JP2016166299A - Lithographic printing ink and printed matter of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing ink that suppresses misting, has good fluidity of the ink and can give a high-quality glossy printed matter, and a printed matter.SOLUTION: A lithographic printing ink comprising a rosin-modified phenolic resin (A) is provided. The rosin-modified phenolic resin (A) is prepared by allowing rosin (a) to react with a resol type phenolic resin (b) and a polyhydric alcohol, in which the rosin (a) is an oxidized rosin (a1).SELECTED DRAWING: None

Description

  The present invention relates to a new and useful lithographic printing ink and printed matter. More specifically, the present invention relates to a printing ink and printed matter that are suitably used for offset lithographic printing such as newspaper printing, sheet-fed printing, and off-wheel printing, which are excellent in printability.

  In recent years, in the printing industry, 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 ink manufacturers have made various improvements.

  The lithographic printing ink is an ink having a relatively high viscosity of about 10 to 100 Pa · s. The mechanism of the lithographic printing machine is that ink is supplied from the ink fountain of the printing machine via a plurality of rollers to the image area on the printing plate, dampening water is supplied to the non-image area in printing with water, and non-printing in waterless printing. The image area is made of a silicon layer, and the ink is repelled to form an image on the paper.

  Further, since the off-wheel printing has a printing speed several times that of the sheet-fed printing, ink scattering (misting) easily occurs between the ink kneading rollers of the printing press. In order to suppress misting, it can be achieved by making the ink hard. However, the ink transfer failure between rollers due to insufficient fluidity, and the flaking of printed matter due to poor transferability due to poor transfer from blanket to paper, Deterioration is inevitable.

  Numerous combinations and modification methods have been developed for suppressing misting without impairing the quality of printed matter. There are documents aiming to improve the fluidity and misting resistance of ink by using two different types of rosin-modified phenolic resins (Patent Document 1), and resins obtained by phenol-modifying cyclopenta petroleum resins (Patent Documents 2 to 3). However, sufficient performance has not been obtained yet.

JP 2011-89021 A JP 2007-161836 A JP 2006-45395 A

  The present invention has been made in order to solve such problems in the prior art, and the problem is to suppress misting during printing and to transfer ink between rollers due to insufficient fluidity. It is an object of the present invention to provide an excellent printing ink that is free from defects, glossiness of printed matter due to deterioration of flaking property due to poor transfer from blanket to paper, and gloss deterioration.

  As a result of sincere research to solve the above problems, when lithographic printing ink containing rosin-modified phenolic resin prepared by a specific manufacturing method is used, ink fluidity, misting during printing, and gloss of printed matter As a result, the present invention has been completed.

  That is, the present invention relates to a lithographic printing ink containing a rosin-modified phenol resin (A) obtained by reacting a rosin (a), a resole type phenol resin (b) and a polyhydric alcohol, wherein the rosin (a) is Oxidized rosins (a1) are included, and the oxidized rosins (a1) have a cloudiness temperature of 50 to 200 ° C. when the oxidized rosins (a1) / No. 0 solvent H = 1/9 wt%. It relates to lithographic printing ink.

  Furthermore, the present invention relates to the above lithographic printing ink, wherein a C4 to C12 alkylphenol is used as the phenol species of the resol type phenol resin.

Furthermore, this invention relates to the printed matter formed by printing the said lithographic printing ink.

  As a result of investigations aimed at solving the present problems, the present inventor has achieved fluidity of ink, misting during printing, and gloss of printed matter by using the rosin-modified phenol resin (A) of the present invention. Excellent printing workability can be realized without loss, and an excellent printed matter can be provided.

  First, the rosin modified phenolic resin (A) of the present invention will be described. The rosin-modified phenol resin (A) is obtained by reacting rosins (a), resole-type phenol resins (b) and polyhydric alcohols (c). In the present invention, at least oxidized rosin (a1) is used as the rosin (a).

  The rosins (a) in the present invention include natural rosins such as gum rosin, wood rosin and tall oil rosin, polymerized rosin derived from the natural rosin, and unsaturated carboxylic acids obtained by adding unsaturated carboxylic acids to natural rosin and polymerized rosin. Examples include saturated acid-modified rosin. The unsaturated acid-modified rosin is, for example, maleic acid-modified rosin, maleic anhydride-modified rosin, fumaric acid-modified rosin, itaconic acid-modified rosin, crotonic acid-modified rosin, cinnamic acid-modified rosin, acrylic acid-modified rosin, methacrylic acid Examples thereof include modified rosin and acid-modified polymerized rosin corresponding thereto. These may be used alone or in combination of two or more.

  The oxidized rosin (a1) is obtained by oxidizing the rosin (a) described above. Since rosins have many double bonds, they are easily oxidized even at room temperature. As a method of promoting oxidation, finely pulverized rosins are easily oxidized by sending air at 50 ° C. or lower. In that case, it is not preferable that the temperature is 50 ° C. or higher because the rosin surface melts and hardens. Further, it is oxidized more easily by heating to 100 ° C. or higher and blowing air into liquefied rosins, and the cloudiness temperature increases as the oxidation proceeds.

By using oxidized rosin, the rosin-modified phenolic resin (A) can be finished with high polymer viscosity. Although the reason is not clear, it is considered that the peroxide site generated when the double bond of rosins is oxidized becomes a cross-linking point and the rosin-modified phenol resin (A) has a bulk structure, thereby improving the misting property. Similarly, when an unsaturated acid-modified rosin modified with an unsaturated acid such as maleic anhydride is used, it is finished in a polymer high-viscosity resin compared with ordinary unmodified rosins. The phenol resin is extremely deteriorated in compatibility with solvent for ink and vegetable oil, and fluidity of ink and gloss of printed matter are remarkably deteriorated. The compatibility can be determined by measuring the cloudiness temperature and is determined under the following measurement conditions.
The cloudiness temperature is a measured value of the temperature at which the rosin oxide (a1) / No. 0 solvent H = 1/9 weight ratio is heated and dissolved and then gradually cooled and becomes cloudy. No. 0 Solvent H was manufactured by JX Nippon Oil & Energy Corporation.

  The cloudiness temperature of the oxidized rosins (a1) is preferably 50 to 200 ° C. More preferably, it is 70-160 degreeC. If the temperature exceeds 200 ° C., the compatibility of the synthesized rosin-modified phenolic resin with the solvent for ink and vegetable oil deteriorates, and the fluidity of the ink and the gloss of the printed matter deteriorate. When the temperature is less than 50 ° C., a crosslinking effect is not observed, and a rosin-modified phenol resin having a low molecular weight and a low viscosity is obtained.

  The resol type phenol resin (b) is a resin obtained by reacting aldehydes and phenols in the presence of an alkaline catalyst. 1.0-4.0 mol is preferable with respect to 1 mol of phenols, More preferably, it is 1.5-3.0 mol. As the alkaline catalyst, metal hydroxide catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, and organic amines can be used. The reaction is carried out at 60 to 120 ° C. under normal pressure or pressure. As phenols, all aromatic compounds having a phenolic hydroxyl group can be used, such as carboxylic acid, cresol, 4-amylphenol, bisphenol A, pt-butylphenol, pt-octylphenol, p-nonylphenol, and p-dodecylphenol. P-alkyl-substituted phenols are preferred. Examples of aldehydes include formaldehyde and paraformaldehyde.

  More preferably, the alkyl chain of the alkylphenol is a C4 to C13 alkylphenol. In the case of a resin produced with C4 or higher, compatibility with the ink solvent is improved, and it is suitable for the fluidity of the ink. In addition, since it is easy to form a resin having a bulk structure at C13 or less, the elasticity of the ink is improved, and the occurrence of stains and misting during printing can be suppressed.

  Although it does not specifically limit as polyhydric alcohol (c) of this invention, 1, 2- ethanediol, 1, 2- propanediol, 1, 3- propanediol which is a linear alkylene dihydric alcohol as a dihydric alcohol. 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, 6-hexadecanediol, 1,2-hexadecanediol and the like are branched alkylene dihydric alcohols such as 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2- Propyl-1,3-propanediol, 2,4-dimethyl-2,4-dimethylpentanediol, 2,2-diethyl-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- 1,2-cyclohexa, in which 1,3-propanediol, 2,4-diethyl-1,5-pentanediol and the like are cyclic alkylene dihydric alcohols Diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone and the like, and polyethylene glycol (n = Examples thereof include polyether polyols such as 2 to 20), polypropylene glycol (n = 2 to 20), and polytetramethylene glycol (n = 2 to 20), polyester polyols, and the like.

  Furthermore, as trihydric or higher alcohol, glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, Examples include diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol, tripentaerythritol and the like.

  In these reactions, a catalyst can be used as necessary. 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, triphenyl phosphine, etc. may be used in combination.

Next, the usage form as a lithographic printing ink in the present invention will be described. The lithographic printing ink in the present invention is used in the form of, for example, sheet-fed ink, heat-set rotary ink, newspaper ink (cold-set rotary ink), or the like. In general, the following compositions can be exemplified.
5-30% by weight of pigment
Rosin modified phenolic resin (A) Varnish 35-70 wt%
Other resins 0 to 30% by weight
Hydrocarbon solvent 0-60% by weight
Vegetable oil 0-70% by weight
Drying accelerator 0 to 5% by weight
Other additives 0-10% by weight
When used as a VOC-free type ink, the hydrocarbon solvent is 0% by weight in the above composition. At this time, the fatty acid monoester compound may be contained in an amount of 0 to 60% by weight as necessary.

  The rosin-modified phenolic resin (A) obtained by the present invention is used as a varnish prepared by dissolving in a vegetable oil and / or a hydrocarbon solvent and / or a fatty acid monoester. It is also possible to add a gelling agent to impart elasticity and use it as a gel varnish with a crosslinked structure in the resin skeleton. As the gelling agent, a metal complex is generally used, and an aluminum complex compound can be given as a typical compound. Examples of such aluminum complex compounds include cyclic aluminum compounds such as cyclic aluminum oxide stearate (Kawaken Fine Chemical: Algomer 1000S), and aluminum alcoholates such as aluminum ethylate and aluminum isopropylate (Kawaken Fine Chemical: AIPD). , Aluminum-sec-butyrate (Kawaken Fine Chemical: ASPD), aluminum isopropylate-mono-sec-butyrate (Kawaken Fine Chemical: AMD), etc., aluminum alkyl acetates such as aluminum-di-n-butoxide-ethyl acetoacetate ( Hope Pharmaceutical: Chelope-A1-EB2), Aluminum-di-n-butoxide-methylacetoacetate (Hope Pharmaceutical: Che ope-A1-MB2), aluminum-di-iso-butoxide-methyl acetoacetate (Hope Pharmaceutical: Chelope-A1-MB12), aluminum-di-iso-butoxide-ethyl acetoacetate (Hope Pharmaceutical: Chelope-A1-EB102) Aluminum-di-iso-propoxide-ethyl acetoacetate (Hope Pharmaceutical: Chelope-A1-EP12, Kawaken Fine Chemical: ALCH), Aluminum-Tris (ethyl acetoacetate) (Kawaken Fine Chemical: ALCH-TR), Aluminum-Tris (Acetylacetonate) (Kawaken Fine Chemical: Aluminum Chelate-A), Aluminum-Bis (ethylacetoacetate) -Monoacetylacetonate (Kawaken Fine Chemical: A Mikireto D) or the like, aluminum soaps such as aluminum stearate (NOF Corporation), aluminum oleate, aluminum naphthenate, can be exemplified aluminum laurate, and aluminum acetylacetonate and the like. These gelling agents are usually used in the range of 0.1 to 10% by weight with respect to 100 parts by weight of the varnish, and are reacted at 160 to 270 ° C. under a nitrogen stream.

  As other resins, in addition to the rosin-modified phenolic resin (A) of the present invention obtained by the method described above, a binder resin can be blended, and lithographic printing inks such as rosin-modified alkyds, fatty acid-modified alkyds, petroleum resins, and polyesters. If it is resin applied to, it can be used individually or in combination of 2 or more types.

  Examples of the pigment include inorganic pigments and organic pigments. Inorganic pigments such as yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, bengara, etc. -Soluble azo pigments such as naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid allylide, acetoacetyl allylide, pyrazolone, β-naphthol, β-oxynaphthoic acid allylide, acetoacetyl allylide Insoluble azo pigments such as 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 , Dioxazine , Selenium (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene, etc.), isoindolinone, metal complex, quinophthalone, etc. In addition, various publicly known pigments such as heterocyclic pigments can be used.

  As the hydrocarbon solvent, a naphthene hydrocarbon solvent and / or a paraffin hydrocarbon solvent are preferable. A naphthenic hydrocarbon solvent and / or a paraffinic hydrocarbon solvent is a so-called aromaless (free) solvent. Commercially, AF Solvents 4-7, 0 Solvent H manufactured by JX Nippon Oil & Energy Idemitsu Kosan Co., Ltd. Supersol LA35, LA38, etc. Exxon Chemical Exxol D80, D110, D120, D130, D160, D100K, D120K, D130K etc., Riki Chemical D-SOL280, D-SOL300 However, the present invention is not limited to these examples, and these can be mixed and used at an arbitrary weight ratio. Particularly preferred are those having an aniline point in the range of 60 ° C to 110 ° C. When the aniline point is higher than 110 ° C., the solubility with the resin of the present invention is poor, the fluidity when used as an offset ink is insufficient, the ink transfer on the printing press is inferior, and transfer failure occurs, Later leveling on the printing medium is insufficient, which causes poor gloss. On the other hand, when the aniline point is lower than 60 ° C., the solvent releasability from the ink film after printing is deteriorated, resulting in poor drying, which causes blocking, show-through, and the like.

  Vegetable oil is triglyceride in which at least one fatty acid has at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. If a suitable vegetable oil is mentioned, the vegetable oil whose iodine value is at least 100 or more is preferable, and also the vegetable oil whose iodine value is 120 or more is more preferable. By setting the iodine value to 120 or more, the drying property by oxidative polymerization of the ink film can be enhanced, and it is particularly effective for a sheet-fed printing method that does not use a hot air dryer. Examples are: Asa seed oil, flaxseed oil, eno oil, prickly oil, olive oil, cacao oil, kapok oil, kaya oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil , Japanese radish seed oil, soybean oil, daikon oil, camellia oil, corn oil, rapeseed oil, niger oil, nuka oil, palm oil, castor oil, sunflower oil, grape seed oil, gentian oil, pine seed oil, cottonseed oil, palm Oil, peanut oil, dehydrated castor oil, and the like.

  Next, as a drying accelerator, acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octylic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, Lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, secanoic acid, tall oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, dimethylhexanoic acid, 3,5,5-trimethylhexa Metal salts of organic carboxylic acids such as noic acid and dimethyloctanoic acid, such as calcium, cobalt, lead, iron, manganese, zinc and zirconium salts, can be used as well as publicly known compounds. In order to accelerate curing, a plurality of these can be used in combination as appropriate.

  Furthermore, other additives can be used in the planographic printing ink of the present invention as necessary. For example, anti-friction agent, anti-blocking agent, slip agent, anti-scratch agent include natural wax such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, Fischer Trops wax, polyethylene wax, polypropylene Synthetic waxes such as wax, polytetrafluoroethylene wax, polyamide wax, and silicone compound can be exemplified. Further, examples of the anti-skinning agent include phenols such as cresol, guaiacol, o-isopropylphenol, and oximes such as butyraloxime, methylethylketoxime, and cyclohexanone oxime.

  As a method for producing the lithographic printing ink of the present invention, a part of the pigment and the resin varnish is kneaded and dispersed with a kneader, a three-roller, an attritor, a sand mill, or the like between room temperature and 100 ° C. Next, the remaining ink components are mixed and adjusted with a three roll, gate mixer or the like.

  Next, the present invention will be described in detail with specific examples. In the examples, “parts” and “%” refer to parts by weight and% by weight unless otherwise specified. The particle size of the base ink was measured with a grindometer according to JIS-K5600-2-5.

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC). Specifically, it was measured under the conditions of solvent tetrahydrofuran in terms of polystyrene using gel permeation chromatography (GPC) HLC8220 manufactured by Tosoh Corporation.
The acid value was measured according to JIS K2501-2003.

(Resol type phenol resin production example 1) (b)
Into a stirrer, reflux condenser with water separator, and 4-neck flask with thermometer, 2204 parts of paranonylphenol, 653 parts of 92% paraformaldehyde, 22 parts of sodium hydroxide, and 1869 parts of xylene are charged, and the temperature is increased while blowing nitrogen gas. And reacted at 90 ° C. for 5 hours. After cooling to 50 ° C., 23 parts of sulfuric acid was added and the mixture was allowed to stand after neutralization and stirring. After removing the aqueous layer, a resol type phenol resin (b) having an active ingredient of 60% was obtained.

(Rosinphenol resin production example 1) (A1)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries), and the cloudiness temperature was adjusted to 50 ° C at 140 ° C while blowing air. It heated until it became, and the oxidation rosin (a1) was manufactured. Subsequently, the temperature was raised to 200 ° C. while blowing nitrogen gas, and then 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol-type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 52000 and a cloudiness temperature of 81 ° C. ( A1) was obtained.

(Rosin phenol resin production example 2) (A2)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries), and the cloudiness temperature reached 70 ° C at 140 ° C while blowing air. It heated until it became, and the oxidation rosin (a1) was manufactured. Subsequently, the temperature was raised to 200 ° C. while blowing nitrogen gas, and then 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol-type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 65000 and a cloudiness temperature of 81 ° C. ( A2) was obtained.

(Rosin phenol resin production example 3) (A3)
A stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer were charged with 600 parts of Chinese rosin X (Chinese gum rosin manufactured by Arakawa Chemical Industries, Ltd.) and the cloudiness temperature reached 100 ° C at 140 ° C while blowing air. It heated until it became, and the oxidation rosin (a1) was manufactured. Subsequently, the temperature was raised to 200 ° C. while blowing nitrogen gas, and then 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol-type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 74000 and a cloudiness temperature of 88 ° C. ( A3) was obtained.

(Rosin phenol resin production example 3) (A4)
A stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer were charged with 600 parts of Chinese rosin X (Chinese gum rosin manufactured by Arakawa Chemical Industries, Ltd.), and the cloudiness temperature was 150 ° C at 140 ° C while blowing air. It heated until it became, and the oxidation rosin (a1) was manufactured. Subsequently, the temperature was raised to 200 ° C. while blowing nitrogen gas, and then 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol-type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 86000 and a cloudiness temperature of 95 ° C. ( A4) was obtained.

(Rosin phenol resin production example 3) (A5)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries), and the cloudiness temperature reached 180 ° C at 140 ° C while blowing air. It heated until it became, and the oxidation rosin (a1) was manufactured. Subsequently, the temperature was raised to 200 ° C. while blowing nitrogen gas, and then 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol-type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value became 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 101000 and a cloudiness temperature of 99 ° C. ( A5) was obtained.

(Rosin phenolic resin production example 3) (A6)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin manufactured by Arakawa Chemical Industries), and the cloudiness temperature was 210 ° C at 140 ° C while blowing air. It heated until it became, and the oxidation rosin (a1) was manufactured. Subsequently, the temperature was raised to 200 ° C. while blowing nitrogen gas, and then 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol-type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 130000 and a cloudiness temperature of 118 ° C. ( A6) was obtained.

(Rosin phenolic resin production example 3) (A7)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries) with a cloudiness of 7 ° C, and the temperature was raised to 200 ° C while blowing nitrogen gas. After warming, 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol type phenol resin production example 1 was added dropwise over 5 hours. Further, 60 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 13,000 and a cloudiness temperature of 38 ° C. ( A7) was obtained.

(Rosin phenol resin production example 3) (A8)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries) with a cloudiness of 7 ° C, and the temperature was raised to 200 ° C while blowing nitrogen gas. After warming, 24 parts of maleic anhydride is charged and kept warm for 1 hour. Next, 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol type phenol resin production example 1 was dropped over 5 hours. Further, 76 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and a rosin phenol resin having a weight average molecular weight (Mw) of 82000 and a cloudiness temperature of 170 ° C. ( A8) was obtained.

(Rosin phenol resin production example 3) (A9)
A stirrer, a reflux condenser with a water separator, and a thermometer four-necked flask were charged with 600 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries) with a cloudiness of 7 ° C, and the temperature was raised to 200 ° C while blowing nitrogen gas. After warming, 12 parts of maleic anhydride is charged and kept warm for 1 hour. Next, 400 parts (as an active ingredient) of the phenol resin (b) obtained in Resol type phenol resin production example 1 was dropped over 5 hours. Further, 68.4 parts of glycerin and 1.2 parts of p-toluenesulfonic acid as a catalyst were added and reacted at 255 ° C. until the acid value reached 20, and rosin phenol having a weight average molecular weight (Mw) of 68000 and a cloudiness temperature of 150 ° C. Resin (A9) was obtained.

(Manufacture of varnish)
In a four-necked flask with a stirrer, reflux condenser and thermometer, 430 parts of rosin phenol resin (A1) obtained in Production Example 1 of rosin phenol resin, 300 parts of soybean oil, AF Solvent No. 5 (JX Nippon Oil & Energy Corporation) 260 parts of aroma-free hydrocarbon solvent) and 10 parts of ALCH (Kawaken Fine Chemical Co., Ltd. gelling agent) were charged and reacted at 190 ° C. for 1 hour under a nitrogen stream to obtain varnish (V1).
Varnishes (V2) to (V9) were obtained in the same manner as varnish (V1) except that rosin-modified phenolic resin (A1) was changed to rosin-modified phenolic resins (A2) to (A9).

Example 1
200 parts of Mitsubishi Carbon MA7 (Mitsubishi Chemical Corporation), 600 parts of varnish (V1) and 200 parts of AF solvent are kneaded using three rolls with a roll temperature of 60 ° C. until the particle size becomes 7.5 microns or less. A lithographic printing ink (X1) was obtained.

(Examples 2-5, Comparative Examples 1-4)
Lithographic printing inks (X2) to (X9) having a particle size of 7.5 microns or less (Example) except that the varnish (V1) was changed to varnishes (V2) to (V9) in the same manner as in Example 1. 2 to 5 and Comparative Examples 1 to 4) were obtained.

(Evaluation of ink)
Using the inks obtained in Examples 1 to 5 and Comparative Examples 1 to 4, gloss, misting, and fluidity are evaluated. Table 1 shows examples of performance evaluation results and Table 2 shows comparative examples.

  About the composition obtained by the Example and the comparative example, gloss, misting, and fluidity | liquidity were evaluated by the following method.

(Evaluation of misting)
Evaluation of misting: 1.5 cc of ink was placed on an incometer type misting tester and rotated at 1800 rpm for 2 minutes. The ink jumped with the rotation, and the superiority and inferiority of the misting were compared with the change in the weight increase of the aligned paper along the rotating body. When misting is poor, the amount of ink flying increases and the paper weight increases.
Increase in paper weight is less than 0.1 g: ○
0.1 or more and less than 0.2: △
0.2g or more: ×
The misting properties were evaluated relative to those measured with our misting tester. In the order of good misting, (good) ○, Δ, × (poor).

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

(Measurement method of fluidity)
2.1 cc of ink is put on a metal plate with a hemispherical depression and left to stand for 15 minutes, then the length that flows in 10 minutes by tilting to 60 degrees is measured and evaluated based on the following evaluation criteria. went. Higher values indicate less ink tightness and better fluidity.
(Evaluation criteria) ○: 80 mm or more, Δ: 70 mm or more, less than 80 mm, ×: less than 70 mm

  As shown in Tables 1 and 2, the inks X1 to X5 in which the rosin temperature of the rosin (a1) is between 50 and 180 are all Δ or more in terms of misting, gloss and fluidity, but the cloudiness temperature is 210. X6 which is ° C. has poor gloss, and X7 whose turbidity temperature of rosins (a) is 7 ° C. is poor in misting. Further, rosins (a) had a cloudiness temperature of 7 ° C., and maleic anhydride-modified X8 and X9 had good misting but poor gloss and fluidity.

Claims (3)

A lithographic printing ink comprising a rosin-modified phenolic resin (A),
The rosin-modified phenol resin (A) is obtained by reacting a rosin (a), a resole type phenol resin (b) and a polyhydric alcohol,
The rosins (a) include oxidized rosins (a1), and
The lithographic printing ink according to claim 1, wherein the rosin oxide (a1) has a turbidity temperature of 50 to 200 ° C. when the oxidized rosin (a1) / No. 0 solvent H = 1/9 by weight.   2. The lithographic printing ink according to claim 1, wherein the resol type phenolic resin is obtained by polymerizing a C4 to C12 alkylphenol.   A printed matter obtained by printing the planographic printing ink according to claim 1 or 2 on a substrate.