JPH09268211A - Rosin-modified phenol resin and printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rosin-modified phenol resin capable of dissolving in a solvent for printing ink reduced in an aromatic component even if the resin is a resin having >=50000 average molecular weight, especially having good fluidity and gloss. SOLUTION: This rosin-modified phenol resin comprises a rosin or its derivative component, a phenol-formaldehyde-addition condensation product component and a polyol component and a part of the polyol component is at least one kind of diols selected from the compounds A and B represented by the following formulas. A: CH3 (CH2 )j C(CH2 OH)2 (CH2 )k CH3 [(j) and (k) represent each an integer of 1-3], B: CH3 (CH2 )m C(OH)HC(R)H(CH2 )n OH [(m) and (n) are each an integer of 1-3; R is methyl group or ethyl group]. This printing ink is obtained by dissolving the rosin-modified phenol resin in a petroleum-based solvent in which an aromatic component is reduced.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art A conventional printing ink solvent contains, in addition to paraffinic and naphthenic components, about 15 to 30% by weight of an aromatic component which is unfavorable for hygiene. By the way, 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-modified phenol resin. Further, recently, as the speed of the printing machine has been increased, there is a tendency to deal with it by polymerizing the rosin phenol resin in order to prevent misting of the printing ink.
The average molecular weight (MW) of rosin phenol generally used in printing inks is 10,000 to 500,000, preferably 50,000 to 20.
It is ten thousand. However, if the average molecular weight is 50,000 or more, the solubility with the above-mentioned solvent is deteriorated, the fluidity of the ink is deteriorated, and the gloss is further deteriorated.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a rosin-modified phenolic resin which is soluble in a solvent for printing ink having a reduced aromatic component even in a resin having an average molecular weight of 50,000 or more, and in particular, fluidity and gloss are improved by using the same. To develop good ink.

[0004]

The present invention comprises a rosin or its derivative component, a phenol-formaldehyde addition condensate component, and a polyol component, a part of the polyol component being a compound (A) represented by the following general formula or It relates to a rosin-modified phenol resin, which is at least one kind of diol selected from the compound (B). _{(A): CH 3 (CH} 2) j C (CH 2 OH) 2 (CH 2) k CH 3 ( In the formula, j, k is an integer of 1~3.) (B): CH 3 _{(CH 2) m C (OH} ) HC (R) H (CH 2) n OH ( in the formula, m, n is an integer of 1 to 3, R represents a methyl group or an ethyl group.). Further, the present invention relates to the rosin-modified phenolic resin, wherein the polyol component is contained in the rosin-modified phenolic resin in the range of 1 to 10% by weight. The present invention further relates to the above rosin-modified phenolic resin having a solubility defined by the following formula of 45% or less. Solubility (%) = {resin (2g) / [resin (2g) + solvent (Xg)]} × 100 (where X is the solvent 2g and normal tetradecane solvent is added, and the mixture is heated and dissolved at 180 to 200 ° C.) The minimum amount of normal tetradecane that becomes cloudy when cooled to 25 ° C.) In the present invention, the rosin-modified phenol resin is dissolved in a petroleum solvent having an aromatic component of 1% by weight or less and contained. The invention relates to a printing ink.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of rosin and its derivatives include gum rosin, wood rosin, tall oil rosin, disproportionated rosin and polymers thereof, and maleic acid, itaconic acid, crotonic acid and the like. Examples thereof include a rosin derivative having an unsaturated carboxylic acid added thereto.

In the present invention, the phenol-formaldehyde addition condensate is preferably a resole type phenol resin. As the phenol component of this resol type phenol resin, there are carboxylic acid, cresol, t- or sec-
Butylphenol, amylphenol, cyclohexylphenol, octylphenol, nonylphenol,
Dodecylphenol, pentadecanephenol, octadecanephenol, nonadecanephenol, dioctylphenol, phenylphenol, cumylphenol, and other phenols, catechol, resorcin, hydroquinone, bisphenol, and other polyhydric phenols are mentioned. It is preferable to mainly use alkylphenols which are low in cost, for example, nonylphenol and octylphenol. Of course, phenols such as (dodecyl, pentadecane, octadecane, nonadecane, dioctyl) have further improved solubility but slightly higher cost. Formaldehyde, paraformaldehyde, etc. are mentioned as an aldehyde component, and 0.2-4 mol is made to react with 1 mol of phenol components by a conventional method.

The present invention uses at least one diol selected from the compound (A) or the compound (B) as a part of the polyol component. When all of the polyol components are the diols used in the present invention, it is difficult to increase the molecular weight of the rosin-modified phenol resin, which is not preferable. By using at least one kind of the diols according to the present invention in combination with other trihydric, tetrahydric or higher valency polyols, it is possible to maintain good solubility of the rosin-modified phenolic resin. In addition to the above, the molecular weight can be appropriately increased, which is preferable.

Examples of the polyol component which can be used in combination in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, pentyl glycol, neopentyl glycol,
Hexanediol, glycerin, diglycerin, trimethylolpropane, ditrimethylolethane, pentaerythritol, dipentaerythritol and the like can be mentioned. The diol of the present invention constitutes a part or all of the polyol component. Therefore, the diol component of the present invention is used in the range of 1 to 10% by weight in the rosin-modified phenol resin. 1% by weight of the diols of the present invention
If it is less than 10, it is not preferable because the solubility of the rosin-modified phenolic resin is insufficient, and if it exceeds 10% by weight, it is not preferable because the molecular weight of the rosin-modified phenolic resin is difficult to increase. In that case, the drying property is deteriorated, which is not preferable. The rosin-modified phenol resin of the present invention has a weight average molecular weight of 50,000 or more, preferably 70,000 to 200,000.

The present invention optionally uses an acid catalyst.
As the acid catalyst, sulfonic acids such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, and mineral acids such as sulfuric acid and hydrochloric acid need to be heated to 220 ° C. or higher using a catalyst. However, since the reaction product is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, or triphenyl phosphate may be used in combination.

Further, it is possible to prevent metal rust by neutralizing hydrogen ions derived from the remaining acid catalyst and the like. As the neutralizing agent, it is possible to use salts of hydroxides, oxides or carboxylates of lithium, cesium, magnesium, calcium, strontium, barium, aluminum, zinc, titanium, zirconium, antimony, selenium and the like. is there.

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 phenols and aldehydes at a predetermined ratio,
Further, 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. to give calcium hydroxide, calcium oxide, magnesium hydroxide, magnesium oxide, etc. Is mixed with water and added as a slurry. Ammonium water and amines can also be used as catalysts, and both basic salts and amines are 0.0
It can be synthesized in the range of 5 to 0.1 mol. If it is less than 0.05 mol, the reaction will be slow and the amount of unreacted substances will increase, and if it is more than 0.1 mol, the solubility of the obtained printing ink resin will deteriorate. The amount of water is preferably 3% to 10% by weight. The amount of water is 3
If the amount is less than 10% by weight, coloring of the completed resol type phenol resin will be large, and if it is more than 10% by weight, the progress of condensation will be slow and a resol type phenol resin having a necessary molecular weight cannot be obtained.

At the reaction temperature of 65 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. After that, neutralization water washing is performed with an acid such as hydrochloric acid, formic acid, or acetic acid.

[As a method for synthesizing a resin composition] 40-70% by weight of rosin was charged into a reaction kettle and heated while being blown with nitrogen gas to dissolve it, and the temperature was raised to 220-260 ° C. 30-50% by weight of resin
(Solid content%) is added dropwise for 2 to 5 hours, then 1 to 15% by weight of a polyol component is added, and further 0 to 1% by weight of an acid catalyst is added if necessary, and an acid value of 25 or less is pumped out. The order of preparation is one example, and the order may be changed if necessary. Furthermore, the resin for 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 ink, or a part of petroleum resin modification, acrylic modification, urethane modification, etc. Modification by is also possible.

The aniline point of the printing ink solvent in which the aromatic component used in the present invention is reduced to 1% or less 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 substrate is poor and the printed matter is not glossy. I can only get it. In addition, an ink using a solvent having an aniline point lower than 65 ° C. may have poor removability of the solvent from the ink film during drying and may deteriorate in drying.

The printing ink of the present invention comprises: pigment 5 to 25 (wt%) rosin phenol resin 15 to 45 alkyd resin 0 to 10 drying oil 0 to 30 solvent for printing ink 10 to 45 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 a 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 compounds such as ink dryers, drying inhibitors, etc., and adjusting them to have an appropriate viscosity, they become offset inks such as sheet-fed offset inks and offset wheel inks. It can be used both as a usual printing ink to be used and as a printing ink for waterless lithographic printing which does not use fountain solution. It can also be used as newspaper ink or letterpress ink.

[0018]

Now, the present invention will be described in further detail with reference to specific examples. In the examples, “part” means part by weight and “%” means% by weight. Production Example 1 (Synthesis of Resol-Type Phenolic Resin) A 4-neck flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 108 parts of cresol, 56.3 parts of paraformaldehyde, and 140 parts of xylene, and heated and stirred while blowing nitrogen gas. 1.8 parts of calcium hydroxide is dispersed in 18 parts of water at 55 ° C., the dispersion is added, the temperature is raised to 70 ° C., and the reaction is carried out at the same temperature for 6 hours. Then, it is cooled, neutralized with hydrochloric acid, and washed with 100 parts of water three times. This resol type phenol resin is referred to as a resol solution a. Solid content of this resol (evaporate the solvent in a 120 ° C hot air oven)
Was 52%. The same reaction was performed with the number of parts shown in Table 1 below to obtain resol solutions a to d.

Production Example 2 Rosin was placed in a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, dissolved by heating, and then heated to 260 ° C. while adding a resol solution dropwise, and allowed to react for 1 to 3 hours. After that, a polyol component is charged, and if necessary, a liquid in which paratoluenesulfonic acid dissolved in water is dispersed is added dropwise to react until the decrease in charged acid value stops, and then pumping out. By this procedure, rosin-modified phenolic resin was synthesized in the number of parts shown in Table 2 to obtain resins of Comparative Examples and Examples.
The resin properties are also shown in Table 2.

[0020]

[Table 1]

[0021]

[Table 2]

Note) Resol solution that reacts with rosin represents parts by weight as solid content.

[Table 3]

The above resin was dissolved in a solvent and linseed oil at 180 ° C. according to the formulation shown in Table 3 and the temperature was lowered to 160 ° C.
0.8% by weight of CH was added and stirred for 1 hour to obtain varnishes of Comparative Examples and Examples.

The ink formulation is shown in Table 4. The ink was prepared by adjusting the tack to be 8.0 to 8.6 by a three-roll method according to a conventional method and used as the inks of Comparative Examples and Examples.

[0025]

[Table 4]

The inks of the comparative examples and the examples were used with a sheet-fed printing machine Lithrone 26 manufactured by Komori Corporation to obtain 130 inks.
A printing test was performed on 6000 sheets each at 00 RPH to compare the transferability of ink, misting, and gloss of printed matter.
As the paper, NPI coat manufactured by Nippon Paper Industries Co., Ltd. was used. Ink tack values, flow values and print test results are shown in Table 5.

[0027]

[Table 5]

[0028]

According to the method of the present invention, the aromatic component is
It is possible to obtain a resin composition which is sufficiently dissolved in a solvent for printing ink reduced to less than 10% by weight, and the printing ink using these resins has excellent fluidity and shows sufficient transferability on a printing machine. Moreover, there was no deterioration of misting, and the gloss of the printed matter was excellent.

Claims (4)

[Claims] 1. A rosin or its derivative component, a phenol-formaldehyde addition condensate component, and a polyol component, at least a part of which is selected from the compound (A) or the compound (B) represented by the following general formula. A rosin-modified phenolic resin characterized by being one type of diol. _{(A): CH 3 (CH} 2) j C (CH 2 OH) 2 (CH 2) k CH 3 ( In the formula, j, k is an integer of 1~3.) (B): CH 3 _{(CH 2) m C (OH} ) HC (R) H (CH 2) n OH ( in the formula, m, n is an integer of 1 to 3, R represents a methyl group or an ethyl group.) 2. The resin containing 1 to 1 of the polyol component.
The rosin-modified phenolic resin according to claim 1, wherein the rosin-modified phenolic resin is contained in an amount of 0% by weight. 3. The solubility defined by the following formula is 45%.
The rosin-modified phenolic resin according to claim 1, wherein: Solubility (%) = {resin (2g) / [resin (2g) + solvent (Xg)]} × 100 (where X is the solvent 2g and normal tetradecane solvent is added, and the mixture is heated and dissolved at 180 to 200 ° C.) , The minimum amount of normal tetradecane that becomes cloudy when cooled to 25 ° C.) 4. A printing ink comprising the rosin-modified phenolic resin according to any one of claims 1 to 3 dissolved in a petroleum solvent having an aromatic component of 1% by weight or less.