JP2012188608A - Lithographic ink and its printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lithographic printing ink having good printability and a printed matter having good film properties, using a resin having excellent production stability.
In a rosin-modified phenolic resin (A) obtained by reacting a rosin (a), a resole type phenolic resin (b) and a polyhydric alcohol (c),
The rosin (a) contains a rosin-modified phenolic resin (A) having a weight solid content of less than 40 parts by weight with respect to 100 parts by weight of the total weight solids of the rosin (a) and the resol type phenol resin (b). A lithographic printing ink characterized by
[Selection figure] 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, web printing, and waterless printing, which are excellent in printability.

  Conventionally, for example, Non-Patent Document 1 describes that rosin-modified phenolic resins are widely used as lithographic ink resins. In general, this rosin-modified phenolic resin is obtained by reacting a resol-type phenolic resin obtained by reacting phenols and formaldehyde under a basic catalyst with rosins and various polyhydric alcohols. The bulky structure obtained by the reaction of rosins and resol type phenolic resin can realize ink viscoelasticity suitable for printability required for lithographic ink. Conventionally, as a resin structure, inexpensive rosins are contained in the resin at 50% or more, preferably 60% or more. For example, Patent Document 1 discloses a rosin-modified phenol resin obtained by reacting 50 to 150 parts by weight of a phenol resin with 100 parts by weight of rosin.

  As the rosins, gum rosin obtained from rosin is often used, but since it is a natural raw material, the isomer composition ratio varies depending on the production area and year of production, and the reactivity tends to vary. In order to keep the finished properties of the resin within an appropriate range, it is necessary to adjust the reaction temperature and reaction time for each lot, or to add phenol resin later. Furthermore, rosins are also concerned about risks such as a decrease in production due to factors such as climate change and price fluctuations.

  Further, in the case of a printed matter printed with a lithographic printing ink using vegetable oil, since the glass transition temperature of the vegetable oil film is low, blocking that the printed surface adheres when a load is applied to the stacked printed matter is likely to occur. Patent Documents 2 and 3 disclose that a polysiloxane-based blocking inhibitor is contained for preventing such blocking. However, the post-processing suitability tends to be inferior by containing a siloxane compound.

JP 2001-164166 A Japanese Patent Laid-Open No. 2-6570 JP 2006-282767 A

Japan Society of Color Material, 63, 271 1990

  An object of the present invention is to provide a lithographic printing ink having good printability and a printed matter having good film properties, using a resin having excellent production stability.

In the rosin-modified phenol resin (A) obtained by reacting the rosins (a), the resol type phenol resin (b) and the polyhydric alcohol (c),
Production of rosin-modified phenolic resin (A) in which rosins (a) are less than 40 parts by weight of solids based on 100 parts by weight of total solids of rosins (a) and resole-type phenolic resin (b) The present inventors have found that a lithographic printing ink having excellent stability and good printability and a printed matter having good film properties can be obtained by using the resin, and the present invention has been completed.

That is, the present invention provides a rosin-modified phenolic resin (A) obtained by reacting rosins (a), a resole type phenolic resin (b) and a polyhydric alcohol (c).
The rosin (a) contains a rosin-modified phenolic resin (A) having a weight solid content of less than 40 parts by weight with respect to 100 parts by weight of the total weight solids of the rosin (a) and the resol type phenol resin (b). The present invention relates to a lithographic printing ink.

The present invention also provides a rosin-modified phenolic resin (A) obtained by reacting rosins (a), resole-type phenolic resin (b), polyhydric alcohol (c) and vegetable oil (d).
The vegetable oil (d) is 5 to 30% by weight with respect to the total amount of the rosins (a), resol type phenolic resin (b), polyhydric alcohol (c) and vegetable oil (d). The present invention relates to a lithographic printing ink as described above.

The present invention also provides a rosin-modified phenolic resin (A) obtained by reacting rosins (a), resol type phenolic resin (b), polyhydric alcohol (c), vegetable oil (d) and petroleum resin (e).
With respect to the total amount of rosins (a), resol type phenol resin (b), polyhydric alcohol (c), vegetable oil (d) and petroleum resin (e), the petroleum resin (e) is in a weight-solid ratio. The present invention relates to the above-described planographic printing ink, which is 5 to 30% by weight.

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

  The lithographic printing ink of the present invention uses a resin with excellent production stability, has good printability, and can provide a high-quality printed matter.

  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), resol type phenol resins (b) and polyhydric alcohols (c).

  As the rosins (a) in the present invention, natural rosins such as gum rosin, wood rosin, tall oil rosin, polymerized rosin derived from the natural rosin, stable rosin obtained by disproportionation or hydrogenation of natural rosin or polymerized rosin And an unsaturated acid-modified rosin obtained by adding an unsaturated carboxylic acid to a natural rosin or a polymerized 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 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 aldehydes, 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 the phenols, all aromatic compounds having a phenolic hydroxyl group can be used, such as carboxylic acid, cresol, amylphenol, bisphenol A, pt-butylphenol, pt-octylphenol, p-nonylphenol, and p-dodecylphenol. Among them, p-alkyl substituted phenols are preferable. Examples of aldehydes include formaldehyde and paraformaldehyde.

  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.

  The rosin-modified phenolic resin (A) of the present invention is obtained by reacting rosins (a), resol type phenolic resins (b) and polyhydric alcohols (c). It is preferable that the rosins (a) are less than 40 parts by weight of the solids content with respect to 100 parts by weight of the total weight solids of the rosins (a) and the resol type phenol resin (b). When the rosin (a) is 40 parts by weight or more, unreacted rosins are liable to deteriorate the blocking property, which is not preferable. Furthermore, in the polyhydric alcohol (c), the hydroxyl group in the polyhydric alcohol is 0.1 to 1.5 mol, preferably 0.3 to 1.2 mol, relative to 1 mol of the carboxylic acid group in the rosin (a). Is preferable for reaction control.

  The synthesis reaction of the rosin-modified phenol resin (A) can be performed according to a conventional method. For example, the rosins (a) are heated and melted, and the resol type phenol resin (b) is dropped in the range of 150 to 250 ° C. and reacted for 1 to 8 hours. Next, a polyhydric alcohol (c) is added and it is made to react in the range of 200-280 degreeC. Alternatively, the rosin (a) and the polyhydric alcohol (c) may be reacted, and then the resol type phenol resin (b) may be reacted. 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.

  The rosin-modified phenolic resin (A) of the present invention can be obtained by reacting vegetable oil (d) and / or petroleum resin (e) as necessary. By incorporating the vegetable oil (d) and the petroleum resin (e) into the reaction system, the desired molecular weight, melt viscosity, and soluble rosin-modified phenolic resin (A) are easily obtained. The vegetable oil (d) and the petroleum resin (e) are each preferably 5 to 30% by weight with respect to the total amount in terms of weight / solid content, so that the effect is easily exhibited.

  The vegetable oil (d) is triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. 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.

  Furthermore, as the vegetable oil (d), a recovered vegetable oil that has been collected and regenerated, such as tempura oil, can be used. As the regenerated vegetable oil, oil regenerated with a water content of 0.3% by weight or less, an iodine value of 90 or more, and an acid value of 3 or less is preferable. By setting the water content to 0.3% by weight or less, it becomes possible to remove impurities that affect the emulsification behavior when converted to ink, such as salt contained in moisture, and by regenerating with an iodine value of 90 or more. It is possible to react efficiently with the resol type phenolic resin (b), and by removing and regenerating vegetable oil with an acid value of 3 or less, impurities that adversely affect the emulsification behavior when inked are removed. It becomes possible to do. Examples of the method for regenerating the recovered vegetable oil include, but are not limited to, filtration, removal of precipitates by standing, and decolorization by activated clay.

  The petroleum resin (e) is obtained by polymerizing an unsaturated compound having a large number of carbon atoms when naphtha is decomposed, and is aliphatic based on a C5 fraction, aromatic based on a C9 fraction, There are an alicyclic system using cyclopentadiene (dicyclopentadiene) as a raw material, and a copolymer system using a C5 fraction and a C9 fraction as a raw material. Examples of the C5 fraction include isoprene, piperylene, cyclopentadiene, pentenes, and pentanes. Examples of the C9 fraction include vinyltoluene, indene, and dicyclopentadiene. Thermal polymerization is performed in the presence of a catalyst or without catalyst. Is obtained. As the catalyst, Friedel-Craft type Lewis acid catalyst such as boron trifluoride and its complex with phenol, ether, acetic acid and the like are usually used. It can be obtained by copolymerizing allyl alcohol, vinyl acetate or the like, and maleic anhydride, acrylic acid or the like can be added to the obtained petroleum resin.

  Commercially available petroleum resins can be used as appropriate, and examples of aliphatic petroleum resins include quinton A100, quinton B170, quinton K100, quinton M100, quinton R100, quinton C200S, and Maruzen Petrochemicals manufactured by ZEON Corporation. Marcaretz T-100AS, Marcaretz R-100AS, and Aromatic Petroleum Resin made by JX Nippon Oil & Energy Co., Ltd. Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neo Polymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer 130S, Neopolymer S, Tosoh Petcole LX, Petocol LX-HS, Petocol 100T, Petocol 120, Petco 120HS, Petol 130, Petol 140, Petol 140HM, Petol 140HM5, Petol 150, Petol 150AS, Toho High Resin # 120S, Toho High Resin RS-21, Toho High Resin RS-9, copolymer petroleum resin, manufactured by Toho Chemical Industry Co., Ltd. As quinton D100, quinton N180, quinton P195N, quinton S100, quinton S195, quinton S195, quinton U185, quinton G100B, quinton G115, quinton D200, quinton E200SN, quinton N295, Tosoh 60 PetroTac 70, PetroTac 90, PetroTac 100, PetroTac 100V, PetroTac 90HM, DCPD The oil resin, manufactured by Maruzen Petrochemical Co. MARUKAREZ M-890A, MARUKAREZ M-845A, manufactured by Nippon Zeon Co., Ltd. Quinton 1325, Quinton 1345, Quinton 1500, Quinton 1525L, Quinton 1700, and the like.

  The rosin-modified phenolic resin (A) obtained by the above reaction preferably has a weight average molecular weight of 5,000 to 300,000 in terms of polystyrene measured by gel permeation chromatography (GPC), an acid value of 40 or less, and a melting point of 100 ° C. or more. Outside the above range, the drying property and emulsification property when used in an ink are likely to be insufficient, which is not preferable.

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,
5-30% by weight of pigment
Resin 10-40% 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
Is used in the composition consisting of 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. Further, as the resin, 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 such as rosin-modified alkyd, fatty acid-modified alkyd, petroleum resin, polyester If it is resin applied to ink, it can be used individually or in combination of 2 or more types.

  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 mentioned 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 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.

  The vegetable oil can be selected from those similar to the vegetable oil (d) described above. 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 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.

  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 weight average molecular weight of the resin was measured in terms of standard polystyrene by gel permeation chromatography (GPC) HLC8220 manufactured by Tosoh Corporation. The particle size of the base ink was measured with a grindometer according to JIS-K5600-2-5. 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.

(Resol type phenol resin production example 1)
A 4-necked flask equipped with a stirrer, reflux condenser and thermometer is charged with 402 parts of paraoctylphenol, 98 parts of para-t-butylphenol, 178 parts of 92% paraformaldehyde, 5 parts of calcium hydroxide and 357 parts of xylene, and blown with nitrogen gas. The temperature was raised while reacting at 90 ° C. for 5 hours. After cooling to 50 ° C., 5.3 parts of sulfuric acid was added and the mixture was allowed to stand after neutralization and stirring. After removing the aqueous layer and calcium sulfate, a resol type phenol resin (b1) having a nonvolatile content of 65% was obtained.

(Resol type phenol resin production example 2)
In the same apparatus as in Phenol Resin Production Example 1, 500 parts of paraoctylphenol, 166 parts of 92% paraformaldehyde, 5 parts of calcium hydroxide, and 352 parts of xylene were heated and heated while blowing nitrogen gas, and reacted at 90 ° C. for 5 hours. It was. After cooling to 50 ° C., 5.3 parts of sulfuric acid was added and the mixture was allowed to stand after neutralization and stirring. After removing the aqueous layer and calcium sulfate, a resol type phenol resin (b2) having a nonvolatile content of 65% was obtained.

(Resol type phenol resin production example 3)
In the same apparatus as in phenol resin production example 1, 289 parts paraoctylphenol, 210 parts para t-butylphenol, 192 parts 92% paraformaldehyde, 5 parts calcium hydroxide and 364 parts xylene were heated and heated while blowing nitrogen gas. , Reacted at 90 ° C. for 5 hours. A resol type phenol resin (b3) having a nonvolatile content of 65% was obtained.

(Resol type phenol resin production example 4)
In the same apparatus as in Phenol Resin Production Example 1, 500 parts of para t-butylphenol, 228 parts of 92% paraformaldehyde, 5 parts of calcium hydroxide, and 382 parts of xylene were charged, and the temperature was raised while blowing nitrogen gas, 90 ° C. for 5 hours. Reacted. A resol type phenol resin (b4) having a nonvolatile content of 65% was obtained.

(Rosin phenol resin production example 1)
A stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer were charged with 150 parts of Chinese rosin X (Chinese gum rosin made by Arakawa Chemical Industries), heated to 200 ° C. while blowing nitrogen gas, and then resole 539 parts of the phenolic resin (b1) obtained in type 1 phenol resin production example 1 was added dropwise over 3 hours. Furthermore, 15 parts of glycerin and 1.5 parts of paratoluenesulfonic acid were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A1) having an acid value of 12 and a weight average molecular weight (Mw) of 22,000.

(Rosin phenol resin production example 2)
In the same apparatus as in rosin phenol resin production example 1, 195 parts of Chinese rosin and 50 parts of soybean oil were charged, heated to 200 ° C. while blowing nitrogen gas, and then resole type obtained in resol type phenol resin production example 2 469 parts of phenol resin (b2) was added dropwise over 3 hours. Furthermore, 20 parts of glycerin and 1.5 parts of paratoluenesulfonic acid were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A2) having an acid value of 14 and a weight average molecular weight (Mw) of 50000.

(Rosin phenol resin production example 3)
In a device similar to rosin phenol resin production example 1, 195 parts of Chinese rosin and 177 parts of palm oil were charged and heated to 200 ° C. while blowing nitrogen gas, and then the resol type obtained in Resol type phenol resin production example 3 469 parts of phenol resin (b3) was added dropwise over 3 hours. Furthermore, 4 parts of glycerin, 18 parts of pentaerythritol and 2.5 parts of calcium oxide were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A3) having an acid value of 15 and a weight average molecular weight (Mw) of 56000. .

(Rosin phenol resin production example 4)
In the same apparatus as in Production Example 1 of rosin phenol resin, X175 parts of Chinese rosin, 78 parts of soybean oil, 53 parts of neopolymer 120 (aromatic petroleum resin manufactured by JX Nippon Oil & Energy Corporation) were charged and 200 parts were introduced while blowing nitrogen gas. After raising the temperature to 0 ° C., 500 parts of the resol type phenol resin (b3) obtained in Resol type phenol resin production example 3 was dropped over 3 hours. Furthermore, 18 parts of glycerin and 2.5 parts of calcium oxide were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A4) having an acid value of 13 and a weight average molecular weight (Mw) of 38000.

(Rosin phenol resin production example 5)
In the same apparatus as in Production Example 1 of rosin phenol resin, 100 parts of Chinese rosin X and 179 parts of Petol 150 (aromatic petroleum resin manufactured by Tosoh Corporation) were charged and heated to 200 ° C. while blowing nitrogen gas. 615 parts of a resol type phenol resin (b4) obtained in Resin Production Example 4 was added dropwise over 3 hours. Furthermore, 10 parts of glycerin and 2.5 parts of calcium oxide were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A5) having an acid value of 11 and a weight average molecular weight (Mw) of 33,000.

(Rosin phenol resin production example 6)
In the same apparatus as in the phenol resin production example 1, 250 parts of Chinese rosin X was charged, heated to 200 ° C. while blowing nitrogen gas, and then 385 parts of the phenol resin (b1) obtained in the resol type phenol resin production example 1 was added. The solution was added dropwise over 3 hours. Furthermore, 13 parts of glycerin and 1.5 parts of paratoluenesulfonic acid were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A6) having an acid value of 21 and a weight average molecular weight (Mw) of 23,000.

(Rosin phenol resin production example 7)
In the same apparatus as in rosin phenol resin production example 1, 350 parts of Chinese rosin, 79 parts of soybean oil, and 53 parts of neopolymer 120 were charged, heated to 200 ° C. while blowing nitrogen gas, and then resol type phenol resin production example 3 231 parts of the resol type phenol resin (b3) obtained in 1 above was added dropwise over 3 hours. Furthermore, 28 parts of glycerin and 2.5 parts of calcium oxide were added and reacted at 250 ° C. for 15 hours to obtain a rosin phenol resin (A7) having an acid value of 23 and a weight average molecular weight (Mw) of 34,000.

[Example 1]
In the same apparatus as in rosin phenol resin production example 1, 45 parts of rosin phenol resin (A1) obtained in rosin phenol resin production example 1, 10 parts of soybean oil, AF7 (Aroma-free hydrocarbon solvent manufactured by JX Nippon Oil & Energy Corporation) ) 44 parts, 1 part of ALCH (Kawaken Fine Chemical Co., Ltd. gelling agent) was charged and reacted at 190 ° C. for 1 hour under a nitrogen stream to obtain varnish (V1). Furthermore, 18 parts of Lionol Blue FG7330 (Toyo Ink Manufacturing Co., Ltd. indigo pigment) and 60 parts of varnish (V1) were kneaded using three rolls with a roll temperature of 60 ° C. until the particle size became 7.5 microns or less. A base ink was obtained. Next, 22 parts of AF7 was added and adjusted to produce a lithographic printing ink (C1) with a tack of 6.5.

[Example 2]
By the same operation as in Example 1, varnish (V2) was obtained with the composition shown in Table 1, and lithographic printing ink (C2) was obtained with the composition shown in Table 2.

Example 3
By the same operation as in Example 1, varnish (V3) was obtained with the composition shown in Table 1, and lithographic printing ink (C3) was obtained with the composition shown in Table 2.

Example 4
In the same manner as in Example 1, varnish (V4) was obtained with the composition shown in Table 1, and lithographic printing ink (C4) was obtained with the composition shown in Table 2.

Example 5
By the same operation as in Example 1, varnish (V5) was obtained with the composition shown in Table 1, and lithographic printing ink (C5) was obtained with the composition shown in Table 2.

[Comparative Example 1]
By the same operation as in Example 1, varnish (V6) was obtained with the composition shown in Table 1, and lithographic printing ink (C6) was obtained with the composition shown in Table 2.

[Comparative Example 2]
By the same operation as in Example 1, varnish (V7) was obtained with the composition shown in Table 1, and lithographic printing ink (C7) was obtained with the composition shown in Table 2.

<Evaluation of off-wheel printing test>
Each of the inks of Examples 1 to 6 and Comparative Examples 1 and 2 was changed to 66.5 kg of NPI-coated paper (manufactured by Nippon Paper Industries Co., Ltd.) at 800 rpm with a Mitsubishi BT2-800 NEO off-wheel printer (manufactured by Mitsubishi Heavy Industries). A printing test of 20,000 sheets was performed, and the solid state of the printed material, glossy soiling, and the blocking property of the printed material were compared. The fountain solution is 1.5% tap water made by AQUAMAG NS (Toyo Ink Mfg. Co., Ltd.). In order to compare the printing state near the lower limit of the water width, the dampening water is 2 Printing was done with a% water dial value higher. The results are shown in Table 3.

  As shown in Table 3, in the rosin-modified phenol resin (A) obtained by reacting the rosins (a), the resole type phenol resin (b) and the polyhydric alcohol (c), the rosins (a) and the resole type phenol The rosin (a), which tends to cause a difference depending on the place of production and the year of production, contains a rosin-modified phenolic resin (A) having a weight solid content of less than 40 parts by weight with respect to 100 parts by weight of the total solid content of the resin (b). The lithographic printing inks of Examples 1 to 5 had good fillability and background stain when printed. Moreover, since the lithographic printing ink of Examples 1-5 has few low molecular weight components resulting from rosins, blocking became favorable compared with Comparative Examples 1-2. Furthermore, the lithographic printing inks of Examples 2 to 5 in which vegetable oil and petroleum resin were reacted had excellent gloss because the fluidity of the ink was good.

  The resin used in the lithographic offset printing ink according to the present invention is excellent in production stability, and by using the resin, printing excellent in lithographic printing suitability such as inking property and emulsification ability becomes possible. Furthermore, it is possible to provide a printed matter excellent in blocking and gloss.

Claims (4)

In the rosin-modified phenolic resin (A) obtained by reacting the rosins (a), the resol type phenolic resin (b) and the polyhydric alcohol (c),
The rosin (a) contains a rosin-modified phenolic resin (A) having a weight solid content of less than 40 parts by weight with respect to 100 parts by weight of the total weight solids of the rosin (a) and the resol type phenol resin (b). A lithographic printing ink characterized by In the rosin-modified phenolic resin (A) obtained by reacting the rosins (a), the resol type phenolic resin (b), the polyhydric alcohol (c) and the vegetable oil (d),
The vegetable oil (d) is 5 to 30% by weight with respect to the total amount of the rosins (a), resol type phenolic resin (b), polyhydric alcohol (c) and vegetable oil (d). The lithographic printing ink according to claim 1. In the rosin-modified phenolic resin (A) obtained by reacting the rosins (a), the resol type phenolic resin (b), the polyhydric alcohol (c), the vegetable oil (d) and the petroleum resin (e),
With respect to the total amount of rosins (a), resol type phenol resin (b), polyhydric alcohol (c), vegetable oil (d) and petroleum resin (e), the petroleum resin (e) is in a weight-solid ratio. The lithographic printing ink according to claim 1 or 2, wherein the content is 5 to 30% by weight. A printed matter obtained by printing the lithographic printing ink according to any one of claims 1 to 3.