JP2007002165A - Resin composition for printing ink varnish, printing ink varnish and printing ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a printing ink varnish, suitably applicable to both a sheet-feed ink and a web offset ink, to provide a printing ink varnish using the composition and to provide a printing ink using the varnish. <P>SOLUTION: The resin composition for a printing ink varnish is obtained by reacting (A) a rosin ester resin prepared by esterifying a resin which may be acid-modified with a polyhydric alcohol, and (B) a resol type phenol resin in (C) a reaction solvent containing (c) ≥70 wt.% drying oil and/or semi-drying oil at 160-240°C. The varnish is prepared by mixing the composition with (D) a hydrocarbon-based solvent. The printing ink contains the varnish and a pigment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a printing ink varnish resin solution that can be suitably used for both sheet-fed ink and off-wheel ink and is also suitable for flushing, a printing ink varnish formed using this printing ink varnish resin composition, and The present invention relates to a printing ink using this printing ink varnish.

  As a lithographic printing ink varnish, for example, a resin varnish for printing ink obtained by condensing a rosin ester resin and a phenol formaldehyde initial condensate at 140 to 240 ° C. in a system containing a solvent is known, and its molecular weight is large. There is a description that a printing ink varnish having a high softening point and excellent solubility in an ink solvent and a printing ink excellent in high-speed printing suitability can be obtained (for example, see Patent Document 1).

  However, the lithographic printing ink varnish described in Patent Document 1 reacts with a rosin ester resin and a phenol formaldehyde initial condensate in a solvent, and therefore has a boiling point depending on the use such as for sheet-fed ink or for off-wheel ink. It was necessary to use a different solvent, and there was a drawback that it was inferior in versatility. For example, a printing ink using a varnish obtained by reacting in a solvent having a relatively high boiling point is suitable for a sheet-fed ink, but as an off-ring ink, the solvent has a high boiling point, so that the drying property is inferior. On the contrary, printing ink using varnish obtained by reacting in a solvent having a relatively low boiling point is suitable for off-wheel ink, but as sheet-fed ink, the boiling point of the solvent is low. In addition, the ink transfer from the roller to the roller tends to be unstable, and problems such as poor stability during printing tend to occur, and the versatility is poor.

JP-A-10-088052 (page 1-2)

  An object of the present invention is to provide a resin composition for printing ink varnish that can be suitably used for both sheet-fed ink and off-wheel ink, a printing ink varnish using the resin composition for printing ink varnish, and the printing ink varnish. It is in providing the printing ink which uses this.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a rosin ester resin and a resole-type phenol resin are used as a reaction solvent or drying oil and / or semi-drying oil and / or semi-drying oil (c) only. In a reaction solvent containing a large amount of drying oil (c), the composition obtained by reacting at 160 to 240 ° C. is a resin composition containing a printing ink varnish resin and a reaction solvent. Alternatively, a solvent component other than the semi-drying oil (c), for example, a solvent such as AF Solvent No. 6 or AF Solvent No. 7 is not contained or contained in a small amount. It is possible to select a suitable solvent for each printing method such as printing and off-wheel printing, and it is versatile. This resin composition is a printing ink for sheet-fed ink and off-ring ink. It is suitable for use as an ink, and by using this printing ink varnish, it is suitable as a sheet-fed ink, an off-wheel ink, etc., and it is easy to obtain a printing ink with excellent drying properties and high stability during printing. The headline and the present invention were completed.

  That is, the present invention provides a rosin ester resin (A) obtained by esterifying an acid-modified rosin with a polyhydric alcohol and a resole type phenol resin (B), a drying oil and / or a semi-drying oil. The present invention provides a resin composition for printing ink varnish characterized by being reacted at 160 to 240 ° C. in a reaction solvent (C) having a content of (c) of 70% by weight or more.

  Further, the present invention comprises a printing ink varnish characterized by mixing the resin composition for printing ink varnish and a hydrocarbon solvent (D), and the printing ink varnish and a pigment. The present invention provides a printing ink characterized by the above.

  The resin composition for a printing ink varnish of the present invention is a highly versatile one that can be suitably used for both sheet-fed ink and off-wheel ink, and is a printing ink using a printing ink varnish obtained using the same. Has excellent drying properties and high stability during printing.

  The rosin ester resin (A) used in the present invention is a rosin ester resin obtained by esterifying a rosin that may be acid-modified with a polyhydric alcohol. As the rosin that may be acid-modified used here, Are those that react with the resol type phenol resin (B), such as gum rosin, wood rosin, tall oil rosin, polymerized rosin, rosins purified by distillation, etc., and these rosins are acid-modified. Acid-modified rosins and the like, and acid-modified rosins are preferable. Also, gum rosin and acid-modified gum rosin are preferred because they are excellent in reactivity with resol-type phenol resins and can provide a high-viscosity rosin-modified phenol resin.

  As the acid-modified rosins, those obtained by modifying rosins such as gum rosin, wood rosin, tall oil rosin, polymerized rosin, and purified products thereof with monobasic acids having unsaturated groups, dibasic acids or anhydrides thereof are preferable. . Examples of the monobasic acid, dibasic acid or anhydride thereof having an unsaturated group include 1 in one molecule such as (meth) acrylic acid, an adduct of 2-hydroxyethyl (meth) acrylate and succinic anhydride. Compound having both α, β-ethylenically unsaturated group and one carboxyl group; one α, β- per molecule such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride Examples thereof include compounds having both an ethylenically unsaturated group and two carboxyl groups or no hydroxyl groups thereof, among which fumaric acid, maleic acid and maleic anhydride are preferred. The amount of monobasic acid, dibasic acid or anhydride thereof having an unsaturated group when acid-modifying rosins is usually 1 to 30 parts by weight with respect to 100 parts by weight of rosins. 1 to 20 parts by weight is preferable because a printing ink excellent in the above can be obtained.

  Examples of the polyhydric alcohol include glycerin, diglycerin, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol. Among them, glycerin and pentaerythritol are preferable.

  The rosin ester resin (A) is a resin obtained by reacting with a polybasic acid not having an α, β-ethylenically unsaturated group for the purpose of increasing its molecular weight, for example, acid-modified. Alternatively, a polybasic acid having no α, β-ethylenically unsaturated group may be used in combination when esterifying rosins with polyhydric alcohols or acid-modifying rosins. Examples of the polybasic acid having no α, β-ethylenically unsaturated group include succinic acid, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and trimellitic anhydride. The amount of the polybasic acid having no α, β-ethylenically unsaturated group is usually 1 to 30 parts by weight with respect to 100 parts by weight of rosins, and in particular, a printing ink having excellent emulsification ability is obtained. Therefore, 1 to 20 parts by weight is preferable.

  Examples of the method for producing the rosin ester resin (A) include esterification at 200 to 300 ° C, preferably 250 to 285 ° C in the presence of an acid-modified rosin and a polyhydric alcohol in an esterification catalyst. The method of making it react is mentioned. In this case, the ratio of the rosins and polyhydric alcohol used is usually preferably such that the hydroxyl group in the polyhydric alcohol is 1.5 molar equivalents or less with respect to 1 molar equivalent of the carboxylic acid in the rosins. A ratio of 8 to 1.1 molar equivalents is particularly preferred.

  As the rosin ester resin (A), a rosin ester resin having an acid value of 70 mgKOH / g or less is usually used. Among them, a rosin ester resin having an acid value of 18 mgKOH / g or less, for example, an acid value of 5 to 18 mgKOH / g is preferable. The hydroxyl value of the rosin ester resin (A) is preferably 50 mgKOH / g or less, for example, a hydroxyl value of 1 to 50 mgKOH / g.

  The resol type phenolic resin (B) used in the present invention is not particularly limited, and phenols and formaldehyde are metal hydroxides such as sodium, potassium, calcium, magnesium and zinc, oxides, organic acid salts and ammonia. Examples include condensates obtained by reacting in the presence of an alkali catalyst such as an aqueous solution and an organic amine compound, and resoles of novolak-type phenol resins. Among them, phenols (P) and formaldehyde (F) are used as alkali catalysts. In the presence, a condensate obtained by reacting in a range where F / P (molar ratio) is 1.5 to 3.0 is preferable, and F / P (molar ratio) is 2.0 to 2.6. A condensate obtained by reacting in a range is more 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. Examples of the weight average molecular weight include 200 to 1,600, with 700 to 1,300 being preferred.

  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. In addition, formaldehyde includes a formaldehyde supply material, and examples thereof include formaldehyde and rose formaldehyde.

  The reaction solvent (C) used in the present invention only needs to contain 70% by weight or more of a drying oil and / or semi-drying oil (c), and in particular, a drying oil and / or semi-drying oil (c). Is preferably 90% by weight or more, and more preferably composed only of drying oil and / or semi-drying oil (c). Examples of other reaction solvents that can be contained together with the drying oil and / or the semi-drying oil (c) include various organic solvents that can be used as a solvent for a lithographic printing ink.

  Among the drying oils and / or semi-drying oils (c), examples of the drying oil include 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. Of these, soybean oil and / or linseed oil are preferred. The reaction solvent (C) using soybean oil and / or linseed oil is most preferably a reaction solvent having a content of soybean oil and / or linseed oil of 90% by weight or more.

  The organic solvent that can be used as the other reaction solvent is preferably a hydrocarbon solvent having a boiling point of 160 ° C. or more, for example, a paraffin solvent, an isoparaffin solvent, a naphthene solvent, an aromatic component-containing paraffin solvent. And petroleum solvents having a boiling point of 200 ° C. or higher. 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 from the recent environmental and hygiene considerations.

  In the production of the resin composition for a printing ink varnish of the present invention, the ratio of the dry solvent and / or the semi-dry oil (c) used in the reaction solvent (C) having a content of 70% by weight or more is the rosin ester resin (A). It is 5-100 weight part normally with respect to 100 weight part, Preferably it is 10-50 weight part.

  The resin composition for a printing ink varnish of the present invention comprises the rosin ester resin (A) and the resol type phenol resin (B), a reaction solvent having a dry oil and / or semi-dry oil (c) content of 70% by weight or more. In (C), it is a composition comprising a resin for printing ink varnish and a reaction solvent, which is subjected to a condensation reaction at 160 to 240 ° C., and is a solution at the temperature at the end of the reaction (160 to 240 ° C.). It may be solid at room temperature (25 ° C.). As the resin composition for the printing ink varnish, among them, a printing ink that is superior in printing suitability and drying properties such as mist resistance and tack stability can be obtained. Therefore, with respect to 100 parts by weight of the rosin ester resin (A) It is preferable that 50 to 150 parts by weight of the resol type phenolic resin (B) is subjected to a condensation reaction. In addition, the resin composition for printing ink varnishes made to react at the temperature of less than 160 degreeC has a slow reaction of rosin ester resin (A) and a resole type phenol resin (B), and is not industrially suitable. Moreover, the resin composition for printing ink varnishes made to react at the temperature exceeding 240 degreeC becomes a printing ink which is easy to generate | occur | produce a roller pool at the time of printing, a water stick entanglement, a ground stain, etc., and is unpreferable. The reason for this is not clear, but at a temperature higher than 240 ° C., decomposition of the reaction product and decomposition of the unreacted resol type phenol resin (B) occur simultaneously with the reaction of the rosin ester resin (A) and the resol type phenol resin (B). The present inventors presume that the decomposed product that occurs and is produced may reduce the printability. In the case of this reaction, the reaction at a temperature exceeding 240 ° C. has a large decrease in printability, so it is necessary that there is absolutely no deterioration in printability, which is presumed to be caused by the formation of decomposition products. It is preferable to make it react at 180-230 degreeC from it, and it is most preferable to make it react at 190-220 degreeC.

  As the resin composition for printing ink varnish of the present invention, since a printing ink having excellent mist resistance and drying property can be obtained, the weight average molecular weight of the resin for printing ink varnish (resin content in the resin composition for printing ink varnish) Is preferably obtained by reacting the rosin ester resin (A) with the resol-type phenol resin (B) until it reaches 100,000 or more, and the weight average molecular weight of the resin for printing ink varnish is 120,000 to 400,000 More preferably, it is obtained by reacting until.

  The printing ink varnish of the present invention can be obtained by mixing the resin composition for printing ink varnish and the hydrocarbon solvent (D). During the mixing, a drying oil and / or a semi-drying oil (c) is used as necessary. Can be used in combination. When drying oil and / or semi-drying oil (c) are used in combination, the resin component and the drying oil and / or semi-drying oil (c) in the resin composition for printing ink varnish are mixed by mixing at 160 to 240 ° C. It is preferable to make it react, and it is more preferable to mix at 180-230 degreeC and to make it react partially.

  When producing the printing ink varnish of the present invention, the use ratio of the drying oil and / or semi-drying oil (c) used as necessary is usually 5 to 70 parts by weight, preferably 100 parts by weight of the printing ink varnish. Is in the range of 10 to 50 parts by weight. Among them, the use ratio of the drying oil and / or semi-drying oil (c) when used for sheet-fed ink is usually 20 to 50 parts by weight, preferably 25 to 45 parts by weight in 100 parts by weight of the printing ink varnish. The use ratio of the drying oil and / or semi-drying oil (c) when used for off-wheel ink is usually 5 to 40 parts by weight, preferably 10 to 10 parts by weight in 100 parts by weight of the printing ink varnish. This is a range of 30 parts by weight.

  When producing the printing ink varnish, the resin composition for printing ink varnish, the hydrocarbon-based solvent (D), and if necessary, the drying oil and / or the semi-drying oil (c) were mixed or mixed. Later, when the gelling agent (E) is further mixed and the resin component in the resin composition for printing ink varnish reacts with the gelling agent (E), it becomes a printing ink varnish with higher viscosity and excellent mist resistance. In particular, after reacting the resin component in the resin composition for printing ink varnish with the drying oil and / or semi-drying oil (c) in the presence of the hydrocarbon solvent (D), the gelling agent (E More preferably, the resin component in the resin composition for printing ink varnish is reacted with the gelling agent (E). In addition, the temperature at the time of mixing a gelatinizer (E) and making the resin part in a liquid mixture and a gelatinizer (E) react is 60-240 degreeC, Preferably it is 80-200 degreeC. 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 (E) 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, mono-sec-butoxy aluminum 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 (E) 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.

  As the printing ink varnish of the present invention, the bubble viscosity at 25 ° C. when adjusted to include 42 to 48% by weight of AF solvent 6 in the varnish for sheet-fed ink varnish is used for off-wheel ink. In the varnish, it is preferable that the bubble viscosity at 25 ° C. when adjusted to include 42 to 48% by weight of AF solvent 7 in the varnish is 2,000 to 40,000 dPa · S. What becomes 4,000-15,000 dPa * S is more preferable, and what becomes 4,500-7,000 dPa * S is especially preferable. Furthermore, as printing ink varnishes such as the varnish for sheet-fed ink and the varnish for off-wheel ink, the emulsification rate [LITHOTRONIC EMULSIFITION TESTER (manufactured by NOVOCONTROL GmbH), 40 ° C., 1,500 rpm, water supply speed The emulsification rate (EC%) measured at 2 ml / min] is preferably 100% by weight or less, more preferably 80% by weight or less, and particularly preferably 5 to 50% by weight.

  The 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, a color base in which pigments such as yellow, red, indigo and black are directly dispersed in the printing ink varnish of the present invention or dispersed in advance in a dispersion resin, or in the case of the flash method, a color base dispersed in a flash resin. If necessary, add a friction resistance improver, rheology control agent, ink dryer, drying inhibitor, additional solvent, other resin components, etc., and knead to adjust to an appropriate viscosity. Thus, a lithographic printing ink such as a sheet-fed ink or an off-wheel ink can be obtained. 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 using the printing ink varnish of the present invention can be suitably used in various lithographic printing presses, and exhibits excellent printability that cannot be achieved with conventional printing inks.

  Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, “part” and “%” are based on weight unless otherwise specified.

Reference Example 1 (Preparation of resol type phenol resin)
A pressurized reaction kettle equipped with a stirrer and a thermometer was charged with 2060 parts of p-octylphenol, dissolved by heating at 120 ° C., and 350 parts of 92% paraformaldehyde powder (water content 8%) and calcium hydroxide 7.4. A part is added, and it heats to 130 degreeC, and is made to react for 2 hours, and is abbreviated as a resol type phenol resin [henceforth "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.

Reference example 2 (same as above)
In a pressure reaction kettle equipped with a stirrer and a thermometer, 1500 parts of p-tert-butylphenol was charged and dissolved by heating at 120 ° C., 350 parts of 92% paraformaldehyde powder (water content 8%) and 7 parts of calcium hydroxide .4 parts is added, heated to 130 ° C., reacted for 2 hours, and resol type phenol resin (hereinafter abbreviated as “resole resin (2)”). Was prepared. The obtained resol resin (2) had a polystyrene-reduced weight average molecular weight (Mw) of 880 as measured by GPC method.

Reference Example 3 (Preparation of rosin ester resin)
A reaction kettle equipped with a stirrer, a thermometer, a condensed water separator and a nitrogen introduction tube was charged with 1,000 parts of gum rosin having an acid value of 165 mgKOH / g and 98.5 parts of maleic anhydride, and the temperature was raised to 200. When the temperature reached ℃, 160 parts of pentaerythritol and 6 parts of calcium acetate were added, and the temperature was further raised 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 119 ° C., and a weight average molecular weight (Mw) of 1,600.

Reference example 4 (same as above)
In a reaction vessel similar to Reference Example 3, 1,000 parts of gum rosin having an acid value of 165 mgKOH / g, 205 parts of rice bran fatty acid, and 136.5 parts of fumaric acid were charged, and when the temperature reached 200 ° C. 195 parts of erythritol and 6 parts of calcium formate were added, and the temperature was further raised 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 (2)”. ] Was obtained. The obtained RE resin (2) had an acid value of 14.9 mgKOH / g, a softening point of 107 ° C., and a weight average molecular weight (Mw) of 12,000.

Example 1
In a reactor similar to that of Reference Example 3, 100 parts of RE resin (1) heated to 170 ° C. and 25 parts of soybean oil were added, and 48 parts of resole resin (1) heated to 110 ° C. was further added to raise the temperature. And it was made to react at 180 degreeC for 4 hours, and the resin composition for printing ink varnish of this invention was obtained. The obtained resin composition was solid at room temperature [Hereinafter, this resin composition is abbreviated as solid resin (1). ]. When the same amount of toluene was added to the solid resin (1), the Gardner viscosity at 25 ° C. was GH [weight average molecular weight (Mw) of the resin was 110,000. 〕Met.

  78.6 parts of soybean oil, 44.4 parts of AF solvent 6 and 0.6 parts of BHT (2,6-di-tert-butyl-4-methylphenol) with respect to 173 parts of the obtained solid resin (1) After stirring and mixing at 180 ° C. for 30 minutes, ethyl acetoacetate aluminum dinormal butyrate which is a gelling agent at 160 ° C. so that the bubble viscosity at 25 ° C. falls within the range of 5,500 to 10,000 Pa · s. In the range of 0.5 to 4 parts, and the mixture is heated and stirred for 1 hour, and the printing ink varnish of the present invention (hereinafter abbreviated as varnish (1)). ] Was obtained.

  The resulting varnish (1) had a bubble viscosity at 25 ° C. of 5,600 dPa · s, tack value value (TV) when rotated at 400 rpm and 32 ° C. for 1 minute with an incometer (manufactured by Toyo Seiki Co., Ltd.). Was 12. Moreover, the heptane tolerance of the toluene solution prepared by melt | dissolving 1 g of obtained varnish (1) in 2 g of toluene was 10 ml / 3g. Furthermore, the emulsification rate (EC%) of this varnish (1) measured at a stirring speed of 1,500 rpm, a temperature of 40 ° C., and a water supply speed of 2 ml / min with a LITHOTRONIC EMULSIFICATION TESTER (manufactured by NOVOCONTROL GmbH) is 48%. there were.

  Next, 83 parts of the obtained varnish (1), 17 parts of Carmine 6B [Dainippon Ink Chemical Co., Ltd. red pigment], Dainippon Ink & Chemicals Co., Ltd. dryer (manganese naphthenate and cobalt octylate) Mixture) 0.5 parts kneaded with 3 rolls, and added AF solvent No. 6 with the amount of use adjusted so that TV becomes 8, to obtain sheet-fed ink (1), and the obtained sheet The ink (1) was evaluated for gloss, TV stability over time and drying (sheet-fed ink) as described below. The results are shown in Table 1.

  Gloss: 0.15 ml of sheet-fed ink (1) is developed on art paper with a RI tester (manufactured by Akira Seisakusho Co., Ltd.) in two split rolls, and the gloss of the ink developed on the art paper after standing for one day Values were measured with a 60 ° -60 ° gloss meter.

  Stability of TV over time: 1 minute of tack value (TV) when 1.31 ml of ink (1) is placed on an incometer (manufactured by Toyo Seiki Co., Ltd.) and rotated at 32 ° C. and 400 rpm for 10 minutes. It is represented by the difference (ΔTV) between the value when rotating (initial value) and the maximum value. A smaller ΔTV is preferable because of better stability over time.

  Dryability (sheet-fed ink): After 0.4 ml of ink (1) is applied to art paper using an RI tester (manufactured by Akira Seisakusho), an auto ink setting tester (manufactured by Toyo Seiki Seisakusho) is used. The color developed product was divided by time, the degree of ink adhesion from the color developed product to another art paper was observed using a roller, and the time (minutes) until the ink no longer adhered was measured.

Example 2
Soybean oil 24.3 parts, AF solvent 7 No. 131.6 parts and BHT (2,6-di-tert-butyl-4-methylphenol) with respect to 173 parts of the solid resin (1) obtained in Example 1 After adding 0.3 part and stirring and mixing at 180 ° C. for 30 minutes, ethyl acetoacetate aluminum which is a gelling agent at 160 ° C. so that the bubble viscosity at 25 ° C. falls within the range of 5,500 to 10,000 Pa · s. A necessary amount of dinormal butyrate is added in the range of 0.5 to 4 parts, and the mixture is heated and stirred for 1 hour, and then the printing ink varnish of the present invention (hereinafter abbreviated as varnish (2)). ] Was obtained.

  The resulting varnish (2) had a bubble viscosity at 25 ° C. of 7,500 dPa · s, a tack value value (TV) when rotated at 400 ° C. and 32 ° C. for 1 minute with an incometer (manufactured by Toyo Seiki Co., Ltd.). Was 9. The heptane tolerance of the toluene solution prepared by dissolving 1 g of the obtained varnish (2) in 2 g of toluene was 13 ml / 3 g. Furthermore, the emulsification rate (EC%) of this varnish (2) was 50%.

  Next, 83 parts of the obtained varnish (2) and 17 parts of Carmine 6B [Red Pigment made by Dainippon Ink & Chemicals, Inc.] are kneaded with 3 rolls, and the amount used is adjusted so that TV becomes 8. The adjusted AF solvent 7 was added to obtain an off-ring ink (2), and the obtained off-ring ink (2) was measured for gloss and TV over time in the same manner as in Example 1, and the following: Thus, dryness (off-wheel ink) was evaluated. The results are shown in Table 1.

  Drying property (off-wheel ink): 0.15 ml of RI tester (manufactured by Akira Seisakusho Co., Ltd.) Two types of ink were spread on art paper with a two-part roll, and passed through an oven at 100 ° C. for 10 seconds, immediately. After overlapping the print surfaces of the two types of ink, the state of the print surface when peeled again was visually determined. A case where no change was observed on the print surface compared to the situation before the print surface was matched was accepted, and a case where a change was seen was rejected.

Example 3
In a reactor similar to that of Reference Example 3, 100 parts of RE resin (2) was added with 25 parts of soybean oil, mixed and maintained at 170 ° C., and further heated to 110 ° C. 60 parts of resole resin (2) The mixture was heated to 200 ° C. for 2 hours to obtain a resin composition for printing ink varnish of the present invention. The obtained resin composition was solid at room temperature [Hereinafter, this resin composition is abbreviated as solid resin (2). ]. When the same amount of toluene was added to the solid resin (2), the Gardner viscosity at 25 ° C. was LM [weight average molecular weight (Mw) of the resin was 190,000. 〕Met.

  Add 62.3 parts of soybean oil to 185 parts of the obtained solid resin (2), adjust the temperature to 180 ° C. and heat and mix for 30 minutes, then add 43.5 parts of AF Solvent No. 6 and 0.6 part of BHT. Further, after stirring and mixing at the same temperature for 30 minutes, ethyl acetoacetate aluminum dinormal butyrate was added at 0.5 to 5 at 160 ° C. so that the bubble viscosity at 25 ° C. was in the range of 5,500 to 10,000 dPa · s. The necessary amount is added within the range of parts, and the mixture is heated and stirred for 1 hour, and the printing ink varnish of the present invention (hereinafter abbreviated as varnish (3)). ] Was obtained.

  The obtained varnish (3) had a cell viscosity at 25 ° C. of 6,000 dPa · s, TV of 18, heptane tolerance of 15 ml / 3 g, and EC% of 49%.

  A sheet-fed ink (3) was obtained in the same manner as in Example 1 except that the obtained varnish (3) was used. The stability over time and the drying property (sheet-fed ink) were evaluated. The results are shown in Table 1.

Example 4
Example 3 28.3 parts of soybean oil were added to 185 parts of the obtained solid resin (2), the temperature was adjusted to 180 ° C., and the mixture was heated and mixed for 30 minutes, then 142.2 parts of AF Solvent No. 7 and BHT 0.3 Then, the mixture was further stirred and mixed at the same temperature for 30 minutes, and then ethyl acetoacetate aluminum dinormal butyrate was added at a temperature of 160 ° C. so that the bubble viscosity at 25 ° C. was in the range of 5,500 to 10,000 dPa · s. A necessary amount is added in the range of 5 to 5 parts, and the mixture is heated and stirred for 1 hour, and the printing ink varnish of the present invention (hereinafter abbreviated as varnish (4)). ] Was obtained.

  The obtained varnish (4) had a bubble viscosity at 25 ° C. of 7,800 dPa · s, TV of 14, heptane tolerance of 14 ml / 3 g, and EC% of 52%.

  An off-wheel ink (4) was obtained in the same manner as in Example 2 except that the obtained varnish (4) was used. The stability over time was measured, and the drying property (off-ring ink) was evaluated as follows. The results are shown in Table 1.

  An off-wheel ink (4) was obtained in the same manner as in Example 2 except that the obtained varnish (4) was used. The stability over time was measured, and the drying property (off-ring ink) was evaluated as follows. The results are shown in Table 1.

Comparative Example 1
A comparative resin composition for printing ink varnish was obtained in the same manner as in Example 1 except that AF Solvent 7 was used instead of soybean oil. The obtained resin composition was solid at room temperature [Hereinafter, this resin composition is abbreviated as solid resin (1 ′). ]. When the same amount of toluene was added to this solid resin (1 ′), the Gardner viscosity at 25 ° C. was KL [weight average molecular weight (Mw) of the resin was 110,000. 〕Met.

  Add 103.6 parts of soybean oil to 173 parts of the obtained solid resin (1 ′), adjust the temperature to 180 ° C. and heat mix for 30 minutes, then add 19.5 parts of AF Solvent No. 6 and 0.6 part of BHT. In addition, after stirring and mixing at the same temperature for 30 minutes, the ethyl acetoacetate aluminum dinormal butyrate is in the range of 0.5 to 5 parts at 160 ° C. so that the bubble viscosity at 25 ° C. is in the range of 5500 to 10000 dPa · s. The required amount was added, and the mixture was heated and stirred for 1 hour, and a comparative printing ink varnish (hereinafter abbreviated as “varnish (1 ′)”). ] Was obtained.

  The obtained varnish (1 ′) had a bubble viscosity at 25 ° C. of 6,800 dPa · s, TV of 10, heptane tolerance of 8 ml / 3 g, and EC% of 49%.

  A sheet-fed ink (1 ') was obtained in the same manner as in Example 1 except that the obtained varnish (1') was used. The resulting sheet-fed ink (1 ') was glossed in the same manner as in Example 1. And the stability over time of TV and the drying property (sheet-fed ink) were evaluated. The results are shown in Table 1.

Comparative Example 2
A comparative resin composition for printing ink varnish was obtained in the same manner as in Example 1 except that AF Solvent 6 was used instead of soybean oil. The obtained resin composition was solid at room temperature [hereinafter, this resin composition is abbreviated as solid resin (2 ′). ]. When the same amount of toluene was added to the solid resin (2 ′), the Gardner viscosity at 25 ° C. was LM [the weight average molecular weight (Mw) of the resin was 110,000. 〕Met.

  49.3 parts of soybean oil are added to 173 parts of the obtained solid resin (2 ′), the temperature is adjusted to 180 ° C. and heated and mixed for 30 minutes, and then 106.6 parts of AF Solvent No. 7 and 0.3 part of BHT are added. In addition, after stirring and mixing at the same temperature for 30 minutes, the ethyl acetoacetate aluminum dinormal butyrate is in the range of 0.5 to 5 parts at 160 ° C. so that the bubble viscosity at 25 ° C. is in the range of 5500 to 10000 dPa · s. After adding the necessary amount, the mixture was heated and stirred for 1 hour, and the printing ink varnish of the present invention (hereinafter abbreviated as “varnish (2 ′)”). ] Was obtained.

  The obtained varnish (2 ′) had a bubble viscosity at 25 ° C. of 7,800 dPa · s, TV of 9, heptane tolerance of 9 ml / 3 g, and EC% of 51%. Also,

  An off-ring ink (2 ') was obtained in the same manner as in Example 2 except that the obtained varnish (2') was used. The obtained off-ring ink (2 ') was glossed in the same manner as in Example 2. And the stability over time of TV were measured, and the drying property (off-wheel ink) was evaluated as follows. The results are shown in Table 1.

Claims (14)

Content ratio of rosin ester resin (A) obtained by esterifying rosin which may be acid-modified with polyhydric alcohol and resol type phenol resin (B), and drying oil and / or semi-drying oil (c) Is a resin composition for a printing ink varnish, which is obtained by reacting at a temperature of 160 to 240 ° C. in a reaction solvent (C) of 70% by weight or more. The reaction solvent (C) is used in an amount of 5 to 100 parts by weight per 100 parts by weight of the rosin ester resin (A), and the reaction is carried out until the weight average molecular weight of the resin for printing ink varnish reaches 100,000 or more. The resin composition for printing ink varnish described in 1. The resin composition for printing ink varnish according to claim 2, wherein the reaction solvent (C) is a reaction solvent having a content of soybean oil and / or linseed oil of 90% by weight or more. The resin composition for printing ink varnish according to claim 2, which is reacted at 180 to 230 ° C. The resin composition for a printing ink varnish according to claim 2, wherein the amount of the resol type phenol resin (B) used is 100 to 150 parts by weight relative to 100 parts by weight of the rosin ester resin (A). The resin composition for printing ink varnish according to any one of claims 1 to 5, wherein the resin composition for printing ink varnish is reacted until the weight average molecular weight of the resin for printing ink varnish becomes 120,000 to 400,000. It is a resin solution for flash varnishes, The resin composition for printing ink varnishes as described in any one of Claims 1-5. A printing ink varnish comprising the resin composition for printing ink varnish according to any one of claims 1 to 6 and a hydrocarbon solvent (D). The resin composition for the printing ink varnish, the hydrocarbon solvent (D), the drying oil and / or the semi-drying oil (c) are mixed at 160 to 240 ° C. Or the printing ink varnish of Claim 8 which makes a semi-drying oil (c) react. The resin composition for printing ink varnish, the hydrocarbon solvent (D), and the gelling agent (E) are mixed at 160 to 240 ° C. to react the resin component in the resin composition for printing ink varnish with the gelling agent (E). The printing ink varnish according to claim 8. A resin composition for printing ink varnish, a hydrocarbon solvent (D), a gelling agent (E), a drying oil and / or a semi-drying oil (c) are mixed at 160 to 240 ° C. in the resin composition for printing ink varnish. The printing ink varnish according to claim 8, which is obtained by reacting a resin component, a gelling agent (E), and a drying oil and / or semi-drying oil (c). The printing ink varnish according to claim 11, wherein the drying oil and / or the semi-drying oil (c) is soybean oil and / or linseed oil. The resin component in the resin composition for printing ink varnish and the gelling agent (E) and / or drying oil and / or semi-drying oil (c) are reacted at 180 to 230 ° C. The printing ink varnish according to any one of the above. A printing ink comprising the printing ink varnish according to any one of claims 8 to 13 and a pigment.