JP2020066649A - Rosin-modified resin for active energy ray curable lithographic printing ink and manufacturing method therefor, varnish for active energy ray curable lithographic printing ink, active energy ray curable lithographic printing ink, and printed matter - Google Patents

Abstract

To provide an active energy ray curable lithographic printing ink capable of achieving both of printing coated film suitability such as curing property, glossiness and adhesion property, and printing suitability such as misting resistance, and a printed matter thereof.SOLUTION: There is provided a rosin-modified resin for active energy ray curable lithographic printing ink, which is a reaction product between an addition reaction mixture of rosin acids (A) and α,β-unsaturated carboxylic acid or acid anhydride thereof (B), and polyol (C) containing diol (c) having one cyclohexane ring, containing the rosin acids (A) of 35 to 60 mass% based on total blend amount, and the diol (c) containing the cyclohexane ring of 10 to 45 mass% and having weight average molecular weight of less than 10,000.SELECTED DRAWING: None

Description

  The present invention relates to a rosin-modified resin for an active energy ray-curable lithographic printing ink, a method for producing the same, a varnish for an active energy ray-curable lithographic printing ink, an active energy ray-curable lithographic printing ink, and a printed matter.

  Inks used in lithographic printing usually have a relatively high viscosity of 5 to 100 Pa · s. In the mechanism of a lithographic printing machine, ink is supplied from the ink fountain of the printing machine through multiple rollers to the image area of the printing plate to form a pattern, and the ink on the printing plate is transferred onto a substrate such as paper. Form an image. In planographic printing using dampening water to form the above pattern, dampening water is supplied to the non-printing areas so that the non-printing areas repel ink. On the other hand, in planographic printing that does not use fountain solution, a silicone layer is formed on the non-printing areas so that the non-printing areas repel ink.

  Especially in lithographic printing using a fountain solution, the emulsion and the fountain solution have an important emulsion balance. Therefore, the ink used in the lithographic printing is required to have appropriate emulsification suitability and high-speed printing suitability. If the amount of emulsified ink is too large, the ink is likely to be deposited on the non-image area and stains are likely to occur. On the other hand, when the emulsification amount of the ink is small, the dampening water is easily discharged onto the ink surface when printing with a small pattern. Therefore, the ink transfer property between the rolls and the ink transfer property to the substrate are deteriorated, and stable printing becomes difficult.

  Further, in recent years, demands for labor saving, labor saving, automation, and speeding up at the time of printing have been increasing, and in particular, the printing speed has been increasing more and more. An ink that can stably obtain a high-quality printed matter for a long time without trouble under various printing conditions is desired, and various improvements of the ink have been studied so far.

  On the other hand, the active energy ray-curable lithographic printing ink contains an unsaturated compound, such as an acrylic acid ester compound, which is curable with respect to active energy rays, as a constituent component. Therefore, when the above-mentioned ink is irradiated with active energy rays, it is instantly cured and forms a tough film by three-dimensional crosslinking of the above-mentioned unsaturated compound. In addition, since the above ink cures instantly, post-processing can be performed immediately after printing. From such a viewpoint, the active energy ray-curable ink is preferably used in packaging packaging printing, foam printing in the commercial field, and the like, in which a strong film is required to improve productivity and protect designs.

  Generally, an active energy ray-curable lithographic printing ink is composed of a binder resin, an active energy ray-curable compound such as an acrylic acid ester compound, a pigment, a radical polymerization initiator, and various additives.

  The active energy ray-curable lithographic printing ink (hereinafter, also simply referred to as “ink”) is required to have printability such as emulsification suitability, scumming resistance, and misting resistance. At the same time, the ink is required to have print film characteristics such as curability, adhesion, and gloss.

  Furthermore, in packaging packages in which an active energy ray-curable lithographic printing ink is used, polyethylene and PET are often used from the viewpoints of visibility of contents, designability, and price. However, the surface of these plastics has a strong resilience, and although the printability is imparted by performing corona treatment or primer treatment, the adhesiveness is not sufficient, and the problem of poor adhesion often occurs.

In order to meet the above requirements, unsaturated polyester resins, epoxy acrylate resins, urethane acrylate resins, polyester acrylate resins and the like have been studied as binder resins for active energy ray-curable lithographic printing inks.
For example, Patent Document 1 discloses a polyester resin containing a polyvalent carboxylic acid, which is obtained by an addition reaction of a rosin acid and an α, β-unsaturated carboxylic acid. However, the ink using the disclosed resin tends to have insufficient fluidity and the glossiness of the printed matter tends to be insufficient.
Further, Patent Document 2 discloses a polyester resin containing a polyvalent carboxylic acid and a hydrogenated bisphenol obtained by an addition reaction of a rosin acid and an α, β-unsaturated carboxylic acid. However, since the disclosed resin mainly contains hydrogenated bisphenol A containing two cyclohexane rings as an alcohol component, it tends to be insufficient in compatibility between the adhesion to a plastic substrate and the printability.
As described above, various studies have been conducted on the binder resin for the active energy ray-curable lithographic printing ink, but the printability and printing film characteristics required for the active energy ray-curable lithographic printing ink are sufficiently satisfied. There is nothing that can be done, and further improvement is desired.

JP, 2010-070742, A JP, 2011-225748, A

  In view of the above situation, the present invention is an active energy ray-curable lithographic printing plate that is compatible with print film properties such as curability, glossiness, and adhesion, and emulsification suitability, scumming resistance, and misting resistance. To provide a printing ink and its printed matter.

  As a result of diligent studies, the present inventors have conducted an addition reaction of rosin acids and an α, β-unsaturated carboxylic acid or an acid anhydride thereof, and then reacted a polyol containing a diol containing one cyclohexane ring. By using the rosin-modified resin obtained as described above as a binder resin, it was found that an active energy ray-curable lithographic printing ink capable of achieving both excellent printability and printing film properties can be obtained, and the present invention has been completed.

That is, the present invention provides a polyol (C) containing an addition reaction mixture of a rosin acid (A) and an α, β-unsaturated carboxylic acid or an acid anhydride thereof (B), and a diol (c) containing one cyclohexane ring. ) Is a reaction product of rosin-modified resin for active energy ray-curable lithographic printing ink,
The rosin acid (A) is contained in an amount of 35 to 60% by mass based on the total amount blended,
The diol (c) containing one cyclohexane ring is contained in an amount of 10 to 45% by mass based on the total amount blended,
The present invention relates to an active energy ray-curable rosin-modified resin for lithographic printing inks having a weight average molecular weight of less than 10,000.

  The present invention also relates to the above-mentioned active energy ray-curable rosin-modified resin for lithographic printing inks, which has an acid value of 60 to 130 mgKOH / g.

  The present invention also relates to an active energy ray-curable lithographic printing ink varnish containing the active energy ray-curable lithographic printing ink rosin-modified resin and an active energy ray-curable compound.

  The present invention also relates to an active energy ray-curable lithographic printing ink containing the rosin-modified resin for active energy ray-curable lithographic printing ink and an active energy ray-curable compound.

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

Further, the present invention is a method for producing a rosin-modified resin for an active energy ray-curable lithographic printing ink,
Step 1 of carrying out a reaction of adding an α, β-unsaturated carboxylic acid or its acid anhydride (B) to the rosin acid (A),
Step 2 of carrying out an esterification reaction of the reaction mixture obtained in the above Step 1 and a polyol (C) containing a diol (c) containing one cyclohexane ring,
The rosin acid (A) is contained in an amount of 35 to 60% by mass based on the total amount blended,
The diol (c) containing one cyclohexane ring is contained in an amount of 10 to 45% by mass based on the total amount blended,
The present invention relates to a method for producing an active energy ray-curable rosin-modified resin for lithographic printing inks having a weight average molecular weight of less than 10,000.

  By using the rosin-modified resin disclosed in the present specification as a binder resin, it becomes possible to provide an active energy ray-curable lithographic printing ink that can achieve both printability and print film characteristics. By using the above-mentioned ink, it is possible to efficiently obtain a high-quality printed matter even when printed under the conventional lithographic printing conditions.

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

  The "conjugated double bond" described in the present invention refers to a bond in which a plurality of double bonds are alternately arranged with a single bond interposed therebetween. However, the π-electron conjugated system contained in the aromatic compound is excluded from the conjugated double bond.

  In addition, the “cyclohexane ring” described in the present invention refers to a 6-membered cyclic hydrocarbon having a cyclic structure in which all carbon-carbon bonds are single bonds.

Hereinafter, the monomers constituting each structural unit will be described.
<Rosin acids (A)>
The rosin acid (A) used to obtain the rosin-modified resin of the present invention refers to a monobasic acid having a cyclic diterpene skeleton. Rosin acid, disproportionated rosin acid, hydrogenated rosin acid, or an alkali metal salt of the compound, or the like, specifically, abietic acid having a conjugated double bond, and a conjugated compound thereof, neoabietic acid, Examples thereof include parastolic acid, levopimaric acid, pimaric acid having no conjugated double bond, isopimaric acid, sandaracopimaric acid, and dehydroabietic acid. Examples of natural resins containing these rosin acids (A) include gum rosin, wood rosin, tall oil rosin and the like.

  The amount of the rosin acid (A) used to obtain the rosin-modified resin of the present invention is 35 to 60 mass% based on the total amount of the resin raw material. If the content of the rosin acid (A) is 35% by mass or more, the curability of the active energy ray-curable lithographic printing ink containing the resin will be good, but if the content exceeds 60% by mass, the active energy will increase. It is not preferable because the compatibility with the radiation curable compound tends to deteriorate.

  As the rosin acid (A) in the present invention, the compound having the conjugated double bond is preferably contained in the entire rosin acid (A) in an amount of 40% by mass or more, and more preferably 50% by mass or more. preferable. When the compound having a conjugated double bond in the rosin acid (A) is less than 40% by mass, the amount of the Diels-Alder addition reaction product with the α, β-unsaturated carboxylic acid or its acid anhydride (B) becomes small. As a result, the pigment dispersibility tends to deteriorate, which is not preferable.

<Α, β-Unsaturated carboxylic acid or its acid anhydride (B)>
Examples of the α, β-unsaturated carboxylic acid or its acid anhydride (B) used for obtaining the rosin-modified resin of the present invention include maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid, and the like. The acid anhydride of is exemplified. In view of reactivity with the rosin acids (A), maleic acid or its acid anhydride is preferable.

  In the present invention, the blending amount of the α, β-unsaturated carboxylic acid or its acid anhydride (B) is preferably in the range of 70 to 180 mol% with respect to the rosin acid (A), and 70 to 155. It is more preferably in the range of mol%. When the blending amount of the α, β-unsaturated carboxylic acid or its acid anhydride (B) is adjusted within the above range, it is easy to obtain a rosin-modified resin having excellent curability, adhesiveness, and gloss.

<Carboxylic acid other than (A) and (B) (other organic acids)>
In order to obtain the rosin-modified resin of the present invention, in addition to the rosin acid (A) and the α, β-unsaturated carboxylic acid or its acid anhydride (B), other organic acids are used alone or in combination of two or more. You can also
The amount of the other organic acid compounded is preferably 0 to 30% by mass, and more preferably 0 to 20% by mass, based on the total amount of the resin raw material compounded.

  Specific examples of the other organic acids include, but are not limited to, the following.

(Organic monobasic acid)
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, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecane Saturated fatty acids such as acids, arachidic acid, and behenic acid,
Crotonic acid, linderic acid, tsuzuic acid, myristoleic acid, palmitoleic acid, undecylenic acid, oleic acid, elaidic acid, gadoleic acid, gondolenic acid, cetoleic acid, erucic acid, brassic acid, linoelaidic acid, linolenic acid, and arachidone. Unsaturated fatty acids such as acids,
Aromatic monobasic acids such as benzoic acid, methylbenzoic acid, tert-butylbenzoic acid, naphthoic acid, orthobenzoylbenzoic 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.

(Alicyclic polybasic acid or its acid anhydride)
1,2,3,6-tetrahydrophthalic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid Examples thereof include acids, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and acid anhydrides thereof.

(Other organic polybasic acids or their acid anhydrides)
Oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenylsuccinic acid, alkenylsuccinic acid such as pentadecenylsuccinic acid, o-phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid Examples thereof include acids and their acid anhydrides.

<Polyol (C)>
The polyol (C) is a compound obtained by a Diels-Alder reaction between an organic acid having a conjugated double bond contained in a rosin acid (A) and an α, β-unsaturated carboxylic acid or its acid anhydride (B), rosin. Among the acids (A), an organic acid not having a conjugated double bond, and other organic acids, and an carboxylic acid in each of them react with each other to form an ester bond.
The rosin-modified resin of the present invention contains the diol (c) containing one cyclohexane ring as the polyol (C) in an amount of 10 to 45% by mass based on the total amount of the resin raw materials to be obtained. To which appropriate flexibility is imparted, and it becomes possible to achieve both excellent printability of the ink using the rosin-modified resin and development and improvement of adhesion.

<Diol (c) containing one cyclohexane ring>
Examples of the diol (c) containing one cyclohexane ring used to obtain the rosin-modified resin of the present invention include 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanediol, and 1,3. -Cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned.

<Polyol other than (c)>
In order to obtain the rosin-modified resin of the present invention, a polyol other than the diol (c) containing one cyclohexane ring may be used alone or in combination of two or more.
Specific examples of the polyol other than (c) include the following, but are not limited to these.

(Straight chain alkylene bifunctional polyol)
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-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16 -Hexadecanediol, 1,2-hexadecanediol and the like.

(Branched alkylene bifunctional polyol)
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, dimethyloloctane, 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 bifunctional polyol)
1,2-cycloheptanediol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone and the like.

(Trifunctional or higher functional polyol)
Glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, diglycerin, ditrimethylolpropane, dipentaerythrium Linear, branched, and cyclic polyhydric alcohols such as liter, sorbitol, inositol, and tripentaerythritol.

(Other polyols)
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.

  In the present invention, the amount of the polyol (C) containing the diol (c) containing one cyclohexane ring is preferably 10 to 55% by mass based on the total amount of the resin raw material. When the blending amount of the polyol (C) is within this range, it becomes easy to develop the adhesiveness and improve the print film suitability and print suitability. The content of the polyol (C) is more preferably 20 to 50% by mass, further preferably 25 to 45% by mass.

  The rosin-modified resin of the present invention has a weight average molecular weight of less than 10,000, more preferably 3,000 to 8,000. When the weight average molecular weight is less than 10,000, the misting resistance can be exhibited and improved.

<Method for producing rosin-modified resin>
The rosin-modified resin of the present invention is obtained by (1) a reaction of a rosin acid (A) with an α, β-unsaturated carboxylic acid or its acid anhydride (B), and (2) a reaction of the above (1). It is produced by reacting the above reaction mixture and other organic acids with a polyol (C) containing a diol (c) containing one cyclohexane ring.
The reaction of the above (1) is a Diels of the conjugated double bond (diene) in the rosin acid (A) and the double bond (dienophile) in the α, β-unsaturated carboxylic acid or its acid anhydride (B). It is an alder addition reaction. In addition, the reaction of (2) above is carried out by the reaction mixture obtained in the reaction of (1) and the carboxyl group in the other organic acids and the hydroxyl group in the polyol (C) containing the diol (c) containing one cyclohexane ring. Is an esterification reaction between and.

  The Diels-Alder addition reaction product of the conjugated double bond in the rosin acid (A) and the α, β-unsaturated carboxylic acid or its acid anhydride (B) becomes a polyvalent carboxylic acid compound. Therefore, it becomes possible to polymerize by the esterification reaction with the polyol (C). In addition, the Diels-Alder addition reaction can eliminate the conjugated double bond in the rosin acid (A) and can introduce the polycyclic structure derived from the rosin acid (A) into the rosin-modified resin. Usually, the conjugated double bond in the rosin acid (A) causes curing inhibition upon irradiation with active energy rays for ink curing. However, in the present invention, since the conjugated double bond in the rosin acid (A) is eliminated by the Diels-Alder addition reaction, it becomes easy to improve the curability of the ink.

  As described above, according to the method for producing a rosin-modified resin of the present invention, it is possible to achieve both printability such as emulsification suitability, scumming resistance, and misting resistance, and film strength such as curability, glossiness, and abrasion resistance. Is possible. In addition, as described above, by incorporating a flexible cyclohexane ring into the structure, it is possible to exhibit excellent adhesion in addition to the above-mentioned film characteristics.

  The conditions of the Diels-Alder addition reaction are not particularly limited and can be performed according to a conventional method. The reaction temperature can be determined in consideration of the boiling point of the compound used and the reactivity. 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 usable polymerization inhibitors include hydroquinone, p-methoxyphenol, methylhydroquinone, methoxyhydroquinone, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-hydroxytoluene, and t. -Butylcatechol, 4-methoxy-1-naphthol, phenothiazine and the like.

  The conditions for the esterification reaction are not particularly limited, and the esterification reaction 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. 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, trifluoromethyl sulfuric acid. , Trifluoromethylacetic acid and the like. Further, other examples of usable catalysts include metal complexes such as tetrabutyl zirconate and tetraisobutyl titanate, magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide, zinc acetate. And metal salt catalysts such as These catalysts are usually used in the range of 0.01 to 5% by mass based on the total amount of all the components used in the production of the rosin-modified resin. In order to suppress the coloration of the resin due to the use of the catalyst, hypophosphorous acid, triphenylphosphite, triphenylphosphate, triphenylphosphine and the like can be used together during the production of the resin.

In the production of the rosin-modified resin, the monomers (A) to (C) constituting the resin can be blended at the same time or can be blended stepwise.
For example, a mixture of a rosin acid (A), an α, β-unsaturated carboxylic acid or its acid anhydride (B), another organic acid, and a polyol (C) containing a diol (c) containing one cyclohexane ring. Can be used to carry out the reaction in two stages. In this case, first, the reaction temperature may be adjusted so that the Diels-Alder addition reaction between the rosin acid (A) and the α, β-unsaturated carboxylic acid or its acid anhydride (B) occurs. More specifically, first, the reaction temperature may be controlled to a temperature at which the Diels-Alder addition reaction proceeds, maintained for a certain period of time, and then heated to a temperature at which the esterification reaction proceeds to carry out the reaction.
Alternatively, rosin acid (A), α, β-unsaturated carboxylic acid or acid anhydride thereof (B) are blended, and after Diels-Alder addition reaction, other organic acids and one cyclohexane ring are contained. The esterification reaction may be carried out by blending the polyol (C) containing the diol (c).

In the present invention, the method for producing a rosin-modified resin is
Step 1 of carrying out a reaction of adding an α, β-unsaturated carboxylic acid or its acid anhydride (B) to the rosin acid (A),
Step 2 of performing an esterification reaction with the reaction mixture obtained in the above Step 1, other organic acids, and a polyol (C) containing a diol (c) containing one cyclohexane ring,
The rosin-modified resin has a weight average molecular weight of less than 10,000.

  In the above production method, step 1 is preferably carried out at a reaction temperature in the range of 80 ° C to 200 ° C. In addition, step 2 is preferably carried out at a reaction temperature in the range of 200 ° C to 300 ° C.

  The acid value of the rosin-modified resin of the present invention is preferably in the range of 60 to 130 mgKOH / g, more preferably in the range of 65 to 130 mgKOH / g, and even more preferably in the range of 65 to 125 mgKOH / g. When the acid value is 60 mgKOH / g or more, it is possible to obtain an ink exhibiting excellent adhesion, particularly to a plastic film substrate. Further, when the acid value is 130 mgKOH / g or less, a suitable ink suitable for emulsification can be obtained.

  In the rosin-modified resin of the present invention, the ratio of hydroxyl group / carboxyl group is preferably 0.75 to 1.40, more preferably 0.85 to 1.35.

  In the rosin-modified resin of the present invention, if the hydroxyl group / carboxyl group ratio is less than 0.75, the weight average molecular weight (Mw) tends to increase.

  In the rosin-modified resin of the present invention, when the ratio of hydroxyl group / carboxyl group exceeds 1.40, the melting point of the resin tends to be low and the film strength becomes weak.

  The melting point of the rosin-modified resin of the present invention is preferably 50 ° C or higher, more preferably in the range of 60 to 100 ° C, and even more preferably in the range of 60 to 80 ° C. The melting point can be measured using MeltingPoint M-565 manufactured by BUCHI under the conditions of a temperature rising rate of 0.5 ° C / min.

<Varnish for active energy ray curable lithographic printing ink>
The rosin-modified resin of the present invention can be used to form an active energy ray-curable lithographic printing ink varnish.

  The active energy ray-curable lithographic printing ink varnish of the present invention contains at least the rosin-modified resin of the present invention and an active energy ray-curable compound, and contains 30 parts of the rosin-modified resin of the present invention based on the total mass of the varnish. -80 mass% and an active energy ray-curable compound are preferably 20-70 mass%.

  In the varnish for active energy ray-curable lithographic printing ink of the present invention, the compounding ratio of the rosin-modified resin of the present invention to the active energy ray-curable compound is preferably 30:70 to 75:25 by mass, and 35 The range of: 65 to 70:30 is more preferable.

In the present specification, the active energy ray-curable compound means a compound having a (meth) acryloyl group in the molecule.
As specific examples of the active energy ray-curable compound that can be used to form the varnish for the active energy ray-curable lithographic printing ink of the present invention,
Monofunctional active energy ray curable compounds such as 2-ethylhexyl acrylate, methoxydiethylene glycol acrylate, acryloylmorpholine,
Ethylene glycol diacrylate, polyethylene glycol diacrylate (n = 2 to 20), propylene glycol diacrylate, polypropylene glycol diacrylate (n = 2 to 20), alkane (carbon number 4 to 12) glycol diacrylate, alkane (carbon number) 4-12) Glycol ethylene oxide adduct (2 to 20 mol) diacrylate, alkane (C 4 to 12) glycol propylene oxide adduct (2 to 20 mol) diacrylate, hydroxypivalyl hydroxypivalate diacrylate, tri Cyclodecane dimethylol diacrylate, hydrogenated bisphenol A diacrylate, bisphenol A ethylene oxide adduct (2 to 20 mol) diacrylate, hydrogenated bisphenol A propylene oxide Objects (2-20 mol) bifunctional active energy ray-curable compound such as diacrylate,
Glycerin triacrylate, glycerin ethylene oxide adduct (3 to 30 mol) triacrylate, glycerin propylene oxide adduct (3 to 30 mol) triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide adduct (3 to 30 mol) ) Triacrylate, trimethylolpropane propylene oxide adduct (3 to 30 moles) triacrylate and other trifunctional active energy ray-curable compounds,
Pentaerythritol tetraacrylate, pentaerythritol ethylene oxide adduct (4 to 40 mol) tetraacrylate, pentaerythritol propylene oxide adduct (4 to 40 mol) tetraacrylate, diglycerin tetraacrylate, diglycerin ethylene oxide adduct (4 to 40 mol) Mol) tetraacrylate, diglycerin propylene oxide adduct (4 to 40 mol) tetraacrylate, ditrimethylol propane tetraacrylate, ditrimethylol propane ethylene oxide adduct (4 to 40 mol) tetraacrylate, ditrimethylol propane propylene oxide adduct ( 4 to 40 mol) tetrafunctional active energy ray-curable compound such as tetraacrylate, and dipentaerythritol hexaa Examples thereof include polyfunctional active energy ray-curable compounds such as acrylate, dipentaerythritol ethylene oxide adduct (6 to 60 mol) hexaacrylate, and dipentaerythritol propylene oxide adduct (6 to 60 mol) hexaacrylate. As the active energy ray-curable compound, the exemplified compounds may be used alone or in combination of two or more kinds.

  The active energy ray-curable compound can be appropriately selected according to the required cured film characteristics. In addition to the above compounds, oligomers such as polyester acrylate, polyurethane acrylate, and epoxy acrylate can be used together, if necessary.

  The active energy ray-curable lithographic printing ink varnish of the present invention may further contain a photopolymerization inhibitor in addition to the above components. In such an embodiment, a photopolymerization inhibitor can be added and used by a conventional method. When a photopolymerization inhibitor is added to the above-mentioned varnish, the content thereof should be 3% by mass or less based on the total quality of the active energy ray-curable lithographic printing ink varnish from the viewpoint of not impairing the curability. Preferably, it is more preferably used in the range of 0.01 to 1% by mass.

  Specific examples of usable photopolymerization inhibitors include (alkyl) phenol, hydroquinone, catechol, resorcin, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine. , P-benzoquinone, nitrosobenzene, 2,5-di-tert-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N- ( 3-oxyanilino-1,3-dimethylbutylidene) aniline oxide, dibutylcresol, cyclohexanone oxime cresol, guaiacol, o-isopropylphenol, butyraldoxime, methylethylketoxime, and 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 used. Preference is given to using.

The active energy ray-curable lithographic printing ink varnish of the present invention can be produced, for example, by mixing the above components under a temperature condition between room temperature and 160 ° C.
For example, a varnish obtained by heating and melting a rosin-modified resin, trimethylolpropane triacrylate, and hydroquinone under a temperature condition of 100 ° C. can be preferably used.

<Active energy ray-curable lithographic printing ink>
The rosin-modified resin of the present invention can be used to form an active energy ray-curable lithographic printing ink.

  The active energy ray-curable lithographic printing ink of the present invention contains at least the rosin-modified resin of the present invention and an active energy ray-curable compound.

  Further, the active energy ray-curable lithographic printing ink of the present invention contains a pigment when used as a colored ink, but becomes an overcoat varnish or a clear ink when a pigment is not used. Therefore, the use of the pigment is not limited.

  Examples of the active energy ray-curable compound include the compounds exemplified above as the constituent components of the varnish.

  The active energy ray-curable lithographic printing ink of the present invention contains the rosin-modified resin of the present invention in an amount of 5 to 40% by mass, the active energy ray-curable compound in an amount of 20 to 70% by mass, and a pigment in an amount of 0 to 50% by mass. It is preferable that the total content of each component is 100% by mass. Here, the rosin-modified resin of the present invention and the above active energy ray-curable compound may be prepared in advance in the form of varnish and used.

Pigments that can be used may be various publicly known pigments, and inorganic pigments and organic pigments can be used.
Specific examples of inorganic pigments include yellow lead, zinc yellow, navy blue, barium sulfate, cadmium red, titanium oxide, zinc white, rouge, alumina white, calcium carbonate, magnesium carbonate, aluminum silicate, silicon dioxide, ultramarine blue, carbon black, Examples include graphite and aluminum powder.
Specific examples of organic pigments include β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid-based arylide-based, acetoacetic acid arylide-based, and pyrazolone-based soluble azo pigments,
β-naphthol-based, β-oxynaphthoic acid-based allylide-based, acetoacetic acid allylide-based monoazo, acetoacetic acid allylide-based disazo, and pyrazolone-based insoluble azo pigments,
Phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorine or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine,
Quinacridone type, dioxazine type, slene type (pyrantron, antoanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo type, anthraquinone type, perinone type, perylene type), isoindolinone type, metal complex type, quinophthalone type, etc. Examples thereof include polycyclic pigments and heterocyclic pigments.

  The active energy ray-curable lithographic printing ink of the present invention is cured by irradiation with active energy rays. When the ink is cured with ultraviolet rays, it is preferable to add a photopolymerization initiator to the ink. Generally, photopolymerization initiators can be roughly classified into two types: a type in which a bond is cleaved in a molecule by light to generate an active species, and a type in which a hydrogen abstraction reaction occurs between molecules to generate an active species.

  As the former, for example, 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) propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenylketone, [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzyldimethylketal, oligo {2-hydroxy-2-methyl-1- [4- (1 -Methylvinyl) phenyl] propane}, 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy Acetophenone series such as 2-propylketone, benzoin series such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, mixture of 1-hydroxycyclohexyl-phenyl ketone and benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( Acylphosphine oxides such as 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzyl, methylphenylglyoxyester, and 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone Is mentioned.

Examples of the latter include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ′. , 4,4'-Tetra (t-butylperoxycarbonyl) benzophenone, benzophenone series such as 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthones, thioxanthones such as 2,4-dichlorothioxanthone, Michler's ketone, aminobenzophenones such as 4,4′-bisdiethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, , 10-phenanthrenequinone, and a camphor quinone and the like.
The photopolymerization initiators may be used alone or in combination of two or more if necessary.

When the active energy ray-curable lithographic printing ink of the present invention is irradiated with ultraviolet rays to cure the ink, it is sufficient to add a photopolymerization initiator to the ink, but in order to further improve the curability, photosensitization is performed. Agents can also be used in combination.
Examples of the photosensitizer include triethanolamine, methyldiethanolamine, dimethylethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. Examples include amines such as (2-dimethylamino) ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate.

  When ultraviolet rays are used as the active energy rays, the content of the photopolymerization initiator is preferably 0.01 to 15% by mass, based on the total mass of the active energy ray-curable lithographic printing ink, and 0.05. It is more preferably from 10 to 10% by mass. When the blending amount is 0.01% by mass or more, the curing reaction proceeds sufficiently. Further, when the content is 15% by mass or less, it is easy to suppress the occurrence of thermal polymerization reaction and bring the stability of the active energy ray-curable lithographic printing ink into a suitable state. When ionizing radiation other than ultraviolet rays is used as the active energy ray, a photopolymerization initiator may not be added.

  The active energy ray-curable lithographic printing ink may further contain various additives such as a photopolymerization inhibitor, an antifriction agent, an antiblocking agent, and a slip agent, depending on the purpose. Various additives can be added to the ink by a conventional method. When adding various additives to the ink, it is preferable to adjust the blending amount within a range that does not impair the effects of other ink materials. The content of each additive is preferably 15% by mass or less based on the total mass of the active energy ray-curable lithographic printing ink. When the photopolymerization inhibitor is used, for example, the compounds exemplified as the photopolymerization inhibitor usable in the varnish for active energy ray-curable lithographic printing ink can be used.

  Irradiation with active energy rays is preferably carried out in an atmosphere substituted with an inert gas such as nitrogen gas, but irradiation in air may also be performed. Before irradiating with active energy rays, the coating layer of active energy ray-curable lithographic printing ink is heated with an infrared heater or the like, or after irradiation with active energy rays, cured layer of active energy ray-curable lithographic printing ink It is effective to heat the resin with an infrared heater or the like in order to finish the curing quickly.

In the present specification, the active energy rays typically mean ionizing radiation such as ultraviolet rays, electron rays, X-rays, α rays, β rays and γ rays, microwaves, high frequencies and the like. However, the active energy ray is not limited to the above, and may be any energy species as long as it can generate a radical active species, and may be visible light, infrared light, and laser light.
Examples of the UV generators include LEDs, ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, helium / cadmium lasers, YAG lasers, excimer lasers. , And an argon laser.

  The active energy ray-curable lithographic printing ink can be produced by kneading and mixing the above components under a temperature condition of room temperature to 100 ° C. In order to produce the ink, it is preferable to use various equipment such as a kneader, a triple roll, an attritor, a sand mill and a gate mixer. When a rosin-modified resin is added to produce an ink, it may be added in the form of the rosin-modified resin itself, or in the form of an active energy ray-curable lithographic printing ink varnish containing the rosin-modified resin. May be.

  The active energy ray-curable lithographic printing ink of the present invention can usually be suitably used for lithographic offset printing using a fountain solution. However, the ink is not limited to such an embodiment, and can be preferably used in waterless lithographic printing that does not use dampening water.

  The active energy ray-curable lithographic printing ink of the present invention is a printed matter for forms, printed matter for various books, printed matter for various packaging such as carton paper, various plastic printed matter, printed matter for stickers / labels, art printed matter, metal printed matter (art printed matter, It is applied to printed matter such as beverage can printed matter and food printed matter such as canned food. Further, as another embodiment, it may be used as an overcoat varnish for the printed matter.

  The base material to which the ink is applied is not particularly limited. Specific examples of usable substrates include uncoated paper such as high-quality paper, lightly coated paper, art paper, coated paper, lightweight coated paper, coated paper such as cast coated paper, white paperboard, and ball coated paper. Examples include paperboard, synthetic paper, aluminum vapor-deposited paper, and plastic sheets such as polypropylene, polyethylene, polyethylene terephthalate, and polyvinyl chloride.

  Hereinafter, 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" described in this specification represents a mass part, and "%" shows the mass%.

Details of various measurements performed in the following examples are as follows.
(Weight average molecular weight)
The weight average molecular weight was measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. The calibration curve was prepared using a standard polystyrene sample. Tetrahydrofuran was used as an eluent, and three TSKgel Super HM-M (manufactured by Tosoh Corporation) were used as columns. The measurement was performed under the conditions of a flow rate of 0.6 mL / min, an injection amount of 10 μL, and a column temperature of 40 ° C.

(Acid value)
The acid value was measured by the neutralization titration method. Specifically, first, 1 g of rosin-modified resin was dissolved in 20 mL of a solvent mixed with a mass ratio of xylene: ethanol = 2: 1. Next, 3 mL of a 3% by mass phenolphthalein solution as an indicator was added to the previously prepared solution of the rosin-modified resin, followed by neutralization titration with a 0.1 mol / L ethanolic potassium hydroxide solution. The unit of the acid value is mgKOH / g.

(Component analysis of rosin acids)
The rosin acid used as a raw material was analyzed by a gas chromatography mass spectrometer, and each peak area ratio (%) was calculated with respect to the total rosin acid peak area of 100%. More specifically, the rosin acids include a conjugated rosin acid that causes a Diels-Alder addition reaction with an α, β-unsaturated carboxylic acid or an acid anhydride thereof (B), and a rosin acid other than the conjugated rosin acid. The content ratio was calculated from the ratio of the corresponding peak areas.

(Confirmation of progress of Diels-Alder addition reaction and quantification of the above-mentioned addition reaction product)
The reaction liquid of the Diels-Alder addition reaction was analyzed by a gas chromatography mass spectrometer, and the detection peaks of the rosin acid (A) and the α, β-unsaturated carboxylic acid or its acid anhydride (B) used as raw materials were analyzed. The decrease confirmed the progress of the reaction. The reaction was terminated when there was no change in the decrease in the number of detection peaks.

1. Preparation of rosin-modified resin, varnish, and active energy ray-curable lithographic printing ink composition According to the formulations of Examples and Comparative Examples shown below, a rosin-modified resin, a varnish, and an active energy ray-curable lithographic printing ink composition, respectively. Prepared. The gum rosin used in the following formulation has a content of a conjugated rosin acid that causes a Diels-Alder addition reaction with an α, β-unsaturated carboxylic acid or its acid anhydride (B) is 80% by mass, and The content other than the conjugated rosin acid was 20% by mass.

(Example 1)
To a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 36 parts of gum rosin and 13 parts of maleic anhydride were charged, and heated at 180 ° C. for 1 hour while blowing nitrogen gas. Gave a reaction mixture. Gas chromatographic mass spectrometry of the reaction mixture then confirmed that the Diels-Alder addition reaction was complete, as previously described.
Next, 12 parts of tetrahydrophthalic anhydride, 39 parts of 1,4-cyclohexanedimethanol, and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the above reaction mixture, and the mixture was heated to 210 ° C. Was dehydrated and condensed for 5 hours to obtain Resin 1 (R1). The acid value of Resin 1 (R1) was 96, and the weight average molecular weight (Mw) in terms of polystyrene by GPC measurement was 4,000.
Next, 61 parts of the above resin 1 (R1), 38.9 parts of trimethylolpropane triacrylate, and 0.1 part of hydroquinone were put into a flask similar to the above and mixed, and these were heated and melted at 100 ° C. Thus, Varnish 1 (V1) was obtained.
Furthermore, 41 parts of varnish 1 (V1), 20 parts of lionol blue FG7330 (indigo pigment manufactured by Toyo Color Co., Ltd.), 22 parts of trimethylolpropane ethylene oxide adduct (3 to 30 mol) triacrylate, 11 parts of ditrimethylolpropane tetraacrylate. 9 parts, 4,4'-bis (diethylamino) benzophenone 2.5 parts, 2-methyl-2-monofolino (4-thiomethylphenyl) propan-1-one 2.5 parts, and hydroquinone 0.1 part. The mixture was kneaded with a three-roll mill at 40 ° C. to obtain a mixture. Then, trimethylolpropane ethylene oxide adduct (3 to 30 mol) triacrylate was added to the above mixture so as to adjust the tack of the ink to 9 to 10, and the mixture was adjusted, and the active energy ray-curable lithographic printing ink 1 (C1) was used. Got The tack of the ink was measured by a Toyo Seiki Co. incometer at a roll temperature of 30 ° C. and 400 rpm for 1 minute.

(Example 2)
By the same operation as in Example 1, a resin 2 (R2) having an acid value of 89 and an Mw of 5,200 was obtained with the composition shown in Table 1. Then, a varnish 2 (V2) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 2 (C2) having the composition shown in Table 3 were obtained.

(Example 3)
By the same operation as in Example 1, Resin 3 (R3) having an acid value of 126 and an Mw of 3,400 was obtained with the composition shown in Table 1. Then, a varnish 3 (V3) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 3 (C3) having the composition shown in Table 3 were obtained.

(Example 4)
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 49 parts of gum rosin, 18 parts of maleic anhydride, 33 parts of 1,4-cyclohexanedimethanol, and p-toluenesulfonic acid monohydrate. 0.1 part of the product was charged and heated at 180 ° C. for 1 hour while blowing nitrogen gas. Then, the obtained reaction mixture was subjected to dehydration condensation reaction at 230 ° C. for 6 hours to obtain a resin 4 (R4). The acid value of Resin 4 (R4) was 92, and the weight average molecular weight (Mw) in terms of polystyrene by GPC measurement was 5,000.
Then, varnish 4 (V4) having the composition shown in Table 2 and active energy ray-curable lithographic printing ink 4 (C4) having the composition shown in Table 3 were obtained in the same manner as in Example 1.

(Example 5)
By the same operation as in Example 1, a resin 5 (R5) having an acid value of 85 and an Mw of 3,000 was obtained with the composition shown in Table 1. Then, a varnish 5 (V5) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 5 (C5) having the composition shown in Table 3 were obtained.

(Example 6)
By the same operation as in Example 1, a resin 6 (R6) having an acid value of 64 and an Mw of 9,700 was obtained with the composition shown in Table 1. Then, a varnish 6 (V6) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 6 (C6) having the composition shown in Table 3 were obtained.

(Example 7)
By the same operation as in Example 1, a resin 7 (R7) having an acid value of 86 and an Mw of 4,900 was obtained with the composition shown in Table 1. Then, a varnish 6 (V7) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 6 (C7) having the composition shown in Table 3 were obtained.

(Example 8)
By the same operation as in Example 1, a resin 8 (R8) having an acid value of 102 and an Mw of 4,200 was obtained with the composition shown in Table 1. Then, a varnish 8 (V8) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 8 (C8) having the composition shown in Table 3 were obtained.

(Example 9)
By the same operation as in Example 1, a resin 9 (R9) having an acid value of 121 and an Mw of 4,100 was obtained with the composition shown in Table 1. Then, Varnish 9 (V9) having the composition shown in Table 2 and Active Energy Ray-curable lithographic printing ink 9 (C9) having the composition shown in Table 3 were obtained.

(Example 10)
By the same operation as in Example 1, Resin 10 (R10) having an acid value of 132 and an Mw of 7,200 was obtained with the composition shown in Table 1. Then, a varnish 10 (V10) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 10 (C10) having the composition shown in Table 3 were obtained.

(Example 11)
By the same operation as in Example 1, Resin 11 (R11) having an acid value of 57 and Mw of 4,000 was obtained with the composition shown in Table 1. Then, a varnish 11 (V11) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink 11 (C11) having the composition shown in Table 3 were obtained.

(Comparative Example A)
In a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 49 parts of gum rosin, 19 parts of tetrahydrophthalic anhydride, 32 parts of 1,4-cyclohexanedimethanol, and p-toluenesulfonic acid monohydrate were added. 0.1 part of a Japanese product was charged and a dehydration condensation reaction was carried out at 230 ° C. for 6 hours while blowing nitrogen gas to obtain a resin (RA). The acid value of Resin A (RA) was 128, and the weight average molecular weight (Mw) in terms of polystyrene by GPC measurement was 4,000.
Next, varnish A (VA) having the composition shown in Table 2 and active energy ray-curable lithographic printing ink A (CA) having the composition shown in Table 3 were obtained by the same operation as in Example 1.

(Comparative Example B)
A 4-neck flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 54 parts of gum rosin and 18 parts of maleic anhydride, and heated at 180 ° C. for 1 hour while blowing nitrogen gas. Gave a reaction mixture. Gas chromatographic mass spectrometry of the reaction mixture then confirmed that the Diels-Alder addition reaction was complete, as previously described.
Next, 28 parts of 1,4-cyclohexanedimethanol and 0.1 part of p-toluenesulfonic acid monohydrate as a catalyst were added to the above reaction mixture, and dehydration condensation reaction was carried out at 230 ° C. for 8 hours. Then, a resin B (RB) was obtained. The acid value of Resin B (RB) was 67, and the weight average molecular weight (Mw) in terms of polystyrene by GPC measurement was 12,000.
Then, varnish B (VB) having the composition shown in Table 2 and active energy ray-curable lithographic printing ink B (CB) having the composition shown in Table 3 were obtained in the same manner as in Example 1.

(Comparative Example C)
By the same operation as in Example 1, a resin C (RC) having an acid value of 39 and Mw of 6,000 was obtained with the composition shown in Table 1. Next, a varnish C (VC) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink C (CC) having the composition shown in Table 3 were obtained.

(Comparative Example D)
By the same operation as in Example 1, a resin D (RD) having an acid value of 135 and an Mw of 8,100 was obtained with the composition shown in Table 1. Next, a varnish D (VD) was obtained with the composition shown in Table 2 and an active energy ray-curable lithographic printing ink D (CD) was obtained with the composition shown in Table 3.

(Comparative Example E)
By the same operation as in Example 1, a resin E (RE) having an acid value of 62 and Mw of 2,500 was obtained with the composition shown in Table 1. Next, a varnish E (VE) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink E (CE) having the composition shown in Table 3 were obtained.

(Comparative Example F)
By the same operation as in Example 1, a resin F (RF) having an acid value of 94 and an Mw of 5,500 was obtained with the composition shown in Table 1. Next, a varnish F (VF) having the composition shown in Table 2 and an active energy ray-curable lithographic printing ink F (CF) having the composition shown in Table 3 were obtained.

(Comparative Example G)
By the same operation as in Example 1, a resin G (RG) having an acid value of 63 and an Mw of 7,700 was obtained with the composition shown in Table 1. Next, varnish G (VG) was obtained with the composition shown in Table 2 and active energy ray-curable lithographic printing ink G (CG) was obtained with the composition shown in Table 3.

(Comparative Example H)
By the same operation as in Example 1, a resin H (RH) having an acid value of 75 and an Mw of 2,200 was obtained with the composition shown in Table 1. Then, varnish H (VH) was obtained with the composition shown in Table 2 and active energy ray-curable lithographic printing ink H (CH) was obtained with the composition shown in Table 3.

なお、トリメチロールプロパンエチレンオキサイド付加物トリアクリレートとしては、東亞合成社製アロニックスＭ−３５０を用いた。

As the trimethylol propane ethylene oxide adduct triacrylate, Aronix M-350 manufactured by Toagosei Co., Ltd. was used.

2. Evaluation of active energy ray-curable lithographic printing ink With respect to the active energy ray-curable lithographic printing inks prepared in Examples and Comparative Examples, the print film suitability and print suitability were evaluated according to the following methods.

<Evaluation of print film suitability>

Inks 1 to 11 of Examples and Inks A to H of Comparative Examples were applied to a Maricoat paper (coated cardboard manufactured by Hokuetsu Paper Mills Co., Ltd.) at a rate of 1 g / m ² by using an RI tester (simple color development device manufactured by Akira Seisakusho). And printed with an air-cooled metal halide lamp (manufactured by Toshiba Corp.) of 120 W / cm at 60 m / min.

  The curability and glossiness of the printed matter after ultraviolet irradiation was evaluated according to the following. The results of each evaluation are shown in Table 4.

(Curable)
The curability was visually evaluated by visually observing the state when the printed surface of the printed matter was rubbed with a cotton cloth, and evaluated in four levels according to the following criteria. The usable level is "3" or higher.
4: No change on print surface.
3: Some scratches were found on the printed surface, but no peeling was observed.
2: Peeling is observed on a part (less than 50%) of the printed surface.
1: Peeling is seen on a part (50% or more) or all of the printed surface.

(Solvent resistance)
The solvent resistance was evaluated by scoring the printed surface 30 times with a cotton swab soaked with MEK (methyl ethyl ketone), visually observing the state of the printed surface, and rating it in four levels according to the following criteria. Available levels are "3" and above.
4: No change on print surface.
3: Dissolution was observed on a part of the printed surface, but no peeling was observed.
2: Peeling is observed on a part (less than 50%) of the printed surface.
1: Peeling is seen on a part (50% or more) or all of the printed surface.

(Abrasion resistance)
The abrasion resistance was evaluated by performing a test on the printed surface (coating film) of the printed matter in accordance with JIS-K5701-1. Specifically, Gakushin type friction fastness tester (manufactured by Tester Sangyo Co., Ltd.) As a rubbing paper, a high-quality paper was applied 500 g and the coating film surface was reciprocated 500 times. Then, the change of the friction surface (coating surface) was visually observed, and evaluated in four stages according to the following criteria. Available levels are "3" and above.
4: No change in friction surface.
3: Some scratches were found on the friction surface, but no peeling was observed.
2: Peeling is seen on a part (less than 50%) of the friction surface.
1: Peeling is seen on a part (50% or more) or all of the friction surface.

(Glossiness)
Using a Proof Bow color developing machine, the ink was color-developed on a pearl coat manufactured by Mitsubishi Paper Mills Co., Ltd. to the same concentration to prepare a test sample. Next, a 60 ° gloss value of the test sample was measured using a gloss meter gloss meter model GM-26 (manufactured by Murakami Color Research Laboratory Co., Ltd.). From the obtained gloss value, the glossiness was evaluated according to the following criteria in four levels. The higher the gloss value, the better the gloss. The usable level is "2" or higher, but "3" or higher is more preferable.
4: Gloss value is 60 or more.
3: The gloss value is 50 or more and less than 60.
2: The gloss value is 40 or more and less than 50.
1: The gloss value is less than 40.

Further, the inks 1 to 11 of the examples and the inks A to H of the comparative examples were printed on the PET film at a coating amount of 1 g / m ² by using an RI tester (simple color development device manufactured by Akira Seisakusho). A 120 W / cm air-cooled metal halide lamp (manufactured by Toshiba Corporation) was used to irradiate ultraviolet rays at 60 m / min to obtain a printed matter. A PE film was used instead of the PET film, and a printed matter was obtained in the same manner as the above method.

  The adhesion of each printed matter after ultraviolet irradiation was evaluated according to the following. The evaluation results are shown in Table 4.

(Adhesion)
The PET film and each printed matter on the PE film obtained as described above were subjected to a cellophane tape peeling test to evaluate the adhesion. The surface of the printed matter after the test was visually observed, and the adhesiveness was evaluated in four levels according to the following criteria. Available levels are "3" and above.
4: No change on print surface.
3: Peeling is seen on a part (less than 25%) of the printed surface.
2: Peeling is seen on a part (25% or more and less than 50%) of the printed surface.
1: Peeling is seen on a part (50% or more) or all of the printed surface.

<Evaluation of printability>

Using the inks 1 to 11 of the examples and the inks A to H of the comparative examples, a printing test was performed on 20,000 sheets for each ink. The printing test was carried out using Lithrone 226 (sheet-fed printing press manufactured by Komori Corporation) at a speed of 10,000 sheets / hour for a Mitsubishi Tokubishi art paper weight of 90 kg / ream (manufactured by Mitsubishi Paper Mills). Was carried out under the following conditions.
In the printing test, tap water containing 1.5% Astromark III clear (manufactured by Toyo Ink Co., Ltd.) and 3% isopropyl alcohol was used as dampening water. In order to compare the print states near the boundary of the condition range in which normal printing is possible, printing was performed with a water dial value that was 2% higher than the lower limit of the water width. 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 in order to adjust the supply amount of the dampening water. It means a dial equipped on a printing machine.
For each printed matter obtained in the printing test, the solid inking state and the background stain were compared, and a remarkable difference was found between each printed matter using Inks 1 to 11 of Examples and Inks A to H of Comparative Examples. Was not seen.

(Misting resistance)
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 passes, and the degree of ink scattering was evaluated in four levels according to the following criteria. Available levels are "3" and above.
4: A small amount of ink mist is scattered on a part of the blank paper.
3: Thin ink mist is scattered all over the blank paper.
2: The ink mist is scattered thickly on the entire white paper.
1: Bettari and ink mist are scattered all over the blank paper.

(Evaluation of initial concentration stability)
In addition, in the printing test, the initial density stability was evaluated on a four-point scale according to the following criteria, based on the number of damaged sheets generated before the density fluctuation became stable during printing. The usable level is "2" or higher, but "3" or higher is more preferable. The evaluation results are shown in Table 4.
4: The number of damaged sheets is 200 or less.
3: The number of damaged sheets is 201 or more and 500 or less.
2: The number of damaged sheets is 501 or more and 800 or less.
1: The number of damaged sheets is 801 or more.

As shown in Table 4, the inks 1 to 11 of the examples are usable levels in all evaluations of curability, glossiness, adhesion, and initial density stability, and have excellent print film suitability and printing. It can be seen that both aptitude and suitability can be achieved. On the other hand, with the inks A to H of the comparative example, it was difficult to achieve both print film suitability and print suitability.
More specifically, as seen in Inks 1 to 11 of Examples and Inks B and F to H of Comparative Examples, the rosin-modified resin used as the binder resin contains rosin acids (A) in a preferable amount, In addition, when the product obtained by the Diels-Alder addition reaction with the α, β-unsaturated carboxylic acid anhydride (B) was contained, good results were obtained in the properties of the printed film such as curability.
On the other hand, the inks A, C, and E of the comparative examples resulted in a marked decrease in curability. This is because in the ink A of the comparative example, the rosin-modified resin used as the binder resin did not contain the α, β-unsaturated carboxylic acid anhydride (B), and the rosin-modified resin was added to the compound in the rosin acid (A). It is considered that curing inhibition occurred due to the remaining conjugated double bond contained therein. In the inks C and E of the comparative examples, the α, β-unsaturated carboxylic acid anhydride (B) was blended, but the amount of the rosin acid (A) was low, so the strength of the cured film was insufficient. It is thought to be because.
Further, in the inks A to D of the comparative example, the result was that the misting resistance was lowered. This is because in the ink A of the comparative example, the rosin-modified resin used as the binder resin does not contain the α, β-unsaturated carboxylic acid anhydride (B), and in the ink C of the comparative example, the rosin acids ( Since the amount of A) is small, it is considered that mist is likely to occur due to insufficient cohesive force of the ink. In the ink B of the comparative example, it is considered that the weight average molecular weight (Mw) of the rosin-modified resin used was large, and the filaments generated between the ink rolls of the printing machine were likely to be stretched and easily formed into a mist. In the ink D of Comparative Example, since the amount of the rosin acid (A) was too large, it is considered that the compatibility between the rosin-modified resin and the active energy ray-curable compound was lowered.
Further, the inks B to G of the comparative examples resulted in a decrease in adhesion to PET and / or PE film. In Comparative Example B, the rosin-modified resin has a large weight average molecular weight (Mw) and is excellent in curability, but it is considered that the balance with the adhesiveness is poor. The inks C, F, and G of the comparative examples did not use the diol (c) containing one cyclohexane ring, or lacked in the blending amount, and used neopentyl glycol or hydrogen used as the polyol (C). With bisphenol A modified, it is considered that the resulting rosin-modified resin is not sufficiently flexible. In the ink D of the comparative example, it is considered that the adhesion was lowered due to the reduced compatibility of the rosin-modified resin and the active energy ray-curable compound as described above. In the ink E of the comparative example, since the amount of the rosin acid (A) is low, it is considered that the strength of the cured film was not sufficient as described above, and the effect of this was that the adhesion to the substrate was lowered.
On the other hand, the ink H of the comparative example, in which the amount of the diol (c) containing one cyclohexane ring was too large, had insufficient MEK resistance and abrasion resistance. It is considered that this is because the strength of the printed film was lowered due to the excessive amount of the component (c).
Further, when the rosin-modified resin of 60 to 130 mgKOH / g is used like the inks of Examples 1 to 9, the compatibility of the printing film and the printability is compatible with the inks of Examples 10 and 11. Better results.

Claims (6)

A reaction product of an addition reaction mixture of a rosin acid (A) and an α, β-unsaturated carboxylic acid or its acid anhydride (B) with a polyol (C) containing a diol (c) containing one cyclohexane ring. A rosin-modified resin for active energy ray-curable lithographic printing ink,
The rosin acid (A) is contained in an amount of 35 to 60% by mass based on the total amount blended,
The diol (c) containing one cyclohexane ring is contained in an amount of 10 to 45% by mass based on the total amount blended,
A rosin-modified resin for an active energy ray-curable lithographic printing ink having a weight average molecular weight of less than 10,000.   The rosin-modified resin for active energy ray-curable lithographic printing ink according to claim 1, which has an acid value of 60 to 130 mgKOH / g.   A varnish for active energy ray-curable lithographic printing ink, comprising the rosin-modified resin for active energy ray-curable lithographic printing ink according to claim 1 or 2, and an active energy ray-curable compound.   An active energy ray-curable lithographic printing ink comprising the rosin-modified resin for active energy ray-curable lithographic printing ink according to claim 1 or 2, and an active energy ray-curable compound.   A printed matter obtained by printing the active energy ray-curable lithographic printing ink according to claim 4 on a substrate. A method for producing a rosin-modified resin for an active energy ray-curable lithographic printing ink,
Step 1 of carrying out a reaction of adding an α, β-unsaturated carboxylic acid or its acid anhydride (B) to the rosin acid (A),
Step 2 of performing an esterification reaction containing the reaction mixture obtained in Step 1 above and a polyol (C) containing a diol (c) containing one cyclohexane ring,
The rosin acid (A) is contained in an amount of 35 to 60% by mass based on the total amount blended,
The diol (c) containing one cyclohexane ring is contained in an amount of 10 to 45% by mass based on the total amount blended,
A method for producing an active energy ray-curable rosin-modified resin for a lithographic printing ink having a weight average molecular weight of less than 10,000.