JP2017137421A - Resin for lithographic printing ink and lithographic printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin for lithographic printing ink capable of providing a printed matter which has good flowability of ink, can reduce scumming at the time of printing, and is excellent in glossiness, and to provide lithographic printing ink containing the same.SOLUTION: There is provided a method for producing a rosin-modified phenol resin (A) formed by reacting rosin polyol ester formed by reacting rosins (a), polyol (b) and regenerated vegetable oil (c) with a resol type phenolic resin (d), where an acid value of the polyol ester when the resol type phenolic resin (d) is reacted is less than 50.0 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to a resin used for lithographic printing ink (hereinafter abbreviated as “ink”) used for printed matter such as books, leaflets, catalogs, newspapers, etc., and has high gloss and reduces stains during printing. The present invention relates to a rosin modified phenolic resin.

  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 multiple rollers, and in lithographic printing using dampening water, dampening water is supplied to the non-image area area. In waterless planographic printing that does not use fountain solution, 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.

  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.

  Patent Document 3 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 4 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.

  Moreover, although the applicant disclosed the ink which can make a highly glossy printed matter, the further improvement is performed (patent documents 5-8).

JP 2003-31482 A JP 2007-169574 A JP 57-2319 A Japanese Patent Publication No.57-9730 JP 2012-188607 A JP 2014-173056 A Japanese Patent Laying-Open No. 2015-189892 Japanese Patent Laying-Open No. 2015-189893

  An object of the present invention is to provide a resin for a lithographic printing ink that can reduce background stains and obtain a highly glossy printed matter even during long-time printing, and a lithographic printing ink containing the same.

  As a result of sincere research to solve the above problems, lithographic printing inks containing rosin-modified phenolic resin made from the following materials have excellent gloss of printed matter and can reduce background stains during printing. As a result, the present invention has been completed.

  That is, the present invention relates to a rosin-modified phenol obtained by reacting a rosin polyol ester obtained by reacting a rosin (a), a polyol (b) and a regenerated treated vegetable oil (c) with a resol type phenol resin (d). In the resin production method, the present invention relates to a method for producing a rosin-modified phenolic resin (A), wherein the acid value of the rosin polyol ester when the resole-type phenol resin (d) is reacted is less than 50.0 mgKOH / g.

  In the present invention, the rosin-modified phenolic resin (A) is 5 to 75% by weight of rosins (a), 1 to 20% by weight of polyol (b), and regenerated vegetable oil (c) 5 in weight to solid content ratio. The present invention relates to a process for producing the above-mentioned rosin-modified phenol resin (A), characterized by reacting at ~ 30 wt% and resole-type phenol resin (d) at 15-85 wt%.

In the present invention, the rosin polyol ester is obtained by reacting the rosin (a), the polyol (b), the regenerated vegetable oil (c), and the petroleum resin (e).
The rosin-modified phenol resin (A) is, in terms of the weight-solid content ratio, rosins (a) 5 to 74% by weight, polyol (b) 1 to 20% by weight, regenerated vegetable oil (c) 5 to 30% by weight, resole The present invention relates to a process for producing the rosin-modified phenolic resin (A), which is reacted with 15 to 85% by weight of a phenol resin (d) and 5 to 30% by weight of a petroleum resin (e).

  The present invention also relates to a method for producing the rosin-modified phenolic resin (A), wherein the regenerated vegetable oil (c) is a vegetable oil regenerated from the vegetable oil used in the production of food and drink.

  Moreover, this invention relates to the lithographic printing ink characterized by containing the rosin modified phenol resin (A) manufactured with the said manufacturing method.

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

  By using printing ink containing rosin-modified phenolic resin synthesized from rosin polyol ester introduced with vegetable oil and reduced to below the specified acid value, it reduces scumming during printing under various conditions. Time-stable printing is possible, and a glossy high-quality printed matter can be provided.

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

  The rosins (a) of the present invention are obtained by disproportionating or hydrogenating natural rosins such as gum rosin, tall oil rosin, wood rosin, and merck rosin, polymerized rosin derived from the natural rosin, natural rosin and polymerized rosin. Stabilized rosin, natural rosin, polymerized rosin and unsaturated acid-modified rosin obtained by adding unsaturated carboxylic acids to 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 polyol (b) in the present invention includes 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, which are linear alkylene dihydric alcohols, as the 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 regenerated vegetable oil (c) in the present invention is a recovered and regenerated vegetable oil.

  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.

  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 resol type phenol resin (d) 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 (F / P) 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, p-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.

  As a component of the petroleum resin (e) used in the present invention, an aliphatic compound obtained by polymerizing an unsaturated compound having a large number of carbon atoms when naphtha is decomposed, an aliphatic system using a C5 fraction as a raw material, a C9 fraction There is an aromatic system using as raw material, an alicyclic system using cyclopentadiene (dicyclopentadiene) as a raw material, and a copolymer system using C5 and C9 fractions as raw materials, and the weight average molecular weight is about 500 to 100,000. The ones are 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 esterification reaction for obtaining the rosin polyol ester can be performed according to a conventional method. Usually, it is carried out in the range of 150 ° C. to 300 ° C., but can be determined in consideration of the boiling point and reactivity of the compound used. 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) in the present invention is a weight-solid ratio, and the total amount of solids charged (however, polyol, vegetable oil, and petroleum resin are included as solids. The same applies hereinafter) rosins ( a) 5 to 75% by weight is preferable, and resol type phenol resin (d) 15 to 85% by weight is preferable. When the rosin (a) is 5% by weight or more and the resol type phenol resin (d) is 85% by weight or less, the synthetic resin is difficult to gel and the reaction control is easy. Further, when the rosin (a) is 75% by weight or less and the resol type phenol resin (d) is 15% by weight or more, the viscosity and elasticity necessary for the ink can be easily obtained.

  About the vegetable oil (c) which carried out the regeneration process, 5-30 weight% is preferable with respect to the whole preparation solid content prescription amount by weight solid content ratio, More preferably, it is 7-25 weight%. If it is 5% by weight or more, the effect of improving the gloss of the printed matter is easily obtained, and if it is 30% by weight or less, the viscosity and elasticity required for the ink are easily developed.

  In the production method of the rosin-modified phenolic resin (A) of the present invention, rosins (a) are heated and melted at 120 to 260 ° C. in a reaction kettle equipped with a stirrer, and regenerated vegetable oil (c) and polyol (b) are added. The reaction is carried out at 220 ° C. to 280 ° C. for 2 to 15 hours until the acid value becomes less than 50.0 mgKOH / g. The resol type phenol resin (d) is added thereto, and the reaction is performed at 220 to 300 ° C. for 1 to 12 hours.

  Here, adding the resol type phenol resin (d) after the acid value becomes less than 50.0 mgKOH / g is essential for solving the problems of the present invention. Printing ink using a resin having an acid value of 50.0 mgKOH / g or more and added with a resol type phenolic resin tends to be excessively emulsified, and causes scumming during printing. On the other hand, a printing ink using a resin having an acid value of less than 50.0 mgKOH / g and added with a resol type phenol resin has good emulsifying properties and can be stably printed for a long time.

  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 (polystyrene conversion, solvent: tetrahydrofuran) by gel permeation chromatography (GPC) is 5,000 to 300. About 10,000, more preferably 10,000 to 150,000. If it is 5,000 or more, the ink viscosity is suitable and misting is unlikely to occur, and if it is 300,000 or less, the resin has good solubility, so that the ink fluidity is favorable and the gloss is improved. To do. Regarding the solubility of the resin, No. 0 Solvent H (JX Nippon Oil & Energy Corporation) was used, and the resin / No. 0 Solvent H = 2g / 18g was dissolved by heating at 200 ° C. taking measurement. The lower the temperature at which white turbidity is, the better the compatibility between the resin and the solvent is, and a temperature of about 30 to 170 ° C is preferred.

  To the rosin-modified phenol resin (A) thus obtained, vegetable oils, petroleum-based solvents for ink, and gelling agents can be added and dissolved by heating, if necessary, to produce a lithographic printing ink varnish.

  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 solvent 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 solvent, and gelling agent in the varnish for lithographic printing ink may be determined appropriately according to the intended use. The proportion of the modified phenolic resin is about 5 to 75% by weight, the proportion of the vegetable oil is about 0 to 80% by weight, the proportion of the petroleum solvent is about 0 to 80% by weight, and the proportion of the gelling agent is 0 to 4%. %, Preferably about 0 to 3% by weight. Further, rosin-modified phenolic resin (A), rosin-modified phenolic resin produced by a method other than the present invention (may be other than the above weight average molecular weight), petroleum resin and the like can be used in combination.

  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 according to the present invention 5 to 75 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 0-5% 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.

  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-8320) manufactured by Tosoh Corporation. A calibration curve was prepared with a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C. Furthermore, in the present invention, “molecular weight” means a weight average molecular weight unless otherwise specified.

(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%.

(Resol type phenol resin production example 2)
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, and a xylene solution of a resol type phenol resin having a nonvolatile content of 60% (active ingredient 60%) was obtained.

(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 and 200 parts of petroleum resin “Petol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, and 50 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) and 10 parts of glycerin were added and reacted at 260 ° C. for 6 hours to obtain an acid value of 12.2. Further, 640 parts of a resol type phenolic resin A (as a solid content) was added dropwise at 250 ° C. over 6 hours, followed by reaction at 250 ° C. for 3 hours while removing xylene, a weight average molecular weight (Mw) 78240, acid value 14.5 Of resin 1 was obtained.

(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, 160 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), glycerin 40 The acid value was 30.5 by reacting at 260 ° C. for 3 hours. Further, 400 parts of a resol type phenol resin B (as solid content) was added dropwise at 250 ° C. over 3 hours, and then reacted at 250 ° C. for 3 hours while removing xylene, and a weight average molecular weight (Mw) 46400, acid value 18.8. Of resin 2 was obtained.

(Example 3 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 300 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), glycerin 50 The acid value was set to 7.6 by reacting at 270 ° C. for 8 hours. Further, 250 parts of a resol type phenol resin A (as a solid content) was added dropwise at 250 ° C. over 4 hours, followed by reaction at 250 ° C. for 2 hours while removing xylene, and a weight average molecular weight (Mw) 74200, acid value 16.6. Of resin 3 was obtained.

(Example 4 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 60 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.), glycerin 90 The acid value was 47.8 by reacting at 260 ° C. for 4 hours. Further, 100 parts of a resol type phenol resin A (as a solid content) was added dropwise at 250 ° C. over 1 hour, followed by reaction at 250 ° C. for 2 hours while removing xylene, and a weight average molecular weight (Mw) 32100, acid value 22.4. Of resin 4 was obtained.

(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 and 150 parts of petroleum resin “Petocol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, charged with 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) and 50 parts of glycerin, and reacted at 260 ° C. for 6 hours to give an acid value of 22.4. Further, 200 parts of a resol type phenol resin A (as solid content) was added dropwise at 250 ° C. over 2 hours, followed by reaction at 250 ° C. for 4 hours while removing xylene, a weight average molecular weight (Mw) of 56520, an acid value of 14.8. Of resin 5 was obtained.

(Example 6 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 360 parts of gum rosin, 300 parts of petroleum resin “Petol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, charged with 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) and 40 parts of glycerin, and reacted at 270 ° C. for 5 hours to give an acid value of 18.2. Further, 200 parts of resol type phenol resin B (as solid content) was added dropwise at 250 ° C. over 2 hours, followed by reaction at 250 ° C. for 5 hours while removing xylene, and a weight average molecular weight (Mw) of 24600, acid value of 14.6. Of resin 6 was obtained.

(Example 7 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 and 150 parts of petroleum resin “Petol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, charged with 110 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) and 40 parts of pentaerythritol, and reacted at 270 ° C. for 4 hours to give an acid value of 38.8. Further, 300 parts of a resol type phenol resin A (as a solid content) was added dropwise at 250 ° C. over 3 hours, followed by reaction at 250 ° C. for 4 hours while removing xylene, and a weight average molecular weight (Mw) 42100, acid value 21.4. Of resin 7 was obtained.

(Example 8 of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 360 parts of gum rosin and 50 parts of petroleum resin “Petol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, 350 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) and 40 parts of glycerin were added, and reacted at 260 ° C. for 5 hours to obtain an acid value of 18.5. Furthermore, 200 parts of resol type phenol resin A (as solid content) was added dropwise at 250 ° C. over 2 hours, followed by reaction at 250 ° C. for 2 hours while removing xylene, weight average molecular weight (Mw) 79700, acid value 16.8. Of resin 8 was obtained.

(Comparative example A of resin synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, 600 parts of gum rosin was melted at 200 ° C. while blowing nitrogen gas, and 340 parts of a resol type phenolic resin A (as a solid content) was 200 ° C. For 2 hours. Thereafter, the temperature was raised to 250 ° C. while removing xylene, and 60 parts of glycerin was added at 250 ° C. and reacted for 13 hours to obtain a resin A having a weight average molecular weight (Mw) of 46500 and an acid value of 19.8.

(Comparative Example B for Resin Synthesis)
In a four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer, melt 560 parts of gum rosin at 200 ° C. while blowing nitrogen gas, charge 60 parts of glycerin, and react at 260 ° C. for 6 hours. The acid value was 58.5. Further, 380 parts of a resol type phenol resin B (as solid content) was added dropwise at 250 ° C. over 3 hours, followed by reaction at 250 ° C. for 4 hours while removing xylene, and a weight average molecular weight (Mw) of 32200, an acid value of 18.8. Resin B was obtained.

(Comparative Example C 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 and 100 parts of petroleum resin “Petol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, charged with 60 parts of glycerin, and reacted at 270 ° C. for 5 hours to give an acid value of 24.4. Further, 200 parts of a resol type phenol resin A (as a solid content) was added dropwise at 250 ° C. over 3 hours, followed by reaction at 250 ° C. for 3 hours while removing xylene, a weight average molecular weight (Mw) 46200, an acid value of 20.2. Resin C was obtained.

(Comparative Example D 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 and 100 parts of petroleum resin “Petol 120 (trade name)” (manufactured by Tosoh Corporation: weight average molecular weight 1700) The mixture was melted at 200 ° C. while blowing nitrogen gas, charged with 100 parts of regenerated vegetable oil (manufactured by Marusho Co., Ltd.) and 50 parts of glycerin, and reacted at 260 ° C. for 3 hours to give an acid value of 62.4. Further, 250 parts of resol type phenolic resin B (as solid content) was added dropwise at 250 ° C. over 2 hours, followed by reaction at 250 ° C. for 2 hours while removing xylene, weight average molecular weight (Mw) 64210, acid value 17.6. Resin D was obtained.

  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-based solvent (AF solvent 7 manufactured by JX Nippon Oil & Energy Corporation), gelling agent (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) 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 varnishes 1 to 8 and varnishes A to D obtained by the above method, carbon pigment Mitsubishi Carbon MA7 (manufactured by Mitsubishi Chemical), and petroleum solvent (AF solvent 7 manufactured by JX Nippon Oil & Energy Corporation) The mixture composition of No. 3 was kneaded and dispersed using three rolls according to a conventional method, and inks of Examples 1 to 8 and Comparative Examples A to D were obtained.

  The lithographic printing inks obtained in the examples and comparative examples were evaluated for gloss value, fluidity and background stain by the following methods. The evaluation results are shown in Table 4.

<Evaluation of gloss value>
Gloss value is 60% gloss with gloss meter gloss meter model GM-26 (manufactured by Murakami Color Research Laboratory Co., Ltd.) with proof bow color developing machine and the same density on pearl coat manufactured by Mitsubishi Paper Industries. Was measured. The higher the value, the better the gloss.
(Evaluation criteria) ◎: 60 or more, ○: 50 or more to less than 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) A: 80 mm or more, B: 70 mm or more and less than 80 mm, X: less than 70 mm

<Evaluation of dirt>
A printing test was performed on 20,000 sheets of each ink using a Mitsubishi BT2-800 NEO off-wheel printing machine (manufactured by Mitsubishi Heavy Industries, Ltd.) at 800 rpm and printing paper of 66.5 kg of NPI-coated paper (manufactured by Nippon Paper Industries Co., Ltd.). The dampening water is a water dial that is 2% higher than the lower limit of the water width in order to compare the printing state near the lower limit of the water width using 1.5% tap water of AQUAMAG NS (Toyo Ink). Printing was performed with the values, and the presence or absence of smudges on the printed paper surface was confirmed.
(Evaluation criteria) Dirt generation: Yes, No dirt generation: No

  As Table 4 shows, an ink using a rosin-modified phenolic resin comprising a rosin polyol ester in which rosins (a), polyols (b), and regenerated vegetable oil (c) are reduced to an acid value of less than 50.0. The gloss was good and there was no scumming. Further, Examples 1 and 5 to 8 containing rosin-modified phenolic resins added with 5 to 30% by weight of a petroleum resin had remarkably good fluidity.

Claims (6)

  In the method for producing a rosin-modified phenol resin obtained by reacting a rosin polyol ester obtained by reacting a rosin (a), a polyol (b) and a regenerated vegetable oil (c) with a resol type phenol resin (d), A method for producing a rosin-modified phenolic resin (A), wherein the acid value of the rosin polyol ester when the resole-type phenolic resin (d) is reacted is less than 50.0 mgKOH / g.   The rosin-modified phenolic resin (A) is, in terms of weight to solid content, rosins (a) 5 to 75% by weight, polyol (b) 1 to 20% by weight, regenerated vegetable oil (c) 5 to 30% by weight and resole The method for producing a rosin-modified phenolic resin (A) according to claim 1, wherein the reaction is carried out at 15 to 85% by weight of the type phenol resin (d). The rosin polyol ester is obtained by reacting rosins (a), polyol (b), regenerated vegetable oil (c) and petroleum resin (e),
The rosin-modified phenol resin (A) is, in terms of the weight-solid content ratio, rosins (a) 5 to 74% by weight, polyol (b) 1 to 20% by weight, regenerated vegetable oil (c) 5 to 30% by weight, resole The production of rosin-modified phenolic resin (A) according to claim 1 or 2, characterized in that it is reacted with 15 to 85% by weight of phenolic resin (d) and 5 to 30% by weight of petroleum resin (e). Method.   The method for producing a rosin-modified phenolic resin (A) according to any one of claims 1 to 3, wherein the regenerated vegetable oil (c) is a vegetable oil obtained by regenerating the vegetable oil used for the production of food and drink.   A lithographic printing ink comprising a rosin-modified phenolic resin (A) produced by the production method according to claim 1.   A printed matter obtained by printing the lithographic printing ink according to claim 5 on a substrate.