WO2012070093A1

WO2012070093A1 - Process for manufacturing rosin-modified phenol resin for offset printing ink and process for manufacturing varnish for offset printing ink

Info

Publication number: WO2012070093A1
Application number: PCT/JP2010/006916
Authority: WO
Inventors: 圭大石; 伊藤　元陽; 智之大森
Original assignee: 星光Pmc株式会社
Priority date: 2010-11-26
Filing date: 2010-11-26
Publication date: 2012-05-31
Also published as: CN103080246A

Abstract

[Problem] To provide a process for manufacturing a rosin-modified phenol resin for offset printing ink suitable for high-speed printing, and a process for manufacturing a varnish for offset printing ink. [Solution] A process for manufacturing a rosin-modified phenol resin for offset printing ink, wherein the rosin-modified phenol resin is a resin that is derived from a rosin, an alkylphenol-aldehyde condensate, and a polyhydric alcohol and has an acid value of 30 or lower and that is characterized both by being manufactured by reacting a rosin with the condensate, and thereafter adding both a polyhydric alcohol in an amount such that the amount of the hydroxyl of the polyhydric alcohol is 0.5 to 0.9 mol relative to one mol of the carboxyl contained in the rosin and a sulfonic acid catalyst to react the rosin, which has reacted with the condensate, with the polyhydric alcohol in the presence of the sulfonic acid catalyst, and by having a metal content of up to 150ppm; and a process for manufacturing a varnish for offset printing ink.

Description

Method for producing rosin-modified phenolic resin for offset printing ink and method for producing varnish for offset printing ink

The present invention relates to a method for producing a rosin-modified phenolic resin for offset printing ink and a method for producing a varnish for offset printing ink.

The rosin-modified phenolic resin is a resin obtained by reacting rosins with a phenolic resin, and / or a polyol, and is widely used as a resin for printing ink, particularly an offset printing resin because of its excellent printability.

In the past, the offset printing industry has increased the demand for labor saving, automation, and high speed during printing, and as a result, there has been offset printing technology that can provide high-quality prints stably for a long time under various printing conditions. It has been demanded. However, as the offset printing speed increases, there is a problem that a high-quality printed matter cannot be obtained due to a decrease in gloss of printing ink and poor printability.

Also, as the offset printing speed increases, stains are likely to occur on the printing plate and printed matter. Therefore, development of a lithographic ink resin that reduces the stains is desired.

As a means for improving “dirt”, a rosin-modified phenol resin having a metal content of 10 ppm or less has been proposed (see, for example, Patent Document 1), which does not contain a rosin-modified phenol resin and contains an α-olefin polymer. A method using a lithographic printing ink composition (see, for example, Patent Document 2) has been proposed. In addition, a rosin having a specific molecular weight obtained by heat-reacting a rosin, a resol type phenol resin using a phenol having an alkyl group having 10 to 20 carbon atoms, and a polyhydric alcohol in the presence of an acid catalyst. A rosin-modified phenol, which is a modified phenolic resin and specifies the solubility of the resin, has been proposed as a printing ink for offset printing (see Patent Document 3). However, the resin for offset ink obtained by these means is insufficient for increasing the printing speed. Therefore, at present, development of an ink resin suitable for high-speed printing while maintaining solubility in a solvent is desired.

JP 2008-274150 A JP 2005-290084 A Japanese Patent No. 3298268 (Japanese Patent Laid-Open No. 7-126338)

The problem to be solved by the present invention is to solve the conventional technical problems and provide a method for producing a rosin-modified phenolic resin for offset printing ink and a method for producing a varnish for offset printing ink suitable for high-speed printing. is there.

As a result of intensive investigations, the present inventors have found a method for producing a rosin-modified phenolic resin suitable for increasing the offset printing speed and suitable for obtaining an offset ink with less contamination of the printing plate and printed matter, and completed the present invention. It came to do.

That is, the means of the present invention for solving the above-mentioned problem is:
(1) A rosin-modified phenol resin derived from rosins, a condensate of an alkylphenol and an aldehyde, and a polyhydric alcohol and having an acid value of 30 or less, wherein the rosins and the condensate are reacted. Later, the polyhydric alcohol is added in an amount of 0.5 mol to 0.9 mol with respect to 1 mol of the carboxyl group contained in the rosins, and the sulfonic acid catalyst is added. A rosin-modified phenol resin for offset printing ink, wherein the rosin after reacting with the condensate is reacted with a polyhydric alcohol in the presence of a sulfonic acid catalyst, and the maximum metal content is 150 ppm. Manufacturing method,
(2) The method for producing a rosin-modified phenol resin for offset printing ink according to (1), wherein the metal is derived from a catalyst used when producing the condensate. It is a method for producing a rosin-modified phenolic resin for printing ink,
(3) The rosin-modified phenol resin for offset printing ink obtained by the method for producing a rosin-modified phenol resin for offset printing ink described in (1) or (2) above is dissolved in at least a vegetable oil and / or an ink solvent. In the lithotronic emulsification test, the product of the maximum emulsification rate and the torque increase rate is 1.0 or more and 4.0 or less.
It is.

The present invention provides a method for producing a rosin-modified phenolic resin and a method for producing a varnish for an offset printing ink, which are suitable for increasing the offset printing speed and capable of obtaining an offset printing ink with less contamination of a printing plate and printed matter. it can.

The present invention relates to a rosin-modified phenol resin derived from rosins, a condensate of alkylphenol and an aldehyde, and a polyhydric alcohol, having an acid value of 30 or less, and the condensation of rosins with an alkylphenol and an aldehyde An amount of polyhydric alcohol in which the amount of hydroxyl group of the polyhydric alcohol is 0.5 mol or more and 0.9 mol or less with respect to 1 mol of the carboxyl group contained in the rosin after reacting with the product, and the sulfonic acid catalyst In the presence of a sulfonic acid catalyst, an esterification reaction between a carboxyl group present in a rosin and a hydroxyl group in a polyhydric alcohol after the reaction of the rosin with a condensate of an alkylphenol and an aldehyde is added. This is a method for producing a rosin-modified phenol resin for offset printing ink.

The rosin-modified phenol resin for offset printing ink of the present invention includes rosins, condensates of alkylphenols and aldehydes (in the present invention, condensates of alkylphenols and aldehydes may be simply referred to as “condensates”), and It is a resin obtained using polyhydric alcohol as an essential raw material.
The rosins refer to rosins and rosin derivatives. Rosin is a natural resin, and gum rosin, tall rosin, wood rosin and the like are called rosins. Gum rosin and tall rosin have an acid value of 165 or more and 170 or less, and wood rosin has an acid value of 160 to 170. Therefore, gum rosin, tall rosin and wood rosin have a common acid value. Examples thereof include rosin derivatives such as hydrogenated rosin, polymerized rosin, and disproportionated rosin. The rosin derivatives also include modified rosins obtained by modifying them with α, β-unsaturated carboxylic acids such as maleic anhydride, fumaric acid, acrylic acid, etc. as necessary.

The hydrogenated rosin can be obtained by saturating a part or all of the unsaturated bonds by hydrogenating rosin.

The above-mentioned polymerized rosin is a rosin that can be obtained by polymerizing rosin in the presence of a catalyst such as sulfuric acid, and is a mixture containing not only a dimer but also a monomer and a multimer of trimers or more.

The disproportionated rosin can be obtained by transferring hydrogen between molecules by heating or the like to saturate the unsaturated bond of one molecule and at the same time unsaturate the other saturated bond.

As the alkylphenol, cresol, amylphenol, bisphenol A, parabutylphenol, paraoctylphenol, paranonylphenol, paradodecylphenol, dibutylphenol, dimethylphenol and the like can be used. These may be used alone or in combination. Parabutylphenol, paraoctylphenol, and paranonylphenol are particularly preferable from the viewpoints of market price, availability, and performance of resin for offset ink.

As the aldehyde, formaldehyde such as formaldehyde, paraformaldehyde and trioxane, acetaldehyde, propionaldehyde and the like can be used. Of these, formaldehyde and paraformaldehyde are particularly preferable from the viewpoint of reactivity and the like. The ratio of alkylphenol to aldehyde is preferably 1.7 mol or more and 2.3 mol or less with respect to 1 mol of alkylphenol. Within the above range, handling as a rosin-modified phenolic resin is easy.

Examples of the condensate include a normal resole prepared by previously reacting an alkylphenol and an aldehyde in the presence of a basic catalyst, and / or an alkylphenol and an aldehyde in advance in the presence of an acidic catalyst, and then further adding an aldehyde. Can be used in the presence of a basic catalyst. These may be used alone or in combination.

Examples of the basic catalyst include metal catalysts such as sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, zinc oxide, ammonia, methylamine, dimethylamine, diethylamine, trimethylamine, ethylamine, diethylamine, triethylamine and the like. Examples thereof include alkanolamines such as alkylamine, ethanolamine, diethanolamine, and triethanolamine. Examples of the acidic catalyst 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 of the catalyst used is preferably 0.01 parts by weight or more and 2.5 parts by weight or less with respect to 100 parts by weight of the condensate. When the amount of the catalyst used is less than 0.01 parts by weight, a condensate cannot be obtained, and when it exceeds 2.5 parts by weight, it is difficult to obtain a rosin-modified phenol resin having a low metal content.

In the method for producing a rosin-modified phenol resin for offset printing ink of the present invention, the use ratio of the condensate with respect to the total amount of rosins, condensate and polyhydric alcohol is preferably 20% by mass or more and 65% by mass or less, and 25% by mass. % To 50% by mass is particularly preferable. If it is less than 20% by mass, the molecular weight of the rosin-modified phenol resin for offset printing ink becomes low, which may cause insufficient viscosity or induce misting during printing. When it exceeds 65% by mass, the affinity between the rosin-modified phenol resin for offset printing ink and the solvent is remarkably increased, and drying at the time of printing may become too slow.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, octanediol, nonanediol, and neopentylglycol. Trihydric or higher alcohols such as dihydric alcohol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and the like. These may be used alone or in combination. Among these, glycerin and / or pentaerythritol is preferable for the purpose of appropriately adjusting the molecular weight, melting point, etc. of the rosin-modified phenol resin for offset printing ink. The amount of the polyhydric alcohol used is such that the amount of the hydroxyl group of the polyhydric alcohol is in the range of 0.5 to 0.9 mol with respect to 1 mol of the carboxyl group of the rosin used.
By setting it as this range, it becomes a rosin-modified phenol resin for offset printing ink suitable for offset printing ink.

Examples of the sulfonic acid catalyst used in the esterification reaction include sulfonates such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, and sulfuric acid. The amount of the sulfonic acid catalyst used is preferably 0.20 part by weight or more and 0.40 part by weight or less with respect to 100 parts by weight in total of the rosin and the polyhydric alcohol.

The acid value of the rosin-modified phenol resin for offset printing ink of the present invention is preferably 30 or less, and more preferably 23 or less and 1 or more. This is because when the acid value is 30 or less, there is a tendency that troubles such as smearing hardly occur during printing.

The melting point of the rosin-modified phenol resin for offset printing ink of the present invention is not particularly limited, but is preferably 130 ° C. or higher and 200 ° C. or lower. This is because when the temperature is lower than 130 ° C., the drying property and the set are significantly reduced.

The molecular weight of the rosin-modified phenol resin for offset printing ink in the present invention is preferably 10,000 or more and 100,000 or less. It is because a varnish viscosity will become a thing suitable for use as it is the said range.

The preferred rosin-modified phenolic resin for offset printing ink in the present invention has a heptane tolerance value of 10 mL / g or more. The heptane tolerance value is an index indicating the compatibility between the resin and the petroleum solvent and / or the vegetable oil. The higher the heptane tolerance value, the higher the compatibility. In the present invention, the heptane tolerance is obtained by adding n-heptane dropwise to a 33.3% toluene solution of rosin-modified phenolic resin and dividing the cloudy n-heptane amount (mL) by the resin amount (g) dissolved in toluene. Value. The term “cloudiness” as used herein refers to a state in which no solubility is exhibited at any concentration.

The rosin-modified phenolic resin for offset printing ink in the present invention preferably contains no metal, and even if a metal is contained, the maximum content of the metal is 150 ppm. When the amount of the metal contained in the rosin-modified phenol resin for offset printing ink exceeds 150 ppm, the emulsification resistance may be deteriorated or cloudy. Although the metal content has never been reduced as much as possible, the metal content contained in the rosin-modified phenol resin for offset printing ink is a metal derived from the catalyst used in the production of the condensate. Complete removal results in increased production costs of the condensate. In particular, when it is less than 3 ppm, the cost increases due to a problem in the production process.

The varnish for offset printing ink in the present invention contains a rosin-modified phenol resin for offset printing ink and at least a vegetable oil and / or a solvent for ink, and in addition to a gelling agent for imparting elasticity, if necessary, oxidation Additives such as inhibitors can be included.

As the vegetable oil used in the varnish for offset printing ink, various known oils can be used without limitation. For example, flaxseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil, vegetable oil such as flaxseed oil fatty acid methyl, soybean oil fatty acid methyl, flaxseed oil fatty acid ethyl, soybean oil fatty acid ethyl, flaxseed oil fatty acid propyl, soybean oil Examples thereof include monoesters of the above vegetable oils such as fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl and the like. These may be used alone or in combination of two or more. In these, the vegetable oil which has an unsaturated bond in a molecule | numerator from the point of the drying property of printed matter is preferable, and soybean oil is especially preferable from the point with a small load with respect to an environment.

As the ink solvent used for the varnish for offset printing ink, a conventionally known ink solvent can be used without any particular limitation. For example, No. 0 solvent, 4 solvent, 5 solvent, 6 solvent, 7 solvent, AF solvent 4, AF solvent 5, AF solvent 6, which are petroleum solvents manufactured by Nippon Oil Corporation, AF solvent 7 etc. are mention | raise | lifted. These may be used alone or in combination of two or more. In particular, it is preferable to use an AF solvent having a boiling point of about 200 ° C. or more and an aromatic hydrocarbon content of about 1% by weight or less from the viewpoint of environmental measures. When printing ink with reduced environmental load is required, only vegetable oils may be used without using ink solvents.

Examples of gelling agents used in varnishes for offset printing ink include aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, aluminum Various known materials such as triacetyl acetate, tetraisopropoxy titanium, tetrabutoxy titanium, dipropoxy bis (acetylacetonato) titanium, tetrabutoxy zirconium, tolylene diisocyanate, diphenyl diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate Can be used without any particular limitation. These may be used alone or in combination of two or more.

As the antioxidant used in the varnish for offset printing ink, various known ones such as 2,6-di-tert-butyl-4-methylphenol can be used without any particular limitation.

The varnish for offset printing ink can be produced by mixing and stirring the above components, but when mixing and stirring, these are usually heated to a temperature in the range of 100 ° C to 240 ° C. Each component is dissolved and mixed, and is obtained using additives as necessary.

The ratio of the rosin-modified phenol resin for offset printing ink in the varnish for offset printing ink is preferably 30% by mass to 60% by mass, and particularly preferably 35% by mass to 50% by mass. It is because a varnish viscosity will become a thing suitable for use as it is the said range.

The lysotronic emulsification test of the varnish for offset printing ink in the present invention is measured under the following conditions using a high speed lithotronic emulsification tester manufactured by Novo Control.
Conditioning time (preliminary stirring time without adding water) ... 300 sec
Stirring speed ... 1200rpm
Amount of sample (varnish): 25g
Temperature ... 40 ° C
Dripping amount of water ... 2mL / min propeller ... propeller angle 10 °, thickness 1.5mm
Distance between propeller and cup bottom: 1mm
When dripping water, the water injection needle is brought into contact with the cup wall surface so that the water gently enters the ink, and the torque curve noise due to water drops is minimized.

The maximum emulsification rate and the torque increase rate are as follows.

The maximum emulsification rate (EC (Emulsification Capacity: unit%). Hereinafter, sometimes abbreviated as EC) is calculated by the following formula.
In the calculation, the value of EC is defined as the maximum emulsification rate when the torque starts to fluctuate in an unstable manner and the standard deviation of the latest 10 measured values of the torque value exceeds 100.

EC (%) = (Drip amount of water) / (Sample amount) × 100

The torque increase rate is calculated by the following formula.
Torque increase rate (%) = (Tmax−Tmin) / Tmin × 100
Here, T min is the minimum torque, T max is the maximum torque value, and is defined as follows.

When water is dripped into the sample varnish in the cup while stirring, the initial torque decreases and shows the minimum torque value. Thereafter, the torque value increases with the increase in the amount of water dripping, indicating the maximum torque value. If dripping is further continued, a part of the water is separated from the sample, causing a sharp decrease in torque and an unstable torque curve.

Since the product of the maximum emulsification rate and the torque increase rate calculated as described above is 1.0 or more and 4.0 or less, the problem of initial emulsification and the problem of overemulsification does not occur, and appropriate emulsification resistance is obtained. ,preferable.

The offset printing ink contains the rosin-modified phenolic resin for offset printing ink and / or the varnish, pigment, vegetable oil and / or solvent for the offset printing ink, and if necessary, an additive for offset ink, for example, Further, a surfactant, a wax, a drying accelerator (dryer) and a drying inhibitor for improving ink fluidity and ink surface coating may be contained.

Examples of pigments contained in the offset printing ink include yellow, red, indigo and black pigments. The content of the pigment is preferably 3% by mass or more and 30% by mass or less.

As the vegetable oil used in the offset printing ink, various known oils can be used without limitation. For example, flaxseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil, vegetable oil such as flaxseed oil fatty acid methyl, soybean oil fatty acid methyl, flaxseed oil fatty acid ethyl, soybean oil fatty acid ethyl, flaxseed oil fatty acid propyl, soybean oil Examples thereof include monoesters of the above vegetable oils such as fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl and the like. These may be used alone or in combination of two or more.

As the solvent used in the offset printing ink, a conventionally known ink solvent can be used without any particular limitation. For example, No. 0 solvent, 4 solvent, 5 solvent, 6 solvent, 7 solvent, AF solvent 4, AF solvent 5, AF solvent 6, which are petroleum solvents manufactured by Nippon Oil Corporation, AF solvent 7 etc. are mention | raise | lifted. These may be used alone or in combination of two or more. In particular, it is preferable to use an AF solvent having a boiling point of about 200 ° C. or more and an aromatic hydrocarbon content of about 1% by weight or less from the viewpoint of environmental measures. When printing ink with reduced environmental load is required, only vegetable oils may be used without using ink solvents. The content of the solvent is preferably 5 to 50% by mass.

When the varnish for offset printing ink in the present invention is not used, the content of the rosin-modified phenol resin for offset printing ink used in the offset printing ink in the offset printing ink is preferably 10% by mass or more and 50% by mass or less. 15 mass% or more and 40 mass% or less are still more preferable. If it is less than 10% by mass, the viscosity of the offset printing ink is not sufficient, and at the same time, the pigment dispersion cannot be stabilized, causing problems such as aggregation. If it exceeds 50% by mass, the viscosity of the offset printing ink may become too high.
Even when the offset printing ink is prepared using the offset printing ink varnish and the offset printing ink rosin modified phenolic resin in the present invention, the content of the offset printing ink rosin modified phenolic resin in the offset printing ink is 10 mass% or more and 50 mass% or less are preferable, and 15 mass% or more and 40 mass% or less are still more preferable.

The content of the vegetable oil and / or solvent used in the offset printing ink in the offset printing ink is the total amount excluding all other components. The use ratio of the vegetable oil and the solvent may be changed according to the purpose. For example, in the case of a non-VOC ink characterized by not containing a solvent, only vegetable oils are used without containing a solvent. For example, in the case of offset rotary printing ink that performs hot air drying, the amount of vegetable oil used is reduced and a large amount of solvent is used. In recent years, soybean oil ink has attracted attention as an environmentally friendly ink, and many offset rotary printing inks contain soybean oil or the like.

Drying accelerators (dryers) used in offset printing inks include metal soaps that are salts of metals such as cobalt, manganese, lead, iron, and zinc with carboxylic acids such as octylic acid, naphthenic acid, and neodecanoic acid. Is possible.

As the drying inhibitor, hydroquinone, methoquinone, tert-butyl hydroquinone and the like can be used.

The offset printing ink additive used in the offset printing ink may be added at any stage in the production of the offset printing ink as long as it can be uniformly mixed with the offset printing ink. It may be added at the final stage of production of offset printing ink, or may be added in advance at the stage of production of varnish for offset printing ink. It is also possible to add it to other resins to be used and use it as a varnish for offset printing ink.

The offset printing ink can be obtained by kneading and preparing using a known ink manufacturing apparatus such as a roll mill, a ball mill, an attritor, or a sand mill.

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In addition, in an example, a part and% are a mass part and the mass%, respectively.

Example 1
(Production Example 1: Production of condensate F-1)
In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 2200 parts of p-nonylphenol, 652 parts of 92% paraformaldehyde, and 1500 parts of toluene were charged, and the contents of the four-necked flask were placed at 50 ° C. Then, 30 parts of 48% sodium hydroxide was charged into the four-necked flask at this temperature. The contents of the four-necked flask were heated to 80 ° C. and reacted for 6 hours, and then the contents of the four-necked flask were neutralized with 40 parts of 35% hydrochloric acid and washed with 500 parts of water. After leaving still for 6 hours, the aqueous layer was removed, and further 500 parts of water was added and washed with water. After standing for 6 hours, the aqueous layer was removed to obtain a condensate F-1.
(Production of rosin-modified phenolic resin 1 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 800 parts of the condensate F-1 produced in Production Example 1 was added to the gum rosin, and the temperature was further raised to 215 ° C. 20 parts and 40 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.77 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 5 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin 1 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin 1 for offset printing ink had a melting point of 150 ° C., an acid value of 20 mg KOH / g, heptane tolerance of 21 mL / g, a weight average molecular weight of 80,000, and a catalyst-derived metal content of 23 ppm.

Example 2
(Production Example 2: Production of condensate F-2)
A four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 1200 parts of pt-butylphenol, 412 parts of p-octylphenol, 652 parts of 92% paraformaldehyde, and 1500 parts of toluene. After the contents of the neck flask were heated to 50 ° C., 50 parts of 48% sodium hydroxide was charged into the four-neck flask at this temperature. The contents of the four-necked flask were heated to 80 ° C. and reacted for 6 hours, and then the contents of the four-necked flask were neutralized with 40 parts of 35% hydrochloric acid and washed with 500 parts of water. After standing for 6 hours, the aqueous layer was removed, and further 500 parts of water was added and washed with water. After standing for 6 hours, the aqueous layer was removed to obtain a condensate F-2.
(Production of rosin-modified phenolic resin 2 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 570 parts of the condensate F-2 produced in Production Example 2 was added to the gum rosin, and the temperature was further raised to 215 ° C. 10 parts and 55 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.82 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 5 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin 2 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin 2 for offset printing ink had a melting point of 180 ° C., an acid value of 18 mg KOH / g, a heptane tolerance of 15 mL / g, a weight average molecular weight of 13,000, and a catalyst-derived metal content of 12 ppm.

Example 3
(Production Example 3: Production of condensate F-3)
In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 2060 parts of p-octylphenol, 652 parts of 92% paraformaldehyde, and 1500 parts of toluene were charged, and the contents of the four-necked flask were placed at 50 ° C. Then, 50 parts of 48% sodium hydroxide was put into a four-necked flask at this temperature. The contents of the four-necked flask were heated to 80 ° C. and reacted for 6 hours, and then the contents of the four-necked flask were neutralized with 40 parts of 35% hydrochloric acid and washed with 500 parts of water. After standing for 6 hours, the aqueous layer was removed, and further 500 parts of water was added and washed with water. After standing for 6 hours, the aqueous layer was removed to obtain a condensate F-3.
(Production of rosin-modified phenolic resin 3 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 650 parts of the condensate F-3 produced in Production Example 3 was added to the gum rosin, and the temperature was further raised to 215 ° C. 65 parts were added, and the temperature was further increased to 250 ° C. after the addition. In addition, the usage-amount of glycerol is equivalent to 0.89 mol of hydroxyl groups in glycerol with respect to 1 mol of carboxyl groups of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 5 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin 3 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin 3 for offset printing ink had a melting point of 160 ° C., an acid value of 19 mg KOH / g, heptane tolerance of 17 mL / g, a weight average molecular weight of 20,000, and a catalyst-derived metal content of 10 ppm.

Example 4
(Production Example 4: Production of condensate F-4)
In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 1500 parts of pt-butylphenol, 652 parts of 92% paraformaldehyde, and 1500 parts of toluene were charged, and the contents of the four-necked flask were charged. After heating to 50 ° C., 50 parts of 48% sodium hydroxide was charged into the four-necked flask at this temperature. The contents of the four-necked flask were heated to 80 ° C. and reacted for 6 hours, and then the contents of the four-necked flask were neutralized with 40 parts of 35% hydrochloric acid and washed with 500 parts of water. After leaving still for 6 hours, the aqueous layer was removed, and further 500 parts of water was added and washed with water. After standing for 6 hours, the aqueous layer was removed to obtain a condensate F-4.
(Production of rosin-modified phenolic resin 4 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 570 parts of the condensate F-4 produced in Production Example 4 was added to the gum rosin, and the temperature was further raised to 215 ° C. 10 parts and 55 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.82 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 5 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin 4 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin 4 for offset printing ink had a melting point of 185 ° C., an acid value of 21 mg KOH / g, a heptane tolerance of 13 mL / g, a weight average molecular weight of 20,000, and a catalyst-derived metal content of 10 ppm.

Example 5
(Production of rosin-modified phenolic resin 5 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the melted gum rosin, 870 parts of the condensate F-3 produced in Production Example 3 was added to the gum rosin, and the temperature was further raised to 215 ° C. 10 parts and 40 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.64 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 5 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin 5 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 10 minutes using a vacuum pump. The obtained rosin-modified phenol resin 5 for offset printing ink had a melting point of 175 ° C., an acid value of 20 mg KOH / g, heptane tolerance of 16 mL / g, a weight average molecular weight of 100,000, and a catalyst-derived metal content of 16 ppm.

Example 6
(Production of rosin-modified phenolic resin 6 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 500 parts of the condensate F-2 produced in Production Example 2 was added to the gum rosin, and the temperature was further raised to 215 ° C. 20 parts and 40 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.77 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of dodecylbenzenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 5 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin 6 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin 6 for offset printing ink had a melting point of 174 ° C., an acid value of 21 mg KOH / g, a heptane tolerance of 20 mL / g, a weight average molecular weight of 28,000, and a catalyst-derived metal content of 20 ppm.

Comparative Example 1
(Production of rosin-modified phenolic resin C1 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 650 parts of the condensate F-3 produced in Production Example 3 was added to the gum rosin, and the temperature was further raised to 215 ° C. 65 parts and 1 part of zinc oxide were added, and the temperature was further increased to 250 ° C. after the addition. In addition, the usage-amount of glycerol is equivalent to 0.89 mol of hydroxyl groups in glycerol with respect to 1 mol of carboxyl groups of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 8 hours while maintaining at 250 ° C., and kept at 250 ° C. for 60 minutes at 20 mmHg using a vacuum pump. To produce a rosin-modified phenolic resin C1 for offset printing ink. The obtained rosin-modified phenol resin C1 for offset printing ink had a melting point of 175 ° C., an acid value of 22 mgKOH / g, heptane tolerance of 9 mL / g, a weight average molecular weight of 80,000, and a catalyst-derived metal content of 18 ppm. This comparative example is an example in which no sulfonic acid catalyst is used.

Comparative Example 2
(Production of rosin-modified phenolic resin C2 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 800 parts of the condensate F-1 produced in Production Example 1 was added to the gum rosin, and the temperature was further raised to 215 ° C. 20 parts and 40 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.77 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 2 hours, and kept at 250 ° C. in the four-necked flask. A rosin-modified phenol resin C2 for offset printing ink was produced by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin C2 for offset printing ink had a melting point of 150 ° C., an acid value of 31 mg KOH / g, a heptane tolerance of 14 mL / g, a weight average molecular weight of 30,000, and a catalyst-derived metal content of 25 ppm. This comparative example is an example in which the acid value of the rosin-modified phenol resin for offset printing ink is high.

Comparative Example 3
(Production Example 5: Production of condensate F-5)
In a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 2200 parts of p-nonylphenol, 652 parts of 92% paraformaldehyde, and 1500 parts of toluene were charged, and the contents of the four-necked flask were placed at 50 ° C. Then, 50 parts of 48% sodium hydroxide was put into a four-necked flask at this temperature. The contents of the four-necked flask were heated to 80 ° C. and reacted for 6 hours, and then the contents of the four-necked flask were neutralized with 40 parts of 35% hydrochloric acid and washed with 500 parts of water. After standing for 6 hours, the aqueous layer was removed to obtain a condensate F-5.
(Production of rosin-modified phenolic resin C3 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the molten gum rosin, 650 parts of the condensate F-5 produced in Production Example 5 was added to the gum rosin, and the temperature was further raised to 215 ° C. 20 parts and 40 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 0.77 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 2 hours, and kept at 250 ° C. in the four-necked flask. A rosin-modified phenol resin C3 for offset printing ink was produced by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin C3 for offset printing ink had a melting point of 150 ° C., an acid value of 22 mgKOH / g, heptane tolerance of 14 mL / g, a weight average molecular weight of 78,000, and a catalyst-derived metal content of 400 ppm. This comparative example is an example in which the catalyst-derived metal content of the rosin-modified phenol resin for offset printing ink is high.

Comparative Example 4
(Production of rosin-modified phenolic resin C4 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the melted gum rosin, 870 parts of the condensate F-3 produced in Production Example 3 was added to the gum rosin, 10 parts of glycerin, 40 parts of pentaerythritol, and 2 parts of paratoluenesulfonic acid, After charging one after another, the temperature was raised to 250 ° C. The total amount of glycerin and pentaerythritol used corresponds to 0.64 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 2 hours while maintaining at 250 ° C., and the vacuum pump was kept at 250 ° C. with a vacuum pump. The rosin-modified phenol resin C4 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes. The obtained rosin-modified phenol resin C4 for offset printing ink had a melting point of 160 ° C., an acid value of 21 mg KOH / g, heptane tolerance of 19 mL / g, a weight average molecular weight of 20,000, and a catalyst-derived metal content of 16 ppm. This comparative example is an example in which raw materials for rosin-modified phenol resin for offset printing ink are reacted together.

Comparative Example 5
(Production of rosin-modified phenolic resin C5 for offset printing ink)
A four-necked separable flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer was charged with 800 parts of gum rosin and heated to 170 ° C. while blowing nitrogen gas to melt the gum rosin. While stirring the melted gum rosin, 870 parts of the condensate F-3 produced in Production Example 3 was added to the gum rosin, and the temperature was further raised to 215 ° C. 50 parts and 30 parts of pentaerythritol were added, and the temperature was further increased to 250 ° C. after the addition. The total amount of glycerin and pentaerythritol used corresponds to 1.06 mol of hydroxyl group in glycerin and pentaerythritol with respect to 1 mol of the carboxyl group of the used gum rosin. During the temperature rise, toluene and water were taken out of the reaction system with a reflux condenser with a water separator, reacted for 4 hours while maintaining at 250 ° C., and a part of the contents of the four-necked separable flask was collected. When the acid value reached 50 mgKOH / g, 2 parts of paratoluenesulfonic acid was charged into a four-necked separable flask, reacted at 250 ° C. for 2 hours, and kept at 250 ° C. in the four-necked flask. The rosin-modified phenol resin C5 for offset printing ink was manufactured by reducing the pressure at 20 mmHg for 60 minutes using a vacuum pump. The obtained rosin-modified phenol resin C5 for offset printing ink had a melting point of 179 ° C., an acid value of 20 mg KOH / g, heptane tolerance of 12 mL / g, a weight average molecular weight of 120,000, and a catalyst-derived metal content of 15 ppm. In this comparative example, the amount of the hydroxyl group of the polyhydric alcohol is an addition amount higher than 0.9 mol relative to 1 mol of the carboxyl group contained in the rosins.

Abbreviations in Table 1 are as follows.
Resin: Rosin-modified phenol resin for offset printing ink HT: Heptane tolerance Mw: Weight average molecular weight content: Content of catalyst-derived metal used in the production of the condensate (ppm)

Preparation of varnish for offset printing ink 40 parts of pulverized material obtained by finely pulverizing each rosin-modified phenol resin for offset printing ink obtained in Examples 1 to 6 and Comparative Examples 1 to 5, 30 parts of soybean oil, and Place 30 parts of AF-5 solvent in a 4-neck separable flask, raise the temperature of the contents of the 4-neck separable flask while blowing nitrogen gas, and stir the contents for 1 hour while heating to 190 ° C. And then cooled. ALCH (Kawaken Fine Chemicals) at 130 ° C so that the viscosity of the contents of the four-necked separable flask (measured at 25 ° C with an E-type viscometer manufactured by Toyo Seiki Co., Ltd.) is 10 to 35 Pa · s. 1.4 parts of a solution obtained by dissolving 0.7 part of a gelling agent (manufactured) by 0.7 part of AF-5 solvent was added, the temperature was raised to 160 ° C., and the temperature was kept at that temperature for 1 hour. If the viscosity of the contents of the four-neck separable flask deviates from 10 to 35 Pa · s, varnish 1 to 6 for offset printing ink (offset of Examples 1 to 6) can be added by adding AF-5 solvent or ALCH. And varnishes C1 to C5 for offset printing ink (each using the rosin modified phenolic resin for offset printing ink of Comparative Examples 1 to 5). Table 2 shows the results of a lithotronic emulsification test of the obtained varnish for offset printing ink as follows.

(Risotronic emulsification test)
EC (%) and torque increase rate (%) were determined for 25 g of varnish for offset printing ink using a lithotronic emulsification tester (manufactured by NOVOCONTROL) under the conditions specified in the present invention. It is preferable that it is 1.0 or more and 4.0 or less because the emulsification resistance becomes appropriate without causing problems of initial emulsification and over-emulsification.

“Varnish” in Table 2 represents a varnish for offset printing ink.

Abbreviations in Table 2 are as follows.
EC: maximum emulsification rate (EC (Emulsification Capacity: unit%))
Increase rate: Torque increase rate product: Product of maximum emulsification rate and torque increase rate

(Preparation of offset printing ink)
54 parts of each of the varnishes for offset printing ink 1 to 6 and varnishes C1 to C5 for offset printing ink and 18 parts of red pigment ZAB120 manufactured by Dainichi Seika Co., Ltd. are kneaded with three rolls to provide an AF-5 solvent. And gel varnish were added so that the total amount would be 100 parts, and appropriately adjusted so that the tack at 25 ° C. was 9.0, and offset printing inks 1 to 6 and offset printing inks C1 to C5 were obtained. The obtained ink evaluation is shown in Table 3. The method of performance test of offset printing ink is as follows.

(Ink performance test)
Emulsification resistance: 25 g of offset printing ink was changed with a lithotronic emulsification tester (manufactured by NOVOCONTROL), and the lithographic emulsification test conditions and stirring speed of the varnish for offset printing ink defined in the present invention were changed from 1200 rpm to 800 rpm. The product of EC and the rate of torque increase was obtained under the same conditions. It is preferable that the ratio is 0.7 or more and 4.0 or less because the problem of initial emulsification and the problem of overemulsification does not occur and the emulsification resistance becomes appropriate.
○: 0.7 or more and 4.0 or less Δ: If it exceeds 4.0 and less than 7.0, or 0.3 or more and less than 0.7 ×: 7.0 or more, or less than 0.3

Misting: Offset printing ink is attached to INK-O-METER manufactured by Toyo Seiki Co., Ltd., the roller group is rotated, and the scattering state of the offset printing ink at that time is the condition of dirty white paper around the INK-O-METER. Was determined visually.
○: Almost no contamination and no problem in practical use.
Δ: Some dirt is noticeable.
X: Dirt is conspicuous.

Fluidity: 1.3 mL of offset printing ink was placed on a glass plate, tilted at 70 degrees, and judged from the distance (mm) that flowed one day later. A thickness of 200 to 300 mm is preferable because it easily balances the occurrence of stains and the ease of ink flow.
○: 200 mm or more and 300 mm or less Δ: Over 300 mm and less than 400 mm or 100 mm or more and less than 200 mm x: 400 mm or more or less than 100 mm

“Ink” in Table 3 represents offset printing ink.

By using the rosin-modified phenolic resin for offset printing ink of the present invention from the comparison results of Examples and Comparative Examples in Tables 1 to 3, an offset ink suitable for increasing the speed of offset printing and having less stain on the printing plate and printed matter is obtained. You can see that

By using the rosin-modified phenolic resin for offset printing ink of the present invention, it is possible to provide an offset ink that is suitable for increasing the speed of offset printing and has less stain on the printing plate and printed matter.

Claims

A rosin-modified phenol resin derived from a rosin, a condensate of an alkylphenol and an aldehyde, and a polyhydric alcohol having an acid value of 30 or less, and after reacting the rosin with the condensate, The polyhydric alcohol is added in an addition amount such that the hydroxyl group amount of the monohydric alcohol is 0.5 mol or more and 0.9 mol or less with respect to 1 mol of the carboxyl group contained in the rosin, and the sulfonic acid catalyst is added to the condensation. A method for producing a rosin-modified phenol resin for offset printing ink, wherein the rosin after reacting with a product and a polyhydric alcohol are reacted in the presence of a sulfonic acid catalyst, and the maximum metal content is 150 ppm.
The method for producing a rosin-modified phenol resin for offset printing ink according to claim 1, wherein the metal is derived from a catalyst used when the condensate is produced.
A rosin-modified phenol resin for offset printing ink obtained by the method for producing a rosin-modified phenol resin for offset printing ink according to claim 1 or 2 is dissolved in at least a vegetable oil and / or a solvent for ink, and in a lithotronic emulsification test. A method for producing a varnish for offset printing ink, wherein the product of the maximum emulsification rate and the torque increase rate is 1.0 or more and 4.0 or less.