JP2021098827A - Active energy ray-curable lithographic printing ink and its printed matter - Google Patents

Abstract

To provide active energy ray-curable lithographic printing ink which has a high emulsification viscoelasticity maintenance ratio, staining resistance and misting suitability, and a printed matter using the same.SOLUTION: Active energy ray-curable lithographic printing ink contains a resin, a (meth)acrylate compound and an extender pigment. The resin contains a rosin-modified resin and a diallyl phthalate resin. A content of the rosin-modified resin is 50-80 mass% in a total amount of the resin.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable lithographic printing ink having good printability and a printed matter thereof.

The lithographic printing ink is an ink having a relatively high viscosity of 5 to 100 Pa · s. In the mechanism of a flat plate printing machine, ink is supplied from the ink fountain of the printing machine to the image area of the plate surface via multiple rollers, and in flat plate printing using dampening water, dampening water is supplied to the non-image area. As a result, in flat plate printing without dampening water, the non-image portion made of the silicon layer repels the ink, and an image is formed.

In particular, in lithographic printing using dampening water, the emulsification balance between the ink and the fountain solution is important, and an ink having appropriate emulsification characteristics and suitable for high-speed printing is required. If the maximum emulsification amount of the ink is low, the dampening water cannot be carried in the ink and the dampening water is discharged to the ink surface, and the ink transfer between rolls and the ink transfer to the paper deteriorate, so stable printing is possible. Becomes difficult. Further, when the ink is emulsified and the viscoelasticity is lowered, the ink transfer property between the rolls is deteriorated, the ink is left over on the rolls, and stains are generated at the time of printing or restarting the printing.

Furthermore, in recent years, there has been an increasing demand for automation and speeding up at the time of printing, and in particular, the printing speed is becoming faster and faster. With the increase in printing speed, ink misting has become an issue, and the printing environment has deteriorated due to stains around the printing machine, and the paper surface has become dirty due to large particles of ink flying. As described above, there is a demand for inks that can stably obtain high-quality printed matter for a long time without trouble under various printing conditions, and ink makers have made various improvements.

On the other hand, the active energy ray-curable ink contains an unsaturated compound having active energy ray curability such as an acrylic ester compound as a constituent component, and is instantly cured by irradiation with active energy rays. Form a tough film by dimensional cross-linking. Since it cures instantly, post-processing can be performed immediately after printing, so active energy rays are used in packaging package printing and foam printing in the commercial field, where a strong film is required to improve productivity and protect the design. Curable inks are preferably used.

Generally, the active energy ray-curable ink is composed of a resin, an active energy ray-curable compound, a pigment, a radical polymerization initiator, and various additives.

It is effective to use a resin in order to exhibit printability such as emulsification suitability and background stain resistance in active energy ray-curable ink. Dialyl phthalate resin is well known as a resin used for active energy ray-curable ink, but diallyl phthalate resin alone has a low maximum emulsification amount, and when it becomes highly emulsified, dampening water is added to the ink. It is difficult to perform stable printing because the viscoelasticity is lowered and the ink transfer between rolls and the ink transfer to paper are deteriorated.

In order to improve the emulsification suitability of the resin, unsaturated polyester resin, epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, rosin-modified resin and the like have been studied.
In Patent Documents 1 and 2, printability and curability are improved by adding α, β-unsaturated carboxylic acid or an acid anhydride thereof, an organic monobasic acid, and a polyol to a conjugated loginic acid as a rosin-modified resin. However, since the rosin-modified resin alone has high hydrophilicity, it has a high affinity with dampening water, which causes stains during printing and misting due to a decrease in viscous elasticity. Improvement of stain resistance and misting suitability was an issue.

International Publication No. 2017/1642446 Japanese Unexamined Patent Publication No. 2010-0707742

An object of the present invention is to provide an active energy ray-curable lithographic printing ink having a high emulsified viscoelasticity retention rate, ground stain resistance, and misting suitability.

As a result of intensive research to solve the above problems, in the active energy ray-curable flat plate ink composition containing a resin, a (meth) acrylate compound, and an extender pigment, a rosin-modified resin and a diallyl phthalate resin are used as resins. When the content of the rosin-modified resin is 50 to 80% by mass in the total amount of the resin, the active energy ray-curable slab printing ink having a high emulsifying viscoelasticity retention rate, stain resistance and misting suitability is produced. We have found that it can be obtained and completed the present invention.

That is, the present invention is an active energy ray-curable lithographic printing ink containing a resin, a (meth) acrylate compound, and an extender pigment.
The resin contains a rosin-modified resin (A) and a diallyl phthalate resin.
The present invention relates to an active energy ray-curable lithographic printing ink characterized in that the content of the rosin-modified resin (A) is 50 to 80% by mass in the total amount of the resin.

Further, in the present invention, the (meth) acrylate compound is an alkylene oxide-modified (meth) acrylate compound having two or more (meth) acryloyl groups and having an octanol / water partition coefficient (LogP) of 2.5 or more. (B) relates to the above-mentioned active energy ray-curable lithographic printing ink, which comprises 10% by mass or more in the total amount of the ink.

The present invention also relates to the above-mentioned active energy ray-curable lithographic printing ink, wherein the extender pigment contains at least two kinds selected from the group consisting of silica, magnesium carbonate, and talc.

Further, in the present invention, the rosin-modified resin (A) is a structural unit (a12) derived from a compound in which α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) is added to a conjugated logic acid (A1). ), A structural unit (a3) derived from the organic monobasic acid (A3) excluding the conjugated carboxylic acid (A1), and a structural unit (a5) derived from the polyol (A5).
The present invention relates to the above-mentioned active energy ray-curable lithographic printing ink in which the weight ratio of the structural unit (a12) to the structural unit (a3) is in the range of 100: 10 to 100: 350.

The present invention also relates to a printed matter having a printed layer formed on a substrate by using the above-mentioned active energy ray-curable lithographic printing ink.

The present invention is an active energy ray-curable flat plate printing ink having a high emulsified viscoelasticity retention rate, ground stain resistance, and misting suitability by using a rosin-modified resin having a high emulsifying amount and a diallyl phthalate resin in combination at a constant ratio. The printed matter can be provided.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following description, and various modifications can be made without departing from the gist of the present invention.

The active energy ray-curable slab printing ink of the present invention contains a rosin-modified resin (A), a diallyl phthalate resin, a (meth) acrylate compound, and an extender pigment, and the content of the rosin-modified resin is in the total amount of the resin. It is characterized by containing 50 to 80% by mass of.

Hereinafter, the constituent components of the ink will be specifically described.
<Rosin modified resin (A)>
In the present specification, the "rosin-modified resin (A)" is a polymer of a loginate and a component containing at least a polyol (A5).
When the rosin-modified resin (A) is used as the binder resin for the active energy ray-curable lithographic printing ink, the conjugated double bond contained in the rosin acids causes curing inhibition. Therefore, the rosin-modified resin (A) is prepared by adding a compound in which α, β-unsaturated carboxylic acid or an acid anhydride (A2) thereof is added to loginic acids in order to reduce or eliminate the conjugated double bond in the resin. It may be a resin obtained by further esterification.

The rosin-modified resin includes a structural unit (a12) derived from a compound obtained by adding α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) to a conjugated logonic acid (A1), and the conjugated loginic acid (A12). It has a structural unit (a3) derived from an organic monobasic acid (A3) excluding A1) and a structural unit (a5) derived from a polyol (A5), and has the structural unit (a12) and the structural unit (a3). ), The weight ratio (a12): (a3) is 100: 10 to 100: 350, and the rosin-modified resin (A) is preferable.
The weight ratio (a12): (a3) is preferably 100: 10 to 100: 350, more preferably 100: 10 to 100: 300, and preferably 100: 10 to 100: 250. More preferred. In the rosin-modified resin (A), when the weight ratio (a12): (a3) ratio is within the above range, it becomes easy to develop glossiness in the printed film. Further, it is easy to obtain a resin having a public molecular weight distribution, which tends to improve the solubility in the active energy ray-curable compound (B) and the misting resistance of the ink.

The weight ratio (a12): (a3) is the weight ratio of the structural unit (a12) and the structural unit (a3) in the rosin-modified resin (A), and the structural unit (a12) in the rosin-modified resin (A). It means the value of the weight of the structural unit (a3) when the weight of is 100. The weight of the structural unit (a12) and the weight of the structural unit (a3) are those of the monomers (A1), (A2), and (A3) used for producing the rosin-modified resin (A). It is calculated by subtracting the remaining amount of each monomer after the reaction is completed from the charged amount. The specific calculation method will be described in detail in Examples.

The rosin-modified resin (A) preferably further has a structural unit (a4) derived from a polybasic acid or an anhydride thereof (A4). Since the rosin-modified resin (A) further has the structural unit (a4), the print suitability and the print film suitability are more likely to be improved.

The rosin-modified resin (A) is a compound obtained by adding α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) to a conjugated logonic acid (A1), and is an organic substance excluding the conjugated logonic acid (A1). It may be a polymer compound obtained by reacting a monochloric acid (A3) and a polybasic acid or an anhydride thereof (A4) with a polyol (A5). The polymer compound has a rosin-modified structure in which the structural units (a12), (a3), and (a4) derived from the respective monomers and the structural unit (a5) are bonded to each other via an ester bond. It is a polyester resin.

The rosin-modified resin (A) is a structural unit (a1) derived from a conjugated loginic acid (A1) and / or a structural unit derived from an α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2). (A2) may be further included.

Although not particularly limited, for example, as α, β-unsaturated carboxylic acid or its acid anhydride (A2), a compound having two carboxyl groups such as (maleic anhydride) maleic acid is used, and polybasic acid or its acid anhydride thereof is used. When a compound having two carboxyl groups such as succinic anhydride is used as the anhydride (A4), the rosin-modified resin (A) typically has a partial structure represented by the following formulas (I) to (VI). May have. Among them, the partial structures represented by the following formulas (IV) to (VI) are specific examples of the terminal structure of the resin. However, the partial structure of the rosin-modified resin (A) is not limited to these.

Although details will be described later, in the case where the α, β-unsaturated carboxylic acid or its acid anhydride (A2) is involved in the reaction as a polybasic acid or its anhydride (A4), the following formula (I), (II)
, And, instead of the structural unit (a4) contained in (IV), a structural unit (a2) derived from α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) may be contained. Further, when the component (A1) remains after the reaction (Deels-Alder addition reaction described later) by adding the component (A2) to the component (A1), a part of the structural unit (a3) is the component (A1). It may be a structural unit (a1) derived from.

(Example of partial structure of rosin-modified resin (A))

Hereinafter, the monomers constituting each structural unit will be described.
<(A1) Conjugated rosin acid>
The compound having the structural unit (a12) constituting the rosin-modified resin (A) is subjected to a Diels-Alder reaction between the conjugated loginate (A1) and an α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2). It is formed.
The conjugated rosin acid (A1) is a rosin acid having a conjugated double bond. As used herein, the term "rosin acids" means organic monobasic acids having a cyclic diterpene skeleton and derivatives thereof. The rosin acids may be, for example, rosin acid, disproportionated rosin acid, hydrogenated rosin acid, and alkali metal salts of these compounds. Further, the "conjugated double bond" means a bond in which a plurality of double bonds are alternately connected with a single bond in between. However, the conjugated double bond of the π-electron conjugated system contained in the aromatic compound is not included. That is, the "conjugated rosin acid (A1)" described in the present specification means the above-mentioned rosin acids excluding hydrogenated rosin acid having no conjugated double bond.

Specific examples of the conjugated rosin acid (A1) include abietic acid and its conjugated compounds, neoabietic acid, palastolic acid, and levopipmaric acid. Moreover, as a natural resin containing these conjugated rosin (A), gum rosin, wood rosin, tall oil rosin and the like can be mentioned. Generally, the natural resin contains rosin acids having no conjugated double bond together with the conjugated rosin acid (A), but in the present invention, these natural resins may be used. Rosin acids that do not have a conjugated double bond participate in the reaction as an organic monobasic acid (A3) described later. Further, the conjugated logonic acid (A1) may form a structural unit (a1) derived from the compound according to the blending amount of the rosin-modified resin (A) at the time of production.

<Α, β-unsaturated carboxylic acid or acid anhydride thereof (A2)>
Specific examples of α, β-unsaturated dicarboxylic acid or its acid anhydride (A2) that can be used to obtain a compound having a structural unit (a12) constituting the rosin-modified resin (A) are crotonic acid and methacrylic acid. , Maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, cinnamic acid, 2,4-hexadienoic acid and the like, and acid anhydrides thereof. From the viewpoint of reactivity with the conjugated rosin acid (A1), maleic acid or an acid anhydride thereof is preferable. The α, β-unsaturated carboxylic acid or the acid anhydride (A2) thereof may form a structural unit (a2) derived from the compound according to the blending amount of the rosin-modified resin (A) at the time of production. Good.

<Organic monobasic acid (A3)>
The organic monobasic acid (A3) that can be used to obtain the structural unit (a3) constituting the rosin-modified resin (A) may be an organic monobasic acid that does not have a conjugated double bond, and known materials may be used. It can be used arbitrarily. As a specific example
Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecic acid, stearic acid, nonadecan Saturated fatty acids such as acids, araquinic acid, and behenic acid,
Crotonic acid, linderic acid, tsuzuic acid, myristoleic acid, palmitreic acid, undecylenic acid, oleic acid, elaidic acid, gadrainic acid, gondolic acid, setreic acid, erucic acid, brassic acid, linoelaidic acid, linolenic acid, and arachidon Unsaturated fatty acids such as acids,
Aromatic monobasic acids such as benzoic acid, methyl benzoic acid, tertiary butyl benzoic acid, naphthoic acid, orthobenzoyl benzoic acid,
Examples thereof include compounds having a conjugated double bond, such as conjugated linoleic acid, eleostearic acid, parinaric acid, and calendic acid, but not having a cyclic diterpene skeleton.
Further, rosin acids having no conjugated double bond, such as pimaric acid, isopimaric acid, sandalacopimaric acid, and dehydroabietic acid, can also be used as the organic monobasic acid (A3). As the organic monobasic acid (A3) used in the present invention, only rosin acids having no conjugated double bond may be used.

<Polybasic acid or its anhydride (A4)>
The rosin-modified resin (A) preferably contains a structural unit (a4) derived from a polybasic acid or an anhydride thereof (A4), if necessary. As the polybasic acid or its anhydride (A4), an aromatic polybasic acid or its anhydride, an aliphatic polybasic acid or its anhydride can be used, and as the aliphatic polybasic acid or its anhydride, the aliphatic polybasic acid or its anhydride can be used. , A linear structure, or a branched structure. Further, it may have a cyclic structure, that is, an alicyclic polybasic acid or an anhydride thereof.
Specific examples of the polybasic acid or anhydride (A4) that can be used to obtain the structural unit (a4) constituting the rosin-modified resin (A) are described below.

As the aliphatic polybasic acid or its anhydride, alkyl succinic acid such as succinic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenyl succinic acid, pentadecenyl succinic acid or alkenyl succinic acid. Acids and the like, and their anhydrides are mentioned.
As the alicyclic polybasic acid or its anhydride, 1,2,3,6-tetrahydrophthalic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3 , 6-Tetrahydrophthalic acid, Hexahydrophthalic acid, 3-Methylhexahydrophthalic acid, 4-Methylhexahydrophthalic acid, Hymic acid, 3-Methylhymic acid, 4-Methylhymic acid, etc., and their anhydrides. Things can be mentioned.
Examples of the aromatic polybasic acid or its anhydride include o-phthalic acid, terephthalic acid, trimellitic acid, pyrrolitic acid and the like, and their anhydrides.
In addition, fatty acids of natural fats and oils, such as tung oil fatty acid, flaxseed oil fatty acid, soybean oil fatty acid, palm oil fatty acid, (dehydrated) castor oil fatty acid, palm oil fatty acid, safflower oil fatty acid, cottonseed fatty acid, rice bran oil fatty acid, olive oil fatty acid. , Rapeseed oil fatty acids and the like. Further, dimer acids of these fatty acids, for example, tung oil dimer fatty acid, linseed oil dimer fatty acid and the like can also be used.
These can be used alone or in combination of two or more.

As the polybasic acid or its anhydride (A4), the dibasic acid anhydride among the compounds exemplified in the above-mentioned α, β-unsaturated carboxylic acid or its acid anhydride (A2) can also be used. As a specific example, acid anhydrides such as maleic acid, fumaric acid, citraconic acid, and itaconic acid can also be used.

When an excess amount of α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) is used with respect to the conjugated loginate (A1) during the production of the rosin-modified resin (A), the rosin-modified resin (A2) A) will contain a structural unit (a2) involved in the esterification reaction between the polyol (A5) and the component (A2).
For example, when a dibasic acid anhydride such as maleic anhydride is used as the α, β-unsaturated carboxylic acid or its acid anhydride (A2), the excess amount of the dibasic acid anhydride is polybasic acid or its anhydride. Involved in the reaction as part of the substance (A4). That is, in such a case, the ratio of the structural unit (a4) in the rosin-modified resin (A) is an amount containing an excess amount of the structural unit (a2) derived from the component (A2).

The ratio of the structural unit (a4) in the rosin-modified resin (A) is preferably in the range of 5.0 to 65.0 mol% based on the total number of moles of all the structural units excluding the structural unit (a5) described later. , 6.5-60.0 mol% is more preferred, and 8.0-50.0 mol% is even more preferred.

In the present specification, the ratio (mol%) of each structural unit in the rosin-modified resin (A) is used for producing the rosin-modified resin (A), similarly to the weight ratio of the structural units described above. It is a value calculated based on the amount obtained by subtracting the remaining amount of each component after the completion of the reaction from the amount of the monomer charged corresponding to each structural unit.

<Polyol (A5)>
The polyol (A5) that can be used to obtain the structural unit (a5) constituting the rosin-modified resin (A) is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. The polyol (A5) is a compound obtained by a deal alder reaction with a conjugated logic acid (A1), an α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2), an organic monobasic acid (A3), and many. An ester bond is formed by reaction with a carboxylic acid in a basic acid or its anhydride (A4).

Specific examples of the dihydric alcohol include the following.
(Linear alkylene divalent alcohol)
1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1 , 6-Hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1, 9-Nonandiol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16 -Hexadecanediol, 1,2-hexadecanediol, etc.

(Branched alkylene divalent alcohol)
2-Methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,2-Dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane, 2-ethyl-1,3-hexanediol, 2,5-dimethyl -2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol and the like.

(Cyclic alkylene dihydric alcohol)
1,2-Cyclohexanediol, 1,4-Cyclohexanediol, 1,4-Cyclohexanedimethanol, 1,2-Cycloheptanediol, Tricyclodecanedimethanol, Hydrogenated Bisphenol A, Hydrogenated Bisphenol F, Hydrogenated Bisphenol S , Hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, etc.

Other specific examples include polyether polyols such as polyethylene glycol (n = 2 to 20), polypropylene glycol (n = 2 to 20), polytetramethylene glycol (n = 2 to 20), polyester polyols and the like.

Specific examples of trihydric or higher-valent polyhydric alcohols include the following.
Glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, diglycerin, ditrimethylolpropane, dipentaelis Examples thereof include linear, branched, and cyclic polyhydric alcohols such as lithol, sorbitol, inositol, and tripentaerythritol.

The various dihydric alcohols and the trihydric or higher polyhydric alcohols may be used alone or in combination of two or more. The polyol (A5) preferably contains a divalent alcohol and a trihydric or higher polyhydric alcohol. The ratio of the dihydric alcohol is preferably in the range of 20 to 95 mol% based on the total amount of the polyol (A5). When the ratio of the dihydric alcohol in the polyol (A5) is within the above range, it becomes easy to improve the emulsified viscoelasticity retention rate and the stain resistance.

The rosin-modified resin (A) is
(1) Reaction of conjugated loginate (A1) with α, β-unsaturated carboxylic acid or its acid anhydride (A2), and (2) Compounds and organic monobases obtained by the reaction of (1) above. It can be produced by reacting a carboxylic acid-containing compound containing an acid (A3) and a polybasic acid or an anhydride thereof (A4) with a polyol (A5).
The reaction of (1) above is a reaction between a conjugated double bond (diene) in a conjugated logonic acid (A1) and a double bond (dienofil) in an α, β-unsaturated carboxylic acid or its acid anhydride (A2). It is a Diels-Alder addition reaction. Further, the reaction of (2) above is carried out with the carboxyl groups in each compound of the deal alder addition reaction product obtained in the reaction of (1), the organic monobasic acid (A3), and the polybasic acid or its anhydride (A4). , Is an esterification reaction with a hydroxyl group in the polyol (A5).

The deal alder addition reaction product of the conjugated loginate (A1) and the α, β-unsaturated carboxylic acid or its acid anhydride (A2) is a polyvalent carboxylic acid compound. Therefore, polymerization is possible by the esterification reaction with the polyol (A5). Further, by using the organic monobasic acid (A3) in combination during the esterification reaction, excessive polymerization can be suppressed and the molecular weight distribution can be controlled.

From the above, by using the rosin-modified resin (A), it is possible to improve the emulsified viscoelasticity retention rate and the stain resistance.

The conditions for the Diels-Alder addition reaction are not particularly limited and can be carried out according to a conventional method. The reaction temperature can be determined in consideration of the boiling point of the compound used and the reactivity. In one embodiment, the reaction temperature is preferably in the range of 80 to 200 ° C, more preferably in the range of 100 to 200 ° C, and even more preferably in the range of 100 to 180 ° C.
The Diels-Alder addition reaction may be carried out in the presence of a polymerization inhibitor. Specific examples of the polymerization inhibitors that can be used include hydroquinone, p-methoxyphenol, methylhydroquinone, methoxyhydroquinone, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-hydroxytoluene, t. -Butylcatechol, 4-methoxy-1-naphthol, phenothiazine and the like can be mentioned.

The conditions for the esterification reaction are also not particularly limited, and can be carried out according to a conventional method. The reaction temperature can be determined in consideration of the boiling point of the compound used and the reactivity. In one embodiment, the reaction temperature is preferably in the range of 200 to 300 ° C, more preferably in the range of 200 to 280 ° C, and even more preferably in the range of 200 to 260 ° C.

Further, if necessary, a catalyst can be used in the esterification reaction. Examples of usable catalysts include organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, and trifluoromethylsulfate. , Trifluoromethylacetic acid and the like. In addition, as other examples of catalysts that can be used, metal complexes such as tetrabutylzirconate, tetraisobutyltitanate, magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide, zinc acetate. And the like, such as a metal salt catalyst. These catalysts are usually used in the range of 0.01 to 5% by weight based on the total amount of all the components used in the production of the rosin-modified resin (A). Hypophosphorous acid, triphenylphosphine, triphenylphosphate, triphenylphosphine and the like can also be used in combination during the production of the resin in order to suppress the coloring of the resin due to the use of the catalyst.

In the production of the rosin-modified resin (A), the monomers (A1) to (A5) constituting the resin can be blended at the same time or stepwise.
For example, conjugated logonic acid (A1), α, β-unsaturated carboxylic acid or its acid anhydride (A2), organic monobasic acid (A3), polyol (A5), and further used as needed. The reaction can be carried out in two steps using the polybasic acid to be prepared or a mixture thereof with an anhydride (A4). In this case, first, the reaction temperature may be adjusted so that the Diels-Alder addition reaction between the conjugated loginate (A1) and the α, β-unsaturated carboxylic acid or its acid anhydride (A2) occurs. More specifically, the reaction temperature may first be controlled to the temperature at which the Diels-Alder addition reaction proceeds, maintained for a certain period of time, and then heated to the temperature at which the esterification reaction proceeds to carry out the reaction.

Alternatively, a conjugated logic acid (A1) and an α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) are blended, subjected to a deal alder addition reaction, and then an organic monobasic acid (A3) and a polyol. (A5), and if used, a polybasic acid or an anhydride thereof (A4) may be blended to carry out an esterification reaction.

When an excess amount of α, β-unsaturated carboxylic acid or its acid anhydride (A2) was used with respect to the conjugated loginate (A1), the component (A2) that was not involved in the deal alder addition reaction continues. It will be consumed in the esterification reaction in the same manner as polybasic acid or its anhydride (A4). As the polybasic acid or its anhydride (A4), the same compound as the α, β-unsaturated carboxylic acid or its acid anhydride (A2) may be used.

The blending amount of α, β-unsaturated carboxylic acid or its acid anhydride (A2) is preferably in the range of 80 to 200 mol% with respect to the conjugated logonic acid (A1), and is 90 to 200 mol%. It is more preferably in the range of 100 to 200 mol%, and further preferably in the range of 100 to 200 mol%. When the blending amount of α, β-unsaturated carboxylic acid or its acid anhydride (A2) is adjusted within the above range, a rosin-modified resin (A) having suitable emulsifying properties and excellent printability can be obtained. Easy to obtain.

The weight average molecular weight of the rosin-modified resin (A) is preferably in the range of 2500 to 50000, more preferably in the range of 2500 to 35000, and particularly preferably in the range of 3000 to 30000. When the weight average molecular weight of the rosin-modified resin (A) is within the above range, the ink using the resin has suitable emulsifying properties and excellent printability. The weight average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

<Diallyl phthalate resin>
The diallyl phthalate resin is a resin obtained by polymerizing a diallyl phthalate monomer. As the diallyl phthalate resin, known ones can be used, and specific examples thereof include Daiso Dap series (Daiso Dap A, Daiso Dap K) manufactured by Osaka Soda Co., Ltd.

<Active energy ray-curable lithographic printing ink>
The active energy ray-curable lithographic printing ink of the present invention contains a rosin-modified resin (A) and a diallyl phthalate resin.

The active energy ray-curable lithographic printing ink of the present invention contains 50 to 80% by mass of the rosin-modified resin (A) in the total amount of the resin.

The resin content in the total amount of the ink is preferably 10 to 30%, more preferably 10 to 20%. Furthermore, it is preferably 10 to 15%.

The active energy ray-curable slab printing ink of the present invention is an alkylene having two or more (meth) acryloyl groups as a (meth) acrylate compound and an octanol / water partition coefficient (LogP) of 2.5 or more. It contains 10% by mass or more of the oxide-modified (meth) acrylate compound (B) in the total amount of the ink.
The alkylene oxide-modified (meth) acrylate compound (B) preferably has three or more (meth) acryloyl groups.

As the alkylene oxide-modified (meth) acrylate compound (B) containing two or more (meth) acryloyl groups and having an octanol / water partition coefficient (LogP) of 2.5 or more, the ethylene oxide-modified bisphenol A diacrylate ( LogP = 5.47), propylene oxide-modified bisphenol A diacrylate (LogP = 6.10), propylene oxide-modified trimethylolpropane triacrylate (LogP = 3.01), propylene oxide-modified pentaerythritol tetraacrylate (LogP = 2. 61) and the like.

The (meth) acrylate compound can be appropriately selected according to the required physical properties, and in addition to the compounds exemplified above, if necessary, (meth) such as bisphenol A diacrylate and pentaerythritol tetraacrylate ) It is also possible to use an acrylate compound in combination.

Specifically, monofunctional active energy ray-curable compounds such as 2-ethylhexyl acrylate, methoxydiethylene glycol acrylate, and acryloyl morpholine,
Ethylene glycol diacrylate, polyethylene glycol diacrylate (n = 2-20), propylene glycol diacrylate, polypropylene glycol diacrylate (n = 2-20), alkylene (4 to 12 carbon atoms) glycol diacrylate, alkylene (carbon number) 4-12) Glycolethylene oxide adduct (2-20 mol) diacrylate, alkylene (4-12 carbon carbon) glycol propylene oxide adduct (2-20 mol) diacrylate, hydroxypivalyl hydroxypivalate diacrylate, tri Bifunctional activity of cyclodecanedimethylol diacrylate, bisphenol A ethylene oxide adduct (2-20 mol) diacrylate, hydrogenated bisphenol A diacrylate, hydrogenated bisphenol A ethylene oxide adduct (2-20 mol) diacrylate, etc. Energy ray curable compound,
Glycerin triacrylate, glycerin ethylene oxide adduct (3-30 mol) triacrylate, glycerin propylene oxide adduct (3-30 mol) triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide adduct (3-30 mol) ) Triacrylate, trimethylolpropane propylene oxide adduct (3 to 30 mol) Trifunctional active energy ray-curable compound such as triacrylate,
Pentaerythritol tetraacrylate, pentaerythritol ethylene oxide adduct (4-40 mol) tetraacrylate, pentaerythritol propylene oxide adduct (4-40 mol) tetraacrylate, diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane ethylene A tetrafunctional active energy ray-curable compound such as an oxide adduct (4-40 mol) tetraacrylate and a ditrimethylolpropane propylene oxide adduct (4-40 mol) tetraacrylate.
Dipentaerythritol pentaacrylate, dipentaerythritol ethylene oxide adduct (5 to 50 mol) pentaacrylate, dipentaerythritol propylene oxide adduct (5 to 50 mol) pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol ethylene oxide adduct Polyfunctional active energy ray-curable compound such as (6 to 60 mol) hexaacrylate, dipentaerythritol propylene oxide adduct (6 to 60 mol) hexaacrylate, etc.
And mixtures thereof.

The (meth) acrylate compound can be appropriately selected according to the required physical properties, and in addition to the compounds exemplified above, oligomers such as polyester acrylate, polyurethane acrylate, and epoxy acrylate are used in combination as necessary. It is also possible to do.

When the resin and (meth) acrylate compound described in the present invention are prepared in advance in the form of a varnish and used, the resin is 20 to 70% by mass and the (meth) acrylate compound is 30 to 80% by mass. It is preferable to adjust the content. In addition to the above components, the varnish may further contain additives such as a photopolymerization inhibitor described later. The varnish can be produced, for example, by mixing the above components under a temperature condition between room temperature and 160 ° C.

<Constitution pigment>
The active energy ray-curable lithographic printing ink of the present invention contains an extender pigment. Examples of the extender pigment include clay, talc, barium sulfate, calcium carbonate, heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, bentonite and the like, and at least 2 selected from the group consisting of silica, magnesium carbonate and talc. It preferably contains seeds. Furthermore, it is preferable to contain three kinds of silica, magnesium carbonate, and talc.
The extender pigment preferably contains 1 to 5% by weight of each. When the type and blending amount of the extender pigment are adjusted within the above ranges, it is easy to obtain an active energy ray-curable lithographic printing ink having a high emulsified viscoelasticity retention rate and excellent misting suitability.

Further, the active energy ray-curable lithographic printing ink of the present invention contains a pigment (excluding the above-mentioned extender pigment) when it is used as a coloring ink, but is used as a clear ink or an overcoat varnish when no pigment is used. be able to. Therefore, the use of pigments is not limited.

Examples of pigments that can be used include inorganic pigments and organic pigments.
Examples of inorganic pigments include yellow lead, zinc yellow, dark blue, cadmium red, titanium oxide, zinc flower, petals, ultramarine blue, carbon black, graphite, etc., and examples of organic pigments include β-naphthol type and β-oxynaphthoic acid. Soluble azo pigments such as β-oxynaphthoic acid-based allylide, acetoacetate allylide, pyrazolone, β-naphthol, β-oxynaphthoic acid-based allylide, acetoacetate allylide monoazo, acetoacetate allylide dysazo, Insoluble azo pigments such as pyrazolones, copper phthalocyanine blue, halogenated (chlorine or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine pigments such as phthalocyanine, quinacridone, dioxazine, slene (pyrantron, Anthanthron, indantron, antrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalocyanine, etc. Examples include various publicly known and public pigments.

When the active energy ray-curable lithographic printing ink of the present invention uses ultraviolet rays, it is preferable to add a photopolymerization initiator. The photopolymerization initiator can be roughly classified into two types: one in which a bond is cleaved in a molecule by light to generate an active species, and the other in which a hydrogen abstraction reaction occurs between molecules to produce an active species. When an electron beam or the like is used as the active energy ray, a photopolymerization initiator is not required.

Examples of those in which the bond is cleaved in the molecule by light to generate an active species include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethoxyacetophenone, 4-( 2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1-hydroxycyclohexylphenyl ketone, [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, benzyl dimethyl ketal, oligo {2-hydroxy- 2-Methyl-1- [4- (1-methylvinyl) phenyl] propane}, 4-[(2-acryloyl) oxyethoxy] phenyl-2-hydroxy-2-propyl ketone and other acetophenone-based, benzoin, benzoin isopropyl Ether, benzoin type such as benzoin isobutyl ether, mixture of 1-hydroxycyclohexylphenyl ketone and benzophenone, (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide There are acylphosphine oxides such as, benzyl, methylphenylglioxyester and the like.

Examples of substances that undergo a hydrogen abstraction reaction between molecules to produce an active species include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, and 4-benzoyl-4. Benzophenones such as'-methyl-diphenylsulfide, acrylicized benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2- Thioxanthone-based isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, etc., Michler ketone, aminobenzophenone-based, such as 4,4'-bisdiethylaminobenzophenone, 10-butyl-2- There are chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrene quinone, camphorquinone and the like.
These photopolymerization initiators may be used alone or in combination of two or more as required.

When the active energy ray-curable lithographic printing ink of the present invention is cured by irradiating it with ultraviolet rays, it is cured only by adding a photopolymerization initiator, but in order to further improve the curability, a photosensitizer should be used in combination. You can also. Examples of the photosensitizer include triethanolamine, methyldiethanolamine, dimethylethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. There are amines such as (2-dimethylamino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, and 2-ethylhexyl 4-dimethylaminobenzoate.

When ultraviolet rays are used as the active energy rays, the blending amount of the photopolymerization initiator is 0.01 to 15% by mass, preferably 0.05 to 10% by mass in the printing ink. If it is less than 0.01% by mass, it is difficult to sufficiently carry out the curing reaction, and if it exceeds 15% by mass, a thermal polymerization reaction is likely to occur and the stability of the ink is likely to be impaired, which is not preferable.

In addition, a polymerization inhibitor can be added to the active energy ray-curable lithographic printing ink of the present invention.

Specific examples of photopolymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiline, p. -Benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperon, aluminum N-nitrosophenyl hydroxylamine, tri-p-nitrophenylmethyl, N- (3-) Oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutyl cresol, cycloquinone oxime cresol, guayacol, o-isopropylphenol, butyraldoxime, methylethylketoxim, cyclohexanone oxime and the like. Although not particularly limited, one or more compounds selected from the group consisting of hydroquinone, p-methoxyphenol, t-butylhydroquinone, p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone may be selected. It is preferable to use it.
When a photopolymerization inhibitor is added, the blending amount is preferably 3% by mass or less, preferably in the range of 0.01 to 1% by mass, based on the total mass of the ink, from the viewpoint of not impairing the curability. It is more preferred to use.

Further, the active energy ray-curable lithographic printing ink of the present invention can be added with various additives such as an anti-friction agent, an anti-blocking agent and a slip agent.

The atmosphere for irradiating the active energy rays is preferably an atmosphere in which an inert gas such as nitrogen gas is substituted, but there is no problem even if the atmosphere is irradiated in the atmosphere as long as there is no problem in curability. Before irradiating the active energy ray, the active energy ray-curable composition layer is heated with an infrared heater or the like, or after irradiating the active energy ray, the active energy ray-curable flat plate printing ink curing layer is heated with an infrared heater or the like. This is effective for terminating curing quickly.

The active energy rays of the present invention refer to ultraviolet rays, electron beams, X-rays, α rays, β rays, γ rays, microwaves, high frequencies, etc., but any energy species may be used as long as they can generate radically active species. , Visible light, infrared light, laser light. Specifically, ultra-high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp, helium / cadmium laser, YAG laser, excima laser, argon laser, LED (light emission). There is a diode) and so on.

In the active energy ray-curable lithographic printing ink of the present invention, the above printing ink components are mixed with a kneader, three rolls, an attritor, a sand mill, a gate mixer, etc. Manufactured using. In order to add the rosin-modified polyester resin for producing an ink, it may be added in the form of the rosin-modified polyester resin itself or in the form of a varnish.

The active energy ray-curable lithographic printing ink of the present invention is usually applied to lithographic offset printing using dampening water, but is also suitably used for waterless lithographic printing not using dampening water. The active energy ray-curable slab printing ink of the present invention includes foam printed matter, various book printed matter, various packaging printed matter such as carton paper, various plastic printed matter, seal / label printed matter, art printed matter, metal printed matter (art printed matter, art printed matter, It is applied to printed matter such as beverage can printed matter and food printed matter such as canned matter). It may also be used as an overcoat varnish.

As an example of the composition of the active energy ray-curable lithographic printing ink used in the present invention,
Resin 10 to 30% by mass
(Meta) Acrylate compound 30-75% by mass
Pigments (organic pigments / inorganic pigments) 0-40% by mass
Constituent pigment 1 to 15% by mass
Photopolymerization initiator 0 to 15% by mass
Other ingredients 1-15% by mass
Can be mentioned.

As the base material, non-coated paper such as high-quality paper, finely coated paper, art paper, coated paper, lightweight coated paper, coated paper such as cast coated paper, white paperboard, paperboard such as ball coat, and synthetic paper. Examples include paper, aluminum coated paper, and plastic sheets such as polypropylene, polyethylene, polyethylene terephthalate, and polyvinyl chloride.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, "part" in this invention represents part by mass, and "%" shows mass%.

In the present invention, the octanol / water partition coefficient (LogP) is determined by ChemDraw Ultra ver. Calculated using 13.0.

In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. The calibration curve was prepared from a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

A rosin-modified polyester resin and an active energy ray-curable lithographic printing ink composition were prepared according to the formulations shown below.

<Example of Resin Synthesis for Examples> Synthesis of Resin 1 In a stirrer, a reflux condenser with a water separator, and a four-necked flask with a thermometer, 25 parts of gumrosin and 7 parts of maleic anhydride were charged, and 180 parts were blown with nitrogen gas. It was heated at ° C. for 1 hour.
Then, 40 parts of t-butylbenzoic acid, 2 parts of succinic anhydride, 26 parts of neopentyl glycol and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and dehydration condensation was carried out at 230 ° C. for 14 hours. Then, a resin A1 having a weight average molecular weight (Mw) of 25,000 was obtained.

<Example of preparing varnish for examples> Preparation of resin varnish 30 parts of resin A1 obtained in a four-necked flask equipped with a stirrer, a reflux cooler, and a thermometer, 69.8 parts of dipentaerythritol tetraacrylate, and t-butylhydroquinone. 0.2 parts were mixed and heated and melted at 100 ° C. to obtain a resin varnish 1.

<Example of resin synthesis for examples> Synthesis of resin 2 17.5 parts of gumrosin and 5 parts of maleic anhydride are charged into a stirrer, a reflux condenser with a water separator, and a four-necked flask with a thermometer, and while blowing nitrogen gas. , 180 ° C. for 1 hour.
Then, 41 parts of t-butylbenzoic acid, 16.5 parts of phthalic anhydride, 20 parts of pentaerythritol, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added, and dehydration was performed at 230 ° C. for 14 hours. Condensation was carried out to obtain a resin A2 having a weight average molecular weight (Mw) of 21,000.

<Example of preparing varnish for examples> Preparation of resin varnish 30 parts of resin A2 obtained in a four-necked flask equipped with a stirrer, a reflux cooler, and a thermometer, 69.8 parts of dipentaerythritol tetraacrylate, and t-butylhydroquinone. 0.2 parts were mixed and heated and melted at 100 ° C. to obtain a resin varnish 2.

<Example of Preparation of Resin Varnish for Examples> Preparation of Resin Varnish 3 30 parts of resin A2 obtained in a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 69.8 parts of propylene oxide-modified trimethylol propantriacrylate, t. -0.2 parts of butylhydroquinone was mixed and heated and melted at 100 ° C. to obtain a resin varnish 3.

<Example of varnish preparation for example> Preparation of resin varnish 4 35 parts of diallyl phthalate resin (Osaka Soda Co., Ltd., Daisodap A) in a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, dipentaerythritol tetraacrylate 64 .8 parts and 0.2 parts of t-butylhydroquinone were mixed and heated and melted at 100 ° C. to obtain a resin varnish 4.

<Example of Ink Production for Examples> Production of Example 1 25 parts of the obtained resin varnish 1 and 10 parts of the resin varnish 4 were prepared. I. Pigment Red 57: 1 (red pigment) 16 parts, bisphenol A diacrylate 11 parts, propylene oxide-modified trimethylolpropane triacrylate 14 parts, silica 3 parts, magnesium carbonate 3 parts, talc 3 parts, photoinitiator 11 parts, auxiliary Four parts of the agent were kneaded with a three-roll mill at 40 ° C. and adjusted with propylene oxide-modified trimethylolpropane triacrylate so that the ink tack was 6 to 7, and a flat plate printing ink Example 1 was obtained.
The ink tack was measured with an incometer manufactured by Toyo Seiki Co., Ltd. at a roll temperature of 30 ° C., 400 rpm, and a value after 1 minute.

<Examples of Ink Preparation for Examples> Preparation of Examples 2 to 23 Examples 2 to 24 were obtained with the compounding composition shown in Table 1 by the same operation as in Example 1.

<Example of Ink Production for Comparative Example> Production of Comparative Example 1 17 parts of the obtained resin varnish A1, 18 parts of the resin varnish A4, C.I. I. Pigment Red 57: 1 (red pigment) 16 parts, bisphenol A diacrylate 11 parts, propylene oxide-modified trimethylolpropane triacrylate 14 parts, silica 3 parts, magnesium carbonate 3 parts, talc 3 parts, photoinitiator 11 parts, auxiliary Four parts of the agent were kneaded with a three-roll mill at 40 ° C. and adjusted with propylene oxide-modified trimethylolpropane triacrylate so that the ink tack was 6 to 7, to obtain Comparative Example 1 of flat plate printing ink.

<Example of Ink Preparation for Comparative Example> Preparation of Comparative Examples 2 to 8 Comparative Examples 2 to 8 were obtained with the compounding composition shown in Table 2 by the same operation as in Comparative Example 1.

The following were used as the extender pigment, the photoinitiator, and the auxiliary agent.
Silica: Erosil R972V (manufactured by Aerosil Japan)
Magnesium carbonate: Magnesium carbonate TT (manufactured by Naikai Salt Industries)
Talc: High Filler 5000PJ (manufactured by Matsumura Sangyo Co., Ltd.)
Photoinitiator: SB-PI769 (manufactured by IGM resin B.V) 5 parts, SB-PI718 (manufactured by IGM resin B.V) 6 parts Auxiliary agent: KTL-4N (manufactured by Shamlock Technologies)

The lithographic printing inks obtained in Examples and Comparative Examples were evaluated for emulsified viscoelasticity retention rate, ground stain resistance, and misting suitability by the following methods. The results are shown in Tables 1 and 2.

<Emulsification of emulsified viscoelasticity retention rate>
For each of the flat plate printing inks of Examples 1 to 24 and Comparative Examples 1 to 8, a lithotronic emulsification tester (manufactured by NOVOCONTOR) was used, and the speed was 1 ml / min at a rotation speed of 1200 rpm at 40 ° C. for 25 g of ink. The torque required for stirring when 25% by mass of water was forcibly emulsified with respect to the flat plate printing ink was measured, and the torque maintenance rate before and after emulsification was defined as the emulsified viscoelastic maintenance rate. did.
⊚: Emulsified viscoelasticity retention rate 90% or more 〇: Emulsified viscoelasticity retention rate 85% or more, less than 90% Δ: Emulsified viscoelasticity retention rate 80% or more, less than 85% ×: Emulsified viscoelasticity retention rate less than 80% Usable Levels are ◎, 〇, and △.

<Ground stain resistance>
For each of the lithographic printing inks of Examples 1 to 24 and Comparative Examples 1 to 8, using Lithrone 226 (sheet-fed printing press manufactured by Komori Corporation), the weight of Mitsubishi Tokuryo Art paper was 90 kg / ream (manufactured by Mitsubishi Paper Mills Limited). A printing test of 20,000 sheets of each ink was performed at 10,000 sheets / hour, and the solid texture state and ground stains of the printed matter were visually confirmed. The resistance to background stains was evaluated from the number of sheets of waste paper until the background stains on the printed matter disappeared during printing. The evaluation criteria are shown below.
⊚: Number of waste papers less than 500 〇: Number of waste papers 500 or more and less than 1000 Δ: Number of waste papers 1000 or more and less than 1500 ×: Number of waste papers 1500 or more The usable levels are ◎ and 〇. ..
The dampening water is Astromark 44UV (manufactured by Nikken Kagaku Kenkyusho Co., Ltd.) 1.5% tap water, and the lower limit of the water width is used to compare the printing conditions near the lower limit of the water width. Printing was performed with a water dial value that was 2% higher than the value. The "lower limit of the water width" means the minimum supply amount of dampening water that enables normal printing, and the "water dial" means the above-mentioned dampening water supply amount in order to adjust the supply amount. It means a dial provided in a printing machine.

<Aptitude for misting>
In the above printing test, a blank sheet was attached to the inside of the safety cover of the printing machine at the time of printing, the blank sheet was taken out after 10,000 threads, and the degree of ink scattering was evaluated on a 4-point scale according to the following criteria. Available levels are ◎ and 〇.
⊚: A small amount of ink mist is scattered on a part of the blank paper.
〇: Ink mist is thinly scattered on the entire surface of the blank paper.
Δ: Ink mist is scattered on the entire surface of the blank paper.
X: Ink mist is scattered all over the blank sheet.

From the above, it was found that the active energy ray-curable ink composition of the present invention has a high emulsified viscoelasticity retention rate and ground stain resistance, and is also excellent in misting suitability.

Claims (5)

An active energy ray-curable lithographic printing ink containing a resin, a (meth) acrylate compound, and an extender pigment.
The resin contains a rosin-modified resin (A) and a diallyl phthalate resin.
An active energy ray-curable lithographic printing ink characterized in that the content of the rosin-modified resin (A) is 50 to 80% by mass in the total amount of the resin. The (meth) acrylate compound contains an alkylene oxide-modified (meth) acrylate compound (B) having two or more (meth) acryloyl groups and an octanol / water partition coefficient (LogP) of 2.5 or more. The active energy ray-curable flat plate printing ink according to claim 1, wherein the total amount contains 10% by mass or more. The active energy ray-curable lithographic printing ink according to claim 1 or 2, wherein the extender pigment contains at least two kinds selected from the group consisting of silica, magnesium carbonate, and talc. The rosin-modified resin (A) is a structural unit (a12) derived from a compound obtained by adding α, β-unsaturated carboxylic acid or an acid anhydride thereof (A2) to a conjugated logonic acid (A1), and the conjugated system. It has a structural unit (a3) derived from an organic monobasic acid (A3) excluding a carboxylic acid (A1) and a structural unit (a5) derived from a polyol (A5).
The active energy ray-curable lithographic printing ink according to any one of claims 1 to 3, wherein the weight ratio of the structural unit (a12) to the structural unit (a3) is in the range of 100: 10 to 100: 350. A printed matter having a printed layer formed on a base material using the active energy ray-curable lithographic printing ink according to any one of claims 1 to 4.