JP2018002958A - Active energy ray-curable printing ink and printed matter of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide active energy ray-curable printing ink that can reduce migration after cured and has excellent curability, and a printed matter of the ink.SOLUTION: The active energy ray-curable printing ink comprises: an active energy ray-polymerizable compound (A); a polymerization initiator (B) obtained by Michael addition reaction of an α-aminoacetophenone skeleton-containing compound (I) functioning as a Michael addition donor having a specific molecular structure and a reactive compound (II) functioning as a Michael receptor; and a sensitizer (C) having a number average molecular weight of 500 or more and 1500 or less and an absorption wavelength in the wavelength range from 300 to 450 nm.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable printing ink and a printed material thereof.

Conventionally, an active energy ray curing system has been widely applied from the viewpoint of high production efficiency, lowering of curing energy, and VOC reduction. Among them, the ultraviolet curing system is mainstream because the equipment introduction cost is lower and the installation area is smaller than other active energy ray curing systems.
The photopolymerization initiator, which is an essential component in the ultraviolet curing system, differs from the reactive monomer that becomes a high molecular weight polymer and is fixed to the cured film after curing, and the photopolymerization initiator itself or its decomposition product in the cured product. Remains. Since most photopolymerization initiators currently distributed are low molecular weight compounds, the remaining photopolymerization initiator itself or a decomposition product thereof also has a low molecular weight, which causes odor and the like.

  Further, in recent years, it has been pointed out that the residue may migrate to the material side in contact with the cured product. In particular, in the case of ultraviolet curable ink used for printed food packaging, the residue is the back side of the printed product in direct contact with food. Due to the risk of migration, the restrictions on the migration of photopolymerization initiators are becoming stricter year by year.

  On the other hand, attempts have been made to reduce migration by increasing the molecular weight of the photopolymerization initiator. For example, Patent Literature 1 and Patent Literature 2 disclose oligomer-type photopolymerization initiators having a plurality of functional groups having photopolymerization initiation ability in the molecule. The method disclosed in this document has an effect of reducing odor and migration by oligomerizing the photopolymerization initiator. However, the effect is still insufficient for recent regulations, and the curing performance is inferior.

  Patent Document 3 discloses an ultraviolet curable polymerization initiator obtained by Michael addition reaction of a photopolymerization initiator having an α-aminoacetophenone structure and a polyfunctional acrylate. In the method disclosed in Patent Document 3, a reactive group is introduced into the photopolymerization initiator group, and the photopolymerization initiator group is immobilized on the cured coating film, whereby the odor of the photopolymerization initiator from the cured film is obtained. Can be greatly suppressed. However, the photoinitiator disclosed in Patent Document 3 is also slightly inferior in photoinitiating ability, and has caused problems such as poor curing particularly in applications requiring a curing rate such as ultraviolet curable ink.

JP 2005-505615A Special table 2008-519760 WO11 / 001928

  The problem to be solved by the present invention is to provide an active energy ray-curable printing ink that can reduce migration after curing and is excellent in curability, and a printed matter thereof.

  As a result of intensive studies, the present inventors have found that the active energy ray-polymerizable compound (A), the polymerizable initiator (B) having an α-aminoacetophenone skeleton having a specific structure, and a number average molecular weight of 500 to 1500. In addition, the printing ink using the sensitizer (C) having an absorption wavelength of 300 to 450 nm can remarkably improve the curability, particularly the curability inside the printed material, and in addition, effectively migrates after curing. The present inventors have found that it can be reduced and have completed the present invention.

  That is, the present invention relates to an α-aminoacetophenone skeleton-containing compound (I) having a function as a Michael addition donor represented by the following general formula (1) and a reactive compound (II) having a function as a Michael acceptor. A polymerizable initiator (B) obtained by Michael addition reaction with

一般式（１）

（一般式（１）中、
Ｒ_１は炭素原子数１〜１０のアルキル基又はアリール基を表し、Ｒ_２〜Ｒ_３は各々独立して炭素原子数１〜６のアルキル基又はアリール基を表し、またＲ_２とＲ_３とはそれぞれ一体となって環を形成してもよく、Ｒ_４〜Ｒ_７は各々独立して水素原子または脂肪族基又はアリール基を表し、Ｘ_１は水素原子又は炭素原子数１〜６のアルキル基を表し、Ｙ_１は下記一般式（２）又は一般式（３）で表される基を表す。）

General formula (1)

(In general formula (1),
R ₁ represents an alkyl group or aryl group having 1 to 10 carbon atoms, R _{2 to} R ₃ each independently represents an alkyl group or aryl group having 1 to 6 carbon atoms, and R ₂ and R ₃ May be combined together to form a ring, R _{4 to} R ₇ each independently represents a hydrogen atom, an aliphatic group or an aryl group, and X ₁ is a hydrogen atom or an alkyl having 1 to 6 carbon atoms. Y ₁ represents a group represented by the following general formula (2) or general formula (3). )

一般式（２）

（一般式（２）中、Ｘ_２及びＸ_３は各々独立して、炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基又はオキシアルキレン基を表す。）

General formula (2)

(In general formula (2), X ₂ and X ₃ each independently represent a linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms.)

一般式（３）
（一般式（３）中、Ｘ_４は置換基を有するか若しくは無置換の炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基又はオキシアルキレン基を表し、Ｒ_８およびＲ_９は各々独立して脂肪族基又はアリール基を表す。）、及び数平均分子量５００以上１５００以下であってかつ波長３００〜４５０ｎｍに吸収波長を持つ増感剤（Ｃ）とを併用することを特徴とする活性エネルギー線硬化型印刷インキに関する。

General formula (3)
(In the general formula (3), X ₄ represents a substituted or unsubstituted C 2-6 linear or branched alkylene group or oxyalkylene group, and R ₈ and R ₉ each represents Independently represents an aliphatic group or an aryl group), and a sensitizer (C) having a number average molecular weight of 500 or more and 1500 or less and having an absorption wavelength of 300 to 450 nm. The present invention relates to an active energy ray-curable printing ink.

  The present invention also relates to a printed matter obtained by printing the active energy ray-curable printing ink on a substrate and irradiating the active energy ray to be cured.

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray-curable printing ink which can reduce the migration after hardening, and is excellent in sclerosis | hardenability, and its printed matter can be provided.

FIG. 1 is a ¹ H-NMR chart of the compound (5) obtained in Synthesis Example 1.

  As described above, the polymerizable initiator (B) used in the active energy ray-curable printing ink of the present invention has an α-aminoacetophenone skeleton having a function as a Michael addition donor represented by the following general formula (1). A polymerizable initiator (B) obtained by a Michael addition reaction between the containing compound (I) and a reactive compound (II) having a function as a Michael acceptor,

一般式（１）

（一般式（１）中、Ｒ_１は炭素原子数１〜１０のアルキル基又はアリール基を表し、Ｒ_２〜Ｒ_３は各々独立して炭素原子数１〜６のアルキル基又はアリール基を表し、またＲ_２とＲ_３とはそれぞれ一体となって環を形成してもよく、Ｒ_４〜Ｒ_７は各々独立して水素原子または脂肪族基又はアリール基を表し、Ｘ_１は水素原子又は炭素原子数１〜６のアルキル基を表し、Ｙ_１は下記一般式（２）又は一般式（３）で表される基を表す。）

General formula (1)

(In General Formula (1), R ₁ represents an alkyl group or aryl group having 1 to 10 carbon atoms, and R _{2 to} R ₃ each independently represents an alkyl group or aryl group having 1 to 6 carbon atoms. R ₂ and R ₃ may be combined together to form a ring, R _{4 to} R ₇ each independently represents a hydrogen atom, an aliphatic group or an aryl group, and X ₁ represents a hydrogen atom or The alkyl group having 1 to 6 carbon atoms is represented, and Y ₁ represents a group represented by the following general formula (2) or general formula (3).

一般式（２）

（一般式（２）中、Ｘ_２及びＸ_３は各々独立して、炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基又はオキシアルキレン基を表す。）

General formula (2)

(In general formula (2), X ₂ and X ₃ each independently represent a linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms.)

一般式（３）
（一般式（３）中、Ｘ_４は置換基を有するか若しくは無置換の炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基又はオキシアルキレン基を表し、Ｒ_８およびＲ_９は各々独立して脂肪族基又はアリール基を表す。）と、数平均分子量３２０以上２０００以下であってかつ波長２００〜３００ｎｍに吸収波長を持つα−ヒドロキシケトン骨格含有光重合開始剤（Ｂ２）とを併用するものである。前記重合性開始剤（Ｂ）を用いることにより、優れた耐マイグレーション性を発現させることができ、また、前記α−ヒドロキシケトン骨格含有光重合開始剤（Ｂ２）を用いることにより、優れた耐マイグレーション性を保持しつつ、印刷物表面の硬化性を高めることができる。

General formula (3)
(In the general formula (3), X ₄ represents a substituted or unsubstituted C 2-6 linear or branched alkylene group or oxyalkylene group, and R ₈ and R ₉ each represents Independently represents an aliphatic group or an aryl group) and an α-hydroxyketone skeleton-containing photopolymerization initiator (B2) having a number average molecular weight of 320 or more and 2000 or less and an absorption wavelength of 200 to 300 nm. It is used together. By using the polymerizable initiator (B), excellent migration resistance can be developed, and by using the α-hydroxyketone skeleton-containing photopolymerization initiator (B2), excellent migration resistance can be obtained. It is possible to improve the curability of the printed surface while maintaining the properties.

Here, R ₁ in the general formula (1) is methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group. , Heptyl group, octyl group, nonyl group, decyl group, 2-ethylbutyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, 1-methylhexyl group, isoheptyl group, 1,1,3, 3-tetramethylbutyl group, 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group, 1,1,3-trimethylhexyl group, 1,1 , 3,3-tetramethylpentyl group, an alkyl group having 1 to 10 carbon atoms such as an isodecyl group. Among these, an ethyl group is preferable from the viewpoint of the reactivity of radicals generated by light irradiation.

Next, R ₂ and R ₃ are each independently a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group. A linear or branched alkyl group having 1 to 12 carbon atoms such as heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, etc. A hydroxyalkyl group having 2 to 4 carbon atoms;
A methoxyethyl group; an ethoxyethyl group; an alkylene group in which R ₂ and R ₃ together form a ring structure with a nitrogen atom;

に相当する構造として、下記構造式

As the structure corresponding to

で表されるピロリジン構造やピペリジン構造を形成するブチレン基、ペンテン基；Ｒ_２及びＲ_３と一体となって窒素原子と共にモルホリン骨格、Ｎ−メチルピペラジン骨格、２，６−ジメチルモルホリン骨格を形成する環構形成部位、即ち

A butylene group and a pentene group that form a pyrrolidine structure or a piperidine structure represented by the formula: together with R ₂ and R ₃ form a morpholine skeleton, an N-methylpiperazine skeleton, and a 2,6-dimethylmorpholine skeleton together with a nitrogen atom. Ring formation site, ie

に相当する構造として、下記構造式

As the structure corresponding to

を形成する構造部位を表す。これらのなでも特に合成上の収率の高さの点から炭素原子数１〜１２の直鎖状または分岐上のアルキル基が好ましい。

Represents the structural site that forms Among these, a linear or branched alkyl group having 1 to 12 carbon atoms is particularly preferable from the viewpoint of high yield in synthesis.

R _{4 to} R ₇ are each independently a hydrogen atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, pentyl group, hexyl group, Heptyl, octyl, 2-ethylbutyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, 1-methylhexyl, isoheptyl, 1,1,3,3-tetramethylbutyl, An alkyl group having 1 to 8 carbon atoms such as 2,2,4,4-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, 2-ethylhexyl group; or a phenyl group. Among these, it is preferable that all of R _{4 to} R ₇ are hydrogen atoms from the viewpoint of easy availability of raw materials.

In the general formula (1), X ₁ is a single bond or a linear or branched methylene group having 1 to 6 carbon atoms, an ethylene group, an alkylene group such as propylene. Here, examples of the substituent include the substituents described for the aliphatic group which may have the substituent.

Next, in General Formula (1), Y ₁ represents a group represented by General Formula (2) or General Formula (3).

Here, the general formula (2) constituting Y ₁ is represented by the following structural formula.

一般式（２）
斯かる一般式（２）中、Ｘ_２及びＸ_３は各々独立して、炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基又はオキシアルキレン基を、Ｘ_５は、単結合、−Ｏ−または−ＮＨ−を表す。Ｘ_２及びＸ_３は、具体的には、鎖状若しくは分岐状のメチレン基、エチレン基、プロピレン基、ブチレン基、オキシメチレン基、オキシプロピレン基、オキシブチレン基等があげられる。

General formula (2)
In the general formula (2), X ₂ and X ₃ each independently represent a linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms, X ₅ represents a single bond, — O— or —NH— is represented. Specific examples of X ₂ and X ₃ include a chain or branched methylene group, ethylene group, propylene group, butylene group, oxymethylene group, oxypropylene group, and oxybutylene group.

  Specific examples of the structure represented by the general formula (2) described in detail above include the following structures.

Next, general formula (3) constituting Y ₁ is represented by the following structural formula.

一般式（３）

ここで一般式（３）中、Ｘ_４は置換基を有するか若しくは無置換の炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基又はオキシアルキレン基を表し、Ｒ_８およびＲ_９は各々独立して脂肪族基又はアリール基を表す。ここで、Ｘ_４における置換基とは、具体的には、鎖状若しくは分岐状のメチレン基、プロピレン基、ブチレン基、オキシメチレン基、オキシプロピレン基、オキシブチレン基等が挙げられる。

General formula (3)

Here, in the general formula (3), X ₄ represents a substituted or unsubstituted linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms, and R ₈ and R ₉ are Each independently represents an aliphatic group or an aryl group. Here, specific examples of the substituent in X ₄ include a chain or branched methylene group, a propylene group, a butylene group, an oxymethylene group, an oxypropylene group, and an oxybutylene group.

R ₈ and R ₉ each independently represents an aliphatic group or an aryl group. Here, examples of the aliphatic group and the aryl group include those constituting R _{1 to} R ₇ described above.

As the general formula (1), R ₁ is an ethyl group, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a hydrogen atom, and R ₅ is a hydrogen atom. , R ₆ is a hydrogen atom, R ₇ is a hydrogen atom, X ₁ is a hydrogen atom, Y ₁ is a piperazinyl group; R ₁ is an ethyl group, R ₂ is a methyl group, R ₃ is a dodecyl group, R ₄ is a hydrogen atom, R ₅ is a hydrogen atom, R ₆ is a hydrogen atom, R ₇ is a hydrogen atom, X ₁ is a hydrogen atom, Y ₁ Is a piperazinyl group; R ₁ is an ethyl group, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is a hydrogen atom, R ₅ is a hydrogen atom, and R ₆ is a hydrogen atom, _{R 7} is a hydrogen atom, _{X 1} is hydrogen atom, _{Y 1} is 2,5-di Chirupiperajiniru a group compound; R ₁ is an ethyl group, R ₂ is a methyl group, R ₃ is a methyl group, R ₄ is hydrogen atom, R ₅ is a hydrogen atom, R ₆ is hydrogen A compound in which R ₇ is a hydrogen atom, X ₁ is a hydrogen atom, and Y ₁ is a methyl (2- (methylamino) ethyl) amino group; R ₁ is an ethyl group, and R ₂ is A methyl group, R ₃ is a methyl group, R ₄ is a hydrogen atom, R ₅ is a hydrogen atom, R ₆ is a hydrogen atom, R ₇ is a hydrogen atom, and X ₁ is a methyl group And Y ₁ is preferably a piperazinyl group.

  Specific examples of the compound represented by the general formula (1) include compounds represented by the following structural formulas (5) to (9).

（６）

(6)

（７）

(7)

（８）

(8)

（９）

(9)

  Especially, what is represented by the said Structural formula (5) is preferable from the height of sclerosis | hardenability.

A compound having the cyclic secondary amino group only at Y ₁ in the general formula (1) is preferable because the curability is very high. Such a compound is a compound of the structural formula (23), the structural formula (24), or the structural formula (25).

In addition, the compound having the cyclic secondary amino group only in Y ₂ in the general formula (1) has very high curability, and the cleavage product generated by absorption of active energy rays can be converted into a polymer matrix. This is particularly preferable because uptake is also promoted. Examples of such a compound include compounds represented by structural formula (14), structural formula (15), structural formula (17), structural formula (18), structural formula (20), and structural formula (21).

Further, the compound having a cyclic secondary amino group in Y ₁ and Y ₂ in the general formula (1) is preferable from the point of migration of the substances derived from the photopolymerization initiator can be highly inhibited. Examples of such a compound include compounds represented by Structural Formula (5), Structural Formula (6), Structural Formula (8), Structural Formula (9), Structural Formula (11), and Structural Formula (12).

These α-aminoacetophenone skeleton-containing compounds (I) can be produced by the following synthesis method depending on the introduction means of Y ₁ -and Y _2- in the general formula (1).

That is, by reacting a halogenated benzene with an acid halide compound, an alkyl acetophenone having a halogen atom on the α carbon atom of the carbonyl and a halogen atom on the aromatic nucleus is synthesized, and then a secondary monoamine compound. (HN (R ₂ ) (R ₃ )) is reacted. Next, benzyl bromide having a substituent (—X ₁ —X ₂ —OR) as a substituent on the aromatic nucleus is reacted (where R is an alkyl group), and treated with alkali to end with a hydroxyl group ( Or a thiol group), and a reaction with a secondary amino group-containing compound (Y ₁ -H), followed by a reaction with a secondary amino group-containing compound (Y ₂ -H), The target α-aminoacetophenone skeleton-containing compound (I) can be produced.

More specifically, the above method can be produced according to the following reaction formula, for example, taking the compound represented by the structural formula (5) as an example. (In the following structural formulas, C, CH, and CH ₂ may be omitted.)

  That is, the brominated compound (101) is substituted with dimethylamine to give a dimethylamino compound (102), and further reacted with benzyl bromide (103) having a substituent at the 4-position to lead to a quaternary ammonium chloride, A (103) intermediate having an α-aminoacetophenone skeleton is synthesized by a 1.2-rearrangement reaction (Stevens transfer) with a base. Then, it can be made to react with piperazine at 60 ° C. to 160 ° C. to produce a compound (5) whose target Michael addition donating function is a piperazino group.

Here, in the reaction formula of the above-described method, R _{1 to} R ₆ , X ₁ , X ₂ , Y ₁ , Y ₂ are synonymous with the general formula (1), and Hal is a fluorine atom, a bromine atom, a chlorine atom. Represents a halogen atom such as

In the above method, as the secondary monoamine compound (HN (R ₂ ) (R ₃ )), dimethylamine, diethylamine, methylbutylamine, methyloctylamine, methyldodecylamine, ethylhexylamine, diethanolamine, diisopropanolamine, diisobutanol Examples include amine, 2,2′-diethoxydiethylamine, 2,2′-dimethoxydiethylamine, morpholine, pyrrolidine, piperidine, N-methylpiperazine, and 2,6-dimethylmorpholine. The reaction conditions for reacting the secondary monoamine compound (HN (R ₂ ) (R ₃ )) are, for example, carbonates such as calcium carbonate, potassium carbonate and sodium carbonate, and tertiary amines such as triethylamine and diisopropylethylamine. In the presence of a base such as 0 ° C. to 80 ° C. Moreover, when making a secondary amine act as a base, it can manufacture using excess amount.

  Since the α-aminoacetophenone skeleton-containing compound (I) that functions as a Michael addition donor represented by the general formula (1) described in detail above has a Michael addition donating function, the compound has a function as a Michael acceptor. Michael addition reaction with (II) gives a Michael addition reactant.

  In the present invention, as the compound (II) having a function as a Michael acceptor, a reactive compound having a reactive group that contributes to curing by light irradiation (hereinafter abbreviated as “photocurable group”). When used, the resulting Michael addition reactant has both a photoinitiating ability and a photocuring function, functions well as a reactive initiator, and further improves the effect of preventing migration.

(Reactive compound (II) having a function as a Michael acceptor)
Since the reactive compound (II) having a function as a Michael acceptor that can be used here is a polyfunctional reactive compound having a plurality of photocurable groups, the photocuring function is particularly good. preferable.

  Here, examples of the polyfunctional reactive compound having a plurality of photocurable groups include α, β-unsaturated carbonyl compounds such as maleimide compounds, maleic acid ester compounds, fumaric acid ester compounds, and (meth) acrylate compounds. It is done. Among these, a (meth) acrylate compound is particularly preferable because it is easy to control the Michael addition reaction particularly during synthesis and has high reactivity during photocuring and can be expected to effectively prevent migration.

  Examples of (meth) acrylate compounds include, for example, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) ) Acrylate, hexanediol di (meth) acrylate, bifunctional acrylate such as neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and its modified alkylene oxide such as ethylene oxide and propylene oxide, pentaerythritol tri Tetra (meth) acrylate and its modified alkylene oxide such as ethylene oxide and propylene oxide, ditrimethylolpropane tetra (meth) acrylate and its Alkylene oxide modified products such as tylene oxide and propylene oxide, polyfunctional (meth) acrylates such as dipentaerythritol tetra or penta or hexa (meth) acrylate and its caprolactone modified product, bisphenol A diglycidyl ether and trimethylolpropane triglycidyl ether Such as epoxy (meth) acrylate obtained by reaction of polyglycidyl ether with (meth) acrylic acid, polyisocyanate compounds such as isophorone diisocyanate and hexamethylene diisocyanate trimer, hydroxyethyl (meth) acrylate and pentaerythritol tris Many urethane (meth) acrylates, trimellitic acid, succinic acid, etc. obtained by reaction with acrylates having hydroxyl groups such as (meth) acrylate Polyester (meth) acrylate obtained by a reaction between a basic acid, a polyol such as ethylene glycol or neopentyl glycol, and a (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate or pentaerythritol tri (meth) acrylate, Examples include, but are not limited to, polymers of glycidyl (meth) acrylate and monofunctional (meth) acrylate and high molecular weight poly (meth) acrylate obtained by reaction with (meth) acrylic acid. is not. These reactive compounds may be used alone or in combination.

  Especially, since it becomes a high molecular weight body after hardening and it can fix | immobilize firmly with a cured film, as said reactive compound, a trifunctional or more than trifunctional (meth) acrylate compound is the most preferable. When a trifunctional or higher functional (meth) acrylate having three or more (meth) acryloyl groups is selected as the reactive compound having a function as a Michael acceptor, the photocurable group of the Michael addition reactant of the present invention Is preferably 2 or more.

(Michael addition reaction)
In the present invention, the Michael addition reaction between the α-aminoacetophenone skeleton-containing compound (I) and the reactive compound (II) having a function as the Michael acceptor is not particularly limited and is a known and usual reaction. Can be done under conditions. As a general method, there is a method in which the α-aminoacetophenone skeleton-containing compound (I) and the reactive compound (II) having a function as the Michael acceptor are mixed at 0 to 150 ° C. in a reaction vessel. For example, a catalyst or a solvent can be used.

  Usable catalysts include, for example, tetraethylammonium fluoride, tetrabutylammonium hydroxide, potassium hydroxide, tetramethylguanidi, diazabicycloundecene, sodium t-butyrate, tri-n-octylphosphine, triphenyl A phosphine etc. are mentioned.

  Examples of organic solvents include saturated hydrocarbons such as pentane, hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, methanol, ethanol, isopropanol, 2-butanol, t-butanol, ethylene glycol, and carbitol. Alcohols such as dimethyl ether, diethyl ether, 1,4-dioxane, tetrahydrofuran (THF), amides such as dimethylformamide (DMF), halogen solvents such as chloroform and dichloromethane, dimethyl sulfoxide (DMSO), etc. Can do.

  The mixing ratio of the α-aminoacetophenone skeleton-containing compound (I) and the reactive compound (II) having a function as the Michael acceptor is not particularly limited, but the α-aminoacetophenone skeleton-containing compound ( The equivalent ratio [(i) / (ii)] of the nucleophilic functional group (i) in I) and the functional group (ii) having the Michael demand ability in the reactive compound (II) is 1/1. It is preferably 5 to 1/30. When the equivalent ratio [(i) / (ii)] exceeds 1 / 1.5, the possibility of migration from the coating film of the compound (I) or a decomposition product thereof increases, and the equivalent ratio [(i) / ( If ii)] is less than 1/30, the curing performance of the Michael addition reaction product tends to be inferior. From the viewpoint of the curing performance of the resulting Michael addition reaction product and the amount of the coating film eluate, the equivalent ratio [(i) / (ii)] is particularly preferably 1/2 to 1/20.

  Examples of the Michael addition reactant thus obtained include the following formulas (M1) to (M8).

（Ｍ１）

(M1)

（Ｍ２）

(M2)

（Ｍ３）

(M3)

（Ｍ４）

(M4)

（Ｍ５）

(M5)

（Ｍ６）

(M6)

（Ｍ７）

(M7)

（Ｍ８）

(M8)

  In the present invention, a Michael addition reaction product (hereinafter referred to as “the Michael addition reaction product”) between the α-aminoacetophenone skeleton-containing compound (I) having a function as a Michael addition donor and a reactive compound (II) having a function as a Michael acceptor. (This is abbreviated as “Michael addition reaction product (III)”.) Is preferably used as a photopolymerization initiator because it exhibits excellent curability and a good effect of reducing migration. .

  Next, in the present invention, the sensitizer (C) used together with the polymerization initiator (B) has a number average molecular weight of 500 or more and 1500 or less and an absorption wavelength at a wavelength of 300 to 450 nm is a high wavelength region. And has a function of efficiently transmitting the energy obtained by the absorption to the polymerization initiator (B). Here, when the number average molecular weight of the high molecular weight compound constituting the sensitizer (C) is less than 500, migration tends to be caused. On the other hand, when the number average molecular weight exceeds 1500, the effect as a sensitizer is obtained. Becomes lower.

  Examples of such a sensitizer (C) include a high molecular weight substance of diethylaminobenzophenone, a high molecular weight of Michler's ketone, a high molecular weight compound having a thioxanthyl structure, and the like, from the point of excellent absorption performance for light having a wavelength of 300 to 450 nm. High molecular weight compounds having a thioxanthyl structure are preferred. Examples of such a thioxanthyl structure include those represented by the following structural formula:

（式中、Ｘは塩素原子又は水素原子である。）
該構造を有する高分子量化合物は、チオキサンチル構造を一分子内に２〜４個有するものが、増感作用が良好なものとなる点から好ましく、斯かる化合物としては、具体的には、脂肪族トリオールのアルキレンオキシド付加体のトリ９−オキソ−６Ｈ−チオキサンテン−カルボキシレート（ＲＡＨＮ社製３官能型増感剤「ジェノポールＴＸ１」：数平均分子量８２０）、ポリ（オキシ−１，４−ブチレン）グリコールのジ（９−オキソ−９Ｈ−チオキサンチニル）オキシ酢酸エステル（２官能型増感剤ＩＧＭレジン社製「オムニポールＴＸ」数平均分子量６６０）、ペンタエリスリトールのテトラ−ポリ（オキシ−２，３−プロピレン）グリコール付加体の（１−クロロ−９−オキソ−９Ｈ−チオキサンチニル）オキシ酢酸エステル（ＬＡＭＢＳＯＮ社製「スピードキュア７０１０」数平均分子量１３５０）等が挙げられる。

(In the formula, X is a chlorine atom or a hydrogen atom.)
The high molecular weight compound having this structure is preferably one having 2 to 4 thioxanthyl structures in one molecule from the viewpoint of good sensitizing action. Tri9-oxo-6H-thioxanthene-carboxylate of an alkylene oxide adduct of triol (trifunctional sensitizer “Genopor TX1” manufactured by RAHN: number average molecular weight 820), poly (oxy-1,4-butylene) ) Di (9-oxo-9H-thioxanthinyl) oxyacetate ester of glycol ("OMNIPOL TX" number average molecular weight 660 manufactured by IGM Resin Co., Ltd., bifunctional sensitizer), tetra-poly (oxy-2,3) of pentaerythritol -(Propylene) glycol adduct (1-chloro-9-oxo-9H-thioxanthinyl) oxyacetate (LAM) SON Co., Ltd. "Speed Cure 7010" number average molecular weight 1350), and the like.

  In the present invention, by using the sensitizer (C) having an absorption band in a long wavelength region of 300 to 450 nm together with the polymerization initiator (B), the curability inside the printed material at the time of printing is good. In addition, particularly when a colorant component that easily absorbs a wavelength of 300 to 450 nm, such as black ink, is used, internal crosslinking can be favorably promoted. Therefore, in the present invention, since excellent curability can be expressed without using a large amount of a polymerization initiator or sensitizer, the amount of those used can be reduced, and migration of the initiator and sensitizer is suppressed. Can be prevented satisfactorily. Specifically, the usage-amount of the said sensitizer (C) can be used in the range used as 5-500 mass parts with respect to 100 mass parts of said polymerization initiators (B).

  Moreover, when using the high molecular weight compound which has a thioxanthyl structure among the said sensitizer (C), and also when using together an amine-type sharpener, this sensitizer (C) itself functions also as a polymerization initiator. Therefore, the curability can be further improved.

Such amine-based sensitizers include, for example, an aminobenzoate compound (“Genopor AB-2” manufactured by RAHN) and a compound having two dimethylaminobenzoate structures in one molecule (“ESACURE A198” manufactured by Lamberti). ), A compound having an aminobenzoyl group at both ends of a polyethylene glycol chain (“Omnipol ASA” manufactured by IGM Resin), ethyl-4-dimethylaminobenzoate (“ESACURE A198” manufactured by Lamberti), and the like. Among these, aminobenzoate compound ("Genopor AB-2" manufactured by RAHN), which has a relatively high molecular weight from the viewpoint of migration prevention, and a compound having two dimethylaminobenzoate structures in one molecule ("Lamberti" ESACURE A198 ") and a compound having an aminobenzoyl group at both ends of a polyethylene glycol chain (" Omnipol ASA "manufactured by IGM Resin) are preferred.
The amount of the amine-based sensitizer used is preferably in the range of 5 to 100 parts by mass with respect to 100 parts by mass of the sensitizer (C).

  The active energy ray-curable printing ink of the present invention is an α-hydroxyketone having a number average molecular weight of 320 or more and 2000 or less and an absorption wavelength of 200 to 300 nm in addition to the polymerization initiator (B) as a polymerization initiator. It is preferable to use the skeleton-containing polymerization initiator (B2) in combination from the viewpoint that the curability can be further improved while maintaining excellent migration resistance. That is, since the α-hydroxyketone skeleton-containing polymerization initiator (B2) has a number average molecular weight in the range of 320 to 2000, the curability is improved while appropriately suppressing the migration of the initiator (B2) itself. be able to. Moreover, since it has an absorption wavelength in wavelength 200-300 nm, the sclerosis | hardenability of the surface in printed matter can be improved greatly. Therefore, by using the α-hydroxyketone skeleton-containing polymerization initiator (B2) together with the polymerization initiator (B) as a polymerization initiator and using the sensitizer (C), Sensitivity can be increased from a short wavelength region to a long wavelength region, a wide range of use can be made from UV varnish to black ink, and excellent curability can be exhibited in any wavelength region.

  As such an α-hydroxyketone skeleton-containing polymerization initiator (B2), specifically, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl } -2-Methyl-propan-1-one (number average molecular weight: 340.4), oligo (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone) (number average molecular weight : 424.57), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) phenoxy] phenyl} -2-methylpropanone (number average molecular weight: 342.39) An α-hydroxyketone photopolymerization initiator having an average molecular weight of 320 or more and 1000 or less, and a polyurethane structure as a main skeleton, an acryloyl group and 2-hydroxy-2-methyl-propionyl-phenol The group, a compound having two respectively in one molecule, for example, BASF Corp. "Irgacure LEX201" (number average molecular weight: 1100), and the like.

  In the present invention, among these, an α-hydroxyketone photopolymerization initiator having a number average molecular weight of 320 or more and 1000 or less is preferable from the viewpoint of excellent curability.

Here, the number average molecular weight in the sensitizer (C) and the α-hydroxyketone skeleton-containing polymerization initiator (B2) was measured under the following conditions by gel permeation chromatography (GPC) (polystyrene conversion). Value.
Measurement apparatus: The measurement was performed using the HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: 4 TSKgelGMH _HR- N manufactured by Tosoh Corporation are used.
Column temperature: 40 ° C.
Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight.
Sample injection volume: 100 microliters.
Standard: Monodisperse polystyrene detector: differential refractometer.

  Here, the use ratio of the polymerization initiator (B) and the α-hydroxyketone skeleton-containing polymerization initiator (B2) is such that the mixing ratio [(B) / (B2)] on a mass basis is 30/100. A ratio of ˜800 / 100 is preferable from the viewpoint of good balance between curability and migration reduction effect. Particularly, the α-hydroxyketone skeleton-containing polymerization initiator (B2) has a number average molecular weight of 320 or more. In the case of using an α-hydroxyketone photopolymerization initiator that is 1000 or less, the curability of the initiator is remarkably increased, and therefore the blending ratio of the polymerization initiator (B) having a high effect of reducing migration is increased. Can do. From such a viewpoint, the blending ratio [(B) / (B2)] on a mass basis is a ratio of 100/100 to 800/100, so that both low migration and curability can be achieved at a high level. It is preferable from the point which can be performed. In this case, the blending ratio of the sensitizer (C) is a ratio of 5 to 300 parts by mass with respect to 100 parts by mass of the polymerization initiator (B ″). It is preferable from the viewpoint of achieving both at a high level.

  Next, the active energy ray polymerizable compound (A) used in the active energy ray curable printing ink of the present invention is a maleimide compound, a maleate ester compound, a fumarate ester compound having various ethylenic double bonds, ( Although a meth) acrylate compound, a vinyl ether compound, etc. are mentioned, a (meth) acrylate compound is preferable from the point which is excellent in the ease of material acquisition, and the cure rate.

  Here, as the (meth) acrylate compound, a polyfunctional (meth) acrylate compound having a plurality of reactive groups contributing to curing by irradiation is preferable. Specifically, diethylene glycol di (meth) acrylate, dipropylene glycol di- Bifunctional such as (meth) acrylate, tripropylene glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate Acrylate: Trimethylolpropane tri (meth) acrylate, trimethylolpropane modified with alkylene oxide such as ethylene oxide or propylene oxide, tri (meth) acrylate, pentaerythritol tri or tetra Tetrahydric alcohol tri- or tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, or ditrimethylolpropane modified with ethylene oxide or propylene oxide such as ethylene oxide or propylene oxide. Monovalent polyvalents such as polyfunctional (meth) acrylates such as tri- or tetra (meth) acrylate of tetrahydric alcohol modified with oxide, dipentaerythritol tetra or penta or hexa (meth) acrylate, and caprolactone modified product of dipentaerythritol (Meth) acrylate;

Epoxy (meth) acrylates obtained by reaction of polyglycidyl ethers such as bisphenol A diglycidyl ether and trimethylolpropane triglycidyl ether with (meth) acrylic acid; polyisocyanate compounds such as isophorone diisocyanate and hexamethylene diisocyanate trimer And urethane (meth) acrylate obtained by reaction of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate and other acrylates having hydroxyl groups; polybasic acids such as trimellitic acid and succinic acid, ethylene glycol, Reaction between a polyol such as neopentyl glycol and a (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate or pentaerythritol tri (meth) acrylate Polyesters obtained by (meth) acrylate;
Oligomeric polyvalent (meth) acrylates such as high molecular weight poly (meth) acrylate obtained by reaction of a polymer of glycidyl (meth) acrylate and monofunctional (meth) acrylate and (meth) acrylic acid, etc. Can be mentioned.

  Among these, the reactive compound is most preferably a tri- or higher functional monomer type (meth) acrylate compound because it becomes a high molecular weight body after curing and can be firmly fixed by a cured film. Moreover, in this invention, it is preferable to mix | blend the said oligomer type polyvalent (meth) acrylate as binder resin in addition to the said monomer type (meth) acrylate compound more than trifunctional. In this case, the mixing ratio of the trifunctional or higher monomer type (meth) acrylate compound and the oligomer type polyvalent (meth) acrylate is such that the mass ratio [the former / the latter] is 10/100 to 300/100. Is preferred.

  In addition, from the viewpoint of adjusting the viscosity of the active energy ray-curable printing ink of the present invention, when it is desired to reduce the viscosity of the ink, the active energy ray polymerizable compound (A) is a monomer type monofunctional compound. A monofunctional (meth) acrylate compound or a monofunctional vinyl ether compound can be used in combination.

  Here, as monofunctional (meth) acrylate compounds, for example, (meth) acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. Hydroxyalkyl (meth) acrylates; butoxyethyl acrylate, alkoxyalkyl (meth) acrylates such as methoxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, methoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Polypropylene glycol mono (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, noni Polyalkylene glycol (meth) acrylates such as phenoxy polypropylene glycol (meth) acrylate; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, isobornyl (meth) acrylate; benzyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, tetrahydrofurfuryl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminomethyl S (meth) acrylate and other (meth) acrylates; diacetone (meth) acrylamide, Examples include (meth) acrylamide such as acryloylmorpholine.

  On the other hand, examples of the monofunctional vinyl ether compound include alkyl vinyl ethers and cycloalkyl vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether and 3-hydroxypropyl vinyl ether. It is done.

  When these monofunctional (meth) acrylate compounds or monofunctional vinyl ether compounds are used, the amount used is such an amount that does not induce an increase in the migration amount of the unreacted monomer and a decrease in the abrasion resistance of the ink coating film. Specifically, in the active energy ray polymerizable compound (A), it is preferably in a range of 30% by mass or less.

  The active energy ray-curable printing ink of the present invention comprises the above-described active energy ray-polymerizable compound (A), polymerization initiator (B), α-hydroxyketone skeleton-containing polymerization initiator (B2), sensitizer ( In addition to C) and amine-based sensitizers, pigments, binder resins, and other various additives can be blended as necessary.

  Here, the mixing ratio of each component is a monomer type monofunctional compound or a monomer type polyvalent (meth) acrylate compound (hereinafter abbreviated as “monomer type active energy ray polymerizable compound (A)”). , With respect to 100 parts by mass of a mixture of the polymerization initiator (B) and the α-hydroxyketone skeleton-containing polymerization initiator (B2) (hereinafter, (B) and (B2) are abbreviated as “initiator component”). 1 to 70 parts by weight of the pigment and 3 to 70 parts by weight of the binder resin can be used. From the balance between the color density and printability of the printed matter, the monomer type active energy ray polymerizable compound (A) and the start It is preferable that they are 5-30 mass parts of pigments, and 5-50 mass parts of the said binder resin with respect to 100 mass parts of mixtures with an agent component. The offset ink obtained in this way is preferably designed to be usually 3 to 200 Pa · s (25 ° C.), although it depends on the printing apparatus used.

  The binder resin used here may be any resin that has appropriate pigment affinity and dispersibility and has rheological properties required for printing ink, and is an oligomer type exemplified as the active energy ray polymerizable compound (A). In addition to polyvalent (meth) acrylates, for example, non-reactive resins include diallyl phthalate resin, epoxy resin, polyurethane resin, polyester resin, petroleum resin, rosin ester resin, poly (meth) acrylate ester, cellulose derivative, vinyl chloride A vinyl acetate copolymer, a polyamide resin, a polyvinyl acetal resin, a butadiene-acrylonitrile copolymer, and the like, or an epoxy acrylate compound, a urethane acrylate compound having at least one polymerizable group in the resin molecule, Polyester acrylate Compounds, and the like.

  In the case where a compound having at least one polymerizable group in the non-reactive resin or resin molecule is blended as a binder resin, the monomer-type active energy ray polymerizable compound (A) and the non-reactive resin or resin molecule The blending ratio with the compound having at least one polymerizable group therein is preferably such that the mass ratio [the former / the latter] is 10/100 to 300/100.

  As the pigment used in the present invention, an inorganic pigment or an organic pigment can be used. Inorganic pigments include yellow lead, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, alumina white, calcium carbonate, ultramarine, carbon black, graphite, bengara, iron oxide, contact method, furnace method, thermal method, etc. Carbon black produced by the above method can be used. In the present invention, as described above, even if carbon black that easily absorbs long-wavelength UV light is used, excellent curability is exhibited. Therefore, when carbon black is blended, a UV printing ink with good curability is produced. It becomes possible.

  Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acidic dye chelates), nitro pigments, nitroso pigments, aniline black, various fluorescent pigments, metal powder pigments Various known and publicly used pigments can be used.

  The average particle diameter of the pigment is appropriately designed according to the application. For example, when applying the active energy ray-curable composition of the present invention to a printing ink such as an offset ink, the average particle size of the pigment is preferably in the range of 10 to 500 nm, more preferably about 50 to 300 nm. Is.

  When a pigment is used, it is preferable to use a pigment dispersant for the purpose of enhancing dispersion stability with respect to the active energy ray polymerizable compound. Specifically, “Ajisper PB821”, “PB822”, “PB817” manufactured by Ajinomoto Fine Techno Co., “Solsperse 5000”, “24000GR”, “32000”, “33000”, “36000” manufactured by Lubrizol, “39000”, “44000”, “Disparon DA-703-50”, “DA-705”, “DA-725” manufactured by Enomoto Kasei Co., Ltd., “DISPERBYK111”, “YK168”, “YK180” manufactured by BYK, etc. However, it is not limited to these. Further, the amount of the pigment dispersant used is preferably in the range of 3 to 80% by mass, particularly preferably in the range of 5 to 60% by mass with respect to the pigment. When the amount used is less than 3% by mass, the dispersion stability tends to be insufficient, and when it exceeds 80% by mass, the viscosity of the ink tends to increase.

The active energy ray curable printing ink of the present invention may further use a photoinitiator such as a photosensitizer or a tertiary amine in order to further improve the curing performance.
The photosensitizer is not particularly limited, and examples thereof include thioxanthone series such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzophenone series such as 4,4′-bis (diethylamino) benzophenone, anthraquinone and the like. .

  On the other hand, the tertiary amine is not particularly limited, and examples thereof include ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and the like.

  In addition, a high molecular weight compound in which a plurality of photosensitizers or tertiary amines are branched with a polyhydric alcohol or the like in one molecule can be used as appropriate. The photoinitiator aid is preferably used in an amount of 0.03 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on the total amount of the active energy ray-curable printing ink.

Moreover, a well-known photoinitiator can also be used together in the range which does not impair the effect of this invention. Specifically, benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like are preferred. In addition, molecular cleavage types other than these include 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
Even if 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are used in combination Further, benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4′-methyl-diphenyl sulfide, etc., which are hydrogen abstraction type photopolymerization initiators, can also be used in combination.

  Further, if necessary, various coupling agents; extender pigments; antioxidants; polymerization inhibitors within a range that does not depart from the object of the present invention, in particular, within a range that can maintain storage stability, heat resistance, solvent resistance, and the like. Stabilizers, fillers, and other auxiliaries can be added.

  Extender pigments are widely used for the purpose of improving physical properties and imparting functionality such as adjustment of ink fluidity, prevention of misting during printing, and prevention of penetration into paper substrates. Examples of extender pigments include publicly known organic pigments for coloring, such as extender pigments for printing inks published in “Handbook of Pigments (edited by the Japan Pigment Technical Association)”, calcium carbonate, magnesium carbonate Kaolin clay, talc, bentonite, mica, barium sulfate, silica, aluminum hydroxide and the like can be used.

  The coupling agent is a compound that chemically binds the inorganic material and the organic material, or improves the affinity with a chemical reaction and enhances the function of the composite material. For example, γ- (2-aminoethyl) ) Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane; γ-methacryloxypropyltrimethoxysilane; silane compounds such as γ-glycidoxypropyltrimethoxysilane, tetra-isopropoxytitanium And titanium compounds such as tetra-n-butoxy titanium, and aluminum compounds such as aluminum isopropylate. These addition amounts are 0.1-10 mass parts with respect to 100 mass parts of active energy ray hardening-type printing inks of this invention, Preferably it is 0.2-5 mass parts.

  Antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,4,6-tri-t-butylphenol, 2,2′-methylene-bis (4-methyl- 6-t-butylphenol) and the like, 2,2,6,6-tetramethylpiperidine derivative antioxidants called HALS, phosphorus-based and sulfur-based secondary antioxidants. . On the other hand, examples of the polymerization inhibitor include, but are not limited to, nitrosamine salts and the like. These antioxidants and polymerization inhibitors can be used alone or in combination of two or more. These addition amount is 0.01-2.0 mass parts with respect to 100 mass parts of active energy ray-curable compositions of this invention, Preferably it is 0.03-1.0 mass part.

  Other auxiliary agents include, for example, paraffin wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, silicon compound for the purpose of imparting friction resistance, anti-blocking property, slipperiness or anti-scratch property; Depending on the required performance, ultraviolet absorbers, infrared absorbers, antibacterial agents and the like can be mentioned. It is preferable that the addition amount of these adjuvants is 0-10 mass parts with respect to 100 mass parts of composition whole quantity.

  In order to obtain the active energy ray-curable printing ink of the present invention, the components described above may be mixed, and the mixing order and method are not particularly limited. For example, each of the above components at a temperature between room temperature and 100 ° C., kneader, three rolls, sand mill, gate mixer, ultrasonic homogenizer, high pressure homogenizer, paint shaker, sand grinder, dyno mill, disperse mat, bead mill, SC mill, nanomizer, etc. Can be obtained by using a kneaded meat, a mixing machine, a preparation machine or the like. Among these, it is preferable to produce by a kneader, a three-roll roll, and a bead mill from the viewpoint that a highly viscous offset ink can be efficiently produced.

  The active energy ray-curable printing ink of the present invention can be printed on a printing substrate and polymerized and cured with active energy rays to obtain a printed matter. The active energy rays used here refer to ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays, microwaves, high frequencies, visible rays, infrared rays, laser rays, and the like. Of these, ultraviolet rays are preferred.

  Ultraviolet rays having a wavelength of 180 to 400 nm are effective, but light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm are particularly useful for the active energy ray-curable composition and the active energy ray-curable ink composition of the present invention. It is effective for curing. Examples of the light source include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, a short arc lamp, a helium / cadmium laser, and an argon laser. , Excimer laser, and LED lamp.

Although the amount of ultraviolet irradiation is not unconditionally determined because it is affected by the type of light source used and the amount of the compound (M) and reaction product, a range of 10 to 2000 J / m ² is preferable from the viewpoint of productivity.

  The active energy ray-curable printing ink of the present invention described in detail above is used when the offset ink is printed in multiple colors, such as yellow (yellow), red (magenta), indigo (cyan), and black (black). The active energy ray-curable printing ink of the present invention may be used for one color of the process four-color ink, or may be used for all colors. For example, when the printed material is used for food packaging, it is preferable to use the active energy ray-curable composition of the present invention for all colors in order to suppress migration as much as possible.

  The printing substrate used in the printed matter of the present invention is not particularly limited. For example, paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, various synthetic papers, polyester resins, acrylic resins , Vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, polycarbonate film or the like Examples thereof include sheets, cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

^[1 H-NMR measurement conditions]
Apparatus: JEOL Ltd. FT-NMR
JNM-LA300 (300MHz)
Measuring solvent: deuterated chloroform (CDCl ₃ -d1)
Internal standard: Tetramethylsilane (TMS)

[Synthesis of α-aminoacetophenone skeleton-containing compound (I) having a function as a Michael addition donor]

Synthesis Example 1 [Synthesis of Compound (5) (2-Dimethylamino-1- (4-piperazinylphenyl) -2-benzyl-butan-1-one)]
[Step 1]

A 1 L four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, alkali trap and dropping funnel was charged with 121.8 g of aluminum chloride (anhydrous) and 300 mL of dehydrated dichloromethane, and using an ice bath under a nitrogen stream. Ice-cooled. To this was added 200 g of 2-bromobutyryl bromide. A mixed solution of 83.6 g of fluorobenzene and 100 mL of dehydrated dichloromethane was dropped into the previous flask using a dropping funnel over 20 minutes. After completion of dropping, the ice bath was removed and stirring was continued for 2 hours.
After completion of the stirring, the reaction solution was put into 1 L of ice water and stirring was continued for 2 hours. After standing, liquid separation was performed, and the lower layer was collected. Washed twice with 2N hydrochloric acid, washed once with saturated aqueous sodium hydrogen carbonate solution, and washed twice with saturated brine. After drying overnight with magnesium sulfate, dichloromethane was distilled off under reduced pressure to obtain 2-bromo-1- (4-fluorophenyl) -1-butanone (101).

Yield: 214.3 g, Yield: 100%
¹ H-NMR (CDCl ₃ ): 1.11 ppm (t, 3H, —CH ₃ ), 2.20 ppm (m, 2H, —CH ₂ —), 5.04 ppm (dd, 1H, Br— CH 3 ), 7 .19 ppm (m, 2H, aromatic), 8.07 ppm (m, 2H, aromatic)
[Step 2]

  A 2 L four-necked flask equipped with a stirrer and a thermometer was charged with 157.7 g of the intermediate (101) and 500 mL of methyl ethyl ketone, and cooled with ice using an ice bath. 174g of 50% dimethylamine aqueous solution was dripped there over 30 minutes using the dropping funnel. After completion of the dropwise addition, the ice bath was removed and stirring was continued for a whole day and night. Toluene and water were added for liquid separation, and after washing twice with water and once with saturated saline, the organic layer was dried with magnesium sulfate all day and night. The solvent was distilled off under reduced pressure to obtain an intermediate (102).

Yield: 134.6 g, Yield: 100%
¹ H-NMR (CDCl ₃ ): 0.85 ppm (t, 3H, —CH ₃ ), 1.71 ppm (m, 1H, —CH ₂ —), 1.92 ppm (m, 1H, —CH ₂ —), _{2.31ppm (s, 6H, N- CH} 3), 3.77ppm (m, 1H, - CH -), 7.11ppm (m, 2H, aromatic), 8.10ppm (m, 2H, aromatic)
[Step 3]

  A 500 mL four-necked flask equipped with a stirrer, a thermometer, and a condenser tube was charged with 79.5 g of the intermediate (102), 71.5 g of benzyl bromide, and 120 mL of methyl ethyl ketone, and stirred at 50 ° C. for 3 hours. Then, 71 mL of 8M sodium hydroxide aqueous solution was added, and it stirred at 60 degreeC for 1 hour. After completion of the stirring, the pH was adjusted to 8 using an aqueous hydrochloric acid solution, 120 mL of ethyl acetate was added, the aqueous layer was separated, and the organic layer was dried with magnesium sulfate all day and night. The solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol to obtain an intermediate (103).

Yield: 85.5 g, Yield: 75.2%
¹ H-NMR (CDCl ₃ ): 0.67 ppm (t, 3H, —CH ₃ ), 1.82 ppm (m, 1H, —CH ₂ —), 2.06 ppm (m, 1H, —CH ₂ —), _{2.36ppm (s, 6H, N- CH} 3), 3.19ppm (s, 2H, - CH 2 -Ph), 7.04ppm (m, 2H, aromatic), 7.19ppm (m, 5H, aromatic) 8.00 ppm (d, 2H, aromatic), 8.40 ppm (m, 2H, aromatic)
[Step 4]

30.0 g of intermediate (103), 90 mL of dimethyl sulfoxide (DMSO) and 34.5 g of anhydrous piperazine were added to a 300 L four-necked flask equipped with a stirrer, a thermometer and a condenser, and the mixture was added at 100 ° C. under a nitrogen stream. For 24 hours. After completion of the reaction, the reaction mixture was extracted with methylene chloride, washed twice with water, and dried with magnesium sulfate all day and night. The solvent was distilled off under reduced pressure to obtain the compound (5) (2-dimethylamino-1- (4-piperazinylphenyl) -2-benzyl-butan-1-one).
A ¹ H-NMR chart of the compound (5) obtained is shown in FIG.

Yield: 34.5 g, Yield: 94.1%
¹ H-NMR (CDCl ₃ ): 0.65 ppm (t, 3H, —CH ₃ ), 1.84 ppm (m, 1H, —CH ₂ —), 2.04 ppm (m, 1H, —CH ₂ —), _{2.35 (s, 6H, N- CH} 3), 3.02ppm (m, 4H, _{piperidine), 3.18 (m, 2H,} - CH 2 -Ph), 3.29ppm (m, 4H, piperidine) 6.80 ppm (d, 2H, aromatic), 7.21 ppm (m, 5H, aromatic), 8.34 ppm (d, 2H, aromatic)

  Synthesis Example 2 [Synthesis of Compound (6) (2-Methyldodecylamino-1- (4-piperazinylphenyl) -2-benzyl-butan-1-one)]

  Compound (6) (2-dodecylmethylamino-1- (4-piperazinylphenyl) was prepared according to the method described in Example 1 except that methyldodecylamine was used instead of dimethylamine aqueous solution in Step 2 of Synthesis Example 1. ) -2-Benzyl-butan-1-one).

¹ H-NMR (CDCl ₃ ): 0.66 ppm (t, 3H, —CH ₃ ), 0.84 ppm (t, 3H, —CH ₃ ), 1.20 ppm (m, 18H, —CH ₂ —), 1 .34ppm (m, 2H, N- CH 2 - CH 2 -CH 2 -), 1.83ppm (m, 1H, - CH 2 -), 2.00ppm (m, 1H, - CH 2 -), 2. _{30 (s, 3H, N- CH} 3), 2.40 (m, 1H, N- CH 2 -), 2.60 (m, 1H, N- CH 2 -), 3.05ppm (m, 4H, _{piperidine), 3.22 (m, 2H,} - CH 2 -Ph), 3.35ppm (m, 4H, piperidine), 6.80ppm (d, 2H, aromatic), 7.21ppm (m, 5H, aromatic) , 8.34 ppm (d, 2H, aromatic

  Synthesis Example 3 [Synthesis of Compound (7) (2-Dimethylamino-1- (4- (2,5-dimethylpiperazinyl) phenyl) -2-benzyl-butan-1-one)]

  Compound (7) (2-dimethylamino-1- (4- (2,5)) was prepared according to the method described in Example 1, except that 2,5-dimethylpiperazine was used instead of piperazine in Step 4 of Synthesis Example 1. -Dimethylpiperazinyl) phenyl) -2-benzyl-butan-1-one) was synthesized.

¹ H-NMR (CDCl ₃ ): 0.65 ppm (t, 3H, —CH ₃ ), 1.25 ppm (d, 3H, piperidine— CH ₃ ), 1.29 ppm (d, 3H, piperidine— CH ₃ ), 1.84 ppm (m, 1H, —CH ₂ —), 2.04 ppm (m, 1H, —CH ₂ —), 2.35 (s, 6H, N— CH ₃ ), 3.01 to 3.41 ppm ( m, 6H, _{piperidine), 3.18 (m, 2H,} - CH 2 -Ph), 6.80ppm (d, 2H, aromatic), 7.21ppm (m, 5H, aromatic), 8.34ppm (d, 2H, aromatic)

  Synthesis Example 4 [Compound (8) [Synthesis of 2-dimethylamino-1- (4- (methyl (2- (methylamino) ethyl) aminophenyl) -2-benzyl-butan-1-one (8)])

In Step 4 of Synthesis Example 1, compound (8) (2-dimethylamino-1- (4- (methyl) was prepared according to the method described in Example 1, except that N, N′-dimethylethylenediamine was used instead of piperazine. 2- (methylamino) ethyl) aminophenyl) -2-benzyl-butan-1-one) was synthesized.

¹ H-NMR (CDCl ₃ ): 0.65 ppm (t, 3H, —CH ₃ ), 1.84 ppm (m, 1H, —CH ₂ —), 2.04 ppm (m, 1H, —CH ₂ —), _{2.35 (s, 6H, N- CH} 3), 2.40 (s, 3H, N- CH 3), 2.45 (s, 3H, N- CH 3), 2.68-2.81 ( _{m, 4H, N- CH 2 CH} 2 N -), 3.18 (m, 2H, - CH 2 -Ph), 6.80ppm (d, 2H, aromatic), 7.21ppm (m, 5H, aromatic) , 8.34 ppm (d, 2H, aromatic)

  Synthesis Example 5 [Compound (9) [Synthesis of 2-dimethylamino-1- (4-piperazinylphenyl) -2- (4-methylbenzyl) -butan-1-one]]

  Compound (9) (2-dimethylamino-1- (4-piperazini) was prepared in the same manner as in Example 1 except that 4-methylbenzyl bromide was used instead of benzyl bromide in Step 3 of Synthesis Example 1. Ruphenyl) -2- (4-methylbenzyl) -butan-1-one).

¹ H-NMR (CDCl ₃ ): 0.65 ppm (t, 3H, —CH ₃ ), 1.84 ppm (m, 1H, —CH ₂ —), 2.04 ppm (m, 1H, —CH ₂ —), _{2.35 (s, 6H, N- CH} 3), 2.30 (s, 3H, Ph- CH 3), 3.02ppm (m, 4H, piperidine), 3.18 (m, 2H, - CH 2 -Ph), 3.29 ppm (m, 4H, piperidine), 6.80 ppm (d, 2H, aromatic), 7.21 ppm (m, 4H, aromatic), 8.34 ppm (d, 2H, aromatic)

[Synthesis of polymerizable initiator (B) obtained by Michael addition reaction]

Synthesis Example 6
To a 300 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple was added 51.5 g of ethylene oxide-modified pentaerythritol tetraacrylate (“Miramer 4004” manufactured by MIWON) and 36.6 g of the compound (5) obtained in Synthesis Example 1, The mixture was stirred at room temperature for 24 hours to obtain 88.1 g of the Michael addition reactant of the present invention (the compound (M1) described above). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction charging was 1: 3.6.

Synthesis example 7
In a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 11.4 g of ethylene oxide-modified trimethylolpropane triacrylate (“Aronix M-350” manufactured by Toagosei Co., Ltd.) and the compound obtained in Synthesis Example 1 (5 ) 12.2 g was added, and the mixture was stirred at room temperature for 24 hours to obtain 23.6 g of the Michael addition reaction product of the present invention (the aforementioned compound (M2)). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction preparation was 1: 2.4.

Synthesis Example 8
In a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 12.5 g of tripropylene glycol diacrylate (“Aronix M-220” manufactured by Toagosei Co., Ltd.) and the compound (5) obtained in Synthesis Example 1 12.2 g was added, and the mixture was stirred at room temperature for 24 hours to obtain 24.7 g of the Michael addition reaction product of the present invention (the compound (M3) described above). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction preparation was 1: 2.5.

Synthesis Example 9
In a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 19.5 g of ditrimethylolpropane tetraacrylate (“KAYARAD T1420” manufactured by Nippon Kayaku Co., Ltd.) and compound (5) 12 obtained in Synthesis Example 1 .2 g was added and stirred at room temperature for 24 hours to obtain 31.7 g of the Michael addition reaction product of the present invention (the above-mentioned compound (M4)). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction preparation was 1: 5.0.

Synthesis Example 10
In a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 10.7 g of ethylene oxide-modified trimethylolpropane triacrylate (“Aronix M-350” manufactured by Toagosei Co., Ltd.) and the compound obtained in Synthesis Example 2 (6 13.0 g was added, and the mixture was stirred at room temperature for 24 hours to obtain 23.7 g of the Michael addition reaction product of the present invention (the aforementioned compound (M5)). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction charging was 1: 3.0.

Synthesis Example 11
In a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 16.6 g of ethylene oxide-modified trimethylolpropane triacrylate (“Aronix M-350” manufactured by Toagosei Co., Ltd.) and the compound (7 13.1 g was added, and the mixture was stirred at room temperature for 24 hours to obtain 29.7 g of the Michael addition product of the present invention (the above-mentioned compound (M6)). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction preparation was 1: 3.5.

Synthesis Example 12
In a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 13.2 g of ethylene oxide-modified trimethylolpropane triacrylate (“Aronix M-350” manufactured by Toagosei Co., Ltd.) and the compound obtained in Synthesis Example 4 (8 ) 12.2 g was added and stirred at room temperature for 24 hours to obtain 25.4 g of the Michael addition reaction product of the present invention (the aforementioned compound (M7)). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction preparation was 1: 2.8.

Synthesis Example 13
To a 100 mL three-necked flask equipped with a stirrer, a condenser and a thermocouple, 12.4 g of ethylene oxide-modified trimethylolpropane triacrylate (“Aronix M-350” manufactured by Toagosei Co., Ltd.) and the compound obtained in Synthesis Example 5 (9 12.7 g was added, and the mixture was stirred at room temperature for 24 hours to obtain 25.1 g of the Michael addition reaction product of the present invention (the above-mentioned compound (M8)). The ratio [(i) / (ii)] of the group (i) having a Michael addition-donating function and the group (ii) having a Michael accepting function at the time of reaction charging was 1: 2.6.

Examples 1-8 and Comparative Examples 1-9 (Manufacture and evaluation of printing ink)
It mix | blended with the raw material composition shown in Table 1 and Table 2, and manufactured by carrying out uniform stirring with a mixer, and then kneading meat dispersion using a roll mill. As the roll mill, “SDY-300” manufactured by Buehler Co., Ltd. was used, and a printing ink was obtained by carrying out a roll pass for 3 s under the conditions of a roll temperature of 40 ° C. and a roll pressure of 1,600 kPa · s. Next, the following various evaluations were performed. The results are shown in Tables 1 and 2.
In addition, as a coloring material, carbon black is 16% by weight (as carbon black, Raven 1060Ultra is used in Examples 1 to 12, and 3% by weight of phthalocyanine blue and 2% by weight of dioxazine violet are used as complementary color components (a total of 21% by weight of coloring materials). %), 2% by weight of talc and 2% by weight of magnesium carbonate (total 4% by weight) as viscosity and fluidity regulators, 2% by weight of wax as auxiliary agent and 10% by weight of p-methoxyphenol and ethylene oxide 1% by weight (mixture of modified pentaerythritol tetraacrylate 90% by weight) (a total of 3% by weight of auxiliaries) was added in common to all examples and comparative examples, and complementary colors phthalocyanine blue and dioxazine violet were carbon. Cancels the yellowness of black It blended small amounts for the purpose of increasing the jet-blackness further.
The number average molecular weight of the initiator used in each example and comparative example is a value measured (polystyrene conversion) under the following conditions by gel permeation chromatograph (GPC).
Measurement apparatus: The measurement was performed using the HLC8220 system manufactured by Tosoh Corporation under the following conditions.
Separation column: 4 TSKgelGMH _HR- N manufactured by Tosoh Corporation are used.
Column temperature: 40 ° C.
Moving layer: Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd.
Flow rate: 1.0 ml / min. Sample concentration: 1.0% by weight.
Sample injection volume: 100 microliters.
Standard: Monodisperse polystyrene detector: differential refractometer.

[Manufacture of printed matter]
The ultraviolet curable ink thus obtained was uniformly stretched on the rubber roll and metal roll of the RI tester using a simple color developing machine (RI tester, manufactured by Toyoe Seiko Co., Ltd.) and using 0.10 ml of ink. , Uniformly applied to the surface of milk carton paper (polyethylene laminated paper, Tetra Rex, Tetra Pak) in the range of black ink density 1.6-1.8 (measured with X-Rite SpectroEye densitometer) The color was developed as described above to produce a printed matter. The RI tester is a test machine that develops ink on paper or film, and can adjust the amount of ink transferred and the printing pressure.
[UV irradiation by UV lamp light source]
The printed matter after the ink application was irradiated with UV, and the ink film was cured and dried. Specifically, using a UV irradiation device equipped with a water-cooled metal halide lamp (output 100 W / cm1 light) and a belt conveyor (made by Eye Graphics Co., Ltd., with a cold mirror), the printed material is placed on the conveyor and directly under the lamp (irradiation) A distance of 11 cm) was passed under the predetermined conditions described below. The ultraviolet irradiation amount in each condition was measured using an ultraviolet integrated light quantity system (UNIMETER UIT-150-A / light receiving device UVD-C365 manufactured by USHIO INC.).

[Evaluation of ink composition 1: curability]
The curability was confirmed immediately after irradiation by the nail scratch method on the printed surface. While the conveyor speed (m / min) of the UV irradiation device was changed, the printed material was irradiated with ultraviolet rays, and the fastest conveyor speed without damage was described. Therefore, it can be said that the faster the conveyor speed, the better the drying property of the ink.

[Evaluation of ink composition 2: internal curability]
Using an RI tester, an ink is developed on a corona-treated PET film original with an ink density of 2.2, and the developed product is irradiated with ultraviolet rays of a metal halide lamp of about 120 mJ / cm ² to dry the ink. It was. After drying, using a cutter knife, the ink surface was scratched on the grid surface at a pitch of 2 mm, and cellophane tape (manufactured by Nichiban Co., Ltd.) was attached. The cellophane tape was peeled from the ink surface in a normal direction at a constant speed, and the amount of ink taken on the cellophane tape surface and the amount of scratches on the ink surface were measured. Therefore, it can be evaluated that the internal drying property of the ink is better as the ink is taken on the cellophane tape surface and the ink surface is less damaged.
The area ratio at which ink was removed from the cellophane tape surface and the ink surface was damaged was evaluated according to the following criteria.
○: Less than 5% Δ: 5% or more and less than 20% ×: 20% or more

[Evaluation of printed matter 1: low migration]
Regarding the evaluation of low migration, the basic evaluation procedure is the European Printing Ink Association (EuPIA Guideline on printing contest), the guidelines of the European Printing Ink Council (European Printing Ink Association). articles, November 2011 (Replaces the September 2009 version)).
First, the printed matter described above has a conveyor speed of 40 m / min. The ink layer was dried by UV irradiation twice. The UV integrated light quantity under these conditions was about 120 mJ / cm 2. Subsequently, the cured ink layer on the upper surface of the printed material is superposed so that the back surface of the milk carton blank paper (hereinafter, the non-printed milk carton paper on which the ink is not developed is referred to as the milk carton blank paper) is contacted with a hydraulic press. The unreacted components in the cured ink layer were migrated to the back side of the milk carton white paper by pressing for 48 hours under a press pressure of 40 kg / cm 2 and a room temperature of 25 ° C. After pressing, the milk carton blank paper was removed and molded to prepare a 1000 ml liquid container. In this liquid container, the back surface to which the ink component has transferred faces inward. Next, 1000 ml of an aqueous ethanol solution (mixed solution of 95% by weight of ethanol and 5% by weight of pure water) prepared as a simulated liquid food was poured into a liquid container and sealed. In this condition, the total area of the inner surface of the liquid container in contact with 1000 ml of the ethanol aqueous solution was about 600 cm ² . The sealed liquid container was allowed to stand at room temperature and 25 ° C. for 24 hours, and the ink components transferred to the back of the milk carton white paper were extracted into an aqueous ethanol solution. Thereafter, the ethanol aqueous solution is taken out from the liquid container, and the initiator used in the liquid chromatograph mass spectrometry is identified and each elution concentration (migration concentration) is quantified. From the total value of the migration concentration of each initiator component, three levels are obtained. We evaluated the migration performance. As an example, in a printed matter using ultraviolet curable ink using initiators A, B, and C3, the migration concentration of initiator A is 10 ppb, the migration concentration of initiator B is 5 ppb, and the migration concentration of initiator C is In the case of 15 ppb, the total migration concentration of the initiator component is evaluated as A + B + C = 10 + 5 + 15 = 30 ppb. In quantification of liquid chromatograph mass spectrometry, a calibration curve using the above ethanol aqueous solution was prepared in advance for each of the initiators used, and calculation was performed by using this.
A: Less than 20 ppb ○: Less than 20-30 ppb Δ: More than 30 ppb and less than 60 ppb ×: More than 60 ppb −: Not detected

[Print Evaluation 2: Odor]
The printed material cured by the curing method was cut into a length of 5 cm and a width of 2.5 cm, and 10 sections were prepared. 10 pieces are quickly put into a collection vial with an outer diameter of 40 mm, a height of 75 mm, an inner diameter of 20.1 mm, and a volume of 50 ml, and the lid is closed and stored in a constant temperature bath at 60 ° C. for 1 hour. I let you. Next, the collection vial was allowed to stand until it reached room temperature, and the odor intensity of each sample was evaluated in 10 stages by 10 monitors who evaluated the odor intensity.
The odor evaluation results of 10 people were averaged to determine the odor intensity of the sample. A higher numerical value means a lower odor.
○: 10 to 7
Δ: 6-4
X: 3 to 1

Omnipol 910: polyethylene glycol di {β-4- [4- (2-dimethylamino-2-benzyl) butanoylphenyl] piperazine} propionate, average molecular weight 910), Insight High Technology, Inc. Irgacure 369: 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1, manufactured by BASF; Escure One: oligo (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, Lamberti “Esacure One”), number average molecular weight 424.57,
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, “Irgacure 184” manufactured by BASF, molecular weight 204
Omnipol TX: di (9-oxo-9H-thioxanthinyl) oxyacetate ester of poly (oxy-1,4-butylene) glycol, bifunctional sensitizer “Omnipol TX” number average molecular weight manufactured by IGM Resin
-Genopol TX-1: Tri-9-oxo-6H-thioxanthene-carboxylate of an alkylene oxide adduct of aliphatic triol (Trifunctional sensitizer "Genopol TX-1" manufactured by RAHN: number average molecular weight 820),
SPEEDCURE DETX: 2,4-diethylthioxanthen-9-one, “SPEEDCURE DETX” manufactured by LAMBSON, number average molecular weight 268,
EAB-SS: 4,4′-bis (diethylamino) benzophenone, “EAB-SS” manufactured by Daido Kasei Kogyo Co., Ltd., number average molecular weight 324,
-Genopol AB-2: aminobenzoate compound ("Genopol AB-2" manufactured by RAHN)
Carbon black: “Raven 1060 Ultra” manufactured by Colombian Chemical Co., average primary particle size 30 nm, specific surface area (NSA) 66 m ² / g,
・ Phthalocyanine blue: DIC's copper phthalocyanine "FASTOGEN BLUE TGR-1")
・ Dioxazine violet: “Hoster Palm Violet RL 02” manufactured by Clariant
-Talc: hydrous magnesium silicate, "High filler # 5000PJ" manufactured by Matsumura Sangyo Co., Ltd.
・ Magnesium carbonate: “Magnesium carbonate TT” manufactured by Naikai Shigyo Co., Ltd.
Wax: Polyolefin wax, “S-381-N1” manufactured by Shamrock
Stabilizer solution: a mixed solution of 10% by mass of p-methoxyphenol (“Metoquinone” manufactured by Seiko Chemical Co., Ltd.) and 90% by mass of ethylene oxide-modified pentaerythritol tetraacrylate (“SR494NS” manufactured by Sartomer)

Claims (6)

Active energy ray polymerizable compound (A),
Michael addition reaction of α-aminoacetophenone skeleton-containing compound (I) having a function as a Michael addition donor represented by the following general formula (1) and a reactive compound (II) having a function as a Michael acceptor Polymerizable initiator (B) obtained by

General formula (1)

(In general formula (1),
R ₁ represents an alkyl group or aryl group having 1 to 10 carbon atoms, R _{2 to} R ₃ each independently represents an alkyl group or aryl group having 1 to 6 carbon atoms, and R ₂ and R ₃ May be combined together to form a ring, R _{4 to} R ₇ each independently represents a hydrogen atom, an aliphatic group or an aryl group, and X ₁ is a hydrogen atom or an alkyl having 1 to 6 carbon atoms. Y ₁ represents a group represented by the following general formula (2) or general formula (3). )

General formula (2)

(In general formula (2), X ₂ and X ₃ each independently represent a linear or branched alkylene group or oxyalkylene group having 2 to 6 carbon atoms.)

General formula (3)
(In the general formula (3), X ₄ represents a substituted or unsubstituted C 2-6 linear or branched alkylene group or oxyalkylene group, and R ₈ and R ₉ each represents Independently represents an aliphatic group or an aryl group), and a sensitizer (C) having a number average molecular weight of 500 or more and 1500 or less and having an absorption wavelength of 300 to 450 nm. Active energy ray curable printing ink.   The active energy ray-curable type according to claim 1, wherein the sensitizer (C) having a number average molecular weight of 500 or more and 1500 or less and having an absorption wavelength at a wavelength of 300 to 450 nm has a thioxanthyl structure in the molecular structure. Printing ink. The α-aminoacetophenone skeleton-containing compound (I) having a function as a Michael addition donor represented by the general formula (1) is a compound represented by the following structural formulas (5) to (9): 2. The active energy ray-curable printing ink according to 1.

(5)

(6)

(7)

(8)

(9)
  The active energy ray-curable printing ink according to claim 3, wherein the compound (II) having a plurality of polymerizable groups having a function as a Michael acceptor is a polyfunctional (meth) acrylate compound.   In addition to the active energy ray polymerizable compound (A), the polymerizable initiator (B), and the sensitizer (C), the number average molecular weight is 320 or more and 2000 or less and has an absorption wavelength at a wavelength of 200 to 300 nm. The active energy ray-curable offset ink according to any one of claims 1 to 4, comprising an α-hydroxyketone skeleton-containing photopolymerization initiator (B2).   A printed matter obtained by printing the active energy ray-curable printing ink according to any one of claims 1 to 5 on a substrate and irradiating and curing the active energy ray.

Images