JPH05306316A - Resin composition and printing ink - Google Patents

Abstract

PURPOSE:To provide a resin composition soluble in a printing ink solvent having low aromatic content and low toxicity and to provide a printing ink containing the resin composition. CONSTITUTION:This resin composition is produced by reacting a rosin and/or its derivative containing carboxyl group with a drying oil and a phenol- formaldehyde addition condensation product in the presence of an acid catalyst and reacting the residual carboxyl group of the product with a monohydric alcohol. The printing ink contains the resin composition and a printing ink solvent containing <=1wt.% of aromatic components.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is soluble in a solvent for low-aromatic, low-toxicity printing ink and a printing ink containing the same.

[0002]

BACKGROUND OF THE INVENTION Aromatic components such as benzene, toluene, xylene in various solvents that have been widely used in the past are generally irritating to the human body and nerves, as regulated by the Industrial Safety and Health Law. Strict regulations are being adopted to bring about obstacles. In addition, as the ILO (International Labor Organization) recently adopted a treaty to protect the safety of workers who handle chemical products, the momentum to protect the human body from the damage of chemical products is increasing internationally. ..

Conventional printing ink solvents are paraffinic,
In addition to the naphthenic component, the aromatic component is contained in an amount of 15 to 20% by weight. However, in general, a solvent for a printing ink containing a reduced amount of aromatic components has poor solubility in a printing ink resin, that is, a rosin phenol resin. 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, the solubility of the ink is particularly deteriorated and the fluidity of the ink is deteriorated.

As a prior art, patents on rosin phenol resins modified with vegetable oil (Japanese Patent Publication Nos. 62-5469 and 62-5).
470, Sho 63-62523), a patent for a rosin phenol resin using an acid catalyst (Japanese Patent Publication No. 01-25517), and a patent for a rosin phenol resin modified with a vegetable oil using an acid catalyst (JP-A-02-67377). .. However, none of them has a weight average molecular weight (Mw) of 50,000 or more and is soluble in a solvent for printing ink having an aromatic component of 1% or less.

[0005]

DISCLOSURE OF THE INVENTION The present invention is to develop a rosin phenol resin which can dissolve even a resin having an average molecular weight of 50,000 or more in a solvent for a printing ink having a reduced aromatic component, and an ink using the resin.

[0006]

According to the present invention, rosin and / or its carboxyl group-containing derivative are reacted with a drying oil and a phenol-formaldehyde addition condensate in the presence of an vinegar catalyst, and the residual carboxylic acid is reacted with a monohydric alcohol. The present invention relates to a printing ink containing the resin composition and / or the printing ink solvent in which the aromatic component is reduced to 1% or less.

In the present invention, the rosin and / or its carboxyl group-containing derivative (A) is rosin or its derivative. Examples of rosin and / or its derivatives include gum rosin, wood rosin, tall oil rosin, disproportionated rosin and polymers thereof, and rosin derivatives to which unsaturated carboxylic acids such as maleic acid, itaconic acid and crotonic acid are added. Is mentioned.

As the drying oil used in the present invention, soybean oil,
Examples include unsaturated vegetable oils such as linseed oil, tung oil, rice bran oil, dehydrated castor oil, and deer oil, and polymerized oils in which an unsaturated group remains in a part of the polymers of these vegetable oils. The amount of these drying oils in the resin is preferably 30% by weight or less, more preferably 0.5 to 10% by weight. When the amount added is 30% by weight or more, the obtained resin gels.

In the present invention, the phenol-formaldehyde addition condensate is preferably a resol type phenol resin. The phenol component of this resol-type phenol resin is silica, cresol, t- or sec.
-Butylphenol, amylphenol, cyclohexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, and other phenols; catechol, resorcin, hydroquinone, bisphenol, and other polyhydric phenols; long-chain alkylphenols such as butylphenol, nonylphenol, octylphenol From the viewpoint of solubility, it is preferable to mainly contain. Examples of aldehyde components include formaldehyde and p-formaldehyde,
0.2 to 4 mol is reacted by a conventional method with respect to 1 mol of the phenol component.

To obtain the resin composition according to the present invention, p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
It is necessary to catalyze sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, and mineral acids such as sulfuric acid and hydrochloric acid, and to heat them at 150 ° C or higher. However, since the reaction product is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenylphosphite, or triphenylphosphate may 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 metal hydroxides, oxides or carboxylates such as lithium, cesium, magnesium, calcium, strontium, barium, aluminum, zinc, titanium, zirconium, antimony and selenium can be used. is there. In addition, when synthesizing the resin of the present invention, a small amount of glycerin, trimethylolethane,
A polyol such as trimethylolpropane, pentaerythritol, or dipentaerythritol may be used in combination.
In this case, the ratio of the OH groups contained in the polyol to the COOH groups contained in the rosin and / or its derivative is less than 0.8 (OH group / COOH group <0.8).
If a polyol having an OH group larger than this is used in combination, the solubility deteriorates.

Further, rosin and / or its carboxyl group-containing derivative and 30% by weight or less of the drying oil in the resin are reacted with a part of the phenol / formaldehyde addition condensate without a catalyst, and the remaining phenol / formaldehyde is then reacted. It is also possible to carry out the reaction of the addition condensate in the presence of an acidic catalyst. Further, the monohydric alcohol is an alcohol having 4 or more carbon atoms, preferably 8 or more carbon atoms, such as octanol, diadol 13 (Mitsubishi Kasei Co., Ltd.).
Manufactured by Nissan Petrochemical Co., Ltd.,
Abitol (hydrogenated rosin alcohol manufactured by Rica Hercules Co., Ltd.) and the like can be mentioned.

The rosin-modified phenolic resin of the present invention can be synthesized as follows. In addition,% shows weight%. [Synthesis of Resol-Type Phenolic Resin] The reaction vessel is charged with the above-mentioned phenols and aldehydes 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%. It is preferable to use an insoluble basic salt such as calcium hydroxide, calcium oxide, magnesium hydroxide, or magnesium oxide at 50 ° C. with stirring and heating. These salts are mixed with water and added as a slurry. Ammonium water and amines can also be used as catalysts, and both basic salts and amines can be synthesized 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 the amount of unreacted substances will increase. The amount of water is preferably 3% to 10%. When the amount of water is 3% or less, the coloring of the completed resol type phenol resin becomes large, and when it is 10% or more, the progress of condensation is slowed down, and the resol type phenol resin having a necessary molecular weight cannot be obtained.

At the reaction temperature of 90 to 110 ° C. after addition of the catalyst, 5
After continuing the reaction 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. After that, neutralized water washes with hydrochloric acid, formic acid, and acetic acid.

[As a method for synthesizing a resin composition] Rosins and a drying oil are charged into a reaction kettle and heated while being blown with N ₂ gas to dissolve them, and the temperature is raised to 260 ° C. The reaction is carried out while dropping the mixture of the acid catalysts, and after the acid value becomes 40 or less, a monohydric alcohol is added to obtain a rosin-modified phenol resin having an acid value of 30 or less. Further, the monohydric alcohol may be added dropwise to the mixture of the resol-type phenol resin and the acid catalyst for the reaction. Further, the resin for printing ink of the present invention is used in combination with rosin-modified phenol resin, alkyd resin, petroleum resin, etc., which have been conventionally used in printing ink, or some petroleum resin modification, acrylic modification, urethane modification, etc. Modification by is also possible.

The aniline point of the solvent for printing ink in which the aromatic component used in the present invention is reduced to 1% is preferably 65 to 95 ° C. 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.

Generally, printing inks are pigments 10 to 25 (wt%) rosin 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 additives 0 to It consists of 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 product such as a drying oil alkyd resin). Is dissolved in 50 to 150 parts. In actual use, a gel varnish is prepared 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 compounds such as ink dryers, drying inhibitors, etc., and adjusting them to obtain an appropriate viscosity, they become offset inks such as sheet-fed offset inks and offset wheel 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.

[0020]

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) 350 parts of p-octylphenol and p-formaldehyde 20 in a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
0 parts and xylene 413 parts were charged, and the mixture was heated and stirred while blowing N ₂ gas, and at 65 ° C., 7 parts calcium hydroxide and 7 parts water.
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 Phenol Solution 1. This phenol solids (100
The solvent was evaporated in a hot air oven at 0 ° C) was 52%.

Production Example 2 A group A in Table 1 was placed in a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and the phenol solution 1 was added dropwise at 260. Furthermore, p- dissolved in phenol liquid 1 and a small amount of water
A solution in which toluenesulfonic acid is dispersed is added dropwise. Further, Group B is added to carry out an esterification reaction and draw out.

[0022]

[Table 1]

[0023]

[Table 2]

The above resin was dissolved in a solvent, 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 properties between the conventional printing ink solvent and the printing ink solvent of the present invention.

[0025]

[Table 3]

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%.

[0027]

[Table 4]

The ink formulation and properties are shown in Table 5.

[0029]

[Table 5]

The ink was prepared by a conventional method.

[0031]

EFFECTS OF THE INVENTION By making a resin composition in which an aromatic component is reduced to 1% or less in a solvent for a printing ink and a printing ink using the resin composition, the ink suitability is sufficiently maintained and the environment at the work site is improved. It can improve and protect the health of field workers.

Claims (2)

[Claims] 1. A method comprising reacting rosin and / or a carboxyl group-containing derivative thereof with a drying oil and a phenol formaldehyde addition condensate in the presence of an acid catalyst, and further reacting a residual carboxylic acid group with a monohydric alcohol. And a resin composition. 2. A printing ink comprising the resin composition according to claim 1 and a solvent for a printing ink containing 1% by weight or less of an aromatic component.