JP2005307132A - Resin for offset ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin for offset printing ink capable of obtaining performances equal to or more than that of a conventional rosin-modified phenol resin without using an alkylphenol and formaldehyde. <P>SOLUTION: This resin for offset ink having a softening point of 120-220°C and a weight-average molecular weight of 5,000-300,000 is obtained by reacting a polymerized rosin (1), at least one (2) among a vegetable oil, a polymerized vegetable oil, a vegetable oil fatty acid, and other higher fatty acids, rubber (3), an unsaturated dibasic acid (4) and a polyhydric alcohol (5). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a commercial offset ink used for printing posters, calendars, flyers, catalogs, and the like, and a binder resin used for newspaper offset inks.

Conventionally, rosin-modified phenolic resin obtained by reacting rosin, polyhydric alcohol, and phenolic resin has been used as a binder resin for offset ink. Depending on the purpose, the rosin-modified phenol resin may be further modified by adding polymerized rosin, unsaturated dibasic acid, vegetable oil, petroleum resin, etc., but the basic rosin, Polyhydric alcohols and phenol resins have become essential constituent materials.

  For rosin, gum rosin, tall rosin and wood rosin with different raw materials were used, and rosins from different origins such as China, Indonesia, Vietnam, USA and Argentina were used according to their purpose. As the polyhydric alcohol, glycerin, pentaerythritol, dipentaerythritol and the like have been properly used depending on the purpose. Similarly, phenolic resins such as bisphenol A, alkylphenolic resol type phenolic resins such as pt-butylphenol, p-octylphenol, nonylphenol, dodecylphenol have been used depending on the purpose.

Rosin-modified phenolic resin has been promoted for offset inks as providing excellent ink performance, but its constituent materials, bisphenol A and alkylphenol, are suspected of environmental hormones (exogenous endocrine disrupting chemicals) Currently, investigations are underway on their effects on the environment and organisms. In addition, formaldehyde, which is a constituent component of phenolic resin, is problematic in terms of odor and its harmfulness, and is moving toward elimination in many fields such as paints, adhesives and the like. Therefore, the present inventors have proposed a novel resin (Japanese Patent Laid-Open No. 2002-309146) containing a polymerized rosin, an unsaturated dibasic acid, a polyhydric alcohol, and a polyfunctional acrylate as essential components. It was found that the gloss was inferior and the saturated emulsification rate was high, that is, the emulsification suitability was inferior.

  In view of this situation, the present inventors have made extensive studies, and as a result, at least one of polymerized rosin, vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, and other higher fatty acids, rubber, unsaturated dibasic acid, and polyhydric acid. By using a combination of monohydric alcohols as an essential component of the resin, the conventional bisphenol A and alkylphenol, which are suspected of being an environmental hormone, can be used without the use of formaldehyde, which is problematic in terms of odor and toxicity. The inventors have found that a resin having performance equal to or higher than that of rosin-modified phenolic resin and excellent in emulsification ability can be obtained, and the present invention has been completed.

That is, the present invention relates to polymerized rosin (I), vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, at least one of other higher fatty acids (b), rubber (c), unsaturated dibasic acid (d), and polyvalent The present invention relates to a resin for offset ink having a softening point of 120 to 220 ° C. and a weight average molecular weight of 5,000 to 300,000 obtained by reacting alcohol.

The resin for offset printing inks of the present invention does not use bisphenol A or alkylphenol, which are suspected of environmental hormones (exogenous endocrine disrupting chemicals), and does not use formaldehyde that has problems with odor and toxicity. Is synthesized. Moreover, if the resin for offset ink of the present invention is used, an ink can be obtained in which important ink performance related to pigment dispersibility and emulsification suitability is equal to or higher than that of conventionally used rosin-modified phenol resins.

  In the present invention, polymerized rosin (I) is produced by dimerizing rosin using a catalyst such as sulfuric acid, and removing unreacted rosin by a method such as distillation if necessary. It can be produced by itself or a commercially available product may be used. The softening point of the polymerized rosin is approximately 80 to 140 ° C., and the dimerization rate is approximately 20 to 80%. The softening point and dimerization rate of the polymerized rosin can be adjusted by adding rosin to the polymerized rosin.

  In the present invention, at least one (b) of vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, and other higher fatty acids may be any conventionally known one. For example, soybean oil, linseed oil, castor oil, dehydrated castor oil, regenerated Examples include vegetable oil, polymerized linseed oil, soybean oil fatty acid, linseed oil fatty acid, castor oil fatty acid, stearic acid, hydroxystearic acid, linoleic acid, linolenic acid, tall oil fatty acid and the like. In addition, the component (ro) is approximately 1 to 20 parts by mass per 100 parts by mass of the polymerized rosin (including rosin added for adjusting the softening point and dimerization rate, hereinafter abbreviated to include rosin). It is desirable to do. When the component (b) is less than 1 part by mass, the resulting resin has low solubility in an ink solvent, and the pigment dispersibility tends to be insufficient. Moreover, when a component (b) exceeds 20 mass parts, a softening point will become low and it will become difficult to fit in the expected range (120-220 degreeC).

  In the present invention, as the rubber (c), any conventionally known rubber can be used regardless of the type of natural rubber, isoprene rubber, butadiene rubber and the like. Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber and the like. Also, a liquid having a relatively low molecular weight or a functional group modified may be used. The rubber is preferably about 1 to 20 parts by mass per 100 parts by mass of polymerized rosin (including rosin), and within this range, the softening point and weight average molecular weight of the resin should be within the expected range. Is easy.

  In the present invention, the unsaturated dibasic acid (d) may be any conventionally known one as long as it reacts with the unsaturated bond of rosin, and examples thereof include maleic anhydride, maleic acid, fumaric acid and the like. Can do. The unsaturated dibasic acid is preferably about 0.5 to 15 parts by mass per 100 parts by mass of polymerized rosin (including rosin), and within this range, the softening point and weight average molecular weight of the resin are determined. It is easy to fit within the period.

  In the present invention, conventionally known polyhydric alcohol (e) is used. For example, ethylene glycol, diethylene glycol, butanediol, 2-methylpentanediol, hexanediol, neopentylglycol, glycerin, trimethylolpropane, dimethylol. Propionic acid, trimethylolethane, pentaerythritol, dipentaerythritol and the like can be mentioned. The polyhydric alcohol is preferably about 5 to 20 parts by mass per 100 parts by mass of polymerized rosin (including rosin), and within this range, the softening point and weight average molecular weight of the resin are within the intended range. Easy to pay.

  In this invention, the softening point of resin needs to be 120-220 degreeC. When the softening point is lower than 120 ° C., the ink setting and drying properties become poor. On the other hand, when the softening point exceeds 220 ° C., it becomes difficult to prepare an ink varnish. In addition, the measuring method of the softening point in this invention shall follow the ring and ball method of JISK2207.

  In the present invention, the weight average molecular weight of the resin needs to be 5,000 to 300,000. If the weight average molecular weight is less than 5,000, it is difficult to obtain the elasticity required for the ink varnish, and the ink is inferior in misting resistance. On the other hand, if it is 300,000 or more, it is difficult to obtain the viscosity required for the ink varnish, and the fluidity of the ink is poor. The weight average molecular weight in the present invention is measured by gel permeation chromatography and is a value converted to the molecular weight of monodisperse standard polystyrene.

  The resin for offset ink in the present invention includes at least one of polymerized rosin (I), vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, and other higher fatty acids (b), rubber (c), unsaturated dibasic acid (d) ), And polyhydric alcohol (e), for example, gum rosin, tall rosin, ester of vegetable oil fatty acid, alkyd resin, DCPD petroleum resin, C5 petroleum resin, C9 petroleum resin, etc. It is also possible to adjust the softening point, molecular weight, solubility, viscosity and the like.

  The resin for offset ink in the present invention includes at least one of polymerized rosin (I), vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, and other higher fatty acids (b), rubber (c), unsaturated dibasic acid (d) ) And polyhydric alcohol (e), for example, after reacting component (ii) with component (ii) and component (c), component (b) and component (e) ), Or component (b) and component (c) may be reacted with component (d) and then reacted in the order of component (e) and component (a). The order of is not particularly limited.

  As an example of synthesis, polymerized rosin (I), vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, at least one of higher fatty acids (b), rubber (c), unsaturated dibasic acid (d) are reacted. The reactor can be charged and reacted at a temperature of 150 to 250 ° C., and then the reaction product can be charged with polyhydric alcohol (e) and reacted at a temperature of 200 to 280 ° C. The latter reaction may be non-catalytic, for example, a metal catalyst such as calcium oxide, magnesium oxide, zinc oxide, calcium acetate, magnesium acetate, zinc acetate, or a non-metal catalyst such as phosphoric acid or p-toluenesulfonic acid. An appropriate catalyst can be added to react. Moreover, in order to remove condensed water, it can also be made to react by adding suitable refluxing solvents, such as xylene.

Hereinafter, the present invention will be described in detail by way of examples. In addition, the part of preparation represents a mass part.

Synthesis example 1
In a reaction vessel equipped with a stirrer and a water separator, 720 parts of polymerized rosin (softening point 140 ° C., dimerization rate 80%), 240 parts of Chinese gum rosin, 120 parts of polymerized linseed oil, isoprene rubber manufactured by Nippon Zeon (trade name Nipol IR2200) ) 60 parts, heated and stirred while blowing nitrogen gas, reacted with 60 parts of maleic anhydride at 200 ° C., charged with 135 parts of pentaerythritol and 1.2 parts of magnesium oxide and dehydrated and condensed at 270 ° C. Was reacted until about 20 was obtained.

Synthesis example 2
In the same reaction vessel as in Synthesis Example 1, 720 parts of polymerized rosin (softening point 140 ° C., dimerization rate 80%), 240 parts of Chinese gum rosin, 120 parts of polymerized linseed oil, styrene butadiene rubber manufactured by Nippon Zeon (trade name Nipol 1500) ) 60 parts, heated and stirred while blowing nitrogen gas, reacted with 60 parts of maleic anhydride at 200 ° C., charged with 135 parts of pentaerythritol and 1.2 parts of magnesium oxide and dehydrated and condensed at 270 ° C. Was reacted until about 20 was obtained.

Comparative Synthesis Example 1
720 parts of polymerized rosin (softening point 140 ° C., dimerization rate 80%), 240 parts of Chinese gum rosin and 120 parts of polymerized linseed oil were charged in the same reaction vessel as in Synthesis Example 1, and heated and stirred while blowing nitrogen gas. After reacting 60 parts of maleic anhydride at ℃, 135 parts of pentaerythritol and 1.2 parts of magnesium oxide were charged and subjected to dehydration condensation at 270 ℃ until the acid value was about 20. Thereafter, 12 parts of 1.6-hexanediol diacrylate was reacted at 230 ° C. to obtain Resin 3.

Comparative Synthesis Example 2
Into the same reaction vessel as in Synthesis Example 1, 900 parts of Chinese gum rosin was charged and heated and stirred while blowing nitrogen gas. After reacting 15 parts of maleic anhydride at 200 ° C., octylphenol-based resol type phenolic resin 540 at 230 ° C. The part was added dropwise in 3 hours. Thereafter, 95 parts of glycerin and 0.9 part of magnesium oxide were charged and dehydrated and condensed at 270 ° C. until the acid value reached about 20, whereby Resin 4 was obtained. The octylphenol-based resol type phenolic resin was charged with 1000 parts of octylphenol and 300 parts of paraformaldehyde (purity 92%) in the same reaction vessel as in Example 1, heated and stirred, and 10 g of 10% aqueous sodium hydroxide solution as a catalyst at 80 ° C. After the addition, the mixture was kept at 90 ° C. for 4 hours for synthesis.

  The obtained resin was evaluated for softening point, acid value, falling ball viscosity of linseed oil varnish, solubility in solvent for ink (AF7 Solvent manufactured by Mitsubishi Oil Corporation), and weight average molecular weight. The measurement was performed by the following method, and the results are summarized in Table 1.

  Linseed oil varnish viscosity: Resin and linseed oil were mixed at a mass ratio of 1: 2, and heated and dissolved, and measured with a falling ball viscometer.

  Solubility in ink solvent (AF7 solvent solubility): The maximum amount of AF7 solvent that can exist in a state that does not become cloudy when the resin is dissolved in AF7 solvent and left at 25 ° C. Expressed as AF7 solvent amount converted per 1 g of resin.

Weight average molecular weight: The molecular weight (polystyrene conversion) was measured by GPC analysis.

  For each resin in Table 1, 40 parts of resin, 20 parts of soybean oil, and 40 parts of AF7 solvent were charged in a reaction vessel, heated with stirring while blowing nitrogen gas, and kept at 200 ° C. for 1 hour to obtain a varnish. When this was cooled to 100 ° C., 1 part of ALCH-50 (manufactured by Kawaken Fine Chemical Co., Ltd.) was added as a gelling agent, and the temperature was raised to 180 ° C. and kept for 1 hour to obtain a gel varnish.

  Next, 100 parts of gel varnish and 30 parts of Carmine 6B were kneaded with a three-roll mill, and further adjusted with an AF No. 7 solvent so that the tack became 6 to 7 to obtain a test red ink.

Table 2 shows the properties and evaluation results of each ink. The tack was measured using a digital incometer (manufactured by Toyo Seiki Seisakusho).

  The ink performance evaluation in Table 2 was performed as follows.

  Flow: Measured using a parallel plate viscometer (manufactured by Toyo Seiki Seisakusho).

  Gloss: After 0.3 ml of ink was developed on art paper with an RI tester (Made Seisakusho), it was dried in a hot air dryer at 120 ° C. for 5 seconds, and after 24 hours at room temperature, a gloss meter (Gardner) The specular reflectance at 60 ° was measured using

  Emulsification rate: Using Lysotronic (manufactured by Novo Control), ion-exchanged water was added dropwise to 25 g of ink at a rate of 2 ml / min, and the emulsification rate when saturated was measured.

  Misting amount: The amount of mist splashed below the roll was precisely weighed when 1.3 ml of ink was rotated at 2000 rpm per minute for a digital incometer (manufactured by Toyo Seiki Seisakusho).

  From Tables 1 and 2, Resin 1 and Resin 2 have the same resin properties as Resin 4 (conventional rosin-modified phenolic resin), and the ink using this is resin 4 (conventional rosin-modified phenolic resin). The performance is equivalent to or better than the ink used. Further, it is clear that the ink using the resin 1 and the resin 2 does not contain alkylphenol or formaldehyde which is suspected of being harmful, unlike the ink using the resin 4 (conventional rosin-modified phenol resin). On the other hand, the resin 1 and the resin 2 are superior in gloss of the ink and have a low emulsification rate as compared with the resin 3 (containing no component (c)).

Claims (2)

  Polymerized rosin (I), vegetable oil, polymerized vegetable oil, vegetable oil fatty acid, at least one of other higher fatty acids (ro), rubber (c), unsaturated dibasic acid (d), and polyhydric alcohol (e) Resin for offset ink having a softening point of 120 to 220 ° C. and a weight average molecular weight of 5,000 to 300,000 obtained by reacting as an essential component   Ingredient (ii) 1 to 20 parts by weight of component (b) per 100 parts by weight, 1 to 20 parts by weight of ingredient (c), 0.5 to 15 parts by weight of ingredient (d), 5 to 5 parts of ingredient (e) Resin for offset ink according to claim 1, obtained by reacting in a range of 20 parts by mass.