JP6874898B1 - Rosin-modified phenolic resin, lithographic printing inks, and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin for lithographic printing ink, which is excellent in glossiness of printed matter and fluidity of ink, and can obtain a printed matter in which blank residue is not generated even during long-time printing, and a lithographic printing ink containing the same. ..
A reaction product of rosins (b), a resole-type phenol resin (c), and a polyol (d).
The rosins (b) contain 0.1 to 3.5% by mass of monoterpenes (a1) and sesquiterpenes (a2) with respect to the total amount of rosins.
The hydroxyl value of the resole-type phenol resin (c) is 15 to 40 mgKOH / g.
A rosin-modified phenolic resin (A), characterized in that Mw / Mn, which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), is 10 to 60.
[Selection diagram] None

Description

The present invention relates to a resin used for lithographic printing ink (hereinafter, abbreviated as "ink") used for printed matter such as books, leaflets, catalogs, newspapers, etc. The present invention relates to a resin for lithographic printing ink, which is characterized in that a high-gloss printed matter can be obtained.

The lithographic printing ink is an ink having a relatively high viscosity of 5 to 100 Pa · s. In the mechanism of a lithographic printing machine, ink is supplied from the ink fountain of the printing machine to the image area of the plate surface via a plurality of rollers, and dampening water is supplied to the non-image area of the plate surface. Further, the image formed on the plate surface is transferred to the blanket and then transferred to the paper.

In recent years, there has been an increasing demand for labor saving, labor saving, automation, and high speed at the time of printing, and it is required to support a wide range of papers from coated paper to uncoated paper. An ink that can stably obtain a high-quality printed matter for a long time under various printing conditions is desired. In particular, the ink has good fluidity, excellent glossiness of the printed matter, and printing such as blank residue. There is a strong demand for inks that can reduce troubles. The blank residue means that a mixture of ink and paper dust is deposited on the boundary between the image area and the non-image area of the blanket at the time of printing, and if the amount of accumulation is large, image formation failure is caused.

Conventionally, as a method of improving the glossiness of printed matter, petroleum-based solvent, vegetable oil, etc. are increased to reduce the viscosity of the ink to improve the smoothness of the printed surface, or low-molecular-weight, highly soluble resin or petroleum resin is used. By increasing the resin component in the ink system, the permeation of the ink into the printed paper substrate is suppressed as much as possible, and the ink film thickness is maintained.

However, when the amount of petroleum-based solvent or vegetable oil is increased in order to reduce the ink viscosity, the tack value of the ink is lowered, and the transfer between rollers on the printing machine tends to be worsened. In addition, if the resin component in the ink system is increased by using a low-molecular-weight, highly soluble resin or petroleum resin, the tack value of the ink rises too much, paper peeling occurs, and emulsification control becomes difficult, resulting in ink printing. The aptitude tends to be impaired, and there is a limit to improving the glossiness of the printed matter while maintaining the printability.

In addition to the above method, there is also a method of increasing the compatibility in the ink system by using a petroleum solvent having high solubility in the resin component in the ink system to reduce the viscosity of the ink and increase the concentration of the resin component. is there. However, the solubility of the above petroleum-based solvent in the resin does not provide a sufficient gloss effect. In addition, most of the petroleum-based solvents having high solubility in the above resin components are mainly composed of aromatic hydrocarbons having a large adverse effect on the human body, which causes environmental load such as printing work environment and air pollution in printing. Therefore, it has been postponed for use recently.

Further, an offset ink composition having excellent glossiness has been developed by containing a fatty acid ester in the ink (Patent Documents 1 and 2). However, with these methods, it is difficult to control the penetration of fatty acid esters into paper, and there are situations in which the paper used for printing is restricted and the drying property of the ink is not sufficiently satisfactory.

Improvements have also been made to the rosin-modified phenolic resin used in inks. Patent Document 3 discloses a method of reacting a polyhydric alcohol and an initial condensate of phenol formaldehyde with a monoesterified product obtained by partially esterifying a mixture of rosin and animal and vegetable oil fatty acids with monoalcohol. However, in this method, by using a monoalcohol for esterification, cross-linking by an ester bond with rosin and animal and vegetable oil fatty acids is not performed, and it becomes difficult to control the molecular weight.

Patent Document 4 discloses a rosin-modified phenol resin obtained by reacting cyclic terpenylphenol, but it requires a great cost to obtain cyclic terpenylphenol by reaction or extraction. Further, Patent Document 4 does not describe the stain suppression during printing and the behavior on a printing machine required in the market, and has not yet provided the ink desired in the market.

Patent Document 5 discloses a resin metal salt obtained by neutralizing an α, β-unsaturated carboxylic acid adduct of rosin in which a low boiling point component is distilled off to 2% or less with two or more kinds of metal compounds. However, it is a resin for gravure printing, and it does not solve the problem in lithographic printing, not printing through a blanket. Further, the resin metal salt is not suitable as a resin for lithographic printing ink because it is impossible to obtain the viscosity and elasticity required for the lithographic printing ink. Furthermore, it is said that heating is performed at 250 ° C. to 300 ° C. in order to distill off the low boiling point component to 2% or less, but when heated to this temperature, the resin acid in the rosin changes to dehydroabietic acid, which has low reactivity. Reactivity at the time of resinification cannot be ensured.

Japanese Unexamined Patent Publication No. 2003-313482 Japanese Unexamined Patent Publication No. 2007-169574 Japanese Unexamined Patent Publication No. 2004-269752 JP 2015-193790 Japanese Unexamined Patent Publication No. 9-169953

An object of the present invention is to provide a resin for lithographic printing ink in order to obtain a lithographic printing ink which is excellent in ink fluidity, has little blank residue during long-term printing, and can obtain a high-gloss printed matter. To do.

As a result of diligent research conducted by the present inventors to solve the above problems, the flat plate printing ink containing the rosin-modified phenol formaldehyde (A) prepared from the following materials has excellent ink fluidity and takes a long time. We have found that it is possible to obtain a high-gloss printed matter with a small amount of blank residue during printing, and have completed the present invention.

That is, the present invention is a reaction product of rosins (b), a resole-type phenol resin (c), and a polyol (d).
The rosins (b) contain 0.1 to 3.5% by mass of monoterpenes (a1) and sesquiterpenes (a2) with respect to the total amount of rosins.
The hydroxyl value of the resole-type phenol resin (c) is 15 to 40 mgKOH / g.
The present invention relates to a rosin-modified phenol formaldehyde (A), which is characterized in that Mw / Mn, which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), is 10 to 60.

The present invention also relates to the rosin-modified phenolic resin (A), wherein the rosins (b) contain 20 to 80% by mass of a cyclic diterpene having a conjugated double bond.

Further, the present invention is based on the total mass of the rosin-modified phenolic resin raw material.
Rosin (b) 30-85% by mass,
Resol type phenol resin (c) 7 to 67% by mass,
The present invention relates to the above-mentioned rosin-modified phenol resin (A), which is a reaction product with 3 to 20% by mass of the polyol (d).

The present invention also relates to the rosin-modified phenol formaldehyde (A) having a weight average molecular weight of 7,000 to 120,000 and an acid value of 5 to 50 mgKOH / g.

The present invention also relates to a lithographic printing ink characterized by containing the rosin-modified phenolic resin (A).

The present invention also relates to a printed matter in which the above-mentioned lithographic printing ink is printed on a base material.

By using the resin for lithographic printing ink of the present invention, it has been possible to provide a lithographic printing ink which is excellent in ink fluidity, has little blank residue during long-term printing, and can obtain a high-gloss printed matter.

Terpenes such as monoterpenes and sesquiterpenes are biological substances produced by plants, insects, and fungi. Some rosins, which are raw materials for rosin-modified phenolic resins used as resins for lithographic printing inks, also contain these terpenes.
In the rosins (b) used as the raw material of the rosin-modified phenol resin (A) of the present invention, the total content of the monoterpenes (a1) and the sesquiterpenes (a2) is the total amount of the rosins (b). It is characterized by being 0.1 to 3.5% by mass as a reference.

The rosins (b) are obtained by distilling raw pine tar, and the distillation temperature is preferably 200 ° C. or lower. When the temperature is 200 ° C. or higher, the isomerization of diterpenes in rosin proceeds, and the reactivity at the time of resin synthesis decreases.

By using rosins (b) having a total content of monoterpenes (a1) and sesquiterpenes (a2) of 0.1 to 3.5% by mass as a raw material for the rosin-modified phenol resin (A), The compatibility with the ink component is improved, and the glossiness of the printed matter using the ink is improved. However, if rosin having a total content of monoterpenes (a1) and sesquiterpenes (a2) exceeding 3.5% by mass is used, the viscoelasticity and pigment dispersibility required for the ink are lowered, and the printed matter is printed. Insufficient ground stains and ink fluidity. The total content of the monoterpenes (a1) and the sesquiterpenes (a2) is preferably 0.5 to 3.0% by mass.

The rosins (b) used in the present invention are particularly prepared when the total content of the monoterpenes (a1) and sesquiterpenes (a2) is 0.1 to 3.5% by mass based on the total amount of the rosins. There are no restrictions, gum rosin, wood rosin, tall rosin, polymerized rosin derived from the rosin, stabilized rosin obtained by disproportionate or hydrogenating natural rosin or polymerized rosin, unsaturated carboxylic acids in natural rosin or polymerized rosin. An unsaturated acid-modified rosin obtained by addition can be used. The unsaturated acid-modified rosin is, for example, maleic acid-modified rosin, maleic anhydride-modified rosin, fumaric acid-modified rosin, itaconic acid-modified rosin, crotonic acid-modified rosin, silicate-modified rosin, acrylic acid-modified rosin, and methacrylate-modified rosin. Etc., or acid-modified polymerized rosins corresponding to these can be mentioned. One of these may be used alone, or two or more thereof may be mixed and used.

The monoterpines (a1) are not particularly limited, but are α-pinene, β-pinene, camphene, α-pherandrene, β-pherandrene, α-myrcene, β-myrcene, curene, limonene, γ-terpinene, Examples thereof include α-terpinene, α-terpineol, β-terpineol, and γ-terpineol.

The sesquiterpenes (a2) are not particularly limited, but are α-sedrene, β-sedrene, α-copane, β-copane, isologinhorene, longihorene, caryophyllene, β-humulene, α-farnesene, β-farnesene, β- Examples include caryophyllene, α-guien, β-guien, γ-guien, α-elemen, β-element, γ-element, δ-element, α-bisabolen, β-bisaborene, γ-bisabolen, aromadendrene, and cedrene. Will be done.

The contents of monoterpenes (a1) and sesquiterpenes (a2) in the rosins (b) can be determined by the peak area ratio of gas chromatography. Specifically, it can be obtained by the ratio (%) of the peak areas corresponding to (a1) and (a2) to 100% of the total peak area of the rosins (b). If the total content of the monoterpenes (a1) and sesquiterpenes (a2) in the rosins (b) is 0.1 to 3.5% by mass based on the total amount of the rosins, the monoterpenes It may contain only one of the class (a1) and the sesquiterpenes (a2).

Further, in the case of rosins having a content of monoterpenes (a1) and sesquiterpenes (a2) of more than 3.5% by mass, the content of monoterpenes (a1) and sesquiterpenes (a2) is contained by purification. The amount is 0.1 to 3.5% by mass, and it can also be used as rosins (b). Examples of the purification method include known methods such as a distillation method.

In the case of rosines having a content of monoterpenes (a1) and sesquiterpenes (a2) less than 0.1% by mass, monoterpenes (a1) and / or sesquiterpenes (a2) are added. By setting the content of monoterpenes (a1) and sesquiterpenes (a2) to 0.1 to 3.5% by mass, they can also be used as rosins (b).

A plurality of diterpenic acids are contained in rosins such as gum rosin, wood rosin, and tall oil rosin. In the present invention, by adjusting the amount of the cyclic diterpene having a conjugated double bond to 20 to 80% by mass, it is possible to obtain a higher elastic resin, and the blank residue can be reduced.

The content of the cyclic diterpene having a conjugated double bond can be determined by the peak area ratio of gas chromatography. It can be determined by the peak area ratio (%) of the cyclic diterpene having a conjugated double bond with respect to 100% of the total peak area of the rosins (b). Cyclic diterpenes having a conjugated double bond include abietic acid, neoavietic acid, palastolic acid, and levopipmaric acid.

The resole-type phenol resin (c) can be obtained by a conventional method. As an example of the synthesis method, phenols and formaldehydes are charged, a volatile organic solvent (xylene, etc.) is added, and a condensation reaction is carried out in the presence of a metal oxide catalyst, a metal hydroxide catalyst, or an alkali catalyst. can get. The ratio of phenols to formaldehydes is usually a mol ratio, preferably phenols: formaldehydes = 1: 1 to 1: 3, more preferably 1: 1.5 to 1: 2.5, and sodium hydroxide. , Potassium hydroxide, calcium hydroxide, lithium hydroxide, etc., or in the presence of an alkaline catalyst such as organic amine, addition / condensation under normal pressure or pressure. Condensates are used. The obtained resole-type phenol resin is neutralized with sulfuric acid or the like, washed with water, and used for the reaction with rosins (b).

Examples of the phenols include all aromatic compounds having a phenol hydroxyl group, such as coalic acid, cresol, p-amylphenol, bisphenol A, p-butylphenol, p-octylphenol, p-nonylphenol, and p-dodecylphenol. , These may be used alone or in combination of two or more.
Examples of formaldehyde include formaldehyde and paraformaldehyde.

As the resol type phenol resin (c) obtained as described above, a resin having a hydroxyl value in the range of 15 to 40 mgKOH / g is used. As a result, the hydrophilic group of the rosin-modified phenol resin (A) can be adjusted to an appropriate range, excessive uptake of water during printing can be suppressed, and blank residue can be reduced. The hydroxyl value is measured by the neutralization titration method. As long as the hydroxyl value of the resole-type phenol resin is within the above range, one type may be used alone, or two or more types may be mixed and used. Further, in order to keep the hydroxyl value of the resol-type phenol resin in the above range, the reaction temperature, time, catalyst amount and the like when synthesizing the resol-type phenol resin may be adjusted.

The polyol (d) in the present invention includes, as divalent alcohols, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, and 1,2-butane, which are linear alkylene divalent alcohols. Diol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol , 1,7-Heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecandiol, 1,2-hexadecandiol, etc.
Bifurcated alkylene dihydric alcohols 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl -2,4-dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane, 2-ethyl-1,3 -Hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1 , 5-Pentanediol, etc.
As cyclic alkylene divalent alcohols, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptandiol, tricyclodecanedimethanol, hydrogenated catechol, hydrogenated resorcin. , Hydrogenated hydroquinone, etc.
Further, examples thereof include polyether polyols such as polyethylene glycol (n = 2 to 20), polypropylene glycol (n = 2 to 20), polytetramethylene glycol (n = 2 to 20), polyester polyols and the like.

In addition, glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, 3-methylpentane-1,3,5-triol, hydroxymethylhexanediol, trimethyloloctane, which are trihydric or higher alcohols, Examples thereof include diglycerin, ditrimethylolpropane, dipentaerythritol, sorbitol, inositol, tripentaerythritol and the like.

The rosin-modified phenol resin (A) of the present invention contains 30 to 85% by mass of rosins (b), 7 to 67% by mass of resol type phenol resin (c), and a polyol (d) based on the total amount of the charged formulation. 3 to 20% by mass is preferable. When the rosins (b) are 30% by mass or more and the resole-type phenol resin (c) is 67% by mass or less, the synthetic resin is difficult to gel and the reaction control is easy. When the rosins (b) are 85% by mass or less and the resole-type phenol resin (c) is 7% by mass or more, the viscosity and elasticity required for the ink can be easily obtained. Further, more preferably, the rosins (b) are 35 to 80% by mass, and the resol type phenol resin (c) is 10 to 60% by mass. By keeping it within the above range, the effect is more likely to be exhibited.

As a method for producing the rosin-modified phenol resin (A) of the present invention, a known method can be adopted. For example, rosins (b) are heated and melted in a reaction vessel at 120 to 200 ° C., a resole-type phenol resin (c) is added, and the reaction is carried out for 1 to 10 hours. After that, a method of adding the polyol (d) and a catalyst as needed and subjecting it to an esterification reaction at 200 to 300 ° C. for 5 to 30 hours,
The rosins (b) are heated and melted at 120 to 200 ° C., the polyol (d) and a catalyst if necessary are added, and the esterification reaction is carried out at 200 to 300 ° C. for 1 to 20 hours. Examples thereof include a method in which the phenol resin (c) is added and reacted at 200 to 300 ° C. for 1 to 20 hours.
Examples of the catalyst include organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, trifluoromethylsulfate and trifluoro. Methylacetic acid and the like can be exemplified. Furthermore, metal complexes such as tetrabutylzirconate and tetraisobutyltitanate, and metal salt catalysts such as magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide and zinc acetate can also be used. is there. These catalysts are usually used in the range of 0.01 to 5% by mass in the total resin. Hypophosphorous acid, triphenylphosphine, triphenylphosphate, triphenylphosphine and the like can also be used in combination in order to suppress coloration of the resin due to the use of a catalyst.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the rosin-modified phenolic resin (A) obtained by the above method can be determined by gel permeation chromatography (GPC) (polystyrene conversion, solvent: tetrahydrofuran). Mw / Mn, which indicates the ratio of the weight average molecular weight to the number average molecular weight, is 10 to 60. Further, Mw / Mn is preferably 15 to 55.
When Mw / Mn is in the range of 10 to 60, the ink fluidity is good and the blank residue can be reduced. On the other hand, when Mw / Mn is less than 10, the ink fluidity is insufficient, and when Mw / Mn exceeds 60, blank residue is remarkably generated.
The weight average molecular weight is preferably 7,000 to 120,000, more preferably 10,000 to 110,000, and particularly preferably 15,000 to 80,000. When it is 7,000 or more, the viscoelasticity of the ink is preferable, and the generation of background stains and the residue of blanks during printing can be suppressed. When it is 120,000 or less, the glossiness of the printed matter becomes preferable.

The acid value of the rosin-modified phenolic resin (A) in the present invention is preferably 5 to 50 mgKOH / g, more preferably 7 to 40 mgKOH / g. By setting the acid value within the above range, the emulsification suitability when made into an ink becomes suitable, and the occurrence of background stains can be suppressed. The acid value is a value measured by the neutralization titration method.

A varnish for lithographic printing ink can be produced by adding vegetable oils, a petroleum-based solvent for ink, a gelling agent and the like to the rosin-modified phenol resin (A) as needed and dissolving them by heating.

As the vegetable oils used for the varnish for lithographic printing ink, various known ones can be used without limitation. Specifically, for example, there are flaxseed oil, tung oil, soybean oil, safflower oil, dehydrated castor oil, and heat-polymerized oils and oxidation-polymerized oils of these vegetable oils. In addition, 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 fatty acid propyl, flaxseed oil fatty acid butyl, soybean oil fatty acid butyl, flaxseed oil fatty acid isobutyl, soybean oil fatty acid. Examples thereof include the above-mentioned monoesters of vegetable oils such as isobutyl. These may be used alone or in combination of two or more as appropriate. It is also preferable to use the recovered and regenerated vegetable oil as vegetable oils. The use of recycled vegetable oil can reduce waste and CO ₂ emissions, and can reduce the environmental burden.

As the regenerated vegetable oil, an oil regenerated with a water content of 0.3% by weight or less, an iodine value of 90 or more, and an acid value of 3 or less is preferable, and an iodine value of 100 or more is more preferable. By setting the water content to 0.3% by weight or less, it is possible to remove impurities such as salts contained in the water that affect the emulsification behavior of the ink, and by regenerating with an iodine value of 90 or more, the drying property That is, it is possible to obtain a good oxidative polymerization property, and further, by selecting and regenerating a vegetable oil having an acid value of 3 or less, it is possible to suppress overemulsification of the ink. Examples of the method for regenerating the recovered vegetable oil include, but are not limited to, methods such as filtration, removal of precipitates by standing, and decolorization with activated clay or the like.

As the petroleum-based solvent for lithographic printing ink used for the lithographic printing ink varnish, a conventionally known solvent for printing ink can be used without particular limitation. Specifically, for example, No. 0 solvent, No. 4 solvent, No. 5 solvent, No. 6 solvent, No. 7 solvent, AF solvent No. 4, AF solvent No. 5, AF solvent No. 6, AF solvent No. 7 manufactured by JXTG Energy Co., Ltd. And so on. These may be used alone or in combination of two or more as appropriate. In particular, as an environmental measure, it is preferable to use an aroma-free solvent having an aromatic hydrocarbon content of 1% by weight or less.

Various known gelling agents include, for example, aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. You can use various things.

The composition ratios of the rosin-modified phenolic resin (A), vegetable oils, petroleum-based solvent, and gelling agent in the varnish for lithographic printing ink may be appropriately determined according to the intended use, but usually
Rosin-modified phenolic resin 5-60% by mass,
About 0 to 80% by mass of vegetable oils,
Petroleum solvent ~ 80% by mass,
The ratio of gelling agent is about 0 to 4% by mass,
Is. Further, the rosin-modified phenol resin (A) of the present invention can be used in combination with a rosin-modified phenol resin outside the scope of the present invention, a petroleum resin, or the like.

As the above-mentioned petroleum resin, commercially available ones can be appropriately used, and as the aliphatic petroleum resin, Quinton A100, Quinton B170, Quinton K100, Quinton M100, Quinton R100, Quinton C200S, Maruzen Petrochemical Co., Ltd. manufactured by Nippon Zeon Co., Ltd. can be used as appropriate. Marcaret's T-100AS, Marcaret's R-100AS, as aromatic petroleum resins, JXTG Energy's Neopolymer L-90, Neopolymer 120, Neopolymer 130, Neopolymer 140, Neopolymer 150, Neopolymer 170S, Neopolymer 160, Neopolymer E-100, Neopolymer E-130, Neopolymer 130S, Neopolymer S, Toso Petcol LX, Petcol LX-HS, Petcol 100T, Petcol 120, Petcol 120HS, Petcol 130, Petcol 140, Petcol 140HM, Petcol 140HM5, Petcol 150, Petcol 150AS, as copolymerized petroleum resins, Quinton D100, Quinton N180, Quinton P195N, Quinton S100, Quinton S195, Quinton U185, Quinton G100B, Quinton D115, Quinton D , Quinton E200SN, Quinton N295, Toso Petrotack 60, Petrotack 70, Petrotack 90, Petrotack 100, Petrotack 100V, Petrotack 90HM, DCPD-based polymer resin, Marukaretsu M-890A manufactured by Maruzen Petrochemical Co., Ltd. , Polymers M-845A, Quinton 1325 manufactured by Nippon Zeon Co., Ltd., Quinton 1345, Quinton 1500, Quinton 1525L, Quinton 1700 and the like.

The varnish for lithographic printing ink can be produced by various known methods. For example, each of the above components can be produced by heating and dissolving at 100 to 250 ° C., preferably 120 to 200 ° C.

A lithographic printing ink is produced by the rosin-modified phenolic resin (A) of the present invention (which may be blended as the above-mentioned lithographic printing ink varnish), pigments, petroleum-based solvents and additives.
Pigments used in the present invention include white pigments such as titanium oxide, yellow pigments such as mineral furnace yellow, nables yellow, naphthol yellow S, Hansa yellow G, quinoline yellow lake, permanent yellow NCG, and tartoazine lake, and Indus. Rembrilliant Orange RK, Pyrazon Orange, Balkan Orange, Benzidine Orange G, Indus Rembrilliant Orange GK and other orange pigments, Permanent Red 4R, Lionol Red, Pyralozone Red, Watching Let's Calcium Salt, Lake Red D, Brilliant Carmine 6B , Eosin Lake, Rhodamin Lake B, Alizarin Lake, Brilliant Carmine 3B and other red pigments, First Violet B, Methyl Violet Lake and other purple pigments, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phtalocyanin Blue, Metal-free Phthalocyanin Blue pigments such as blue, phthalocyanine blue partially chlorinated, first sky blue, induslen blue BC, green pigments such as pigment green B, malacaide green lake, finasuiery green G, carbon black, acetylene black, run black, aniline Examples include black pigments such as black.

In addition, various additives for the purpose of abrasion resistance, blocking prevention, slippage, and scratch prevention can be used as other additives in the lithographic printing ink, and if necessary, leveling agents, antistatic agents, etc. Surfactants, antifoaming agents, etc. may be added.

As an example of the composition of the lithographic printing ink of the present invention,
5 to 75% by mass of varnish for lithographic printing ink containing the rosin-modified phenolic resin (A) produced by the present invention.
・ Vegetable oils 0 to 80% by mass
・ Petroleum solvent 0-80% by mass
・ Pigment 5-40% by mass
・ Other resins 0-40% by mass
・ Other additives 0-5% by mass
Etc. are mentioned as preferable compositions.
The other resins represent rosin-modified phenolic resins (or rosin-modified phenolic resin varnishes), petroleum resins (or petroleum resin varnishes), alkyd resins, etc. other than those of the present invention, which are generally used in flat plate printing ink compositions. ..

The lithographic printing ink of the present invention can usually be suitably used for lithographic offset printing using dampening water. However, the ink is not limited to such an embodiment, and can be suitably used in waterless lithographic printing that does not use dampening water.
The printing press for obtaining the printed matter of the present invention can be used without particular limitation as long as it is an offset printing press, and examples thereof include an offset rotary printing press, a newspaper printing press, and a sheet-fed printing press.

The base material to which the ink is applied can be used without particularly limiting the paper used for lithographic printing. Specific examples of usable base materials include coated paper such as art paper, coated paper, and cast coated paper, non-coated paper such as high-quality paper, medium-quality paper, and newspaper paper, and synthetic paper such as YUPO. ..

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the scope of rights of the present invention in any way. In the present invention, unless otherwise specified, "parts" represents "parts by mass" and "%" represents "% by mass".

(Weight average molecular weight and number average molecular weight)
In the present invention, the weight average molecular weight and the number average molecular weight of the rosin-modified phenol resin (A) were measured by gel permeation chromatography (HLC-8320) manufactured by Tosoh Corporation. The calibration curve was prepared from a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and three TSKgel SuperHM-M (manufactured by Tosoh Corporation) were used as the column. The measurement was performed at a flow rate of 0.6 ml / min, an injection volume of 10 μl, and a column temperature of 40 ° C.

(Acid value)
The acid value of the rosin-modified phenolic resin (A) was measured according to the neutralization titration method. Specifically, first, 2 g of a rosin-modified phenol resin was precisely weighed and dissolved in 20 mL of a mixed solvent having a mass ratio of xylene: ethanol = 2: 1. Next, 3 mL of a 3 mass% phenolphthalein solution was added as an indicator to the previously prepared solution of the rosin-modified phenol resin, and then neutralization titration was performed with a 0.1 mol / L ethanolic potassium hydroxide solution. The unit of acid value is mgKOH / g.

The hydroxyl value of the resole-type phenol resin (c) was measured by the neutralization titration method. Specifically, first, 4 g of a xylene solution (solid content 60%) of the resol type phenol resin (c) is precisely weighed, and 20 ml of pyridine is added to dissolve it. To this, 10 ml of an esterifying agent prepared by dissolving phthalic anhydride and imidazole in pyridine is added, and the mixture is reacted at 100 ° C. for 30 minutes with stirring. After cooling, 2 ml of distilled water is added and stirred, and 30 ml of acetone is further added. After adding 3 mL of a 3 mass% phenolphthalein solution as an indicator to this, neutralization titration was performed with a 0.5 mol / L ethanolic potassium hydroxide solution. The unit of hydroxyl value is mgKOH / g.

(Quantification of terpenes content in rosins)
Regarding the contents of monoterpenes (a1) and sesquiterpenes (a2) in the rosins (b), each component was identified by mass spectrometry, and then all of the rosins (b) were subjected to gas chromatography. It was calculated by the peak area ratio (%) to the peak area of 100%. A gas chromatograph mass spectrometer manufactured by Agilent Technologies Co., Ltd. was used as the measuring device. The gas chromatograph section used 6890N, and the mass spectrometer used 5973N. HP-5MS 30 m × 0.25 mm id, 0.25 μm was used for the column, and helium gas having a flow rate of 2.0 ml / min was used as the carrier gas. The detector conditions were measured by a full scan (m / z 40-500) and a 250 ° C. transfer line.

(Cyclic diterpenes with conjugated double bonds in rosin)
The content of the cyclic diterpenes having a conjugated double bond in the rosins (b) can be determined by the peak area ratio of gas chromatography, and each component is identified by a mass spectrometer, and then the rosins (b). ) Was calculated by the peak area ratio (%) to 100% of the total peak area. A gas chromatograph mass spectrometer manufactured by Agilent Technologies Co., Ltd. was used as the measuring device. The gas chromatograph section used 6890N, and the mass spectrometer used 5973N. HP-5MS 30 m × 0.25 mm id, 0.25 μm was used for the column, and helium gas having a flow rate of 2.0 ml / min was used as the carrier gas. The detector conditions were measured by a full scan (m / z 40-500) and a 250 ° C. transfer line.

(Synthesis Example 1 of Resol Type Phenolic Resin)
To a four-necked flask equipped with a stirrer, a cooler, and a thermometer, 1000 parts of paraoctylphenol, 350 parts of 92% paraformaldehyde, 5 parts of 98% calcium hydroxide, and 882 parts of xylene were added, and the reaction was carried out at 90 ° C. for 4 hours. I let you. Then, 220 parts of tap water was added, 25 parts of 98% sulfuric acid was added dropwise, and the mixture was neutralized and washed with water. After stirring and standing, the upper layer was taken out to obtain a xylene solution of a resol-type phenol resin having a non-volatile content (solid content) of 60%, which was used as a resol solution R1. The hydroxyl value of this resole-type phenol resin was 37.0.

(Synthesis Example 2 of Resol Type Phenolic Resin)
In a four-necked flask with a stirrer, reflux condenser, and thermometer, 500 parts of paraoctylphenol, 182 parts of para-t-butylphenol, 533 parts of paranonylphenol, 395 parts of 92% paraformaldehyde, 20 parts of 98% calcium hydroxide, and 1052 xylene. The temperature was raised while blowing nitrogen gas, and the reaction was carried out at 90 ° C. for 6 hours. 260 parts of tap water was added, 103 parts of 98% sulfuric acid was added dropwise, and the mixture was neutralized and washed with water. After stirring and standing, the upper layer was taken out to obtain a xylene solution of a resol-type phenol resin having a non-volatile content (solid content) of 60%, which was used as a resol solution R2. The hydroxyl value of this resole-type phenol resin was 20.9.

(Synthesis Example 3 of Resol Type Phenolic Resin)
A four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer is charged with 200 parts of paraoctylphenol, 583 parts of para-t-butylphenol, 475 parts of 92% paraformaldehyde, 4 parts of 98% calcium hydroxide, and 813 parts of xylene, and nitrogen. The temperature was raised while blowing gas, and the reaction was carried out at 90 ° C. for 2 hours. 203 parts of tap water was added, 21 parts of 98% sulfuric acid was added dropwise, and the mixture was neutralized and washed with water. After stirring and standing, the upper layer was taken out to obtain a xylene solution of a resol-type phenol resin having a non-volatile content (solid content) of 60%, which was used as a resol solution R3. The hydroxyl value of this resole-type phenol resin was 44.2.

(Example 1)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% of monoterpenes, 0.7% of sesquiterpenes, and 56% of cyclic diterpenes with conjugated double bonds. 585 parts of gum rosin was charged, melted at 180 ° C. while blowing nitrogen, and 360 parts (as solid content) of resole solution R1 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 255 ° C., 54 parts of glycerin and 1 part of p-toluenesulfonic acid were added with stirring, and the mixture was reacted for 12 hours to obtain a weight average molecular weight of 36500, a weight average molecular weight / number average molecular weight of 38, and an acid value of 22. Resin 1 was obtained.

(Example 2)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.8% monoterpenes, 2.0% sesquiterpenes, and 48% cyclic diterpenes with conjugated double bonds. 702 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 235 parts (as a solid content) of the resole solution R2 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 255 ° C., 62 parts of glycerin and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 10 hours to obtain a weight average molecular weight of 21800, a weight average molecular weight / number average molecular weight of 28, and an acid value of 18. Resin 2 was obtained.

(Example 3)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% monoterpenes, 0.9% sesquiterpenes, and 82% cyclic diterpenes with conjugated double bonds. 640 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 301 parts (as a solid content) of the resole solution R1 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 252 ° C., 58 parts of glycerin and 1 part of p-toluenesulfonic acid were added with stirring, and the mixture was reacted for 10 hours to obtain a weight average molecular weight of 24600, a weight average molecular weight / number average molecular weight of 30, and an acid value of 20. Resin 3 was obtained.

(Example 4)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.1% monoterpenes, 0.4% sesquiterpenes, and 50% cyclic diterpenes with conjugated double bonds. 270 parts of the terpene to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 717 parts (as a solid content) of the resole solution R1 was added dropwise at 200 ° C. over 4 hours. Next, the temperature was raised to 255 ° C., 12 parts of glycerin and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 9 hours to obtain a weight average molecular weight of 38200, a weight average molecular weight / number average molecular weight of 36, and an acid value of 53. Resin 4 was obtained.

(Example 5)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.3% of monoterpenes, 1.1% of sesquiterpenes, and 36% of cyclic diterpenes with conjugated double bonds. 622 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 280 parts (as a solid content) of the resole solution R2 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 255 ° C., 95 parts of glycerin and 3 parts of p-toluenesulfonic acid were added with stirring, and the mixture was reacted for 12 hours to obtain a weight average molecular weight of 51200, a weight average molecular weight / number average molecular weight of 48, and an acid value of 4. Resin 5 was obtained.

(Example 6)
A four-necked flask equipped with a stirrer, a condenser with a water separator, and a thermometer contains 0.4% of monoterpenes, 0.7% of sesquiterpenes, and 54% of cyclic diterpenes with conjugated double bonds. 802 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 120 parts (as a solid content) of the resole solution R2 was added dropwise at 200 ° C. over 1.5 hours. Next, the temperature was raised to 260 ° C., 76 parts of pentaerythritol and 2 parts of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 9 hours to have a weight average molecular weight of 4700, a weight average molecular weight / number average molecular weight = 12, and an acid value of 10. Resin 6 was obtained.

(Example 7)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.8% of monoterpenes, 1.9% of sesquiterpenes, and 44% of cyclic diterpenes with conjugated double bonds. 565 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 376 parts (as a solid content) of the resole solution R1 was added dropwise at 200 ° C. over 2.5 hours. Next, the temperature was raised to 255 ° C., 45 parts of glycerin, 13 parts of pentaerythritol, and 1 part of calcium oxide were added with stirring, and the mixture was reacted for 11 hours. Weight average molecular weight 14200, weight average molecular weight / number average molecular weight = 18, acid. A resin 7 having a value of 21 was obtained.

(Example 8)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.8% of monoterpenes, 1.9% of sesquiterpenes, and 44% of cyclic diterpenes with conjugated double bonds. 577 parts of gum rosin was charged, melted at 180 ° C. while blowing nitrogen, and 369 parts (as a solid content) of resole solution R1 was added dropwise at 200 ° C. over 2.5 hours. Next, the temperature was raised to 255 ° C., 47 parts of glycerin, 6 parts of pentaerythritol, and 1 part of zinc oxide were added with stirring and reacted for 12 hours. Weight average molecular weight 39100, weight average molecular weight / number average molecular weight = 40, acid. A resin 8 having a value of 24 was obtained.

(Example 9)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% monoterpenes, 1.0% sesquiterpenes, and 37% cyclic diterpenes with conjugated double bonds. 431 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 527 parts (as a solid content) of the resole solution R1 was added dropwise at 200 ° C. over 3.5 hours. Next, the temperature was raised to 250 ° C., 41 parts of glycerin and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 16 hours to obtain a weight average molecular weight of 131200, a weight average molecular weight / number average molecular weight of 58, and an acid value of 14. Resin 9 was obtained.

(Comparative Example A)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 624 gum rosins containing 51% cyclic diterpenes having a conjugated double bond without containing monoterpenes and sesquiterpenes. Partially charged, melted at 180 ° C. while blowing nitrogen, and 321 parts (as a solid content) of resole solution R1 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 250 ° C., 54 parts of glycerin and 1 part of p-toluenesulfonic acid were added with stirring, and the mixture was reacted for 10 hours to obtain a weight average molecular weight of 9800, a weight average molecular weight / number average molecular weight of 9, and an acid value of 28. Resin A was obtained.

(Comparative Example B)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 1.0% of monoterpenes, 2.8% of sesquiterpenes, and 44% of cyclic diterpenes with conjugated double bonds. 540 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 409 parts (as a solid content) of the resole solution R1 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 250 ° C., 50 parts of glycerin and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 15 hours to obtain a weight average molecular weight of 86200, a weight average molecular weight / number average molecular weight of 58, and an acid value of 13. Resin B was obtained.

(Comparative Example C)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.2% monoterpenes, 1.0% sesquiterpenes, and 36% cyclic diterpenes with conjugated double bonds. 510 parts of gum rosin was charged, melted at 180 ° C. while blowing nitrogen, and 432 parts (as solid content) of resole solution R1 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 250 ° C., 46 parts of glycerin, 11 parts of pentaerythritol, and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 16 hours to have a weight average molecular weight of 108200 and a weight average molecular weight / number average molecular weight of 62. , A resin C having an acid value of 12 was obtained.

(Comparative Example D)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.8% of monoterpenes, 1.4% of sesquiterpenes, and 51% of cyclic diterpenes with conjugated double bonds. 600 parts of the gum rosin to be prepared was charged, melted at 180 ° C. while blowing nitrogen, and 353 parts (as a solid content) of the resole solution R3 was added dropwise at 200 ° C. over 2 hours. Next, the temperature was raised to 255 ° C., 46 parts of glycerin and 1 part of p-toluenesulfonic acid were added with stirring, and the mixture was reacted for 11 hours to obtain a weight average molecular weight of 22400, a weight average molecular weight / number average molecular weight of 17, and an acid value of 25. Resin D was obtained.

Table 1 shows the compounding composition and resin physical properties of the resins 1 to 9 of Examples and the resins A to D of Comparative Examples.

<Examples of varnishes, comparative examples>
A rosin-modified phenolic resin (resins 1 to 9, resins A to D) was charged into a four-necked flask equipped with a stirrer, a reflux condenser with a water separator, and a thermometer with the composition shown in Table 2, and nitrogen gas was added. Varnishes (varnishes 1 to 9, varnishes A to D) were produced by heating and stirring at 190 ° C. for 1 hour while blowing. The AF solvent 7 in Table 2 used a petroleum solvent (AF solvent No. 7 manufactured by JXTG Energy Co., Ltd.), and the ALCH used a gelling agent (ALCH manufactured by Kawaken Fine Chemicals Co., Ltd.).

<Examples and comparative examples of lithographic printing ink>
The varnishes (1-9, A to D) obtained by the above method, the carbon pigment Mitsubishi Carbon MA7 (manufactured by Mitsubishi Chemical Co., Ltd.), and the petroleum solvent (AF Solvent No. 7 manufactured by JXTG Energy Co., Ltd.) are shown in Table 3. The inks of Examples 1 to 9 and Comparative Examples A to D were produced by dispersing the kneaded meat in the compounding composition using three rolls according to a conventional method.

The lithographic printing inks obtained in Examples and Comparative Examples were evaluated for glossiness, fluidity, and bran residue by the following methods. The evaluation results are shown in Table 4.

<Evaluation of glossiness>
Gloss is spread to the same density on the pearl coat manufactured by Mitsubishi Paper Mills Limited with a proof bow color spreader, and 60 ° gloss is applied with a gloss meter gloss meter model GM-26 (manufactured by Murakami Color Technology Research Institute Co., Ltd.). The value was measured. The higher the value, the better the glossiness. If it is ⊚ to Δ, it is practically preferable.
(Evaluation criteria) ◎: 60 or more, 〇: 56 or more and less than 60, Δ: 50 or more and less than 56, ×: less than 50

<Measurement method of liquidity>
Put ink in a metal plate with a hemispherical recess of 2.1 cc, let it stand for 15 minutes, then tilt it to 60 degrees and measure the length of flow in 10 minutes, and evaluate based on the following evaluation criteria. went. The higher the value, the less the ink is tight and the better the fluidity. If it is ⊚ to Δ, it is practically preferable.
(Evaluation criteria) ◎: 80 mm or more, 〇: 70 mm or more and less than 80 mm, Δ: 60 mm or more and less than 70 mm, ×: less than 60 mm

<Blanc remaining evaluation>
In the printing test, an off-wheel printing machine NEO800 manufactured by Mitsubishi Heavy Industries, Ltd. was used to visually observe the printed matter and blanket when 50,000 copies were continuously printed under the following conditions with a general pattern and density. I checked the rest of the status.
If the evaluation is ⊚ to Δ, it is practically preferable. The "lower limit of the water width" means the minimum supply amount of dampening water that enables normal printing, and the "water dial" means the above-mentioned dampening water supply amount in order to adjust the supply amount. It means a dial provided in a printing machine.
CTP version: XP-F manufactured by FUJIFILM Corporation
Paper: Pearl Coat N manufactured by Mitsubishi Paper Mills Limited
Damping water: 2% aqueous solution of Aqua Unity WKK manufactured by Toyo Ink Co., Ltd. Printing speed: 600 rpm
Chiller set temperature: 25 ° C
Water dial value: 2% higher than the lower limit of water width (evaluation standard)
⊚: There is no pattern defect due to poor ink transfer on the printed matter, and there is little adhesion of ink / paper powder mixed components to the blanket. 〇: There is no pattern defect due to poor ink transfer on the printed matter, but there is ink / paper powder mixed component adhesion on the blanket.
Δ: There is a slight defect in the pattern due to poor ink transfer on the printed matter, and there is adhesion of the ink / paper powder mixed component on the blanket.
X: There is a pattern defect on the printed matter due to poor ink transfer, and a large amount of ink / paper powder mixed components adhere to the blanket.

Examples 1 to 9 showed better results than Comparative Examples A to D. In particular, in Examples 1 to 2 and 7 to 8, the gloss value, fluidity, and bran residue were particularly good results.
In Comparative Example A using rosins containing neither monoterpenes nor sesquiterpenes, the weight average molecular weight / number average molecular weight was less than 10, the gloss value and fluidity were inferior, and a large amount of bran residue was deposited. It was a level that was not suitable for practical use. Comparative Example B in which the total content of monoterpenes and sesquiterpenes exceeded 3.5% was inferior in fluidity. Further, in Comparative Example C in which the esterification reaction time was long and the weight average molecular weight / number average molecular weight was 60 or more, the bran residue was inferior, and both were at levels unsuitable for practical use. Further, in Comparative Example D in which a resol-type phenol resin having a hydroxyl value of 40 mgKOH / g or more was used, the bran residue was inferior.

Claims (6)

A reaction product of rosins (b), a resole-type phenol resin (c), and a polyol (d).
The rosins (b) contain 0.1 to 3.5% by mass of monoterpenes (a1) and sesquiterpenes (a2) with respect to the total amount of rosins.
The hydroxyl value of the resole-type phenol resin (c) is 15 to 40 mgKOH / g.
A rosin-modified phenolic resin (A), characterized in that Mw / Mn, which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), is 10 to 60. The rosin-modified phenol resin (A) according to claim 1, wherein the rosins (b) contain 20 to 80% by mass of a cyclic diterpene having a conjugated double bond. Based on the total mass of the rosin-modified phenolic resin raw material
Rosin (b) 30-85% by mass,
Resol type phenol resin (c) 7 to 67% by mass,
The rosin-modified phenol resin (A) according to claim 1 or 2, wherein the polyol (d) is a reaction product with 3 to 20% by mass. The rosin-modified phenol form (A) according to any one of claims 1 to 3, which has a weight average molecular weight of 7,000 to 120,000 and an acid value of 5 to 50 mgKOH / g. A lithographic printing ink containing the rosin-modified phenolic resin (A) according to any one of claims 1 to 4. A printed matter in which the lithographic printing ink according to claim 5 is printed on a base material.