JP6930675B1 - Rosin-modified phenolic resin, lithographic printing inks, and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lithographic printing ink resin which is excellent in glossiness and ink fluidity of a printed matter and can obtain a printed matter which does not generate stains and blank residue even during long-time printing, and a lithographic printing ink containing the same. Offer. SOLUTION: A reaction product of rosins (b), phenols (c), formaldehydes (d) and polyols (e), and the rosins (b) are monoterpenes (a1). And sesquiterpenes (a2) are contained in an amount of 0.1 to 3.5% by mass based on the total amount of rosins, and Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is 10 to 60. A rosin-modified phenolic resin (A). [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., and improves the fluidity of the ink to prevent stains. The present invention relates to a resin for lithographic printing ink, which is characterized in that a high-gloss printed matter can be obtained with a small amount of blank residue.

The lithographic printing ink is an ink having a relatively high viscosity of 5 to 100 Pa · s. In the mechanism of the flat plate 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. Further, there is a demand for an ink that can stably obtain a high-quality printed matter for a long time without generating stains under various printing conditions. In particular, there is a strong demand for inks that have good ink fluidity, excellent glossiness of printed matter, and can reduce printing troubles such as blank residue. The blanket 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 deposition 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 components in the ink system are increased by using a low-molecular-weight, highly soluble resin or petroleum resin, the tack value of the ink will rise too much, paper peeling will occur, and emulsification will be difficult to control, making 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. be. 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 during 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 a phenol formaldehyde initial condensate 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 suppression of stains 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 JP-A-2007-169574 Japanese Unexamined Patent Publication No. 2004-269752 JP 2015-193790 Japanese Unexamined Patent Publication No. 9-169953

The present invention provides a resin for lithographic printing ink for obtaining a lithographic printing ink having excellent ink fluidity, less stains and blank residue during long-term printing, and capable of obtaining a high-gloss printed matter. The purpose.

As a result of diligent research conducted by the present inventors to solve the above problems, the lithographic 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 less stains and blank residue during printing, and have completed the present invention.

That is, the present invention is a reaction product of rosins (b), phenols (c), formaldehydes (d) and polyols (e).
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 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 phenol resin raw material.
Rosin (b) 30-85% by mass,
The rosin-modified phenol resin (1), which is a reaction product of 5 to 50% by mass of phenols (c), 3 to 20% by mass of formaldehyde (d), and 3 to 20% by mass of polyols (e). Regarding A).

The present invention also relates to the rosin-modified phenol formaldehyde (A) having a weight average molecular weight of 4,000 to 110,000 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.

Further, the present invention is a method for producing a rosin-modified phenolic resin (A).
A step of reacting rosins (b), phenols (c), and formaldehydes (d), and
A step of reacting the compound obtained in the above step with the polyols (e), and
Including
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 present invention relates to a method for producing a rosin-modified phenol form (A), which comprises a Mw / Mn, which is a ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn), of 10 to 60.

Further, the present invention is a method for producing a rosin-modified phenolic resin (A).
A step of reacting rosins (b), phenols (c), formaldehydes (d), and polyols (e) is included.
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 present invention relates to a method for producing a rosin-modified phenol form (A), which comprises a Mw / Mn, which is a ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn), of 10 to 60.

By using the resin for lithographic printing ink of the present invention, it has been possible to provide a lithographic printing ink which has excellent ink fluidity, has less stains and 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 printing is performed. Occurrence of stains and insufficient fluidity of ink. The total content of monoterpenes (a1) and 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 the sesquiterpenes (a2) is 0.1 to 3.5% by mass based on the total amount of the rosins. There is no limitation, 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, silicic acid-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, isologinholene, longiholene, caryophyllene, β-humulene, α-farnesene, β-farnesene, β- Examples include caryophyllene, α-guaien, β-guaien, γ-guaien, α-element, β-element, γ-element, δ-element, α-bisabolen, β-bisaborene, γ-bisabolen, aromadendrene, cedrene, etc. 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 with respect to 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 rosins 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.

As the phenols (c), all aromatic compounds having a phenol hydroxyl group can be used, and coal acid, cresol, p-amylphenol, bisphenol A, p-butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol and the like can be used. These may be used alone or in combination of two or more.

As the formaldehydes (d), formalin, paraformaldehyde, etc., which are aqueous solutions of formaldehyde, can be used.

The polyols (e) in the present invention include, as divalent alcohols, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-propane, which are linear alkylene divalent alcohols. Butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexane Glycol, 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 dihydric alcohols, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, 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 has 30 to 85% by mass of rosins (b), 5 to 50% by mass of phenols (c), and formaldehyde (d) 3 with respect to the total amount of the prepared formulation on a mass basis. -20% by mass and 3 to 20% by mass of the polyols (e) are preferable. When the rosins (b) are 30% by mass or more, the phenols (c) are 50% by mass or less, and the formaldehydes (d) are 20% 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, the phenols (c) are 5% by mass or more, and the formaldehydes (d) are 3% by mass or more, the viscosity and elasticity required for the ink can be easily obtained. Further, more preferably, rosins (b) are 35 to 75% by mass, phenols (c) are 7 to 45% by mass, and formaldehydes (d) are 4 to 17% 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 synthetic method generally called one-pot synthesis is used.
As one embodiment of one-pot synthesis, there are the following manufacturing methods.
Rosin (b) is heated and melted at 100 to 140 ° C. in a synthetic kettle, phenols (c) and formaldehyde (d) are added as necessary with an alkaline catalyst, and the mixture is reacted for 1 to 8 hours. After that, the polyols (e) and, if necessary, an esterification catalyst are added, and the esterification reaction is carried out at 220 to 300 ° C. for 3 to 20 hours.
As the early alkaline catalyst, an alkaline catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, calcium oxide, magnesium oxide, zinc oxide or the like, or an alkaline catalyst such as an organic amine can be used. be. These catalysts are usually used in the range of 0.01 to 5% by mass in the total resin. These alkaline catalysts may be used alone or in combination of two or more.
Examples of the early esterification 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, and trifluoromethylsulfate. Examples thereof include trifluoromethylacetic acid. 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. be. 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 the coloring of the resin due to the use of a catalyst.

Further, as another embodiment of the one-pot synthesis, there is the following manufacturing method.
Rosin (b) is heated and melted in a synthetic kettle at 100 to 140 ° C., phenols (c), formaldehyde (d), polyols (e) and, if necessary, an alkaline catalyst are added, and the mixture is added for 0 to 8 hours. React. Then, if necessary, an esterification catalyst is added, and the esterification reaction is carried out at 220 to 300 ° C. for 3 to 20 hours. As the alkaline catalyst and the esterification catalyst, those described in the preceding paragraph can be used.

The one-pot synthesis method used as a method for producing this resin can reduce the initial investment in the pot, and further, since the amount of wastewater generated is small, the production cost can be suppressed.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the rosin-modified phenol 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 4,000 to 110,000, more preferably 5,000 to 100,000. When it is 4,000 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. 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 varnish for lithographic printing ink, a conventionally known solvent for printing ink can be used without particular limitation. Specific examples thereof include No. 0 solvent, AF solvent No. 4, AF solvent No. 5, AF solvent No. 6, AF solvent No. 7 manufactured by ENEOS, and the like. 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 D100, Quinton M100, Quinton R100, and aromatic petrochemicals manufactured by Nippon Zeon Co., Ltd. can be used. ENEOS 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, Petcol LX manufactured by Toso, Petcol LX-HS, Petcol 100T, Petcol 120, Petcol 120HS, Petcol 130, Petcol 140, Petcol 140HM, Petcol 140HM5, Petcol 150, Petcol 150AS, as a copolymerized petroleum resin , Japan Zeon Quinton D100, Quinton N180, Quinton P195N, Quinton S100, Quinton S195, Quinton U185, Quinton G100B, Quinton G115, Quinton D200, Quinton E200SN, Quinton N295, Toso Petrotac 60, Petrotac 70 Tuck 90, Petro Tack 100, Petro Tack 100V, Petro Tack 90HM, DCPD-based petroleum resins include Marukaretsu M-890A, Marukaretsu M-845A manufactured by Maruzen Petrochemical Co., Ltd., Quinton 1325, Quinton 1345, Quinton 1500 manufactured by Nippon Zeon Co., Ltd. Quinton 1525L, Quinton 1700 and the like can be mentioned.

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), a pigment, a petroleum solvent, and an additive.
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 Toso Co., Ltd. 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 rosin-modified phenol resin solution, and then neutralization titration was performed with a 0.1 mol / L ethanolic potassium hydroxide solution. The unit of acid 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 with 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 with a full scan (m / z 40-500) and a 250 ° C. transfer line.

(Example 1)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.3% of monoterpenes, 0.8% of sesquiterpenes, and 68% of cyclic diterpenes with conjugated double bonds. 647 parts of gum rosin is charged, melted at 120 ° C while blowing nitrogen, 192 parts of parat-butylphenol, 92 parts of paraformene (active ingredient 92%), and 3 parts of calcium hydroxide are charged and reacted at 120 ° C for 4 hours. I let you. Then, the temperature was raised to 255 ° C., 66 parts of glycerin was added with stirring, and the mixture was reacted for 12 hours to obtain a resin 1 having a weight average molecular weight of 14200, a weight average molecular weight / number average molecular weight = 30, and an acid value of 19.

(Example 2)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% of monoterpenes, 0.5% of sesquiterpenes, and 55% of cyclic diterpenes with conjugated double bonds. 608 parts of gum rosin is charged and melted at 120 ° C while blowing nitrogen, 247 parts of paraoctylphenol, 86 parts of paraformaldehyde (active ingredient 92%), 3 parts of calcium hydroxide and 1 part of zinc oxide are charged, and 4 parts at 120 ° C. Reacted for time. Then, the temperature was raised to 255 ° C., 55 parts of glycerin was added with stirring, and the mixture was reacted for 13 hours to obtain a resin 2 having a weight average molecular weight of 20900, a weight average molecular weight / number average molecular weight = 44, and an acid value of 26.

(Example 3)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% of monoterpenes, 0.9% of sesquiterpenes, and 72% of cyclic diterpenes with conjugated double bonds. 666 parts of gum rosin to be prepared and melted at 120 ° C. while blowing nitrogen, 80 parts of parat-butylphenol, 110 parts of paraoctylphenol, 76 parts of paraformaldehyde (active ingredient 92%), 3 parts of calcium hydroxide are charged, 120 parts. The reaction was carried out at ° C. for 4 hours. Next, the temperature was raised to 257 ° C., 41 parts of glycerin, 23 parts of pentaerythritol, and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 12 hours to have a weight average molecular weight of 24600 and a weight average molecular weight / number average molecular weight = 30. , Resin 3 having an acid value of 20 was obtained.

(Example 4)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.3% of monoterpenes, 0.8% of sesquiterpenes, and 50% of cyclic diterpenes with conjugated double bonds. 811 parts of gum rosin to be prepared, melted at 120 ° C while blowing nitrogen, charged with 60 parts of parat-butylphenol, 33 parts of paraformene (active ingredient 92%), and 4 parts of calcium hydroxide, and reacted at 120 ° C for 4 hours. I let you. Then, the temperature was raised to 265 ° C., 92 parts of pentaerythritol was added with stirring, and the mixture was reacted for 10 hours to obtain a resin 4 having a weight average molecular weight of 7600, a weight average molecular weight / number average molecular weight of 22, and an acid value of 52.

(Example 5)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% of monoterpenes, 1.0% of sesquiterpenes, and 83% of cyclic diterpenes with conjugated double bonds. 520 parts of gum rosin to be prepared, melted at 120 ° C while blowing nitrogen, 284 parts of parat-butylphenol, 154 parts of paraformene (active ingredient 92%), and 5 parts of calcium hydroxide were charged and reacted at 120 ° C for 5 hours. I let you. Next, the temperature was raised to 260 ° C., 37 parts of glycerin was added with stirring, and the mixture was reacted for 11 hours to obtain a resin 5 having a weight average molecular weight of 34600, a weight average molecular weight / number average molecular weight of 42, and an acid value of 36.

(Example 6)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 1.0% of monoterpenes, 1.4% of sesquiterpenes, and 60% of cyclic diterpenes with conjugated double bonds. 332 parts of gum rosin is charged, melted at 120 ° C while blowing nitrogen, 453 parts of parat-butylphenol, 177 parts of paraformene (active ingredient 92%), and 8 parts of calcium hydroxide are charged and reacted at 120 ° C for 3 hours. I let you. Next, the temperature was raised to 250 ° C., 30 parts of glycerin was added with stirring, and the mixture was reacted for 12 hours to obtain a resin 6 having a weight average molecular weight of 54200, a weight average molecular weight / number average molecular weight = 56, and an acid value of 26.

(Example 7)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 1.2% of monoterpenes, 2.0% of sesquiterpenes, and 44% of cyclic diterpenes with conjugated double bonds. 527 parts of gum rosin to be prepared and melted at 120 ° C while blowing nitrogen, 314 parts of paraoctylphenol, 109 parts of paraformaldehyde (active ingredient 92%), 3 parts of calcium hydroxide and 2 parts of zinc oxide are charged, and 5 parts at 120 ° C. Reacted for time. Then, the temperature was raised to 255 ° C., 45 parts of glycerin was added with stirring, and the mixture was reacted for 11 hours to obtain a resin 7 having a weight average molecular weight of 28900, a weight average molecular weight / number average molecular weight of 33, and an acid value of 32.

(Example 8)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.9% of monoterpenes, 1.8% of sesquiterpenes, and 56% of cyclic diterpenes with conjugated double bonds. 763 parts of gum rosin is charged, melted at 120 ° C while blowing nitrogen, 116 parts of parat-butylphenol, 56 parts of paraformene (active ingredient 92%), and 2 parts of calcium hydroxide are charged and reacted at 120 ° C for 4 hours. I let you. Next, the temperature was raised to 255 ° C., 46 parts of glycerin and 17 parts of pentaerythritol were added with stirring, and the mixture was reacted for 12 hours to produce a resin 8 having a weight average molecular weight of 3800, a weight average molecular weight / number average molecular weight of 16, and an acid value of 42. Got

(Example 9)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.8% of monoterpenes, 0.9% of sesquiterpenes, and 72% of cyclic diterpenes with conjugated double bonds. 558 parts of gum rosin to be prepared and melted at 120 ° C while blowing nitrogen, 110 parts of para-t-butylphenol, 152 parts of paraoctylphenol, 120 parts of paraformaldehyde (active ingredient 92%), 1 part of zinc oxide are charged, and 120 ° C. Was reacted for 6 hours. Next, the temperature was raised to 250 ° C., 45 parts of glycerin, 13 parts of pentaerythritol, and 1 part of paratoluenesulfonic acid were added with stirring, and the mixture was reacted for 15 hours to have a weight average molecular weight of 127200 and a weight average molecular weight / number average molecular weight of 59. , A resin 9 having an acid value of 17 was obtained.

(Example 10)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% of monoterpenes, 1.0% of sesquiterpenes, and 77% of cyclic diterpenes with conjugated double bonds. 602 parts of gum rosin to be prepared and melted at 120 ° C. while blowing nitrogen, 100 parts of para-t-butylphenol, 137 parts of paraoctylphenol, 95 parts of paraformaldehyde (active ingredient 92%), 49 parts of glycerin, 14 parts of pentaerythritol, Three parts of calcium oxide were charged and reacted at 120 ° C. for 2 hours. Then, the temperature was raised to 260 ° C. and reacted for 12 hours to obtain a resin 10 having a weight average molecular weight of 24600, a weight average molecular weight / number average molecular weight = 42, and an acid value of 21.
(Example 11)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 1.0% of monoterpenes, 1.2% of sesquiterpenes, and 46% of cyclic diterpenes with conjugated double bonds. 654 parts of gum rosin to be prepared and melted at 120 ° C. while blowing nitrogen to add 187 parts of parat-butylphenol, 102 parts of paraformaldehyde (active ingredient 92%), 47 parts of glycerin, 7 parts of pentaerythritol, and 3 parts of zinc oxide. It was charged and reacted at 120 ° C. for 4 hours. Then, the temperature was raised to 257 ° C. and reacted for 12 hours to obtain a resin 11 having a weight average molecular weight of 36200, a weight average molecular weight / number average molecular weight = 50, and an acid value of 30.

(Comparative Example A)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains monoterpenes and gum rosin containing 66% cyclic diterpenes having a conjugated double bond without containing sesquiterpenes. 624 parts were charged and melted at 120 ° C while blowing nitrogen, 214 parts of para-t-butylphenol, 102 parts of paraformene (active ingredient 92%), 1 part of calcium hydroxide and 2 parts of zinc oxide were charged, and 4 at 120 ° C. Reacted for time. Then, the temperature was raised to 255 ° C., 57 parts of glycerin was added with stirring, and the mixture was reacted for 10 hours to obtain a resin A having a weight average molecular weight of 12200, a weight average molecular weight / number average molecular weight = 18, and an acid value of 28.

(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, 1.1% of sesquiterpenes, and 52% of cyclic diterpenes with conjugated double bonds. 550 parts of gum rosin is charged, melted at 120 ° C while blowing nitrogen, 316 parts of para-t-butylphenol, 90 parts of paraformene (active ingredient 92%), and 4 parts of calcium hydroxide are charged and reacted at 120 ° C for 2 hours. I let you. Next, the temperature was raised to 255 ° C., 39 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 7700, a weight average molecular weight / number average molecular weight of 9, and an acid value of 36. 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 1.2% of monoterpenes, 2.5% of sesquiterpenes, and 48% of cyclic diterpenes with conjugated double bonds. 487 parts of gum rosin was charged and melted at 120 ° C. while blowing nitrogen, and 340 parts of paraoctylphenol, 119 parts of paraformaldehyde (active ingredient 92%) and 3 parts of zinc oxide were charged and reacted at 120 ° C. for 4 hours. Next, the temperature was raised to 255 ° C., 35 parts of glycerin and 16 parts of pentaerythritol were added with stirring, and the mixture was reacted for 14 hours. Resin C having a weight average molecular weight of 77200, a weight average molecular weight / number average molecular weight of 56, and an acid value of 16. Got

(Comparative Example D)
A four-necked flask equipped with a stirrer, a cooler with a water separator, and a thermometer contains 0.4% of monoterpenes, 1.0% of sesquiterpenes, and 34% of cyclic diterpenes with conjugated double bonds. 537 parts of gum rosin to be prepared and melted at 120 ° C. while blowing nitrogen, 66 parts of parat-butylphenol, 212 parts of paraoctylphenol, 120 parts of paraformaldehyde (active ingredient 92%), 4 parts of calcium hydroxide are charged, 120 parts. The reaction was carried out at ° C. for 6 hours. Next, the temperature was raised to 250 ° C., 60 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 106200, a weight average molecular weight / number average molecular weight of 62, and an acid value of 14. Resin D was obtained.

Table 1 shows the compounding composition and resin physical properties of the resins 1 to 11 of Examples and the resins A to D of Comparative Examples.

<Examples of varnishes, comparative examples>
A rosin-modified phenolic resin (resins 1 to 11, 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 11, varnishes A to D) were produced by heating and stirring at 190 ° C. for 1 hour while blowing. In Table 2, AF solvent 7 used a petroleum solvent (AF solvent No. 7 manufactured by ENEOS), and ALCH used a gelling agent (ALCH manufactured by Kawaken Fine Chemicals Co., Ltd.).

<Examples of lithographic printing inks, comparative examples>
The varnish (1-11, 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 ENEOS Co., Ltd.) are blended in Table 3. In the composition, the kneaded meat was dispersed using three rolls according to a conventional method to produce the inks of Examples 1 to 11 and Comparative Examples A to D.

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

<Evaluation of glossiness>
The glossiness is spread to the same density on the pearl coat manufactured by Mitsubishi Paper Mills Limited with a proof bow color spreader, and 60 ° glossiness is achieved with the 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 the ink / paper powder mixed component to 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 due to poor ink transfer on the printed matter, and a large amount of ink / paper powder mixed components adhere to the blanket and accumulate.

<Dirt evaluation>
The printed matter at the time of printing 50,000 copies obtained by the above blank residue evaluation was visually observed to confirm the presence or absence of stains.
(Evaluation criteria) ◎: No stains, 〇: 80% halftone dots are slightly disturbed, △: 80% halftone dots are entangled with ink, ×: stains are generated, market evaluation Not worth it.

Table 4 shows the results of various evaluations.

Examples 1 to 11 showed better results than Comparative Examples A to D. In particular, in Examples 1 to 3, the gloss value, fluidity, stain, and bran residue were particularly good results. In addition, the gloss value, fluidity, stains, and bran residue were particularly good results for Examples 10 to 11 having different production methods.
Comparative Example A using rosins containing neither monoterpenes nor sesquiterpenes was significantly inferior in gloss value and fluidity. Further, in Comparative Example B in which the weight average molecular weight / number average molecular weight was less than 10, deterioration of fluidity, stains, and bran residue were generated, which was not suitable for practical use. Comparative Example C, in which the total content of monoterpenes and sesquiterpenes exceeded 3.5%, was inferior in fluidity and stain. Further, in Comparative Example D 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 the level was not suitable for practical use.

Claims (8)

It is a reaction product of rosins (b), phenols (c), formaldehydes (d), and polyols (e).
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.
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. Rosin (b) 30-85% by mass,
The first or second claim, wherein it is a reaction product of 5 to 50% by mass of phenols (c), 3 to 20% by mass of formaldehyde (d), and 3 to 20% by mass of polyols (e). Rosin-modified phenolic resin (A). The rosin-modified phenol form (A) according to any one of claims 1 to 3, which has a weight average molecular weight of 4,000 to 110,000 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. A method for producing a rosin-modified phenolic resin (A).
A step of reacting rosins (b), phenols (c), and formaldehydes (d), and
A step of reacting the compound obtained in the above step with the polyols (e), and
Including
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.
A method for producing a rosin-modified phenol resin (A), wherein Mw / Mn, which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), is 10 to 60. A method for producing a rosin-modified phenolic resin (A).
A step of reacting rosins (b), phenols (c), formaldehydes (d), and polyols (e) is included.
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.
A method for producing a rosin-modified phenol resin (A), wherein Mw / Mn, which is a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), is 10 to 60.