TWI585165B - Ink with adhesive, ink with varnish and ink - Google Patents

Description

Adhesive for ink, varnish for ink and ink

The present invention relates to a binder for ink using a rosin-modified phenol resin, a resin varnish containing the binder for ink, and an ink obtained by using the varnish (printing ink) ).

The "rosin-modified phenolic resin" is usually a resin obtained by reacting rosin, a phenol resin or a polyhydric alcohol, and has been used as a resin for printing ink, for example, lithographic printing. Resin for offset printing ink (see Patent Documents 1, 2, etc.).

The lithographic ink is usually obtained by dissolving such a rosin-modified phenol resin in a solvent for ink, obtaining a varnish, blending the pigment, and mixing them, but if the pigment is not sufficiently dispersed, it may cause ink printing. The fluidity is poor, or the gloss of the printed matter is lowered. Therefore, in order to sufficiently disperse the pigment, it is considered that the mechanical dispersion step is carried out for a long period of time, but the productivity is lowered.

In addition, in the ink manufacturer, it is to make up for the dispersion step. For the purpose of dispersing the rosin-modified phenol resin, various additives have been studied. For example, Patent Document 3 discloses that the pigment dispersibility of the ink can be improved by using a certain amount of a specific insoluble azo pigment composition or the like. ).

On the other hand, it has also been attempted to improve the pigment dispersibility from the viewpoint of the physical properties of the rosin-modified phenol resin. For example, the applicant of the present application, as shown in Patent Document 4, has found that by defining the weight contained in the rosin-modified phenol resin. The amount of the low molecular component having an average molecular weight of 400 or less can improve the fluidity of the ink. However, further improvements are being asked.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 1-36668

Patent Document 2: Japanese Laid-Open Patent Publication No. 1-170676

Patent Document 3: Japanese Laid-Open Patent Publication No. 6-49386

Patent Document 4: Japanese Laid-Open Patent Publication No. 2009-227785

SUMMARY OF THE INVENTION A primary object of the present invention is to provide a novel rosin-modified phenol resin-based ink-bonding agent which is excellent in pigment dispersibility, can improve the fluidity of an ink, and imparts excellent gloss to a printed matter.

The inventors of the present invention have considered that the molecular weight distribution of the prior rosin-modified phenol resin is so large that the performance of the binder is insufficient, and it has been found that by adjusting a certain molecular weight distribution by using a certain amount of a specific phosphorus compound, A rosin-modified phenol resin as a target is obtained.

That is, the present invention relates to a binder for ink using a rosin-modified phenol resin, a varnish for ink containing the binder for ink and a vegetable oil, and an ink obtained by using the varnish for ink. ink. The above-mentioned binder for ink is obtained by using a rosin-modified phenol resin having a polydispersity (Mw/Mn) (Mw represents a weight average molecular weight, Mn represents a number average molecular weight) of 7 to 10, and the rosin-modified phenol resin is The rosin ester (B) and the condensate (C) of phenol and formaldehyde are obtained by reaction, and the rosin ester (B) is in the formula (1): (RO-) ₃ -P (In the formula, R represents an alkyl group having 1 to 12 carbon atoms or a phenyl group having an alkyl group having 1 to 12 carbon atoms), in the presence of an organophosphorus compound (A), by using rosin The compound (b-1) and the polyol (b-2) are obtained by esterification under the condition that the amount of the component (A) of the component (b-1) is 0.05 to 0.5% by weight.

In the lin-modified phenol resin of the present invention, the rosin-modified phenol resin is excellent in dispersibility of the pigment, and the gloss of the printed matter is good, in addition to the fluidity of the ink to be used. Therefore, the binder can be used, in particular, as a lithographic ink resin, such as a lithographic sheet ink. (offset sheet-fed ink) (sheet-fed ink) or offset rotary printing ink (offset rotary ink), newspaper ink (newspaper ink) A resin for lithographic ink printing, etc. Further, it can also be used as a resin for a letterpress printing ink or a gravure printing ink. Further, a surface treatment agent as a pigment can also be utilized.

[Best Embodiment of the Invention]

The binder for ink of the present invention is obtained by using a rosin-modified phenol resin which is a rosin ester (B) (hereinafter, referred to as (B) component), and a phenol and formaldehyde. The condensate (C) (hereinafter, referred to as (C) component) is obtained by a reaction, and the rosin ester (B) is in the formula (1): (RO-) _{3 -} P (wherein R represents an organophosphorus compound (A) (hereinafter, referred to as a component (A)) represented by an alkyl group having 1 to 12 carbon atoms or a phenyl group having an alkyl group having 1 to 12 carbon atoms. Esterification of rosin (b-1) (hereinafter, referred to as (b-1) component) and polyol (b-2) (hereinafter, referred to as (b-2) component) in the presence of And get.

As the component (A), any of those skilled in the art can be used without any particular limitation as long as it is a compound represented by the above formula (1). In addition, the carbon number in the formula is 1 to 12, as long as it is linear, branched, or cyclic. The structure of either one is sufficient. Specific examples of the component (A) can be exemplified by triphenyl phosphite, tricresyl phosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, 4,4'-butylene phosphite - Bis(3-methyl-6-tris-butylphenyl-di-tridecyl)ester, cyclic neopentane tetrayl bis(octadecyl phosphite), phosphite (nonylphenyl) An ester, bis(nonylphenyl) phosphite, and the like. Among the above, preferred is triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, hexamethylene phosphite, and bisphosphonium phosphite. Ester). These may be used alone or in combination of two or more. In this case, it is easy to obtain, and it is easy to achieve the desired effect of the present invention (that is, pigment dispersibility, ink flowability, gloss of the ink film, etc.. Hereinafter, when it is called the efficacy of the present invention, The same.) is preferably triphenyl phosphite.

Examples of the component (b-1) include natural rosin such as gum rosin, tall oil rosin, and wood rosin, or a purified product thereof (hereinafter, , referred to as "raw material rosins"; polymerized rosin derived from raw rosin; disproportionation and/or hydrogenation of raw rosin or polymeric rosin Stabilized rosin obtained; for raw rosin or polymerized rosin, (meth)acrylic acid, fumaric acid (fumaric acid), itaconic acid (anhydride), crotonic acid, cinnamic acid, etc. α,β-unsaturated acid modified rosin obtained by a Diels-Alder addition reaction of α,β-unsaturated carboxylic acid; the α,β-unsaturated acid is modified Quality rosin into one Stabilized rosin obtained by unevenness or hydrogenation is used. These may be used alone or in combination of two or more. Further, the amount of the rosin species and the α,β-unsaturated carboxylic acid used in the α,β-unsaturated acid-modified rosin is not particularly limited, but from the viewpoint of the efficacy of the present invention, usually 100 weights relative to the former The latter is in the range of about 1 to 30 parts by weight.

The component (b-2) is not particularly limited as long as it is a compound having at least two hydroxyl groups in one molecule, and various conventionally used ones can be used. Specific examples thereof include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and neopentyl glycol; and triols such as glycerin, trimethylolethane, and trimethylolpropane. a tetraol such as pentaerythritol, diglycerin or di-trimethylolpropane; or a hexavalent or higher polyhydric alcohol such as dipentaerythritol. These may be used alone or in combination of two or more. In view of the above, the viewpoint of the controllability of the physical properties (softening point, weight average molecular weight, and the like) of the rosin-modified phenol resin of the present invention and the viewpoint of the efficacy of the present invention are preferably triols and/or Tetrahydrins.

In the present invention, the component (A) must be used in an amount of 0.05 to 0.5% by weight based on the component (b-1). By making it 0.05% by weight or more, the fluidity of the ink and the gloss of the ink film can be made good. Further, by making it 0.5% by weight or less, the insoluble matter in the production of the rosin-modified phenol resin of the present invention can be reduced, and further, in the effect of the present invention, the fluidity and ink of the ink can be made particularly. The gloss of the film became good. From this point of view, the amount of (A) component used is relative to (b- The component 1) is preferably from about 0.1 to 0.4% by weight, more preferably from about 0.15 to 0.35% by weight.

The amount of the component (b-1) and the component (b-2) to be used is not particularly limited, and from the viewpoint of the efficacy of the present invention, the total number of hydroxyl groups (OH) of the component (b-2) is preferably The ratio (OH/COOH) of the total number of carboxyl equivalents (COOH) of the component (b-1) is usually in the range of about 0.5 to 1.5.

The component (B) is obtained by subjecting the component (b-1) to the component (b-2) in an esterification reaction in the presence of a specific amount of the component (A) as described above. The reaction conditions are not particularly limited. For example, the components (A), (b-1), and (b-2) are each fed to the reaction vessel in a specific amount, and the presence of various conventional catalysts is required as needed. Next, the esterification reaction is carried out at about 100 to 300 ° C for about 1 to 24 hours.

Examples of the catalyst include mineral acids such as hydrochloric acid and sulfuric acid; sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; and metal oxides such as zinc oxide, magnesium oxide, and calcium oxide. a metal hydroxide such as magnesium hydroxide or calcium hydroxide; or an acetate such as calcium acetate, magnesium acetate or zinc acetate. These may be used alone or in combination of two or more. Further, the amount of use thereof is not particularly limited, and it is usually preferably about 0 to 5 by weight based on the total amount of the components (b-1) and (b-2) in order to achieve the polydispersity described later. %.

The component (C) may be any conventional one as long as it is a condensate of phenol and formaldehyde, such as a resol-type phenolic resin or a novolac type phenolic resin. Wait.

Examples of the phenols include carbolic acid (phenol), cresol, amylphenol, bisphenol A, butylphenol, octylphenol, nonylphenol, and dodecylphenol. Further, examples of the formaldehyde include formaldehyde (formalin), paraformaldehyde, and the like.

Further, as the soluble phenol resin, in the presence of various basic catalysts, the phenol (P) and the formaldehyde (F) are usually at about 1 to 3 in F/P (mole ratio). Addition within the scope. a condensate formed by a condensation reaction. In addition, the above-mentioned novolac type phenol resin may be exemplified by addition of F/P in the range of about 0.5 to 2 in the presence of various acid catalysts. a condensate formed by a condensation reaction. In addition, each condensate may be neutralized. Washed by. Further, the production of each condensate can be carried out in the presence of water or an organic solvent (xylene or the like). The component (C) is preferably a soluble phenol resin from the viewpoint of high molecular weight of the rosin-modified phenol resin and the viewpoint of the effects of the present invention. Further, as the acid catalyst and the alkaline catalyst, the same ones as those used in the production of the component (B) can be used.

The amount of the component (B) and the component (C) to be used is not particularly limited, and may be appropriately determined depending on the intended use, but the effect of the present invention is not limited. It is generally assumed that when the total amount is 100% by weight, it is about 41 to 88% by weight and about 59 to 12% by weight, preferably about 46 to 80% by weight and about 54 to 20% by weight, respectively. Preferably, it is 67 to 77% by weight and 33 to 23% by weight.

Further, the reaction conditions of the component (B) and the component (C) are not particularly limited. For example, the two components are each fed to the reaction vessel in a specific amount, and in the presence of various conventional catalysts, The reaction can be carried out at 200 to 300 ° C for about 1 to 20 hours. The foregoing can be used as a catalyst.

The rosin-modified phenol resin of the present invention is obtained in this manner, and from the viewpoint of the efficacy of the present invention, it is characterized by polydispersity (Mw/Mn) (Mw represents a weight average molecular weight, and Mn represents a number average molecular weight). ) is set to 7~10, preferably 8~9. The polydispersity is an index indicating the magnitude of the molecular weight distribution, and the rosin-modified phenol resin of the present invention may be referred to as a narrow molecular weight distribution because of its small value. Further, since the polydispersity is set to 7 or more, in particular, the gloss of the ink film becomes good, and since it is set to 10 or less, in particular, the fluidity of the ink and the gloss of the ink film become good.

Further, any of Mw and Mn is a polystyrene-converted value according to a gel permeation chromatography method, and can be measured by a commercially available apparatus. Further, each of Mw and Mn may be set in consideration of the aforementioned polydispersity, but usually Mw is about 20,000 to 60,000 ( It is preferably 30,000 to 50,000), and Mn is about 3,000 to 6,000 (preferably 4,000 to 5,000). Mw and Mn are, for example, a change in the amount of the component (A) or the component (C), or a change in the type or amount of the esterification catalyst, or a use of the (b-1) component in a polyfunctional group (for example, Butene acid (anhydride) modified rosin, etc.) to adjust.

Further, the other physical properties of the rosin-modified phenol resin are not particularly limited, but from the viewpoint of the efficacy of the present invention, the acid value (JIS K5601-2-1) is usually about 10 to 50 mgKOH/g. It is preferably 10 to 30 mgKOH/g.

Further, the softening point (JIS K5601-2-2) is also not particularly limited, but is usually about 140 to 190 ° C, preferably 150 to 180 ° C from the viewpoint of the efficacy of the present invention.

The varnish for ink according to the present invention contains the binder for ink according to the present invention (rosin-modified phenol resin) and vegetable oil, and may contain a petroleum solvent or a gelling agent as needed.

As vegetable oils, for example, in addition to vegetable oils such as linseed oil, tung oil, safflower oil, dehydrated castor oil, and soybean oil, For example, linseed oil fatty acid methyl ester, soybean oil fatty acid methyl ester, linseed oil fatty acid ethyl ester, soybean oil fatty acid ethyl ester, linseed oil A monoester of the aforementioned vegetable oil, such as fatty acid propyl ester, soybean oil fatty acid propyl ester, linseed oil fatty acid butyl ester, soybean oil fatty acid butyl ester or the like. These may be used alone or in combination of two or more. Among these, in view of the drying property of the printed matter, the vegetable oil, particularly a vegetable oil having an unsaturated bond in a molecule, is preferred.

Examples of the petroleum solvent for ink use include a petroleum solvent manufactured by JX Nippon Oil & Energy Corporation, a solvent No. 0, a solvent No. 4, a solvent No. 5, and a solvent No. 6. , No. 7 solvent, AF solvent No. 4, AF solvent No. 5, AF solvent No. 6, AF solvent No. 7, and the like. These may be used alone or in combination of two or more. In particular, when considering the solubility in the rosin-modified phenol resin of the present invention or the environmental influence, it is preferable that the boiling point is 200 ° C or higher and the content of the aromatic hydrocarbon is 1 Less than weight%.

Examples of the gelling agent include, for example, aluminum octoate, aluminum stearate, aluminum triisopropoxide, aluminum tributyl sulphate, dipropylene sulphate monoethyl decyl acetate, and dibutyl sulphate monoacetic acid acetic acid. An aluminum-based chelating agent such as ester or aluminum triacetate. These may be used alone or in combination of two or more.

The varnish for ink of the present invention can be produced by mixing and stirring the above components. Further, the temperature at the time of mixing and stirring is not particularly limited, and is preferably about 100 to 240 °C. Further, in addition to the varnish, an antioxidant or the like may be blended as an additive.

The ink of the present invention is formed by using the varnish for ink of the present invention, and blends the pigment (yellow, red, blue, black) and various conventional additives, such as a roll mill, a ball mill, and a vertical stirring. A conventional ink manufacturing apparatus such as an attritor or a sand mill is milled. Obtained by modulating into an appropriate ink constant. The additive may be, for example, a surfactant, a wax, or the like for improving the fluidity of the ink or the film on the surface of the ink.

"Embodiment"

Hereinafter, the present invention will be specifically described by way of Production Examples and Examples, but the scope of the present invention is not limited thereto. In addition, "parts" in the following are the parts by weight.

Further, in each case, the so-called "33% by weight of linseed oil viscosity" is a mixture of resin and linseed oil in a weight ratio of 1:2, and is used by Nippon Rheology Equipment Inc. Cone and plate type viscometer, the viscosity value obtained by measurement at 25 ° C (the same below).

In addition, any of the number average molecular weight and the weight average molecular weight is a gel permeation chromatography instrument (manufactured by Tosoh Corporation, HLC-8120GPC), and a commercially available column (East Soda) ) company-made, TSK-GEL), and tetrahydrofuran (THF) as a polystyrene-converted value measured by eluent, and the measured number average molecular weight and weight The amount-average molecular weight was calculated as a polydispersity (Mw/Mn) value.

[Manufacturing Example 1] (Manufacture of (C) component)

In a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 1,000 parts of octylphenol, 396 parts of 92% polyformaldehyde, 584 parts of xylene, and 500 parts of water were fed. The temperature was raised to 50 ° C with stirring. Then, in the same reaction vessel, 89 parts of a 45% sodium hydroxide solution was fed, and while the reaction system was slowly heated to 90 ° C while cooling, the temperature was kept for 2 hours, and sulfuric acid was further added dropwise to adjust the pH to About 6. Thereafter, the aqueous layer containing formaldehyde or the like was removed, washed again, and the contents were cooled to obtain a 70% by weight xylene solution of soluble octylphenol (C-1).

[Manufacturing Example 2] (Manufacture of (C) component)

In the same reaction vessel as in Production Example 1, 1,000 parts of butyl phenol, 543 parts of 92% polyacetal, 646 parts of xylene, and 500 parts of water were fed, and the temperature was raised to 50 ° C with stirring. Next, in the same reaction vessel, 89 parts of a 45% sodium hydroxide solution was fed, and while the reaction system was slowly heated to 90 ° C while cooling, the temperature was kept for 2 hours, and sulfuric acid was further added dropwise to adjust the pH to About 6. Thereafter, the aqueous layer containing formaldehyde or the like was removed, washed again, and the contents were cooled to obtain a 70% by weight xylene solution of soluble butylphenol (C-2).

[Manufacturing Example 3] (Manufacture of (C) component)

In the same reaction vessel as in Production Example 1, 1,000 parts of nonylphenol, 370 parts of 92% polyacetal, 573 parts of xylene, and 500 parts of water were fed, and the temperature was raised to 50 ° C with stirring. Next, in the same reaction vessel, 89 parts of a 45% sodium hydroxide solution was fed, and while the reaction system was slowly heated to 90 ° C while cooling, the temperature was kept for 2 hours, and sulfuric acid was further added dropwise to adjust the pH to About 6. Thereafter, the aqueous layer containing formaldehyde or the like was removed, washed again, and the contents were cooled to obtain a 70% by weight xylene solution of soluble nonylphenol (C-3).

[Example 1]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 0.7 part of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 500 parts of a solution of the component (C-1) (solid content: 350 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (1). Raw materials and physical properties are shown in Table 1 (the same below).

[Embodiment 2]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 500 parts of a solution of the component (C-1) (solid content: 350 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (2).

[Example 3]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 4.8 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 500 parts of a solution of the component (C-1) (solid content: 350 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (3).

[Example 4]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, a solution of (C-1) component 386 parts (solid content 270 parts), followed by a solution of (C-2) component 114 parts (solid content 80 parts), at 230 ~ 260 ° C The temperature range was added dropwise to the system over a period of 4 hours. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (4).

[Example 5]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Then, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 357 parts of the (C-1) component (250 parts solid content), followed by 143 parts of the (C-3) component (100 parts solid content) at a temperature of 230 to 260 ° C The range was added to the system in 4 hours. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (5).

[Embodiment 6]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Then, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite and 2.5 parts of calcium hydroxide were fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 614 parts of a solution of the component (C-1) (solid content: 430 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (6).

[Embodiment 7]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Then, 10 parts of maleic anhydride was added, and the temperature was raised to 220 ° C under stirring, and the temperature was kept for 1 hour to produce a maleic anhydride-modified rosin. Then, 93 parts of glycerin was added to the reaction system, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 614 parts of a solution of the component (C-1) (solid content: 430 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil. 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (7).

[Embodiment 8]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Then, 103 parts of neopentyl alcohol was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 500 parts of a solution of the component (C-1) (solid content: 350 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (8).

[Embodiment 9]

In the same reaction vessel as in Production Example 1, 1,000 parts of tall oil rosin was fed, and the mixture was heated to 180 ° C while stirring in a nitrogen atmosphere to be melted. Then, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 500 parts of a solution of the component (C-1) (solid content: 350 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (9). Raw materials and physical properties are shown in Table 1 (the same below).

[Embodiment 10]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Then, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 357 parts of a solution of the component (C-1) (solid content: 250 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (10). Raw materials and physical properties are shown in Table 1 (the same below).

[Example 11]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated while stirring to a temperature of 180 ° C in a nitrogen atmosphere to be melted. Then, 93 parts of glycerin was added, and the temperature was raised to 280 ° C with stirring. After the temperature was raised, 2.5 parts of triphenyl phosphite was fed and reacted until the acid value was 25 mgKOH/g or less. After further cooling to 230 ° C, 600 parts of a solution of the component (C-1) (solid content: 420 parts) was added dropwise to the system over a period of 4 hours in a temperature range of 230 to 260 °C. After the dropwise addition, the viscosity was adjusted to 33% by weight of linseed oil and the viscosity was 2.5Pa. s, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (11). Raw materials and physical properties are shown in Table 1 (the same below).

[Comparative Example 1]

In the same reaction vessel as in Production Example 1, 1,000 parts of gum rosin was fed, and the mixture was heated to 220 ° C with stirring to be melted. Then, 571 parts (400 parts of solid content) of the solution of the component (C-1) was added dropwise to the system over 4 hours. After completion of the dropwise addition, 84 parts of glycerin and 2.0 parts of p-toluenesulfonic acid were fed, and the reaction was carried out at a temperature of 220 to 260 ° C until the acid value was 25 or less. Thereafter, the pressure was reduced at 0.02 MPa for 10 minutes to obtain a rosin-modified phenol resin (1').

[Comparative Example 2]

In Example 2, the rosin-modified phenol resin (2') was obtained in the same manner except that the triphenyl phosphite was changed to 0.3 part.

[Comparative Example 3]

In the second embodiment, the rosin-modified phenol resin (3') was obtained in the same manner except that the amount of triphenyl phosphite was changed to 5.3 parts. However, since a large amount of insoluble matter was generated, physical properties were not measured.

[Comparative Example 4]

In Example 6, 5.0 parts of calcium hydroxide was changed to obtain a rosin-modified phenol resin (4').

[Comparative Example 5]

In Example 7, 50 parts of maleic anhydride was changed to obtain a rosin-modified phenol resin (5').

(Modulation of varnish)

45.0 parts of the rosin-modified phenol resin (1) of Example 1, 40.0 parts of linseed oil, and 43.5 parts of AF solvent No. 7 (manufactured by JX Nippon Oil and Energy Co., Ltd., non-aromatic petroleum solvent) were fed to the container. The mixture was mixed at 200 ° C for 30 minutes and then cooled to 80 ° C. Then, 1.5 parts of dipropylene oxide monoethyl decyl acetate (trade name: Chelope EP-2, manufactured by Hope Chemical Co., Ltd.) was added, and the mixture was heated to 200 ° C to carry out gelation. The reaction took 1 hour to obtain a gel varnish. Regarding the resins of the other examples and comparative examples, a gel varnish was also obtained in the same manner.

(modulation of ink)

Using the gel varnish of the foregoing examples and comparative examples, the ink was conditioned by grinding with a three-roll mill at the following blending ratio.

According to the above blending ratio, suitably prepared at 30 ° C, 400 rpm The ink value of the inkometer is 6.5 ± 0.5, and the flow value (diameter value) of the parallel plate at 25 ° C is 38.0 ± 1.0. .

(Performance test of ink)

The various properties of the inks prepared by using the gel varnishes of the examples and comparative examples were evaluated. The results are shown in Table 1.

(luster)

0.4 ml of ink was developed on an RI tester (Ishikawajima Industrial Machinery Co., Ltd.) on an art paper at 23 ° C, 50%. RH was conditioned for 24 hours, and a reflectance of 60 to 60 was measured with a glossmeter.

(fluidity)

In a room which was air-conditioned at 25 ° C, 1.3 ml of ink was placed on the end of the glass at an angle of 60 ° to the horizontal, and the distance which flowed in 30 minutes was measured. The larger the value, the better the fluidity.

In Table 1, TPP means triphenyl phosphite, gum Ro means gum rosin, tall oil Ro means tall oil rosin, MAn-Ro means maleic anhydride modified rosin, Gly means glycerin, and Pen means new pentylene Tetraol.

Claims (8)

A binder for printing ink obtained by using a rosin-modified phenol resin obtained by reacting a rosin ester (B) and a condensate (C) of phenol with formaldehyde, and The rosin ester (B) is obtained by esterifying the rosin (b-1) and the polyol (b-2) in the presence of the organophosphorus compound (A) represented by the formula (1). And the esterification is carried out under the condition that the amount of the component (A) is 0.05 to 0.5% by weight based on the component (b-1); the formula (1) is: (RO-) ₃ -P; In the formula (1), R represents an alkyl group having 1 to 12 carbon atoms or a phenyl group having an alkyl group having 1 to 12 carbon atoms; and the rosin-modified phenol resin is characterized by: (B) component and ( The amount of the component C), when the total amount is 100% by weight, is about 41 to 88% by weight and about 59 to 12% by weight, respectively; the weight average molecular weight Mw is 20,000 to 60,000, and the number average molecular weight Mn It is 3,000 to 4,940, and the polydispersity is also Mw/Mn of 7 to 9. The binder for ink according to claim 1, wherein the component (A) is triphenyl phosphite. The binder for ink according to claim 1 or 2, wherein the rosin-modified phenol resin has an acid value of 10 to 50 mgKOH/g. The binder for ink according to claim 1 or 2, wherein the rosin-modified phenol resin has a softening point of 140 to 190 °C. A varnish for inks containing the binder for ink according to any one of claims 1 to 4 and a vegetable oil. The varnish for ink according to claim 5, further comprising a petroleum solvent. The varnish for ink according to claim 5 or 6, further comprising a gelling agent. An ink obtained by using the varnish for ink according to claim 7.