JPH0573790B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a resin for printing ink and a method for producing the same. [Prior Art] Hitherto, rosin-modified phenolic resins have been used as resins for printing inks, particularly as resins for offset printing inks. However, in recent years, there has been a strong demand for printing ink resins to be suitable for high-speed printing due to demands for labor-saving and high-speed printing.
In particular, when the solvent is absorbed into the coated layer of paper fibers, the ink rapidly thickens, and the color does not transfer to the back side of the printed matter that is being piled up one after another.
The required performance is also becoming more sophisticated. In recent high-speed printing, in addition to gloss, an even more important characteristic is the ability to quickly set the ink before it reaches a dry state. When the gloss of the printing ink and its solubility in ink solvents are modified by a resin, a large amount of long-chain alkyl phenol is used as the phenol component of the rosin-modified phenolic resin, or a cotton-like resin such as higher fatty acids or drying oil alkyd resin is used. The combined use of modifying components has been practiced. However, in general, gloss and drying/setting properties are contradictory, and it is often difficult to maintain a balance between the two.The softening point of the resin obtained by the above method is significantly lowered, and the ink is There is a strong tendency for drying and slow setting. The present applicant has already reported in JP-A-59-191776 that a rosin-modified phenolic resin with a low acid value obtained by reacting a rosin and a resol type phenolic resin in the presence of an acid catalyst has a high solubility in an ink solvent. The patent discloses that it has a high gloss and satisfies required performances such as drying properties, setting, and misting to some extent. However, since the softening point of the resin is still not high enough, there is room for improvement in terms of drying properties and setting. Therefore, there is a demand for the development of a resin for printing ink that maintains a certain level of gloss under high-speed printing and also satisfies required performances such as drying properties, setting, and misting (hereinafter referred to as printability). [Problems to be Solved by the Invention] In view of the actual situation that conventionally known rosin-modified phenolic resins cannot satisfy printability (especially drying properties and setting) during high-speed printing, the present inventors have solved the drawbacks. The aim was to develop a new resin for printing ink that could be used. [Means for Solving the Problems] In view of the above-mentioned problems, the present inventors focused on the molecular structure, physical constants, softening point, etc. of the rosin-modified phenolic resin, and conducted various manufacturing methods to obtain the desired resin. We conducted a thorough study. As a result, JP-A-59
It has been found that all of the above problems can be solved if a specific rosin derivative is used instead of rosin, which is the resin raw material in Publication No. 191776. The present invention was completed based on this new knowledge. That is, the present invention provides a reaction product obtained by subjecting a reactant A obtained by heating a rosin and a phenol to a reaction in the presence of an acid catalyst and an esterification reaction of a resol type phenolic resin B in the presence of an acid catalyst. A printing ink resin consisting of a resin, a rosin, and a phenol are subjected to a heating reaction in the presence of an acid catalyst, and a reaction product A and a resol type phenolic resin B are subjected to an esterification reaction in the presence of an acid catalyst. This invention relates to a method for producing a resin for printing ink. [Function and Examples] The present invention relates to a resin for printing ink having a novel molecular structure that is clearly different from that of conventional resins, and a method for producing the same. All of the problems seen with phenolic resins are eliminated, and a printing ink with excellent high-speed printing suitability can be obtained. Below, the method for producing a printing ink resin of the present invention and the characteristics of the obtained printing ink resin will be explained. The reactant A (hereinafter referred to as intermediate A) in the present invention is a reactant obtained by subjecting rosins and phenols to a heating reaction in the presence of an acid catalyst. Here, rosin refers to gum rosin, oil rosin, tall oil rosin, disproportionated rosin, polymerized rosin, and the like. Phenols include carbolic acid,
Cresol is preferred. Preferred acid catalysts include para-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, sulfuric acid, hydrochloric acid, boron trifluoride, anhydrous aluminum chloride, and the like. This intermediate can be easily produced by employing the following method. That is, for 1 mole of the rosin, 1.5 to 4 moles of phenols are added in the presence of an acid catalyst at a rate of about 140%.
React at ~180°C for 4-14 hours. Furthermore, unreacted phenols are distilled off while gradually increasing the temperature in the reaction system until the final temperature reaches 250 to 300°C. There are no particular restrictions on the amount of acid catalyst used, but it is usually 0.05 to 0.5% by weight based on the rosin. Although the structure of Intermediate A is unclear, it is thought that the main reaction product is a Friedel-Crafts reaction between phenols and rosins, in which the hydrogen atom at the para position of the phenols is replaced by the rosin. It will be done. The intermediate A has an acid value of 100 to 110 mgKOH/g and a hydroxyl value.
The reaction conditions can be adjusted as appropriate by manipulating the reaction conditions so as to have a range of 60 to 90 mgKOH/g and a softening point of 100 to 125°C. Examples of the resol type phenol resin (hereinafter referred to as resin B) used in the reaction with intermediate A include the following. That is, a resol-type phenolic resin obtained by reacting a formaldehyde supplying substance such as formaldehyde or paraformaldehyde with the following phenols in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, or ammonium. An example may be an initial condensate. Specific examples of the phenols include carbolic acid, cresol, sec-butylphenol,
Examples include t-butylphenol, amylphenol, cyclohexylphenol, octylphenol, nonylphenol, dodecylphenol, phenylphenol, cumylphenol, among others, alkylphenols such as butylphenol, octylphenol, and nonylphenol are the main components. This is preferable from the viewpoint of solubility. Resin B is easily produced by employing known methods. Specifically, it is produced by appropriately setting the following reaction conditions. That is, the amount of formaldehyde used is usually about 1 to 4 mol, preferably 1.5 to 3 mol, per 1 mol of the phenols. The alkaline catalyst is usually used in an amount of 0.5 to 30 mol% based on the phenols. The reaction temperature is about 40 to 100°C, and the reaction time is about 2 to 8 hours. Resin B obtained in this way usually has a molecular weight (weight average molecular weight in terms of polystyrene)
It is best to adjust it appropriately so that it is in the range of about 400 to 3500. The resin for printing ink of the present invention can be obtained by subjecting the thus obtained intermediate A and resin B to an esterification reaction using an acid catalyst under the following conditions. Further, if necessary, a polyhydric alcohol can be used in combination as a reaction component. In obtaining the resin for printing ink of the present invention, the charging ratio of intermediate A and resin B is appropriately determined in consideration of the gloss, solubility, and softening point of the resin for ink to be obtained, and is usually 100 parts of intermediate A. Approximately 5 to 140 parts (parts by weight, the same shall apply hereinafter), preferably 20 parts
It is recommended that the number of copies be in the range of ~100 copies. Less than 5 copies or
If it exceeds 140 parts, the softening point of the obtained ink resin tends to decrease, and especially if it exceeds 140 parts, there is a disadvantage that the color tone deteriorates. There are no particular restrictions on the type of acid catalyst;
Various materials used in the production of the intermediate A can be used as they are. The amount of the catalyst used is usually 0.01 to 0.3% by weight based on the intermediate. Incidentally, if necessary, triphenyl phosphite, triphenyl phosphate, etc. may be used as a co-catalyst for esterification, and these are also effective in preventing deterioration of the color tone of the resulting resin. In the present invention, the esterification reaction means that only intermediate A and resin B are used, and when a polyhydric alcohol is not used, a carboxyl group derived from rosin present in intermediate A and a carboxyl group derived from rosin present in intermediate A are used. refers to the dehydration reaction that occurs between the hydroxyl group derived from the phenols of resin B or the methylol group of resin B or the phenolic hydroxyl group derived from the phenol of resin B. On the other hand, when a polyhydric alcohol is used, the dehydration reaction It also includes the dehydration reaction between carboxyl groups derived from rosin and alcoholic hydroxyl groups derived from polyhydric alcohols. The esterification reaction is carried out as follows. That is, the esterification reaction involves, for example, predetermined amounts of each of the intermediate A, resin B, and optionally a polyhydric alcohol in the presence of an acid catalyst.
The ester reaction is carried out at 200 to 270°C with stirring for 5 to 15 hours until the desired acid value and softening point are achieved. In the esterification reaction, there is no particular restriction on the timing of charging the acid catalyst, and intermediate A, resin B, and polyhydric alcohol may be charged at the same time, or intermediate A may be heated in advance and then mixed with the acid catalyst. After the resin B and the acid catalyst are mixed and dropped, the polyhydric alcohol may be charged. As mentioned above, the polyhydric alcohol is used as an optional component in the esterification step of the present invention, and the type thereof is not particularly limited in the present invention, and various known ones can be used. Specific examples of such polyhydric alcohols include glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, and pentaerythritol. Since the amount of polyhydric alcohol used is closely related to the solubility of the resulting printing ink resin,
The content is limited to some extent, and is usually limited to a maximum of 10% by weight, preferably 6% by weight, based on Intermediate A. If it exceeds 10% by weight, it is not preferable because solubility decreases. The reaction product thus obtained has an acid value of usually 50 mgKOH/g or less, preferably 40 mgKOH/g.
g or less. This is because if the acid value exceeds 50 mgKOH/g, problems such as staining tend to occur during printing. Further, the softening point of the reaction product is usually 160°C or higher, preferably 170°C or higher. This is because if the temperature is lower than 160°C, the drying property and setting will be significantly reduced. The resin for printing ink of the present invention can be prepared using various known pigments, petroleum solvents, drying oils,
It can be made into a printing ink by appropriately blending additives and kneading it. The printing ink is
In addition to being particularly useful for offset printing, it can also be suitably used for letterpress printing and gravure printing. In preparing the ink, it is of course possible to use an appropriate amount of a known resin for printing ink such as a rosin-modified phenolic resin. Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples, but the present invention is not limited to these Examples. Reference example 1 Gum rosin 1000 (3.0 mol) and carbolic acid were placed in a flask equipped with a stirrer, a Liebig condenser, and a thermometer.
1000 (10.6 mol) and 0.7 part of para-toluenesulfonic acid as an acid catalyst were charged, and the temperature was raised to 150 to 170°C. Next, the reaction was carried out at the same temperature for 5 hours, and the temperature was further raised to 250 to 260°C while distilling off unreacted carbolic acid, yielding about 1250 parts of a rosin-phenol reaction product (hereinafter referred to as intermediate). The acid value of the intermediate is
107mgKOH/g, softening point 110℃, hydroxyl value 75
It was mgKOH/g. Reference Example 2 Same operation as in Reference Example 1 except that the amount of carbolic acid used was reduced to 570 parts (6.1 mol) and the reaction time at 150 to 170°C was extended to 10 to 13 hours. An intermediate with an acid value of 105 mgKOH/g, a softening point of 120°C, and a hydroxyl value of 70 mgKOH/g was obtained.
I got a department. Reference example 3 Add paraoctylphenol 1000 to a flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer.
(4.85 mol), 37% formalin 800 parts (9.87 mol)
and 110 parts of 48% sodium hydroxide were charged, and the temperature was raised to 90°C while stirring, and the reaction was carried out at the same temperature for 3 hours. Next, 500 parts of toluene was added and dissolved, and then a hydrochloric acid solution of 120 parts of 6N hydrochloric acid and 1000 parts of water was added to neutralize the sodium hydroxide, and the mixture was allowed to stand still. By separating the supernatant water layer and the resin layer and further washing the resin layer with water, about 1500 parts of a toluene solution of a resol type phenolic resin initial condensate with a non-volatile content of 66% was obtained. Further, the molecular weight of the resin was 1000. Reference example 4 In reference example 3, paraoctylphenol
The same operation as in Reference Example 3 was carried out, except that 700 parts (3.4 moles) of para-octylphenol and 220 parts (1.47 moles) of para-shaributylphenol were used instead of 1000 parts. Approximately 1,350 parts of a toluene solution of a resol type phenolic resin initial condensate having a non-volatile content of 64% was obtained. Further, the molecular weight of the resin was 1150. Reference Example 5 In Reference Example 3, paraoctylphenol
The same operation as in Reference Example 3 was carried out except that 700 parts (3.4 mol) of para-octylphenol and 320 parts (1.45 mol) of para-nonylphenol were used instead of 1000 parts, and a resol type phenolic resin initial condensation with a non-volatile content of 66% was obtained. Approximately 1,500 parts of a toluene solution of the same substance was obtained. Further, the molecular weight of the resin was 950. Reference Example 6 In Reference Example 3, paraoctylphenol
The same operation as in Reference Example 3 was performed except that 850 parts (4.13 mol) of para-octylphenol and 110 parts (0.73 mol) of para-octylphenol were used instead of 1000 parts, and a resol type phenolic resin with a non-volatile content of 66% was obtained. Approximately 1515 parts of a toluene solution of the initial condensate was obtained. Further, the molecular weight of the resin was 1100. Example 1 The intermediate obtained in Reference Example 1 was placed in a flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer.
1,000 parts and 600 parts of a toluene solution of the resol type phenolic resin initial condensate obtained in Reference Example 3 (equivalent to 400 parts as solid content), 1 part of para-toluenesulfonic acid as an esterification catalyst, and triphenylphosphite as a co-catalyst. Pour 1 part and heat to 250-260℃ while distilling toluene off.
The esterification reaction was carried out for 10 hours, yielding about 1300 parts of the resin for printing ink of the present invention. The acid value of this thing is 16
mgKOH/g, the softening point is 184℃, and the tolerance to normal paraffin solvent (manufactured by Nippon Oil Co., Ltd., trade name "Nisseki No. 0 Solvent") is 25℃.
It was 2.0g/g. Examples 2 to 8 In Example 1, the type of intermediate used, the amount of the intermediate used, the type of toluene solution of the resol type phenolic resin initial condensate used, the amount of the solution used,
At least one of the amount of paratoluenesulfonic acid used and the amount of triphenylphosphite used
Various resins were obtained by carrying out the same operations as in Example 1 except that the seeds were changed as shown in Table 1. The acid value, softening point, and tolerance of these items are
Shown in the table. Example 9 The intermediate obtained in Reference Example 1 was placed in a flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer.
1000 parts, 900 parts of toluene solution of the resol type phenolic resin initial condensate obtained in Reference Example 3 (equivalent to 600 parts as solid content), 0.2 part of para-toluenesulfonic acid and 0.5 part of triphenyl phosphorite were charged, and toluene was added. 250-260 while distilling off
The temperature was raised to ℃. Furthermore, at the same temperature, glycerin
50 parts were charged and the esterification reaction was carried out for 6 hours, yielding about 1500 parts of resin. The acid value of this thing is 21mg
KOH/g, softening point is 173℃, tolerance is
It was 1.3 g/g at 25°C. Comparative Example 1 In the reaction apparatus of Example 1, 1000 parts of gum rosin, 1515 parts of a toluene solution of the resol type phenolic resin initial condensate obtained in Reference Example 3 (equivalent to 1000 parts as a solid), and para-toluenesulfone as an esterification catalyst. 3 parts of acid and 3 parts of triphenyl phosphorite as a co-catalyst were charged, the temperature was raised while toluene was distilled off, and the esterification reaction was carried out at 250-260°C for 2 hours, yielding about 2000 parts of resin for printing ink. The acid value of this material is 20mgKOH/g, and the softening point is
The temperature was 152°C, and the tolerance was 12.0g/g at 25°C. Comparative Example 2 In the same reaction apparatus as used in Example 1, 1000 parts of gum rosin, 1515 parts of a toluene solution of the resol type phenolic resin initial condensate obtained in Reference Example 6 (equivalent to 1000 parts as solid content), and ester were added. 3 parts of para-toluenesulfonic acid as a catalyst and 3 parts of triphenyl phosphite as a co-catalyst were charged, and heated to 250-260°C while distilling toluene off.
The esterification reaction was carried out for 2 hours, yielding approximately 2000 parts of resin for printing ink. The acid value of the obtained resin is 20 mg.
KOH/g, softening point is 163℃, tolerance is
It was 9.0 g/g at 25°C. Inks were prepared by the following method using the printing ink resins of the present invention obtained in Examples 1 to 9 and the comparative printing ink resins obtained in Comparative Examples 1 to 2. Performance was evaluated. The evaluation results are shown in Table 3. (Preparation of ink) A varnish was obtained by mixing and dissolving 45 parts of resin, 20 parts of linseed oil, and 35 parts of Nisseki No. 5 solvent. This varnish was kneaded using three rolls at the following blending ratio to form an ink. Carmine 6B (red pigment) 20 parts The above varnish 65-70 parts Nisseki No. 5 solvent 4-9 parts Friction improver (wax-based compound) 5 parts Ink dryer 1 part Based on the above formulation, the tack value of the ink is 9 ±
0.5, and the flow value was adjusted to be 18±0.5. (Gloss) After applying 0.4 ml of ink on art paper using an RI tester (manufactured by Mei Seisakusho Co., Ltd.), the humidity was controlled at 20°C and 65% RH for 24 hours, and the reflectance at 60°-60° ( %) was measured using a gloss meter. (Set) After spreading 0.4ml of ink onto art paper using an RI tester (manufactured by Mei Seisakusho Co., Ltd.), divide the displayed color object into sections according to time, and use the RI tester roller to separate art from the displayed color object. Observe the degree of ink adhesion on the paper,
The time (minutes) until the ink stopped adhering was measured. (Misting) Charge 4ml of ink to an incormeter,
The roll was rotated at 400 rpm for 1 minute and then at 1200 rpm for 3 minutes, and the degree of ink scattering on white paper placed directly below the roll was observed and evaluated.

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[Table] [Effects of the Invention] The printing ink resin of the present invention has significantly improved the drawbacks of conventionally known rosin-modified phenolic resins, and has excellent gloss, set, and high gloss even under high-speed printing.
Since it can sufficiently satisfy printing suitability such as misting, it has the effect of being able to provide a printing ink that meets today's demands such as high-speed printing.

Claims (1)

[Scope of Claims] 1. A reaction obtained by subjecting a rosin and a phenol to a heating reaction in the presence of an acid catalyst to cause an esterification reaction between a reactant A and a resol type phenolic resin B in the presence of an acid catalyst. Printing ink resin made from the product. 2. The printing ink resin according to claim 1, which is obtained by carrying out an esterification reaction using a polyhydric alcohol in an amount not exceeding 10% by weight based on the amount of the reactant A charged. 3 The resol type phenolic resin B has 4 carbon atoms.
The resin for printing ink according to claim 1, which is a resol type phenolic resin using an alkylphenol having 12 to 12 alkyl groups as the main component of the phenol. 4. A resin for printing ink, characterized in that a reaction product A obtained by heat-reacting rosins and phenols in the presence of an acid catalyst and a resol type phenolic resin B are subjected to an esterification reaction in the presence of an acid catalyst. Manufacturing method.