WO2019039449A1 - Oxidative polymerization drying-type offset printing ink composition and printed matter - Google Patents

Abstract

Provided is an oxidative polymerization drying-type offset printing ink composition which prevents ink set-off even when powder is not sprayed or the amount of powder sprayed is reduced compared to the conventional case. This oxidative polymerization drying-type offset printing ink composition comprises: a varnish containing a rosin-modified phenol resin having a cloud point of 100-210°C in AF Solvent No. 6; a dryer; a pigment; and a petroleum wax having a melting point of 80°C or lower and containing normal paraffin, wherein the viscosity of the composition is 10-60 Pa·s as measured by an L-type viscometer, the content of the normal paraffin is 0.1-3 mass%, and the content of the pigment is within a specified range.

Description

Oxidation polymerization dry type offset printing ink composition and printed matter

The present invention relates to an oxidative polymerization dry type offset printing ink composition and a printed matter printed using the oxidative polymerization dry type offset printing ink composition.

In the oxidative polymerization dry type offset printing ink composition, the oxidatively polymerizable components contained in the varnish are polymerized by oxygen in the air to form a cured film. In order to promote oxidative polymerization, a drier such as a metal salt of an organic acid such as octylic acid and a transition metal such as cobalt or manganese is generally blended. In some cases, a thermal drying method may be used in combination.

As described above, even if a drier is blended or a heat drying system is used in combination, it takes several hours to dry the printed matter printed by the offset polymerization ink composition of the oxidation polymerization drying type. During this time, since the printed matter is stored in piles, a problem called offset occurs, in which the printing surface (printing ink composition) immediately after printing is subsequently printed and attached to the back side of the superposed printed matter.
As a method of preventing offset, so-called powder spraying, in which fine powder is sprayed on a printing surface immediately after printing, is widely performed (Patent Document 1).

Japanese Patent Application Laid-Open No. 59-45157

However, although powder dispersion as described in Patent Document 1 is effective for preventing offset, the gloss of the printed material is reduced, or the adhesion between the film and the paper surface is reduced when, for example, a polypropylene film is attached to a printing surface as post-processing. There is a risk of problems such as In addition to the scattering and floating of powder around the printing machine to deteriorate the working environment, the scattered powder may promote the wear of the printing machine.

The present invention has been made in view of such circumstances, and it is an oxidation polymerization drying type offset printing ink which prevents offset even when powder is not applied or when the amount of powder applied is reduced more than before. It is intended to provide a composition.

The present invention provides a varnish comprising a rosin-modified phenolic resin having a cloud point of 100 ° C. to 210 ° C. of AF Solvent No. 6, a drier, a pigment, and a petroleum wax having a melting point of 80 ° C. or less and normal paraffins. The viscosity is 10 Pa · s or more and 60 Pa · s or less, the content of normal paraffin is 0.1 mass% or more and 3 mass% or less, and the content of pigment is within the specified range. The present invention relates to an oxidative polymerization dry type offset printing ink composition characterized by being contained therein.

According to the oxidative polymerization dry type offset printing ink composition of the present invention, it is possible to make the reverse resistance of the printed matter favorable.

<Oxidation polymerization dry type offset printing ink composition>
The oxidative polymerization dry type offset printing ink composition of the present invention is characterized by containing a varnish, a drier, a pigment and a petroleum wax. Hereinafter, the oxidative polymerization dry type offset printing ink composition of this invention is explained in full detail. Moreover, below, an oxidation polymerization drying type offset printing ink composition is also only called printing ink.

The varnish used in the printing ink of the present invention contains, as an essential component, a rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6, and if necessary, other resins, vegetable oils or fatty acid esters Or mixtures thereof, petroleum solvents, chelating agents, other auxiliary agents, etc. by heating and dissolving. In the present specification, the cloud point of AF solvent No. 6 refers to NO mass part No. CHEMICAL MORTECTOR CHEMONTORONIC II, and 180 parts by mass of AF solvent No. 6 (manufactured by JXTG Energy Co., Ltd.) and 20 parts by mass of resin It is the white turbidity lower limit temperature at the time of heating and mixing.

Such rosin-modified phenolic resin can be obtained by, for example, resol having an average number of nuclei of 1.5 to 3.0 obtained by heating reaction of formaldehyde and / or paraformaldehyde with phenols, rosins and a polyhydric alcohol Resin obtained by reacting with a rosin ester resin obtained by the reaction of (1) or a resol having an average number of nuclei of 1.5 to 3.0 and a rosin, and then esterified with a polyhydric alcohol The resulting resin can be used.

Examples of phenols used for preparation of resol include phenol, cresol, amylphenol, p-tertiary butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol, bisphenol A and the like, among which p-tertiary It is preferable to use an alkylphenol having a substituent having 4 to 12 carbon atoms at the para position such as butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol and the like.

As rosins, conventionally known ones can be used without particular limitation. A gum rosin, wood rosin, tall oil rosin, polymerized rosin, acid-modified rosin, and those rosins purified by distillation or the like can be mentioned.

When an acid-modified rosin is used, it is preferable to use a dibasic acid or an anhydride thereof as a compound used for modifying the rosin. Fumaric acid, maleic acid, maleic anhydride, adipic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic anhydride and the like can be mentioned. Among them, fumaric acid, maleic acid and maleic anhydride are preferably used.

Examples of polyhydric alcohols include glycerin, diglycerin, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, dipentaerythritol, and sorbitol. Among them, glycerin and pentaerythritol are preferably used.

The weight average molecular weight of the rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6 is preferably 15,000 or more, and more preferably 30,000 or more. Moreover, it is preferable that it is 150,000 or less. In addition, the weight average molecular weight in this specification is a value measured by the gel permeation chromatography (GPC) of the following conditions.

Measuring device; Tosoh Co., Ltd. HLC-8320 GPC
Column; Tosoh Corp. TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL
Detector; RI (differential refractometer)
Data processing; Tosoh Corp. multi station GPC-8020 model II
Measurement condition: Column temperature 40 ° C
Solvent: Tetrahydrofuran Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene sample: 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered with a microfilter (100 μl)

The rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of the AF solvent No. 6 used in the present invention preferably has a softening point of 150 ° C. or more, more preferably 160 ° C. or more. Moreover, it is preferable that a softening point is 200 degrees C or less. The softening point in this specification is measured by the ring and ball method in accordance with JIS K 5601-2-2. Specifically, a brass ring filled with a sample is held horizontally in a glycerin bath, and Place a constant weight steel ball in the center, raise the bath temperature at a constant speed, gradually soften the sample, descend the steel ball and finally reach the bottom plate with a thickness of 25 mm, with a thermometer reading Let it be the softening point.

As other resins that can be used in combination with the rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6 described above, conventionally known resins can be used without particular limitation. Rosin resin, rosin modified phenolic resin, rosin ester, petroleum resin, acrylic resin, polyester, alkyd resin, petroleum resin modified rosin / phenol resin, petroleum resin modified rosin ester, petroleum resin modified alkyd resin, alkyd resin modified rosin / phenol resin, Alkyd resin modified rosin ester, acrylic modified rosin / phenol resin, acrylic modified rosin ester, urethane modified rosin / phenol resin, urethane modified rosin ester, urethane modified alkyd resin, epoxy modified rosin / phenol resin, epoxy modified rosin ester, epoxy modified alkyd Resin etc. are illustrated. These resins may be used alone or in combination of two or more.

When the printing ink of the present invention contains a rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6 and a resin other than that, AF solvent among the total of resins contained in the printing ink The proportion of the rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less at No. 6 is preferably 75% by mass or more, more preferably 85% by mass or more, and 90% by mass or more More preferable.

As a solvent used for preparation of a varnish, a conventionally well-known thing can be used and there is no restriction | limiting in particular.
As vegetable oils, non-drying oils such as castor oil, peanut oil and olive oil, soybean oil, cottonseed oil, rapeseed oil, semi-drying oils such as sesame oil and corn oil, drying oils such as linseed oil, eno oil and soy sauce, regenerated vegetable oil And plant-derived components such as plant esters can be used.

As vegetable oils, regenerated vegetable oils can also be used. The regenerated vegetable oil is a vegetable oil which is recovered from oil used for cooking and the like and regenerated. The regenerated vegetable oil is preferably an oil regenerated with a water content of 0.3% by mass or less, an iodine value of 90 or more, and an acid value of 3 or less, more preferably an iodine value of 100 or more. By setting the water content to 0.3% by mass or less, it becomes possible to remove impurities that affect the emulsification behavior of the ink, such as salts contained in the water, and by making the iodine value 90 or more, the drying property is achieved. That is, it becomes possible to obtain good oxidative polymerization, and by selecting and regenerating vegetable oil having an acid value of 3 or less, it is possible to suppress over-emulsification of the ink. As a method for regenerating the recovered vegetable oil, methods such as filtration, removal of precipitates by standing, and decolorization by activated clay etc. are exemplified.

Examples of fatty acid esters include soybean oil fatty acid methyl ester, soybean oil fatty acid butyl ester, soybean oil fatty acid isobutyl ester, soybean oil fatty acid 2-ethylhexyl ester, linseed oil fatty acid butyl ester, linseed oil fatty acid isobutyl ester, tall oil fatty acid butyl ester Ester, tall oil fatty acid 2-ethylhexyl ester, tall oil octyl ester, tall oil fatty acid pentaerythritol ester, palm oil fatty acid methyl ester, palm oil fatty acid butyl ester, palm oil fatty acid isobutyl ester, palm oil fatty acid 2-ethylhexyl ester, castor oil Examples thereof include fatty acid methyl esters, castor oil fatty acid butyl esters, castor oil fatty acid isobutyl esters, and castor oil fatty acid 2-ethylhexyl esters.

As the petroleum-based solvent, hydrocarbons having 6 to 20 carbon atoms are preferably used. Specifically, paraffin solvents such as n-pentane, isopentane, n-hexane, 2-methylpentane, n-heptane, n-octane, trimethylpentane and the like, naphthenes such as cyclohexane, cyclohexylmethane, octadecylcyclohexane, methylisopropylcyclohexane and the like A system solvent, "AF Solvent No. 4", "AF Solvent No. 5", "AF Solvent No. 6", "AF Solvent No. 7" manufactured by JXTG Energy Co., Ltd., etc. may be mentioned.

The chelating agent is, for example, a derivative of aluminum n-butoxide, aluminum-iso-butoxide or aluminum-sec-butoxide, and one of each group of n-butoxy group, iso-butoxy group and sec-butoxy group is Ethyl acetate or a compound substituted with methylacetoacetate can be used.

The color pigment used in the printing ink of the present invention is not particularly limited, and various organic pigments and inorganic pigments can be used. For example, as the yellow pigment, Disazo Yellow (Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 17, Pigment Yellow 1), Hansa Yellow, etc. may be mentioned, and as the red pigment, Brilliant Carmine 6B, Lake Red C, Watching Red, etc. Can be mentioned. Examples of the base pigment include phthalocyanine blue, phthalocyanine green and alkali blue, and examples of the black pigment include furnace carbon black, carbon black such as channel black, and aniline black.

The printing ink of the present invention is used by adjusting it to have a viscosity of 10 Pa · s or more and 60 Pa · s or less as measured by a method using an L-shaped viscometer described in JIS K5701-1. At that time, the content of the pigment contained in the printing ink of the present invention is such that the content of the yellow pigment in the yellow ink is 7% by mass to 15% by mass of the printing ink, and the content of the red pigment in the red ink is printed 13% by mass or more and 20% by mass or less of the ink, the content of the amber pigment in the amber ink is 16% by mass or more and 23% by mass or less, and the content of the black pigment in the black ink is 17% by mass or more and 24% by mass or less It is.

In addition to the color pigment, an extender pigment may be contained. The extender pigment is not particularly limited, and may be one or more kinds of publicly known pigments such as clay such as wax clay, talc, barium sulfate, calcium carbonate, ground calcium carbonate, barium carbonate, silica, bentonite, titanium oxide, etc. It can be used.

As the dryer, any dryer that is usually used for oxidative polymerization drying type printing inks can be used without particular limitation. For example, a metal such as cobalt, manganese, lead, iron, zinc, calcium, cerium, rare earth, etc. and a carboxylic acid such as octylic acid, naphthenic acid, neodecanoic acid, tung oil, linseed oil acid, soybean oil acid, resin acid Salts, that is, metal soaps, or borates with metals such as cobalt, manganese, lead, iron, zinc, calcium, cerium, rare earth and the like can be mentioned. These dryers may be used alone or in combination of two or more.

The petroleum wax used for the printing ink of the present invention has a melting point of 80 ° C. or less and is solid at normal temperature. It is preferable to use one having a melting point of 50 ° C. or higher in order to further improve the reverse transfer resistance. The petroleum wax is an amorphous one obtained by refining petroleum. Normal paraffins, isoparaffins, cycloparaffins, and mixtures thereof are exemplified. In the present invention, those containing 80% by mass or more of normal paraffins are preferably used, and those containing 85% by mass or more of normal paraffins are more preferable. By combining the rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less with the above-mentioned AF Solvent No. 6 with such petroleum-based wax, the reversion resistance of the printing ink is improved. be able to.

The petroleum wax may be added as it is to the printing ink, but is preferably added as a compound obtained by cooling to room temperature after heating and stirring with a solvent. As a solvent to be used at this time, the same ones as those used for the adjustment of the varnish described above can be appropriately used, and there is no particular limitation.

The petroleum wax is preferably used so that the content of normal paraffin is 0.1% by mass or more of the printing ink. In addition, when the content of wax is too large, post-processability is deteriorated, so that the content of normal paraffin is preferably 3% by mass or less of printing ink, and is preferably 1% by mass or less. Preferably it is 0.5 mass% or less.

The printing ink of the present invention preferably contains particles having an average particle diameter D50 of not less than 2 μm and not more than 7 μm in addition to the petroleum wax described above. D50 is also called a median diameter, and represents 50% of the cumulative particle size distribution curve based on volume, counting from the particle size smaller in the particle size distribution.
Such particles may be spherical or amorphous. Examples thereof include polyethylene wax, polytetrafluoroethylene wax, Fischer-Tropsch wax, resin particles and composites thereof, and one or more of them may be used in combination. By using such particles in combination with the petroleum wax, it is possible to improve the reverse transfer resistance and the post-processability (sliding property).

In the printing ink of the present invention, it is more preferable to use starch in addition to the petroleum wax described above. By using starch in combination with petroleum-based wax, the reverse transfer resistance can be further improved. It is preferable to use one having an average particle diameter D50 of 10 μm to 20 μm.
The total content of particles having an average particle diameter D50 of 2 μm to 7 μm and a starch having an average particle diameter D50 of 10 μm to 20 μm in the printing ink is preferably 0.5 mass% or more, 3.0 mass It is preferable that it is% or less.

The printing ink of the present invention comprises phosphoric acid, ammonium salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, ammonium salt of citric acid, alkali metal salt of citric acid, It is preferred to include one or more stain inhibitor particles selected from the group consisting of magnesium salts of citric acid. The content of the stain inhibitor particles is preferably 0.01% by mass or more and 0.5% by mass or less of the printing ink, and more preferably 0.01% by mass or more and 0.2% by mass or less. The amount of dampening water used during printing can be suppressed, setting delay can be prevented, and back-off resistance can be improved.

The printing ink of the present invention may optionally contain auxiliary agents such as anti-skinning agents, viscosity modifiers, dispersants, anti-stain agents other than those described above, emulsion modifiers, antioxidants and the like. You may use together petroleum-based wax mentioned above in the range which does not impair the effect of this invention, and wax other than wax particle | grains whose average particle diameter D50 is 2 micrometers-7 micrometers. As these assistants, conventionally known ones can be suitably used.

The reason why the printing ink of the present invention is excellent in reverse transfer resistance is presumed as follows.
In the printing ink of the present invention, the setting time when printing on coated paper or mat-coated paper is shortened by using a rosin-modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less for AF Solvent No. 6. In addition, the combination of the rosin-modified phenolic resin of the present invention and a petroleum wax is low in compatibility and easily separated after printing. These synergetic effects make it easy for the petroleum wax to collect on the surface of the ink coating, and a small amount of wax can effectively prevent offset.

Furthermore, by setting the viscosity of the printing ink to 10 Pa · s or more and 60 Pa · s or less, and by setting the pigment concentration at that time to the above-mentioned range, the piling property and the flowability are excellent, and the water taken into the ink coating at the time of printing The amount is appropriate and can prevent set delay. This makes it possible to effectively prevent the offset.

The printing ink of the present invention alone reduces, for example, the amount of powder applied even if the yellow ink of the present invention and ordinary (not using the present invention) red ink, black ink, black ink are used in combination, and Settling can be prevented. Furthermore, when the yellow ink, the red ink, the black ink and the black ink of the present invention are used as a set, the time until the printing ink printed on the paper can be set more effectively can be shortened, and the reverse transfer resistance is good. It can be

<Manufacturing method>
The printing ink of the present invention can be produced by a conventionally known method using the above-mentioned raw materials. Color pigments, extender pigments, etc. in varnishes prepared by heating and dissolving resins, vegetable oils or fatty acid esters or mixtures thereof and, if necessary, petroleum solvents, chelating agents, other auxiliary agents, etc. A solvent and other additives are added as necessary, and after thorough premixing with a stirrer, milling is performed with a shot mill, roll mill or the like. After milling, the varnish, petroleum-based solvent, vegetable oil, other waxes, additives such as antioxidants, emulsion modifiers and the like are added and thoroughly mixed with stirring. The petroleum wax may be added at the time of premixing, or may be added after milling.
The amount of these raw materials is adjusted in accordance with the viscosity and flowability required for the printing ink. Moreover, the addition time of these raw materials is not fixed, and is appropriately adjusted based on the mixing state.

<Printed material>
The printed matter of the present invention is obtained by printing using a printing ink composition as described above by a lithographic offset printing press. The substrate is not particularly limited, and conventionally known ones can be used, but it is particularly suitable for printing on coated paper, matte coated paper, and wood free paper. The printed matter of the present invention has less offset.

Hereinafter, the present invention will be described by way of Examples and Comparative Examples, but the present invention is not limited thereto. Composition and other values are on a mass basis unless otherwise stated.

<Synthesis of Rosin-Modified Phenolic Resin>
(Synthesis of rosin modified phenolic resin 1)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 1000 parts of para-butylphenol, 360 parts of 92% paraformaldehyde, 1000 parts of xylene, 10 parts of 50% sodium hydroxide, The temperature is raised to 95 ° C., and the reaction is carried out for 6 hours while maintaining the same temperature, then 300 parts of water and 13 parts of hydrochloric acid are added and neutralized, then 1000 parts of water is added and the supernatant is taken out to the same apparatus as above. The temperature was raised to 120 ° C., and the mixture was stirred for 30 minutes, and the supernatant was taken out to obtain resol-type phenolic resin 1 with a solid content of 57%. As a result of measuring the weight average molecular weight of resol type phenol resin 1, the average number of nuclei was 1.7.

In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 970 parts of gum rosin with an acid value of 165 mg KOH / g and 14 parts of maleic anhydride are charged and the temperature is raised to 180 ° C. Part, 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C., and the reaction was carried out while maintaining the same temperature until the acid value became 20 mg KOH / g or less. The temperature is then lowered to 180 ° C., and while maintaining the same temperature, the resol type phenol resin 1 is dropped at a dropping rate of 2.5 parts / min using a dropping funnel, and the 25 ° C. Gardner viscosity of the 50% toluene solution becomes F to G. The dripping was stopped when it became, and after 30 minutes, the resin was taken out to obtain a rosin modified phenolic resin 1. The amount of the resol-type phenol resin 1 dropped was 570 parts. The weight average molecular weight of the rosin modified phenolic resin 1 was 65,000, the AF-6 solvent cloud point was 110, and the softening point was 168 °.

(Synthesis of rosin modified phenolic resin 2)
In a pressure reaction kettle equipped with a stirrer and a thermometer, charge 1000 parts of para-butylphenol and heat to dissolve at 120 ° C, add 285 parts of 92% paraformaldehyde and 8 parts of calcium hydroxide and raise the temperature to 130 ° C. After reacting for 2 hours while maintaining the same temperature, pressure was released and stirring was further performed at the same temperature for 20 minutes, and the resol-type phenol resin 2 was taken out. As a result of measuring the weight average molecular weight of resol type phenol resin 2, the average number of nuclei was 3.0.

In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 1050 parts of gum rosin with an acid value of 165 mg KOH / g and 14 parts of maleic anhydride are charged and the temperature is raised to 180 ° C. Part, 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C., and the reaction was performed until the acid value became 20 mg KOH / g or less while maintaining the same temperature. The temperature is then lowered to 180 ° C, and while maintaining the same temperature, the resol type phenol resin 2 is gradually charged, and the addition is stopped when the Gardner viscosity of the 50% toluene solution becomes F to G, and after 30 minutes the resin is reduced The resin was taken out to obtain a rosin modified phenolic resin 2. The amount of the resol-type phenol resin 2 added was 700 parts. The weight average molecular weight of the rosin modified phenolic resin 2 was 145,000, the AF-6 solvent cloud point was 195 degrees, and the softening point was 176 degrees.

(Synthesis of rosin modified phenolic resin 3)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, charge 1000 parts of para-butylphenol, 445 parts of 92% paraformaldehyde, 1000 parts of xylene, 10 parts of 50% sodium hydroxide, The temperature is raised to 95 ° C, and the reaction is carried out for 6 hours while maintaining the same temperature, then 300 parts of water and 13 parts of hydrochloric acid are added and neutralized, then 1000 parts of water is added and the supernatant is taken out. The resol-type phenolic resin 3 was obtained. As a result of measuring the weight average molecular weight of resol type phenol resin 3, the average number of nuclei was 1.0.

In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 970 parts of gum rosin with an acid value of 165 mg KOH / g and 14 parts of maleic anhydride are charged and the temperature is raised to 180 ° C. Part, 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C., and the reaction was carried out while maintaining the same temperature until the acid value became 20 mg KOH / g or less. The temperature is then lowered to 180 ° C, and while maintaining the same temperature, the resol type phenol resin 3 is dropped at a dropping rate of 2.5 parts / min using a dropping funnel, and the 25 ° C Gardner viscosity of 50% toluene solution becomes F to G The dripping was stopped when it became, and after 30 minutes, the resin was taken out to obtain a rosin modified phenolic resin 3. The amount of the resol-type phenol resin 3 dropped was 480 parts. The weight average molecular weight of the rosin modified phenolic resin 3 was 52000, the AF-6 solvent cloud point was 60 degrees, and the softening point was 162 degrees.

(Synthesis of rosin modified phenolic resin 4)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet, 1000 parts of para-butylphenol, 300 parts of 92% paraformaldehyde, 1000 parts of xylene, 10 parts of 50% sodium hydroxide, The temperature is raised to 95 ° C., and the reaction is carried out for 6 hours while maintaining the same temperature, then 300 parts of water and 13 parts of hydrochloric acid are added and neutralized, then 1000 parts of water is added and the supernatant is taken out to the same apparatus as above. The temperature was raised to 120 ° C. and stirring was carried out for 140 minutes, and the supernatant was taken out to obtain resol-type phenolic resin 4 with a solid content of 56%. As a result of measuring the weight average molecular weight of resol type phenol resin 4, the average number of nuclei was 3.8.

In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet, 1010 parts of gum rosin with an acid value of 165 mg KOH / g and 14 parts of maleic anhydride are charged, and heated to 180 ° C. Part, 2 parts of zinc oxide were added, and the temperature was raised to 250 ° C, and the reaction was performed until the acid value became 20 mgKOH / g or less while maintaining the same temperature. The temperature was then lowered to 180 ° C, and while maintaining the same temperature, the resol type phenol resin 4 was dropped at a dropping rate of 2.5 parts / min using a dropping funnel, and the Gardner viscosity of the 50% toluene solution became F to G Dropping was stopped at the time, and after 30 minutes, the resin was taken out to obtain a rosin modified phenolic resin 4. The amount of the resol-type phenol resin 4 dropped was 1430 parts. The weight average molecular weight of the rosin modified phenolic resin 4 was 215,000, the AF-6 solvent cloud point was 222 °, and the softening point was 190 ° C.

<Adjustment of resin varnish for printing ink>
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet, 450 parts of rosin-modified phenol resin 1 and 400 parts of soybean salad oil (manufactured by Nisshin Oillio Co., Ltd.) are charged. The mixture was heated and stirred for 1 hour. Thereafter, 140 parts of AF-6 solvent was added, the temperature was lowered to 160 ° C., 10 parts of ethyl acetoacetate aluminum dinormal butyrate was added, and the temperature was maintained for 1 hour to obtain resin varnish 1 for printing ink.
Resin varnishes 2 to 4 for printing ink were obtained in the same manner except that rosin modified phenolic resins 2 to 4 were used instead of rosin modified phenolic resin 1, respectively.

<Adjustment of base ink>
(Adjustment of base ink Y)
18 parts of SYMULER Fast Yellow GFconc (manufactured by DIC Corporation), 72 parts of resin varnish 1 for printing ink, 10 parts of AF-6 solvent, and measured according to the method described in the JIS K5701-1 kneading degree test The base ink Y1 was adjusted by milling using a three-roll mill until the depth of the groove at the position A was 7.5 μm or less. Base inks Y2 to Y4 were obtained in the same manner, except that resin varnishes 2 to 4 for printing ink were used instead of resin varnish 1 for printing ink.

(Adjustment of base ink M)
28 parts of SYMULER Brilliant Carmine 6B 226 (manufactured by DIC Corporation), 60.4 parts of resin varnish 1 for printing ink, 11.6 parts of AF-6 solvent, and subjected to JIS K5701-1 hardness test The base ink M1 was adjusted by milling using a three-roll mill until the depth of the groove at position A measured by the method described above was 7.5 μm or less. Base inks M2 to M4 were obtained in the same manner except that resin varnishes 2 to 4 for printing ink were used instead of resin varnish 1 for printing ink.

(Adjustment of base ink C)
30 parts of FASTGEN Blue FA 5375 (manufactured by DIC Corporation), 58 parts of resin varnish 1 for printing ink, 12 parts of AF-6 solvent, and measured according to the method described in the JIS K5701-1 degree of hardness test The base ink C1 was adjusted by milling using a three-roll mill until the groove depth of A became 7.5 μm or less. Base inks C2 to C4 were obtained in the same manner except that resin varnishes 2 to 4 for printing ink were used instead of resin varnish 1 for printing ink.

(Adjustment of base ink B)
28 parts of carbon black MA7 (Mitsubishi Chemical Corp.), 60.4 parts of resin varnish 1 for printing ink, 11.6 parts of AF-6 solvent, and described in JIS K5701-1 hardness test The base ink B1 was adjusted by milling using a three-roll mill until the depth of the groove at position A measured by the above method became 7.5 μm or less. Base inks B2 to B4 were obtained in the same manner except that resin varnishes 2 to 4 for printing ink were used instead of resin varnish 1 for printing ink.

<Adjustment of printing ink>
69.0 parts of base ink Y1, 24.5 parts of resin varnish 1 for printing ink, 0.3 parts of petroleum wax compound, 0.1 part of PTFE wax, 1.0 part of cobalt octylate solution, AF- Yellow ink Y1 was obtained using 5.1 parts of a No. 6 solvent. The content of normal paraffins in the yellow ink Y1 was 0.13% by mass, and the content of pigments was 14.0% by mass.

Similarly, yellow inks Y2 to Y11, red inks M1 to M11, base inks C1 to C11, and black inks B1 to B11 were prepared with the formulations shown in Tables 1 to 4, respectively. The viscosities of yellow inks Y1 to Y11, red inks M1 to M11, base inks C1 to C11, and black inks B1 to B11 were in the range of 10 Pa · s to 60 Pa · s. The viscosity of the ink was measured using a L-type viscometer according to the method described in JIS K 5701-1. The components other than the base ink and the printing ink resin varnish used for the adjustment of the ink are as follows.

(Petroleum wax compound)
After heating and stirring 35 parts of petroleum-based wax having a melting point of 61 ° C. and a normal paraffin ratio of 90% with 65 parts of an AF No. 6 solvent, it was cooled to room temperature and used as a compound.
(Starch compound)
What disperse | distributed 20 parts of starches with an average particle diameter D50 of 20 micrometers with 80 parts of resin varnish 1 for printing inks was used.

(Antifouling compound)
Until the depth of the groove at position A becomes 7.5 μm or less when 20 parts of sodium hexametaphosphate is measured with 80 parts of resin varnish 1 for printing ink according to the method described in the degree of mixing test of JIS K5701-1 Dispersed and kneaded ones were used.
(Cobalt octylate solution)
A solution of 50 parts of cobalt octylate dissolved in 50 parts of soybean oil was used.

<Evaluation>
Printing was performed using the adjusted printing ink under the following conditions, and the performance evaluation of the printed matter was performed. The results are summarized in Tables 5-8.
(Printing conditions)
Printing machine; Man-Roland made Roland 704 printing machine (separate continuous water supply system)
Dampened water; Presert SD100 (made by DIC Graphics Corporation) concentration 2.0%
Printing speed: 8,000 sheets / hour temperature and humidity; room temperature 25 ° C, humidity 55%
Printing paper; OK Top Coat N (manufactured by Oji Paper Co., Ltd.)

(Reset resistance)
3,000 copies of a pattern consisting of a solid part and a non-image part were printed and stacked on top. After 6 hours, it was visually evaluated whether there was any offset of the ink.
○ ... good. The level of the moist feeling of the ink on the paper is evaluated by the number of +.
The more + there is, the less moist feeling and the better.
Δ: A slight offset is seen.
X: Blocking occurs in which printed materials are attached to each other because many parts are offset.

(Pilling nature)
The deposition state on the blanket on the printing press roller after 3,000 sheets printing was evaluated by visual inspection and touch.
○ ... good.
Δ: A slight amount of deposit is seen.
X ... There are many deposits.

(Liquidity)
The ink was poured into the ink fountain of the printing press, and the flow state of the ink during printing was evaluated visually.
○ ... good.
X: The ink is not consumed uniformly, and the ink does not move in the pot.

(Suitable for post processing)
Using a bar coater N0.6, the printed matter was coated with an aqueous varnish (DIC Safe C 1151, made by DIC Graphics Inc.), and dried overnight at room temperature. The next day, the post-processing aptitude was evaluated by a peeling test with cellophane tape.
... ... Cellophane tape can be taken from the ground part of the print.
Δ: Cellophane tape can be partially taken from the ink surface.
X: The cellophane tape is peeled off from the interface between the ink and the varnish.

As apparent from Tables 5 to 8, the printing ink of the present invention exhibited excellent back-off resistance, piling property, flowability and post-processability.

Claims (9)

A varnish containing a rosin modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6,
With the dryer,
Yellow pigment,
A petroleum wax having a melting point of 80 ° C. or less and containing normal paraffins;
The viscosity measured by an L-type viscometer is 10 Pa · s or more and 60 Pa · s or less,
The content of the normal paraffin is 0.1% by mass or more and 3% by mass or less,
Content of the said yellow pigment is 7 mass% or more and 15 mass% or less, The oxidation polymerization drying type offset printing ink composition characterized by the above-mentioned. A varnish containing a rosin modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6,
With the dryer,
With red pigment,
A petroleum wax having a melting point of 80 ° C. or less and containing normal paraffins;
The viscosity measured by an L-type viscometer is 10 Pa · s or more and 60 Pa · s or less,
The content of the normal paraffin is 0.1% by mass or more and 3% by mass or less,
Content of the said red pigment is 13 mass% or more and 20 mass% or less, The oxidation polymerization drying type offset printing ink composition characterized by the above-mentioned. A varnish containing a rosin modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6,
With the dryer,
藍 pigment,
A petroleum wax having a melting point of 80 ° C. or less and containing normal paraffins;
The viscosity measured by an L-type viscometer is 10 Pa · s or more and 60 Pa · s or less,
The content of the normal paraffin is 0.1% by mass or more and 3% by mass or less,
An oxidative polymerization dry-type offset printing ink composition, wherein the content of the amber pigment is 16% by mass to 23% by mass. A varnish containing a rosin modified phenolic resin having a cloud point of 100 ° C. or more and 210 ° C. or less of AF Solvent No. 6,
With the dryer,
Ink pigment,
A petroleum wax having a melting point of 80 ° C. or less and containing normal paraffins;
The viscosity measured by an L-type viscometer is 10 Pa · s or more and 60 Pa · s or less,
The content of the normal paraffin is 0.1% by mass or more and 3% by mass or less,
Content of the said black pigment is 17 mass% or more and 24 mass% or less, The oxidation polymerization drying type offset printing ink composition characterized by the above-mentioned. The oxidative polymerization dry-type offset printing ink composition according to any one of claims 1 to 4, characterized in that it contains particles having an average particle diameter D50 of 2 μm to 7 μm. The oxidative polymerization dry-type offset printing ink composition according to any one of claims 1 to 5, characterized in that it comprises starch having an average particle diameter D50 of 10 μm to 20 μm. Phosphoric acid, ammonium salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal dihydrogen salt of phosphoric acid, citric acid, ammonium salt of citric acid, alkali metal salt of citric acid, magnesium salt of citric acid The oxidative polymerization dry-type offset printing ink composition as described in any one of the Claims 1 thru | or 6 containing one or more antifouling agents chosen from a group. An oxidative polymerization dry type offset printing ink composition according to claim 1;
An oxidative polymerization dry type offset printing ink composition according to claim 2;
An oxidative polymerization dry type offset printing ink composition according to claim 3;
The oxidative polymerization drying type offset printing ink composition of Claim 4, and an ink set characterized by the above-mentioned. A substrate,
A printed material comprising: an ink coating film of the oxidative polymerization dry type offset printing ink composition according to any one of claims 1 to 8 disposed on the substrate.