JP2014173056A - Resin for a lithographic printing ink, lithographic printing ink, and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin for a lithographic printing ink resin capable of yielding a high-quality printed matter imparting a glossy appearance and accompanied by scarce misting; and a lithographic printing ink including the same.SOLUTION: A resin for a lithographic printing ink accompanied by scarce misting and a lithographic printing ink including the same are provided by a method for manufacturing a rosin-modified phenol resin (A) which is a method for manufacturing a rosin-modified phenol resin by reacting a rosin (a), a resol-type phenol resin (b), a regenerated vegetable oil (c), and a polyol (d) wherein an acid catalyst is further added at a stage where the acid value has reached 80 (mgKOH/g) or below as a result of the progress of a synthesizing reaction.

Description

  The present invention relates to a resin used for lithographic printing ink (hereinafter referred to as "ink") used for printed matter such as books, leaflets, catalogs, newspapers, etc., and without particularly impairing the fluidity of the ink, The present invention relates to a rosin-modified phenolic resin characterized by using a recovered and regenerated vegetable oil as a resin synthesis raw material.

The lithographic printing ink is an ink having 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 a plurality of rollers. In lithographic printing without dampening water, the non-image area is made of a silicon layer, and the ink is repelled to form an image on the paper.

In particular, in lithographic printing using fountain solution, the emulsification balance between the ink and the fountain solution is important. If the emulsification amount of the ink is too high, the ink easily deposits on the non-image area and stains occur. However, if the amount of emulsification is small, dampening water will be sprinkled on the ink surface when printing with a small number of images, resulting in poor ink transfer between rolls and ink inking onto paper, 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 ink manufacturers have made various improvements. Highly glossy inks are particularly demanded as printing inks that can produce high-quality printed matter, and a problem that has been pointed out in recent years as the printing speed increases, There is ink scattering (misting).

  Conventionally, as a method of improving the gloss of printed matter, increase the petroleum solvent and vegetable oil, etc., reduce the viscosity of the ink to improve the smoothness of the printing surface, or use low molecular weight highly soluble resin or petroleum resin, etc. By increasing the resin component in the ink system, a method has been used in which the ink film thickness is maintained by suppressing the penetration of the ink into the printing paper as much as possible.

  However, when petroleum-based solvents and vegetable oils are increased in order to reduce the ink viscosity, the tack value of the ink is lowered, and the transition between rollers on the printing press tends to deteriorate. In addition, formulations that increase the resin component in the ink system using low-molecular high-solubility resins, petroleum resins, etc., increase the tack value of the ink, causing paper peeling, making it difficult to control emulsification, and printing the ink. Suitability was hindered, and there was a limit to improving the gloss of printed matter while maintaining printability.

  In addition to the above method, a method of increasing the compatibility in the ink system by using a class of petroleum-based solvent that is highly soluble in the resin component in the ink system, thereby reducing the viscosity of the ink and increasing the concentration of the resin component There is also. However, the gloss effect cannot be sufficiently obtained by the solubility of the above petroleum-based solvent in the resin. In addition, most of the above petroleum-based solvents are mainly composed of aromatic hydrocarbons, which have a large adverse effect on the human body, and they have recently been used in printing due to environmental impacts such as the printing work environment and air pollution. I have forgotten.

  Moreover, the offset ink composition excellent in gloss is developed by containing fatty acid ester in ink (patent documents 1, 2). However, in these methods, it is difficult to control the permeation of fatty acid ester into the paper, and there are situations where the paper used at the time of printing is restricted and the ink drying property is not satisfactory.

  As a method for reducing misting, there is a method in which extender pigments such as calcium carbonate, organic bentonite, and silicon dioxide are kneaded to reduce the resin component contained in the ink. However, this method is effective in reducing misting, but there is a risk of poor ink flow due to a decrease in fluidity of the ink and deterioration in transferability. In addition, extender pigments are generally hard and difficult to finely disperse, and coarse particles may remain in the ink. The coarse particles adversely affect the printing plate, blanket thick cylinder, guide roll, etc., and promote plate wear. This causes printing defects such as blurring of lines and rubbing stains due to accumulation.

As a resin to be included in the varnish for offset printing ink, a rosin-modified phenol resin is generally used because of its excellent printability, but the amount of gelling agent used for varnishing is more than usual. Thus, studies have been made with the aim of reducing the misting by reducing the ratio of the resin contained in the varnish. However, in this method, the ink becomes excessively emulsified, which may cause printing troubles such as water rod entanglement, reduced transferability, and roller peeling.

  Improvements have also been made to rosin-modified phenolic resins. Patent Document 3 discloses a method in which a polyester and a phenol formaldehyde initial condensate are reacted with a monoester obtained by partially esterifying a mixture of rosin and animal and vegetable oil fatty acids with monoalcohol. However, in this method, by using a monoalcohol for esterification, cross-linking by an ester bond with rosin and animal and vegetable oil fatty acid is not performed, and it becomes difficult to increase the molecular weight.

  Further, Patent Document 4 discloses an oil-modified rosin phenol resin obtained by reacting a resole type phenol / formaldehyde initial condensate, vegetable oil having an iodine value of 100 or more, rosin, polyhydric alcohol and the like. Patent Document 5 discloses an oil-modified rosin phenol resin obtained by reacting phenols, formaldehyde, animal and vegetable oils having an iodine value of 100 or more, rosin, monovalent alcohol, and / or polyhydric alcohol. Yes. However, the use of virgin vegetable oil used for food is not preferable from the viewpoint of environmental friendliness.

  Patent Document 6 discloses a method of reacting tall oil rosin ester and phenol formaldehyde initial condensate in an ink solvent. Although it is possible to increase the molecular weight by reacting in an ink solvent, simply increasing the molecular weight causes a decrease in solubility, and satisfactory gloss cannot be obtained at the time of ink formation.

Although an acid catalyst is generally used as an ester synthesis catalyst for a rosin-modified phenol resin, it is usually added simultaneously with a polyol. However, when an acid catalyst is added, the carboxy group of rosins is decomposed by decarboxylation reaction, and the carboxyl group is lost before sufficiently reacting with the polyol, making it difficult to become a polymer / high viscosity resin. Japanese Patent Publication No. 1-25517 discloses a method of directly esterifying the OH group of resole to the carboxyl group of rosins without using a polyol, but also synthesizes a polymer / high viscosity resin. Is difficult. JP-A-7-70269 describes a method of reacting turpentine oil with a phenolic OH group with an acid catalyst at an acid value of 40 or less. However, it is difficult to completely react turpentine oil, and an alkyl chain is structurally Problems such as increased misting will occur.

JP 2003-31482 A JP 2007-169574 A Japanese Patent No. 4142470 JP 57-2319 A JP-A-57-61017 Japanese Patent Publication No. 1-25517 JP-A-7-70269

  An object of the present invention is to provide a resin for a lithographic printing ink that can be stably printed for a long time, can obtain a glossy, high-quality printed matter, and has little misting, and a lithographic printing ink containing the same.

That is, the present invention relates to a method for producing a rosin-modified phenolic resin obtained by reacting rosins (a), resol type phenolic resin (b), regenerated vegetable oil (c) and polyol (d). In addition, the present invention relates to a method for producing a rosin-modified phenolic resin (A), wherein an acid catalyst is further added when the acid value becomes 80 (mgKOH / g) or less.

Furthermore, the present invention relates to a regenerated vegetable oil (5) to 75% by weight of rosins (a) and 15 to 85% by weight of resole type phenolic resin (b) in the total weight solids of rosin modified phenolic resin (A) ( The present invention relates to a method for producing the above rosin-modified phenolic resin (A), wherein c) is 5 to 30% by weight and polyol (d) is 0.1 to 20% by weight.

Furthermore, this invention relates to the manufacturing method of said rosin modified phenolic resin (A) characterized by the regenerated vegetable oil (c) being the vegetable oil which regenerated the vegetable oil used for manufacture of food and drink.

Furthermore, this invention relates to the manufacturing method of said rosin modified phenol resin (A) characterized by adding an acid catalyst when an acid value becomes 45-80 (mgKOH / g).

Furthermore, the present invention relates to a rosin-modified phenol resin (A) synthesized by the above production method.

Furthermore, this invention relates to the lithographic printing ink characterized by containing said rosin modified phenol resin (A).

Furthermore, this invention relates to the printed matter formed by printing a lithographic printing ink on a base material (K).

  The resin for lithographic printing ink produced by the production method of the present invention and the lithographic printing ink containing the same can suppress misting, can perform stable printing for a long time under various printing conditions, and are glossy. High quality prints can be obtained.

  First, the rosins (a) of the present invention will be described.

  The rosins (a) of the present invention include natural rosins such as gum rosin, tall oil rosin and wood rosin, polymerized rosin derived from the natural rosin, and stable products obtained by disproportionating or hydrogenating natural rosin and 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) of the present invention can be obtained by a conventional method. As an example of the synthesis method, it is obtained by adding phenols (P) and aldehydes (F), adding a volatile organic solvent (such as xylene), and performing a condensation reaction in the presence of a metal oxide catalyst or an alkali catalyst. . The ratio (P / F) of phenols (P) to aldehydes (F) is usually a molar ratio, preferably 1.0 to 4.0, more preferably 1.5 to 3.0, sodium hydroxide , Various known products obtained by addition / condensation in the presence of a metal hydroxide catalyst such as potassium hydroxide, calcium hydroxide or lithium hydroxide or in the presence of an alkali catalyst such as an organic amine under normal pressure or pressure. A condensate is used. As the phenols, all aromatic compounds having a phenol hydroxyl group can be used, and examples thereof include carboxylic acid, cresol, amylphenol, bisphenol A, p-butylphenol, p-octylphenol, p-nonylphenol, and p-dodecylphenol. Of these, alkyl-substituted phenols are preferred. These may be used alone or in combination of two or more. Examples of aldehydes include formaldehyde and paraformaldehyde.

The regenerated vegetable oil (c) in the present invention is a recovered and regenerated vegetable oil. The regenerated vegetable oil is preferably an 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, more preferably an iodine value of 100 or more. By making the moisture content 0.3% by weight or less, it becomes possible to remove impurities that affect the emulsification behavior of the ink, such as salt contained in moisture, and by regenerating with an iodine value of 90 or more, drying properties That is, it becomes possible to make it good in oxidative polymerizability, and it becomes possible to suppress over-emulsification of ink by selecting and regenerating vegetable oil having an acid value of 3 or less. 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 virgin vegetable oil used in the regenerated vegetable oil 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. In the present invention, a more preferred vegetable oil is preferably a vegetable oil having an iodine value of at least 90, more preferably a vegetable oil having an iodine value of 100 or more. By setting the iodine value to 100 or more, the reaction point in the vegetable oil molecule increases, which is advantageous for increasing the molecular weight.

  Examples of the acid catalyst added at an acid value of 80 (KOHmg / g) or less according to the present invention include sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and minerals such as sulfuric acid and hydrochloric acid. An acid etc. are mentioned. When used as the esterification catalyst of the present invention, it is necessary to heat to 150 ° C. or higher. However, since the reactant is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. may be used in combination.

  If an acid catalyst is added before the acid value falls below 80, the carboxyl group of the remaining rosins is decarboxylated and lost, so that the rosins and polyols do not react sufficiently and a high molecular weight resin cannot be synthesized. For this reason, ink misting and the like deteriorate.

The acid catalyst amount of the present invention is preferably used in the range of 0.01 to 5% by weight in the total resin. If it is less than 0.01% by weight and exceeds 5% by weight, the resin viscosity and elasticity required for the ink cannot be obtained.

The polyol (d) in the present invention is a linear alkylene dihydric alcohol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol as a dihydric alcohol. 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1 , 2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanedio 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1, and the like, 1,2-hexadecanediol and the like are branched alkylene dihydric alcohols , 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-1,3 -Propanediol, 2,4-diethyl-1,5-pentanediol and the like are cyclic alkylene dihydric alcohols, 1,2-cyclohexanediol, Lohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, tricyclodecane dimethanol, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, polyethylene glycol (n = 2 to 20), Examples thereof include polyether polyols such as polypropylene glycol (n = 2 to 20) and polytetramethylene glycol (n = 2 to 20), and polyester polyols.

  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 polyol used in the present invention is preferably 0.1 to 20% by weight in terms of weight to solid content in the rosin-modified phenol resin (A). If the amount is less than 0.1% by weight, it becomes difficult to obtain a resin having a molecular weight necessary for printing ink. If the amount exceeds 20% by weight, unreacted polyol remains in the resin, and the ink is not printed when printed. Line stains occur.

The petroleum resin component used in the petroleum resin (e) of the present invention is an aliphatic compound obtained by polymerizing an unsaturated compound having a large number of carbon atoms when naphtha is decomposed, and a C9 fraction as a raw material, C9 There are aromatics based on fractions, alicyclics based on cyclopentadiene (dicyclopentadiene), and copolymers based on C5 and C9 fractions, with a weight average molecular weight of 500- A thing of about 100,000 is common. 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, copolymer petroleum resins include ZEON Corporation Quinton D100, Quinton N180, Quinton P195N, Quinton S100, Quinton S195, Quinton S185, Quinton G100B, Quinton G115, Quinton D200, Quinton E200SN, Quinton N295, Tosoh PetroTac 60, PetroTac 70, PetroTac 90, PetroTac 100V, PetroTac 90HM, DCPD petroleum resin Petrochemicals Marcaretz M-890A, Marcaretz M-845A, Nippon Zeon Quinton 1325, Qui Ton 1345, Quinton 1500, Quinton 1525L, Quinton 1700, and the like.

The rosin-modified phenolic resin (A) in the present invention is preferably 5 to 75% by weight of rosins (a) and 15 to 85% by weight of resole-type phenolic resin (b) in terms of weight to solid content. When the rosin (a) is less than 5% by weight and the resol type phenol resin (b) is more than 85% by weight, the synthetic resin is easily gelled and the reaction control becomes difficult. Further, when the rosin (a) exceeds 75% by weight and the resol type phenol resin (b) is less than 15% by weight, the viscosity and elasticity required for the ink cannot be obtained. Still more preferably, the rosin (a) is 20 to 40% by weight and the resol type phenol resin (b) is 40 to 70% by weight. By reducing the weight-solid content ratio of rosin, there is little blurring of resin and ink properties due to the rosin production area, and the effect is more easily manifested.

About the vegetable oil (c) which carried out the regeneration process, 5-30 weight% is preferable by weight solid content ratio, More preferably, it is 7-25 weight%. If it is less than 5% by weight, the effect of improving the gloss of the printed matter cannot be obtained, and if it exceeds 30% by weight, the viscosity and elasticity required for the ink cannot be obtained.

  In the present invention, petroleum resin (e) can be used to improve the fluidity of the ink. The petroleum resin (e) used in the present invention is preferably 5 to 30% by weight, more preferably 7 to 30% by weight in terms of weight to solid content. If it is less than 5% by weight, sufficient fluidity cannot be obtained in the ink, and if it exceeds 30% by weight, the viscosity and elasticity required for the ink cannot be obtained.

  As a method for producing the rosin-modified phenolic resin of the present invention, for example, rosins (a), regenerated vegetable oil (c), and petroleum resin (e) are heated and melted at 120 to 260 ° C. in a reaction kettle, and then resole type A phenol resin (b) is added and it is made to react at 180-300 degreeC for 1 to 30 hours. Thereafter, polyol (d) is added at 220 to 280 ° C. and esterified with rosins for 1 to 10 hours. The acid value is 80 (mg KOH / g) or less, preferably between 80 and 45 (mg KOH / g). There is a method of adding the acid catalyst and reacting for 2 to 20 hours.

If an acid catalyst is added before the acid value reaches 80 (mgKOH / g), the remaining carboxyl groups of the rosins are decarboxylated and lost while the rosins and polyols are not yet sufficiently reacted. Therefore, it becomes difficult to synthesize a high molecular weight resin, resulting in poor ink misting. If the acid value is 45 (mgKOH / g) or less, a resin having a high molecular weight to a certain extent further undergoes a reaction, so that a further increase in the high molecular weight proceeds and it is difficult to control the reaction. Although misting is good, a resin having maintained solubility cannot be obtained by further increasing the molecular weight, and the gloss of the ink deteriorates.

  The weight average molecular weight of the rosin modified phenolic resin (A) obtained by the above method is not particularly limited, but the weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC) is about 5,000 to 300,000. Those are preferable, and more preferably 10,000 to 150,000. If it is less than 5,000, the viscosity of the ink is low and misting is likely to occur, and if it is 300,000 or more, the solubility of the resin is deteriorated, so that the fluidity of the ink is deteriorated and the gloss is deteriorated. .

  The rosin-modified phenolic resin (A) obtained by the present invention can be prepared by adding vegetable oils, petroleum-based solvent for ink, and gelling agent as needed, and dissolving by heating to produce a varnish for lithographic printing ink.

  Various known oils can be used without limitation as vegetable oils used in lithographic printing ink varnishes. Specific examples include linseed oil, tung oil, soybean oil, safflower oil, dehydrated castor oil, or heat-polymerized oil and oxidized polymerized oil of these vegetable oils. Linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, linseed oil fatty acid isobutyl, soybean oil fatty acid Monoesters of the aforementioned vegetable oils such as isobutyl can be raised. These may be used alone or in combination of two or more. Furthermore, the above-mentioned regenerated vegetable oil (c) can be used as vegetable oils.

  As the petroleum solvent for lithographic printing ink used in the lithographic printing ink varnish, a conventionally known printing ink solvent can be used without any particular limitation. Specifically, for example, No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF, manufactured by JX Nippon Oil & Energy Corporation, AF Solvent 7 etc. are mention | raise | lifted. These may be used alone or in combination of two or more. In particular, as an environmental measure, it is preferable to use an aroma-free solvent having an aromatic hydrocarbon content of 1% by weight or less.

  Examples of the gelling agent include various known materials such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. Can be used.

  The composition ratio of the rosin-modified phenolic resin (A), vegetable oil, petroleum-based solvent, and gelling agent in the varnish for lithographic printing ink may be appropriately determined depending on the use. Is about 5 to 60% by weight, the proportion of vegetable oil is about 0 to 80% by weight, the proportion of petroleum solvent is about 0 to 80% by weight, the proportion of gelling agent is about 0 to 4% by weight, preferably It is about 0 to 3%. The rosin-modified phenolic resin (A) of the present invention and rosin-modified phenolic resins generally used for lithographic printing inks (produced by methods other than the present invention or other than the above weight average molecular weight), petroleum resins, etc. Can also be used together.

A lithographic printing ink is produced from the lithographic printing varnish, pigment, petroleum solvent and additives. Examples of pigments used in the present invention include white pigments such as titanium oxide, yellow pigments such as mineral furnace yellow, navel yellow, naphthol yellow S, hansa yellow G, quinoline yellow lake, permanent yellow NCG, tartrazine lake, and indus. Orange pigments such as Rembrilliant Orange RK, Pirazone Orange, Vulcan Orange, Benzidine Orange G, Indus Len Brilliant Orange GK, Permanent Red 4R, Lionol Red, Pyrarozone Red, Watching Lettuce Calcium Salt, Lake Red D, Brilliant Carmine 6B , Red pigments such as eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B, purple such as first violet B, methyl violet lake Paint, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, indanthrene blue BC and other blue pigments, pigment green B, malachide green lake And green pigments such as FINA SWIRY GREEN G, and black pigments such as carbon black, acetylene black, lan black, and aniline black.

Also, as other additives in the lithographic printing ink, various additives for the purpose of anti-friction, anti-blocking, slip, anti-scratch can be used, leveling agents, antistatic agents, A surfactant, an antifoaming agent, etc. may be added.

As an example of the composition of the lithographic printing ink of the present invention,
-Rosin modified phenolic resin (A) produced by the present invention 5-60 wt%
・ Vegetable oils (including regenerated vegetable oil (c)) 0-80% by weight
・ Petroleum solvent 0-80% by weight
-Gelling agent 0-4% by weight
・ Pigment 5-40% by weight
・ Other resin 0-40% by weight
・ Other additives 1 to 5% by weight
Etc. are mentioned as preferred compositions. The other resin represents a rosin-modified phenol resin, a petroleum resin, or an alkyd resin generally used for a lithographic printing ink composition. When used as a VOC free type ink, the petroleum 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.

  In the present invention, as the substrate (K), paper used for lithographic printing can be used without any particular limitation. Specifically, coated paper such as art paper, coated paper, cast paper, high quality paper, medium quality paper, uncoated paper such as newspaper paper, and synthetic paper such as YUPO are selected.

  The printing method of the ink containing the rosin-modified phenolic resin (A) obtained by the present invention is not particularly limited as long as it is a general offset printing. For example, oxidation polymerization type sheet-fed printing, Examples include off-wheel printing with a drier, newspaper printing with penetrating drying, and waterless printing that does not use dampening water.

  The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the present invention, “part” represents “part by weight” and “%” represents “% by weight” unless otherwise specified.

In the present invention, the weight average molecular weight was measured by gel permeation chromatography (HLC-8220) 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 phenol resin was dissolved in 20 ml of a solvent mixed in a weight ratio of xylene: ethanol = 2: 1. Thereafter, 3 ml of a 3% by weight phenolphthalein solution was added as an indicator and neutralized with a 0.1 mol / l aqueous potassium hydroxide solution. The unit is mgKOH / g.

In the present invention, the iodine value is measured according to JISK0070.

(Synthesis example 1 of resol type phenol resin)
To a four-necked flask equipped with a stirrer, cooler, and thermometer, 1000 parts of paraoctylphenol, 350 parts of 92% paraformaldehyde, 10 parts of 98% calcium hydroxide, and 480 parts of xylene were added and reacted at 90 ° C. for 5 hours. It was. Thereafter, 400 parts of xylene and 250 parts of tap water were added, and 10 parts of 98% sulfuric acid was added dropwise. After stirring and allowing to stand, the upper layer portion was taken out to obtain a xylene solution of a resol type phenol resin having a nonvolatile content of 60%.

(Synthesis example 2 of resol type phenol resin)
To a four-necked flask equipped with a stirrer, a cooler and a thermometer, add 1000 parts of para-t-butylphenol, 480 parts of 92% paraformaldehyde, 10 parts of 98% calcium hydroxide, and 530 parts of xylene, and continue at 90 ° C. for 5 hours. Reacted. Thereafter, 430 parts of xylene and 250 parts of tap water were added, and 10 parts of 98% sulfuric acid was added dropwise. After stirring and allowing to stand, the upper layer portion was taken out to obtain a xylene solution of a resol type phenol resin having a non-volatile content of 60%.

(Production Example 3 of Resol Type Phenolic Resin)
In a four-necked flask equipped with a stirrer, reflux condenser and thermometer, 150 parts of paraoctylphenol, 200 parts of para t-butylphenol, 650 parts of paranonylphenol, 320 parts of paraformaldehyde, 5 parts of 98% calcium hydroxide and 480 parts of xylene. The temperature was increased while charging and blowing nitrogen gas, and the reaction was performed at 90 ° C. for 5 hours. Thereafter, 385 parts of xylene and 250 parts of tap water were added, and 5.3 parts of 98% sulfuric acid was added. After stirring and standing, the upper layer portion was taken out to obtain a xylene solution of a resol type phenol resin having a non-volatile content of 60%.

(Example 1 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 100 parts of gum rosin is melted at 200 ° C. while blowing nitrogen gas, 50 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), petroleum resin “Petocol” 120, 230 parts manufactured by Tosoh Corporation, weight average molecular weight 1700 "was added. After adding dropwise 1000 parts of resol type phenol resin A (solid content 60%) over 5 hours at 200 ° C., the temperature was raised to 250 ° C. while removing xylene. The reaction was continued for 4 hours until KOH. Thereafter, 1 part of p-toluenesulfonic acid was added as a catalyst, and the mixture was further reacted for 6 hours to obtain a resin 1 having a weight average molecular weight (Mw) of 132000 and an acid value of 6.

(Example 2 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 400 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) was added. After adding 733 parts of resol type phenol resin B (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, 50 parts of glycerin was added at 250 ° C., and the acid value was 60 mg / kg without catalyst. It was made to react for 3 hours until it became KOH. Thereafter, 1 part of p-toluenesulfonic acid was added as a catalyst and reacted for 6 hours to obtain a resin 2 having a weight average molecular weight (Mw) of 70000 and an acid value of 14.

(Example 3 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 300 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 235 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) was added. After adding 667 parts of resole type phenol resin A (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 50 parts of glycerin was added at 250 ° C., and the acid value was 45 mg / kg without catalyst. The reaction was allowed to proceed until KOH was reached. Thereafter, 1.5 parts of p-toluenesulfonic acid was charged as a catalyst and reacted for 8 hours to obtain a resin 3 having a weight average molecular weight (Mw) of 88000 and an acid value of 16.

(Example 4 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 500 parts of gum rosin is melted at 200 ° C. while blowing nitrogen gas, 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), petroleum resin “Petocol” 120, manufactured by Tosoh Corporation, 50 parts by weight of average molecular weight 1700 were added. After adding dropwise 475 parts of resol type phenol resin (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 50 parts of glycerin was added at 250 ° C., and the acid value was 55 mg / kg without catalyst. The reaction was continued for 6 hours until KOH. Thereafter, 1.5 parts of p-toluenesulfonic acid was added as a catalyst and reacted for 7 hours to obtain a resin 4 having a weight average molecular weight (Mw) of 76000 and an acid value of 14.

(Example 5 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 500 parts of gum rosin is melted at 200 ° C. while blowing nitrogen gas, 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), petroleum resin “Petocol” 120, manufactured by Tosoh Corporation, 135 parts by weight average molecular weight 1700 was added. After adding 333 parts of a resol type phenolic resin (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, 50 parts of glycerin was added at 250 ° C., and an acid value of 60 mg / kg without any catalyst. The reaction was allowed to proceed until KOH was reached. Thereafter, 1.5 parts of p-toluenesulfonic acid was added as a catalyst, and the mixture was further reacted for 7 hours to obtain a resin 5 having a weight average molecular weight (Mw) of 92000 and an acid value of 13.

(Example 6 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 345 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), petroleum resin “Petocol” 120, 300 parts manufactured by Tosoh Corporation, weight average molecular weight 1700 ”was added. After adding 333 parts of a resol type phenol resin (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, 40 parts of glycerin was added at 250 ° C., and an acid value of 50 mg / kg was obtained without catalyst. The reaction was continued for 7 hours until KOH. Thereafter, 1.5 parts of p-toluenesulfonic acid was added as a catalyst, and the mixture was further reacted for 7 hours to obtain a resin 6 having a weight average molecular weight (Mw) of 62000 and an acid value of 15.

(Example 7 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 750 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 50 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) was added. After adding dropwise 217 parts of resol type phenol resin C (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 50 parts of glycerin was added at 250 ° C., and the acid value was 75 mg / kg without catalyst. The reaction was continued for 4 hours until KOH. Thereafter, 2 parts of p-toluenesulfonic acid was charged as a catalyst and reacted for 8 hours to obtain a resin 7 having a weight average molecular weight (Mw) of 74000 and an acid value of 13.

(Example 8 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 500 parts of gum rosin is melted at 200 ° C. while blowing nitrogen gas, 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), petroleum resin “Petocol” 120, 130 parts manufactured by Tosoh Corporation, weight average molecular weight 1700 "was added. After adding 333 parts of a resol type phenolic resin A (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 50 parts of pentaerythritol was added at 250 ° C. and acid value 45 mg without catalyst. The reaction was continued for 10 hours until / KOH was reached. Thereafter, 2 parts of p-toluenesulfonic acid was added as a catalyst and reacted for 8 hours to obtain a resin 8 having a weight average molecular weight (Mw) of 90000 and an acid value of 12.

(Comparative example A of resin synthesis)
In a four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer, 620 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 517 parts of resole phenolic resin A (60% solid content) was 200. After dropping at 5 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 60 parts of glycerin was added at 250 ° C. and reacted for 2 hours until the acid value became 100 mg / KOH without catalyst. Thereafter, 1 part of p-toluenesulfonic acid was added as a catalyst and reacted for 9 hours to obtain a resin A having a weight average molecular weight (Mw) of 62,000 and an acid value of 18.

(Comparative Example B for Resin Synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 570 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 600 parts of resole phenolic resin B (solid content 60%) was 200 parts. After dropwise addition at 5 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 60 parts of glycerin was added at 250 ° C. and reacted for 5 hours until the acid value became 60 mg / KOH without catalyst. Thereafter, 1 part of p-toluenesulfonic acid was added as a catalyst, and the mixture was further reacted for 6 hours to obtain a resin B having a weight average molecular weight (Mw) of 44000 and an acid value of 17.

(Comparative Example C of Resin Synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 505 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and the petroleum resin “Petocol 120, manufactured by Tosoh Corporation, weight average molecular weight 1700 100 parts were added. After adding dropwise 533 parts of resol type phenol resin (solid content 60%) at 200 ° C. over 5 hours, the temperature was raised to 250 ° C. while removing xylene, and 60 parts of glycerin was added at 250 ° C., and the acid value was 45 mg / kg without catalyst. The reaction was continued for 7 hours until KOH. Thereafter, 1.5 parts of p-toluenesulfonic acid was added as a catalyst, and the mixture was further reacted for 7 hours to obtain a resin C having a weight average molecular weight (Mw) of 82000 and an acid value of 17.

(Comparative Example D of Resin Synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator and a thermometer, 485 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), petroleum resin “Petocol” 120, manufactured by Tosoh Corporation, weight average molecular weight 1700) "was added. Resol type phenolic resin C417 parts (solid content 60%) was added dropwise at 200 ° C. over 5 hours, then the temperature was raised to 250 ° C. while removing xylene, 50 parts of glycerin was added at 250 ° C., and an acid value of 90 mg / kg without any catalyst. The reaction was continued for 2 hours until KOH (acid value unfavorable for adding catalyst) was reached. As a catalyst, 1.5 parts of p-toluenesulfonic acid was charged and reacted for 9 hours to obtain a resin D having a weight average molecular weight (Mw) of 88000 and an acid value of 13.

  Table 1 shows the blending composition of the resin synthesis resins 1 to 8 and resins A to D in the solid content by weight% of the rosin-modified phenolic resin, and the weight average molecular weight and acid value which are the properties of the resin.

<Examples of varnish, comparative example>
To a stirrer, a reflux condenser with a water separator, and a four-neck flask with a thermometer, the rosin-modified phenol resins (resins 1 to 8, Resin 1 to 8, Resins A to D), soybean oil, petroleum solvent (manufactured by JX Nippon Oil & Energy Corporation, AF Solvent 7), gelling agent (manufactured by Kawaken Fine Chemical Co., Ltd., ALCH) with the composition shown in Table 2 and nitrogen While blowing gas, the mixture was heated and stirred at 190 ° C. for 1 hour to produce varnishes (varnishes 1 to 8, varnishes A to D).

<Examples of lithographic printing ink, comparative examples>
Each of the varnishes 1 to 8 and varnishes A to D obtained by the above method, a carbon pigment / Mitsubishi Carbon MA7 (manufactured by Mitsubishi Chemical), and a petroleum solvent (manufactured by JX Nippon Oil & Energy Corporation, AF Solvent 7) The mixture composition shown in Table 3 was subjected to kneaded dispersion using three rolls according to a conventional method to obtain inks of Examples 1 to 8 and Comparative Examples A to D.

  The lithographic printing inks obtained in Examples and Comparative Examples were evaluated for gloss value and fluidity by the following methods. The evaluation results are shown in Table 4.

<Evaluation of gloss value>
The gloss value is 60 ° with a gloss meter gloss meter model GM-26 (Murakami Color Research Laboratory Co., Ltd.) with the same density on Pearl Coat N (Mitsubishi Paper Co., Ltd.) with a proof bow color machine. Gloss was measured. The higher the value, the better the gloss.
(Evaluation criteria) ◎: 60 or more, ○: 50 or more to less than 60, x: less than 50

<Measurement method of fluidity>
2.1 ml of ink is put on a metal plate with a hemispherical depression and allowed to stand for 15 minutes, then the length that flows at 10 degrees tilted for 10 minutes is measured and evaluated based on the following evaluation criteria. went. Higher values indicate less ink tightness and better fluidity.
(Evaluation criteria) A: 80 mm or more, B: 70 mm or more and less than 80 mm, X: less than 70 mm

<Missing evaluation method>
1.5 ml of the watermark 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.
Paper weight increase is less than 0.1 g: ○
0.1 g or more: ×

As shown in Table 4, in the method for producing a rosin-modified phenolic resin obtained by reacting rosins (a), resol type phenolic resin (b) and regenerated vegetable oil (c), an acid value of 80 (mgKOH / g ) When it became below, Examples 1-8 which added the acid catalyst had high gloss value, and there was little misting. Furthermore, Examples 1, 4 to 6 and 8 containing the petroleum resin (e) had particularly good fluidity.

Claims (7)

  In the method for producing rosin-modified phenolic resin obtained by reacting rosins (a), resol type phenolic resin (b), regenerated vegetable oil (c) and polyol (d), the synthesis reaction proceeds and the acid value is 80 A method for producing a rosin-modified phenolic resin (A), wherein an acid catalyst is further added when the amount becomes (mg KOH / g) or less.   Rosin modified phenolic resin (A) in the total weight solids, rosins (a) is 5 to 75% by weight, resol type phenolic resin (b) is 15 to 85% by weight, regenerated vegetable oil (c) is 5 to 30%. The method for producing a rosin-modified phenolic resin (A) according to claim 1, wherein the weight percent and the polyol (d) are 0.1 to 20 weight percent.   The method for producing a rosin-modified phenolic resin (A) according to any one of 1 and 2, wherein the regenerated vegetable oil (c) is a vegetable oil obtained by regenerating the vegetable oil used in the production of food and drink.   The method for producing a rosin-modified phenolic resin (A) according to any one of claims 1 to 3, wherein an acid catalyst is added when the acid value reaches 45 to 80 (mgKOH / g).   A rosin-modified phenolic resin (A) synthesized by the production method according to claim 1. A lithographic printing ink comprising the rosin-modified phenolic resin (A) according to claim 5. A printed matter obtained by printing the lithographic printing ink according to claim 6 on a substrate (K).