JPH11286528A - Rosin-modified phenol resin, its production and resin for printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rosin-modified phenol resin exhibiting sufficiently high solubility to a non-aromatic solvent and having high varnish viscosity. SOLUTION: This rosin-modified phenol resin is obtained by reacting (a) rosins or rosin esters with (b) a carboxylic acid compound having hydroxyl group and (c) a resol type phenol resin, or by reacting (a) rosins with (b) a carboxylic acid compound having hydroxyl group and (c) a resol type phenol resin and then reacting the reaction product with (d) a polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a rosin-modified phenolic resin, a method for producing the same, and a resin for printing ink. The rosin-modified phenolic resin obtained by the present invention is useful as a resin for offset printing inks, particularly a resin for offset printing inks suitable for non-aromatic ink solvents and a resin for offset printing inks suitable for high-speed printing.

[0002]

2. Description of the Related Art Conventionally, an aromatic ink solvent has been used as a solvent for a printing ink resin using a rosin-modified phenol resin. However, in recent years, environmental problems such as air pollution by an organic solvent and work environment. The problem of safety and health has been pointed out, and replacement with non-aromatic ink solvents mainly comprising naphthene and paraffin has been promoted. However, since such a non-aromatic ink solvent has extremely poor solubility in rosin-modified phenolic resins, those having a boiling point usually used as an ink solvent impair printability such as ink fluidity, and as a result, gloss There is a drawback that a printing effect such as a reduction in printing effect is caused. In recent years,
Although the printing speed has been increased, the varnish viscosity of conventional rosin-modified phenolic resins is insufficient, and the suitability of low misting and low tack required for high-speed printing is insufficient. It causes troubles such as paper peeling on printed matter.

Under these circumstances, development of a rosin-modified phenol resin having high solubility in non-aromatic ink solvents and high varnish viscosity has been desired. However, maintaining solubility in the ink solvent and increasing the varnish viscosity are conflicting properties of the resin,
It was difficult to achieve these performances simultaneously.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a rosin-modified phenol resin exhibiting sufficiently high solubility in non-aromatic solvents and having a high varnish viscosity.

[0005]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies in order to find a rosin-modified phenol resin having desired properties. As a result, a rosin-modified phenol obtained by adding a carboxylic acid compound having a hydroxyl group, which can bind to both unreacted hydroxyl groups and carboxyl groups, which has occurred in the conventional rosin-modified phenol resin, during the synthesis reaction of the rosin-modified phenol resin. It has been found that the resin can solve the above problem.

That is, the present invention provides a rosin-modified phenol resin obtained by reacting (a) a rosin or a rosin ester, (b) a carboxylic acid compound having a hydroxyl group and (c) a resole-type phenol resin, and a)
After reacting rosins, (b) a carboxylic acid compound having a hydroxyl group and (c) a resole type phenol resin,
(D) The present invention relates to a rosin-modified phenol resin obtained by reacting a polyol. The present invention also relates to a printing ink resin using the rosin-modified phenol resin. Further, the present invention provides a method for producing a rosin-modified phenol resin, which comprises reacting (a) a rosin or a rosin ester, (b) a carboxylic acid compound having a hydroxyl group, and (c) a resol-type phenol resin. And (d) reacting (a) a rosin, (b) a carboxylic acid compound having a hydroxyl group, and (c) a resole-type phenol resin, and then reacting with (d) a polyol to produce a rosin-modified phenol resin. About the law.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Among the components (a) in the present invention, rosins include gum rosin, tall oil rosin,
Examples thereof include wood rosin, disproportionated rosin, hydrogenated rosin, polymerized rosin, modified products thereof, and salts of these with metals. In addition, rosin esters refer to those obtained by reacting rosins with polyols. Examples of the polyol include various types conventionally known as a polyol component of a rosin-modified phenol resin, such as pentaerythritol and glycerin. These (a) rosins or rosin esters may include rosin esters modified with carboxylic acids as necessary. Specific examples of the component (a) generally include ester gum, maleated rosin, fumarated rosin, maleated rosin ester, and fumarated rosin ester.

The (b) carboxylic acid compound having a hydroxyl group in the present invention refers to one or more of a saturated aliphatic hydrocarbon and / or an unsaturated aliphatic hydrocarbon (each of which may have an aromatic ring). A hydroxyl group and a carboxyl group are substituted. Preferably, the hydroxyl group is a phenolic hydroxyl group and / or the carboxylic acid is an aromatic carboxylic acid. Further, when the carboxylic acid is an aromatic carboxylic acid, orthohydroxybenzoic acid, metahydroxybenzoic acid, preferably contains hydroxybenzoic acid of parahydroxybenzoic acid, particularly preferably contains parahydroxybenzoic acid This is the case.

The component (b) reacts with both unreacted hydroxyl groups and carboxyl groups, which have been produced in the conventional rosin-modified phenol resin, to form an ester bond, and has the effect of increasing the molecular weight of the rosin-modified phenol resin. Have.
This rosin-modified phenol resin having a high molecular weight has a high varnish viscosity and is a raw material of an ink suitable for high-speed printing.
Further, the formed ester bond has a lower polarity than a hydroxyl group or a carboxylic acid, and shows high solubility in a non-aromatic ink solvent. Thereby, it is possible to simultaneously achieve the conflicting resin performances of increasing the varnish viscosity while maintaining the solubility in the ink solvent.
As the component (b), one type may be used alone, or 2
Different types or more may be used in combination.

The (c) resole type phenol resin includes phenols (P) and formaldehyde (F)
Are added and condensed in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., in an F / P (molar ratio) range of usually 1.0 to 3.0. Known condensates can be used. As the component (c), a component obtained by neutralizing and washing with water as necessary can be used. The phenols include phenol, cresol, amylphenol, bisphenol-A, p-butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol and the like. Among these phenols, alkyl-substituted phenols are preferred.

The rosin-modified phenolic resin of the present invention comprises:
(A) a method of reacting rosins or rosin esters, component (b) and component (c) (hereinafter referred to as production method 1), and (a) rosin, component (b) and component (c) And then reacting the component (d) (hereinafter referred to as Production Method 2). The production method 1 specifically includes a method of reacting the component (c) with the component (b) added to the rosin or rosin ester (a). Also, as the manufacturing method 2,
Specifically, a method of reacting the component (c) with the component (a) obtained by adding the rosin and the component (b) and then reacting the component (d) may be mentioned. Those obtained through these reaction sequences have high solubility in non-aromatic solvents. The amount of the component (b) used is about 1 to 20 parts by weight based on 100 parts by weight of the component (a). (A)
The amount of the component (c) used is about 10 to 100 parts by weight based on 100 parts by weight of the component. (A) Component 100
The amount of component (d) used is about 1 to 20 parts by weight based on parts by weight.

The reaction temperature of the component (a) to which the component (b) is added and the component (c) is usually 220 to 26.
It is about 0 ° C. for about 2 to 6 hours. The rosin-modified phenolic resin of the present invention can be obtained by reacting the component (a) with the component (c) and then reacting the component (b).

The rosin-modified phenolic resin of the present invention thus obtained can be used as a resin for printing ink. As for the type of printing ink, it can be used especially for offset printing ink, and can also be suitably used for letterpress printing ink and gravure printing ink. When a rosin-modified phenol resin is used as a resin for a printing ink, a varnish is prepared and used by a known method.

[0014]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but it is needless to say that the present invention is not limited to these Examples. Hereinafter, "parts" indicates parts by weight.

Example 1 A flask equipped with a stirrer, a reflux condenser equipped with a water separator and a thermometer was charged with 1000 parts of gum rosin, and stirred under stirring.
The temperature was raised to 80 ° C. to be melted. Then, 90 parts of pentaerythritol and 5 parts of calcium hydroxide were added,
The temperature was raised to 280 ° C. with stirring, and the reaction was continued until the acid value became 20 or less. After cooling to 180 ° C., 2 parts of parahydroxybenzoic acid were charged and the temperature was raised to 220 ° C. In a warm state, 600 parts (solid content: 420 parts) of a 70% xylene solution of resol-type p-nonylphenol was dropped into the system over 5 hours, and the temperature was gradually raised to 250 ° C. After the completion of the dropwise addition, the pressure was reduced at 160 mmHg for 10 minutes, followed by cooling to obtain 1600 parts of a solid resin. The tolerance of a 33% by weight AF7 solvent (a non-aromatic solvent, manufactured by Nippon Oil Co., Ltd.) solution of the rosin-modified phenol resin thus obtained was 3.
It was 0 g / g.

Comparative Example 1 Into the same flask as in Example 1, 1000 parts of gum rosin were charged and heated to 180 ° C. with stirring to melt. Then, 90 parts of pentaerythritol and 5 parts of calcium hydroxide were added, and the mixture was heated to 280 ° C. with stirring and reacted until the acid value became 20 or less. After cooling to 220 ° C, 600 parts of a 70% xylene solution of resol-type p-nonylphenol (420 parts of solid content) were added to the mixture in a warm state.
The solution was dropped into the system over time, and the temperature was gradually raised to 250 ° C. After the completion of the dropwise addition, the pressure was reduced at 160 mmHg for 10 minutes, followed by cooling to obtain 1600 parts of a solid resin. 33 g of rosin-modified phenol resin thus obtained, 2.5 g of AF7 solvent (Nippon Oil Co., Ltd., non-aromatic solvent)
/ G.

(Preparation of Varnish) Example 1 or Comparative Example 1
45 parts of the rosin-modified phenolic resin, 8 parts of linseed oil and AF Solvent 7 (Nippon Oil Co., Ltd.) 4
6.25 parts, further 0.75 parts of aluminum chelate at 190 ° C
And mixed to obtain a varnish.

(Varnish Performance Test) Varnish Viscosity: Measured at a temperature of 25 ° C. using a cone and plate type viscometer manufactured by Nippon Rheological Instruments Co., Ltd. The viscosity of the varnish using the rosin-modified phenol resin obtained in Example 1 was 1200 Poise. Comparative Example 1 had 900 Poise.

(Preparation of Printing Ink) Printing ink was prepared by using the varnish to prepare a printing ink at the following mixing ratio using a three-roll mill. Phthalocyanine blue (indigo pigment) 15 parts The varnish 65 to 73 parts AF Solvent 7 12 to 20 parts Based on the above composition, the ink flow value was 18.0 ± 1.
It was adjusted appropriately to be 0.

(Performance test of printing ink) Emulsification ratio: 3.9 ml of ink was spread on a dynamic emulsification tester (manufactured by Nippon Rheological Instruments Co., Ltd.), and pure water was supplied at 200 rpm at a rate of 5 ml / min. Supplied. Since the ink reached the maximum emulsification about 1 minute after the supply of water was started, the moisture content in the ink at that time was measured by an infrared moisture meter. The smaller the water content, the better the emulsification resistance. The water content of the ink using the rosin-modified phenolic resin obtained in Example 1 and Comparative Example 1 was 15%.

Tack: 1.3 ml of ink was spread on a roll of an incomometer (manufactured by Toyo Seiki Co., Ltd.), and 400 r
The tack value was read at 1 minute after the start of measurement at 1600 rpm. The tack at 400 rpm of the ink using the rosin-modified phenolic resin obtained in Example 1 was 6.2, and that of Comparative Example 1 was 6.9. In addition, the tack at 1600 rpm of the ink using the rosin-modified phenol resin obtained in Example 1 was 10.2.
The value of Comparative Example 1 was 12.0.

[0022]

According to the present invention, a sufficiently high solubility in a non-aromatic solvent and a high varnish viscosity suitable for high-speed printing can be obtained without impairing various properties required for a printing ink resin. Can be obtained.

Claims (10)

[Claims] 1. A rosin-modified phenol resin obtained by reacting (a) a rosin or a rosin ester, (b) a carboxylic acid compound having a hydroxyl group, and (c) a resol-type phenol resin. 2. A rosin-modified phenol resin obtained by reacting (a) a rosin, (b) a carboxylic acid compound having a hydroxyl group, and (c) a resole-type phenol resin, and then reacting with (d) a polyol. 3. The rosin-modified phenolic resin according to claim 1, wherein the hydroxyl group of the component (b) is a phenolic hydroxyl group and / or the carboxylic acid is an aromatic carboxylic acid. 4. The rosin-modified phenolic resin according to claim 1, wherein the component (b) contains hydroxybenzoic acid. 5. The rosin-modified phenolic resin according to claim 1, wherein the component (b) contains parahydroxybenzoic acid. 6. The rosin-modified phenol resin according to claim 1, wherein the amount of the component (b) is 1 to 20 parts by weight based on 100 parts by weight of the component (a). 7. The rosin-modified phenolic resin according to claim 1, wherein the amount of the component (c) is 10 to 100 parts by weight based on 100 parts by weight of the component (a). 8. A resin for printing ink using the rosin-modified phenol resin according to claim 1. 9. A method for producing a rosin-modified phenol resin, comprising reacting (a) a rosin or a rosin ester, (b) a carboxylic acid compound having a hydroxyl group, and (c) a resol-type phenol resin. 10. A rosin-modified phenol characterized by reacting (a) a rosin, (b) a carboxylic acid compound having a hydroxyl group and (c) a resole-type phenol resin, and then reacting (d) a polyol. Method of manufacturing resin.