JP5600897B2 - A printing ink varnish resin solution, a method for producing cyclopentadiene-modified rosin ester resin 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 cyclopentadiene-modified rosin ester resin used for producing the resin solution for printing ink varnish.

  Conventionally, as a lithographic printing ink, an oil-soluble phenolic resin such as a rosin-modified phenolic resin or the like in a hydrocarbon solvent having a boiling point of 200 ° C. or higher, or a drying oil or a semi-drying oil under heating and stirring is used as a resol type. A lithographic ink using a waterless lithographic ink composition containing a modified phenolic resin obtained by extending a molecular chain with a pararalkylphenol-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. A rosin-modified phenolic resin obtained by reacting a resin and a polyhydric alcohol at 250 ° C. for 10 hours is known.

  On the other hand, 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. A method of using it 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, this printing ink binder uses a large amount of dicyclopentadiene at 80 parts by weight per 100 parts by weight of rosin. For this reason, when ink is formed, mist is easily generated, and further, a phenomenon that ink is scattered in the fountain solution occurs, or ink is deposited on the roller.

Japanese Patent Laid-Open No. 06-016789

  An object of the present invention is to provide a printing ink varnish resin solution that exhibits excellent printability even during high-speed printing, and that can provide a lithographic printing ink that is less likely to cause roller pooling, water rod entanglement, misting, background staining, etc. It is in providing the printing ink obtained using the manufacturing method of the cyclopentadiene modified | denatured rosin ester resin for printing ink varnishes required for manufacture of the 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 inventors have found the following findings (1) to (3) and have completed the present invention.

  (1) The cyclopentadiene-modified rosin ester obtained by using a rosin ester resin as a rosin in the Patent Document 1 and further reacting a small amount of dicyclopentadiene with the rosin ester resin, contrary to the Patent Document 1. Is used to obtain a lithographic printing ink that exhibits excellent printability even during high-speed printing, and is less likely to cause roller accumulation, water rod entanglement, misting, background smudges, and the like.

  (2) The cyclopentadiene-modified rosin ester is prepared by reacting the cyclopentadiene compound (a1) and the rosin ester resin (a2) in a weight ratio of (a1) :( a2) of 2 to 50: 100. can get.

  (3) The printing ink comprising the printing ink varnish and the pigment described in (1) exhibits excellent printability even during high-speed printing, and has roller accumulation, water rod entanglement, misting, soiling, etc. Hard to occur.

  That is, the present invention provides a cyclopentadiene-modified rosin obtained by reacting a cyclopentadiene compound (a1) and a rosin ester resin (a2) at a weight ratio of (a1) :( a2) of 2 to 50: 100. The present invention provides a resin solution for printing ink varnish characterized by containing a rosin-modified phenol resin obtained by reacting an ester resin (A) with a phenol resin (B).

  The present invention also provides a printing ink varnish characterized by reacting the cyclopentadiene compound (a1) and the rosin ester resin (a2) in a weight ratio of (a1) :( a2) of 2 to 50: 100. The present invention provides a method for producing a cyclopentadiene-modified rosin ester resin.

  Furthermore, the present invention provides a printing ink comprising the resin solution for a 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.

  Furthermore, according to the method for producing a cyclopentadiene-modified rosin ester resin for printing ink varnish of the present invention, excellent printability is exhibited even during high-speed printing, and roller accumulation, water rod entanglement, misting, soiling, etc. occur. Therefore, it is possible to easily obtain a resin solution for a printing ink varnish used for preparing a printing ink that is difficult to perform.

The cyclopentadiene-modified rosin ester resin (A) used in the present invention has a weight ratio of the cyclopentadiene compound (a1) and the rosin ester resin (a2) such that (a1) :( a2) is 2 to 50: 100. Obtained by reaction. When the cyclopentadiene compound (a1) is used in an amount of more than 50 parts by weight with respect to 100 parts by weight of the rosin ester resin (a2), when ink is used, mist is likely to be generated, and further, ink is scattered in the dampening water. Or ink is deposited on the roller.

  Among the cyclopentadiene-modified rosin ester resins (A) used in the present invention, the ratio of (a1) :( a2) from 7 to 40: 100 by weight ratio of the cyclopentadiene compound (a1) and the rosin ester resin (a2). The lithographic printing ink obtained by reacting in step (1) exhibits excellent printability even during high-speed printing, and is free from roller accumulation, water rod entanglement, misting, and background staining.

  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.

  Examples of the rosin ester resin (a2) used for the preparation of the cyclopentadiene-modified rosin ester resin (A) 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 cyclopentadiene-modified rosin ester resin (A) used in the present invention is a cyclopentadiene-modified rosin ester resin obtained by reacting dicyclopentadiene with a rosin ester resin obtained by esterifying gum rosin with a polyhydric alcohol. Is preferred.

  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.

  Examples of the method for producing the rosin ester resin (a2) include esterification at 200 to 300 ° C., preferably 250 to 285 ° C., more preferably 160 to 240 ° C. in the presence of a rosin and a polyhydric alcohol in an esterification catalyst. 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 (a2), 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.

  The cyclopentadiene-modified rosin ester resin (A) used in the present invention has a weight ratio of the cyclopentadiene compound (a1) and the rosin ester resin (a2) such that (a1) :( a2) is 2 to 50: 100. Obtained by reaction (copolymerization). 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 (a1) and the rosin ester resin (a2) can be performed by various methods. For example, in the case of a relatively small batch, the cyclopentadiene compound (a1) and the rosin ester resin (a2) can be charged into the reaction system and then heated to a desired temperature. In the case of a relatively large batch, for example, a method in which the rosin ester resin (a2) is introduced into the reaction system, heated to the reaction temperature, and then the cyclopentadiene compound (a1) is added is convenient. .

  When the cyclopentadiene compound (a1) and the rosin ester resin (a2) 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 (a2) and the cyclopentadiene compound (a1) into the system.

  As reaction temperature of a cyclopentadiene compound (a1) and rosin ester resin (a2), it is 200-300 degreeC, for example, Preferably it is 230-270 degreeC. After completion of the reaction, the resulting cyclopentadiene-modified rosin ester 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.

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

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

  Production Method (2) Cyclopentadiene-modified rosin ester resin (A) and phenol resin (b1) are reacted in the presence of a solvent at 160 to 240 ° C. to rosin-modified phenol resin (X1), phenol resin (B) And chain extension reaction at 160 to 240 ° C. in the organic solvent.

  Production method (3) A reaction time of cyclopentadiene-modified rosin ester resin (A) and phenol resin (b1) at 160 to 280 ° C. in the absence of a solvent, and a reaction time at a temperature exceeding 240 ° C. is less than 1 hour. The rosin-modified phenolic resin (X2) is obtained by reacting in such a manner that the rosin-modified phenolic resin (X1) and the phenolic resin (B) are chain-extended at 160 to 240 ° C. in the 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 production method (1), a dry oil can be contained in the reaction system. The drying oil used in the present invention is not particularly limited, but it is possible to use linseed oil, polymerized linseed oil, dehydrated castor oil, soybean oil, tall oil, safflower oil, cinnamon oil, sesame oil, or the like. it can. As content of drying oil, 10-50 weight part is suitable with respect to 100 weight part of solid content in a varnish.

  In the said manufacturing method (1), as temperature at the time of making a cyclopentadiene modified rosin ester resin (A) and a phenol resin (B) 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 cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1) are reacted with the phenol resin (b1) at 160 to 240 ° C. This is preferable because it provides a printing ink that is fast and industrially suitable, and is capable of providing a printing ink that is less susceptible to roller accumulation, water rod entanglement, background smearing, etc. even during high-speed printing. 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 (b1) 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 use ratio of the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1) is such that the phenol resin (b1) is 100 parts by weight of the cyclopentadiene-modified rosin ester resin (A). The ratio is 10 to 100 parts by weight, preferably 20 to 80 parts by weight.

  In the reaction of the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1), the cyclopentadiene-modified rosin ester resin (A) heated to 150 to 240 ° C., preferably 180 to 230 ° C., Usually, the phenol resin (b1) heated to 60 to 150 ° C., preferably 90 to 140 ° C., is charged into the reaction vessel and reacted at 160 to 240 ° C., preferably 180 to 230 ° C. in the absence of 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 between the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1), the phenol resin (b1) is a solvent having a boiling point represented by toluene, xylene, butanol or the like of 160 ° C. or less. A dissolved phenol resin solution 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 cyclopentadiene-modified rosin ester resin (A) and the heated phenol resin solution are respectively used. After putting in the reaction vessel and elevating the temperature while distilling off the solvent to remove the solvent to make the reaction system solvent-free, the solvent is preferably removed until the temperature is raised to 200 ° C. A method of reacting at a lower temperature of 180 to 240 ° C., preferably 200 to 230 ° C. is exemplified. However, it is preferable to use a solvent-free phenol resin as the phenol resin (b1).

  In the method (3), the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1) are reacted at 160 to 280 ° C. without solvent, and the reaction time at a temperature exceeding 240 ° C. is less than 1 hour. It is preferable that the reaction between the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1) is fast and industrially suitable, and the roller stays even during high-speed printing, entangles water rods, and soils. This is preferable because a printing ink that does not easily generate a printing ink can be obtained. 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 use ratio of the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1) is such that the phenol resin (b1) is 100 parts by weight of the cyclopentadiene-modified rosin ester resin (A). The ratio is 10 to 100 parts by weight, preferably 20 to 80 parts by weight.

  In the production method (3), in the reaction of the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1), the cyclopentadiene-modified rosin ester heated to 150 to 280 ° C., preferably 200 to 260 ° C. The resin (A) and a phenol resin heated to usually 60 to 150 ° C., preferably 90 to 140 ° C., are respectively charged into the reaction vessel, and reacted at 160 to 280 ° C., preferably 180 to 260 ° C. without solvent. Let 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 as well, a solution of a phenol resin can be used as the phenol resin (b1), as in the production method (2). When using this phenol resin solution, instead of the heated phenol resin, a solution of phenol resin heated to 40 to 60 ° C. is used, and the heated cyclopentadiene-modified rosin ester resin (A) and the heated phenol resin solution Each was put into a reaction vessel, and the temperature was raised while distilling off the solvent to remove the solvent to make the reaction system solvent-free, and then preferably the solvent was removed until the temperature was raised to 200 ° C. The method of making it react at 180-280 degreeC under a solvent-free, Preferably it is 200-260 degreeC is mentioned.

  Therefore, in the production method (3), the reaction between the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (b1) in the absence of a solvent is the reaction between the cyclopentadiene-modified rosin ester resin (A) and the phenol resin. In the first stage of the reaction, even if the reaction is in the presence of a solvent, the solvent is removed in the middle of the reaction, and then in the absence of solvent for 1 hour or more, for example, The case of reacting at 200 ° C. or higher for 1 hour or longer is also included. In these, the case where it is the reaction under solvent-free from the first step of reaction of a cyclopentadiene modified rosin ester resin (A) and a phenol resin is preferable.

  In addition, examples of the phenol resin (b1) used for the preparation of the rosin-modified phenol resin (X1) and the rosin-modified phenol resin (X2) in the production method (2) and the production method (3) include the phenol resin (B). 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., so that decomposition of the reaction product or unreacted phenolic resin (b1 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 (B) are subjected to a chain extension reaction at 160 to 240 ° C. in the organic solvent. By carrying out a chain extension reaction at 160 to 240 ° C., the reaction of the rosin-modified phenol resin (X1) or the rosin-modified phenol resin (X2) with the phenol resin (B) is quick 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 (B) 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 (B) 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 elongation reaction with the resol type phenol resin (B) at 160 to 240 ° C. in an organic solvent. Well, the rosin-modified phenol resin (X1) and / or (X2) used here is a rosin-modified resin in a molten state obtained by reacting the cyclopentadiene-modified rosin ester resin (A) with the phenol resin (b1). A phenol resin (X1) and / or (X2) that has been cooled and solidified may be used, but in a molten state obtained by reacting the cyclopentadiene-modified rosin ester resin (A) with the phenol resin (b1). A certain rosin-modified phenolic resin (X1) and / or (X2) is used in a molten state without being cooled and solidified. Preferred. 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 (B) used in this case, any of the resole-type phenol resins (b1) used together with the cyclopentadiene-modified rosin ester resin (A) when synthesizing the rosin-modified phenol resins (X1) and (X2). Can also be used. Among such resol type phenolic resins (B), phenols (P) and formaldehyde (F) are used in the presence of an alkali catalyst within a range where F / P (molar ratio) is 1.5 to 3.0. A condensate obtained by reaction 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, cyclopentadiene-modified rosin ester resin (a1) and phenol resin (b1) Rosin-modified phenolic resin (X1) and / or (X2) in a molten state obtained by reacting with an organic solvent, and the temperature of the reaction system is 240 ° C. or lower, preferably 160 to 240 ° C. The rosin-modified phenolic resin (X1) and / or (X2) is dissolved in an organic solvent and mixed with the phenolic resin (B), and the weight average molecular weight is 160 to 240 ° C, preferably 180 to 230 ° C. 100,000 or more, preferably 120,000 to 400,000, or the weight ratio of resin solid / AF-7 / toluene is (40) / (9 11) / (50) Gardner viscosity (25 ° C.) when mixed at a ratio of G or more, preferably 0.5 to 20 hours, preferably 1 to 12 hours until I to Z An extension reaction may be performed.

  In the production method (1), the use amount of the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (B) is preferably a ratio in which (A) :( B) is 100: 15 to 55 by weight ratio. .

  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), the total amount [(B) + (b1)] of cyclopentadiene modified rosin ester resin (A), phenol resin (B), and phenol resin (b1); Is preferably used in a weight ratio of (A): [(B) + (b1)] of 100: 15 to 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 (C) at 160 to 240 ° C. or the rosin-modified phenolic resin (X1) and / or (X2) in an organic solvent, / Or printing ink varnish (II) formed by chain extension reaction with resol type phenol resin (B) at 160 to 240 ° C. in the presence of semi-drying oil (C), and these are further gelling agent (D) if necessary It may have been reacted with.

  As the printing ink varnish (I), a rosin-modified phenol resin (X1) obtained by reacting a cyclopentadiene-modified rosin ester resin (a1) and a phenol resin (b1) at 160 to 240 ° C. without solvent, and / or A rosin-modified phenol obtained by reacting a cyclopentadiene-modified rosin ester resin (a1) and a phenol resin (b1) at 160 to 280 ° C. without solvent and having a reaction time at a temperature exceeding 240 ° C. of less than 1 hour. Resin solution for printing ink varnish obtained by subjecting resin (X2) to chain elongation reaction with resol type phenol resin (B) at 160 to 240 ° C. in an organic solvent, and drying oil and / or semi-drying oil (C) 160 to What is necessary is just to mix at 240 degreeC, Preferably it is 180-230 degreeC, and for printing ink varnish at the time of mixing Resin component and a drying oil and / or semi-drying oils in fat solution (C) a part of or may be reacted. 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.

  Among the drying oil and / or semi-drying oil (C) used in producing the printing ink varnish (I), as the drying oil, animal and vegetable oils having an iodine value of 130 or more, such as flaxseed oil, sika 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.

  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 resin solution for the printing ink varnish and the drying oil and / or semi-drying oil (C) are mixed together with the drying oil and / or the semi-drying oil (C). Mixing agent (D) and reacting resin content in resin solution for printing ink varnish with gelling agent (D), or the resin solution for printing ink varnish and drying oil and / or semi-drying oil (C) Is mixed with the gelling agent (D), and the resin component in the mixed solution and the gelling agent (D) are reacted at 60 to 240 ° C, preferably 80 to 200 ° C. The weight average molecular weight (Mw) and viscosity are high, and it is preferable because it becomes a printing ink varnish 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.

  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) in an organic solvent in the presence of a drying oil and / or a semi-drying oil (C), What is necessary is just what is made to carry out chain | strand extension reaction with a resole type phenol resin (B) at 160-240 degreeC, and is a part of resin in a reaction system and dry oil and / or semi-dry oil (C) in chain | strand extension reaction May have reacted. 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.

  Further, as the drying oil and / or semi-drying oil (C) used here, any of the drying oil and / or semi-drying oil (C) used in producing the printing ink varnish (I) can be used in the same manner. The use ratio is usually 1 to 100 parts by weight, preferably 3 to 80 parts per 100 parts by weight of the total resin content of the rosin-modified phenolic resin (A1) and / or (A2) and the resol type phenolic resin (B). It is a range which becomes a weight part.

  When the printing ink varnish (II) is produced, the rosin-modified phenolic resin (X1) and / or (X2) is added in an organic solvent in the presence of a drying oil and / or a semi-drying oil (C). In the chain elongation reaction at 240 ° C. with the resol type phenol resin (B), the gelling agent (D) is allowed to react with the drying oil and / or the semi-drying oil (C), and the drying oil and / or After the chain elongation reaction in the presence of the semi-drying oil (C), it is further mixed with the gelling agent (D), and the resin component and the gelling agent (D) in this mixed solution are mixed at 60 to 240 ° C. Preferably, the reaction at 80 to 240 ° C. is preferable because a printing ink varnish having a high weight average molecular weight (Mw) and excellent emulsification resistance and mist resistance is obtained, 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 varnish (I), (II) is a range in which the cell viscosity at 25 ° C. is 2000 to 40,000 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.

Synthesis Example 1 (Preparation of resol type phenol resin)
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 allowed to react for 2 hours, and resol type phenol resin [hereinafter abbreviated as “resole resin (1)”. Was prepared. The obtained resole resin (1) had a polystyrene-reduced weight average molecular weight (Mw) of 900 as measured by GPC method.

Synthesis Example 2 (Preparation of rosin ester resin)
In a four-necked flask equipped with a stirrer, reflux condenser and thermometer, 1000 g of gum rosin having an acid value of 165 mgKOH / g and 28.8 g of maleic anhydride were charged, and when the temperature reached 200 ° C., the temperature was 114 g of pentaerythritol. The mixture was further heated to 280 ° C. Thereafter, when the acid value became 15 mg KOH / g or less at 280 ° C., the temperature was lowered and rosin ester resin [hereinafter abbreviated as “RE resin (1)”. ] Was obtained. The obtained RE resin (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.

Example 1
After adding 15 parts of dicyclopentadiene (DCPD) to 100 parts of RE resin (1), the vessel was sealed, mixed, heated to 260 ° C. and held for 1 hour to react RE resin (1) with dicyclopentadiene. To obtain a cyclopentadiene-modified rosin ester resin. After 1 hour, the vessel was unsealed, 48 parts of resole resin (1) heated to 100 ° C. was added to the reaction mixture, and the temperature inside the reaction system was once lowered to 210 ° C. and then increased again. The reaction was terminated when the temperature was raised to 245 ° C. over 20 minutes, and rosin-modified phenol resin [hereinafter abbreviated as RP resin (1M)]. ] Was obtained. The obtained RP resin (1M) had a Gardner viscosity of a 50% toluene solution at 25 ° C. of GH, and the weight average molecular weight (Mw) of the resin was 40,000.

Add 100 parts of melted RP resin (1M) to 25 parts of AF Solvent No. 7 [Non-Aroma Solvent for Ink manufactured by Hitachi Mitsubishi Corporation] and keep the temperature at 200 ° C. In addition, it was kept at the same temperature for further 3 hours, and RP resin (1M) and resole resin (2) [resole resin (1) / AF solvent No. 7 = 80/20] were added and reacted to obtain. When the same amount of toluene was added to the reaction mixture solution, the Gardner viscosity at 25 ° C. of the solution was KL [weight average molecular weight (Mw) of resin component was 260,000. The resin solution for printing ink varnish (RP1) of the present invention containing a rosin-modified phenol resin obtained by reacting a cyclopentadiene-modified rosin ester resin and a phenol resin was obtained.

  Next, 32 parts of soybean oil was heated and mixed at 200 ° C. for 30 minutes with 100 parts of RP (1), then 68 parts of AF solvent 7 and 2,6-di-tert-butyl-4-methylphenol (BHT). ) After adding 0.2 parts and stirring and mixing at 200 ° C. for 30 minutes, the viscosity is 6000-7500 dPa.s. The required amount of ethyl acetoacetate aluminum dinormal butyrate in the range of 0.5 to 1.5 parts was added at 160 ° C. so as to fall within the range of s, and the mixture was heated and stirred for 1 hour to obtain a printing ink varnish [hereinafter referred to as varnish ( Abbreviated as 1)].

  The obtained printing ink varnish (1) has an emulsification rate (EC%) of 25% as measured by a LITHOTRONIC EMULSIFITION TESTER (NOVOCONTROL GmbH) at a stirring speed of 1500 rpm, a temperature of 40 ° C., and a water supply speed of 2 ml / min. there were.

  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.

  Also, using ink (1), printing was performed at 10.4 m / sec. With Mitsubishi LITHOPIA MAX AY-1000, and ink pools on the swim roller and water source roller 2 hours after the start of printing. As a result of observing the state of entanglement between the water rod and the water rod (high-speed printability), almost no entanglement between the roller pool and the water rod occurred.

Comparative Example 1
Resole resin heated to 100 ° C. to a mixture of 15 parts of Marrelets M-845D (Maruzen Petrochemicals aliphatic hydrocarbon resin (petroleum resin)) added to RE resin (1) and mixed and maintained at 260 ° C. (1) When 48 parts are added and mixed, the temperature is once lowered to about 210 ° C., and then the temperature is raised again to 245 ° C. (temperature raising time from 240 to 245 ° C. for 20 minutes). The reaction was terminated and rosin-modified phenol resin [hereinafter abbreviated 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.

Add 25 parts of AF Solvent No. 7 to 100 parts of molten RP resin (2M) and keep the temperature at 200 ° C., add 5 parts of resole resin (2) and hold at the same temperature for another 3 hours. When the same amount of toluene was added to the obtained reaction mixture solution, the Gardner viscosity at 25 ° C. of the solution was LM [weight average molecular weight (Mw) of resin 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 (11)

The cyclopentadiene compound (a1), which is dicyclopentadiene, and the rosin ester resin (a2) obtained by esterifying gum rosin with a polyhydric alcohol have a weight ratio of (a1) :( a2) of 2 to 50: 100. A printing ink varnish comprising a rosin-modified phenol resin obtained by reacting a cyclopentadiene-modified rosin ester resin (A) obtained by reacting at a ratio with a phenol resin (B) which is a resol type phenol resin Resin solution. The cyclopentadiene-modified rosin ester resin (A) is a cyclopentadiene compound (a1), which is dicyclopentadiene, and a rosin ester resin (a2) obtained by esterifying gum rosin with a polyhydric alcohol in a weight ratio of (a1) :( The resin solution for printing ink varnish according to claim 1, which is a resin obtained by reacting a2) at a ratio of 7 to 40: 100. 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 50,000 to 1,000,000. 2. The resin obtained by reacting the rosin-modified phenol resin with a cyclopentadiene-modified rosin ester resin (A) and a phenol resin (B) which is a resol type phenol resin at 160 to 240 ° C. in the presence of a solvent. Resin solution for printing ink varnish. The rosin-modified phenol resin is made to react the cyclopentadiene-modified rosin ester resin (A) and the phenol resin (B) which is a resole type phenol resin in a weight ratio (A) :( B) of 100: 15 to 55. The resin solution for printing ink varnishes according to any one of claims 1 to 5 , wherein the resin solution is obtained as described above. The rosin-modified phenol resin is a resole type resin obtained by reacting cyclopentadiene-modified rosin ester resin (A) and phenol resin (b1) at 160 to 240 ° C. in the presence of a solvent. The resin solution for a printing ink varnish according to claim 1, which is a resin obtained by subjecting a phenol resin (B), which is a phenol resin, to a chain extension reaction in the organic solvent at 160 to 240 ° C. The rosin-modified phenol resin is a cyclopentadiene-modified rosin ester resin (A) , a phenol resin (B) that is a resol type phenol resin, and a phenol resin (b1) in a weight ratio of (A): [(B) + ( The resin solution for a printing ink varnish according to claim 7, which is a resin obtained by reacting at a ratio of b1)] of 100: 15 to 55. Ratio in which (a1) :( a2) is 2 to 50: 100 by weight ratio of cyclopentadiene compound (a1) which is dicyclopentadiene and rosin ester resin (a2) obtained by esterifying gum rosin with polyhydric alcohol A process for producing a cyclopentadiene-modified rosin ester resin for printing ink varnish, characterized by reacting with Ratio in which (a1) :( a2) is 7 to 40: 100 by weight ratio of cyclopentadiene compound (a1) which is dicyclopentadiene and rosin ester resin (a2) obtained by esterifying gum rosin with polyhydric alcohol A process for producing a cyclopentadiene-modified rosin ester resin for a printing ink varnish according to claim 9, which is reacted in the step. A printing ink comprising the resin solution for a printing ink varnish according to any one of claims 1 to 8 and a pigment.