JP6828976B2 - Active energy ray-curable composition, active energy ray-curable printing ink using it, and printed matter. - Google Patents

Description

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

The active energy ray-curable resin composition has a small heat history to the coating base material and is excellent in coating hardness and scratch resistance. Therefore, hard coating agents for various plastic base materials such as home appliances and mobile phones, paper, etc. It is used in various fields such as overcoating agents, binders for printing inks, and solder resists.

Among these various applications, active energy ray-curable offset printing inks are attracting attention mainly for package printing of paper containers, etc. because they have a low environmental load and can be instantly dried. , A diallyl phthalate resin is used as a binder resin, and an ink varnish is prepared and put into practical use in combination with a polymerizable diluent.

Here, dipentaerythritol hexaacrylate (DPHA) is widely used as a polymerizable diluent used in active energy ray-curable offset printing inks because of its excellent curability.

However, dipentaerythritol hexaacrylate itself has high crystallinity, and the flexibility of the coating film after curing is not sufficient, and printing inks using this as a polymerizable diluent bent the printed matter after printing. At that time, the so-called crack phenomenon in which the ink curing layer is cracked is likely to occur. In addition, the cured product is likely to undergo curing shrinkage during the curing reaction, and the cured ink is easily peeled off from the original fabric when dried.

As a varnish for printing ink using a polymerizable diluent instead of dipentaerythritol hexaacrylate, for example, in Patent Document 1 below, printing using a self-polymer of pentaerythritol triacrylate as a binder component is used. Techniques for producing inks are disclosed.

However, when the self-polymer of pentaerythritol triacrylate described in Patent Document 1 is used as a binder resin, the viscosity of the polymer itself is low and it is difficult to adjust the printing ink in the first place, and printing ink is produced. Even if it could be made, it was inferior in printability due to insufficient viscosity and misching during printing.

Japanese Unexamined Patent Publication No. 8-34945

Therefore, the problem to be solved by the present invention is that when used in printing ink, the cured product has excellent flexibility, crack phenomenon and peeling of the cured ink can be effectively prevented, and printability is excellent. It is an object of the present invention to provide an active energy ray-curable composition, an active energy ray-curable printing ink using the same, and a printed matter.

As a result of intensive research to solve the above problems, the present inventors have conducted a Michael addition polymer of a hydroxyl group-containing (meth) acrylate compound (a1), or a hydroxyl group-containing (meth) acrylate compound (a1) and a polyfunctional acrylate. By using the compound (a2) as a polymerizable diluent and adjusting the amount of the compound (a2) to 50 to 1,000 parts by mass per 100 parts by mass of the binder resin, while maintaining good printability, We have found that it is possible to impart appropriate flexibility to the cured ink product, and have completed the present invention.

That is, the present invention is selected from a Michael addition polymer (b1) of a hydroxyl group-containing (meth) acrylate compound and a Michael addition reaction product (b2) of a hydroxyl group-containing (meth) acrylate compound and a polyfunctional acrylate (meth) acryloyl. The group-containing polymerizable diluent (A) and the binder resin (B) having a radically polymerizable functional group are essential components, and the blending amount of the polymerizable diluent (A) is the binder resin (B). The present invention relates to an active energy ray-curable composition, which is characterized in that the ratio is 50 to 1,000 parts by mass per 100 parts by mass.

The present invention further relates to an active energy ray-curable printing ink, which comprises the active energy ray-curable composition.

The present invention further relates to a printed matter printed using the active energy ray-curable printing ink.

According to the present invention, when used in a printing ink, the active energy ray-curable composition has excellent flexibility of the cured ink, can effectively prevent cracking and peeling of the cured ink, and has excellent printability. It is possible to provide a product, an active energy ray-curable printing ink using the product, and a printed material.

FIG. 1 is a cross-sectional view of a ducted testing machine (manufactured by Kawamura RIKEN) used in the emulsification aptitude evaluation test. FIG. 2 is a GPC chart of the PETA polymer (7600 cps) used in Examples 1 and 2.

As described above, the active energy ray-curable composition of the present invention contains a (meth) acryloyl group-containing polymerizable diluent (A) and a binder resin (B) having a radically polymerizable functional group as essential components, and By using the amount of the (meth) acryloyl group-containing polymerizable diluent (A) to be 50 to 1,000 parts by mass per 100 parts by mass of the binder resin (B), printing such as misting can be performed. The aptitude can be dramatically improved, and the flexibility of the cured ink can be increased. Here, the blending amount of the (meth) acryloyl group-containing polymerizable diluent (A) is 80 to 700 mass by mass with respect to 100 parts by mass of the binder resin (B) from the viewpoint of the balance between printability and printed matter properties. It is preferable that the ratio is a part. In particular, when a diallyl phthalate resin (b1) described later is used as the binder resin (B), the ratio is 400 to 700 mass with respect to 100 parts by mass of the binder resin (B) because the resin has a high viscosity. It is preferably in the range of parts, and when urethane (meth) acrylate is used, it is 80 to 300 parts by mass with respect to 100 parts by mass of the binder resin (B) because the viscosity of the resin itself is low. It is preferably in the range.

Here, as described above, the (meth) acryloyl group-containing polymerizable diluent (A) used in the present invention is a Michael addition polymer of the hydroxyl group-containing (meth) acrylate compound (a1) or a hydroxyl group-containing (meth) acrylate. It contains a Michael addition reaction product of the compound (a1) and the polyfunctional acrylate compound (a2) as an essential component.

Examples of the hydroxyl group-containing (meth) acrylate compound (a1) include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylpropandi (meth) acrylate, and tri. (Meta) acrylates of aliphatic polyhydric alcohols such as methylolpropane mono (meth) acrylates, glycerin mono or di (meth) acrylates, dipentaerythritol penta (meth) acrylates; 2-hydroxyethyl (meth) acrylates: bisphenol A Examples thereof include bisphenol-based mono (meth) acrylates such as mono (meth) acrylates, mono (meth) acrylates of bisphenol F, and mono (meth) acrylates of alkylene oxide-added bisphenol F.

Among these, (meth) acrylates of aliphatic polyhydric alcohols are preferable from the viewpoint of good curability and flexibility of the cured ink, and particularly pentaerythritol trimethylolpropane (meth) acrylate and pentaerythritol di (meth) acrylate. , Pentaerythritol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylolpropane mono (meth) acrylate are preferable because these performances are remarkable, and pentaerythritol tri (meth) acrylate is particularly preferable. ..

In the present invention, the Michael addition polymer of the hydroxyl group-containing (meth) acrylate compound (a1) means that the hydroxyl group in each of the above compounds acts as a nucleophilic site in the Michael addition reaction, and the (meth) acryloyl group in another molecule is the Michael receptor. It acts as.

Next, examples of the polyfunctional acrylate compound (a2) include 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, and tricyclodecandy. Methanoldi (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol propoxytetra (meth) acrylate, trimethylolpropanthry (meth) acrylate, (Meta) acrylates of aliphatic polyhydric alcohols such as trimethylolpropane propoxytri (meth) acrylate, glycerin propoxytri (meth) acrylate, dipentaerythritol tetra (meth) acrylate; di (meth) acrylate of bisphenol A, bisphenol F Di (meth) acrylate, bisphenol-based di (meth) acrylate such as di (meth) acrylate of alkylene oxide-added bisphenol F, and the like can be mentioned. Among these, (meth) acrylates of aliphatic polyhydric alcohols are preferable from the viewpoint of good curability and flexibility of the cured ink, and particularly pentaerythritol tetra (meth) acrylate and trimethylolpropane tri (meth). Acrylate is preferable from the viewpoint that these performances become remarkable, and pentaerythritol tetra (meth) acrylate is particularly preferable.

Here, in the Michael addition reaction product of the hydroxyl group-containing (meth) acrylate compound (a1) and the polyfunctional acrylate compound (a2), the hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a1) is a Michael addition reaction. The (meth) acryloyl group in the polyfunctional acrylate compound (a2) acts as a Michael acceptor.

In the present invention, a compound having a (meth) acryloyl group obtained by such a Michael addition reaction is contained as a polymerizable diluent (A), and the polymerizable diluent (A) has a viscosity at 25 ° C. It is preferably 7,000 to 20,000 cps from the viewpoint of excellent balance between printability and flexibility of the cured ink. In the present invention, from the viewpoint of these balances, it is particularly preferable that the viscosity at 25 ° C. is in the range of 7,000 to 10,000 cps, and particularly preferably the viscosity at 25 ° C. is in the range of 7,000 to 8,500 cps.

Among the (meth) acryloyl group-containing polymerizable diluents (A) described above, in particular, the polyfunctional acrylate compound (a2), the hydroxyl group-containing (meth) acrylate compound (a1), and the polyfunctional acrylate compound (a2). A mixture with the Michael addition reactant is preferable because the viscosity of the printing ink can be easily adjusted and excellent printability is exhibited.

Specifically, such a mixture can be obtained by carrying out a Michael addition reaction of a mixture of a hydroxyl group-containing (meth) acrylate compound (a1) and a polyfunctional acrylate compound (a2). Such a Michael addition reaction can be carried out in the presence of a basic catalyst under temperature conditions of room temperature (25 ° C.) to 150 ° C. Further, the viscosity of the (meth) acryloyl group-containing polymerizable diluent (A) produced can be adjusted by the length of this reaction time, and as described above, the viscosity is in the range of 7,000 to 20,000 cps. As described above, it is preferable to adjust the reaction time as appropriate.

When the mixture of the hydroxyl group-containing (meth) acrylate compound (a1) and the polyfunctional acrylate compound (a2) is subjected to a Michael addition reaction to obtain a reaction product having a viscosity of 7,000 to 20,000 cps, the reaction product is obtained. Is an unreacted component of the polyfunctional acrylate compound (a2) and a dimer component which is an addition reaction product of one molecule of the hydroxyl group-containing (meth) acrylate compound (a1) and one molecule of the polyfunctional acrylate compound (a2). It contains a high molecular weight polymer component polymerized in a trimeric or higher. In the present invention, the ratio of the unreacted component of the polyfunctional acrylate compound (a2) to the dimer component is the peak area ratio in the GPC chart [polyfunctional acrylate compound (a2) unreacted component] / [2 amounts]. The body] is preferably in the range of 100/4 to 100/60 from the viewpoint of fluidity and curability. Here, as the peak area ratio in the GPC chart, a method of cutting out each peak from the printed matter of the GPC chart and comparing the weight of the cut pieces for each peak can be mentioned.

For example, as a mixture of the hydroxyl group-containing (meth) acrylate compound (a1) and the polyfunctional acrylate compound (a2), tetra (meth) acrylate of pentaerythritol and tri (meth) acrylate of pentaerythritol are the main components (meth). ) When an acrylate mixture is used, the polyfunctional acrylate compound (a2) is described in the following general formula 1

（式中、Ｒは水素原子、又はメチル基を表す。）
で表され、かつ、水酸基含有（メタ）アクリレート化合物（ａ１）の一分子と多官能アクリレート化合物（ａ２）の一分子の付加反応物である２量体成分は、下記一般式２

(In the formula, R represents a hydrogen atom or a methyl group.)
The dimer component represented by and which is an addition reaction product of one molecule of the hydroxyl group-containing (meth) acrylate compound (a1) and one molecule of the polyfunctional acrylate compound (a2) is represented by the following general formula 2.

（式中、Ｒは水素原子、又はメチル基を表す。）
で表されることとなる。

(In the formula, R represents a hydrogen atom or a methyl group.)
Will be represented by.

Further, the content of the trimer or higher high molecular weight polymer contained in the reaction product is in the range of 30 to 60% by mass in the reaction product based on the peak area in the GPC chart, which causes curing shrinkage. It is preferable because it can be effectively suppressed, the peeling of the cured ink product in the printed matter is prevented, and the flexibility is good.

Next, the binder resin (B) having a radically polymerizable functional group used in the active energy ray-curable resin composition of the present invention is specifically a diallyl phthalate resin (b1) or an epoxy (meth) acrylate (b2). , And urethane (meth) acrylate (b3).

Examples of the diallyl phthalate resin (b1) used here include a diallyl phthalate resin which is a polymer of diallyl phthalate and a polymer of diallyl isophthalate.

Examples of the epoxy (meth) acrylate (b2) include compounds obtained by reacting an epoxy resin with a monocarboxylic acid having a polymerizable unsaturated group. Here, the epoxy resin is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, water. Bisphenol S type epoxy resin, hydrogenated bisphenol AD type epoxy resin, tetrabromo bisphenol A type epoxy resin and other bisphenol type epoxy resin; orthocresol novolac type epoxy resin; phenol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol A Examples thereof include novolac type epoxy resins, brominated phenol novolac type epoxy resins, alkylphenol novolac type epoxy resins, bisphenol S novolac type epoxy resins, methoxy group-containing novolac type epoxy resins, and brominated phenol novolac type epoxy resins. .. Among these, a bisphenol type epoxy resin having an epoxy equivalent in the range of 170 to 500 g / eq, particularly a bisphenol A type epoxy resin, has excellent emulsifying characteristics, and excellent printability can be obtained when used as a printing ink. Is preferable.

On the other hand, examples of the monocarboxylic acid having a polymerizable unsaturated group to be reacted with the epoxy resin include acrylic acid, methacrylic acid and crotonic acid, and acrylic acid and methacrylic acid are particularly preferable from the viewpoint of printability. Acrylic acid is preferred.

Further, the urethane (meth) acrylate (b3) may be obtained by reacting a polyfunctional aromatic isocyanate (b3-a) with a hydroxyl group-containing mono (meth) acrylate (b3-b). In the present invention, in particular, the polyfunctional aromatic isocyanate (b3-a) and the hydroxyl group-containing mono (meth) acrylate (b3-b) are used as the latter with respect to the isocyanate group (b3-a') of the former (b3-a). The reaction was carried out at a ratio of the hydroxyl group (b3-b') of [(b3-b') / (b3-a')] of 0.99 to 0.40, and then the reaction product obtained was subjected to the reaction. A urethane (meth) acrylate resin having a (meth) acryloyl group concentration of 1.5 to 4.0 mmol / g, which is obtained by reacting a polyol (b3-c), has excellent printability and curability. preferable.

Here, the urethane (meth) acrylate resin having a (meth) acryloyl group concentration of 1.5 to 4.0 mmol / g uses an aromatic polyisocyanate (a) as a raw material polyisocyanate, and thus has good printability. It becomes. Further, the aromatic polyisocyanate (b3-a) and the hydroxyl group-containing mono (meth) acrylate (b3-b) are reacted at a ratio in which the latter is relatively large, and then crosslinked with a polyol (b3-c). As a result, the (meth) acryloyl group concentration is high, the molecular weight can be relatively small, and excellent curability and printability as a printing ink can be obtained. Here, when the ratio [(b3-b') / (b3-a')] exceeds 0.99, the hydroxyl group-containing mono (meth) acrylate (b3-b) having high skin irritation in the printing ink ) Is likely to remain, which causes problems in terms of safety and hygiene in handling the printing ink, and the molecular weight of the finally obtained resin does not increase, resulting in deterioration of curability and misting property. On the other hand, when the ratio [(b3-b') / (b3-a')] is less than 0.40, many isocyanate groups that contribute to the cross-linking reaction by the polyol (b3-c) in the next step remain. Therefore, gelation is likely to occur during the synthesis, and even if the resin can be synthesized, the aromaticity in the finally obtained urethane (meth) acrylate resin is lowered, and the offset printing suitability is lowered. To do.

The polyfunctional aromatic isocyanate (b3-a) used here is, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, Diisocyanate compounds such as 1,5-naphthalenediocyanate; polyfunctional polyisocyanates containing three or more isocyanate groups per molecule, such as polymethylene polyphenyl polyisocyanates and adducts of these isocyanate compounds and polyfunctional alcohols. Isocyanate compounds can be mentioned. These polyfunctional aromatic isocyanates may be used alone or in combination of two or more. In the present invention, by giving an aromatic structure to the chemical structure of the raw material polyfunctional isocyanate compound, excellent curability is exhibited when a printing ink using the finally obtained urethane (meth) acrylate resin is produced. Can be done.

Among these, a polyfunctional polyisocyanate compound containing a component having three or more isocyanate groups per molecule (a trifunctional or higher functional component) is particularly preferable because a UV curable ink having more excellent curability can be designed. Specifically, those containing trifunctional or higher functional components in a proportion of 30% by mass or more are preferable. Examples of the aromatic polyisocyanate containing such trifunctional or higher functional components include polymethylene polyphenyl polyisocyanate, and polymethylene polyphenyl polyisocyanate having a viscosity of 100 to 700 mPa · s is more preferable. Here, the viscosity is a value measured with an E-type viscometer (25 ° C.).

Next, the hydroxyl group-containing mono (meth) acrylate (b3-b) to be reacted with the polyfunctional aromatic isocyanate (b3-a) is, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, or hydroxybutyl. Hydroxyl-containing (meth) acrylates such as acrylates and hydroxyethyl vinyl ethers; ethylene oxide adducts of the hydroxyl group-containing (meth) acrylates, propylene oxide adducts of the hydroxyl group-containing (meth) acrylates, tetramethylene glycol adducts, lactone adducts, etc. Can be mentioned. Each of these hydroxyl group-containing mono (meth) acrylates (b3-b) may be used alone, or two or more thereof may be used in combination. Among these, hydroxyethyl acrylate and hydroxypropyl acrylate are particularly preferable because they have excellent curability of the composition.

Examples of the method for reacting the polyfunctional aromatic isocyanate (b3-a) with the hydroxyl group-containing mono (meth) acrylate (b3-b) include the polyfunctional aromatic isocyanate (a) and, if necessary, the polyfunctional aromatic isocyanate (b3-a). Examples thereof include a method in which a known and commonly used urethanization catalyst is added and heated to 20 to 120 ° C., and a predetermined amount of the hydroxyl group-containing mono (meth) acrylate (b3-b) is continuously or intermittently added to the reaction system for reaction. ..

At this time, along with the polyfunctional aromatic isocyanate (b3-a) and the hydroxyl group-containing mono (meth) acrylate (b3-b), higher alcohols typified by lauryl alcohol, stearyl alcohol, and oleyl alcohol, and By using hydroxyl group-containing fats and oils such as castor oil in a proportion of 0.1 to 30 parts by mass of the total 100 parts by mass of the reaction raw material and reacting, the fluidity and misting resistance of the finally obtained printing ink are dramatically improved. Can be improved.

Next, the desired urethane (meth) acrylate resin can be obtained by reacting the reaction product thus obtained with the polyol (b3-c). Here, the polyol (b3-c) is preferably an aliphatic polyhydric alcohol having a molecular weight in the range of 90 to 400 from the viewpoint of curability and printability. That is, when the molecular weight is less than 90, the effect of improving the appropriate offset printing suitability is reduced, while when the molecular weight is more than 400, the finally obtained functional group of the urethane (meth) acrylate resin is obtained. The concentration becomes low, and the effect of improving curability becomes small.

From this point of view, specifically, bifunctional polyols such as neopentyl glycol, 1,3-butanediol, 1,4-butanediol and tripropylene glycol; and trifunctional polyols such as glycerin and trimethylolpropane. Tetrafunctional polyols such as pentaerythritol and ditrimethylolpropane; Hexfunctional polyols such as dipentaerythritol; and ethylene oxide adducts of the trifunctional polyols (addition of 1 to 4 moles per molecule on average), said trifunctional Propylene oxide adduct of type polyol (addition of 1 to 4 mol on average per molecule), 1,3-butanediol adduct of the trifunctional polyol (addition of 1 to 2 mol on average per molecule), said tetrafunctional polyol. Ethylene oxide adduct (addition of 1 to 3 mol per molecule on average), ethylene oxide adduct of the hexafunctional polyol (addition of 1-3 mol on average per molecule), and the like. These polyols (c) may be used alone or in combination of two or more. Among these, urethane (meth) acrylate resin having an appropriate branched structure can be obtained, and trifunctional polyols such as glycerin and trimethylolpropane, neopentyl glycol, can exhibit excellent offset printing suitability and curability. , 1,6-Hexanediol, and tripropylene glycol are preferable, and trifunctional polyols such as glycerin and trimethylolpropane are particularly preferable because they are excellent in misting property and curability.

Here, adding the polyol (b3-c) at a ratio of 1 to 15% by mass with respect to the total mass of the components (b3-a) to (b3-c) is finally obtained as the binder resin. It is preferable because the concentration of the (meth) acryloyl group in (B) is increased and the curability and printability are dramatically improved.

The reaction of the reaction product of the aromatic polyisocyanate (b3-a) and the hydroxyl group-containing mono (meth) acrylate (b3-b) with the polyol (b3-c) is such that the polyol (b3-c) is reacted with respect to the reaction product. A method of adding c), heating to 20 to 120 ° C., and carrying out the reaction until the infrared absorption spectrum of 2250 cm- ¹ showing an isocyanate group disappears can be mentioned.

In the urethane (meth) acrylate resin thus obtained, the reaction product of the aromatic polyisocyanate (b3-a) and the hydroxyl group-containing mono (meth) acrylate (b3-b) is the polyol (b3-c). It becomes a urethane (meth) acrylate resin having a high concentration of (meth) acryloyl group having a structure knotted via. Specifically, the (meth) acryloyl group concentration of the binder resin (B) is in the range of 1.5 to 4.0 mmol / g, whereby excellent curability can be exhibited.

The urethane (meth) acrylate resin (b3) thus obtained has a weight average molecular weight (Mw) in the range of 3000 to 40,000, which is excellent in fluidity, misting property, and printability. It is preferable because it becomes an ink.

Among the above-mentioned binder resins (B), diallyl phthalate resin (b1) has excellent printability, less elution of low molecular weight components due to the resin, and excellent solubility in photocurable compounds. From this point of view, it is preferable, but there is a concern that diallyl phthalate monomer, which may have reproductive toxicity, remains in the diallyl phthalate resin, and urethane (meth) acrylate (b3) is preferable from the viewpoint of safety and hygiene.

In the present invention, gel permeation chromatography for measuring the composition ratios of the unreacted component of the (meth) acryloyl group-containing polymerizable diluent (A), the dimer and the trimeric or higher components. (GPC) measurement conditions and gel permeation chromatography (GPC) measurement conditions for measuring the weight average molecular weight (Mw) of the binder resin (B) are as follows.

Measuring device; HLC-8220GPC manufactured by Tosoh Corporation
Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

Next, examples of the polymerization initiator (C) used in the active energy ray-curable composition of the present invention include 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, benzyl dimethyl ketal, and 1- (4-isopropylphenyl) -2-hydroxy. -2-Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-1-{4- [4 -(2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2- Acetphenone compounds such as diethoxy-1,2-diphenylethane-1-one; 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], 1- [9-ethyl-6- (2-) Oxime compounds such as methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), 3,6-bis (2-methyl-2-morpholinopropanonyl) -9-butylcarbazole Carbazole compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether and the like;

2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2- (dimethylamino) -2- (4-methylbenzyl) -1- (4-morpholinophenyl) butane Aminoalkylphenones such as -1-one, 2-methyl-2-morpholino ((4-methylthio) phenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone Phenyl compounds; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl -Acylphosphine oxide-based compounds such as pentylphosphine oxide; benzyl, methylphenylglioxyester and the like.

On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, and the like.
Hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide,
Benzophenone compounds such as acrylicized benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; aminobenzophenone compounds such as 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone; and others 10- Examples thereof include butyl-2-chloroacrydone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone. These photopolymerization initiators can be used alone or in combination of two or more. Among these, aminoalkylphenone compounds are particularly preferable from the viewpoint of excellent curability, and particularly when a UV-LED light source that generates ultraviolet rays having an emission peak wavelength in the range of 350 to 420 nm is used as an active energy radiation source. Is preferably used in combination with an aminoalkylphenone-based compound, an acylphosphine oxide-based compound, and an aminobenzophenone-based compound from the viewpoint of excellent curability.

The amount of these polymerization initiators (C) used may be in the range of 1 to 20 parts by mass as the total amount used with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. preferable. That is, when the total amount of the polymerization initiator (C) used is 1 part by mass or more, good curability can be obtained, and when it is 20 parts by mass or less, the unreacted polymerization initiator (C) is cured. It is possible to avoid problems such as migration due to remaining in the object and deterioration of physical properties such as hardness of the cured product. From the viewpoint of improving the balance of these performances, in particular, in the range where the total amount used is 3 to 15 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. More preferably.

Further, when irradiating ultraviolet rays as active energy rays to form a cured product film such as a printed matter or a coating film, curability is achieved by using a photosensitizer in addition to the polymerization initiator (C) described above. Can be further improved. Examples of such a photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate. Be done. The amount of these photosensitizers used is 1 to 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention from the viewpoint that the effect of improving the curability is good. The range is preferably 20 parts by mass.

The active energy ray-curable composition of the present invention comprises the (meth) acryloyl group-containing polymerizable diluent (A) described in detail above, a binder resin (B) having a radically polymerizable functional group, and a polymerization initiator (C). In addition, other polymerizable diluents of the (meth) acryloyl group-containing polymerizable diluent (A) can be blended as long as the effects of the present invention are not impaired.

Other polymerizable diluents used here include, for example, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, N, N-dimethyl (meth) acrylamide, acrylamide, acryloylmorpholine, 7-amino-. 3,7-Dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, lauryl (meth) acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrachlorophenyl ( Meta) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) Acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, Bornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate, isobornyl (meth) acrylate, mono (meth) acrylate of bisphenol A, mono (meth) acrylate of bisphenol F, mono (meth) of alkylene oxide-added bisphenol F Acrylate, mono {2- (meth) acryloyloxyethyl} acid phosphate, vinyl sulfonic acid, allylsulfonic acid, 2-methylallylsulfonic acid, 4-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3 -A monofunctional polymerizable monomer such as acryloyloxypropanesulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid; 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 ) ○] nSi (CH ₃ ) ₃ or CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ [Si (CH ₃ ) C ₆ H ₅ ) ₂ O] nSi (CH ₃ ) ₃ (However, n in each equation shall be an integer of 0 or 1-130. ) And other polysiloxane bond-containing monomers; γ- (meth) acryloxipropyltrimethoxysilane, γ- (meth) acryloxipropyltriethoxysilane, γ- (meth) acryloxipropylmethyldimethoxysilane, γ-( Meta) Acryloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane, Vinyl trichlorosilane or N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride; 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4 Various vinyl ethers having tertiary amines such as −diethylaminobutylvinyl ether, 6-dimethylaminohexylvinyl ether; methylvinyl ether, ethylvinyl ether, n-propylvinyl ether, n-butylvinyl ether, iso-butylvinyl ether, 2-ethylhexylvinyl ether, cyclopentylvinyl ether, Vinyl ethers such as cyclohexylvinyl ether; ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanedi (meth) acrylate, Dimethylol tricyclodecanediacrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Di (meth) acrylate of glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol ester of hydroxypivalate, di (meth) acrylate of bisphenol A or bisphenol F, bisphenol such as bisphenol A and bisphenol F. Poly (meth) acrylate of alkylene oxide-added bisphenol, which is a reaction product of a compound to which alkylene oxide is added to (meth) acrylic acid; various unsaturated compounds such as maleic acid, fumaric acid, itaconic acid, and citraconic acid. Bifunctional monomers such as divinyl esters of various divalent carboxylic acids such as basic acids: trimethylolpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other fats Poly (meth) acrylates of group polyhydric alcohols; ethylene oxide-added trimethylolpropantri (meth) acrylates, ethylene oxide-added pentaerythritol tetra (meth) acrylates, ethylene oxide-added dipentaerythritol hexa (meth) acrylates, propylene oxide additions Poly (meth) acrylates of alkylene oxide-added aliphatic polyhydric alcohols such as trimethylpropantri (meth) acrylates, propylene oxide-added pentaerythritol tetra (meth) acrylates, and propylene oxide-added dipentaerythritol hexa (meth) acrylates; Poly of ε-caprolactone-added aliphatic polyhydric alcohols such as −caprolactone-added trimethylolpropanthry (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, and ε-caprolactone-added dipentaerythritol hexa (meth) acrylate Examples include (meth) acrylate.

The above-mentioned other polymerizable diluent is preferably used in the range of 50% by mass or less in the polymerizable diluent component in the active energy ray-curable composition of the present invention. When the other polymerizable diluent is the same substance as the unreacted component contained in the (meth) acryloyl group-containing polymerizable diluent (A), the substance is said to be "other polymerizable". It shall not be included in the "diluent".

When the active energy ray-curable composition of the present invention is used as an active energy ray-curable printing ink, each of the above components (A) to (C) may be mixed at once together with other compounding components, or may be used. , A polymerizable diluent component requiring the (meth) acryloyl group-containing polymerizable diluent (A) is added in advance to the binder resin (B) to prepare a resin solution-like composition for preparation of printing inks. You may. In this case, the resin solution-like composition was prepared by adding butyl acetate to the composition containing the binder resin (B) and the (meth) acryloyl group-containing polymerizable diluent (A) to a non-volatile content of 80% by mass. In this state, setting the viscosity measured with an E-type viscometer (25 ° C.) in the range of 0.5 to 10.0 Pa · s is suitable for subsequent adjustment of the printing ink and offset printing. It is preferable from the point of view.

Further, when adjusting the active energy ray-curable printing ink, the blending ratio of each component is, for example, 15 to 40% by mass of the binder resin (B) and 2 to 2 to 40% by mass of the polymerization initiator (C) in the printing ink. 10% by mass, 30 to 65% by mass of the polymerizable diluent component containing the (meth) acryloyl group-containing polymerizable diluent (A), 10 to 30% by mass of the pigment, and 0.5 to 10% by mass of the other components in total. It can be blended in a proportion of mass%.

When used as an active energy ray-curable printing ink, in addition to the above components (A) to (C), pigments, dyes, extender pigments, organic or inorganic fillers, organic solvents, antistatic agents, defoamers, etc. Additives such as viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant stabilizers, ultraviolet absorbers, antioxidants, leveling agents, pigment dispersants, and waxes can be used.

Examples of the method for producing the active energy ray-curable printing ink of the present invention include a method in which the above-mentioned components are mixed, stirred and mixed with a mixer or the like, and kneaded using a disperser such as a three-roll mill or a bead mill. ..

The active energy ray-curable composition of the present invention and the active energy ray-curable printing ink can be formed into a cured coating film by irradiating the substrate with active energy rays after printing. Examples of this active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet rays are particularly preferable from the viewpoint of curability.

As described above, the active energy rays that cure the active energy ray-curable coating material of the present invention are ionized radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, but they are specific energy sources or Examples of the curing device include sterilizing lamps, fluorescent lamps for ultraviolet rays, UV-LEDs, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, and the like. Examples thereof include ultraviolet rays as a light source, or electron beams generated by a scanning type or curtain type electron beam accelerator.

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

In addition, inorganic fine particles may be used as the extender pigment in the active energy ray-curable printing ink of the present invention. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, clafite, and zinc oxide; lime carbonate powder, precipitated calcium carbonate, plaster, ChinaClay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, etc. Inorganic pigments such as aluminum stearate, magnesium carbonate, barite powder, abrasive powder; and other inorganic pigments, silicone, glass beads, and the like can be mentioned. By using these inorganic fine particles in the range of 0.1 to 20 parts by mass in the ink, it is possible to obtain effects such as adjusting the fluidity of the ink, preventing misting, and preventing penetration into a printing substrate such as paper. is there.

Further, as a printing base material suitable for the active energy ray-curable printing ink of the present invention, paper used for packaging of catalogs, posters, leaflets, CD jackets, direct mails, pamphlets, cosmetics and beverages, pharmaceuticals, toys, equipment, etc. Base material: Films used for various food packaging materials such as polypropylene film and polyethylene terephthalate (PET) film, aluminum foil, synthetic paper, and various other base materials conventionally used as printing base materials can be mentioned.

Further, examples of the printing method of the active energy ray-curable printing ink of the present invention include flat plate offset printing, letterpress printing, gravure printing, gravure offset printing, flexo printing, screen printing and the like.

The present invention can be suitably used in lithographic offset printing in which water is continuously supplied to the plate surface in terms of improving the emulsifying characteristics of the ink. Offset printing machines that continuously supply water are manufactured and sold by a large number of printing machine manufacturers. Examples include Heidelberg, Komori Corporation, Ryobi MHI Graphic Technology, Munroland, KBA, etc. The present invention can be suitably used in any paper supply method, such as a sheet-fed offset printing machine that uses sheet-type printing paper and an offset rotary printing machine that uses reel-type printing paper. More specifically, offset printing machines such as the Speedmaster series manufactured by Heidelberg, the Lithrone series manufactured by Komori Corporation, and the diamond series manufactured by Ryobi MHI Graphic Technology can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to these examples.
(Infrared absorption spectrum measurement conditions)
[Model] FT / IR-4100 manufactured by JASCO Corporation
[Measurement conditions] The reaction completion was confirmed by confirming the infrared absorption spectrum of 2250 cm ^-1 showing the isocyanate group.

(GPC measurement conditions)
The GPC measurement of the PETA polymer [Michael addition polymer of a mixture of pentaerythritol tetraacrylate + pentaerythritol triacrylate + pentaerythritol diacrylate] and the GPC measurement of the urethane acrylate resin are performed by gel permeation chromatography (GPC) under the following conditions. ) Is the value measured by.

Measuring device; HLC-8220GPC manufactured by Tosoh Corporation
Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

Production Example 1 (Synthesis of Urethane Acrylate Resin)
In a four-necked flask equipped with a stirrer, gas introduction tube, condenser, and thermometer, as the first step, polymethylene polyphenyl polyisocyanate (“Millionate MR-400” manufactured by Nippon Polyurethane Industry Co., Ltd.” binuclear component 29 59.4 parts by mass, 0.1 parts by mass of tertiary butyl hydroxytoluene, 0.02 parts by mass of methoxyhydroquinone, 0.02 parts by mass of zinc octylate were added to 75 parts by mass. The temperature was raised to ° C., and 37.3 parts by mass of 2-hydroxyethyl acrylate was added dropwise under stirring for 1 hour. After the dropping, the reaction is carried out at 75 ° C. for 3 hours, and then 3.3 parts by mass of glycerin is added as a second step, and the reaction is further carried out at 75 ° C. to eliminate the infrared absorption spectrum of 2250 cm- ¹ showing an isocyanate group. The reaction was carried out to obtain a urethane acrylate resin having an acryloyl group concentration of 3.22 mmol / g and a weight average molecular weight (Mw) of 5438.

Examples 16 to 30 and Comparative Examples 1 and 2
[Manufacturing method of photocurable printing ink]
The printing inks of Examples and Comparative Examples were produced by blending the raw materials according to the compositions shown in Tables 1 and 2, stirring them uniformly with a mixer, and then producing the kneaded meat with a three-roll mill.

[Evaluation of emulsification characteristics (ducted test)]
The emulsification characteristics of the printing inks adjusted in each Example and Comparative Example were carried out using a ducted tester (manufactured by Kawamura RIKEN).
A cross-sectional view of the ducted tester is shown in FIG. The outer cylinder 3 is a cylindrical metal having a bottom surface with a hollow inside, and has a structure in which the evaluation ink 7 can be charged. After adding the ink 7 (5 grams), the inner cylinder 2 which is a cylindrical rod-shaped metal is inserted until it approaches a distance of 1 mm from the bottom surface of the outer cylinder 3 as shown in FIG. After that, the inner cylinder is rotated clockwise at 2000 rpm, and the outer cylinder is also rotated clockwise at 60 rpm, and the ink 7 is shared and stirred by making a speed difference. When 3 minutes have passed after stirring, the distilled water is dropped directly above the ink 7 at a speed of 0.5 (grams / minute) while continuing the stirring, so that the ink 7 and the dropped distilled water are immediately discharged. Stir and mix (emulsified). The dropping of distilled water is continued for 10 minutes and ends when the total amount of distilled water dropped reaches 5 grams.
The dactet tester has a structure in which the outer cylinder 3 is rotated by the drive motor 5 for the outer cylinder and the inner cylinder 2 is rotated by the drive motor 1 for the inner cylinder, and the temperature of the ink 7 inside the outer cylinder 3 is constant. As a result, the constant temperature water tank 4 is provided and the temperature of the tap water 6 is always maintained at 30 ° C.
After the stirring and mixing of the ink 7 (5 grams) and the distilled water (5 grams) is completed, the weight (grams) of the excess distilled water (the excess water that is not incorporated into the ink) inside the inner cylinder 2 is weighed. As a result, the total weight Y of the distilled water taken into the ink 7 is

Y (grams) = total input distilled water (5 grams) -weight of excess distilled water

The emulsification rate Z of the ink 7 is indicated by
Z (%) = Y ÷ (ink 7 (5 grams) + Y) x 100
Indicated by.
(Here, for example, when all 5 grams of the charged distilled water is taken into the ink and the excess distilled water is 0 grams, it is calculated as Y = 5 (grams) and Z = 50 (%). .)

The lower the value of the ink emulsification rate Z (%), the better the property of properly removing emulsified water, the better the offset printing suitability of the ink described below, and the printing such as overemulsification and the resulting decrease in density. Trouble is less likely to occur. 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 and less than 35%, and the emulsification suitability is medium.
1: The emulsification rate Z (%) is 35% or more, and the emulsification suitability is inferior.

[Printability: Mistingability]
As a method for evaluating misching, 1.5 ml of ink was placed on an incometer-type misching tester and rotated at a machine temperature of 32 ° C. and 1200 rpm for 3 minutes. We compared the superiority and inferiority of misting by the change in the weight increase of the paper that the ink flew along the rotating body as it rotated. If misting is bad, the amount of ink that flies increases and the weight of the paper increases.
(Evaluation criteria)
◯: The weight increase of the test piece is less than 0.050 g, and the misting suitability is good.
Δ: The weight increase of the test piece was 0.050 g to less than 0.150 g, and the misting suitability was medium.
X: The weight increase of the test piece is 0.150 g or more, and the misting suitability is poor.

[Printability: Density stability]
The offset printing suitability of the printing inks obtained in each Example and Comparative Example was evaluated. 9000 sheets per hour using a Munroland offset printing machine (Roland R700 printing machine, 40-inch wide machine) equipped with a water-cooled metal halide lamp (output 160 W / cm, using 3 lights) manufactured by Igraphics as an ultraviolet irradiation device. Offset printing was performed at the printing speed of. Oji Paper Co., Ltd. OK Top Coat Plus (57.5 kg, A size) was used as the printing paper. As the dampening water supplied to the plate surface, an aqueous solution obtained by mixing 98% by weight of tap water and 2% by weight of an etchant (FST-700, manufactured by DIC Corporation) was used.
At this time, first set the water supply dial of the printing machine to 40 (standard water volume), and operate the ink supply key so that the printed matter density becomes the standard process black density 1.8 (measured with the SpectroEye density meter manufactured by X-Rite). Then, when the density became stable, the ink supply key was fixed. After that, under the condition that the ink supply key was fixed, the water supply dial was changed from 40 to 55, and 300 sheets were printed under the condition that the water supply amount was increased, and the ink density of the printed matter after 300 sheets was measured.
Even when the amount of water supplied is increased, the smaller the decrease in the density of the printed matter, the better the emulsification suitability and the better the printability. The printability of the active energy ray-curable ink was evaluated according to the following criteria.
◯: The black density of the printed matter is 1.7 or more, and the offset printing suitability is good.
Δ: The black density of the printed matter is 1.6 or more and less than 1.7, and the offset printing suitability is medium.
X: The black density of the printed matter is less than 1.6, and the offset printing suitability is poor.

[Manufacturing method and flexibility evaluation of colored products]
Using a simple color developer (RI tester, manufactured by Hoei Seiko Co., Ltd.), using 0.10 ml of ink, spread evenly on the rubber roll and metal roll of the RI tester, and coat cardboard (UF coat manufactured by Oji Materia, rice). A colored product was prepared by spreading the color on the surface of 350 g / m2) so as to be uniformly applied over an area of 200 cm2 with a black density of 1.8 (measured with a SpectroEye densitometer manufactured by X-Rite). The RI tester is a testing machine that spreads ink on paper or film, and can adjust the amount of ink transfer and printing pressure.
After the ink was applied, the colored material was irradiated with ultraviolet rays (UV), which are active energy rays, to cure the ink film. Using a water-cooled metal halide lamp (output 100 W / cm 1 lamp) and a UV irradiation device equipped with a belt conveyor (manufactured by Eye Graphics, cold mirror included), place the colored object on the conveyor and directly under the lamp (irradiation distance 11 cm). Was passed at a speed of 100 meters per minute to cure the ink film.

(Bending test)
With the back side of the colored matter pressed against the corner of the desk (angle 90 °), both ends of the printed matter were grasped by hand and squeezed strongly 10 times. Since this evaluation method causes a physical load on the cured coating film of the ink composition on the surface of the printed matter, the flexibility was evaluated in the following three stages by observing the cracks on the surface of the cured coating film after the evaluation. ..
◯: The cured coating film does not crack and has good flexibility.
Δ: The cured coating film has minute cracks, and the flexibility is medium.
X: Clear cracks are generated in the cured coating film, and the flexibility is poor.

(Adhesion test)
As a method for evaluating the adhesion of the cured coating film after irradiation with ultraviolet rays, it was confirmed by a tape peeling test. As the color-developed product, the coated corrugated cardboard in the above [method for manufacturing the color-developed product] was prepared in place of the PP film (Hyp Crystal ST-200). The cellophane tape was strongly pressed against the ink film after irradiation with ultraviolet rays, and was quickly pulled up vertically and peeled off to evaluate the state of adhesion of the ink film to the substrate in the following three stages.
◯: Almost adhered, and 80% or more of the area where the ink coating film and the PP film were not peeled off remained. Less than 40-80% remains ×: The area where the ink coating film and the PP film are not peeled off is less than 40% due to slight adhesion.

〔Liquidity〕
The fluidity was evaluated by the spread meter method (parallel plate viscometer) according to JIS K5101,5701. The printing inks obtained in each Example and Comparative Example spread concentrically over time due to the weight of the load plate (115 grams) from the state of being sandwiched between two horizontally placed parallel plates. After observing, the spread diameter of the ink after 60 seconds was taken as a diamometer value (DM [mm]), and the ink printability was evaluated in the following three stages.
When the composition has a DM of less than 30 mm in this evaluation item, defects in printability such as jar breakage on the printing machine and transfer defects between ink rollers are likely to occur.
◯: 35 mm or more
Δ: 30 to less than 35 mm ×: less than 30 mm

表１〜表２で使用した各成分の詳細は以下の通りである。
カーボンブラック：コロンビアンケミカル社製カーボンブラック「ラーベン １０６０P」
炭酸マグネシウム：ナイカイ塩業社製塩基性炭酸マグネシウム「炭酸マグネシウムＴＴ」
Ｓ−３８１−Ｎ１：ポリオレフィンワックス（シャムロック社製ワックス「Ｓ−３８１−Ｎ１」）
ジアリルフタレート樹脂：ダイソー社製ジアリルフタレート樹脂「ダイソーダップＡ」
ＰＥＴＡ重合体（７６００ｃｐｓ）：ペンタエリスリトールテトラアクリレート＋ペンタエリスリトールトリアクリレート＋ペンタエリスリトールジアクリレートの混合物のマイケル付加重合体［ＧＰＣピーク比（質量比）が3量体以上の高分子量体／2量体／未反応の4官能アクリレート／未反応の３官能以下のアクリレート＝１４０／５３／１００／１６］
ＰＥＴＡ重合体（６５００ｃｐｓ）：ペンタエリスリトールテトラアクリレート＋ペンタエリスリトールトリアクリレート＋ペンタエリスリトールジアクリレートの混合物のマイケル付加重合体［ＧＰＣピーク比（質量比）が3量体以上の高分子量体／2量体／未反応の4官能アクリレート／未反応の３官能以下のアクリレート＝１３０／４９／１０７／２３］
ＰＥＴＡ重合体（４５００ｃｐｓ）：ペンタエリスリトールテトラアクリレート＋ペンタエリスリトールトリアクリレート＋ペンタエリスリトールジアクリレートの混合物のマイケル付加重合体［ＧＰＣピーク比（質量比）が3量体以上の高分子量体／2量体／未反応の4官能アクリレート／未反応の３官能以下のアクリレート＝１２０／４３／１１５／３１］
ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート（ＭＩＷＯＮ社製「ＭＩＲＡＭＥＲ Ｍ６００」、４０００−７０００ｍＰａ・ｓ（２５℃））
ＩＲＧＡＣＵＲＥ ９０７：α-アミノアルキルフェノン（ＢＡＳＦ社製「Ｉｒｇａｃｕｒｅ９０７」）
ＥＡＢ−ＳＳ：４，４’−ビスジメチルアミノベンゾフェノン（大同化成社製「ＥＡＢ−ＳＳ」）
ステアラーＴＢＨ：精工化学社製重合禁止剤（２−ｔｅｒｔ−ブチルハイドロキノン）「ステアラーＴＢＨ」

Details of each component used in Tables 1 and 2 are as follows.
Carbon Black: Carbon Black "Raven 1060P" manufactured by Colombian Chemical Co., Ltd.
Magnesium carbonate: Basic magnesium carbonate "Magnesium carbonate TT" manufactured by Naikai Salt Industries, Ltd.
S-381-N1: Polyolefin wax (wax "S-381-N1" manufactured by Shamlock)
Dialyl phthalate resin: Daiso's diallyl phthalate resin "Daiso Dap A"
PETA polymer (7600 cps): Michael-added polymer of a mixture of pentaerythritol tetraacrylate + pentaerythritol triacrylate + pentaerythritol diacrylate [Polymer / dimer with GPC peak ratio (mass ratio) of trimer or more / dimer / Unreacted tetrafunctional acrylate / unreacted trifunctional or less acrylate = 140/53/100/16]
PETA polymer (6500 cps): Michael-added polymer of a mixture of pentaerythritol tetraacrylate + pentaerythritol triacrylate + pentaerythritol diacrylate [Polymer / dimer with GPC peak ratio (mass ratio) of trimer or more / dimer / Unreacted tetrafunctional acrylate / unreacted trifunctional or less acrylate = 130/49/107/23]
PETA polymer (4500 cps): Michael-added polymer of a mixture of pentaerythritol tetraacrylate + pentaerythritol triacrylate + pentaerythritol diacrylate [Polymer / dimer with GPC peak ratio (mass ratio) of trimer or more / dimer / Unreacted tetrafunctional acrylate / unreacted trifunctional or less acrylate = 120/43/115/31]
DPHA: Dipentaerythritol hexaacrylate (MIWON "MIRAMER M600", 4000-7000 mPa · s (25 ° C))
IRGACURE 907: α-aminoalkylphenone (BASF's "Irgacure 907")
EAB-SS: 4,4'-bisdimethylaminobenzophenone ("EAB-SS" manufactured by Daido Kasei Co., Ltd.)
Stairer TBH: Polymerization inhibitor (2-tert-butyl hydroquinone) "Stairer TBH" manufactured by Seiko Kagaku Co., Ltd.

a: Peak of a high molecular weight body of a trimer or more b: Peak of a dimer c: Peak of an unreacted monomer (tetrafunctional acrylate) d: Peak of an unreacted monomer (acrylate of trifunctional or less) 1 Drive motor for inner cylinder 2 Inner cylinder 3 Outer cylinder 4 Constant temperature water tank 5 Drive motor for outer cylinder 6 Tap water 7 Evaluation ink

Claims (7)

A (meth) acryloyl group-containing polymerization containing a Michael addition polymer of a hydroxyl group-containing (meth) acrylate compound (a1) and a Michael addition reaction product of a hydroxyl group-containing (meth) acrylate compound (a1) and a polyfunctional acrylate compound (a2). The sex diluent (A), the diallyl phthalate resin as the binder resin (B) having a radically polymerizable functional group , and the polymerization initiator (C) are essential components.
The active energy ray-curable offset is characterized in that the blending amount of the polymerizable diluent (A) is 50 to 1,000 parts by mass per 100 parts by mass of the binder resin (B). Printing ink.
However, the (meth) acryloyl group-containing polymerizable diluent (A) has a viscosity at 25 ° C. of 7,000 to 20,000 cps. The (meth) acryloyl group-containing polymerizable diluent (A) is a polyfunctional acrylate compound (a2), and a Michael addition reaction product of a hydroxyl group-containing (meth) acrylate compound (a1) and a polyfunctional acrylate compound (a2). mixtures of claim 1 active energy ray-curable offset printing ink according to. The (meth) acryloyl group-containing polymerizable diluent (A) is a hydroxyl group-containing (meth) acrylate compound (a1) and a polyfunctional acrylate compound mixture according to claim 2, wherein is obtained by Michael addition reaction of (a2) Active energy ray curable offset printing ink . The (meth) acryloyl group-containing polymerizable diluent (A)
The active energy ray-curable offset printing ink according to any one of claims 1 to 3, which is a Michael addition polymer of a mixture of pentaerythritol tetraacrylate, pentaerythritol triacrylate and pentaerythritol diacrylate. The active energy ray-curable offset printing according to any one of claims 1 to 4, wherein the (meth) acryloyl group-containing polymerizable diluent (A) has a viscosity at 25 ° C. of 7,000 to 8,500 cps. ink. The active energy ray curing according to any one of claims 1 to 5, wherein the blending amount of the polymerizable diluent (A) is 400 to 700 parts by mass per 100 parts by mass of the diallyl phthalate resin. Sex offset printing ink. A printed matter obtained by printing the active energy ray-curable offset printing ink according to any one of claims 1 to 6 .

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