JP5600898B2 - Resin solution for printing ink varnish and printing ink. - Google Patents

Description

  The present invention provides a printing ink varnish resin solution that exhibits excellent printability even during high-speed printing in lithographic printing, and is capable of obtaining a lithographic printing ink that is less likely to cause roller accumulation, water rod entanglement, misting, background staining, and the like. The present invention relates to a method for producing a vegetable oil-modified cyclopentadiene resin used for producing a resin solution for a printing ink varnish.

  Conventionally, as a lithographic printing ink, an oil-soluble phenol resin such as a rosin-modified phenol resin or the like is used in a hydrocarbon solvent having a boiling point of 200 ° C. or higher, or in a dry oil or semi-dry oil under heating and stirring. A lithographic ink using a waterless lithographic ink composition containing a modified phenolic resin obtained by extending a molecular chain with a rualkylphenol-formaldehyde initial condensate is known.

  Examples of the rosin-modified phenol resin used in the lithographic printing ink include, for example, a rosin-modified phenol resin obtained by reacting a rosin ester resin and a resole-type phenol resin at 260 ° C. for 2 to 3 hours, and rosin and a resole-type phenol resin. A rosin-modified phenolic resin obtained by reacting with a polyhydric alcohol at 250 ° C. for 10 hours is known.

  In the printing industry, increasing the printing speed has been studied in order to improve productivity. However, the lithographic printing ink obtained using the rosin-modified phenolic resin can be printed without any problem when printed at a normal printing speed, but at high speed printing, for example, at a high speed printing of 8 m / second or more, particularly 10 m / second. At the time of the above high-speed printing, there is a problem that roller accumulation, water rod entanglement, background contamination, etc. are remarkably easily generated in a short time.

  Moreover, it is calculated | required to use mineral oil with few content rates of an aromatic compound instead of mineral oil with much content of the aromatic compound used for printing ink for environmental reasons. As a printing ink varnish used for such a printing ink, for example, a modified cyclopentadiene resin composed of 20 to 80% by weight of a cyclopentadiene compound, 1 to 40% by weight of a natural resin acid and 31 to 70% by weight of a phenol resin is printed. The use as a binder resin for ink is disclosed (for example, see Patent Document 1).

  In Patent Document 1, for example, after reacting 33% by weight of dicyclopentadiene and 18 parts by weight of rosin with respect to a total of 100 parts by weight of dicyclopentadiene, rosin and resol type phenol resin in Example 5, Subsequently, 48 parts by weight of a resol type phenol resin is reacted to obtain a binder for printing ink.

  However, the printing ink obtained by using this printing ink binder easily generates mist, and further causes a phenomenon that the ink is scattered in the fountain solution or the ink is deposited on the roller.

Japanese Patent Laid-Open No. 06-016789

  An object of the present invention is to provide a lithographic printing ink that exhibits excellent printability even during high-speed printing, is less likely to cause roller accumulation, water rod entanglement, misting, background stains, etc. It is providing the printing ink obtained using the resin solution for printing ink varnishes, the manufacturing method of the vegetable oil modified cyclopentadiene resin for printing ink varnishes required for manufacture of this resin solution for printing ink varnishes, and this resin solution for printing ink varnishes.

  As a result of intensive studies to solve the above problems, the present inventor reacted cyclopentadiene with a drying oil and / or a semi-drying oil in a weight ratio of 100: 5 to 50 to produce cyclopentadiene and rosin. By using a rosin-modified phenolic resin obtained by reacting an ester resin and a phenolic resin as a binder for printing ink, it exhibits excellent printability even during high speed printing. A lithographic printing ink in which stains and the like are hardly generated is obtained, and the gloss of the printed matter is found to be good, and the present invention has been completed.

  That is, in the present invention, the cyclopentadiene compound (a1) and the drying oil and / or semi-drying oil (a2) are reacted at a weight ratio of (a1) :( a2) of 100: 5 to 50. A resin solution for a printing ink varnish comprising a rosin-modified phenol resin obtained by reacting an oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (C). To do.

  The present invention also provides a printing ink comprising the resin solution for printing ink varnish and a pigment.

  The resin solution for a printing ink varnish of the present invention exhibits excellent printability even during high-speed printing, and a lithographic printing ink is obtained in which roller accumulation, water rod entanglement, misting, background contamination, etc. are unlikely to occur. In addition, the printing ink of the present invention exhibits excellent printability even during high-speed printing, and is less likely to cause roller accumulation, water rod entanglement, misting, and background stains. Furthermore, according to the high-speed printing method of the present invention, it is possible to perform high-speed printing without occurrence of roller accumulation, water rod entanglement, misting, soiling, and the like.

  The oil-modified cyclopentadiene resin (A) used in the present invention comprises a cyclopentadiene compound (a1) and a drying oil and / or semi-drying oil (a2) in a weight ratio of (a1) :( a2) of 100: 5. It is obtained by reacting at a ratio of ˜50. If the drying oil and / or the semi-drying oil (a2) is used in an amount of less than 5 parts by weight based on 100 parts by weight of the cyclopentadiene compound (a1), it is not preferable because it is difficult to obtain a printing ink having a sufficient gloss. Further, when the drying oil and / or the semi-drying oil (a2) is used in an amount of more than 50 parts by weight with respect to 100 parts by weight of the cyclopentadiene compound (a1), the ink obtained tends to generate mist, This is not preferable because a phenomenon of ink scattering occurs or ink is deposited on a roller.

  Among the oil-modified cyclopentadiene resins (A) used in the present invention, the cyclopentadiene compound (a1) and the drying oil and / or semi-drying oil (a2) are 100: 10 to (a1) :( a2) in a weight ratio. What is obtained by reacting at a ratio of 40 shows excellent printability even during high-speed printing, is less likely to cause roller accumulation, water rod entanglement, misting, background stains, etc. It is preferable because a lithographic printing ink is obtained.

  Examples of the cyclopentadiene compound (a1) used in the preparation of the cyclopentadiene-modified rosin ester resin (A) include cyclopentadiene, dicyclopentadiene, and alkyl substituted derivatives thereof: cyclopentadiene, dicyclopentadiene, and alkyl substituted derivatives thereof. Dimers (including co-dimers); cyclopentadiene, dicyclopentadiene, trimers of these alkyl-substituted derivatives, and the like.

  Examples of the alkyl-substituted derivative include methylcyclopentadiene and the like. Examples of the co-dimer include cyclopentadiene-methylcyclopentadiene. The cyclopentadiene compound (a1) used in the present invention is preferably dicyclopentadiene.

  Among the drying oils and / or semi-drying oils (a2) used for the preparation of the cyclopentadiene-modified rosin ester resin (A), the drying oils include animal and vegetable oils having an iodine value of 130 or more, such as linseed oil, oil deer oil, safflower. Oil, Eno oil. Examples include drill oil, dehydrated castor oil, and polymers thereof. Semi-drying oils include animal and vegetable oils having an iodine value of 100 to 130, such as cottonseed oil, soybean oil, rice bran oil, corn oil, sesame oil, rapeseed oil, and polymers thereof. As the drying oil and / or semi-drying oil (a2), soybean oil and / or linseed oil is preferable, and linseed oil is more preferable.

  The oil-modified cyclopentadiene resin (A) used in the present invention comprises a cyclopentadiene compound (a1) and a drying oil and / or semi-drying oil (a2) in a weight ratio of (a1) :( a2) of 100: 5. This copolymerization obtained by reacting at a ratio of ˜50 is carried out by free radicals or preferably by heat, but this can be carried out in the absence or presence of a solvent.

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and tetrahydronaphthalene; aliphatic hydrocarbons such as isooctane; mineral spirits and alkylated benzene having a boiling range of 100 to 200 ° C.

  Examples of the catalyst that can be suitably used in the free radical polymerization include, for example, peroxides such as di-tert-butyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, and cumer hydroperoxide. Is mentioned. On the other hand, when the thermal polymerization is performed, it is preferable to perform the method at a high pressure because of the high reaction temperature. The pressure in the system is preferably up to 10 bar. It is also advantageous to carry out the reaction in an atmosphere of a gas inert under the reaction conditions, for example nitrogen or carbon dioxide, due to the functionality of the reaction product towards oxidation.

  The reaction of the cyclopentadiene compound (a1) with the drying oil and / or the semi-drying oil (a2) can be performed by various methods. For example, in the case of a relatively small batch, the cyclopentadiene compound (a1) and the drying oil and / or semi-drying oil (a2) are charged into the reaction system, and then they are heated to a desired temperature. Can be done. In the case of a relatively large batch, for example, drying oil and / or semi-drying oil (a2) is charged into the reaction system, this is heated to the reaction temperature, and then the cyclopentadiene compound (a1) is added. The method is convenient.

  When the cyclopentadiene compound (a1) is reacted with the drying oil and / or semi-drying oil (a2) in the presence of a solvent, the solvent is first introduced into the system and the solvent is heated. It is also possible to add drying oil and / or semi-drying oil (a2) and cyclopentadiene compound (a1) into the system.

  The reaction temperature between the cyclopentadiene compound (a1) and the drying oil and / or semi-drying oil (a2) is, for example, 200 to 300 ° C, preferably 230 to 270 ° C. After completion of the reaction, the resulting oil-modified cyclopentadiene resin (A) can be isolated as a solid by distilling off the solvent and unconverted monomer, if desired. These softening points are generally 40-200 ° C.

  Examples of the rosin ester resin (B) used in the present invention include those obtained by esterifying rosins with a polyhydric alcohol. Examples of rosins used herein include those that react with a resol type phenol resin, such as gum rosin, wood rosin, tall oil rosin, polymerized rosin, acid-modified rosin, and those purified by distillation or the like. Of these, gum rosin is preferred because it has excellent reactivity with a resole phenolic resin and a high-viscosity rosin-modified phenolic resin can be obtained.

  Accordingly, the rosin ester resin (B) used in the present invention is preferably a rosin ester resin obtained by esterifying gum rosin with a polyhydric alcohol.

  The acid-modified rosin is preferably modified with a dibasic acid or an anhydride thereof. Examples of the dibasic acid or its anhydride include fumaric acid, maleic acid, maleic anhydride, adipic acid, itaconic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and trimellitic anhydride. Acid, maleic acid and maleic anhydride are preferred.

  Examples of the polyhydric alcohol used for esterification of the rosins include glycerin, diglycerin, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, penta Examples include erythritol, dipentaerythritol, sorbitol, etc. Among them, glycerin and pentaerythritol are preferable.

  As a method for producing the rosin ester resin (B), for example, rosins and a polyhydric alcohol are present in an esterification catalyst at 200 to 300 ° C., preferably 250 to 285 ° C., more preferably 160 to 240 ° C. The method of making it react is mentioned. The ratio of the rosins and polyhydric alcohol used at this time is usually preferably a ratio such that the hydroxyl group in the polyhydric alcohol is 0.5 to 1.5 molar equivalents relative to 1 molar equivalent of the carboxylic acid in the rosins. Among these, a ratio of 0.7 to 1.0 molar equivalent is particularly preferable.

  As the rosin ester resin (B), a rosin ester resin having an acid value of 50 mgKOH / g or less is preferably used, and among them, a rosin ester resin having an acid value of 5 to 10 mgKOH / g or less is preferable.

  As the rosin ester resin (B) used in the present invention, a modified rosin ester resin (modified rosin ester resin) can also be used. As the modified rosin ester resin, for example, a cyclopentadiene modified rosin ester resin (B1) modified with a cyclopentadiene compound (b1) can be preferably used.

  The cyclopentadiene-modified rosin ester resin (B1) is obtained by reacting (copolymerizing) the cyclopentadiene compound (b1) and the rosin ester resin (B). This copolymerization is carried out by free radicals or preferably by heat, but this can be carried out in the absence or presence of a solvent.

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and tetrahydronaphthalene; aliphatic hydrocarbons such as isooctane; mineral spirits and alkylated benzene having a boiling range of 100 to 200 ° C.

  Examples of the catalyst that can be suitably used in the free radical polymerization include, for example, peroxides such as di-tert-butyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, and cumer hydroperoxide. Is mentioned. On the other hand, when the thermal polymerization is performed, it is preferable to perform the method at a high pressure because of the high reaction temperature. The pressure in the system is preferably up to 10 bar. It is also advantageous to carry out the reaction in an atmosphere of a gas inert under the reaction conditions, for example nitrogen or carbon dioxide, due to the functionality of the reaction product towards oxidation.

  The reaction of the cyclopentadiene compound (b1) and the rosin ester resin (B) can be performed by various methods. For example, in the case of a relatively small batch, the cyclopentadiene compound (b1) and the rosin ester resin (B) can be charged into the reaction system and then heated to a desired temperature. In the case of a relatively large batch, for example, it is convenient to add the rosin ester resin (B) into the reaction system, heat it to the reaction temperature, and subsequently add the cyclopentadiene compound (b1). .

  When the cyclopentadiene compound (b1) and the rosin ester resin (B) are reacted in the presence of a solvent, the solvent is first introduced into the system and the solvent is heated, and then preferably a liquid rosin ester resin. It is also possible to add (B) and the cyclopentadiene compound (b1) into the system.

  As reaction temperature of a cyclopentadiene compound (b1) and rosin ester resin (B), it is 200-300 degreeC, for example, Preferably it is 230-270 degreeC. After completion of the reaction, the obtained cyclopentadiene-modified rosin ester resin (B1) can be isolated as a solid by distilling off the solvent and unconverted monomer, if desired. These softening points are generally 40-200 ° C.

  Among the cyclopentadiene-modified rosin ester resin (B1), the cyclopentadiene compound (b1) and the rosin ester resin (B) are reacted at a weight ratio of (b1) :( B) of 2 to 50: 100. The resulting lithographic printing ink exhibits excellent printability even during high-speed printing, and is less likely to cause roller accumulation, water rod entanglement, misting, background stains, and the like. A cyclopentadiene compound ( What is obtained by making b1) and rosin ester resin (B) react by the ratio by which (b1) :( B) is 7-40: 100 by weight ratio is more preferable.

  As the phenol resin (C) used in the present invention, for example, a resol type phenol resin obtained by reacting phenols with a formaldehyde supply substance can be preferably used. The resol-type phenol resin is not particularly limited, and is a condensation product obtained by reacting phenols and formaldehyde in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, or an aqueous ammonia solution. And resolated products of novolak type phenolic resins, etc. Among them, phenols (P) and formaldehyde (F) can be used in the range of F / P (molar ratio) of 1.5 to 3.0. A condensate obtained by reacting in the presence is preferred. As the average number of nuclei of these resol type phenol resins, those having an average of 1 to 10 nuclei are usually used, and among them, those having an average of 3 to 6 nuclei as the main component are preferred. As a weight average molecular weight, the thing of 200-1600 is mentioned, Especially the thing of 700-1300 is preferable.

  The resol type phenolic resin has a high molecular weight (for example, polystyrene) by using a resin obtained by reacting phenols with a formaldehyde supply substance under high temperature (for example, 100 to 150 ° C.) and under pressure. The weight average molecular weight in terms of 55,000 to 1,000,000) is preferable because a high-viscosity rosin-modified phenolic resin can be obtained.

  Examples of the phenols include phenol, cresol, amylphenol, p-tertiary butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol, bisphenol A, and the like. Among them, p-tertiarybutylphenol, p An alkylphenol having a substituent having 4 to 12 carbon atoms in the para position such as octylphenol, p-nonylphenol, p-dodecylphenol and the like is preferable. Examples of the formaldehyde supply material include formaldehyde and rose formaldehyde.

  The rosin-modified phenol resin used in the present invention is obtained by reacting an oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (C). Specifically, for example, rosin-modified phenol resin obtained by the following production method can be mentioned.

  Production method (1): A method in which an oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (C) are condensed at 140 to 240 ° C. in a system containing an organic solvent.

  Production method (2): Rosin-modified phenol resin obtained by reacting oil-modified cyclopentadiene resin (A), rosin ester resin (B), and phenol resin (c1) at 160 to 240 ° C. without solvent. A method in which (X1) is subjected to a chain extension reaction with a phenol resin (C) at 160 to 240 ° C. in an organic solvent.

  Production method (3): An oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (c1) are reacted at 160 to 280 ° C. in the absence of a solvent and exceed 240 ° C. A method in which a rosin-modified phenolic resin (X2) obtained by reacting so that a reaction time at a temperature is less than 1 hour is subjected to a chain elongation reaction with a phenolic resin (C) at 160 to 240 ° C. in an organic solvent.

  As the organic solvent used in the production method (1), those commercially available as printing ink solvents can be used, and those having a boiling point of 160 ° C. or higher that are incompatible with water are suitable.

  Examples of these organic solvents include petroleum solvents having a boiling point of 200 ° C. or higher, such as paraffin solvents, isoparaffin solvents, naphthene solvents, and aromatic component-containing paraffin solvents. Specific examples include AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7 [above, Shin Nippon Oil Co., Ltd.], IP Solvent 2028, IP Solvent 2835 [above, Idemitsu Petrochemical ( Etc.]. Among these, the content of the aromatic component is preferably 1% by weight or less in view of recent environmental and hygiene considerations.

  In the said manufacturing method (1), as a temperature at the time of making oil modified cyclopentadiene resin (A), rosin ester resin (B), and a phenol resin (C) react, 180-230 degreeC is more preferable.

  In order to obtain the rosin-modified phenolic resin used in the present invention in the production method (1), it is preferable to add 0.01 to 3.0 parts by weight of a gelling agent in the reaction system in advance. This makes it possible to produce a varnish resin solution for printing ink that has a higher viscoelasticity.

  Preferred examples of the gelling agent include aluminum compounds such as aluminum alcoholate and aluminum soap, metal soaps such as manganese, cobalt, and zirconium, and gelling agents such as alkanolamines.

  In the method (2), the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) are reacted at 160 to 240 ° C. And rosin ester resin (B) and phenolic resin (c1) are preferred because they are fast and suitable industrially, and printing ink that is resistant to roller accumulation, water rod entanglement, background stains, etc. even during high-speed printing Is preferable. As said reaction temperature, 180-230 degreeC is more preferable. In order to reduce the decrease in high-speed printing suitability, the reaction between the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (c1) at a high temperature exceeding 240 ° C. needs to be less than 1 hour. Less than 5 hours are preferred, and none is more preferred. Most preferably, the reaction is carried out at 230 ° C or lower.

  In the production method (2), the ratio of use of the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) is as follows: the oil-modified cyclopentadiene resin (A) and the rosin ester resin (B ) And 15 to 55 parts by weight of the phenol resin (c1) with respect to 100 parts by weight in total.

  In the production method (2), the reaction between the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) is usually 150 to 240 ° C., preferably 180 to 230 ° C. Heated oil-modified cyclopentadiene resin (A) and rosin ester resin (B), and phenol resin (c1) heated to 60 to 150 ° C., preferably 90 to 140 ° C., are charged into the reaction vessel, respectively. The reaction is carried out at 160 to 240 ° C, preferably 180 to 230 ° C in a solvent. When the temperature after charging is less than 200 ° C., it is preferable to raise the temperature to 200 to 230 ° C. for reaction.

  In the reaction of the oil-modified cyclopentadiene resin (A), rosin ester resin (B), and phenol resin (c1), the phenol resin (c1) is typified by toluene, xylene, butanol or the like. A phenol resin solution dissolved in a solvent having a boiling point of 160 ° C. or lower can also be used. When using this phenol resin solution, instead of the heated phenol resin, a phenol resin solution heated to 40 to 60 ° C. is used, and the heated oil-modified cyclopentadiene resin (A), rosin ester resin (B), Each of the heated phenol resin solutions is put into a reaction vessel, and after raising the temperature while distilling off the solvent, the solvent is removed to make the reaction system solvent-free, and preferably until the temperature is raised to 200 ° C. A method in which the solvent is removed and the reaction is carried out at 180 to 240 ° C., preferably 200 to 230 ° C. in the absence of a solvent. However, it is preferable to use a solventless phenol resin as the phenol resin (c1).

  In the method (3), the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) are reacted at 160 to 280 ° C. in the absence of a solvent and exceed 240 ° C. By reacting so that the reaction time at temperature is less than 1 hour, the reaction between the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) is fast and industrially suitable. Therefore, it is preferable because a printing ink can be obtained in which roller accumulation, water rod entanglement, background smearing and the like are unlikely to occur even during high-speed printing. As the reaction conditions, it is more preferable that the reaction is performed at 180 to 260 ° C. and the reaction time at a temperature exceeding 240 ° C. is less than 0.5 hours.

  In the production method (3), the ratio of use of the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) is the same as that of the rosin ester resin (B) with the oil-modified cyclopentadiene resin (A). ) The ratio of phenol resin (c1) to 15 to 55 parts by weight with respect to 100 parts by weight in total.

  In the production method (3), the reaction between the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) is usually 150 to 280 ° C., preferably 200 to 260 ° C. An oil-modified cyclopentadiene resin (A) and a rosin ester resin (B) heated to 1 and a phenol resin (c1) heated usually at 60 to 150 ° C., preferably 90 to 140 ° C., are put into reaction vessels, respectively. The reaction is carried out at 160 to 280 ° C, preferably 180 to 260 ° C in the absence of a solvent. When the temperature after charging is less than 200 ° C, it is preferable to raise the temperature to 200 to 260 ° C for reaction.

  In this reaction, a phenol resin solution can also be used as the phenol resin (c1) in the same manner as in the production method (2). When using this phenol resin solution, instead of the heated phenol resin (c1), a solution of phenol resin heated to 40 to 60 ° C. is used, and the heated oil-modified cyclopentadiene resin (A) and rosin ester resin are used. Each of the heated phenolic resin solutions is put into a reaction vessel, heated while distilling off the solvent to remove the solvent to make the reaction system solvent-free, and preferably heated to 200 ° C. And a method of reacting at 180 to 280 ° C., preferably 200 to 260 ° C. without solvent.

  Therefore, in the production method (3), the reaction between the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (c1) in the absence of a solvent is an oil-modified cyclopentadiene resin (A ), The rosin ester resin (B), and the phenol resin (c1) from the first stage of the reaction in the absence of a solvent, and in the first stage of the reaction, even in the presence of a solvent, It includes the case where the solvent is removed during the reaction, and then the reaction is carried out in the absence of a solvent for 1 hour or longer, for example, at 200 ° C. or higher for 1 hour or longer. Among these, the solvent-free reaction is preferred from the initial stage of the reaction of the oil-modified cyclopentadiene resin (A), rosin ester resin (B), and phenol resin (c1) in the absence of solvent. .

  The phenol resin (c1) used for the preparation of the rosin-modified phenol resin (X1) or the rosin-modified phenol resin (X2) in the production method (2) or the production method (3) is exemplified as the phenol resin (C). What was done can be used preferably.

  As the rosin-modified phenolic resin used in the present invention, the rosin-modified phenolic resin obtained by the above production method (2) has no reaction at a high temperature exceeding 240 ° C. Therefore, decomposition of the reaction product or unreacted phenolic resin (C1 The high-speed printability estimated to be caused by the decomposition of the

  Among the rosin-modified phenol resins used in the present invention, in the production method (2) or production method (3), after obtaining the rosin-modified phenol resin (X1) or the rosin-modified phenol resin (X2), the rosin-modified phenol resin (X1) ) Or rosin-modified phenolic resin (X2) and phenolic resin (C) are subjected to chain elongation reaction at 160 to 240 ° C. in the organic solvent. By carrying out a chain extension reaction at 160 to 240 ° C., there is an advantage that the reaction between the rosin-modified phenol resin (X1) or the rosin-modified phenol resin (X2) and the phenol resin (C) is fast and industrially suitable. Moreover, it is preferable because a printing ink is obtained in which roller accumulation, water rod entanglement, background smearing, and the like are unlikely to occur even during high-speed printing. The reason for this is not clear, but at a temperature higher than 240 ° C., the reaction product is decomposed or unreacted simultaneously with the reaction between the rosin-modified phenol resin (X1) or the rosin-modified phenol resin (X2) and the phenol resin (B). The present inventors presume that the decomposition of the phenol resin (C) does not occur and the generated decomposition product does not deteriorate the high-speed printability.

  The reaction temperature between the rosin-modified phenol resin (X1) or rosin-modified phenol resin (X2) and the phenol resin (C) is preferably 180 to 230 ° C, and most preferably 190 to 220 ° C.

  As an organic solvent used by the said manufacturing method (2) and manufacturing method (3), the organic solvent etc. which are used by the said manufacturing method (1) are mentioned, for example.

  In the production method (1) or production method (2), the rosin-modified phenol resin (X1) and / or (X2) is subjected to a chain extension reaction with the resol type phenol resin (C) at 160 to 240 ° C. in an organic solvent. The rosin-modified phenol resin (X1) and / or (X2) used here is obtained by reacting an oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (c1). The melted rosin-modified phenolic resin (X1) and / or (X2) may be cooled and solidified, but the oil-modified cyclopentadiene resin (A), rosin ester resin (B), The molten rosin-modified phenolic resin (X1) and / or (X2) obtained by reacting with the phenolic resin (c1) is cooled and solidified. And no, it is preferably used in a molten state. In this case, the rosin-modified phenolic resin (X1) and / or (X2) in the molten state may be used after adjusting the temperature as long as the molten state can be maintained, or may be transferred while maintaining the molten state. It may be used after that.

  As the phenol resin (C) used in this case, any of the phenol resins (C1) used together with the cyclopentadiene-modified rosin ester resin (A) when synthesizing the rosin-modified phenol resins (X1) and (X2) is used. it can. Among such phenol resins (C), phenols (P) and formaldehyde (F) are reacted in the presence of an alkali catalyst within a range where F / P (molar ratio) is 1.5 to 3.0. The condensate obtained is preferred. Moreover, as a weight average molecular weight of a resol type phenol resin (B), the thing of 200-1600 is mentioned, Especially, the thing of 700-1300 is preferable.

  When the rosin-modified phenol resin (X1) and / or (X2) in the molten state is used in the production method (2) or the production method (3), for example, an oil-modified cyclopentadiene resin (A) and a rosin ester resin (B ) And phenolic resin (c1) are reacted in the absence of a solvent, and the rosin-modified phenolic resin (X1) and / or (X2) in a molten state is mixed with an organic solvent to bring the temperature of the reaction system to 240 ° C. Hereinafter, the temperature is preferably lowered to 160 to 240 ° C., and the rosin-modified phenolic resin (X1) and / or (X2) is dissolved in an organic solvent and mixed with the phenol resin (C). Until the weight average molecular weight reaches 100,000 or more, preferably 120,000 to 400,000 at 180 to 230 ° C., or the weight of resin solid / AF-7 / toluene The Gardner viscosity (25 ° C.) when mixed at a ratio such that the ratio is (40) / (9-11) / (50) is G or more, preferably 0.5 to 20 until it becomes I to Z. The chain extension reaction may be performed for a time, preferably 1 to 12 hours.

  In the production method (1), the amount of use of the oil-modified cyclopentadiene resin (A), the rosin ester resin (B), and the phenol resin (C) is [(A) + (B) :( C ) Is preferably 100: 15-55.

  The use ratio of the organic solvent in the production method (2) or the production method (3) is usually 2 to 100 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the rosin-modified phenolic resin (X1) and / or (X2). The proportion of the phenol resin (B) used is usually 2 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the rosin-modified phenol resin (X1) and / or (X2).

  Moreover, in the said manufacturing method (2) and manufacturing method (3), use of the sum total of phenol resin (C) and phenol resin (c1) with respect to the total weight of oil-modified cyclopentadiene resin (A) and rosin ester resin (B). The amount is preferably such that the weight ratio [(A) + (B)]: [(C) + (c1)] is 100: 15-55.

  The printing ink varnish obtained by using the resin solution for printing ink varnish obtained in the present invention includes, for example, a resin solution for printing ink varnish and a drying oil containing a rosin-modified phenol resin obtained by the methods (1) to (3). And / or the printing ink varnish (I) obtained by mixing the semi-drying oil at 160 to 240 ° C. or the rosin-modified phenolic resin (X1) and / or (X2) in an organic solvent in the form of the drying oil and / or the semi-drying oil. These are printing ink varnishes (II) formed by chain extension reaction with phenol resin (C) at 160 to 240 ° C. in the presence of drying oil, and these are further reacted with a gelling agent (D) if necessary. Also good.

  As the printing ink varnish (I), a rosin-modified phenol resin (X1) obtained by reacting an oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (c1) at 160 to 240 ° C. without solvent. ) And / or an oil-modified cyclopentadiene resin (A), a rosin ester resin (B), and a phenol resin (c1) at 160 to 280 ° C. without solvent and at a temperature exceeding 240 ° C. A resin solution for printing ink varnish obtained by subjecting a rosin-modified phenolic resin (X2) having a reaction time of less than 1 hour to chain elongation reaction with a resol type phenolic resin (B) at 160 to 240 ° C. in an organic solvent, and a drying oil And / or a semi-drying oil may be mixed at 160 to 240 ° C, preferably 180 to 230 ° C. Some of the resin component and a drying oil and / or semi-drying oil for printing ink varnish resin solution may be obtained by reaction. In addition, as the resin solution for printing ink varnishes used here, any of the above-described resin solutions for printing ink varnish can be used, and any of those preferable as the resin solution for printing ink varnish can be preferably used.

  Examples of the drying oil and / or semi-drying oil used in producing the printing ink varnish (I) include drying oil and semi-drying oil that can be used for the preparation of the oil-modified cyclopentadiene resin (A). It is done.

  The use ratio of the drying oil and / or semi-drying oil (C) is usually in the range of 1 to 100 parts by weight, preferably 3 to 80 parts by weight with respect to 100 parts by weight of the resin content in the resin solution for printing ink varnish. It is.

  When the printing ink varnish (I) is produced, the gelling agent (D) is added together with the drying oil and / or the semi-drying oil when the resin solution for the printing ink varnish and the drying oil and / or the semi-drying oil are mixed. After mixing and reacting the resin component in the resin solution for printing ink varnish and the gelling agent (D), or mixing the resin solution for printing ink varnish with drying oil and / or semi-drying oil, further gelling agent Mixing with (D) and reacting the resin component in this mixed solution with the gelling agent (D) at 60 to 240 ° C., preferably 80 to 200 ° C., results in a weight average molecular weight (Mw) and viscosity. It is preferable because it is a printing ink varnish that is high and has excellent emulsification resistance and mist resistance, and the latter case is particularly preferable. In this case, petroleum resins such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, and aromatic hydrocarbon resins may be used in combination.

  Examples of the gelling agent (D) include an organic aluminum compound, an organic titanate compound, an organic zinc compound, an organic strength lucium compound, and the like, among which an organic aluminum compound is preferable. Examples of organoaluminum compounds include aluminum alcoholates and aluminum chelate compounds. Among them, aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, ethyl acetylacetate aluminum di -N-Butyrate, ethyl acetyl acetate aluminum-n-butyrate, aluminum trisethyl acetyl acetate are preferred.

  The use ratio of the gelling agent (D) is usually 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the resin solution for printing ink varnish.

  Next, as the printing ink varnish (II), the rosin-modified phenolic resin (X1) and / or rosin-modified phenolic resin (X2) is used in an organic solvent in the presence of a drying oil and / or a semi-drying oil. What is necessary is just a chain extension reaction with the phenol resin (C) at ° C. Even if the resin component in the reaction system reacts with a part of the drying oil and / or semi-drying oil during the chain extension reaction. good. In addition, as the rosin modified phenolic resin (X1) and / or rosin modified phenolic resin (X2) used here, any of the rosin modified phenolic resin (X1) and / or rosin modified phenolic resin (X2) can be used, Any of those preferred for producing a resin solution for printing ink varnish can be preferably used.

  In addition, as the drying oil and / or semi-drying oil used here, any of the drying oil and / or semi-drying oil used in the production of the printing ink varnish (I) can be used in the same manner. In the range of usually 1 to 100 parts by weight, preferably 3 to 80 parts by weight with respect to 100 parts by weight of the total resin content of the modified phenolic resin (X1) and / or (X2) and the resol type phenolic resin (C). is there.

  In producing the printing ink varnish (II), the rosin-modified phenolic resin (X1) and / or (X2) is added at 160 to 240 ° C. in the presence of a drying oil and / or a semi-drying oil in an organic solvent. In the chain elongation reaction with the phenol resin (C), the gelling agent (D) is allowed to react with the drying oil and / or the semi-drying oil, or the chain is formed in the presence of the drying oil and / or the semi-drying oil. After the elongation reaction, it is further mixed with the gelling agent (D), and the resin component in this mixed solution and the gelling agent (D) are reacted at 60 to 240 ° C, preferably 80 to 240 ° C. The printing ink varnish has a high weight average molecular weight (Mw) and is excellent in emulsification resistance and mist resistance, and the latter case is particularly preferable. In this case, petroleum resins such as aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, and aromatic hydrocarbon resins may be used in combination.

  As the gelling agent (D) used here, any of the gelling agents (D) used in producing the printing ink varnish (I) can be used in the same manner, and the use ratio thereof is the rosin-modified phenolic resin (X1). ) And / or (X2) and 100 parts by weight of the total resin content of the resol type phenol resin (B), usually 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight. .

  Also, when the printing ink varnish (I) or (II) is produced, there is no reaction at a high temperature exceeding 240 ° C. in the rosin-modified phenol resins (X1) and (X2). It is preferable to use rosin-modified phenolic resin (X1) because the degradation of the high-speed printing suitability estimated to be caused by decomposition or decomposition of unreacted resol type phenolic resin is less.

  The printing ink varnishes (I) and (II) have a range in which the bubble viscosity at 25 ° C. is 2000 to 40000 dPa.S when the varnish is adjusted to contain 42 to 48% by weight of AF solvent 7 , Preferably 4000-15000 dPa.s. S range, emulsification rate [Emulsification rate (EC%) measured under conditions of 40 ° C., 1500 rpm, water supply rate 2 ml / min using a LITHOTRONIC EMULSIFICATION TESTER (NOVOCONTROL GmbH)] of 100% by weight or less The range is preferably 80% by weight or less, more preferably 5 to 50% by weight.

  The printing ink varnish obtained using such a resin solution for a printing ink varnish of the present invention can be made into a printing ink by kneading together with a pigment and, if necessary, other components. For example, pigments such as yellow, red, indigo, and black are directly dispersed in the printing ink varnish, or are mixed with a color base previously dispersed in a dispersing resin, or in the case of the flash method, mixed with a color base dispersed in a flash resin. By adding a friction resistance improver, a rheology control agent, an ink dryer, a drying inhibitor, an additional solvent, other resin components, etc. as necessary, kneading to adjust to an appropriate viscosity, It can be a lithographic printing ink such as sheet-fed ink or off-wheel ink. This lithographic ink can be used as a normal lithographic printing ink that uses fountain solution, or as a waterless lithographic printing ink that does not use fountain solution. These printing inks can also be used as newspaper printing inks.

  The printing ink obtained by using the printing ink varnish containing the resin solution for printing ink varnish of the present invention can be used in a known and commonly used lithographic printing machine, but in particular, the printing speed is 8 m / second or more, preferably 10 m / second or more. More preferably, when printing is performed in a range of 10 to 18 m / sec, the present invention exhibits excellent printability that cannot be achieved with conventional inks.

  The present invention will be described more specifically with reference examples, examples and comparative examples. In the examples, “part” and “%” are based on weight unless otherwise specified.

Preparation of Synthesis Example 1 [Oil-modified cyclopentadiene resin (A)] 850 g of 97% purity dicyclopentadiene (DCPD) and 250 g of linseed oil were charged into a 2-liter autoclave and stirred at 260 ° C. in a nitrogen atmosphere at 3.5 ° C. Heated for hours. After completion of the heating, the autoclave was cooled, and the content was distilled at 210 ° C./2 mmHg to obtain 920 g of an oil-modified cyclopentadiene resin (A-1). The softening point of the oil-modified cyclopentadiene resin (A-1) was 121 ° C., and the Gardner viscosity at 25 ° C. of a 70% toluene solution was Z4-Z52.

Preparation of Synthesis Example 2 [Rosin Ester Resin (B)] A pressurized reaction kettle equipped with a stirrer and a thermometer was charged with 1000 g of gum rosin with an acid value of 165 mgKOH / g and 28.8 g of maleic anhydride, and the temperature was raised. When the temperature reached 200 ° C., 114 g of pentaerythritol was added, and the temperature was further increased to 280 ° C. Thereafter, at 280 ° C., when the acid value became 15 mgKOH / g or less, the temperature was lowered to obtain a rosin ester resin (B-1). The rosin ester resin (B-1) had an acid value of 14.6 mgKOH / g, a softening point of 114 ° C., and a weight average molecular weight (Mw) of 1200.

Synthesis Example 3 [Preparation of phenol resin (C)]
A pressurized reaction kettle equipped with a stirrer and a thermometer was charged with 2060 g of p-octylphenol, dissolved by heating at 120 ° C., and 782.4 g of 92% paraformaldehyde powder (water content 8%) and 7.4 g of calcium hydroxide. And heated to 130 ° C. and reacted for 2 hours to obtain a resol type phenol resin (C-1). The obtained resol type phenol resin (C-1) had a polystyrene-reduced weight average molecular weight (Mw) of 900 as measured by GPC method.

Example 1
25 parts oil-modified cyclopentadiene resin (A-1), 75 parts rosin ester resin (B-1) and 15 parts aliphatic hydrocarbon resin (Marcaretz M-845D, petroleum resin manufactured by Maruzen Petrochemical Co., Ltd.) And kept at 260 ° C. To this mixture, 48 parts of a resol type phenolic resin (C-1) heated to 100 ° C. was added and mixed, and then the temperature was once lowered to about 210 ° C., and then the temperature was raised again to 245 ° C. The reaction was terminated when the temperature was increased from 240 to 245 ° C. for 20 minutes to obtain a rosin-modified phenolic resin. The obtained rosin-modified phenol resin had a Gardner viscosity of 25% at 50 ° C. in a toluene 50% solution of N—O, and the weight average molecular weight (Mw) of the resin was 40,000.

  Add 25 parts of AF Solvent No. 7 to 100 parts of the melted rosin-modified phenolic resin and keep the temperature at 200 ° C., and then add 5 parts of resole phenolic resin (C-1) to the same temperature for another 3 hours. The resultant reaction mixture solution was reacted until the same amount of toluene was added until the Gardner viscosity at 25 ° C. of the solution reached HI to obtain the resin solution for printing ink varnish of the present invention.

  To 100 parts of this resin solution, 32 parts of soybean oil was added, heated to 200 ° C. and mixed for 30 minutes. After adding 68 parts of AF Solvent No. 7 and 0.2 part of 2,6-di-tert-butyl-4-methylphenol (BHT) and stirring and mixing at 200 ° C. for 30 minutes, the viscosity was 6000-7500 dPa.s. The necessary amount of ethyl acetoacetate aluminum dinormal butyrate in the range of 0.5 to 1.5 parts is added at 160 ° C. so as to fall within the range of s, and the mixture is further heated and stirred for 1 hour to obtain the printing ink varnish of the present invention. A printing ink varnish [hereinafter abbreviated as varnish (1)] using a resin solution was obtained.

  The obtained varnish (1) had an emulsification rate (EC%) of 25% as measured with a LITOTRONIC EMULSIFICATION TESTER (NOVOCONTROL GmbH) at a stirring speed of 1500 rpm, a temperature of 40 ° C., and a water supply speed of 2 ml / min. It was.

  50 parts of the obtained varnish (1) and 15 parts of Carmine 6B [Red Pigment for Ink manufactured by Dainippon Ink & Chemicals, Inc.] were previously dispersed in 50 parts of a color base and dispersed in a dispersing resin and other additives. Add Solvent No. 7 and knead in 3 rolls to obtain ink (1). The resulting ink (1) is developed on art paper and the gloss is confirmed. The printed surface has good gloss. Was. In addition, 1.31 ml of ink (1) was placed on an incometer (manufactured by Toyo Seiki Co., Ltd.), and the ink was scattered on the white paper placed on the bottom and front of the roll when rotated at 42 ° C. and 2000 rpm for 2 minutes. Observation of (misting) confirmed that there was almost no ink scattering.

  Ink (1) was used to print at a printing speed of 10.4 m / sec on Mitsubishi LITHOPIA MAX AY-1000, and a roller pool of ink on the swim roller and water source roller 2 hours after the start of printing. When the state of the entanglement of the water rod was observed (high-speed printability), almost no entanglement between the roller pool and the water rod occurred.

Comparative Example 1
Add 15 parts of Marcaretz M-845D [Aliphatic hydrocarbon resin (petroleum resin) manufactured by Maruzen Petrochemical Co., Ltd.] to the rosin ester resin (B-1), mix and maintain at 260 ° C., warm to 100 ° C. 48 parts of the resol-type phenolic resin (C-1) added and mixed, once the temperature was lowered to about 210 ° C., then the temperature was raised again to 245 ° C. (temperature raised to 240-245 ° C.) The reaction was terminated at the time when the reaction time was 20 minutes, and abbreviated as rosin-modified phenolic resin (hereinafter referred to as RP resin (2M)). ] Was obtained. The obtained RP resin (2M) had a Gardner viscosity of a 50% toluene solution at 25 ° C. of N—O [weight average molecular weight (Mw) of resin content was 40,000. 〕Met.

While adding 25 parts of AF Solvent No. 7 to 100 parts of molten RP resin (2M) and maintaining the temperature at 200 ° C., Resole Resin (C-2) [Resol Resin (C-1) / AF Solvent No. 7 = 80/20] 5 parts was added and kept at the same temperature for 3 hours. When the same amount of toluene was added to the resulting reaction mixture solution, the Gardner viscosity at 25 ° C. of the solution was LM [resin content The weight average molecular weight (Mw) was 260,000. To obtain a resin solution (R′P1) for comparative printing ink varnish.

  Next, 32 parts of soybean oil was heated and mixed at 200 ° C. for 30 minutes with 100 parts of (R′P1), and then 68 parts of AF solvent No. 7 and 0.2 part of BHT were added and stirred and mixed at the same temperature for 30 minutes. , The viscosity is 6000-7500 dPa.s. Add the necessary amount of ethyl acetoacetate aluminum dinormal butyrate in the range of 0.5 to 1.5 parts at 160 ° C. so that it falls within the range of s, and heat and stir for 1 hour. Abbreviated as varnish (1 ′)].

  50 parts of varnish (1 ') and 15 parts of Carmine 6B [Red Pigment for Ink, manufactured by Dainippon Ink and Chemicals Co., Ltd.] were previously dispersed in 50 parts of a color base dispersed in a dispersing resin and other additives. Add AF solvent 7 and knead in 3 rolls to obtain ink (1). The resulting ink (1 ') is developed on art paper and the gloss is confirmed. Did not have. In addition, 1.31 ml of ink (1) was placed on an incometer (manufactured by Toyo Seiki Co., Ltd.), and the ink was scattered on the white paper placed on the bottom and front of the roll when rotated at 42 ° C. and 2000 rpm for 2 minutes. When observing (misting), ink scattering was remarkable.

  Ink (1) was used to print at a printing speed of 10.4 m / sec on Mitsubishi LITHOPIA MAX AY-1000, and a roller pool of ink on the swim roller and water source roller 2 hours after the start of printing. When observing the state of entanglement of the water rod (high-speed printability), the entanglement between the roller pool and the water rod was remarkable.

Claims (7)

Oil-modified cyclopentadiene obtained by reacting cyclopentadiene compound (a1), which is dicyclopentadiene, with linseed oil (a2) at a ratio of (a1) :( a2) of 100: 5 to 50 by weight ratio Containing a rosin-modified phenol resin obtained by reacting a resin (A) and a rosin ester resin (B) obtained by esterifying a gum rosin with a polyhydric alcohol and a phenol resin (C) which is a resol type phenol resin ; Characteristic resin solution for printing ink varnish. The ratio by which the weight ratio of (a1) :( a2) is 100: 10 to 40 of the cyclopentadiene compound (a1) in which the oil-modified cyclopentadiene resin (A) is dicyclopentadiene and linseed oil (a2). The resin solution for printing ink varnish according to claim 1, which is a resin obtained by reacting with a resin. The resin solution for a printing ink varnish according to claim 1, wherein the acid value of the rosin-modified phenolic resin is 5 to 10 mg KOH / g. The resin solution for printing ink varnish according to claim 1, wherein the rosin-modified phenol resin has a weight average molecular weight of 60,000 to 1,000,000. In the presence of a solvent, the rosin-modified phenol resin comprises an oil-modified cyclopentadiene resin (A) and a rosin ester resin (B) obtained by esterifying a gum rosin with a polyhydric alcohol and a phenol resin (C) which is a resol type phenol resin. The resin solution for printing ink varnish according to claim 1, which is a resin obtained by reacting at 140 to 240 ° C. The rosin-modified phenol resin is an oil-modified cyclopentadiene resin (A) and a rosin ester resin (B) obtained by esterifying gum rosin with a polyhydric alcohol and a phenol resin (C) which is a resol type phenol resin in a weight ratio [ The resin solution for a printing ink varnish according to any one of claims 1 to 5 , which is a resin obtained by reacting (A) + (B)] :( C) at a ratio of 100: 15 to 55. A printing ink comprising the resin solution for a printing ink varnish according to any one of claims 1 to 6 and a pigment.