JP2019019317A - Manufacturing method of rosin-modified phenol resin for offset printing ink, rosin-modified phenol resin for offset printing ink, varnish for offset printing ink, and offset printing ink - Google Patents

Abstract

To provide a manufacturing method capable of providing a rosin-modified phenol resin for offset printing ink, having excellent dryness property, misting resistance, glossiness and emulsification resistance while maintaining solubility to an aliphatic hydrocarbon solution, the rosin-modified phenol resin for offset printing ink, a varnish for offset printing ink containing the rosin-modified phenol resin, and an offset printing ink containing the varnish for offset printing ink.SOLUTION: A manufacturing method of a rosin-modified phenol resin for offset printing ink by reacting a rosins (A), formaldehyde (B), phenol and/or p-alkyl phenol (C), and polyol (D) in the presence of an alkali earth metal catalyst (E), with use ratio (molar ratio) of the (B) component and (C) component, [(B)/(C)] of 4 to 10, is used.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a rosin-modified phenol resin for offset printing ink, a rosin-modified phenol resin for offset printing ink, a varnish for offset printing ink, and an offset printing ink.

  In offset printing, the speed of printing presses is increasing due to improved profitability and shorter delivery times of printed materials. This causes a problem that a large amount of ink mist is scattered from the printing press and the working environment at the time of printing deteriorates (hereinafter referred to as misting property). As a method for improving this, there are a method of imparting conductivity by making the resin for ink high polarity, a method of increasing the elasticity of the ink as a high molecular weight, etc. It tends to decrease.

  Although it has been proposed to use a petroleum resin composition for printing ink as a means for improving gloss, it has been difficult to satisfy a wide variety of ink performance with a petroleum resin alone (see Patent Document 1). In addition, it has been proposed to use a rosin-modified phenol resin having a weight average molecular weight of 30,000 to 250,000 using a C10-20 alkylphenol and an acid catalyst as a resin for printing ink, and the resin satisfies various ink performances. This was difficult and lacked versatility (see Patent Document 2). Further, offset printing is required to have a drying property, and as a means for that, it is known to react formaldehyde with alkylphenol in an excessive amount. For example, the present applicant has disclosed a resin for offset printing ink containing 3-alkylphenol having an alkyl group having 10 to 20 carbon atoms in the meta position as a resin component (see Patent Document 3). However, in the case of 3-alkylphenol, the ink resin obtained by reacting with gum rosin together with an excessive amount of formaldehyde has poor solubility in an aliphatic hydrocarbon solvent, and there is a problem that insoluble matter is generated.

Japanese Patent Laid-Open No. 7-033951 JP-A-8-2833641 JP-A-6-041487

  An object of the present invention is to provide a rosin-modified phenolic resin for offset printing inks that has excellent drying properties, misting resistance, gloss and emulsification resistance when used as an offset printing ink while maintaining solubility in an aliphatic hydrocarbon solvent. Is a rosin-modified phenol resin for offset printing ink, an offset printing ink varnish containing the rosin-modified phenol resin, and an offset printing ink containing the ink varnish.

  The inventors of the present invention have intensively studied to solve the above problems by a method for producing a rosin-modified phenolic resin characterized by reacting with a higher use ratio of formaldehyde to phenol and / or alkylphenol than in the past. As a result, the present invention has been completed. That is, the present invention relates to the following method for producing a rosin-modified phenol resin for offset printing ink, rosin-modified phenol resin for offset printing ink, varnish for offset printing ink, and offset printing ink.

1. Rosin (A), formaldehyde (B), phenol and / or p-alkylphenol (C), and polyol (D) are reacted in the presence of an alkaline earth metal catalyst (E), and (B) The manufacturing method of the rosin modified phenol resin for offset printing inks whose use ratio (molar ratio) [(B) / (C)] of a component and (C) component is 4-10.

2. (A) The manufacturing method of the rosin modified phenol resin for offset printing inks of the preceding clause 1 whose component is at least 1 sort (s) chosen from the group which consists of gum rosin, tall oil rosin, and wood rosin.

3. The method for producing a rosin-modified phenol resin for offset printing ink according to item 1 or 2, wherein the p-alkylphenol has an alkyl group having 1 to 9 carbon atoms in the para position.

  (D) The manufacturing method of the rosin modified phenol resin for offset printing inks in any one of the preceding clauses 1-3 whose component is triol and / or tetraol.

5. (E) The manufacturing method of the rosin modified phenol resin for offset printing inks in any one of the preceding clauses 1-4 whose component is an alkaline-earth metal hydroxide.

6). (E) The manufacturing method of the rosin modified phenol resin for offset printing inks in any one of the preceding clauses 1-5 whose usage-amount of a component is 0.1-10 weight part with respect to 100 weight part of (A) component.

7). Cloudiness when obtained as a 10% by weight solution of an aliphatic hydrocarbon solvent obtained by the production method of any one of the preceding items 1 to 6 and having an aromatic content of less than 1% by weight and an aniline point of 60 to 80 ° C. A rosin-modified phenolic resin for offset printing ink having a point of 100 ° C. or higher.

8). The varnish for offset printing inks containing the rosin modified phenolic resin for offset printing inks of the preceding clause 7, and vegetable oils.

9. Furthermore, the varnish for offset printing ink of the preceding clause 8 containing a petroleum solvent and / or a gelatinizer.

10. The offset printing ink containing the varnish for offset printing inks of the preceding clause 9.

  According to the method for producing a rosin-modified phenol resin for offset printing ink according to the present invention, when the obtained rosin-modified phenol resin for offset printing ink maintains solubility in an aliphatic hydrocarbon solvent and is used as an offset printing ink. In particular, the printing ink is excellent in drying property, misting resistance, gloss and emulsification resistance, and the printing ink can be suitably used particularly as an offset sheet-fed ink.

  The method for producing a rosin-modified phenolic resin for offset printing ink according to the present invention includes rosins (A) (hereinafter referred to as component (A)), formaldehyde (B) (hereinafter referred to as component (B)), phenol and / or p. -Alkylphenol (C) (hereinafter referred to as (C) component) and polyol (D) (hereinafter referred to as (D) component) in the presence of alkaline earth metal catalyst (E) (hereinafter referred to as (E) component) It is made to react with.

  (A) It does not specifically limit as a component, Various well-known things can be used. For example, natural rosin such as gum rosin, tall oil rosin and wood rosin, polymerized rosin derived from the natural rosin, purified product of natural rosin and polymerized rosin (hereinafter collectively referred to as “raw material rosin”), Examples thereof include a disproportionated rosin obtained by disproportionating a raw material rosin, a hydrogenated rosin obtained by hydrogenating the raw material rosin, and an unsaturated carboxylic acid-modified rosin obtained by adding an unsaturated carboxylic acid to the raw material rosin. The unsaturated carboxylic acids are not particularly limited, and examples thereof include unsaturated monocarboxylic acids such as crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like. An unsaturated dicarboxylic acid is mentioned. Moreover, the usage-amount of unsaturated carboxylic acids is also not specifically limited, Usually, about 1-30 weight part of unsaturated carboxylic acids are with respect to 100 weight part of raw material rosins. The component (a1) may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of gum rosin, tall oil rosin and wood rosin is preferable from the viewpoint of reactivity with the component (C).

  (B) It does not specifically limit as a component, For example, formalin, paraformaldehyde, etc. are mentioned.

  Although it does not specifically limit as content of (B) component, From the point of the environmental load by discharge | emission outside a reaction system, normally 5-80 weight part with respect to 100 weight part of (A) component in conversion of solid content. About 10 to 30 parts by weight.

  Component (C) is phenol and / or p-alkylphenol. It does not specifically limit as p-alkylphenol, Various well-known things can be used. For example, p-methylphenol (p-cresol), pn-butylphenol, p-isobutylphenol, pt-butylphenol, pn-pentylcresol (p-amylphenol), p-octylphenol, p-nonylphenol, Examples include p-decylphenol, p-dodecylphenol, p-tetradecylphenol, p-hexyldecylphenol and the like. These may be used alone or in combination of two or more. Among the p-alkylphenols, those having an alkyl group having 1 to 9 carbon atoms in the para position are preferable, and pt-butylphenol and p-octylphenol are more preferable from the viewpoint of obtaining a high molecular weight rosin-modified phenol resin.

  Although it does not specifically limit as content of (C) component, From the point from which a high molecular weight rosin modified phenol resin is obtained, normally 3-100 weight part with respect to 100 weight part of (A) component in conversion of solid content. About 5 to 80 parts by weight.

  The use ratio of the component (B) and the component (C) is usually 4 or more and 10 or less in each molar ratio [(B) / (C)]. When (B) / (C) exceeds 10, insoluble matter is likely to be generated or formaldehyde is likely to be discharged out of the system. Further, (B) / (C) is preferably 4 or more and 8 or less, more preferably 4 or more and 7 or less. When (B) / (C) is 4 or more, a reaction product of the (A) component and the (B) component is also easily generated, thereby increasing the viscosity and cloud point of the rosin-modified phenol resin, and offset printing. When used as an ink, it has excellent drying and misting resistance. In the following, the use ratio of (B) / (C) is also expressed as F / P ratio.

  The component (D) is not particularly limited as long as it has two or more hydroxyl groups in one molecule, and various known ones can be used. For example, diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol; Examples include triols such as glycerin, trimethylolethane, and trimethylolpropane; tetraols such as pentaerythritol, diglycerin, ditrimethylolethane, and ditrimethylolpropane; and pentavalent or higher polyols such as dipentaerythritol. These may be used alone or in combination of two or more. Among these, triol and / or tetraol are preferable from the viewpoint of misting resistance of the offset printing ink.

  The ratio of component (D) used is not particularly limited, but from the viewpoint of emulsification resistance of the offset printing ink, the total hydroxyl group equivalent number (OH) of component (D) and the total carboxyl group equivalent number of component (A) The ratio (OH / COOH) to (COOH) is preferably about 0.5 to 1.5.

  The component (E) is not particularly limited as long as it is derived from an alkaline earth metal, and various known materials can be used. For example, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, barium hydroxide; alkaline earth metal oxides such as magnesium oxide, calcium oxide, barium oxide; magnesium acetate, calcium acetate, barium acetate, etc. Examples include alkaline earth metal acetates. These may be used alone or in combination of two or more. Among these, alkaline earth metal hydroxides are preferable and barium hydroxide is more preferable from the viewpoint of the drying property of the offset printing ink.

  Although it does not specifically limit as the usage-amount of (E) component, Usually, it is 0.1-10 weight part with respect to 100 weight part of (A) component. When the amount used is 0.1 parts by weight or more, the offset printing ink has excellent drying properties. On the other hand, if it exceeds 10 parts by weight, insoluble matters are likely to be generated. Moreover, from the same point as above, it is preferably 0.1 to 4 parts by weight, more preferably 0.1 to 3 parts by weight.

The method for producing a rosin-modified phenol resin for offset printing ink of the present invention is obtained by reacting the components (A) to (D) in the presence of the component (E). Although it does not specifically limit as the manufacturing method, For example, the method of (1)-(4) etc. are mentioned.
(1) A method in which the components (A) to (D) are charged all at once and reacted in the presence of the component (E) (2) A condensate of the component (A) with the components (B) and (C) described later Are reacted in the presence of the component (E) and then the component (D) is reacted. (3) After the components (A) and (D) are reacted, the component (B) and ( Method of adding the condensate of component C) and component (E) and further reacting (4) reacting component (A), component (B), and component (C) in the presence of component (E) And then further reacting the component (D)

  In these production methods, the order of addition is not particularly limited. Among these, the reaction product of the component (A) and the component (B) is easily generated, and has excellent drying properties and misting resistance when used as an offset printing ink. A production method is preferred.

  In addition, the production conditions are not particularly limited, and the reaction temperature is usually about 100 to 300 ° C. and the reaction time is about 1 to 24 hours. However, the method for producing the rosin-modified phenol resin for offset printing ink of the present invention is reactive. From this point, it is preferable to carry out the reaction at a reaction temperature of about 100 to 260 ° C. for a reaction time of about 8 to 24 hours.

  In addition, about (B) component and (C) component, you may make it react separately and may use it as a phenol-formaldehyde condensate or a p-alkylphenol-formaldehyde condensate. Examples of the condensate include a resol type phenol resin. Although it does not specifically limit as a resole type phenol resin, The condensate etc. which made (B) component and (C) component carry out addition and condensation reaction in presence of (E) component are mentioned.

  In addition, as a catalyst used for the production of the condensate, an organic amine such as triethylamine; a zinc-based catalyst such as zinc oxide, zinc hydroxide, and zinc acetate may be used in combination with the component (E).

  Moreover, the said condensate can be manufactured in presence of organic solvents, such as toluene and xylene, and water. Furthermore, although manufacturing conditions are not specifically limited, For example, (B) component and (C) component may be prepared, respectively, and it may be made to react at about 100-300 degreeC reaction temperature for about 1 to 24 hours of reaction time.

  The weight average molecular weight of the rosin-modified phenolic resin obtained by the above production method (referred to as polystyrene conversion value in gel permeation chromatography; the same applies hereinafter) is not particularly limited, but from the viewpoint of drying and misting resistance of offset printing ink, Usually, it is about 10,000-150,000, Preferably it is about 12,000-130,000, More preferably, it is about 15,000-100,000.

  Other physical properties are not particularly limited, and for example, the softening point (JIS K5601) is usually about 120 to 200 ° C., and the acid value (JIS K5601) is usually about 5 to 30 mgKOH / g.

  The rosin modified phenolic resin also maintains solubility in aliphatic hydrocarbon solvents. Specifically, when the rosin-modified phenol resin is made into a 10% by weight solution of an aliphatic hydrocarbon solvent having an aromatic content of less than 1% by weight and an aniline point of 70 to 100 ° C. ( That is, the temperature when turbidity is 100 ° C. or higher, preferably 100 to 180 ° C., and in the present invention, this cloud point is used as an indicator of solubility. Examples of the “aliphatic hydrocarbon solvent having an aromatic content of less than 1% and an aniline point of 70 to 100 ° C.” include, for example, No. 0 solvent or AF solvent (naphthenic aliphatic group) of JXTG Energy Co., Ltd. Hydrocarbon solvents (No. 4, No. 5, No. 6, No. 7, etc.). The “10 wt% solution” of the aliphatic hydrocarbon solvent is specifically a solution in which the rosin-modified phenol resin (solid) / AF solvent = 1/9 according to the present invention is used, and the AF solvent used Is preferably No. 6.

  The varnish for offset printing ink of the present invention comprises the rosin-modified phenolic resin for offset printing ink of the present invention and vegetable oils.

  The vegetable oils are vegetable oils and derivatives thereof (for example, vegetable oil esters). For example, 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 Examples include vegetable oil monoesters such as oil fatty acid ethyl, soybean oil fatty acid ethyl, linseed oil fatty acid propyl, soybean oil fatty acid propyl, linseed oil fatty acid butyl, soybean oil fatty acid butyl, and these may be used alone or in combination of two or more. Use of the vegetable oils is preferable from the viewpoint of environmental considerations.

  The varnish for offset printing ink of the present invention further contains a petroleum solvent and / or a gelling agent.

  The petroleum solvent is not particularly limited. For example, JXTG Energy's petroleum solvent No. 0 solvent, No. 4 solvent, No. 5 solvent, No. 6 solvent, No. 7 solvent, AF solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7, etc. may be mentioned, and these may be used alone or in combination of two or more. Use of a petroleum solvent is preferable because the drying property of the offset printing ink is improved.

  The gelling agent is not particularly limited, and examples thereof include aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, aluminum dibutoxide monoacetyl acetate, and aluminum triacetyl acetate. Examples thereof include aluminum gelling agents such as these, and these may be used alone or in combination of two or more.

  The varnish for offset printing ink of the present invention is not particularly limited. For example, rosin-modified phenolic resin and vegetable oil, and if necessary, a petroleum solvent and / or a gelling agent are mixed with stirring, and usually 100 to 240. It can be obtained by reacting at a reaction temperature of about ° C. In addition, you may mix | blend additives, such as antioxidant, in the case of reaction.

  The offset printing ink of the present invention includes the varnish for offset printing ink of the present invention. Specifically, varnishes for ink for offset printing, pigments (yellow, red, indigo, black, etc.) and, if necessary, additives such as the above vegetable oils, petroleum-based solvents, surfactants, waxes, etc. , And kneaded using an ink manufacturing apparatus such as a roll mill, a ball mill, an attritor, and a sand mill, and prepared so as to have an appropriate ink constant.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, all “parts” are based on weight.

Example 1
In a reaction vessel equipped with a stirrer, a reflux condenser with a water separator and a thermometer, 1,000 parts of gum rosin, 300 parts of pt-butylphenol (PTBP), 267 parts of paraformaldehyde (F / P ratio = 4.1) The temperature was raised to 100 ° C. with stirring, 16.2 parts of barium hydroxide was added, and the temperature was kept for 4 hours. Then, after heating up to 230 degreeC and adding 84 parts of glycerol, it was made to react at 245-270 degreeC for 12 hours, and the rosin modified phenol resin for offset printing inks was obtained. The acid value, weight average molecular weight, softening point and cloud point of the obtained resin are shown in Table 1 (the same applies hereinafter).

Example 2
The same procedure as in Example 1 was conducted except that barium hydroxide was changed to 3.0 parts of magnesium hydroxide.

Example 3
The same procedure as in Example 1 was conducted except that barium hydroxide was changed to 3.8 parts of calcium hydroxide.

Example 4
A reaction vessel similar to that in Example 1 was charged with 1,000 parts of gum rosin, 106 parts of PTBP, and 130 parts of paraformaldehyde (F / P ratio = 6.2). The temperature was raised to 100 ° C. with stirring, and 16 barium hydroxide was added. 2 parts were added and kept warm for 4 hours. Then, after heating up to 230 degreeC and adding 84 parts of glycerol, it was made to react at 245-255 degreeC for 12 hours, and the rosin modified phenol resin for offset printing inks was obtained.

Example 5
The same operation as in Example 4 was conducted except that barium hydroxide was changed to 3.0 parts of magnesium hydroxide.

Example 6
A reaction vessel similar to Example 1 was charged with 1,000 parts of gum rosin and 82 parts of PTBP, charged with 130 parts of paraformaldehyde (F / P ratio = 7.3), heated to 100 ° C. with stirring, and magnesium hydroxide. Was added and kept warm for 4 hours. Then, after heating up to 230 degreeC and adding 84 parts of glycerol, it was made to react at 245-270 degreeC for 12 hours, and the rosin modified phenol resin for offset printing inks was obtained.

Example 7
A reaction vessel similar to Example 1 was charged with 1,000 parts of gum rosin, 45 parts of maleic anhydride, 350 parts of p-nonylphenol (PNP), and 213 parts of paraformaldehyde (F / P ratio = 4.1) while stirring. The temperature was raised to 100 ° C., 3.0 parts of magnesium hydroxide was added, and the temperature was kept for 4 hours. Thereafter, the temperature was raised to 230 ° C., and 84 parts of pentaerythritol and 8.4 parts of glycerin were added, followed by reaction at 245 to 270 ° C. for 12 hours to obtain a rosin-modified phenol resin for offset printing ink.

Example 8
The same operation as in Example 1 was conducted except that PTBP was changed to 216 parts of p-cresol.

Example 9
In the same reaction vessel as in Example 1, 1,000 parts of gum rosin and 94 parts of carboxylic acid were charged, and 134 parts of paraformaldehyde (F / P ratio = 4.1) were charged. 3.8 parts of calcium was added and kept warm for 4 hours. Then, after heating up to 230 degreeC and adding 88 parts of glycerol, it was made to react at 245-270 degreeC for 12 hours, and the rosin modified phenol resin for offset printing inks was obtained.

Example 10
The same procedure as in Example 1 was conducted except that the amount of barium hydroxide used was changed to 54 parts.

Example 11
In the same reaction vessel as in Example 1, 1,000 parts of tall oil rosin, 10 parts of maleic anhydride, 300 parts of PTBP, and 267 parts of paraformaldehyde (F / P ratio = 4.1) were added and the temperature was raised to 100 ° C. with stirring. Warm, 3.0 parts of magnesium hydroxide was added and kept warm for 4 hours. Then, after heating up to 230 degreeC and adding 89 parts of glycerol, it was made to react at 245-270 degreeC for 12 hours, and the rosin modified phenol resin for offset printing inks was obtained.

Comparative Example 1
The same procedure as in Example 1 was conducted except that barium hydroxide was changed to 0.4 part of aluminum hydroxide. The obtained resin was cloudy and ink evaluation was not performed.

Comparative Example 2
The same procedure as in Example 1 was conducted except that barium hydroxide was changed to 0.21 part of sodium hydroxide.

Comparative Example 3
In the same reaction vessel as in Example 1, 1,000 parts of gum rosin, 300 parts of PTBP, and 130 parts of paraformaldehyde (F / P ratio = 2.0) were heated to 100 ° C. with stirring, and 3 mg of magnesium hydroxide was added. 0.0 part was added and kept warm for 4 hours. Then, after heating up to 230 degreeC and adding 84 parts of glycerol, it was made to react at 245-270 degreeC for 12 hours, and the rosin modified phenol resin for offset printing inks was obtained.

<Preparation of varnish for offset printing ink>
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, 45 parts of rosin-modified phenol resin for offset printing ink of Example 1, 30 parts of soybean oil, and 24. Petroleum solvent (AF Solvent No. 6). 3 parts were charged and mixed at 180 ° C. for 1 hour. Next, 0.7 parts of an aluminum chelating agent (trade name “Kelope EP-2”, manufactured by Hope Pharmaceutical Co., Ltd.) was added at 60 ° C., and the mixture was kept at 190 ° C. for 1 hour to obtain a varnish for offset printing ink. . The varnish for offset printing ink was similarly obtained about the rosin modified phenolic resins of Examples 2 to 11 and Comparative Examples 2 and 3.

<Preparation of offset printing ink and ink performance test>
Using each of the offset printing ink varnishes described above, the mixture was kneaded by a three-roll mill at the following blending ratio, the tack value was 9.0 ± 0.5, and the spread meter flow value (diameter value) was 38.0 ± 1. The offset printing ink according to the present invention was appropriately prepared so as to be 0.0.
Phthalocyanine blue (indigo pigment) 18 parts by weight Gel varnish 66-71 parts by weight AF Solvent No. 6 11-16 parts by weight Cobalt dryer 1 part by weight ) To prepare a pressure of 35 to 45 Pa · s.

(Drying)
After 0.2 ml of offset printing ink was developed on parchment paper using an RI tester (Ishikawajima Industrial Machinery Co., Ltd.), the parchment paper was layered on the colored surface and a C-type drying tester (Toyo Seiki Seisakusho Co., Ltd.) The product was wound around a rotating drum. The drum was rotated by applying the pressing gear, and the time (unit: hr) when the tooth shape of the pressing gear stopped moving was measured and evaluated in 1 to 5 stages. The smaller the value, the better the drying property. The results are shown in Table 1 (the same applies hereinafter).
(Evaluation criteria)
5: Drying time is less than 7 hr 4: Drying time is 7 hr or more and less than 8 hr 3: Drying time is 8 hr or more and less than 10 hr 2: Drying time is 10 hr or more and less than 12 hr 1: Drying time is 12 hr or more is there

(Missing resistance)
2.6 ml of offset printing ink is developed on an incometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), rotated at a roll temperature of 30 ° C. at 400 rpm for 1 minute, and further at 1800 rpm for 2 minutes, onto a white paper placed directly under the roll. The ink scattering degree was observed and evaluated in 1 to 5 stages. The larger the value, the better the misting resistance.
(Evaluation criteria)
5: Slightly scattered ink on white paper 4: Slightly scattered ink on white paper 3: Slightly scattered ink on white paper 2: Highly scattered ink on white paper 1: Very high ink scattering on white paper

(Glossy)
After 0.4 ml of offset printing ink was developed on art paper using an RI tester (manufactured by Ishikawajima Industrial Machinery Co., Ltd.), 23 ° C., 50% R.D. H. The sample was conditioned for 24 hours, and the reflectivity of 60 ° -60 ° was measured with a gloss meter and evaluated in 1 to 5 stages. The larger the value, the better the gloss.
(Evaluation criteria)
5: Gloss value is 70 or more 4: Gloss value is 67 or more and less than 70 3: Gloss value is 64 or more and less than 67 2: Gloss value is 61 or more and less than 64 1: Gloss value is less than 61 is there

(Emulsification resistance (measurement of emulsification rate))
3.9 ml of offset printing ink was developed on a dynamic emulsification tester (manufactured by Nippon Rheology Equipment Co., Ltd.) and pure water was supplied at a roll temperature of 30 ° C. and 200 rpm at a rate of 5 ml / min. Was measured with an infrared moisture meter to calculate the emulsification rate (%) of the offset printing ink. The smaller the value, the better the emulsification resistance.

Claims (10)

  Rosin (A), formaldehyde (B), phenol and / or p-alkylphenol (C), and polyol (D) are reacted in the presence of an alkaline earth metal catalyst (E), and (B) The manufacturing method of the rosin modified phenol resin for offset printing inks whose use ratio (molar ratio) [(B) / (C)] of a component and (C) component is 4-10.   The method for producing a rosin-modified phenol resin for offset printing ink according to claim 1, wherein the component (A) is at least one selected from the group consisting of gum rosin, tall oil rosin and wood rosin.   The method for producing a rosin-modified phenol resin for offset printing ink according to claim 1 or 2, wherein the p-alkylphenol has an alkyl group having 1 to 9 carbon atoms in the para position.   (D) A component is triol and / or tetraol, The manufacturing method of the rosin modified phenol resin for offset printing inks in any one of Claims 1-3.   (E) A component is an alkaline-earth metal hydroxide, The manufacturing method of the rosin modified phenol resin for offset printing inks in any one of Claims 1-4.   (E) The usage-amount of a component is 0.1-10 weight part with respect to 100 weight part of (A) component, The manufacturing method of the rosin modified phenol resin for offset printing inks in any one of Claims 1-5.   When obtained as a 10 wt% solution of an aliphatic hydrocarbon solvent obtained by the production method according to any one of claims 1 to 6 and having an aromatic content of less than 1 wt% and an aniline point of 60 to 80 ° C. A rosin-modified phenolic resin for offset printing ink having a cloud point of 100 ° C or higher.   The varnish for offset printing inks containing the rosin modified phenolic resin for offset printing inks of Claim 7, and vegetable oils.   Furthermore, the varnish for offset printing inks of Claim 8 containing a petroleum solvent and / or a gelatinizer.   An offset printing ink comprising the offset printing ink varnish of claim 9.