JPH07149852A - Rosin modified phenol resin and printing ink - Google Patents

Abstract

PURPOSE:To obtain a rosin modified phenol resin useful as printing ink, having excellent solubility, comprising a component of a rosin, a specific phenol formaldehyde addition condensate component, etc. CONSTITUTION:This rosin modified phenol resin comprises a component of a rosin such as gum rosin and dinonylphenol having >=10wt.% of a phenol component in a phenol formaldehyde addition polymer based on the whole phenol component and is obtained by reacting a phenol formaldehyde addition condensate component of a resol type phenol resin, etc., at 220-260 deg.C for 1 to 3 hours and optionally esterifying the reaction product with a polyol component such as ethylene glycol. The resin is dissolved in a solvent for printing ink having <=1% aromatic component and used as printing ink as a vehicle component.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rosin-modified phenolic resin having excellent solubility, particularly a resin soluble in a solvent for a low aromatic printing ink, and a printing ink containing them.

[0002]

2. Description of the Related Art Conventionally, aromatic components such as benzene, toluene and xylene in various solvents that have been widely used are generally irritating to the human body due to skin irritation, as regulated by the Industrial Safety and Health Law. Strict regulations have been adopted to bring about neurological disorders. Moreover, as recently as the ILO (International Labor Organization) adopted a treaty to protect the safety of workers who handle chemical products, internationally, there is an increasing momentum to protect the human body from the damage of chemical products. .

Conventional printing ink solvents are paraffinic,
In addition to the naphthene-based component, it contains 15 to 20% by weight of an aromatic component. However, in general, a solvent for a printing ink containing a reduced amount of aromatic components has poor solubility with a rosin-modified phenol resin, which is a resin for a printing ink. Generally, a rosin-modified phenol resin is prepared by reacting phenol and formalin with a basic or acidic catalyst at 60 to 100 ° C to obtain a phenol-formaldehyde addition condensate, and then reacting the addition condensate and rosin at 220 to 260 ° C. Further, it can be obtained by further reacting the residual carboxylic acid group with a polyol such as glycerin, or by carrying out an esterification reaction with an acid catalyst without using a polyol. As the phenol component of the phenol-formaldehyde addition polymer, carboxylic acid, cresol, butylphenol, amylphenol, octylphenol, nonylphenol, etc. are used.
Octylphenol and nonylphenol are used to improve the solubility. The average molecular weight (Mw) of rosin phenol used in printing ink is 10,000 to 500,000, preferably 50,000 to 200,000. However, when the average molecular weight is 50,000 or more, these octylphenols and nonylphenols have poor solubility in a solvent in which aromatic components are reduced, the fluidity of the ink is deteriorated, and the gloss of the printed matter is not always sufficient.

[0004]

The present invention particularly develops a rosin phenol resin which is soluble in a solvent for a printing ink having a reduced aromatic component even in a resin having an average molecular weight of 50,000 or more, and an ink using the same. Is.

[0005]

The present invention comprises a rosin component, a phenol formaldehyde addition condensate component, and optionally a polyol component, wherein the phenol component in the phenol formaldehyde addition polymer component is contained in the total amount of phenol components. The present invention relates to a rosin-modified phenolic resin, which comprises 10% by weight or more of dinonylphenol. Further, the present invention relates to a printing ink in which the rosin-modified phenol resin is dissolved in a printing ink solvent to form a vehicle component. Furthermore, the present invention relates to the above printing ink, wherein the printing ink solvent is a printing ink solvent having an aromatic component of 1% by weight or less.

In the present invention, the rosin component is rosin or a derivative thereof, and examples of rosin and / or its derivative include gum rosin, wood rosin, tall oil rosin, disproportionated rosin or polymers thereof, and maleic acid, Examples thereof include rosin derivatives to which unsaturated carboxylic acids such as itaconic acid and crotonic acid are added. The rosin component in the rosin-modified phenol resin is preferably 40 to 70% by weight.

The dinonylphenol used in the present invention is
(2,3), (2,4), (2,5), (2,6),
There are (3,4), (3,5), (3,6) dinonylphenol or a mixture thereof, but it is preferable to use the mixture because the pure one is expensive and uneconomical.

In the present invention, the phenol / formaldehyde addition condensate component is preferably a resol type phenol resin. As the phenol component of this resol type phenol resin, in addition to 10% by weight or more of dinonylphenol, 0 to 90% by weight of silica acid, cresol, t- or sec-butylphenol, amylphenol, cyclohexylphenol, octylphenol, nonylphenol, phenylphenol, You may use together phenols, such as cumyl phenol, and polyhydric phenols, such as catechol, resorcin, hydroquinone, and bisphenol. When the content of dinonylphenol is 10% by weight or less, the solubility in a printing ink solvent containing a reduced amount of aromatic components is reduced, which is not preferable. The method for producing the phenol / formaldehyde addition polymer of the present invention will be described. Phenol, formaldehyde, p in the reaction kettle
-Aldehydes such as formaldehyde are charged at a predetermined ratio, and a solvent such as toluene or xylene is added in an amount such that the solid content of the phenol resin is 40 to 70% by weight, and the mixture is stirred and heated at 50 ° C with water. A basic catalyst such as calcium oxide, calcium oxide, magnesium hydroxide or magnesium oxide is mixed with water and added as a slurry to react. Ammonia water and amines can also be used as the basic catalyst, and these catalysts can be used in the range of 0.05 to 0.1 mol per mol of phenol.
If it is less than 0.05 mol, the reaction will be slow and unreacted substances will increase.
If it is more than 0.1 mol, the solubility in the resin for printing ink is lowered. Further, the amount of water is preferably 3 to 10% by weight based on the total amount. When the amount of water is 3% by weight or less, the coloring of the completed resol-type phenol resin becomes large, and when it is 10% by weight or more, the progress of condensation is slowed down, and a resol-type phenol resin having a necessary molecular weight cannot be obtained. Formaldehyde is reacted in an amount of 0.2 to 4 mol with respect to 1 mol of the phenol component by a conventional method. The proportion of the phenol resin component in the rosin-modified phenol resin is preferably 30 to 60% by weight.

At the reaction temperature of 90 to 110 ° C. after addition of the catalyst, 5
After the reaction is continued for 10 hours, the resol-type phenol resin is obtained by cooling and standing at about 60 ° C. to separate and remove water. When the temperature is slightly higher than room temperature, the resin and water can be easily separated, and the time required for the separation is 1 hour or less. Then, neutralized water washing is performed with hydrochloric acid, formic acid, acetic acid, or the like.

The reaction (mainly the chroman reaction) between the rosin and the phenol-formaldehyde addition condensate is 220 to 2
Perform at 60 ° C. for 1-3 hours. After that, the residual carboxylic acid and the polyol component are esterified. As the polyol component, ethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol and the like are used. The polyol component in the rosin-modified phenol resin is preferably 0 to 10% by weight. The average molecular weight (Mw) of the rosin-modified phenol resin of the present invention is 5 to 2
0,000 is preferable.

Or rosin and about half the amount of phenol
Reacting with formaldehyde addition condensate at the above temperature,
Then, at the same temperature, 0.01 to 1 with the remaining half of the addition condensation product.
The reaction is carried out by adding a weight% of acidic catalyst. In this case, the polyol may not be used. As the acidic catalyst, sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, and mineral acids such as sulfuric acid and hydrochloric acid are used and heated to 150 ° C. or higher.
In this reaction, the product is easily colored, and in order to prevent this, a reducing agent such as hypophosphorous acid, triphenyl phosphite or triphenyl phosphate can be used in combination.

Further, rusting of metal can be prevented by neutralizing hydrogen ions derived from the remaining acid catalyst and the like. As the neutralizing agent, salts of hydroxides, oxides or carboxylates of metals such as lithium, cesium, magnesium, calcium, strontium, barium, aluminum, zinc, titanium, zirconium, antimony and selenium can be used. is there. When synthesizing the rosin-modified phenol resin of the present invention, a small amount of a polyol such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol or dipentaerythritol may be used together. In this case, the ratio of the OH groups contained in the polyol and the COOH groups contained in the rosin and / or its derivative is less than 0.8 (OH groups / C).
OOH groups <0.8). When a polyol having an OH group larger than this is used in combination, the solubility in a solvent or other ink materials is deteriorated.

Furthermore, the resin for a printing ink of the present invention is used in combination with a rosin-modified phenol resin, an alkyd resin, a petroleum resin, etc., which have been conventionally used in printing inks, or a part of a petroleum resin-modified or acrylic-modified resin. Modification by urethane modification, fatty acid, fatty oil, polybasic acid, or polyol modified product thereof is also possible.

The rosin-modified resin of the present invention contains 1 aromatic component.
It can be used as a vehicle for offset printing ink by dissolving it in a solvent for printing ink reduced to less than 10%.
Solvents for printing inks with aromatic components reduced to 1% or less
The main products are mainly paraffinic solvents and naphthenic solvents, and the aniline point thereof is preferably 65 to 95 ° C. Examples of such a solvent include No. 0 and AF4 to No. 7A solvent manufactured by Nippon Oil Co., Ltd. If a solvent having an aniline point higher than 95 ° C. is used, the solubility in the resin used in the ink composition is poor, the fluidity of the ink is insufficient, and as a result, the leveling on the printing medium is poor and there is no gloss. Only prints are available. Further, an ink using a solvent having an aniline point lower than 65 ° C. has a poor removability of the solvent from the ink film during drying and causes deterioration in drying.
In addition, conventionally used printing ink solvents may be appropriately used in combination.

The printing ink of the present invention comprises: pigment 10 to 25 (wt%) rosin-modified phenol resin 20 to 25 alkyd resin 0 to 5 drying oil 0 to 25 solvent for printing ink 10 to 40 drying accelerator 0 to 3 other additions Agent 0-10.

As the pigment, known general pigments such as benzidine yellow, lake red C, carmine 6B, phthalocyanine blue, carbon black and, if necessary, an inorganic pigment or an extender pigment as a fluidity adjusting agent are used.

To make a varnish for printing ink using the resin according to the present invention, 100 parts of the resin of the present invention is used as a solvent and / or a drying oil (polymerized oil, a drying oil modified such as an alkyd resin). Is dissolved in 50 to 150 parts. In actual use, a gel varnish is formed by using a gelling agent such as aluminum octylate, aluminum stearate, zirconium octylate, aluminum triisopropoxide, and aluminum dipropoxide monoacetylacetonate. Anti-friction improver if necessary,
By adding various additives such as ink dryers and compounds such as drying inhibitors, and adjusting them so that the viscosity is appropriate, sheet-fed offset inks, offset wheel inks, etc. become offset inks. It can be used both as a normal printing ink to be used and as a printing ink for driography which does not use fountain solution. It can also be used as newspaper ink or letterpress ink.

[0018]

The present invention will be described below with reference to specific examples. In the examples, “part” means part by weight. The following is a specific example. Production Example 1 (Synthesis of Resol-Type Phenolic Resin) Stirrer, reflux condenser, thermometer, 4-necked flask equipped with p-octylphenol (358 parts), p-formaldehyde (16)
2 parts and xylene 403 parts were charged, the mixture was heated and stirred while blowing N ₂ gas, and 7 parts of calcium hydroxide was added to water 7 at 65 ° C.
It is dispersed in 0 part, the dispersion is added, the temperature is raised to 95 ° C., and the reaction is carried out at the same temperature for 8 hours. Then, it is cooled, neutralized with hydrochloric acid, and washed with water. This resol type phenol resin is referred to as a phenol liquid 1. This phenol solid content (100
C. (evaporating the solvent in a hot air oven) was 52%. The reaction is performed as shown in Table 1 below.

[0019]

[Table 1]

Production Example 2 A rosin of Table 2 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, dissolved by heating, and then heated at 260 while the phenol solution (a to h) was added dropwise. Only 1 to 3
React for hours. Then, a polyol is charged and reacted at the same temperature until the acid value stops decreasing. Alternatively, about half the charged amount of the phenol liquid is added dropwise to the reaction, and the remaining half amount and a liquid in which p-toluenesulfonic acid dissolved in a small amount of water is dispersed are added dropwise to the reaction until the decrease of the charged acid value is stopped. Further, a polyol may be charged and reacted as the case requires. Then pump out. Appendix 2 below
React as follows.

[0021]

[Table 2]

The above resin was dissolved in a solvent and linseed oil at 180 ° C., the temperature was lowered to 160 ° C., ALCH 0.8% was added, and the mixture was stirred for 1 hour to obtain a varnish. Table 3 shows a comparison of the properties of the conventional printing ink solvent and the printing ink solvent of the present invention having an aromatic content of 1% by weight or less.

[0023]

[Table 3]

[0024]

[Table 4]

Other examples of solvents for printing inks, when the fluidity of the ink deteriorates, the following solvents may be used in an amount of 0 to 15%.

[0026]

[Table 5]

The ink formulation and properties are shown in Table 5.

[0028]

[Table 6]

The ink was prepared by a conventional method.

EFFECT OF THE INVENTION By making a rosin-modified phenolic resin in which the aromatic component is reduced to 1% or less in a solvent for a printing ink and a printing ink using the rosin-modified phenolic resin, the ink suitability is sufficiently maintained and the environment at the work site is maintained. Can improve the health of field workers.

Claims (3)

[Claims] 1. A rosin component, a phenol formaldehyde addition condensate component, and optionally a polyol component, wherein the phenol component in the phenol formaldehyde addition polymer component is 1 relative to the total amount of the phenol component.
A rosin-modified phenolic resin comprising 0% by weight or more of dinonylphenol. 2. A printing ink comprising a rosin-modified phenolic resin according to claim 1 dissolved in a solvent for a printing ink as a vehicle component. 3. The printing ink according to claim 2, wherein the printing ink solvent is a printing ink solvent having an aromatic component of 1% by weight or less.