JP2015110750A - Rosin-modified phenolic resin, binder for offset printing ink, varnish for offset printing ink, and offset printing ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rosin-modified phenolic resin that can achieve both of fluidity and setting property of an offset printing ink, particularly an ink using a black pigment, when used as a binder for an offset printing ink, and that contributes to carbon neutrality.SOLUTION: The rosin-modified phenolic resin is obtained by the reaction of rosin (A), a cardanol (B) containing substantially no phosphorus, (C) a phenol excluding (B) component, formaldehyde (D), triol (E), and a divalent metal oxide and/or a divalent metal hydroxide (F), in which a weight ratio [(B)/(C)] of (B) component to (C) component ranges from 100/0 to 10/90.

Description

  The present invention relates to a rosin-modified phenol resin that contributes to carbon neutral, a binder for offset printing ink, a varnish for offset printing ink, and an offset printing ink using the same.

  Global warming due to an increase in the concentration of carbon dioxide in the atmosphere is a serious problem, and various approaches for suppressing carbon dioxide emissions have been proposed. Among them, in recent years, the idea of “carbon neutral” has permeated, and efforts to actively utilize plant-derived raw materials for various industrial products have become active.

  On the other hand, rosin-modified phenolic resin is a high-molecular-weight polymer mainly composed of rosin, alkylphenol, formaldehyde and polyol, which dissolves in various printing ink solvents and exhibits excellent printability. It is used as an ink binder.

  From the viewpoint of carbon neutral, the rosin-modified phenolic resin is carbon neutralized in that plant-derived rosin is used as a main raw material, but there is a problem in that alkylphenol is a petroleum-derived raw material.

  Therefore, as an alternative resin not using alkylphenol as a raw material, rosin polyester resins using rosin, various aliphatic compounds (fatty acids, aliphatic polybasic acids, etc.) and polyol as raw materials have been proposed (see Patent Documents 1 and 2). reference.). However, since this is inferior in wettability to pigments, particularly black pigments such as carbon black, compared to rosin-modified phenolic resins, the fluidity of offset printing inks using black pigments is likely to be impaired. In addition, offset printing ink using black pigment dries quickly and accumulates on the printing press, and may cause various printing troubles, so that an optimum setting property (drying property) is also required.

  In view of the above, there is a current situation in which rosin-modified phenolic resin must be used to ensure the fluidity of the offset printing ink.

  In order to achieve both flowability and setability of offset printing ink using rosin-modified phenolic resin, it is known that the content of phenol component in the printing ink should be limited to a predetermined range (patent Reference 3)), the effect was not sufficient, and it did not contribute to the carbon neutralization.

  In this field, a dispersant such as gilsonite (see Patent Document 4) or a surfactant is often used in combination to improve the fluidity of offset printing ink using a black pigment, but the dispersion effect is strong. Depending on the amount added, various emulsification problems may be induced on the printing press.

JP 2001-139670 A JP 2003-41157 A JP 2006-273379 A Japanese Patent Laying-Open No. 2003-41157 (see paragraphs [0002] and [0003])

  The present invention, when used as a binder for printing ink, has a dispersion effect comparable to various dispersants, and can achieve both fluidity and setability of offset printing ink (especially offset printing ink using black pigment). In addition, an object is to provide a novel rosin-modified phenolic resin that contributes to carbon neutralization.

  As a result of intensive studies, the present inventor has found that the above problem can be solved by using a rosin-modified phenol resin using a specific plant-derived phenol.

  That is, the present invention relates to rosin (A), cardanol (B) substantially free of phosphorus, phenol (C) other than component (B), formaldehyde (D), triol (E), and divalent metal oxide. And / or the divalent metal hydroxide (F) reacts, and the weight ratio [(B) / (C)] of the component (B) to the component (C) is 100/0 to 10/90. Rosin-modified phenolic resin, offset printing ink binder using the rosin-modified phenolic resin, offset printing ink varnish obtained using the offset printing ink binder, and offset printing ink varnish It is related with the offset printing ink obtained using this.

  Since the rosin-modified phenol resin of the present invention uses cardanol, which is a plant-derived phenol component, it contributes to carbon neutralization. In addition, the dispersing action of pigments, particularly black pigments, is comparable to various dispersants, and it is possible to achieve both fluidity and setability of offset printing inks, particularly offset printing inks using black pigments.

  Therefore, the rosin-modified phenolic resin is useful as a raw material for a binder for offset printing ink, a varnish for offset printing ink, and offset printing ink (sheet-fed ink, off-wheel ink, particularly newspaper ink). It is also suitable as a resin for letterpress printing ink and a resin for gravure printing ink.

  The rosin-modified phenolic resin of the present invention comprises rosin (A) (hereinafter also referred to as (A) component), cardanol (B) substantially free of phosphorus (hereinafter also referred to as (B) component), (B). ) Alkylphenol (C) other than the component (hereinafter also referred to as the (C) component), formaldehyde (D) (hereinafter also referred to as the (D) component), and triol (E) (hereinafter also referred to as the (E) component). ), And divalent metal oxide and / or divalent metal hydroxide (F) (hereinafter also referred to as component (F)) are used as reaction components.

  As the component (A), various known rosins or derivatives thereof can be used. Examples of the rosin include natural rosins such as gum rosin, tall oil rosin and wood rosin. Examples of the rosin derivative include polymerized rosin and unsaturated carboxylic acid-modified rosin. These may be used alone or in combination of two or more. Examples of the unsaturated carboxylic acid include unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, and fumaric acid, and unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid. The amount is usually about 1 to 30 parts by weight with respect to 100 parts by weight. Among these, tall oil rosin is preferable from the viewpoint of the balance between fluidity and setability of the printing ink.

  Cardanol, which is component (B), is an alkenylphenol derived from cashew nut shell and is generally a mixture of a plurality of compounds represented by the following structural formula. What was made into a composition can also be used.

  Moreover, in this invention, what hydrogenated cardanol (henceforth hydrogenated cardanol) can also be used as (B) component. As such a thing, 3-pentadecyl phenol is mentioned, for example.

  Although the reason is not clear, rosin-modified phenolic resin obtained by using phosphorus-containing cardanol tends to generate insolubles. Therefore, in the present invention, cardanol which does not substantially contain phosphorus as component (B) is used. Is used. The phrase “substantially does not contain phosphorus” means that when the component (B) is subjected to fluorescent X-ray analysis, the phosphorus content is below the detection limit.

  As the component (C), various known phenols (excluding those corresponding to the component (B)) can be used without any particular limitation. Specifically, for example, phenol (coal acid); methylphenol (cresol), ethylphenol, propylphenol, amylphenol, butylphenol, octylphenol, nonylphenol, dodecylphenol, tetradecylphenol and other alkylphenols; phenylphenol, cumylphenol, etc. These arylphenols and the like may be used, and these may be used alone or in combination of two or more. Among these, alkylphenols having at least one alkyl group having about 8 to 12 carbon atoms in the molecule are particularly preferred from the viewpoint of the balance between the fluidity and setability of the printing ink.

  Examples of the formaldehyde as the component (D) include formalin and paraformaldehyde.

  Examples of the component (E) include various known triols such as glycerin, trimethylolethane, trimethylolpropane, and glycerin is particularly preferable. These may be used alone or in combination of two or more. In addition, although glycerol may be derived from petroleum raw materials, it is preferable that it is natural glycerol derived from fats and oils, such as a coconut, from a carbon neutral viewpoint.

  In addition to the component (E), other polyols can be used in combination. Specifically, for example, diols such as triethylene glycol, diethylene glycol, ethylene glycol and neopentyl glycol, tetraols such as pentaerythritol, diglycerin and ditrimethylolpropane, and pentavalent or higher polyols such as dipentaerythritol. These may be used alone or in combination of two or more. Further, as the other polyol, the tetraol is particularly preferable, pentaerythritol and / or diglycerin. Further, the amount of the other polyol used is not particularly limited, but from the viewpoint of the balance between the flowability and the setability of the printing ink, when the total amount with the component (E) is 100% by weight, it is usually less than 50% by weight. Is preferred.

  The rosin-modified phenolic resin of the present invention is obtained by reacting the (A) component, the (B) component, the (C) component, the (D) component, and the (E) component, and the reaction order is not particularly limited. For example, a method of reacting all the components at once; a method of reacting the component (A) with the components (B), (C) and (D), and then reacting the component (E); ) Component, (C) component and (D) component are reacted once to obtain a phenol-formaldehyde condensate, and this is reacted with the (A) component and (E) component. Moreover, the addition position of the (F) component used as needed is not specifically limited. Also, the reaction temperature and reaction time are not particularly limited, and are usually about 100 to 300 ° C. and about 1 to 24 hours. In the reaction, alkali catalysts such as sodium hydroxide and potassium hydroxide; acetates such as calcium acetate, magnesium acetate and zinc acetate can be used as the catalyst, and these may be used alone. You may combine seeds or more. Note that when only other polyols such as tetraol are used instead of the component (E), insoluble matters are generated in the rosin-modified phenol resin, making it difficult to achieve both the fluidity and the setability of the printing ink.

  As the component (F), various known divalent metal compounds can be used without particular limitation. Specific examples include various known divalent metal oxides and / or divalent metal hydroxides. The former includes magnesium oxide and calcium oxide, and the latter includes magnesium hydroxide and calcium hydroxide. It can be illustrated. These may be used alone or in combination of two or more.

  The rosin-modified phenolic resin of the present invention is obtained by reacting the (A) component, the (B) component, the (C) component, the (D) component, and the (E) component, and the reaction order is not particularly limited. For example, a method of reacting all the components at once; a method of reacting the component (A) with the components (B), (C) and (D), and then reacting the component (E); ) Component, (C) component and (D) component are reacted once to obtain a phenol-formaldehyde condensate, and this is reacted with the (A) component and (E) component. Moreover, the addition position of the (F) component used as needed is not specifically limited. Also, the reaction temperature and reaction time are not particularly limited, and are usually about 100 to 300 ° C. and about 1 to 24 hours. In the reaction, alkali catalysts such as sodium hydroxide and potassium hydroxide; acetates such as calcium acetate, magnesium acetate and zinc acetate can be used as the catalyst, and these may be used alone. You may combine seeds or more.

  The phenol-formaldehyde condensate can be produced by various known methods. Specifically, when the number of moles of the phenol component (component (B), component (C)) is P and the number of moles of the component (D) is F, F / P (molar ratio) is usually 1 to 3. The reaction can be carried out in the presence of various known catalysts within the range, and a resol type phenol resin can be obtained by using, for example, the divalent metal compound such as sodium hydroxide or potassium hydroxide as an alkali catalyst. . Moreover, when the said acid catalyst is used, a novolak-type phenol resin is obtained. The reaction may be performed in the presence of water or an organic solvent (such as xylene). Moreover, the obtained condensate may be further neutralized and washed with water if necessary.

  The amount of the component (A), the component (B), the component (C), the component (D) and the component (E), and the amount of the component (F) used as necessary is not particularly limited. is there.

<When not using the phenol-formaldehyde condensate>
Component (A): about 41 to 88% by weight, preferably about 46 to 74% by weight Component (B) and component (C): about 6 to 43% by weight, preferably about 14 to 39% by weight (D) Component: About 2 to 19% by weight, preferably about 3 to 17% by weight (E) component: about 3 to 9% by weight, preferably about 4 to 8% by weight (F) component: (A) component to (E) component Usually about 0.05 to 5% by weight, preferably about 0.05 to 3% by weight, based on the total of 100% by weight

<When using the phenol-formaldehyde condensate>
Component (A): about 41 to 88% by weight, preferably about 46 to 74% by weight Condensate obtained from component (B), (C) and (D): about 9 to 50% by weight, preferably 22 About 46% by weight (E) component: about 3 to 9% by weight, preferably about 4 to 8% by weight (F) component: (A) component to (E) component, usually 0 0.05 to 5% by weight, preferably 0.05 to 3% by weight

  In the present invention, the weight ratio of the component (B) to the component (C) [(B) / (C)] is set to 100/0 from the viewpoint of maintaining the setability while enhancing the fluidity of the printing ink. It is necessary to limit to about 10/90, preferably about 100/0 to 50/50, and more preferably about 100/0 to 80/20.

  By setting the acid value, weight average molecular weight, and softening point of the rosin-modified phenolic resin of the present invention within the ranges described below, it becomes easy to achieve both fluidity and setability of the printing ink. From this point of view, the rosin-modified phenolic resin is composed of the total carboxyl group equivalent number (COOH) of the component (A) and the total hydroxyl group equivalent number (OH) of the components (B), (C) and (E). The ratio [OH / COOH] is usually in the range of about 0.5 to 1.5, preferably about 0.5 to 1.2.

  The physical properties of the rosin-modified phenolic resin of the present invention thus obtained are not particularly limited, but the softening point is usually about 100 to 160 ° C. (preferably about 110 to 160 ° C.) from the viewpoint of the balance between the fluidity and the setability of the printing ink. The weight average molecular weight should be about 10,000 to 200,000 (preferably about 15,000 to 150,000), and the acid value should be about 10 to 20 mgKOH / g.

  The rosin-modified phenolic resin of the present invention can be used for various applications, but is useful as a binder for printing ink, particularly as a binder for offset printing ink.

  The varnish for offset printing ink of the present invention contains the rosin-modified phenolic resin of the present invention and the printing ink solvent.

  Examples of printing ink solvents include various known vegetable oils and / or petroleum solvents.

  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 fatty acid And monoesters of the vegetable oils such as propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl and the like. Moreover, these may be used independently and may combine 2 or more types. In these, the vegetable oil which has an unsaturated bond in a molecule | numerator from the point of the drying property of printed matter is preferable.

  As the petroleum solvent, a conventionally known petroleum solvent for ink can be used without particular limitation. Specifically, for example, No. 0 Solvent, No. 4, Solvent No. 5, Solvent No. 6, Solvent No. 7, Solvent No. 7, AF Solvent No. 4, AF Solvent No. 5 are petroleum solvents manufactured by JX Nippon Oil & Energy Corporation. No., AF Solvent No. 6, AF Solvent No. 7 and the like. Moreover, these may be used independently and may combine 2 or more types. In particular, from the viewpoint of environmental measures, it is preferable to use a solvent having a boiling point of 200 ° C. or more and an aromatic hydrocarbon content of 1% by weight or less, more preferably a printing ink produced by replacing the petroleum solvent for ink with the vegetable oil. .

  The varnish for offset printing ink of the present invention can further contain various known gelling agents. Specifically, for example, aluminum chelates such as aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, aluminum triacetyl acetate, etc. And polyisocyanates such as isophorone diisocyanate and trimethylhexamethylene diisocyanate.

  The content of each component in the varnish for offset printing ink of the present invention is not particularly limited. Usually, the rosin-modified phenolic resin of the present invention is about 30 to 50% by weight, and the ink solvent is 49 to 68% by weight. The gelling agent is about 0.2 to 2% by weight.

  The varnish for offset printing ink of the present invention can be obtained by heat-mixing the rosin-modified phenolic resin of the present invention and, if necessary, the gelling agent in the solvent for printing ink. Although heating temperature is not specifically limited, Usually, it is about 100-240 degreeC.

  The offset printing ink of the present invention contains the varnish for offset printing ink of the present invention and a pigment.

  Examples of pigments include inorganic pigments such as yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina white, calcium carbonate, ultramarine, graphite, aluminum powder, and carbon black (black pigment). Organic pigments such as azo pigments and phthalocyanine pigments. Among these, printing inks using inorganic pigments, especially black ink pigments, exhibit excellent fluidity and good setting properties. Moreover, although the usage-amount of a pigment is not specifically limited, It is about 5 to 30 weight% normally with respect to the whole quantity of the offset printing ink of this invention.

  The offset printing ink of the present invention is a known varnish and pigment for the offset printing ink of the present invention and, if necessary, an additive for ink (surfactant, wax, etc.) such as a roll mill, a ball mill, an attritor, and a sand mill. It can be obtained by kneading and preparing an appropriate ink constant using an ink production apparatus.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but the present invention is not limited thereto.

  Hereinafter, “parts” means parts by weight. The “acid value” and “softening point” are both measured according to JIS K5601. The “33 wt% linseed oil viscosity” refers to a viscosity measured by using a Gardner standard solution obtained by heating and mixing a resin and linseed oil at a ratio of 1 to 2 by weight. The “weight average molecular weight” is a commercially available gel permeation chromatography apparatus (HLC-8220GPC manufactured by Tosoh Corporation), a commercially available column (TSK-GEL column manufactured by Tosoh Corporation), and tetrahydrofuran as a developing solvent. Measured in terms of polystyrene. The phosphorus content in cardanol was measured using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, ZSX100e).

Production Example 1
In a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, 500 parts of hydrogenated cardanol (trade name “NC-510”, manufactured by Cardolite, phosphorus is not detected in fluorescent X-ray measurement). , P-octylphenol 500 parts, 92% paraformaldehyde 340 parts, xylene 574 parts and water 500 parts were charged, 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, and the temperature of the reaction system was gradually raised to 90 ° C. while cooling, and then kept warm for 1 hour, and sulfuric acid was added dropwise to adjust the pH to around 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 a resol type hydrogenated cardanol / octylphenol resin.

Production Example 2
In a reaction container similar to Production Example 1, 100 parts of cardanol (trade name “NX-2021”, manufactured by Cardolite, phosphorous was not detected in fluorescent X-ray measurement. Hereinafter, simply referred to as cardanol (NX-2021)). , 900 parts of p-octylphenol, 383 parts of 92% paraformaldehyde, 563 parts of xylene and 500 parts of water were charged and heated to 50 ° C. with stirring. Next, 89 parts of 45% sodium hydroxide solution was charged into the same reaction vessel, and the temperature of the reaction system was gradually raised to 90 ° C. while cooling, and then kept warm for 1 hour, and sulfuric acid was added dropwise to adjust the pH to around 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 resole-type cardanol / octylphenol resin.

Production Example 3
In the same manner as in Production Example 2, except that 100 parts of cardanol (NX-2021) was changed to 50 parts and 900 parts of p-octylphenol were changed to 950 parts, a 70% by weight xylene solution of resol type octylphenol / cardanol resin was obtained. It was.

Example 1
A reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer was charged with 1000 parts of Chinese gum rosin and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 2 parts of magnesium oxide were added, the temperature was raised to 230 ° C. with stirring, and 857 parts of a 70 wt% xylene solution of resole-type hydrogenated cardanol / octylphenol resin of Production Example 1 (solid content 600 parts) was added dropwise at 230 ° C. did. Thereafter, 74 parts of glycerin and 25 parts of diglycerin were charged and reacted at 230 to 270 ° C. to adjust the acid value to 25 mg KOH / g and the 33 wt% linseed oil viscosity to be Z to Z-4. The contents were taken out under reduced pressure at 02 MPa for 10 minutes. Table 1 shows the physical properties of the rosin-modified phenol resin thus obtained.

Example 2
In a reaction vessel similar to that in Example 1, 1000 parts of Chinese gum rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 3 parts of calcium hydroxide was added, the temperature was raised to 230 ° C. with stirring, and 714 parts (solid content 500 parts) of a 70 wt% xylene solution of resole-type cardanol / octylphenol resin of Production Example 2 was added dropwise at 230 ° C. . Thereafter, 93 parts of glycerin was charged, reacted at 230 to 270 ° C., adjusted so that the acid value was 25 mg KOH / g and the 33 wt% linseed oil viscosity was Z to Z-4, and the pressure was reduced at 0.02 MPa for 10 minutes. The contents were removed. Table 1 shows the physical properties of the rosin-modified phenol resin thus obtained.

Example 3
In a reaction vessel similar to that in Example 1, 1000 parts of Chinese gum rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Subsequently, 500 parts of cardanol (NX-2021), 136 parts of 92% paraformaldehyde, and 3 parts of calcium hydroxide were charged and reacted at 120 ° C. to 230 ° C. with stirring. Thereafter, 93 parts of glycerin was charged, reacted at 230 to 270 ° C., adjusted so that the acid value was 25 mg KOH / g and the 33 wt% linseed oil viscosity was Z to Z-4, and the pressure was reduced at 0.02 MPa for 10 minutes. The contents were removed. Table 1 shows the physical properties of the rosin-modified phenol resin thus obtained.

Example 4
In a reaction vessel similar to that in Example 1, 1000 parts of Chinese gum rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Subsequently, 250 parts of cardanol (NX-2021), 218 parts of p-dodecylphenol, 136 parts of 92% paraformaldehyde, and 2 parts of magnesium hydroxide were charged and reacted at 120 ° C. to 230 ° C. with stirring. Thereafter, 84 parts of glycerin and 14 parts of trimethylolpropane were charged, reacted at 230 to 270 ° C., and adjusted so that the acid value was 25 mg KOH / g and the 33 wt% linseed oil viscosity was Z to Z-4. The contents were taken out under reduced pressure for 10 minutes. Table 1 shows the physical properties of the rosin-modified phenol resin thus obtained.

Example 5
In Example 3, 500 parts of cardanol (NX-2021) was changed to 250 parts of cardanol (NX-2021) and 250 parts of p-butylphenol to obtain rosin-modified phenolic resin in the same manner. The physical properties are shown in Table 1.

Example 6
In Example 3, 1000 parts of Chinese gum rosin was changed to 1000 parts of Chinese tall oil rosin to obtain rosin-modified phenolic resin in the same manner. The physical properties are shown in Table 1.

Comparative Example 1
In a reaction vessel similar to that in Example 1, 1000 parts of Chinese gum rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Next, 500 parts of phosphorus-containing cardanol (trade name “NX-2023”, manufactured by Cardolite, phosphorous is detected at 5,040 ppm in fluorescent X-ray measurement), 136 parts of 92% paraformaldehyde, and 3 parts of calcium hydroxide are charged and stirred. Was reacted at 120 to 230 ° C. Thereafter, 93 parts of glycerin was charged and reacted at 230 to 270 ° C. to obtain a rosin-modified phenol resin. However, since insoluble matter was generated, it was not subjected to the ink test described later.

Comparative Example 2
In Example 3, rosin-modified phenol resin was obtained in the same manner except that 500 parts of cardanol (NX-2021) was changed to 500 parts of p-octylphenol. The physical properties are shown in Table 1.

Comparative Example 3
In Example 2, 714 parts of a 70% by weight xylene solution of resole type octylphenol / cardanol resin of Production Example 2 (solid content of 500 parts) and 714 parts of a 70% by weight xylene solution of resole type octylphenol / cardanol resin of Production Example 3 ( A rosin-modified phenolic resin was obtained in the same manner except that the solid content was 500 parts. The physical properties are shown in Table 1.

Comparative Example 4
Into a reaction vessel similar to that in Example 1, 676 parts of polymerized rosin (trade name “Sylvatac 140”, manufactured by Silvachem Co., Ltd.), 68 parts of stearic acid and 135 parts of terephthalic acid were charged up to 180 ° C. with stirring in a nitrogen atmosphere. The temperature was raised and melted. Next, 121 parts of pentaerythritol was added, heated to 260 ° C. with stirring, and esterified. When the acid value became 50 or less, 1 part of paratoluenesulfonic acid was added and reacted until the acid value became 20 or less. . Thereafter, the 33 wt% linseed oil viscosity was adjusted to 8 Pa · s, and the content was taken out under reduced pressure at 0.02 MPa for 10 minutes. Table 1 shows the physical properties of the rosin-based polyester resin thus obtained.

Comparative Example 5
In Example 3, 500 parts of cardanol (NX-2021) was added to cashew nut shell oil (trade name “RM-9359I”, manufactured by TaoNguyen, Inc., phosphorous was detected at 40 ppm, and potassium was detected at 5,190 ppm). The rosin-modified phenolic resin was synthesized in the same manner except that the composition was changed to the part. However, after charging with 92% paraformaldehyde, the foamed material violently foamed and the contents flowed out of the reaction vessel, so the synthesis was interrupted.

Comparative Example 6
In a reaction vessel similar to that in Example 1, 1000 parts of Chinese gum rosin was charged and heated to 180 ° C. with stirring in a nitrogen atmosphere and melted. Subsequently, the temperature was raised to 230 ° C. with stirring, and 714 parts (solid content: 500 parts) of a 70 wt% xylene solution of the resole-type cardanol / octylphenol resin of Production Example 2 was added dropwise at 230 ° C. Thereafter, 93 parts of glycerin was charged and reacted at 230 to 270 ° C. When the acid value reached 50 mgKOH / g, 1 part of p-toluenesulfonic acid was charged, and after that, the Weisenberg phenomenon occurred and became a gel-like product, so it was not subjected to the ink test described later.

(Preparation of varnish for offset printing ink)
45 parts of the rosin-modified phenolic resin of Example 1 and 55 parts of soybean oil were mixed and melted at 200 ° C. for 30 minutes, cooled to 80 ° C., and aluminum dipropoxide monoacetyl acetate (trade name “Kelope EP” as a gelling agent. -2 ", manufactured by Hope Pharmaceutical Co., Ltd.) was added in an amount of 0.2 to 2 parts, and the mixture was heated to 200 [deg.] C. and subjected to a gelation reaction for 1 hour. Then, the gel varnish was obtained by diluting with soybean oil and adjusting to 20-30 Pa · s with a cone and plate viscometer manufactured by Nippon Rheology Co., Ltd. Gel varnishes were obtained in the same manner for the resins of Examples 2 to 6 and Comparative Examples 2 to 4.

(Preparation of offset printing ink)
Using the gel varnish of Example 1, printing ink was prepared by kneading with a three roll mill at the following blending ratio.
Carbon black (black pigment) 20 parts by weight Gel varnish 50-60 parts by weight Soybean oil / soybean oil fatty acid butyl ester = 1/1 20-30 parts by weight Based on the above formulation, Corn and Plate manufactured by Nippon Rheology Co., Ltd. It adjusted suitably so that it might become 5-10 Pa.s with a type | mold viscometer.

  Printing inks were prepared in the same manner as in Example 1 for the gel varnishes of Examples 2-6 and Comparative Examples 2-4.

Reference example 1
In addition, in order to confirm the dispersion effect of the black pigment by the rosin modified phenolic resin according to the present invention, 5 parts by weight of Gilsonite (trade name “ER-125”, manufactured by AMERICA GILSONITE) was used in the ink formulation of Comparative Example 2. A printing ink was also prepared.

(Performance test of printing ink)
The performance of the printing inks of Examples 1 to 6, Comparative Examples 2 to 4, and Reference Example 1 was evaluated by the following test. The results are shown in Table 2.
(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. A larger value indicates better fluidity and is an index of pigment dispersibility.
(Set property)
After 0.2 ml of ink was developed on art paper using an RI tester (manufactured by Ishikawajima Sangyo Co., Ltd.), white art paper was superimposed on the color surface. The test piece was attached to the drum of the RI tester, the drum was rotated at regular intervals, and the time (minutes) when the ink stopped moving was set as the set time. The larger the value, the better the setability.

Claims (12)

Rosin (A), cardanol (B) substantially free of phosphorus, phenol (C) other than component (B), formaldehyde (D), triol (E), and divalent metal oxide and / or divalent metal A rosin obtained by reacting a hydroxide (F) and having a weight ratio [(B) / (C)] of component (B) to component (C) of 100/0 to 10/90 Modified phenolic resin. The rosin-modified phenolic resin according to claim 1, wherein the component (A) is tall oil rosin. The rosin-modified phenolic resin according to claim 1 or 2, wherein the component (C) is an alkylphenol having at least one alkyl group having 8 to 12 carbon atoms in the molecule. The rosin-modified phenol resin according to any one of claims 1 to 3, which has a softening point of 100 to 160 ° C. The rosin-modified phenol resin according to any one of claims 1 to 4, having a weight average molecular weight of 10,000 to 200,000. The rosin-modified phenolic resin according to any one of claims 1 to 5, having an acid value of 10 to 20 mgKOH / g. The binder for offset printing inks using the rosin modified phenolic resin in any one of Claims 1-6. An offset printing ink varnish comprising the offset printing ink binder and the printing ink solvent according to claim 7. The varnish for offset printing ink according to claim 8, wherein the solvent for printing ink is vegetable oil and / or petroleum solvent. Furthermore, the varnish for offset printing inks of Claim 8 or 9 containing a gelatinizer. Offset printing ink containing the varnish for offset printing ink in any one of Claims 8-10, and a pigment. The offset printing ink of claim 11, wherein the pigment is a black pigment.