the amount of the hydroxyl group of the α-diol derived from the produced resin component. It is better.

Here, the amount of the nitrogen-containing alkaline catalyst used is reduced from the total mass of the raw material component from the viewpoint of reducing the amount of the α-diol and the emulsifying property in the resin containing the polymerizable unsaturated group. The mass fraction is preferably in a range of 0.01 to 0.6 parts by mass, and particularly preferably in a range of 0.03 to 0.5 parts by mass, particularly 0.05 to 0.3 parts by mass.

Moreover, the method of producing the active energy ray-curable resin composition is obtained by finally obtaining the emulsifiability of the printing ink using the obtained active energy ray-curable resin composition in the presence of a catalyst. The reaction temperature is in the range of 80 to 125 ° C, preferably in the range of 90 to 110 ° C. The epoxy resin (A), the carboxylic acid (B) having a polymerizable unsaturated group, and the acid anhydride (C) are reacted until the epoxy equivalent becomes 8000 g. / eq or more or an acid value of 5.0 KOH / g or less, preferably 2.0 mg KOH / g or less.

When the epoxy equivalent is 8000 g/eq or more and the acid value is 2 or less, the equivalent number (a) of the epoxy group of the epoxy resin (A) and the monocarboxylic acid having a polymerizable unsaturated group are required. The ratio of the equivalent number (b) to the equivalent number (c) of the acid anhydride group in the acid anhydride (C) ((a): {(b) + (c)))) is 0.8 to 1.2, and is preferably The range of 0.9 to 1.1 can be stably synthesized, and thus is preferable.

Further, by using the acid anhydride (C), a branching structure is formed during the reaction, and therefore, in order to suppress gelation, the number of equivalents of the epoxy group (a) and the number of equivalents of the monocarboxylic acid having a polymerizable unsaturated group ( The ratio of b) is (b): (a) = 0.65 to 0.95, and from the viewpoint of stable synthesis, it is preferably from 0.7 to 0.9.

Further, the reaction between the above epoxy resin (A) and the monocarboxylic acid (B) having a polymerizable unsaturated group and the acid anhydride (C) can radically polymerize a portion which does not contain a reaction with a carboxyl group and an epoxy group. The monomer is used as a reaction solvent and is carried out in the reaction solvent.

The radically polymerizable monomer which does not contain the site which reacts with a carboxyl group and an epoxy group used here, for example, N-vinyl pyrrolidone, a propylene group Porphyrin, dicyclopentadienyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, (a) Phenylethyl acrylate, butoxyethyl (meth)acrylate, isodecyl (meth)acrylate, mono(meth)acrylate of bisphenol F, bisphenol added to alkylene oxide Mono (meth) acrylate such as mono (meth) acrylate of F; ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(methyl) Acrylate, tetraethylene glycol di(meth) acrylate, dimethylol tricyclodecanoic acid diacrylate, tripropylene glycol di(meth) acrylate, 1,4-butanediol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate added to alkylene oxide, polyethylene glycol di(meth)acrylic acid Ester, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(meth)acrylate of neopentyl glycol hydroxypivalate, di(methyl) of bisphenol A ) acrylate, di(meth) acrylate of bisphenol F, addition Di(meth)acrylate of bisphenol A of alkylene oxide, di(meth)acrylate of di(meth)acrylate of bisphenol F added with alkylene oxide; trimethylolpropane tris(A) (meth) acrylate, trimethylolpropane tri(meth) acrylate such as addition alkylene oxide, neopentyl alcohol triacrylate, etc.; hexaacrylate of dipentaerythritol; .

In the active energy ray-curable resin composition obtained as described above, the acid value of the resin component in the composition is 5 mgKOH/g or less, preferably 2 mgKOH/g or less, and is stable from the printing ink. It is more preferable that the epoxy equivalent is in the range of 8000 g/eq or more.

Further, in the case where the active energy ray-curable resin composition is used for printing ink, it is easy to adjust the viscosity, and the resin component is dissolved in acetic acid from the viewpoint of excellent ink repellency and roll transferability when printing ink is prepared. The solution viscosity in the 80% by mass solution of the nonvolatile component in the case of butyl ester is preferably in the range of 0.5 to 30 Pa s. From the viewpoint that these effects become remarkable, it is particularly preferably in the range of 1.0 to 10.0 Pa ‧ s.

Further, in the present invention, the reaction of the epoxy resin (A), the monocarboxylic acid (B) having a polymerizable unsaturated group, and the acid anhydride (C) in a nitrogen atom-containing catalyst, particularly triethylamine or chlorine When the reaction is carried out in the presence of tetramethylammonium, the amount of the hydroxyl group derived from the α-diol at the end of the resin can be remarkably lowered, whereby the emulsifying property and the curability can be further achieved at a high level. Specifically, in the terminal structure of the resin component in the final active energy ray-curable resin composition, specifically, in the structural portions represented by the following structural formulas (i) to (vi),

The content of the terminal structure derived from the α-diol represented by the structural formula (v) can be reduced to 5 mol% or less. In order to further improve the above-mentioned emulsification property and hardenability, the content rate is preferably 3 mol% or less.

Further, in the present invention, it is not necessary to include all of the above various terminal structures (the above structural formulas (i) to (vi)) in the resin component, and it is only necessary to use the total number of terminal structures selected from these as a reference. The content of the α-diol structural moiety may be 5 mol% or less.

Here, the existence ratio of the above structural formulae (i) to (vi) can be measured by ¹³ C-NMR, and specifically, can be derived by the area ratio of each peak of the carbon atom represented by * below. Further, when each peak is repeated with another carbon atom in another structure, the area obtained by the other carbon atoms may be removed to obtain a ratio.

Next, a polymerization initiator can also be used as the active energy ray-curable resin composition of the present invention. The polymerization initiator used herein 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 benzyldimethyldiamide. Ketone, 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-methylpropenyl)-benzyl]-phenyl}-2-methyl Propione-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one Ethyl acetophenone-based compound; 1-[4-(phenylthio)-, 2-(O-benzylidene hydrazide)], 1-[9-ethyl-6-(2-methylbenzhydrazide) Anthracene compound such as -9H-carbazol-3-yl]-, 1-(O-ethylindenyl), 3,6-bis(2-methyl-2-N- A benzoin compound such as oxazolyl)-9-butylcarbazole, a benzoin compound such as benzoin, benzoin methyl ether or benzoin isopropyl ether; 2-benzyl-2 -dimethylamino-1-(4-N- Phenylphenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-N- Polinylphenyl)butan-1-one, 2-methyl-2-N- Orolinyl ((4-methylthio)phenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Aminoalkylphenone compounds such as morphylphenyl)butanone; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzene oxide Oxidized fluorenylphosphine-based compound such as mercapto diphenylphosphine, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine; diphenylethylenedione , methyl phenyl acetaldehyde decyl ester and the like.

On the other hand, as the hydrogen capture type photopolymerization initiator, for example, diphenyl ketone, o-benzylidene benzoic acid methyl-4-phenyldiphenyl ketone, 4,4'- Dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4-benzylidene-4'-methyl-diphenyl sulfide, acrylated diphenyl ketone, 3,3', 4,4'-four a diphenyl ketone compound such as (tris-butylperoxycarbonyl)diphenyl ketone or 3,3'-dimethyl-4-methoxydiphenyl ketone; 2-isopropyl-9-oxosulfuric acid 2,4-dimethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 9-oxosulfur a compound; an aminodiphenyl ketone compound such as 4,4'-bisdimethylaminodiphenyl ketone or 4,4'-bisdiethylaminodiphenyl ketone; other 10-butyl- 2-chloroacridone, 2-ethylhydrazine, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators can be used singly or in combination of two or more.

Among these, in particular, from the viewpoint of excellent curability, an aminoalkylphenone compound is preferable, and in particular, UV-in which ultraviolet rays having a peak wavelength of 350 to 420 nm are used are used. When the LED light source is used as an active energy source, it is preferred to use an aminoalkylphenone compound, a phosphinylphosphine compound, and an aminodiphenylketone compound in combination from the viewpoint of excellent curability.

The amount of the polymerization initiator to be used is preferably in the range of 1 to 20 parts by mass based on 100 parts by mass of the resin component in the active energy ray-curable composition of the present invention. In other words, when the total amount of the polymerization initiator used is 1 part by mass or more, good curability can be obtained, and when it is 20 parts by mass or less, the migration of the unreacted polymerization initiator remaining in the cured product can be avoided. The problem of deterioration in physical properties such as solvent resistance and weather resistance. In view of the fact that the balance of properties of the active energy ray-curable composition of the present invention is 100% by mass, the total amount used is 3 to 15 parts by mass. The range is better.

Further, when a cured coating film is formed by irradiating ultraviolet rays as an active energy ray, in addition to the polymerization initiator, the hardenability can be further improved by using a photosensitizer. Examples of such a photosensitizer include an amine compound such as an aliphatic amine, a urea such as o-toluenesulfuric urea, sodium diethyldithiophosphate, or a secondary benzylisothiourea p-toluenesulfonate. Compounds, etc. The amount of the photosensitizer used is preferably 100 parts by mass based on 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. The amount used is in the range of 1 to 20 parts by mass.

The active energy ray-curable composition of the present invention can further be used in combination with a radical polymerizable monomer. Examples of such a radical polymerizable single system include N-vinyl caprolactam, N-vinyl pyrrolidone, and N- Vinyl carbazole, vinyl pyridine, N,N-dimethyl(meth) acrylamide, acrylamide, propylene fluorenyl Porphyrin, (meth)acrylic acid-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth) acrylamide, tertiary octyl (meth) acrylamide, two Acetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl Diethylene glycol (meth) acrylate, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylate Dicyclopentenyl ester, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofuran methyl (meth)acrylate, tetrabromophenyl (meth)acrylate , 4-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, (meth)acrylic acid-2 -Tribromophenoxyethyl ester, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromyl (meth)acrylate , (meth) methacrylate, methyl triethylene glycol (meth) acrylate, (meth) acrylate An oxime ester, a mono(meth) acrylate of bisphenol F, a mono(meth) acrylate of bisphenol F added with an alkylene oxide; an acid mono {2-(methyl) propylene oxirane ethyl} Various phosphate-containing vinyl monomers such as phosphates; vinylsulfonic acid, allylsulfonic acid, 2-methylallylsulfonic acid, 4-vinylbenzenesulfonic acid, 2-(methyl)acrylic acid Various sulfonic acid group-containing vinyl monomers such as oxyethanesulfonic acid, 3-(meth)acryloxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; such as 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(CH2) 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 In the formula, n is set to 0 or an integer of 1 to 130, etc., and various polysiloxane chains containing monomers represented by the formula; γ-(meth) propylene oxypropyltrimethoxy decane, γ- (Meth)propylene oxypropyl triethoxy decane, γ-(methyl) propylene methoxypropyl methyl dimethoxy decane, γ-(methyl) Iridinyl propyl methyl diethoxy decane, γ-(meth) propylene oxypropyl triisopropoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl -β-methoxyethoxy)decane, vinyltriethoxydecane, vinyltrichloromethane or N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl Trimethoxy decane and its hydrochloride; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( a (meth) acrylate having a hydroxyl group such as a methyl acrylate, and an ε-caprolactone reactant of the monomers; 2-dimethylaminoethyl vinyl ether, 2-diethylamino group Various kinds of amines such as ethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether, and 6-dimethylaminohexyl vinyl ether Vinyl ether; vinyl ether having various hydroxyl groups such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether; or 2-hydroxyethoxyallyl ether, 4-hydroxybutoxy allyl ether, trishydroxypropyl Mono- or di-allyl ether, mono- or di-allyl ether of pentaerythritol, etc., allyl ether having a hydroxyl group, and ε-caprolactone reactant of such monomers; methyl Vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclopentyl vinyl ether, cyclohexylethylene Vinyl ethers such as ethers; ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(methyl) Acrylate, tricyclodecanoic acid di(meth)acrylate, dimethylol tricyclodecanoic acid diacrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(methyl) Acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylic acid Ester, di(meth) acrylate of neopentyl glycol hydroxypivalate, di(meth) acrylate of bisphenol A or F, bisphenol A or F of added alkylene oxide Acrylate; maleic acid, fumaric acid, ikon a bifunctional monomer such as divinyl esters of various dibasic acids such as acid and citraconic acid, such as dihydroxymethylpropane tris(meth)acrylate and trishydroxylated alkylene oxide Methylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, neopentyl glycol tri(meth)acrylate with added alkylene oxide, pentaerythritol tetra(methyl) Tris(meth)acrylate such as acrylate, neopentyl alcohol tetra(meth)acrylate added with alkylene oxide; penta(meth)acrylate of dipentaerythritol, added alkylene oxide Bis penta (meth) acrylate of pentaerythritol, hexa (meth) acrylate of dipentaerythritol, hexa (meth) acrylate of dippentaerythritol added with alkylene oxide, etc. And the ε-caprolactone reactant of these monomers.

Among these, in particular, from the viewpoint of excellent curability as a printing ink, penta (meth) acrylate of dipentaerythritol and dipentaerythritol by addition of alkylene oxide are preferable. A penta (meth) acrylate of an alcohol, a hexa(meth) acrylate of dipentaerythritol, or a hexa (meth) acrylate of dippentaerythritol to which an alkylene oxide is added.

The active energy ray-curable composition of the present invention is particularly useful as an active energy ray-curable printing ink. In this case, pigments, dyes, and extender pigments may be used for other blends of the above components. , organic or inorganic fillers, organic solvents, antistatic agents, defoamers, viscosity modifiers, light stabilizers, weather stabilizers, heat resistant Additives, UV absorbers, antioxidants, leveling agents, pigment dispersants, waxes and other additives.

The active energy ray-curable composition of the present invention, in particular, the active energy ray-curable printing ink, after being printed on a substrate, can be formed into a cured coating film by irradiation with an active energy ray. Examples of the active energy ray system include free radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. Among these, especially from the viewpoint of hardenability, ultraviolet rays are preferred.

The active energy ray for hardening the active energy ray-curable coating of the present invention is, as described above, free radiation such as ultraviolet rays, electron rays, alpha rays, beta rays, gamma rays, but specific energy or hardening. Examples of the device include a germicidal lamp, a fluorescent lamp for ultraviolet rays, a UV-LED, a carbon arc, a xenon lamp, a high-pressure mercury lamp for rewriting, a medium-pressure or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, and a metal halide lamp. Natural light or the like is an ultraviolet ray of a light source, or an electron beam generated by a scanning type or a curtain type electron beam accelerator.

Further, the present invention active on pigment energy ray curable ink used in the printing, the common coloring include known organic pigments include, for example: "Handbook organic pigment (OF: Hashimoto Hoon, Publisher: Color Office In the first edition of 2006, the organic pigments for printing inks, such as soluble azo pigments, insoluble azo pigments, condensed azo pigments, metal phthalocyanine pigments, metal-free phthalocyanine pigments, and quinine can be used. Anthrone pigment, anthraquinone pigment, picone pigment, isoindolinone pigment, isoporphyrin pigment, two Pigments, sulphur blue pigments, lanthanide pigments, quinoline yellow 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 fine particles may be used as the extender pigment. Examples of the inorganic fine particles include inorganic coloring pigments such as titanium oxide, graphite, and zinc oxide; carbonated lime powder, precipitated calcium carbonate, gypsum, china clay, vermiculite powder, diatomaceous earth, talc, kaolin, and alumina white. Inorganic pigments such as (alumina white), barium sulfate, aluminum stearate, magnesium carbonate, barite powder, polishing powder; inorganic pigments, or polyfluorene oxide, glass beads, and the like. These inorganic fine particles can be used in an amount of 0.1 to 20 parts by mass in the ink to obtain an effect of adjusting the fluidity of the ink, preventing flying ink, and resisting penetration of a printing substrate such as paper.

Further, examples of the printing substrate suitable for the active energy ray-curable printing ink of the present invention include catalogues, posters, leaflets, CD covers, advertisement direct mail (DM), brochures, cosmetics or beverages, pharmaceuticals, Paper base materials used for packaging materials such as toys and machines; films such as polypropylene film and polyethylene terephthalate (PET) film used for various food packaging materials, aluminum foil, synthetic paper, and the like. Various substrates that have been used as printing substrates.

Moreover, the printing method of the active energy ray-curable printing ink of the present invention may, for example, be lithographic rubber printing, letterpress printing, gravure printing, gravure stencil printing, flexographic printing, screen printing or the like.

The present invention can be suitably utilized in lithographic rubber printing in which water is continuously supplied to a plate, from the viewpoint of improving the emulsification characteristics of the ink. There are many printing press manufacturers for continuous printing of rubber printing machines. For example, Heidelberg Co., Komori Corporation, Mitsubishi Heavy Industries Printing and Paper Machinery Co., Ltd., Manroland Co., RYOBI Co., Ltd., KBA Co., Ltd., and a sheet-fed offset printing machine using a single sheet of printing paper (for example) In the paper supply method of any of the sheet offset presses and the blanket cylinder printing machine using the printing paper of the roll form, the present invention can also be suitably used. More specifically, a rubber 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, Inc., may be used.

[Examples]

The invention will now be described in more detail by way of examples. Further, the present invention is not limited to these examples, and the hydroxyl value and the acid value are measured by the following methods.

[hydroxyl value]

The sample was collected in a flask, and 10 mL of a mass ratio (anhydrous acetic acid: pyridine solution) of 1:9 anhydrous acetic acid-pyridine solution was added thereto, and after fully shaking, it was connected to a reflux condenser and placed in a heating bath at 100 ° C for treatment. After 1 hour, it was cooled, and 10 mL of pure water was added. After cooling at room temperature, 10 mL of n-butanol was added as the wall surface of the flask was cleaned (in the case where the sample was not dissolved, an appropriate amount of pyridine was added to dissolve until it became transparent), and then about 10 drops of phenolphthalein were added. It was determined by titration using 0.5 mol of ‧ KOH base solution.

[acid value]

The sample was dissolved in 15 mL of a neutral solvent (methanol/toluene = 3/7), phenolphthalein was used as an indicator, a few drops were added, and a 0.1 mol/L KOH alcohol solution was used. To titrate, the measurement is performed as an end point when the reddish color does not disappear.

Example 1

A liquid bisphenol A type epoxy resin (EPICLON 850, epoxide equivalent: 188 g/eq, manufactured by DIC Co., Ltd.; hereinafter referred to as "liquid BPA type ring" was placed in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube. 704 parts by mass of oxygen resin), 108 parts by mass of acrylic acid, 74 parts by mass of phthalic anhydride, and 0.1 parts by mass of hydroquinone monomethyl ether (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, triethylamine was added thereto. (catalyst; hereinafter referred to as "TEA") 1.1 parts by mass. Further, 140 parts by mass of di-trimethylolpropane tetraacrylate as a polyfunctional acrylate monomer was added for the purpose of lowering the viscosity at the time of the reaction, and the reaction was carried out at 100 ° C for 15 hours to obtain an epoxy equivalent of 22,400. A polymerizable unsaturated group-containing resin (1) having g/eq, an acid value of 0.6 mgKOH/g, a solution viscosity (butyl acetate nonvolatile component 80% by mass solution) of 5.0 Pas, and a hydroxyl value of 133 mgKOH/g.

Example 2

The synthesis was carried out in accordance with Example 1 except that 74 parts by mass of the phthalic anhydride was changed to 76 parts by mass of tetrahydrophthalic anhydride to obtain an epoxy equivalent of 23,070 g/eq, an acid value of 0.7 mgKOH/g, and a solution viscosity (butyl acetate). The polymerizable unsaturated group-containing resin (2) having a volatile component of 80% by mass of a solution of 4.2 Pas and a hydroxyl value of 130 mgKOH/g.

Example 3

In addition to changing the liquid bisphenol A type epoxy resin to 564 parts by mass, changing the acrylic acid to 180 parts by mass, changing the phthalic anhydride to 74 parts by mass, and changing the di-trimethylolpropane tetraacrylate to 91 parts by mass. The synthesis was carried out in accordance with Example 1 to obtain an epoxy equivalent of 30,820 g/eq and an acid value. A polymerizable unsaturated group-containing resin (3) having a solution viscosity (80% by mass of a butyl acetate nonvolatile component) of 8.6 Pas and a hydroxyl value of 158 mgKOH/g.

Example 4

A liquid bisphenol A type epoxy resin (EPICLON 850, epoxide equivalent: 188 g/eq, manufactured by DIC Co., Ltd.; hereinafter referred to as "liquid BPA type ring" was placed in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube. 376 parts by mass of oxyethylene resin and 37 parts by mass of phthalic anhydride, and after heating to 100 ° C, 1.1 parts by mass of triethylamine (catalyst; hereinafter abbreviated as "TEA") was added, and the reaction was carried out at 100 ° C for 3 hours. Thereafter, 126 parts by mass of acrylic acid and 0.1 parts by mass of hydroquinone monomethyl ether (polymerization inhibitor; hereinafter abbreviated as "MQ") were further charged, and the reaction was carried out at 100 ° C for 15 hours to obtain an epoxy equivalent of 20,300 g/eq. A polymerizable unsaturated group-containing resin (3) having an acid value of 0.65 mgKOH/g, a solution viscosity (80% by mass of a butyl acetate nonvolatile component), and a hydroxyl value of 170 mgKOH/g.

Comparative example 1

A liquid bisphenol A type epoxy resin (EPICLON 850, epoxide equivalent: 188 g/eq, manufactured by DIC Co., Ltd.; hereinafter referred to as "liquid BPA type ring" was placed in a four-necked flask equipped with a stirrer, a thermometer, and a cooling tube. 435 parts by mass of oxygen resin), 164 parts by mass of acrylic acid, and 0.1 parts by mass of hydroquinone monomethyl ether (polymerization inhibitor; hereinafter abbreviated as "MQ"), and after heating to 100 ° C, triphenylphosphine (catalyst; Referred to as "TPP") 1.2 parts by mass. By carrying out the reaction at 100 ° C for 15 hours, an epoxy equivalent of 20,000 g / eq, an acid value of 0.5 mg KOH / g, a solution viscosity (butyl acetate non-volatile component 80% by mass solution) of 1.8 Pas, and a hydroxyl value were obtained. 200mgKOH/g A polymerizable unsaturated group-containing resin (R1).

Comparative example 2

The mixture was synthesized in accordance with Example 1 except that it was changed to 92 parts by mass of acrylic acid and 111 parts by mass of phthalic anhydride, and gelled during the reaction.

[Preparation of Active Energy Line Curing Adhesive for Emulsifying Fitness Evaluation]

The addition of the polymerizable unsaturated group-containing resins (1) to (4) and (R1) as the active energy ray polymerizable property for the purpose of more clearly showing the effect of the emulsification suitability improvement in the present invention The acrylate monomer di-trimethylolpropane tetraacrylate ("SR355NS" manufactured by Sartomer Co., Ltd.) has a viscosity of 41 to 48 Pa‧s as measured by a Raleigh viscometer (L-type viscosity meter (25 ° C)). The active energy ray-curable adhesives (T1) to (T4) and (TR1) for evaluation of emulsification suitability were obtained.

[Method for Evaluating Emulsifying Properties of Active Energy Line Curing Adhesives]

The emulsification suitability evaluation of the prepared active energy ray-curable adhesives (T1) to (T4) and (TR1) was carried out using a catheter tester (developed by Kawamura Scientific).

A cross-sectional view of the catheter testing machine is shown in Fig. 1. The outer cylinder 3 is a cylindrical metal having a bottom surface which is hollowed out, and is configured to be capable of evaluating the binder 7 therein. After the adhesive 7 (5 g) was put in, as shown in Fig. 1, the inner cylinder 2 of the cylindrical rod-shaped metal was inserted so as to be close to 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 also rotated clockwise at 60 rpm. By applying a speed difference, the bonding agent 7 was sheared and stirred. By the time of 3 minutes after stirring, by The distillation was dropped to the upper side of the binder 7 at a rate of 0.5 (g/min) while stirring continuously, and the binder 7 and the distilled water dripped were immediately stirred and mixed. The continuous distillation of distilled water was allowed to drip for 10 minutes, and the amount of distilled water reached a total of 5 grams.

In the catheter testing machine, the outer cylinder 3 is rotated by the outer cylinder drive motor 5, and the inner cylinder 2 has a structure in which the inner cylinder drive motor 1 rotates, and the temperature of the adhesive 7 inside the outer cylinder 3 is fixed. With the constant temperature water tank 4, the temperature of the tap water 6 is always maintained at 30 °C.

After the agitation of the binder 7 (5 g) and distilled water (5 g) was completed, the weight (in grams) of the remaining distilled water (excess moisture not incorporated into the binder) in the inside of the inner cylinder 2 was weighed. From this, it is understood that the total weight Y of the distilled water which has been incorporated into the binder 7 is expressed by the following formula: Y (g) = total distilled water (5 g) - weight of residual distilled water; emulsifying rate of the binder 7 is below Z Formula: Z (%) = Y ÷ (bonding agent 7 (5 grams) + Y) × 100. (Here, for example, 5 gram of distilled water that has been charged is placed in the binder, and when the remaining distilled water is 0 gram, it is calculated as Y = 5 (g) and Z = 50 (%).

The lower the numerical value of the binder emulsification rate Z (%), the more excellent the characteristics of appropriately discharging the emulsified water, and the more excellent the rubber printing suitability of the following ink, and the less likely to cause excessive emulsification or a decrease in concentration due thereto. Etc. Printing problems. 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 to less than 35%, and the emulsification is moderate.

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

[Modulation of active energy ray-curable printing ink]

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" and "Pigment Blue 15:3" manufactured by BASF Corporation), as active energy ray hardenability 10 parts by mass of octyl pentaerythritol hexaacrylate ("DPHA" manufactured by Sartomer Co., Ltd.) and 26.95 parts by mass of di-trimethylolpropane tetraacrylate ("SR355NS" manufactured by Sartomer Co., Ltd.) as an extender pigment 2.5 parts by mass of "Hi-Filler #5000PJ hydrated magnesium silicate" manufactured by Matsumura Industry Co., Ltd., and 1 part by mass of wax (S-381-N1" polyolefin wax manufactured by Shamrock Co., Ltd.) as a photopolymerization initiator (Irgacure 907, manufactured by BASF Corporation) 2-methyl-1-[4-(methylthio)phenyl]-2-N- 3.5 parts by mass of phenylpropan-1-one), as a photoinitiator ("Eb-SS"4,4'-bis(diethylamino)diphenyl ketone) manufactured by Daisei Chemical Co., Ltd., 2.5 parts by mass 0.05 parts by mass of "Q1301" N-nitrosophenylhydroxylamine aluminum (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor, and a mixer was used in a state in which all the raw materials (100 parts by mass in total) were blended ( The uniaxial dissolver was stirred, and then ground using a three-roll mill to obtain an active energy ray-curable ink (I1).

In the same manner as described below, the other polymerizable unsaturated group-containing resins (2) to (4), (R1), and (R2) are obtained by using the same mass of the above-mentioned raw materials and producing them in the same manner. Energy line hardenable inks (I2) ~ (I4) and (IR1).

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

The active energy ray-curable inks (I1) to (I4) and (IR1) thus obtained were uniformly spread by using a simple color spreader (RI Tester, manufactured by Fung Shing Seiko Co., Ltd.) and using 0.10 ml of ink. RI Tester's rubber roller and metal roller are coated with paper ("OK TOPCOAT PLUS 57.5kg, A size" made by Oji Paper Co., Ltd.) on a surface with a blue density of 1.6 (over X-Rite) over an area of about 200 cm ² The company's SpectroEye concentration meter measures a uniform coating method to develop color and create a color display. Furthermore, RI Tester refers to a test machine that spreads ink on paper or film, and can adjust the amount of ink transfer or printing.

[The hardening method using a UV light source]

Ultraviolet (UV) irradiation is applied to the color developing material after the ink is applied to harden the ink film. The UV-illumination device (manufactured by EYE GRAPHICS, equipped with a cold-light mirror) equipped with a water-cooled metal halide lamp (output 100W/cm1 lamp) and a conveyor belt is used to place the color-developed material on the conveyor belt and pass the lamp under the following fixed conditions. Directly below the source (irradiation distance 11cm). The amount of ultraviolet irradiation under each condition was measured using an ultraviolet light accumulation amount system (UNIMETER UIT-150-A/light receiver UVD-C365 manufactured by USHIO Electric Co., Ltd.).

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

The sclerosing property confirms the presence or absence of scratches on the surface of the color developing matter by the nail scratching method immediately after the irradiation. The speed of the conveyor belt (m/min) of the conveyor belt of the UV irradiation device is changed, and the maximum speed of the conveyor belt (m/min) which is scratched even after hardening with nails is described. ). Therefore, the larger the value of the belt speed, the better the hardenability of the ink.

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

The solvent resistance was confirmed by solvent rubbing immediately after the irradiation to confirm the presence or absence of scratches on the surface of the printed matter. The color developing material was irradiated with ultraviolet rays at a belt speed of 50 (m/min) of the aforementioned UV irradiation device to harden the ink. After the hardening, the state change after the surface of the ink-cured coating film was evaluated by rubbing back and forth with a cotton swab containing ethanol was visually observed, and the solvent resistance was evaluated in accordance with the following criteria.

3: No change

2: scratch residue

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

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

1.31 mL of the rubber-printed ink was placed on an Incometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and rotated at 1200 rpm for 3 minutes at 32 ° C to visually observe the amount of scattering of the setting paper placed under the roller. The evaluation of the amount of scattering is performed in the following three stages.

1: Flying ink

2: A little flying ink

3: Only some flying ink

[Eraser printing method for active energy ray-curable ink]

The rubber printability was evaluated for the produced active energy ray-curable inks (I1) to (I4) and (IR1). Manroland's rubber printing machine equipped with a water-cooled metal halide lamp (output 160 W/cm, using three lamps) manufactured by EYE GRAPHICS Co., Ltd. as an ultraviolet irradiation device (Roland R700 press, width 40 inch machine), rubber printing at 9000 sheets per hour. For the printing paper, OK TOPCOAT PLUS (57.5 kg, A size) manufactured by Oji Paper Co., Ltd. was used. The dampening water supplied to the plate-making surface was an aqueous solution containing 98 parts by mass of tap water and 2 parts by mass of an etching solution (FST-700, manufactured by DIC Corporation).

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

For the evaluation method of the suitability of the stencil printing, the water supply dial of the printing press is first set to 40 (standard water amount), and the printed matter concentration becomes the standard program blue density of 1.6 (measured by the SpectroEye concentration meter manufactured by X-Rite Co., Ltd.). The ink supply button is operated to fix the ink supply button at a stable concentration.

Thereafter, under the condition that the ink supply button was fixed, the water supply dial was changed from 40 to 55, 300 sheets were printed under the condition of increasing the amount of water supply, and the blue density of the printed matter after 300 sheets was measured. Even in the state where the amount of water supply is increased, the concentration of the printed matter is less decreased, and the emulsification suitability is more excellent, and the ink having excellent printability can be evaluated. The printability of the active energy ray-curable ink was evaluated in accordance with the following criteria.

3: The blue concentration of the printed matter is 1.5 or more

2: The blue concentration of the printed matter is 1.4 or more and less than 1.5.

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

Claims (9)

An active energy ray-curable composition characterized in that an acid value obtained by reacting an epoxy resin (A) and a monocarboxylic acid (B) having a polymerizable unsaturated group with an acid anhydride (C) is 5.0 mgKOH/g or less. And the hydroxyl value is 180 mgKOH/g or less. The active energy ray-curable composition of claim 1, which further comprises a polymerization initiator. The active energy ray-curable composition of claim 1 or 2, wherein the epoxy resin (A) is a bisphenol type epoxy resin. The active energy ray-curable composition of claim 3, wherein the epoxy resin (A) has an epoxy equivalent of from 170 to 500 g/eq. The active energy ray-curable composition according to any one of claims 1 to 4, which is an epoxy resin (A), a monocarboxylic acid (B) having a polymerizable unsaturated group, in the presence of a basic catalyst The acid anhydride (C) is obtained by a reaction. The active energy ray-curable composition of claim 5, which is equivalent to the number of epoxy groups of the epoxy resin (A) (a), and the equivalent of the carboxyl group of the monocarboxylic acid (B) having a polymerizable unsaturated group. The equivalent ratio [(a)/((b)+(c))]) of the number (b) of the acid anhydride group of the acid anhydride (C) and the acid anhydride (C) is 0.8 to 1.2 and the equivalent ratio [(b)/(a) The ratio of 0.65 to 0.95 is obtained by reacting an epoxy resin (A) and a monocarboxylic acid (B) having a polymerizable unsaturated group with an acid anhydride (C). An active energy ray-curable printing ink characterized by containing the active energy ray-curable composition according to any one of claims 1 to 6. An active energy ray-curable printing ink according to claim 7, wherein the active energy ray-curable printing ink is a stencil printing ink. A printed matter obtained by printing the active energy ray-curable composition according to any one of claims 1 to 6.