JPS6330579A - Printing ink resin - Google Patents

Abstract

PURPOSE:To obtain the title resin having excellent compatibility with a paraffinic solvent, high solutility, and a high melting point, by reacting a resol phenolic resin with an alkyd resin modified with a carboxylic acid, and a rosin (derivative). CONSTITUTION:20-70Wt% resol phenolic resin (A) consisting mainly of at least one phenolic compound selected from among p-t-butylphenol, p-octylphenol and p-nonylphenol is reacted at 150 deg.C or higher in the presence of an acid catalyst (e.g., p-toluenesulfonic acid) and a reducing agent (e.g., hypophosphorous acid) with a modified alkyd resin (B) of an acid value of 100-300 made by modification with a 6C or higher carboxylic acid (e.g., a rosin) and, if necessary, a rosin (derivative) (C) (e.g., a rosin wood), thereby giving a printing ink resin which has a melting point of 130 deg.C or higher and an acid value of 30 or less and is free of turbidity even at a dilution of 70% or higher at 25 deg.C with a paraffinic solvent.

Description

Detailed Description of the Invention Object of the Invention (Field of Industrial Application) The present invention provides an ink solution that does not become cloudy even when the dilution rate at 25°C is 70 M% or more with an ink solvent, especially a solvent mainly composed of an aliphatic hydrocarbon solvent. The present invention relates to a resin for printing ink that has high solubility and a high melting point, with a melting point of 130° C. or higher (capillary method).

(Conventional technology) In recent years, the solvents used in printing inks and paints are fats.

Mainly raw hydrocarbons, that is, paraffin-based ones. The main reason is that there is less risk of air pollution.
Examples include low odor and good release properties from the film when dry. On the other hand, this paraffinic solvent has the drawback of extremely poor melting power.

Therefore, the resins that can be used in combination with paraffinic solvents are severely limited and cannot be fully utilized.

Especially for printing inks, many of the widely used rosin-modified phenolic resins have poor compatibility with paraffinic solvents, and large amounts of higher alcohols and drying oils are used to maintain ink stability. However, if large amounts of these higher alcohols or drying oils are used, the drying oils deteriorate, leading to a decrease in printing efficiency and an increase in fuel consumption during heat drying.

In addition, it is undesirable for resins for off-cent ink to have free carboxyl groups remaining in view of printability, so the carboxyl groups should be blocked with some kind of functional group so that the acid value is 30 or less, preferably 20 or less. ing. Most of them are due to esterification with alcohols, especially polyhydric alcohols. In addition, reactions using isocyanate groups, epoxy groups, etc. may also be used for this purpose. However, all of the rosin-modified phenolic resins produced by these reactions have deteriorated compatibility with paraffinic solvents.

(Problems to be Solved by the Invention) From this point of view, it is desirable to increase the compatibility with paraffinic solvents such as rosin-modified phenolic resins and reduce the amount of higher alcohols and drying oils used. A high softening point is advantageous for drying properties. Such a resin for printing ink has been desired.

"Structure of the Invention" (Means for Solving the Problems) Among printing inks, and even offset inks, the present inventors have developed a heat-set type offset rotary ink (hereinafter referred to as "offset") which often uses paraffin solvents, in particular printing inks, and even offset inks. A modified resin that does not become cloudy even when the dilution rate at 25°C with the solvent is 70% or more and has a high solubility and high melting point (capillary method) or higher as a resin passed through a ring ink (abbreviated as ring ink). It lost to the invention of phenolic resin.

A resol type phenolic resin, an alkyd resin modified with a carboxylic acid having 6 or more carbon atoms, and optionally a rosin or its derivative are reacted at a temperature of at least 150°C in the presence of an acid catalyst to give an acid value of 30 or less. This is a resin for printing ink.

That is, a resol-type phenolic resin as a polyol component, an alkyd resin modified with a carboxylic acid having 6 or more carbon atoms, and further rosin or a derivative thereof as necessary are mixed at a temperature of at least 150°C in the presence of an acid catalyst. This is a resin for printing ink that is reacted to have an acid value of 30 or less, preferably 20 or less.

The phenolic components of the resol type phenolic resin include phenols such as carbolic acid, cresol, tertiary or secondary butylphenol, amylphenol, cyclohexylphenol, octylphenol, nonylphenol, phenylphenol, and cumylphenol.
Catechol, resorcinol.

Examples include polyhydric phenols such as hydroquinone and bisphenol, especially long-chain alkylphenols.

For example, it is preferable to mainly use butylphenol, octylphenol, and nonylphenol from the viewpoint of solubility. Furthermore, the present invention is not necessarily limited to long-chain alkylphenols, and other phenols can also be used in combination with long-chain alkylphenols. However, the combined use of these phenols requires too much use (
In this case, solubility often deteriorates.

Examples of aldehyde components include formaldehyde and p-formaldehyde, and as catalysts for resolization,
0.2 to 4 mol per 1 mol of phenol component is added to an alkali catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, or a known base such as aqueous ammonia, triethylenediamine, amines such as triethylenediamine, etc. catalysts can be used.

The above carboxylic acid-modified alkyd resin includes two carboxylic acids having 6 or more carbon atoms, such as rosin, polymerized rosin, maleated rosin, fumarized rosin, and fatty acids having carbon ffi numbers of 6 to 18.
It is an alkyd resin modified with M-combined oil fatty acid, maleated fatty acid, difumarated fatty acid, etc. In other words,
One or more of rosin-modified alkyd resins, N-combined rosin-modified alkyd resins, maleated rosin-modified alkyd resins, fumarated rosin-modified alkyd resins, fatty acid-modified alkyd resins, maleated fatty acid-modified alkyd resins, fumarated fatty acid-modified alkyd resins, etc. be. Preferably, it is a carboxylic acid-modified alkyd resin having an acid value of 100 to 300. If the acid value is less than 100, the amount of phenol resin to be esterified will be small, and solubility will tend to decrease. Moreover, if the acid 1 side exceeds 300, not only will it be difficult to control the molecular weight of the desired resin, but the amount of phenol resin to be esterified will be too large, which will also affect economic efficiency.

Alkyd resin is a commonly used resin,
It is obtained by reacting a polyhydric carboxylic acid and a polyhydric alcohol. Examples of polycarboxylic acids include benzene polycarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, and aliphatic dicarboxylic acids such as adipic acid and azelaic acid. Polyhydric alcohols include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and neopentyl glycol;
Glycerin, trimethylolethane, tris-2-hydroxyethyl isocyanurate, pentaerythritol,
Examples include one kind of polyols such as diglycerin, dipentaerythritol, and tripentaerythritol, or a mixture thereof.

In addition, as fatty acids having 6 or more carbon atoms, 2 usually have 6 to 6 carbon atoms.
18 fatty acids including caproic acid, caprylic acid, capric acid, lauric acid, tridecanoic acid, palmitic acid, stearic acid, nonadecaic acid, laurolenic acid, myristoleic acid, seamaric acid, oleic acid, linoleic acid, lylunic acid, Rheostearic acid.

These include lylinic acid, etc., and mixtures thereof, such as coconut oil fatty acids, rice bran oil fatty acids, soybean oil fatty acids, linseed oil fatty acids, cottonseed oil fatty acids, tung oil fatty acids, and fish oil fatty acids. °.

Furthermore, when synthesizing the printing ink resin of the present invention, rosin or a derivative thereof can be used in combination with the modified alkyd resin as a carboxylic acid component, if necessary.

Since rosin is a monocarboxylic acid, if it is used in a high proportion, the melting point of the resulting modified phenol resin will be lowered, so it is necessary to contain it in the resin formulation in an amount of 50% by weight or less.

Examples of rosin or derivatives thereof include gum rosin, wood rosin, tall oil rosin, disproportionated rosin, or mixtures thereof, and polymers thereof, and examples of carboxylic acid-modified rosin include maleic acid, fumaric acid, itaconic acid, Examples include rosin derivatives to which unsaturated carboxylic acids such as crotonic acid are added.

In order to obtain the modified phenol resin of the present invention, p-toluenesulfonic acid and dodecylbenzenesulfonic acid are used.

It is necessary to heat to 150° C. or higher using sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, and mineral acids such as sulfuric acid and hydrochloric acid as catalysts. However, under such conditions, the reaction product is easily colored, so it is preferable to use a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. in combination.

The proportion of resol type phenolic resin in this modified phenolic resin is 20% to 70% by weight, and the phenolic OH
Group/C0OH group=1.0/1.0-2.5/
A range that satisfies 1°0 is preferable. If the proportion of the resol-type phenolic resin is less than 20% by weight, the acid value will not decrease and the printability will tend to be poor, and if it exceeds 70% by weight, the molecular weight of the resulting resin will not increase and the economic efficiency will be poor. tends to affect

The resin for printing ink of the present invention is a resin for printing ink that does not become cloudy even when the dilution rate at 25° C. with a paraffinic solvent having 13 to 14 carbon atoms is 70% or more (% by weight in the solution). This printing ink resin is particularly useful for off-line inks with strict physical properties requirements, but also for single-sheet off-cent printing inks,
Of course, it can also be used for letterpress ink, gravure ink, etc.

Furthermore, the resin for printing ink of the present invention may include a rosin-modified phenolic resin, which has been conventionally used for printing ink.
It is also possible to use it in combination with alkyd resins, 20,000 oil resins, etc., and to modify some petroleum resins, acrylics, urethanes, etc.

To make a face for printing ink using the resin of the present invention 1
Resin 100 of the present invention! Solvent and/or drying oil (or polymerized oil, drying oil modified product such as drying oil alkyd resin) are dissolved in an amount of 50 to 150 parts by weight. In actual use, gel varnishes are made using gelling agents such as aluminum octylate, aluminum stearate, zirconium octylate, aluminum triisopropoxide, and aluminum diproboxide monoacetylacetonate, and are colored yellow, red, and indigo. , or pigments such as black ink are dispersed, and if necessary, compounds such as friction improvers, ink dryers, and drying inhibitors are added.
By adjusting the viscosity so that it has a consistent viscosity, it becomes an off-cent ink such as a sheet-fed offset ink or an off-circle ink.

It can also be used as newspaper ink or letterpress ink. Furthermore, in order to make a face for gravure or flexo ink using the resin of the present invention, 100 to 200 parts of aliphatic and alicyclic hydrocarbons having a boiling point of 140°C or less at normal pressure are added to 100 parts by weight of the resin of the present invention. It is sufficient to melt the parts by weight.

Next, the present invention will be explained using specific examples. "Part" and "%" represent 1% by weight.

Production Example 1 (Production of resol type phenolic resin) In a four-bottle flask equipped with a stirrer, a reflux condenser with a water separator, and a temperature needle, 170 parts of p-octylphenol, 22 parts of p-t-butylphenol, and 170 parts of formalin (35%) were added. Department,
Add 12 parts of 93% aqueous sodium hydroxide solution and 100 parts of tap water, and heat to 90°C.

After reacting for 4 hours, 200 parts of toluene was added to dissolve the phenol resin, and 25 parts of 6N hydrochloric acid was added to tap water for 200 seconds.
After diluting it with water and adding it to neutralize it, let it stand.

After removing the aqueous layer, wash twice with 200 parts of water, pH 5 ~
6, the toluene layer was extracted. The toluene solution of this phenol resin had a nonvolatile content of 50%, and the yield was 420 parts. This resol type phenol resin solution is referred to as A resol.

Production Example 2 170 parts of p-octylphenol from Production Example 1, p-t-
22 parts of butylphenol, 2 parts of p-octylphenol
A resol-type phenolic resin solution obtained in the same manner as in Production Example 1 except that the amount was changed to 26 parts is designated as resol B.

Production Example 3 170 parts of p-octylphenol from Production Example 1, p-L-
22 parts of butylphenol, 1 part of p-octylphenol
Resol type phenolic resin f obtained in the same manner as in Production Example 1 except that 70 parts and 60 parts of p-nonylphenol were used.
Let liquid 4 be C resol.

Production example 4 (Production of carboxylic acid-modified alkyd resin)
A flask similar to Production Example 1 was charged with 300 parts of rosin, 90 parts of glycerin, and 15 parts of xylene, and heated while blowing nitrogen gas to dissolve the rosin at 150°C. after that,
Start stirring and reflux xylene at 200°C.4.
When the acid value reached 4 after 5 hours of reaction, phthalic anhydride 27
0 parts was added and reacted at the same temperature for 3 hours to form acid + il[11
70 was taken out and designated as Alkyd A.

Production Example 5 In the same flask as in Production Example 1, add 1250 parts of linseed oil and 1
．． 90 parts of 4-butanediol and 15 parts of xylene were charged, heated and stirred while blowing nitrogen gas to reflux the xylene, and reacted at 200° C. for 2 hours to give an acid value of 6.

At this point, 90 parts of adipic acid.

27 parts of maleic anhydride was added and reacted at the same temperature for 4 hours, and the mixture was taken out with an acid value of 190 to give Alky Nod B.

Example 1 (Production of high melting point, high solubility resin for printing ink) Into the same flask as in Production Example 1, 580 parts of Alkyd A was charged and heated while blowing nitrogen gas.

The mixture was melted at 130°C, stirred, and heated to 260°C while removing xylene through a condenser. Next, a resol solution prepared by adding a mixed solution of 2.5 parts of p-)luenesulfonic acid and 2.5 parts of hypophosphorous acid (50% aqueous solution) to 500 parts of B resol was poured into a dropping funnel for 1 hour and 20 minutes. dripped. Thereafter, a reaction was performed at 260° C. for 5 hours to obtain resin A with an acid value of 18.

Example 2 Alkyne 18500 was prepared by a reaction procedure similar to Example 1.
Resin B was obtained by reacting 100 parts of rosin, and 550 parts of resol A in the presence of 2.5 parts of p-toluenesulfonic acid and 2.5 parts of hypophosphorous acid (50% aqueous solution).

Example 3 Alkyd A380 was prepared by a reaction procedure similar to Example 1.
and 500 parts of C resol were reacted to obtain resin C.

Comparative Example 1 (Conventional Production of Resin for Printing Ink) 400 parts of rosin was charged into the same reaction apparatus as in Production Example 1, heated and stirred at 160°C while blowing nitrogen gas, and further 2
The temperature was raised to 60° C., 550 parts of A resol was added dropwise over 2 hours, the mixture was reacted for 1 hour, 8 parts of glycerin was added, and the mixture was reacted for a further 7 hours and taken out as having an acid value of 19.

This is referred to as comparative resin A.

Comparative Example 2 (Modified phenolic resin with resol type phenolic resin and rosin) Using the same reaction apparatus as in the example, 600 parts of rosin and 550 parts of resol A were mixed with 2.5 parts of p-toluenesulfonic acid.
Comparative resin B was obtained in the same manner as in the example in the presence of 2.5 parts of hypophosphorous acid and 2.5 parts of hypophosphorous acid (50% aqueous solution).

The properties of the resins obtained in Examples and Comparative Examples are shown in the following table.

(*1) Melting point is Yamato Chemical melting point measuring device model AP-2
Measured at 1.

(*2) The clouding point was expressed as the percentage of resin in a solution that became cloudy at 25°C using Nisseki O Turben I-H (n-paraffin manufactured by Nippon Petrochemicals).

(*3) The molecular weight is the weight average molecular weight determined by GPC method.

As shown in the table, resins A and B have high melting points and are highly soluble resins.

Next, the ink evaluation results of the resins obtained in Examples and Comparative Examples are shown.

[Inking evaluation]

The six types of rosin-modified phenolic resins obtained were made into varnishes using the following two types of formulations, and after being made into inks, the printing was evaluated.

a. Preparation of varnish Varnish preparation A - 200 parts of each resin synthesized in Examples 1 to 3 and Comparative Example 1.2, 48 parts of No. 00 polymerized oil, and 152 parts of Nisseki No. 0 Solvent H were put into four Lof flasks. The temperature was raised while blowing nitrogen gas, and the temperature was kept at 180° C. for 30 minutes while stirring.

Varnishing B - 200 parts of each resin synthesized in Examples 1 to 3 and Comparative Example 1, 48 parts of No. 00 polymerized oil, Maggi 47o
Solvent (Maggie Oil Ink Solvent) 152
Four portions of the mixture were put into a Lof flask and made into a varnish in the same manner as varnishing A.

b. Preparation of gel varnish Gel varnish A - Each varnish obtained in varnishing A 18
Pour 8 parts into 4 Lof flasks, stir while blowing nitrogen gas, raise the temperature to 100°C, and add 3 parts of ALCH (gelling agent manufactured by Yoken Fine Chemicals) and Nisseki O Solvent H.
6 parts of the mixed solution was added, and the mixture was warmed to 180° C. and kept at that temperature for 1 hour.

Gel varnish B - In the same manner as gel varnish A, a gel varnish was formed using a mixture of the varnish obtained in varnishing B, ALCH, and Maggi 470.

C. Preparation of ink Ink preparation - Ink was prepared using each of the obtained gel varnishes. In other words, 60 parts of gel varnish and Carmine 6BA (
Disperse 18 parts of red pigment (manufactured by Toyo Ink Manufacturing Company) using a three-roll mill, and use 1st Stone No. 0 Solvent H and varnish and/or gel varnish to make a total of 100 parts.
Also, the tack value is 5.5 to 6.0. Flow value 19.0-20
．． 0 (at 25°C).

The four types of ink obtained were tested using an R1 tester.

After spreading the color on the entire surface of Mitsubishi Pearl Co.) 66.5 kg (coated paper for off-wheels), immediately place it in an oven at 160°C for 4 seconds to dry it, and after leaving it for day and night, use the gloss meter GM26D (6
Gloss was measured at 0°-60°).

In addition, drying performance was expressed as the temperature of the printed paper surface at the time when the aftertank reached by finger touch disappeared.

Table (Ink evaluation results) From the above results, the resin of the present invention has a high melting point and high solubility, and a printing ink using this resin has high gloss and can be dried at low temperatures.

Claims (1)

[Claims] 1. A resol-type phenolic resin, an alkyd resin modified with a carboxylic acid having 6 or more carbon atoms, and optionally a rosin or a derivative thereof are reacted at a temperature of at least 150°C in the presence of an acid catalyst. A resin for printing ink characterized by having an acid value of at least 30 or less. 2. The resin for printing ink according to claim 1, wherein the alkyd resin has an acid value of 100 to 300. 3. The resin for printing ink according to claim 1 or 2, which uses a resol type phenolic resin mainly containing at least one selected from pt-butylphenol, p-octylphenol, and p-nonylphenol. 4. The resin for printing ink according to any one of claims 1 to 3, wherein the proportion of the resol type phenolic resin is 20 to 70% by weight based on the entire reactant.