JP2018150469A - Method for producing rosin-modified resin, and active energy ray-curable lithographic printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for producing rosin-modified resin, and active energy ray-curable lithographic printing ink using the resin which achieves both printability and printing film strength.SOLUTION: A method for producing a rosin-modified resin includes reacting a conjugated rosin acid (A) and α,β-unsaturated dicarboxylic acid or its acid anhydride (B), and then reacting a terminated mono unsaturated monocarboxylic acid (C) and polyol (D), where 75-200 mol of the α,β-unsaturated dicarboxylic acid or its acid anhydride (B) is used with respect to 100 mol of the conjugated rosin acid (A), and 15-60 pts.wt. of the terminated mono unsaturated monocarboxylic acid (C) is used with respect to 100 pts.wt. of the conjugated rosin acid (A).SELECTED DRAWING: None

Description

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

  A lithographic printing ink (hereinafter also simply referred to as “ink”) has a relatively high viscosity of 5 to 100 Pa · s. The mechanism of the lithographic printing machine is such that ink is supplied from the ink fountain of the printing machine to the image line area of the printing plate via multiple rollers, and in lithographic printing using dampening water, dampening water is supplied to the non-image area area. By doing so, or in lithographic printing that does not use fountain solution, an image is formed on the paper as the non-image area formed by the silicon layer repels ink.

  In particular, in lithographic printing using a fountain solution, the emulsification balance between the ink and the fountain solution is important, and the ink is also required to have high emulsification resistance and high-speed printability. If the amount of emulsified ink is too high, the ink will easily deposit on non-image areas and stains will occur. If the amount of emulsified is small, dampening water will be sprinkled on the surface of the ink when printing with a small pattern. Ink transfer between inks and ink inking on paper deteriorate, making it difficult to print stably.

  Furthermore, in recent years, demands for labor saving, labor saving, automation, and high speed during printing have increased, and in particular, the printing speed has been increasingly increased. In addition, there is a demand for a printing ink that can obtain a high-quality printed matter stably for a long time without any trouble under various printing conditions, and various improvements have been implemented so far.

  On the other hand, the active energy ray curable ink contains an unsaturated compound having an active energy ray curability such as an acrylic ester compound as a constituent component, and is instantly cured with irradiation of the active energy ray. A tough film is formed by three-dimensional crosslinking. Because it cures instantaneously, post-processing can be performed immediately after printing, and active energy ray curing is applied to packaging packaging printing and form printing in commercial fields where a strong coating is required to improve productivity and protect the design. Mold inks are preferably used.

  In general, an active energy ray curable lithographic printing ink comprises a binder resin, an active energy ray curable compound such as an acrylic ester compound, a pigment, a radical polymerization initiator, and various additives.

  The active energy ray curable lithographic printing ink is required to have printing suitability such as emulsification suitability and stain resistance. At the same time, printed film strength such as friction resistance, solvent resistance, gloss, and curability is required. 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 active energy ray-curable binder resins. For example, Patent Document 1 discloses a resin obtained by modifying a saturated polyester with an isocyanate group-containing urethane acrylate. However, since these resins have a highly linear structure, it is difficult to obtain sufficient ink viscoelasticity, and printability such as misting property and stain resistance is easily impaired. Patent Document 2 discloses a resin obtained by reacting a hydroxyl-excess polyester compound containing rosin derivative polyvalent carboxylic acid as an essential component with acrylic acid or methacrylic acid. When the residual amount of the conjugated double bond is not sufficient, the inhibition of curing is likely to occur, and the problem that the strength of the printed film including the curability is insufficient is likely to occur. Further, Patent Document 3 discloses a polyester resin containing a polyvalent carboxylic acid obtained by addition reaction of rosins and an α, β-unsaturated dicarboxylic acid. However, degradation of fluidity and gloss is a problem. It was.

JP 2001-348516 A JP-A-2-051516 JP 2010-070742 A

  An object of the present invention is to provide a novel method for producing a rosin-modified resin, and an active energy ray-curable lithographic printing ink that achieves both printability and print film strength using the resin.

  As a result of intensive studies, the inventor made an addition reaction between a conjugated rosin acid and an α, β-unsaturated dicarboxylic acid or an acid anhydride thereof, and then reacted a terminal monounsaturated monocarboxylic acid with a polyol. By using the obtained rosin-modified resin as a binder resin, it was found that an active energy ray-curable lithographic printing ink capable of achieving both excellent printability and printed film strength was obtained, and the present invention was completed.

That is, in the present invention, a conjugated rosin acid (A) is reacted with an α, β-unsaturated dicarboxylic acid or an acid anhydride (B) thereof, and then a terminal monounsaturated monocarboxylic acid (C) is reacted with a polyol. A process for producing a rosin-modified resin that reacts with (D),
α, β-unsaturated dicarboxylic acid or its acid anhydride (B) is used in an amount of 75 to 200 mol per 100 mol of conjugated rosin acid (A),
The present invention relates to a method for producing a rosin-modified resin using 15 to 60 parts by weight of terminal monounsaturated monocarboxylic acid (C) with respect to 100 parts by weight of conjugated rosin acid (A).

  Moreover, this invention relates to the rosin modified resin obtained with the said manufacturing method.

  Moreover, this invention relates to the varnish for active energy ray hardening-type lithographic printing ink containing the said rosin modified resin.

  The present invention also relates to an active energy ray-curable lithographic printing ink comprising the active energy ray-curable lithographic printing ink varnish, an active energy ray-curable compound, and a pigment.

  Moreover, this invention relates to the printed matter which has a printing layer formed from the said active energy ray hardening-type lithographic printing ink on a base material.

  By using the active energy ray-curable lithographic printing ink containing the rosin-modified resin of the present invention, it has high curability and high quality even when printed under conventional conditions, and particularly has both printability and print film strength. I was able to obtain a printed material.

  Hereinafter, the manufacturing method of the rosin modified resin of the present invention, the varnish for active energy ray curable lithographic printing ink, the active energy ray curable lithographic printing ink, and the printed matter thereof will be described in detail. The present invention is not limited to the following, and various modifications can be made without departing from the gist of the present invention.

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

  Further, “rosin acids” in the present invention refers to monobasic acids having a cyclic diterpene skeleton. Specifically, it represents rosin acid, disproportionated rosin acid, hydrogenated rosin acid, or an alkali metal salt of the above compound.

<Conjugated rosin acid (A)>
The conjugated rosin acid (A) used for obtaining the rosin-modified resin of the present invention is a rosin acid having a conjugated double bond. Specific examples include abietic acid and conjugated compounds thereof such as neoabietic acid, parastronic acid, and levopimaric acid. Examples of natural resins containing these conjugated rosin acids (A) include gum rosin, wood rosin, and tall oil rosin. In general, the natural resin includes conjugated rosin acid (A) and rosin acids having no conjugated double bond. However, in the present invention, these natural resins may be used in combination. The rosin acids having no conjugated double bond function as monobasic acids described later.

<Α, β-unsaturated dicarboxylic acid or acid anhydride (B)>

  The α, β-unsaturated dicarboxylic acid or acid anhydride thereof used for obtaining the rosin-modified resin of the present invention includes maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, isocrotonic acid and the like and their acid anhydrides. Things are illustrated. In view of the reactivity with the conjugated rosin acid (A), maleic acid or its acid anhydride is preferred.

<Terminal monounsaturated monocarboxylic acid (C)>
The terminal monounsaturated monocarboxylic acid (C) is a compound having one double bond at the terminal and one carboxylic acid, which is represented by the following general formula (1).

General formula (1)

(Wherein R1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms,
R2 represents a direct bond or a divalent group selected from an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 1 to 10 carbon atoms, an arylene group having 1 to 10 carbon atoms, and a combination thereof. )

The terminal monounsaturated monocarboxylic acid used in the present invention preferably has a total carbon number of 15 or less. Specifically, acrylic acid, methacrylic acid, 2-ethylacrylic acid, 3-butenoic acid, 4- Pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 2-ethyl-3-butenoic acid, 4-methyl-4-pentenoic acid, 5-methyl-5-hexenoic acid, 6-methyl- Examples include 6-heptenoic acid, 3-propyl-3-butenoic acid, 3- (2-propenyl) benzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid and the like.
When there are two or more terminal double bonds, radical polymerization is likely to occur in the production process, which is not suitable.

<Polyol (D)>

  The polyol used for obtaining the rosin-modified resin of the present invention is not particularly limited, and examples of the dihydric alcohol include 1,2-ethanediol, 1,2-propanediol, which is a linear alkylene dihydric alcohol, , 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- 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, where tradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol and the like are branched alkylene dihydric alcohols, 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 are cyclic alkylene dihydric alcohols 1 2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, water Polyether polyol such as polyethylene catechol, hydrogenated resorcin, hydrogenated hydroquinone, polyethylene glycol (n = 2 to 20), polypropylene glycol (n = 2 to 20), polytetramethylene glycol (n = 2 to 20), Examples include polyester polyols.

  Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, Examples include linear, branched and cyclic polyhydric alcohols such as diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol and tripentaerythritol.

The method of the rosin-modified resin of the present invention comprises a conjugated rosin acid (A), an α, β-unsaturated dicarboxylic acid or acid anhydride (B), a terminal monounsaturated monocarboxylic acid (C), and a polyol. (D) is reacted.
The reaction between the conjugated rosin acid (A) and the α, β-unsaturated dicarboxylic acid or its acid anhydride (B) is performed by reacting the conjugated double bond in the conjugated rosin acid (A) with the α, β-unsaturated dicarboxylic acid. Diels-Alder addition reaction with double bond in acid, then conjugated rosin acid (A), α, β-unsaturated dicarboxylic acid or acid anhydride (B), terminal monounsaturated monocarboxylic acid ( C) and a hydroxyl group in the polyol (D) undergo an esterification reaction.

  Since the addition reaction product of the conjugated rosin acid (A) and the α, β-unsaturated dicarboxylic acid or its acid anhydride (B) becomes a polyvalent carboxylic acid compound, the esterification reaction with the polyol (D) Polymerization is possible. In addition, conjugated double bonds in rosins that become curing inhibitors during irradiation with active energy rays disappear due to addition reaction, and by introducing polycyclic structures derived from resin acids, printing suitability such as emulsification characteristics, high-speed printability, curability, etc. And film strength can be achieved at the same time.

  In the production of the rosin-modified resin of the present invention, the above (A) to (D) can be blended simultaneously or stepwise. For example, using a mixture of a conjugated rosin acid (A), an α, β-unsaturated dicarboxylic acid or anhydride thereof (B), a terminal monounsaturated monocarboxylic acid (C), and a polyol (D), two steps Or a conjugated rosin acid (A) and an α, β-unsaturated dicarboxylic acid or its acid anhydride (B), followed by Diels-Alder addition reaction, and then a terminal monounsaturated monocarboxylic acid. Acid (C) and polyol (D) may be blended and esterified. When blending (A) to (D) at the same time, first, Diels-Alder addition reaction between the conjugated rosin acid (A) and the α, β-unsaturated dicarboxylic acid or its acid anhydride (B) occurs. The reaction temperature may be adjusted.

  The conditions for Diels-Alder addition reaction are not particularly limited and can be performed according to a conventional method. The reaction temperature is preferably in the range of 80 ° C. to 200 ° C., but can be determined in consideration of the boiling point and reactivity of the compound used. For example, hydroquinone, p-methoxyphenol, methylhydroquinone, methoxyhydroquinone, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4- Examples thereof include hydroxytoluene, t-butylcatechol, 4-methoxy-1-naphthol, phenothiazine, N-nitroso-N-phenylhydroxylamine aluminum and the like.

  The conditions for the esterification reaction are not particularly limited and can be carried out according to a conventional method. The reaction temperature is preferably in the range of 200 ° C. to 300 ° C., but can be determined in consideration of the boiling point and reactivity of the compound used. Moreover, it is possible to use a catalyst as needed. 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, and trifluoromethylacetic acid. Etc. can be illustrated. Furthermore, metal complexes such as tetrabutyl zirconate and tetraisobutyl titanate, metal salt catalysts such as magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide, and zinc acetate can also be used. is there. These catalysts are usually used in the range of 0.01 to 5% by weight in the total resin. In order to suppress coloring of the resin due to the use of a catalyst, hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, triphenylphosphine and the like can be used in combination.

  When the terminal monounsaturated monocarboxylic acid (C) is used in an amount of 25 parts by weight or more based on 100 parts by weight of the conjugated rosin acid (A), the conjugated rosin acid (A) and the α, β-unsaturated dicarboxylic acid or It is desirable to blend the terminal monounsaturated monocarboxylic acid (C) after the Diels-Alder addition reaction of the acid anhydride (B). The purpose is to inhibit the Diels-Alder addition reaction between the double bond contained in the terminal monounsaturated monocarboxylic acid (C) and the conjugated rosin acid (A).

  The α, β-unsaturated dicarboxylic acid or its acid anhydride (B) is used in an amount of 75 to 200 mol with respect to 100 mol of the conjugated rosin acid (A). Within the above range, the curability and fluidity are excellent.

Further, the terminal monounsaturated monocarboxylic acid (C) is preferably used in an amount of 15 to 60 parts by weight with respect to 100 parts by weight of the rosin (A). Within the above range, the double bond in the terminal monounsaturated monocarboxylic acid (C) is incorporated into the radical polymerization of the active energy ray-curable compound described later, thereby being excellent in curability and fluidity. If it is 15 parts by weight or less, the contribution to curability is small, and if it is 60 parts by weight or more, it is difficult to control the weight average molecular weight of the resin.
The rosin-modified resin of the present invention contains a monohydric alcohol compound, if necessary, other than α, β-unsaturated dicarboxylic acid or its acid anhydride (B), and terminal monounsaturated monocarboxylic acid (C). It can also be obtained by reacting a carboxylic acid-containing compound.
Examples of monohydric alcohol compounds include linear alkyl monohydric alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2- Heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, etc. Can be illustrated.
Further, branched alkyl monohydric alcohols 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl- 1-pentanol, 3,5,5-trimethyl-1-hexanol, 2,6-dimethyl-4-heptanol, isononyl alcohol, 3,7-dimethyl-1-octanol, 2,4-dimethyl-1-heptanol , 2-heptylundecanol and the like.
Examples of cyclic alkyl monohydric alcohols such as cyclohexanol, cyclohexanemethanol, cyclopentanemethylol, dicyclohexylmethanol, tricyclodecane monomethylol, norbonol, water-added rosin alcohol (trade names: Abitol, Hercules Co., Ltd.) can do.

Examples of the carboxylic acid-containing compound other than the α, β-unsaturated dicarboxylic acid or its anhydride (B) and the terminal monounsaturated monocarboxylic acid (C) include compounds having no terminal unsaturated group Is mentioned.
As monobasic acids, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid , Saturated fatty acids such as stearic acid, nonadecanoic acid, arachidic acid, behenic acid, isocrotonic acid, lindelic acid, tuzuic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, gardoleic acid, cetreic acid, erucic acid, brassine Unsaturated fatty acids such as acid, linoleic acid, linoelaidic acid, linolenic acid, eleostearic acid and arachidonic acid, benzoic acid, methylbenzoic acid, tertiary butylbenzoic acid, naphthoic acid, orthobenzoylbenzoic acid, etc. Basic acid,
Further, as described above, rosin acids having no conjugated double bond such as pimaric acid, isopimaric acid, sandaracopimalic acid, and dehydroabietic acid are exemplified.
As the polybasic acid, alkenyl succinic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, dodecenyl succinic acid, pentadecenyl succinic acid, etc. Phthalic acid, isophthalic acid, terephthalic acid, 1,2,3,6-tetrahydrophthalic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydro Phthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, hymic acid, 3-methylhymic acid, 4-methylhymic acid, trimellitic acid, pyromellitic acid, etc. And their anhydrides.

  The rosin-modified resin obtained from the above production method preferably has a polystyrene-equivalent weight average molecular weight of 10,000 to 35,000, an acid value of 60 or less, and a melting point of 60 ° C. or more as measured by gel permeation chromatography (GPC). Within the above range, emulsification suitability and transferability are excellent when printing ink is used.

  The rosin acid used for the reaction is in the range of 10 to 40% by weight in the total reaction compound. When the content is less than 10% by weight, it is not preferable because physical properties such as emulsification characteristics and film strength derived from the polycyclic structure of the resin acid are hardly exhibited. Moreover, when it exceeds 40 weight%, the solubility to an active energy ray hardening compound tends to be inferior, and is not preferable.

<Varnish for active energy ray curable lithographic printing ink>
The varnish for an active energy ray curable lithographic printing ink using the rosin modified resin of the present invention contains, for example, 10 to 50% by weight of the rosin modified resin and 50 to 90% by weight of the active energy ray curable compound. preferable.

The active energy ray-curable compound in the present invention is a compound having an acrylic group in the molecule.
Specifically, 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 (4 to 12 carbon atoms) glycol diacrylate, alkane (carbon number) 4-12) glycol ethylene oxide adduct (2-20 mol) diacrylate, alkane (4-12 carbon atoms) glycol propylene oxide adduct (2-20 mol) diacrylate, hydroxypivalyl hydroxypivalate diacrylate, tri Cyclodecane dimethylol diacrylate, bisphenol A ethylene oxide adduct (2 to 20 mol) diacrylate, hydrogenated bisphenol A diacrylate, hydrogenated bisphenol A ethylene oxide addition (2-20 moles) bifunctional active energy ray-curable compound such as diacrylate,
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) ) Trifunctional active energy ray-curable compounds such as triacrylate, trimethylolpropane propylene oxide adduct (3 to 30 mol) triacrylate,
Pentaerythritol tetraacrylate, pentaerythritol ethylene oxide adduct (4 to 40 mol) tetraacrylate, pentaerythritol propylene oxide adduct (4 to 40 mol) tetraacrylate, diglycerin tetraacrylate, pentaerythritol ethylene oxide adduct (4 to 40 mol) Mol) tetraacrylate, pentaerythritol propylene oxide adduct (4-40 mol) tetraacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane ethylene oxide adduct (4-40 mol) tetraacrylate, ditrimethylolpropane propylene oxide adduct ( 4-40 mol) tetrafunctional vinyl compounds such as tetraacrylate,
Polyfunctional active energy ray-curable compounds such as dipentaerythritol hexaacrylate, dipentaerythritol ethylene oxide adduct (6 to 60 mol) hexaacrylate, dipentaerythritol propylene oxide adduct (6 to 60 mol) hexaacrylate,
And mixtures thereof.

  The active energy ray-curable compound can be appropriately selected according to the required properties of the cured film, and if necessary, oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate and the like can be used in combination. .

  Furthermore, the varnish for an active energy ray-curable lithographic printing ink of the present invention can be used by adding a photopolymerization inhibitor by a conventional method. When added, from the viewpoint of not inhibiting the curability, the blending amount is preferably 3% by weight or less with respect to the total amount of varnish for active energy ray-curable lithographic printing ink.

  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, butyraloxime, methyl ethyl ketoxime, cyclohexanone oxime, etc. Can be mentioned.

  The active energy ray-curable lithographic printing ink varnish of the present invention can be produced, for example, by mixing the above components at a temperature between room temperature and 150 ° C.

<Active energy ray curable lithographic printing ink>
The active energy ray-curable lithographic printing ink using the rosin-modified resin of the present invention is, for example, 5 to 40% by weight of the rosin-modified resin, 30 to 75% by weight of the active energy ray-curable compound exemplified above, and a pigment. Is preferably 5 to 40% by weight.

  Examples of the pigment include inorganic pigments and organic pigments. Examples of inorganic pigments include chrome yellow, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, etc. Soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid allylide, acetoacetate allylide, pyrazolone, etc., β-naphthol, β-oxynaphthoic acid allylide, aceto Insoluble azo pigments such as allyl acetate monoazo, allyl acetoacetate disazo, pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorine or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine, Quinacridone, dioxadi Polynes such as pyranthrone, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc., isoindolinone, metal complex, quinophthalone, etc. Various publicly known pigments such as pigments and heterocyclic pigments can be used.

  When the active energy ray-curable lithographic printing ink of the present invention is cured with ultraviolet rays, it is preferable to add a photopolymerization initiator. In general, photopolymerization initiators can be broadly classified into two types: those in which bonds are cleaved in the molecule by light to generate active species and those in which active species are generated by causing a hydrogen abstraction reaction between molecules.

  Examples of the former include, 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-phenyl Ketone, [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzyldimethyl ketal, oligo {2-hydroxy-2-methyl-1- [4- (1-Methylvinyl) phenyl] propane}, 4- (2-acryloyl-oxyethoxy) phenyl-2-hydro Acetophenone series such as cis-2-propyl ketone, benzoin series such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, mixture of 1-hydroxycyclohexyl-phenyl ketone and benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide Acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzyl, methylphenylglyoxyester, 3,3 ′, 4,4′-tetra (t-butylperoxy) Carbonyl) benzophenone and the like.

  Examples of the latter include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 Benzophenones such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4- Thioxanthones such as diethylthioxanthone and 2,4-dichlorothioxanthone, Michler's ketone, aminobenzophenones such as 4,4′-bisdiethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthrax Emissions, 9,10-phenanthrenequinone, there is 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 with ultraviolet rays, it can be cured only by adding a photopolymerization initiator, but in order to further improve the curability, a photosensitizer must 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 4-dimethylaminobenzoic acid 2-ethylhexyl.

  When ultraviolet rays are used as the active energy ray, the blending amount of the photopolymerization initiator is preferably 0.01 to 15% by weight in the active energy ray-curable lithographic printing ink, more preferably 0.05 to 10% by weight. When the content is 0.01% by weight or more, the curing reaction is sufficiently performed, and when the content is 15 parts by weight or less, the occurrence of the thermal polymerization reaction is suppressed, and the stability of the active energy ray-curable lithographic printing ink is favorable. It can be made preferable. In addition, when using ionizing radiation other than the below-mentioned ultraviolet rays as an active energy ray, it is not necessary to mix | blend a photoinitiator.

  Furthermore, the active energy ray-curable lithographic printing ink of the present invention is used by adding various additives such as a photopolymerization inhibitor, anti-friction agent, anti-blocking agent, slip agent, etc. according to the purpose in a conventional manner. You can also. When these components are added, the blending amount is preferably 15% by weight or less based on the total amount of the active energy ray-curable lithographic printing ink from the viewpoint of not inhibiting the effects of other materials. In addition, when using a photoinitiator, the compound which can be used for the varnish for active energy ray hardening type lithographic printing inks illustrated above, for example can be used.

  The atmosphere for irradiating the active energy ray is preferably an atmosphere substituted with an inert gas such as nitrogen gas, but may be irradiated in the air. Before irradiating the active energy ray, the active energy ray-curable lithographic printing ink layer is heated by an infrared heater or the like, or after irradiating the active energy ray, the active energy ray-curable lithographic printing ink layer is added by an infrared heater or the like. Warming is effective to quickly complete the curing.

  The active energy ray of the present invention refers to ionizing radiation such as ultraviolet rays, electron beams, X-rays, α rays, β rays, γ rays, microwaves, high frequencies, etc., provided that radical active species can be generated. Any energy species may be used, such as visible light, infrared light, and laser light. Examples of those that generate ultraviolet rays 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, There is an argon laser.

  The active energy ray curable lithographic printing ink of the present invention uses the above components at a temperature between room temperature and 100 ° C., using a kneader, a kneader such as a kneader, three rolls, an attritor, a sand mill, and a gate mixer, and a mixing machine. It is preferable to manufacture. When the rosin-modified resin is added, the rosin-modified resin itself may be added, or an active energy ray-curable lithographic printing ink varnish containing the rosin-modified resin may be added.

  The active energy ray-curable lithographic printing ink of the present invention is usually applied to lithographic offset printing using fountain solution, but is also suitably used for waterless printing without using fountain solution. The active energy ray-curable lithographic printing ink of the present invention includes foam prints, various book prints, various packaging prints such as carton paper, various plastic prints, seal / label prints, art prints, metal prints (art prints, Applied to printed matter such as beverage can printed matter, food printed matter such as canned food). Furthermore, it may be used as an overcoat varnish.

  In addition, as the base material, non-coated paper such as fine paper, fine coated paper, art paper, coated paper, lightweight coated paper, coated paper such as cast coated paper, white paperboard, paperboard such as ball coat, synthetic paper Examples thereof include paper, aluminum vapor-deposited paper, and plastic sheets such as polypropylene, polyethylene, polyethylene terephthalate, and polyvinyl chloride.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the present invention, “part” represents part by weight, and “%” represents% by weight.

  In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. A calibration curve was prepared with 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. Furthermore, in the present invention, “molecular weight” means a weight average molecular weight unless otherwise specified.

  In the present invention, the acid value was measured by a neutralization titration method. As a measuring method, 1 g of rosin-modified resin was dissolved in 20 ml of a solvent mixed at a weight ratio of xylene: ethanol = 2: 1. Thereafter, 3 ml of a 3% by weight phenolphthalein solution was added as an indicator, and neutralization titration was performed with a 0.1 mol / l ethanolic potassium hydroxide solution. The unit is mgKOH / g.

  In the present invention, the melting point was measured using MeltingPoint M-565 manufactured by BUCHI at a rate of temperature increase of 0.5 ° C./min.

  In the present invention, the content ratio of the conjugated rosin acid (A) and the monobasic acid contained in the rosin acids can be determined from the peak area ratio of gas chromatography. Specifically, the total rosin acid peak area is 100%. It calculated | required by the peak area ratio (%) with respect to.

  In the present invention, the progress of Diels-Alder addition reaction was confirmed by a decrease in the detection peak of α, β-unsaturated dicarboxylic acid or its acid anhydride (B) by gas chromatography mass spectrometry.

  A rosin-modified resin and an active energy ray-curable lithographic ink composition were prepared according to the formulation shown below. In addition, in the gum rosin blended in the formulation shown below, the content of the conjugated rosin acid (A) was 80% by weight, and the content of the monobasic acid was 20% by weight.

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

[Example 1]
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 10 parts of gum rosin and 5 parts of maleic anhydride and heated at 180 ° C. for 1 hour while blowing nitrogen gas.
Thereafter, 16 parts of benzoic acid, 3 parts of acrylic acid, 38 parts of phthalic anhydride, 28 parts of pentaerythritol, 0.1 part of N-nitroso-N-phenylhydroxylamine aluminum, 0.1 part of p-toluenesulfonic acid monohydrate A resin (R1) having an acid value of 35 and a weight average molecular weight (Mw) of 20,000 polystyrene equivalent in terms of polystyrene measured by GPC was obtained.
Next, 36 parts of resin (R1), 63.9 parts of dipentaerythritol hexaacrylate, and 0.1 part of hydroquinone were mixed in the same flask, and heated and melted at 100 ° C. to obtain varnish (V1).
Furthermore, 62 parts of varnish (V1), 20 parts of Lionol Blue FG7330 (a cyan pigment manufactured by Toyocolor Co., Ltd.), 12.9 parts of trimethylolpropane tetraacrylate, 2.5 parts of 4,4′-bis (diethylamino) benzophenone, 2 -2.5 parts of methyl-2-monophorino (4-thiomethylphenyl) propan-1-one and 0.1 part of hydroquinone were kneaded in a three-roll mill at 40 ° C, and the tack of the ink was 9-10. The lithographic printing ink (C1) was obtained by adjusting with trimethylolpropane tetraacrylate.
The tack of the ink was measured with a roll temperature of 30 ° C., 400 rpm, and 1 minute after using an incometer manufactured by Toyo Seiki Co., Ltd.

[Example 2]
In the same manner as in Example 1, a resin (R2) having an acid value of 17 and Mw of 18,000 was obtained with the composition shown in Table 1. Subsequently, lithographic printing ink (C2) was obtained with the composition shown in Table 2 and varnish (V2) with the composition shown in Table 3.

Example 3
By the same operation as in Example 1, a resin (R3) having an acid value of 25 and Mw of 23,000 was obtained with the composition shown in Table 1. Subsequently, a lithographic printing ink (C3) was obtained with the composition shown in Table 2 and the varnish (V3) with the composition shown in Table 3.

Example 4
In the same manner as in Example 1, a resin (R4) having an acid value of 27 and Mw of 25,000 was obtained with the composition shown in Table 1. Subsequently, a lithographic printing ink (C4) was obtained with the formulation shown in Table 2 and the varnish (V4) with the formulation shown in Table 3.

Example 5
By the same operation as in Example 1, a resin (R5) having an acid value of 22 and Mw of 24,000 was obtained with the composition shown in Table 1. Subsequently, a lithographic printing ink (C5) was obtained with the composition shown in Table 2 and the varnish (V5) with the composition shown in Table 3.

[Comparative Example A]
A stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer were charged with 20 parts of gum rosin and 6 parts of maleic anhydride and heated to 180 ° C. while blowing nitrogen gas.
Thereafter, 35 parts of tertiary butyl benzoic acid, 1 part of acrylic acid, 10 parts of phthalic anhydride, 28 parts of neopentyl glycol, 0.1 part of N-nitroso-N-phenylhydroxylamine aluminum, p-toluenesulfonic acid monohydrate 0.1 part of the product was added and subjected to dehydration condensation at 230 ° C. for 12 hours to obtain a resin (RA) having an acid value of 27 and a weight-average molecular weight (Mw) of 25,000 in terms of GPC measurement polystyrene.
Next, 33 parts of resin (RA), 66.9 parts of dipentaerythritol hexaacrylate, and 0.1 part of hydroquinone were mixed in the same flask, and heated and melted at 100 ° C. to obtain a varnish (VA).
Furthermore, 63 parts of varnish (VA), 20 parts of Lionol Blue FG7330 (a cyan pigment manufactured by Toyocolor Co., Ltd.), 11.9 parts of trimethylolpropane tetraacrylate, 2.5 parts of 4,4′-bis (diethylamino) benzophenone, 2.5 parts of 2-methyl-2-monophorino (4-thiomethylphenyl) propan-1-one and 0.1 part of hydroquinone are kneaded with a three-roll mill at 40 ° C., and the tackiness of the ink is 9-10. Was adjusted with trimethylolpropane tetraacrylate to obtain a lithographic printing ink (CA).
The tack of the ink was measured with a roll temperature of 30 ° C., 400 rpm, and 1 minute after using an incometer manufactured by Toyo Seiki Co., Ltd.

[Comparative Example B]
By the same operation as in Comparative Example A, a resin (RB) having an acid value of 33 and Mw of 28,000 was obtained with the composition shown in Table 1. Subsequently, the lithographic printing ink (CB) was obtained with the composition shown in Table 2 and the varnish (VB) with the composition shown in Table 3.

[Comparative Example C]
Stirrer, reflux condenser with water separator, 4-neck flask with thermometer, 20 parts benzoic acid, 8 parts acrylic acid, 2 parts phthalic anhydride, 31 parts neopentyl glycol, N-nitroso-N-phenylhydroxylamine 0.1 part of aluminum and 0.1 part of p-toluenesulfonic acid monohydrate were added, and dehydration condensation was performed at 230 ° C. for 5 hours while blowing nitrogen gas.
Thereafter, 30 parts of gum rosin and 9 parts of maleic anhydride were charged and heated to 230 ° C. to obtain a resin (RC) having an acid value of 35 and a weight average molecular weight (Mw) of 22,000 in terms of polystyrene measured by GPC.
Next, 36 parts of resin (RC), 63.9 parts of dipentaerythritol hexaacrylate and 0.1 part of hydroquinone were mixed in the same flask, and heated and melted at 100 ° C. to obtain a varnish (VC).
Furthermore, 61 parts of varnish (VC), 20 parts of Lionol Blue FG7330 (a cyan pigment manufactured by Toyocolor Co., Ltd.), 13.9 parts of trimethylolpropane tetraacrylate, 2.5 parts of 4,4′-bis (diethylamino) benzophenone, 2.5 parts of 2-methyl-2-monophorino (4-thiomethylphenyl) propan-1-one and 0.1 part of hydroquinone are kneaded with a three-roll mill at 40 ° C., and the tackiness of the ink is 9-10. Was adjusted with trimethylolpropane tetraacrylate to obtain a lithographic printing ink (CC).
The tack of the ink was measured with a roll temperature of 30 ° C., 400 rpm, and 1 minute after using an incometer manufactured by Toyo Seiki Co., Ltd.

  The lithographic printing inks obtained in the examples and comparative examples were evaluated for cured film properties and printability by the following methods.

<Evaluation of cured film properties>
The lithographic printing inks obtained in Examples 1 to 5 and Comparative Examples A to C were applied to maricoat paper (coated cardboard manufactured by Hokuetsu Paper Co., Ltd.) at 1 g / m using an RI tester (manufactured by Meiko Seisakusho). Printing was performed at a coating amount of ² , and ultraviolet rays were irradiated at 60 m / min using one 120 W / cm air-cooled metal halide lamp (manufactured by Toshiba).

  The curability, MEK resistance, friction resistance, and gloss value of the printed material after ultraviolet irradiation were evaluated. The evaluation results are shown in Table 4.

  The curability was evaluated in four stages by visual observation of the state when the printed surface was rubbed with a cotton cloth. ◎: no change, ○: some scratches but no peeling, △: some (less than 50%) peeling, x: some (50% or more) or all Represents that peeling was observed. The usable level is ◯ or more.

  MEK resistance was evaluated in four stages by visual observation of the state when the printed surface was rubbed 30 times with a cotton swab dipped in MEK. ◎: No change, ○: Part of the surface was dissolved but no peeling was observed, Δ was partly (less than 50%), x was partly (50% or more) Or it represents that peeling was seen in all. The usable level is ◯ or more.

  The friction resistance of the coating film is based on JIS-K5701-1, using a Gakushin type friction fastness tester (manufactured by Tester Sangyo Co., Ltd.), using high-quality paper as a friction paper, The change of the friction surface was visually evaluated in four stages. ◎: no change, ○: some scratches but no peeling, △: some (less than 50%) peeling, x: some (50% or more) or all Represents that peeling was observed. The usable level is ◯ or more.

Gloss value is 60% gloss with gloss meter gloss meter model GM-26 (manufactured by Murakami Color Research Laboratory Co., Ltd.) with proof bow color developing machine and the same density on pearl coat manufactured by Mitsubishi Paper Industries. Was measured. The higher the value, the better the gloss. The usable level is ◯ or more.
(Evaluation criteria) ◎: 60 or more, ○: 50 or more to less than 60, Δ: 40 or more to less than 50, x: less than 40

  As shown in Table 4, the curability of Examples 1 to 5 was good, but Comparative Examples A to C did not reach the practical level. This is probably because Comparative Example A had a low compounding ratio of the terminal monounsaturated monocarboxylic acid (C) to the conjugated rosin acid (A) and did not cause curing acceleration. Comparative Example (B) was conjugated rosin. The blending ratio of α, β-unsaturated dicarboxylic acid anhydride (B) to acid (A) is small, and it is considered that curing inhibition was caused by the conjugated double bond contained in rosins. Comparative Example C is a conjugated system. Since the combination of the rosin acid (A) and the α, β-unsaturated dicarboxylic acid anhydride (B) is the latter half of the entire reaction process, the Diels-Alder addition reaction is incomplete and the conjugated double contained in the rosins. It is considered that the inhibition of curing was caused by the bonding.

  Examples 3, 4 and 5 in which the molecular weight of the resin was large were particularly good in terms of MEK resistance and friction resistance. This is probably because the film strength increases as the molecular weight increases. Comparative Examples A to C are considered to have poor curability as compared with the Examples, and the film strength is inferior compared with the Examples.

  The gloss values of Examples 1 to 5 were particularly good, and Comparative Example A gave good results. This is presumably because the active energy ray-curable lithographic printing ink using a rosin-modified resin produced from a raw material and a process of an appropriate blending amount maintains good fluidity.

Claims (5)

A conjugated rosin acid (A) is reacted with an α, β-unsaturated dicarboxylic acid or its acid anhydride (B), and then a terminal monounsaturated monocarboxylic acid (C) is reacted with a polyol (D). A method for producing a rosin-modified resin,
α, β-unsaturated dicarboxylic acid or its acid anhydride (B) is used in an amount of 75 to 200 mol per 100 mol of conjugated rosin acid (A),
A method for producing a rosin-modified resin, wherein 15 to 60 parts by weight of the terminal monounsaturated monocarboxylic acid (C) is used with respect to 100 parts by weight of the conjugated rosin acid (A).   A rosin-modified resin produced by the production method according to claim 1.   An active energy ray-curable lithographic printing ink varnish comprising the rosin-modified resin according to claim 2.   An active energy ray-curable lithographic printing ink comprising the varnish according to claim 3, an active energy ray-curable compound, and a pigment.   A printed matter having a printing layer formed from the active energy ray-curable lithographic printing ink according to claim 4 on a substrate.