JPH01170676A - Resin for printing ink and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title resin capable of satisfying printability, such as gloss, setting or misting, even under high-speed printing, by reacting a specific rosin phenol reaction product with formaldehyde in the presence of an acid catalyst and then subjecting the resultant novolak substance to esterification reaction. CONSTITUTION:The aimed resin consisting of a reaction product obtained by reacting (A) 100 pts.wt. reactant prepared by reacting 1 mol rosin with 1.5-4 mol phenols in the presence of an acid catalyst with (B) 10-100 pts.wt. alkylphenols having 4-12C alkyl group and (C) 4-22 pts.wt. formaldehyde in the presence of an acid catalyst to provide a novolak substance and subjecting the resultant substance to esterification reaction and meeting present demands, such as resource saving and higher-speed printing.

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 prized as resins for printing inks, especially 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. is absorbed into the paper fibers and coating layer, causing a rapid thickening of the ink, and the color does not transfer to the back side of the printed matter that is piled up one after another.Good setting means that the ink is absorbed from the time of printing to the time of setting. (referring to the short elapsed time), and other performance requirements are also becoming more sophisticated.

However, conventional printing inks using rosin-modified phenolic resin as a vehicle have drawbacks such as insufficient setting and misting (a phenomenon in which the printing ink becomes atomized and scatters when the printing press is operated). .

In general, gloss, drying performance, and setting are contradictory performances, and it is often difficult to maintain a balance between the two. Therefore, the required performance (hereinafter referred to as There is a need for the development of a resin for printing ink that can simultaneously satisfy the following requirements (printability).

[What the invention aims to solve] In view of the actual situation that conventionally known rosin-modified phenolic resins cannot satisfy the printability during high-speed printing, the present inventors have attempted to solve this drawback. The aim was to develop a new resin for printing ink.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors focused on the molecular structure, physical constants, etc. of the rosin-modified phenolic resin and conducted intensive studies on various manufacturing methods to obtain the desired resin. I did it.

As a result, the present inventors conducted a so-called novolac reaction between a specific rosin-phenol reactant and formaldehyde in the presence of an acid catalyst, and then esterified the reaction to obtain a specific phenol-modified rosin resin for the purpose of the present invention. It has been discovered that the resin is an excellent resin for printing ink that satisfies the above requirements (see specification of Japanese Patent Application No. 1982-1920).

Furthermore, in order to provide a resin that further improves the gloss and solubility of the resin for printing ink, the present inventors conducted intensive studies focusing on phenols, which are the raw materials used, and found that in the resin for printing ink, Furthermore, we have found that it is effective to use specific alkylphenols in combination. The present invention was completed based on this new knowledge.

That is, the present invention is directed to (1) reactants obtained by heat-reacting rosins and phenols in the presence of an acid catalyst, alkylphenols containing an alkyl group having 4 to 12 carbon atoms, and formaldehyde in the presence of an acid catalyst; A resin for printing ink consisting of a reaction product obtained by at least forming a novolac compound and then subjecting the novolac compound to an esterification reaction, and (1) a reaction obtained by subjecting rosins and phenols to a heating reaction in the presence of an acid catalyst. Production of a resin for printing ink, which is characterized by reacting alkylphenols having an alkyl group having 4 to 12 carbon atoms and formaldehyde in the presence of an acid catalyst to form a novolac compound, and esterifying the same with jjl. Regarding the law.

[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. This is a new printing ink that has excellent suitability for high-speed printing and eliminates all of the problems encountered with phenolic resins.

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 resin for printing ink of the present invention is produced by forming a novolac compound from a specific intermediate, a specific alkylphenol, and formaldehyde, and then esterifying the novolak compound by holding it at high temperature in the presence or absence of a polyhydric alcohol. It can be obtained by forcing people to do something.

In the first step, the resin for printing ink of the present invention is prepared by adding predetermined amounts of an intermediate, alkylphenols, and formaldehyde, and heating the resin at about 100 to 120°C for 3 to 30 minutes in the presence of an acid catalyst.
React for 6 hours to obtain a novolac compound.

The intermediate in the present invention is a reaction product obtained by subjecting rosins and phenols to a heating reaction in the presence of an acid catalyst.

1+1-, rosins include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, polymerized rosin, and the like. As the phenols, carbolic acid and cresol are suitable. As an acid catalyst, para-toluenesulfonic acid,
Preferred are 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, 1.5 to 4 moles of phenols are added to 1 mole of the rosin at about 140 to 180°C in the presence of an acid catalyst.
Allow to react for 4 to 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 is no particular restriction on the amount of acid catalyst used, but it is usually 0.05% for rosin.
~0.5% (weight %, hereinafter the same). Although the structure of this intermediate is still unclear, it is believed 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 phenol is replaced by the rosin. It will be done.

The intermediate has an acid value of 100 to 110 and a hydroxyl value of BO to 9.
0, and 5! as appropriate by manipulating the reaction conditions so that the softening point is in the range of 100 to 120°C. J can be adjusted.

The alkylphenols used when converting the intermediate into a novolak include those whose alkyl group has 4 to 12 carbon atoms,
Various alkylphenols preferably having 4 to 9 alkylphenols are mentioned, and specific examples thereof include butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, and the like. There are no particular restrictions on the use of the alkylphenols, and it is determined by considering the gloss and solubility of the resulting printing ink resin, but usually 100 parts (parts by weight,
10 to 100 parts, preferably 15 to 100 parts (same below)
It may be within the range of 65 parts. If it exceeds 100 parts, the softening point of the resin for printing ink will be significantly lowered, which is not preferable.

Formaldehyde is an essential component for converting the intermediate into a novolak-type phenol-modified rosin resin.

Formaldehyde herein means a formaldehyde supply substance, and examples thereof include formaldehyde and paraformaldehyde.

The amount of formaldehyde used varies depending on the type of alkylphenol and the amount used, but is usually 4 to 22% based on the intermediate. If the amount of formaldehyde used is less than 4%, the molecular weight of the resulting resin will decrease, and if it exceeds 22%, the molecular weight will be high, and in some cases, gelation will occur, so both are unfavorable. .

There is no particular restriction on the type of acid catalyst used to obtain the novolac body, and various known novolak-forming catalysts used in the production of ordinary novolak resins can be used. Specifically, the various materials used in producing the intermediates can be used as they are. The amount of the acid catalyst used is usually 0. O1 to 0.5%.

There are no particular limitations on the acid value and molecular weight of the novolak compound obtained in this way, but they are usually 80 to 10, respectively.
It is preferably 0.700 to 1200.

Next, as a second step for converting the novolak body into the printing ink resin of the present invention, the novolak body is subjected to an esterification step.

Here, the esterification process is a process that occurs between the carboxyl group derived from rosin and the phenolic hydroxyl group derived from phenol present in the novolak body, if a polyhydric alcohol is not used for the novolac body. On the other hand, when a polyhydric alcohol is used for a novolak compound, not only the dehydration reaction but also the reaction between the carboxyl group derived from the rosin and the alcoholic hydroxyl group derived from the polyhydric alcohol occurs. Refers to a dehydration reaction.

The esterification reaction is carried out as follows.

That is, the esterification reaction is carried out, for example, by combining the novolac compound and a polyhydric alcohol in the presence of an acid catalyst at a temperature of about 200 to 2
The ester reaction is carried out at 70° C. with stirring for 5 to 15 hours until the desired acid value and softening point are achieved.

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. The amount of polyhydric alcohol to be used is closely related to the solubility of the resulting printing ink resin, and is therefore limited to some extent, and is usually at most 10%, preferably up to 6%, based on the novolak. . If it exceeds 10%, the solubility decreases, which is not preferable. Incidentally, triphenyl phosphite or triphenyl phosphate can also be used as a co-catalyst for esterification if necessary.

(The resulting reaction product usually has an acid value of 50
Hereinafter, preferably 40 or less. This is because if the acid value exceeds 50, troubles such as stains tend to occur during printing. Also, the softening point of resin is usually 180
℃ or higher, preferably 170℃ or higher. This is because if the temperature is lower than 160°C, the drying property and setting will be significantly reduced. The solubility of the resin for printing ink of the present invention, which is the reaction product obtained in this way, is appropriately determined in consideration of the workability during printing ink production and printing, and is usually determined by Tolerance is 8
It is preferable that it is more than g/g. Here, the tolerance refers to the amount (g) of solvent used until the dissolved material becomes cloudy when 1 g of resin is dissolved with the solvent.

In addition, in the printing ink resin, methylene bonds based on novolac formation reactions and ester bonds based on esterification reactions clearly exist. This fact is confirmed from the results of NMR and IR measurements. For example, according to IR, 174
A characteristic absorption of the ester bond is observed in 8CI11-'.

The resin for printing ink of the present invention can be made into a printing ink by suitably blending and kneading various known pigments, petroleum solvents, drying oils, additives, etc. in a conventional manner. The printing ink is particularly useful for offset printing, and can also be suitably used for letterpress printing and gravure printing. In preparing the ink, an appropriate amount of a known resin for printing ink such as a rosin-modified phenol resin may be used in combination.

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 such merits and benefits.

Reference Example 1 A flask equipped with a stirrer, a Liebig condenser and a thermometer was charged with 1000 parts of gum rosin, 1000 parts of coal, and 0.7 parts of para-toluenesulfonic acid as an acid catalyst, and heated to 150 to 170°C at rA.

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, and the rosin-phenol reaction product (hereinafter referred to as intermediate) was reacted for about 12 hours.
I got 50 copies. The intermediate has an acid value of 107 and a softening point of 110.
℃, and the hydroxyl value was 75.

Reference Example 2 In Reference Example 1, the amount of carbolic acid used was reduced to 570 parts, and the reaction time at 150 to 170°C was changed to 10 to 13 parts.
The same F ball operation as in Reference Example 1 was carried out except that the time was extended, and about 1200 parts of an intermediate having an acid value of 105, a softening point of 120° C., and a hydroxyl value of 70 was obtained.

Example 1 1000 parts of the intermediate obtained in Reference Example 1, 200 parts of paraoctylphenol, 63 parts of paraformaldehyde, 0.5 part of paratoluenesulfonic acid, and xylene were placed in a flask equipped with a stirrer, a Liebig condenser, and a thermometer. 2
12 parts were charged and the temperature was raised to 00 to 110°C.

After carrying out the novolac formation reaction at the same temperature for 4 hours, the temperature was heated to 250 to 260°C while distilling off xylene. Furthermore, an esterification reaction was carried out at the same temperature for 10 hours,
1137 parts of the resin for printing ink of the present invention was obtained. The acid value of this material was 23, the softening point was 177°C, and the tolerance of the resin to petroleum solvents (manufactured by Nippon Oil Company, trade name: "Shiraishi No. 5 Solvent") was 20 g/g or more at 25°C. .

Example 2 In Example 1, the amounts of paraoctylphenol, paraformaldehyde and xylene used were changed to 4 in each order.
Example 1 except that the parts were changed to 00 parts, 95 parts, and 247 parts.
The same operation as above was carried out to obtain 1346 parts of a resin having an acid value of 25 and a softening point of 178°C. The tolerance of this resin to Shiraishi No. 5 solvent was 20 g/g or more at 25°C.

Example 3 In Example 1, the amounts of paraoctylphenol, paraformaldehyde, paratoluenesulfonic acid, and xylene used were 600 parts, 127.3 parts, and 0.0 parts, respectively.
The same operation as in Example 1 was carried out except that the amounts were changed to 68 parts and 282 parts, and resin 15 with an acid value of 22 and a softening point of 181'C was used.
It sold 54 copies. The tolerance of this resin to Shiraishi No. 5 solvent was 20 g/g or more at 25°C.

Example 4 In Example 1, the amounts of paraoctylphenol, paraformaldehyde, paratoluenesulfonic acid, and xylene used were 900 parts, 157.5 parts, and 0.0 parts, respectively.
The same operation as in Example 1 was carried out except that the amounts were changed to 75 parts and 336 parts, and resin 185 with an acid value of 30 and a softening point of 169°C was used.
I got 2 copies. The tolerance of this resin to petroleum-based solvents (manufactured by Nippon Oil Company, trade name: Shiraishi No. 5 Solvent) is 25.
It was 20g/g or more at ℃.

Example 5 The same operation as in Example 3 was carried out except that para-octylphenol was replaced with para-tert-butylphenol and the amount of paraformaldehyde used was changed to 154.8 parts, and the acid value was 19 and the softening point was 183. 1558 parts of resin were obtained. The tolerance of this resin to Shiraishi No. 5 solvent was 8.3 g/g at 25°C.

Example 6 The same operation as in Example 3 was carried out except that paraoctylphenol was changed to paranonylphenol and the amount of paraformaldehyde used was changed to 127.0 parts, and the acid value was 21 and the softening point was 163°. C resin 1563
I got a department. The tolerance of this resin to Shiraishi No. 5 solvent was 20 g/g or more at 25°C.

Example 7 The same procedure as in Example 1 was carried out up to the novolac formation reaction, and after the temperature was raised to 250 to 260°C, 50 parts of glycerin was added and the esterification reaction was carried out at the same temperature for 8 hours, resulting in an acid value of 21. 1182 parts of resin with a softening point of 176°C was obtained. The tolerance of this resin to Shiraishi No. 5 solvent was 20 g/g or more at 25°C.

Example 8 The same operation as in Example 1 was carried out except that the type of intermediate used in Example 1 was changed to that obtained in Reference Example 2, and 1132 parts of a resin having an acid value of 20 and a softening point of 179°C were used. I got it.

The tolerance of this resin to Nisseki No. 5 solvent is 25.
It was 20g/g or more at °C.

Comparative Example 1 Commercially available rosin modified phenol resin (manufactured by Arayo Kagaku Kogyo ■,
Product name "Tamanol 354", acid value 18, softening point 170℃
, the tolerance for Shiraishi No. 5 solvent is 4 at 25℃.
．． 0g/g) was used.

Comparative Example 2 Using the same reaction apparatus as in Example 1, 1000 parts of the intermediate obtained in Reference Example 1, 45 parts of paraformaldehyde, 1.5 parts of paratoluenesulfonic acid, and 150 parts of xylene
The temperature was raised to 100-110°C. After carrying out the novolac formation reaction at the same temperature for 4 hours, the temperature was heated to 250 to 260° C. while distilling off xylene. Further, an esterification reaction was carried out at the same temperature for 8 hours, yielding about 950 parts of resin for printing ink. The acid value of this thing is 25, soft fζ
The temperature was 177°C, and the tolerance of the resin to Shiraishi No. 5 solvent was 5.7 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 8 and the comparative printing ink resins obtained in Comparative Examples 1 and 2.
Their ink performance was evaluated. The evaluation results are shown in Table 1.

(Preparation of ink) A varnish was obtained by mixing and dissolving 45 parts of resin, 25 parts of linseed oil, and 30 parts of Shiraishi 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 5 parts compound) Dryer for ink 1 part Based on the above formulation, the tack value of the ink is 9 ±0.5, flow value is 18
It was adjusted to be ±0.5.

(Gloss) After applying 0.4 ml of ink on art paper using an RI tester (manufactured by Mei Seisakusho), the humidity was controlled at 20°C and 65% R111 for 24 hours, and the reflectance was 80"-60" ( %) was measured using a gloss meter.

(Set) Ink 0, 4 ml in R1 tester (Made by Mei Seisakusho)
After spreading the colors on art paper, divide the exhibited color by time and use an RI tester roller to observe the degree of ink adhesion from the exhibited color to another piece of art paper until the ink stops adhering. The time (minutes) was measured.

(Misting) Charge 4 ml of ink to the inkometer and
rpm for 1 minute and further at 1200 rpm for 3 minutes, the degree of ink scattering on white paper placed directly below the roll was observed, and evaluated according to the following criteria.

◎: Misting did not occur.

○: Misting occurred slightly.

Δ: Misting occurred to a noticeable extent.

×: Misting was completely generated.

[Margins below] Table 1 [Effects of the Invention] The printing ink resin of the present invention and its manufacturing method significantly improve the drawbacks of conventionally known rosin-edible phenolic resins, and maintain gloss even under high-speed printing. Since it is a material that fully satisfies printing suitability such as setting and misting, it has the effect of providing a printing ink that meets today's demands such as resource saving and high-speed printing.

Patent applicant: Arakawa Chemical Industry Co., Ltd./'-2fi

Claims (1)

[Scope of Claims] 1. A reactant obtained by heat-reacting rosins and phenols in the presence of an acid catalyst, a reaction product of an alkylphenol having an alkyl group having 4 to 12 carbon atoms, and formaldehyde in the presence of an acid catalyst. A resin for printing ink comprising a reaction product obtained by first forming a novolac compound and then subjecting the novolac compound to an esterification reaction. 2. The printing ink according to claim 1, wherein the reaction product is obtained by subjecting the novolak to an esterification reaction using a polyhydric alcohol in an amount not exceeding 10% by weight based on the novolak. resin. 3. A reaction product obtained by heat-reacting rosins and phenols in the presence of an acid catalyst, alkylphenols having an alkyl group having 4 to 12 carbon atoms, and formaldehyde in the presence of an acid catalyst to form a novolac compound, A method for producing a resin for printing ink, which is then subjected to an esterification reaction.