JP5708946B2 - Printing ink binder, printing ink varnish and printing ink - Google Patents

Description

  The present invention relates to a printing ink binder using a rosin-modified phenolic resin, a printing ink resin varnish containing the printing ink binder, and a printing ink obtained using the varnish.

  A rosin-modified phenolic resin is generally a resin obtained by reacting rosins, phenolic resins, and polyols, and has long been used as a printing ink resin, for example, an offset printing ink resin (patents). References 1, 2 etc.).

  Offset printing ink is usually obtained by blending and mixing a pigment in a varnish obtained by dissolving such rosin-modified phenolic resin in an ink solvent. However, if the pigment is not sufficiently dispersed, the flowability of the printing ink is poor. Or the gloss of the printed material decreases. Therefore, it is conceivable to perform a mechanical dispersion process for a long time in order to sufficiently disperse the pigment, but this leads to a decrease in productivity.

  In addition, in the ink manufacturer, various additives have been studied for the purpose of supplementing the dispersing action of the rosin-modified phenol resin in the dispersing step. For example, Patent Document 3 uses a predetermined amount of a predetermined insoluble azo pigment composition or the like. This has been shown to improve the pigment dispersibility of the ink.

  On the other hand, attempts have been made to improve pigment dispersibility in terms of physical properties of rosin-modified phenolic resins. For example, as shown in Patent Document 4, the present applicant has a weight average molecular weight of 400 or less contained in rosin-modified phenolic resins. It has been found that the fluidity of the printing ink can be improved by limiting the amount of the low molecular component. However, further improvements are required.

JP-A-1-36668 JP-A-1-170676 JP-A-6-49386 JP 2009-227785 A

  The present invention provides a novel rosin-modified phenolic resin-based binder for printing ink that has good pigment dispersibility, can improve the fluidity of printing ink, and can impart excellent gloss to printed matter. Is the main purpose.

  The present inventor believes that the conventional rosin-modified phenolic resin has a large range in molecular weight distribution, which may cause insufficient binder performance, and in order to define the molecular weight distribution range, a predetermined phosphorus compound It was found that the desired rosin-modified phenolic resin can be obtained by using a certain amount of.

That is, in the present invention, rosins (b-1) and polyol (b-2) are used in the presence of triphenyl phosphite (A), and the amount of component (A) used relative to component (b-1) is 0. Weight average molecular weight (Mw) obtained by reacting rosin esters (B) obtained by esterification under the conditions of 0.5 to 0.5% by weight and a condensate (C) of phenols and formaldehyde. ) is 3 0,000～ 39,000, with number average molecular weight (Mn) is 3,000～4,940, and a polydispersity (Mw / Mn) is 8-9 rosin-modified phenolic resin The present invention relates to a printing ink binder comprising: a printing ink varnish containing the printing ink binder and vegetable oil; and a printing ink obtained using the printing ink varnish.

  In the printing ink binder of the present invention, the rosin-modified phenolic resin forming the binder is excellent in pigment dispersibility, so that the flowability of the printing ink is improved and the gloss of the printed matter is also improved. Therefore, the binder is particularly useful as a resin for offset printing ink, for example, a resin for offset printing ink such as offset sheet-fed ink (sheet-fed ink), offset rotary ink (off-wheel ink), and newspaper ink. It can also be used as a resin for letterpress printing inks and gravure printing inks. It can also be used as a pigment surface treatment agent.

The printing ink binder of the present invention comprises a rosin (b-1) (hereinafter referred to as component (b-1)) and a polyol (hereinafter referred to as component (b-1)) in the presence of triphenyl phosphite (A) (hereinafter referred to as component (A)). b-2) rosin esters (B) (hereinafter referred to as (B) component) obtained by esterification of (hereinafter referred to as (b-2) component), phenols and formaldehyde condensate (C) (hereinafter referred to as component (B-2)) , (C) component) and a rosin-modified phenolic resin obtained by reacting.

Component (A), available at ease, and desired effect (pigment dispersion of the present invention, printing ink fluidity refers to the gloss or the like of the printing ink film. Hereinafter, the term effects of the present invention likewise It is preferable because it is easy to achieve.

  Examples of the component (b-1) include natural rosins such as gum rosin, tall oil rosin, and wood rosin and purified products thereof (hereinafter referred to as raw rosins); polymerization rosins derived from raw rosins; raw rosins and polymerization Stabilized rosin obtained by disproportionating and / or hydrogenating rosin; raw material rosins and polymerized rosin, α of (meth) acrylic acid, fumaric acid, (anhydrous) itaconic acid, crotonic acid, cinnamic acid, etc. , Β-unsaturated acid-modified rosin obtained by Diels-Alder addition reaction of β-unsaturated carboxylic acids; stabilized rosin obtained by further disproportionation or hydrogenation of the α, β-unsaturated acid-modified rosin, etc. These can be used singly or in combination of two or more. 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. However, from the viewpoint of the effect of the present invention, the latter is usually 1 for 100 parts by weight of the former. It is the range which becomes about 30 weight part.

  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 known compounds can be used. Specifically, for example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, and neopentyl glycol, triols such as glycerin, trimethylolethane, and trimethylolpropane, and tetraols such as pentaerythritol, diglycerin, and ditrimethylolpropane. Examples include polyols having a valence of 6 or more such as all and dipentaerythritol, and these can be used alone or in combination of two or more. Of these, triols and / or tetraols are preferable from the viewpoint of easy control of physical properties (softening point, weight average molecular weight, etc.) of the rosin-modified phenolic resin of the present invention, and the effects of the present invention. .

  In this invention, it is necessary to use (A) component on the conditions used as 0.05 to 0.5 weight% with respect to (b-1) component. By setting it as 0.05 weight% or more, especially the fluidity | liquidity of printing ink and the glossiness of an ink film can be made favorable. In addition, by adjusting the content to 0.5% by weight or less, insoluble matters in the production of the rosin-modified phenolic resin of the present invention can be reduced, and among the effects of the present invention, particularly the fluidity of the printing ink and the ink film The gloss can be improved. From this viewpoint, the amount of component (A) used is preferably about 0.1 to 0.4% by weight, more preferably about 0.15 to 0.35% by weight, based on component (b-1). It is good.

  Although the usage-amount of (b-1) component and (b-2) component is not specifically limited, From the viewpoint of the effect of this invention, the total hydroxyl group equivalent number (OH) of (b-2) component and (b-1) The ratio (OH / COOH) to the total number of carboxyl group equivalents (COOH) of the component is usually in the range of about 0.5 to 1.5.

  As described above, the component (B) is obtained by subjecting the component (b-1) and the component (b-2) to an esterification reaction in the presence of a predetermined amount of the component (A). Although reaction conditions are not specifically limited, For example, (A) component, (b-1) component, and (b-2) component are charged to reaction container for every predetermined amount, and in the presence of various well-known catalysts as needed, 100 What is necessary is just to advance esterification reaction at about -300 degreeC 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, paratoluenesulfonic acid and dodecylbenzenesulfonic acid; metal oxides such as zinc oxide, magnesium oxide and calcium oxide; magnesium hydroxide, Examples thereof include metal hydroxides such as calcium hydroxide; and acetates such as calcium acetate, magnesium acetate, and zinc acetate. These can be used alone or in combination of two or more. The amount used is not particularly limited, but for the purpose of achieving the polydispersity described later, it is usually about 0 to 5% by weight with respect to the total amount of the components (b-1) and (b-2). It is desirable that

  As the component (C), various known products such as a resol type phenol resin and a novolak type phenol resin can be used as long as they are condensates of phenols and formaldehyde.

  Examples of phenols include carboxylic acid, cresol, amylphenol, bisphenol A, butylphenol, octylphenol, nonylphenol, and dodecylphenol. Examples of formaldehyde include formalin and paraformaldehyde.

  In addition, as the resol type phenolic resin, phenols (P) and formaldehyde (F) are added in the range where F / P (molar ratio) is usually about 1 to 3 in the presence of various basic catalysts. -Condensates obtained by condensation reaction are mentioned. Examples of the novolak type phenol resin include condensates obtained by addition / condensation reaction in the presence of various acid catalysts within a range where F / P is usually about 0.5 to 2. Each condensate may be neutralized and washed with water. Each condensate can be produced in the presence of water or an organic solvent (such as xylene). As the component (C), from the viewpoint of increasing the molecular weight of the rosin-modified phenol resin and the effect of the present invention (from the viewpoint of the above), the resol-type phenol resin is preferable. The thing similar to what was used when manufacturing a component can be used.

  (B) The usage-amount of a component and (C) component is not specifically limited, What is necessary is just to determine suitably according to a use, respectively, However, from the viewpoint of the effect of this invention, the sum total of both was normally 100 weight%. In some cases, the order 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, and more preferably 67 to 77% by weight and 33 to 23%. % By weight.

  Further, the reaction conditions for the component (B) and the component (C) are not particularly limited. For example, both components are charged into a reaction vessel in predetermined amounts, and if necessary, in the presence of various known catalysts, about 200 to 300 ° C. For about 1 to 20 hours. As the catalyst, those described above can be used.

Rosin-modified phenolic resin of the present invention thus obtained is, from the viewpoint of the effect of the present invention, the weight average molecular weight (Mw) was 3 0,000～ 39,000, number average molecular weight (Mn) of 3, 000 to 4,940, and the polydispersity (Mw / Mn) is set to 8 to 9, which is a great feature. The polydispersity is an index indicating the molecular weight distribution width, and the rosin-modified phenolic resin of the present invention has a relatively small numerical value, so that it can be said that the molecular weight distribution width is narrow. When the polydispersity is 8 or more, the gloss of the printing ink film is particularly good, and when it is 9 or less, the fluidity of the printing ink and the gloss of the printing ink film are particularly good.

In addition, both Mw and Mn are polystyrene conversion values by a gel permeation chromatography method, and can be measured by a commercially available apparatus . Mw and Mn are, for example, change the amount of the component (A) or component (C), change the type or amount of the esterification catalyst, or (b-1) a polyfunctional one (for example, , (Anhydrous) maleic acid modified rosin, etc.).

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

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

  The varnish for printing ink of the present invention contains the binder for printing ink of the present invention (rosin-modified phenol resin) and vegetable oils, and can contain a petroleum solvent or a gelling agent as necessary.

  Examples of vegetable oils include vegetable oils such as linseed oil, tung oil, safflower oil, dehydrated castor oil, soybean oil, linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil Examples include monoesters of the above vegetable oils such as fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, and the like, and these can be used alone or in combination of two or more. Among these, considering the drying property of the printed matter, the vegetable oil, particularly the vegetable oil having an unsaturated bond in the molecule is preferable.

  As the petroleum solvent for ink, for example, No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent No. 4, which are petroleum solvents manufactured by JX Nippon Oil & Energy Corporation, Examples include AF solvent No. 5, AF solvent No. 6, AF solvent No. 7, and the like. These can be used alone or in combination of two or more. Among these, in consideration of the solubility of the rosin-modified phenolic resin of the present invention and the influence on the environment, those having a boiling point of 200 ° C. or higher and an aromatic hydrocarbon content of 1% by weight or less are preferable.

  Examples of the gelling agent include aluminum chelates such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. An agent is mentioned, These can be used individually by 1 type or in combination of 2 or more types.

  The printing ink varnish of the present invention can be produced by mixing and stirring the above-described components. The temperature during mixing and stirring is not particularly limited, but is preferably about 100 to 240 ° C. In addition, an antioxidant etc. can be mix | blended with this varnish as an additive.

  The printing ink of the present invention uses the varnish for printing ink of the present invention, and is blended with pigments (yellow, red, indigo, black) and various known additives, roll mill, ball mill, attritor, sand mill. It is obtained by kneading and preparing so as to obtain an appropriate ink constant using a known ink manufacturing apparatus. Examples of the additive include a surfactant for improving ink fluidity and an ink surface film, and wax.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the scope of the present invention is not limited by these examples. Hereinafter, “parts” means parts by weight.

  In each example, the 33% by weight linseed oil viscosity is 25 by using a cone and plate viscometer manufactured by Nippon Rheology Co., Ltd. It is the viscosity measured at ° C. (hereinafter the same).

  The number average molecular weight and the weight average molecular weight are both gel permeation chromatography (manufactured by Tosoh Corporation, HLC-8120GPC) and a commercially available column (manufactured by Tosoh Corporation, TSK-GEL) and tetrahydrofuran (THF). ) As a developing solvent, and the polydispersity (Mw / Mn) was calculated from the obtained number average molecular weight and weight average molecular weight.

Production Example 1
(Production of component (C))
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1,000 parts of octylphenol, 396 parts of 92% paraformaldehyde, 584 parts of xylene and 500 parts of water, and the temperature was raised to 50 ° C. with stirring. Warm up. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed to 90 ° C. while cooling, and then kept warm for 2 hours, and sulfuric acid was added dropwise to adjust the pH to about 6. did. Thereafter, the aqueous layer containing formaldehyde and the like was removed, washed again with water, and then the contents were cooled to obtain a 70% by weight xylene solution of resol type octylphenol (C-1).

Production Example 2
(Production of component (C))
A reaction vessel similar to Production Example 1 was charged with 1,000 parts of butylphenol, 543 parts of 92% paraformaldehyde, 646 parts of xylene and 500 parts of water, and the temperature was raised to 50 ° C. with stirring. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed to 90 ° C. while cooling, and then kept warm for 2 hours, and sulfuric acid was added dropwise to adjust the pH to about 6. did. Thereafter, the aqueous layer portion containing formaldehyde and the like was removed, and after washing with water again, the contents were cooled to obtain a 70% by weight xylene solution of resol type butylphenol (C-2).

Production Example 3
(Production of component (C))
A reaction vessel similar to Production Example 1 was charged with 1,000 parts of nonylphenol, 370 parts of 92% paraformaldehyde, 573 parts of xylene and 500 parts of water, and the temperature was raised to 50 ° C. with stirring. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, the reaction system was gradually warmed to 90 ° C. while cooling, and then kept warm for 2 hours, and sulfuric acid was added dropwise to adjust the pH to about 6. did. Thereafter, the aqueous layer containing formaldehyde and the like was removed, washed again with water, and then the contents were cooled to obtain a 70% by weight xylene solution of resol type nonylphenol (C-3).

Reference example 1
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 0.7 part of triphenyl phosphite was added and the reaction was continued until the acid value was 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenolic resin (1) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).

Reference example 2
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of dropping, the rosin-modified phenol resin (2) was obtained by adjusting the viscosity of linseed oil at 33 wt% to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.

Reference example 3
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After the temperature elevation, 4.8 parts of triphenyl phosphite was charged and reacted until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenolic resin (3) was obtained by adjusting the 33% by weight linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.

Reference example 4
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 386 parts of the component (C-1) solution (solid content 270 parts), and then 114 parts of the component (C-2) solution (solid content 80 parts) were in the temperature range of 230 to 260 ° C. The solution was dropped into the system over 4 hours. After completion of the dropwise addition, the rosin-modified phenolic resin (4) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.

Reference example 5
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 357 parts (solid content 250 parts) of the component (C-1), and then 143 parts (solid content 100 parts) of the component (C-3) are in the temperature range of 230 to 260 ° C. The solution was dropped into the system over 4 hours. After completion of the dropwise addition, the rosin-modified phenolic resin (5) was obtained by adjusting the 33% by weight linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.

Reference example 6
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 103 parts of pentalysitol was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenol resin (8) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes.

Example 1
In a reaction vessel similar to Production Example 1, 1,000 parts of tall oil rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. Furthermore, after cooling to 230 degreeC, 500 parts (350 parts of solid content) of the solution of (C-1) component was dripped in the system over 4 hours within the temperature range of 230-260 degreeC. After completion of the dropwise addition, the rosin-modified phenol resin (9) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).

Example 2
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 357 parts (solid content 250 parts) of the component (C-1) was dropped into the system over 4 hours within a temperature range of 230 to 260 ° C. After completion of the dropwise addition, the rosin-modified phenolic resin (10) was obtained by adjusting the 33 wt% linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).

Reference example 7
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged, and the mixture was heated to 180 ° C. and stirred while stirring in a nitrogen atmosphere. Next, 93 parts of glycerin was added, and the temperature was raised to 280 ° C. with stirring. After raising the temperature, 2.5 parts of triphenyl phosphite was added and allowed to react until the acid value became 25 mgKOH / g or less. After further cooling to 230 ° C., 600 parts (component 420 parts) of component (C-1) was dropped into the system over a period of 4 hours within a temperature range of 230 to 260 ° C. After completion of the dropwise addition, the rosin-modified phenolic resin (11) was obtained by adjusting the 33% by weight linseed oil viscosity to 2.5 Pa · s and reducing the pressure at 0.02 MPa for 10 minutes. The raw materials and physical properties are shown in Table 1 (the same applies hereinafter).

Comparative Example 1
In a reaction vessel similar to Production Example 1, 1,000 parts of gum rosin were charged and heated to 220 ° C. with melting to be melted. Subsequently, 571 parts (400 parts of solid content) of the component (C-1) was dropped into the system over 4 hours. After completion of the dropwise addition, 84 parts of glycerin and 2.0 parts of paratoluenesulfonic acid were added and reacted until the acid value became 25 or less within a temperature range of 220 to 260 ° C. Then, rosin modified phenolic resin (1 ′) was obtained by reducing the pressure at 0.02 MPa for 10 minutes.

Comparative Example 2
A rosin-modified phenolic resin (2 ′) was obtained in the same manner as in Example 2, except that triphenyl phosphite was changed to 0.3 part.

Comparative Example 3
In Example 2, except that triphenyl phosphite was changed to 5.3 parts, a rosin-modified phenol resin (3 ′) was obtained in the same manner. However, since a large amount of insoluble matter was generated, the physical properties were measured. There wasn't.

(Preparation of varnish)
45.0 parts of rosin-modified phenolic resin (1) of Example 1, 10.0 parts of linseed oil, AF Solvent No. 7 (manufactured by JX Nippon Oil & Energy Corporation, non-aromatic petroleum solvent) 43. 5 parts were charged into a container, mixed at 200 ° C. for 30 minutes, and then cooled to 80 ° C. Subsequently, 1.5 parts of aluminum dipropoxide monoacetylacetate (trade name Kerop EP-2, manufactured by Hope Pharmaceutical Co., Ltd.) was added, and the gel varnish was obtained by heating to 200 ° C. and allowing the gelation reaction for 1 hour. . Gel varnishes were obtained in the same manner for the resins of other examples and comparative examples.

(Preparation of printing ink)
Using the gel varnishes of the examples and comparative examples, printing ink was prepared by kneading with a three roll mill at the following blending ratio.
18 parts by weight of phthalocyanine blue (indigo pigment)
Gel Varnish 62-70 parts by weight Nisseki AF Solvent No. 7 12-20 parts by weight Based on the above formulation, the incometer tack value at 30 ° C. and 400 rpm is 6.5 ± 0.5, and the flow value of the spread meter at 25 ° C. ( (Diameter value) was appropriately adjusted to be 38.0 ± 1.0.

(Performance test of printing ink)
Various performances of printing inks prepared using the gel varnishes of Examples and Comparative Examples were evaluated. The results are shown in Table 1.

(Glossy)
After 0.4 ml of ink was developed on art paper using an RI tester (manufactured by Ishikawajima Industrial Machinery Co., Ltd.), 23 ° C., 50% R.D. H. For 24 hours, and the reflectivity of 60 ° -60 ° was measured with a gloss meter.

(Liquidity)
In a room air-conditioned at 25 ° C., 1.3 ml of ink was placed on the upper end of a glass plate forming an angle of 60 ° with the ground plane, and the distance of flowing for 30 minutes was measured. It shows that fluidity | liquidity is so favorable that a numerical value is large.

  In Table 1, TPP represents triphenyl phosphite, gum Ro represents gum rosin, tall oil Ro represents tall oil rosin, MAn-Ro represents maleic anhydride-modified rosin, Gly represents glycerin, and Pen represents pentaerythritol. .

Claims (7)

In the presence of triphenyl phosphite (A), rosins (b-1) and polyol (b-2) are used in an amount of 0.05 to 0.5 weight of component (A) relative to component (b-1). % and comprising rosin esters obtained by esterification conditions (B), and is obtained by reacting a condensate of phenol and formaldehyde (C), the weight average molecular weight (Mw) 3 0,000 ~ is 39,000, the number average molecular weight (Mn) is 3,000～4,940, and polydispersity (Mw / Mn) of the printing ink binder comprising using a 8-9 rosin-modified phenolic resin . The binder for printing inks of Claim 1 whose acid value of the said rosin modified phenol resin is 10-50 mgKOH / g. The binder for printing inks of Claim 1 or 2 whose softening point of the said rosin modified phenolic resin is 140-190 degreeC. The varnish for printing inks containing the binder for printing inks in any one of Claims 1-3, and vegetable oil. Furthermore, the varnish for printing inks of Claim 4 containing a petroleum solvent. Furthermore, the varnish for printing inks of Claim 4 or 5 containing a gelatinizer. Printing ink obtained by using the varnish for printing ink according to claim 6.