JPH07126338A - Rosin-modified phenol resin - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a novel rosin-modified phenolic resin having excellent gloss and satisfying printability even when a solvent for non-aromatic ink is used. [Structure] A rosin, a resole-type phenol resin using a phenol having a C10-C20 alkyl group, and a polyhydric alcohol are heated and reacted in the presence of an acid catalyst to give a weight average molecular weight of 3 10,000 to 250,000 rosin-modified phenolic resin, the solubility of which is 30% by weight or less in an aliphatic hydrocarbon solvent having 15 carbon atoms, and does not cause turbidity at 25 ° C. A rosin-modified phenolic resin characterized by:

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing ink resin suitable for a non-aromatic ink solvent.

2. Description of the Related Art Conventionally, aromatic solvents have been used as solvents for printing inks and paints. However, in recent years, environmental problems such as air pollution due to organic solvents and safety and health problems in the working environment have been pointed out, and in response to this, replacement with a non-aromatic ink solvent mainly containing naphthene and paraffin has been studied. There is. However, such a non-aromatic ink solvent has a drawback that it has a very poor dissolving power for a rosin-modified phenol resin. For example, the aniline point of the solvent is about 12 to 16 ° C. higher than that of the aromatic ink solvent having the same boiling point range. Therefore, in the conventional rosin-modified phenolic resin, the solvent is insufficient if it is replaced with the solvent having the same boiling point as it is, and the gloss of the printing ink is lowered and the printability is deteriorated.

Further, as the printing speed has been increased in recent years, in order to satisfy high-speed suitability such as misting resistance,
Increasing the molecular weight of ink resins is becoming indispensable. That is, it is desired to develop a resin for printing ink which has a high solubility in a non-aromatic ink solvent and a high molecular weight, as compared with a conventional rosin-modified phenol resin. As a means for increasing the solubility of a rosin-modified phenolic resin, (1) a method of using a large amount of a phenol having a C9 or less alkyl group as a phenol component of a rosin-modified phenolic resin, (2) a higher fatty acid, a drying oil alkyd resin,
Methods such as the combined use of linear reforming components such as drying oil have been adopted. However, in general, gloss and drying or misting are contradictory properties, and it is often difficult to balance these characteristics, and any of the above means tends to slow down drying and reduce misting resistance. There is.

Further, rosins and a resole-type phenol resin containing at least one phenol component selected from octylphenol and nonylphenol are heated and reacted in the presence of an acid catalyst to lower the acid value and to improve the solubility. An improved resin for printing ink is disclosed in JP-A-59-59.
It is disclosed in Japanese Patent No. 191776. Similarly, a reaction product (A) obtained by reacting a rosin and a phenol in the presence of an acid catalyst, and a resol type phenol resin (B) using an alkylphenol having an alkyl group having 4 to 12 carbon atoms. JP-A-1-275677 discloses a resin for a printing ink in which the acid value is lowered by reacting the above in the presence of an acid catalyst to improve the solubility. However, the resins for printing inks obtained by these means are excellent in solubility in all cases, but cannot obtain a molecular weight sufficient to satisfy high-speed suitability. Therefore, a polyhydric alcohol, epoxy, or the like may be used in combination to increase the molecular weight, but the solubility of these resins is disadvantageously greatly reduced. However, when using non-aromatic ink solvents, it retains sufficient solubility and has high gloss and drying properties, set performance, high speed suitability (misting resistance), emulsification characteristics, etc. (hereinafter referred to as print suitability). That is, there is a demand for the development of a printing ink resin that satisfies both of the above.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have stated that a conventionally known rosin-modified phenol resin aimed at improving gloss cannot satisfy printability in the use of a solvent for a non-aromatic ink. In view of the actual situation, it is an attempt to develop a new rosin-modified phenolic resin that can solve the problem.

In view of the above problems, the present inventors have conducted extensive studies to find a rosin-modified phenolic resin that can provide an offset printing ink composition having the desired properties. As a result, they have found the fact that when the following specific reaction product is used as a binder resin, an excellent printing ink composition that meets this purpose can be easily obtained. The present invention was completed for the first time based on this new finding.

That is, the present invention relates to rosins and C10-C.
A rosin-modified phenolic resin having a weight average molecular weight of 30,000 to 250,000, which is obtained by reacting a resol-type phenolic resin containing 20 alkyl group-containing phenols with a polyhydric alcohol by heating in the presence of an acid catalyst. A rosin-modified phenolic resin having a solubility of 30% by weight or less in an aliphatic hydrocarbon solvent having 15 carbon atoms and having no turbidity at 25 ° C. in the solution. .

The rosin-modified phenol resin of the present invention includes rosins (hereinafter referred to as component (A)), resol type phenol resin (hereinafter referred to as component (B)), polyhydric alcohol (hereinafter referred to as component (C)), An acid catalyst (hereinafter referred to as component (D)) is an essential constituent element. Examples of the component (A) include gum rosin, tall oil rosin, wood rosin, disproportionated rosin, polymerized rosin and modified products thereof.

Examples of the phenols as the component (B) include 4-decylphenol and 4- (1-butylhexyl).
Phenol, 4- (1-methylnonyl) phenol, 4
-(1-Ethyloctyl) phenol, 4- (1-propylheptyl) phenol, 4- (1-ethyl-1-methylheptyl) phenol, 4- [1-methyl-1-
(1-Methylethyl) hexyl] phenol, 4-
(1,1-dimethyloctyl) phenol, 4- [1-
Methyl-1- (1-methylpropyl) pentyl] phenol, 4-undecylphenol, 4- (1-pentylhexyl) phenol, 4- (1-methyldecyl) phenol, 4- ( 1-ethylnonyl) phenol, 4-
(1-Propyloctyl) phenol, 4- (1-butylheptyl) phenol, 4-dodecylphenol, 4
-(1,1,3,3,5,5-hexamethylhexyl)
Phenol, 4- (1-ethyldecyl) phenol, 4
-(1-Propylnonyl) phenol, 4- (1-butyloctyl) phenol, 4- (1-pentylheptyl) phenol, 4- (1-methylundecyl) phenol 4- ( 1,1-dimethyldecyl) phenol, 4-
(1,3,5,7-Tetramethyloctyl) pheno-
4-, 4-tridecylphenol, 4- (1-propyldecyl) phenol, 4- (1-butylnonyl) phenol
4- (1-pentyloctyl) phenol, 4-
(1-hexylheptyl) phenol, 4- (methyldodecyl) phenol, 4-tetradecylphenol, 4
-Pentadecylphenol, 4-hexadecylphenol-
4- (1-methylpentadecyl) phenol, 4-
(1-hexyldecyl) phenol, 4- (1-butyldodecyl) phenol, 4- (1-propyltridecyl) phenol, 4- (1-ethyltetradecyl) phenol, 4- (1-heptylnonyl) phenol, 4-
(1-Pentylundecyl) phenol, 4-heptadecylphenol, 4-octadecylphenol, 4-
(1-Methylheptadecyl) phenol, 4-nonadecylphenol, 4-eicosylphenol, 4- (1-
Examples thereof include methylnonadecyl) phenol. Further, the present invention is not necessarily limited to only C10-C20 alkylphenols, and common general-purpose phenols such as carboxylic acid, cresol, butylphenol,
It can be used in combination with amylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol and the like. However, if the amount of carboxylic acid, cresol, butylphenol, cumylphenol, etc. used is too large, the solubility often decreases.

Examples of the aldehyde component (B) include formaldehyde and paraformaldehyde. The amount of the aldehyde used with respect to the phenol component is 1 to 4 mol, preferably 1.5 to 3 mol, per 1 mol of the phenol component. Resol-type phenolic resin is known, and is obtained by reacting in the presence of an alkali catalyst. Examples of the alkali catalyst include oxides, hydroxides or acetates of sodium, calcium, zinc, potassium, magnesium, etc., ammonia, lower organic amines, etc., and these are 0.1 to 5% by weight relative to the phenol component. Used in proportion. The amount of the component (B) used is appropriately determined in consideration of the solubility and softening point of the resulting rosin-modified phenolic resin. The amount of the component (B) used is usually about 30 to 120 parts by weight, preferably 40 to 100 parts by weight, based on 100 parts by weight of the component (A). If the amount used is less than 30 parts by weight, a rosin-modified phenolic resin having the desired solubility cannot be obtained, and if it exceeds 120 parts by weight, the solubility will be too good. Is worse, and both are not preferable. The component (C) is not particularly limited and various known ones can be used, and specific examples thereof include glycerin, trimethylolethane, trimethylolpropane, diethylene glycol, pentaerythritol and the like.

The amount of component (C) used is 0.2 mol to 0.7 mol, preferably 0.3 to 0.6 mol, per 1 mol of component (A). If the amount used is less than 0.2 mol, a rosin-modified phenol resin having a desired molecular weight cannot be obtained, and if it exceeds 0.7 mol, a rosin-modified phenol resin having a desired solubility is not obtained. I can't get it. Examples of the component (D) include sulfonic acid salts such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, and mineral acids such as sulfuric acid and hydrochloric acid.
The amount is about 0.01 to 2 parts by weight based on 100 parts by weight of (B) in total. In the present invention, the reaction method is not particularly limited, as long as the above-mentioned constituents are used in predetermined amounts.
The ink resin of the present invention can be easily obtained by directly adopting the conventionally known method for producing a rosin-modified phenolic resin.

The solubility of the rosin-modified phenolic resin of the present invention in an aliphatic hydrocarbon solvent having 15 carbon atoms is preferably 30% by weight or less at 25 ° C. The method of expressing the solubility is indicated by the weight% of the resin in the solution at the point where the system is white and becomes turbid after the resin is heated and dissolved in the solvent used, and the solvent is dropped and stirred at 25 ° C. Therefore, the more compatible the resin, the lower the resin weight% at the point of clouding. In the examples of the present specification, the number of carbon atoms is 15
The solubility was measured using normal heptadecane of. The rosin-modified phenol resin of the present invention has a molecular weight of 30,000 to 250,000, preferably 40,000 to 200,000. This is because if it is less than 30,000, the misting resistance is significantly reduced. The softening point of the resin is not particularly limited, but is usually 120 ° C. or higher, preferably 120 to 200.
Approximately ℃. This is because when the temperature is lower than 120 ° C., the drying property and the setting are remarkably reduced. The rosin-modified phenolic resin of the present invention thus obtained is kneaded by appropriately mixing various known pigments, non-aromatic solvents, drying oils, friction resistance improvers, various additives such as dryers, etc. by a conventional method. Printing ink can be obtained by fleshing. The ink can be used not only in offset printing but also in waterless lithographic printing, letterpress printing and gravure printing. In the preparation of the above ink, a known printing ink resin such as a rosin-modified phenol resin may be used in combination within a range that does not reduce the effects of the present invention.

[0011]

EXAMPLES The present invention will be described below with reference to examples. In the examples, parts and% are parts by weight and% by weight, respectively. Production Example 1 (Production Method of Resol-Type Phenolic Resin Initial Condensate) 1000 parts of 4- (1,1-dimethyloctyl) phenol in a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, A mixture of 875 parts of 35% formalin and 60 parts of 93% sodium hydroxide was heated to 90 ° C.
After reacting for a time, 1000 parts of toluene was added, the resin was dissolved in toluene, 125 parts of 6N hydrochloric acid and a hydrochloric acid solution of 1000 parts of water were added, and the mixture was stirred and allowed to stand, and the supernatant layer of PH5-6 was taken out. After washing with water, a toluene solution of resol type phenolic resin (initial condensate) A having a nonvolatile content of 50% is about 20
I got 00 parts.

Production Example 2 4- (1,1 dimethyloctyl) phenol was changed to 4- (1,1,3,3,5,5-hexamethylhexyl) phenol in the process shown in Production Example 1. The same operation was performed to obtain about 2000 parts of a toluene solution of a resol type phenol resin (initial condensate) B having a nonvolatile content of 50%. Production Example 3 In the process shown in Production Example 1, the same operation was performed except that 4- (1,1 dimethyloctyl) phenol was changed to 4-pentadecylphenol, and a resol type phenol resin having a nonvolatile content of 50% (initial Condensate) C toluene solution about 2
000 copies were obtained. Production Example 4 In the process shown in Production Example 1, the same operation was performed except that 4- (1,1-dimethyloctyl) phenol was changed to 4- (1-methylpentadecyl) phenol, and a nonvolatile content of 50 %, About 2000 parts of a toluene solution of a resol type phenol resin (initial condensation product) D was obtained.

Production Example 5 In the process shown in Production Example 1, the same operation was repeated except that 4- (1,1 dimethyloctyl) phenol was changed to 4- (1-methylnonadecyl) phenol, and a nonvolatile content of 50 was obtained.
%, About 2000 parts of a toluene solution of a resol type phenol resin (initial condensate) E was obtained. Production Example 6 In the process shown in Production Example 1, the same operation was performed except that 4- (1,1 dimethyloctyl) phenol was changed to 4-octylphenol, and a resol type phenol resin having a nonvolatile content of 50% (initial condensate). ) F toluene solution about 200
I got 0 copies. Example 1 In a four-necked flask equipped with a stirrer and a Liebig condenser thermometer, 1000 parts of gum rosin, 1200 parts of resol type phenol resin A (corresponding to 600 parts of phenol resin), 40 parts of glycerin, and 3 parts of paratoluenesulfonic acid as a catalyst. Charge, heat while distilling off toluene, 250-
The reaction was carried out at 260 ° C for 3 hours to give an acid value of 20 and a softening point of 169.
About 2000 parts of a rosin-modified phenol resin having a normal clouding point of normal pentadecane of 25% was obtained.

Examples 2 to 5 The same procedure as in Example 1 was repeated except that the resole type phenolic resin A used was changed to the composition shown in Table 1 to obtain a rosin-modified phenolic resin of the present invention. .
The resin constants are shown in Table 1. Examples 6 to 8 In the same manner as in Example 1 except that the resole-type phenol resin A used had the composition shown in Table 1 and the amount of the phenol resin used was changed as shown in Table 1. The reaction was carried out to obtain the rosin-modified phenol resin resin of the present invention. The resin constants are shown in Table 1. Examples 9 to 10 Reactions were performed in the same manner as in Example 1 except that the resole-type phenol resin A used had the composition shown in Table 1 and the amount of glycerin used was changed as shown in Table 1. A rosin-modified phenol resin resin of the present invention was obtained.
The resin constants are shown in Table 1.

Examples 11 to 12 Reactions were performed in the same manner as in Example 1 except that the resol type phenol resin A used was changed to the composition shown in Table 1 to obtain the rosin-modified phenol resin resin of the present invention. It was The resin constants are shown in Table 1. Comparative Examples 1 to 3 Reactions were performed in the same manner as in Example 1 except that the resol-type phenol resin A used had the composition shown in Table 1 and the amount of glycerin used was changed as shown in Table 1. , A comparative resin was obtained. The resin constants are shown in Table 1. Comparative Example 4 The same procedure as in Example 1 was repeated except that the resole-type phenol resin A used had the composition shown in Table 1 and the amounts of glycerin and paratoluenesulfonic acid used were changed as shown in Table 1. Was reacted to obtain a resin for comparison. The resin constants are shown in Table 1. Comparative Examples 5 to 6 The same procedure as in Example 1 was repeated except that the resole-type phenol resin used had the composition shown in Table 1 and the amount of glycerin used was changed as shown in Table 1. Was reacted to obtain a resin for comparison. The resin constants are shown in Table 1.

[0016]

[Table 1]

(Ink preparation) 47 parts of the obtained rosin-modified phenolic resin, 20 parts of linseed oil and 31.6 parts of Nisseki AF Solvent No. 7 (manufactured by Nippon Oil Co., Ltd.), AL-CH
(Kawaken Fine Chemicals gelling agent) 1 1.6 parts of 67 parts gel varnish and 20 parts of pigment (Carmine 6B) Nisseki A
After mixing 13 parts of F Solvent No. 7 and kneading with 3 rolls, the tack value of the ink is 6.0 ± 0.5 and the flow value is 2.
It was appropriately adjusted to be 0 ± 0.5. Table 2 shows the gloss of the inks obtained in each of the examples and comparative examples, the set time, and the presence or absence of misting. The method of ink performance test is as follows.

[0018]

[Table 2]

(Performance test) Mitsuzawa: 0.3 cc of ink was spread on a coated paper with an RI tester (manufactured by Akira Mfg. Co., Ltd.), dried in an oven at 160 ° C. for 3 seconds, and glossed at 60 ° -60 °. It was measured by a meter. Set: 0.3 cc of ink was developed on a coated paper with an RI tester, and then the developed product was put in a circulating air dryer at 160 ° C., and the time (second) when the tackiness to the touch was lost was measured.

Claims (2)

[Claims] 1. A weight average molecular weight obtained by heat-reacting a rosin, a resol-type phenol resin using a phenol having a C10-C20 alkyl group, and a polyhydric alcohol in the presence of an acid catalyst. Of 30,000 to 250,000 is a rosin-modified phenolic resin, and the solubility of the resin causes turbidity at 25 ° C. in the solution of 30% by weight or less in an aliphatic hydrocarbon solvent having 15 carbon atoms. A rosin-modified phenolic resin characterized by the absence thereof. 2. The rosin-modified phenolic resin according to claim 1, wherein the amount of the polyhydric alcohol component used is 0.2 to 0.7 mol per 1 mol of the rosin.