WO2016208376A1 - Rosin-modified phenolic resin, and printing ink - Google Patents

Abstract

Provided are: a printing ink with which a high-gloss printed surface can be obtained; and a printing ink varnish and a rosin-modified phenolic resin which are used in said printing ink. This rosin-modified phenolic resin has, as essential starting materials, rosin (A), a resole resin (B), a polyol compound (C), and a fat (D). The rosin-modified phenolic resin is obtained using a production method for the rosin-modified phenolic resin, said production method being characterized by being provided with: a step (α) in which the rosin (A) and the polyol compound (C) are made to react with each other; a step (β) in which the fat (D) is subsequently made to react therewith; and a step (γ) in which the resole resin (B) is further made to react therewith.

Description

Rosin-modified phenolic resin and printing ink

The present invention relates to a printing ink capable of obtaining a high gloss printing surface, a varnish for printing ink used therefor, and a rosin-modified phenolic resin.

In the case of offset printing such as offset sheet-fed printing, offset rotary printing, and offset newspaper printing, the performance of the resin is very important in order to achieve a more beautiful printing surface. In order to achieve printing inks that are free from smudges and smudges, have excellent gloss, and have a drying property that can withstand high-speed printing, for example, the resin hydrophilicity, solvent solubility, and viscoelasticity are optimized. Resin design is required. In resin design, not only the selection of raw material components and reaction ratios, but also the performance of the resin varies greatly depending on the production method such as the reaction order of each component.

Rosin-modified phenolic resin has been widely used as a resin for offset printing ink. In particular, when a medium chain alkylphenol such as octylphenol or nonylphenol is used as a phenol raw material, it becomes a resin having excellent solvent solubility, and printing inks using this are known to provide a high gloss and beautiful printing surface (patents) However, recently, it has been found that these medium-chain alkylphenols are suspected of being an environmental hormone, and in Europe there is a movement to be designated as a substance of high concern. Therefore, there is a demand for printing ink resins that can exhibit high performance without using these medium-chain alkylphenols.

JP 2003-128972 A

Therefore, an object of the present invention is to provide a printing ink resin that can exhibit high performance without using a medium-chain alkylphenol, and a printing ink using the same.

As a result of intensive research to solve the above-mentioned problems, the present inventors, in the production of rosin-modified phenolic resin, conventionally, after reacting each raw material such as rosin, resole resin, polyol compound, almost the final production process The method of adding oils and fats to the reaction at the stage was common, but the resin obtained by the method of reacting oils and fats prior to the resol resin should give a printing ink with high heptane tolerance and excellent gloss on the printing surface I found. Furthermore, it has been found that according to this method, a rosin-modified phenol resin having sufficiently high solvent solubility can be obtained even when a short-chain alkylphenol such as butylphenol is used instead of a medium-chain alkylphenol such as octylphenol or nonylphenol. As a result, the present invention has been completed.

That is, the present invention is a rosin-modified phenol resin using rosin (A), resole resin (B), polyol compound (C) and oil (D) as essential raw materials, and comprises rosin (A) and polyol compound (C ), A step (β) of reacting oil and fat (D), and a step (γ) of reacting resole resin (B). It relates to a modified phenolic resin.

The present invention further relates to a rosin-modified phenol resin obtained by using an alkylphenol having an alkyl group having 6 or less carbon atoms as a phenolic compound raw material, wherein the heptane tolerance is 350 or more. About.

The present invention further relates to a varnish for printing ink containing the rosin-modified phenolic resin, a gelling agent, and an organic solvent.

The present invention further relates to a printing ink comprising a pigment in the printing ink varnish.

The present invention further relates to a printed matter obtained by printing the printing ink on a paper substrate.

The present invention further relates to a rosin-modified phenolic resin comprising rosin (A), resole resin (B), polyol compound (C) and oil (D) as essential raw materials, wherein rosin (A) and polyol compound (C) And a step (β) of reacting oil and fat (D), and further a step (γ) of reacting resole resin (B). .

According to the present invention, it is possible to provide a printing ink capable of obtaining a highly glossy printing surface, a varnish for printing ink and a rosin-modified phenolic resin used therefor.

The rosin-modified phenolic resin of the present invention is a rosin-modified phenolic resin comprising rosin (A), resole resin (B), polyol compound (C) and oil (D) as essential raw materials, and rosin (A) and polyol compound It is produced by a method comprising a step (α) of reacting (C), a step (β) of reacting fat (D), and a step (γ) of reacting a resole resin (B). To do.

Conventionally, in the production of rosin-modified phenolic resins, a method of reacting raw materials such as rosin, resole resin, polyol compound and the like and then adding oils and fats in almost the final step is generally used. On the other hand, in the present invention, by reacting fats and oils prior to the resol resin, a rosin-modified phenol resin having high solvent solubility and excellent printed surface gloss can be obtained.

Examples of the rosin (A) include natural rosins such as gum rosin, tall oil rosin and wood rosin, as well as rosin derivatives such as hydrogenated rosin, polymerized rosin, disproportionated rosin, reinforced rosin and rosin ester. These may be used alone or in combination of two or more.

The above-mentioned natural rosin is generally made in China, but may be from any origin such as Vietnam, Indonesia, USA, Brazil, India.

Regarding the rosin derivative, the hydrogenated rosin is obtained by saturating a part or all of the unsaturated bonds by hydrogenating rosin. The polymerized rosin is obtained by polymerizing rosin in the presence of a catalyst such as sulfuric acid, and is a mixture containing not only a dimer but also a monomer and a multimer of trimer or higher. The disproportionated rosin is obtained by transferring hydrogen between molecules by heating the rosin or the like to saturate the unsaturated bond of one molecule and simultaneously unsaturate the other saturated bond. . The reinforced rosin is a modified rosin obtained by modifying a rosin with an α, β-unsaturated carboxylic acid such as maleic anhydride, fumaric acid or acrylic acid. The rosin ester is a rosin obtained by modifying rosin with a polyhydric alcohol such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol.

Among these, natural rosin such as gum rosin, tall oil rosin, and wood rosin is preferable because it has excellent reactivity with other components and is industrially inexpensive, and further has an abietane skeleton having an unsaturated bond site. Gum rosin is more preferred because of its high reactivity. The acid value of rosin is preferably in the range of 150 to 200 mgKOH / g.

Examples of the resol resin (B) include those obtained by reacting a phenolic compound and an aldehyde compound in the presence of a basic catalyst. Examples of the phenolic compound include, in addition to phenol, cresol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, xylenol, etc., alkylphenols having an alkyl group having 1 to 10 carbon atoms; methoxyphenol , Ethoxyphenol, ethoxyphenol and the like, alkoxyphenol having an alkoxy group having 1 to 10 carbon atoms, and phenolic compounds derived from natural products such as cardanol. These may be used alone or in combination of two or more.

Above all, it is common to use medium-chain alkylphenols such as octylphenol and nonylphenol from the viewpoint of printing ink having excellent printing workability and gloss on the printed surface. On the other hand, according to the present invention, even when a short-chain alkylphenol having an alkyl group having 6 or less carbon atoms is used in place of these medium-chain alkylphenols, it has the same performance as when a medium-chain alkylphenol is used. Rosin-modified phenol is obtained. The proportion of the short-chain alkylphenol in the total amount of the phenolic compound is not particularly limited. For example, 80% by mass or more of the phenolic compound may be an alkylphenol having an alkyl group having 6 or less carbon atoms.

Examples of the aldehyde compound include formaldehyde, paraformaldehyde, glyoxal, acetaldehyde, propionaldehyde, and the like. These may be used alone or in combination of two or more. Of these, formaldehyde or paraformaldehyde is preferable because of its excellent reactivity.

Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; triethylamine, trimethylamine, Examples include amines such as ethanolamine. These may be used alone or in combination of two or more.

The reaction between the phenolic compound and the aldehyde compound is, for example, using an aldehyde compound at a ratio of 1 to 4 moles per mole of the phenolic compound, and 0.01 to 0.5 moles per mole of the phenolic compound. A method of reacting at a temperature of 50 to 150 ° C. for 1 to 5 hours in the presence of a basic catalyst of a certain degree can be mentioned. After completion of the reaction, neutralization with sulfuric acid, acetic acid, phosphoric acid or the like may be performed as necessary. After neutralization, it is preferable to wash with water and dehydrate under reduced pressure.

Examples of the polyol compound (C) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, hexanediol, octanediol, nonanediol, and neopentyl. Examples thereof include dihydric alcohols such as glycol; trihydric or higher alcohols such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. These may be used alone or in combination of two or more. Among these, since it becomes easy to adjust the molecular weight and viscoelasticity of the obtained rosin-modified phenol resin to preferable values, the trivalent or higher alcohol is preferable, and glycerin or pentaerythritol is preferable.

Examples of the fats and oils (D) include linseed oil, tung oil, rice oil, safflower oil, soybean oil, tall oil, rapeseed oil, palm oil, castor oil, palm oil and fats; fatty acids derived from these fats and oils; Fats and oils: oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, higher fatty acids having 12 to 30 carbon atoms, and the like. These may be used alone or in combination of two or more. Of these, soybean oil is preferred because it has a low environmental impact and is industrially inexpensive.

The rosin-modified phenolic resin of the present invention may contain other components as raw material components together with rosin (A), resole resin (B), polyol compound (C), and oil (D). Examples of other components include petroleum resin (E), polybasic acid compound (F), and terpene resin (G).

The petroleum resin (E) is a resin having a weight average molecular weight of about 500 to 100,000, which is obtained by polymerizing an unsaturated compound produced by the decomposition of naphtha. For example, aliphatics based on C5 fractions, aromatics based on C9 fractions, copolymers based on C5 and C9 fractions, fats based on cyclopentadiene and dicyclopentadiene Examples thereof include those obtained by copolymerization of a cyclic type, further allyl alcohol, vinyl acetate and the like, and those obtained by adding maleic anhydride, acrylic acid and the like to these petroleum resins. Examples of the C5 fraction include isoprene, piperylene, cyclopentadiene, and pentene. Examples of the C9 fraction include vinyl toluene, indene, and dicyclopentadiene. Petroleum resin (E) may be used alone or in combination of two or more.

Commercially available products of petroleum resin (E) are, for example, “Quinton A100”, “Quinton B170”, “Quinton K100”, “Quinton M100”, “Quinton R100”, “Quinton C200S” manufactured by ZEON Corporation, Maruzen Petrochemical Co., Ltd. Aliphatic products such as “Marcaretz T-100AS” and “Marcaretz R-100AS” manufactured by JX Nippon Oil & Energy Corporation “Neopolymer L-90”, “Neopolymer 120”, “Neopolymer 130”, “Neopolymer” 140, “Neopolymer 150”, “Neopolymer 170S”, “Neopolymer 160”, “Neopolymer E-100”, “Neopolymer E-130”, “Neopolymer 130S”, “Neopolymer S”, Tosoh “Petocall LX”, “Petocall LX-HS”, “Petocall 100T” Aromatics such as “Petocol 120”, “Petocol 120HS”, “Petocol 130”, “Petocol 140”, “Petocol 140HM”, “Petocol 140HM5”, “Petocol 150”, “Petocol 150AS”; “Quinton D100”, “Quinton N180”, “Quinton P195N”, “Quinton S100”, “Quinton S195”, “Quinton U185”, “Quinton G100B”, “Quinton G115”, “Quinton D200”, “Quinton E200SN”, “ Copolymers such as Quinton N295, Tosoh's “Petrotac 60”, “Petrotac 70”, “Petrotac 90”, “Petrotac 100”, “Petrotac 100V”, “Petrotac 90HM”; Alicyclics such as “Marcaretz M-890A”, “Marcaretz M-845A” manufactured by Gakusha, “Quinton 1325”, “Quinton 1345”, “Quinton 1500”, “Quinton 1525L”, “Quinton 1700” manufactured by ZEON And the like.

Examples of the polybasic acid compound (F) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, (anhydrous) maleic acid, fumaric acid, and citraconic acid. Aliphatic dibasic acids such as itaconic acid and glutaconic acid or their anhydrides; (anhydrous) alicyclic dibasic acids such as tetrahydrophthalic acid and (anhydrous) hexahydrophthalic acid or their anhydrides; (anhydrous) phthalic acid , Aromatic dibasic acids such as isophthalic acid and terephthalic acid or their anhydrides; octenoic acid, noneic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid Dimerization or trimerization of unsaturated monobasic acids such as nonadecenoic acid, eicosenoic acid, docosenoic acid, ceracoleic acid, linoleic acid Allowed dimer acid and trimer acid obtained; (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid trifunctional or higher aromatic other dibasic acids. These may be used alone or in combination of two or more. Among them, an aliphatic dibasic acid or an anhydride thereof, an alicyclic dibasic acid or an anhydride thereof, an aromatic dibasic acid or an anhydride thereof is preferable because it is easy to adjust a resin having a viscosity suitable for ink. Particularly preferred are group dibasic acids or anhydrides thereof.

Examples of the terpene resin (G) include “YS Resin PX1250”, “YS Resin PX1150”, “YS Resin PX1000”, and “YS Resin PX800” manufactured by Yashara Chemical Co., Ltd.

Each of the rosin (A), resole resin (B), polyol compound (C), oil (D) and petroleum resin (E) used as necessary, polybasic acid compound (F), terpene resin (G), etc. The reaction ratio of the raw material components is appropriately adjusted depending on the use of the printing ink that is the final product, the desired performance, and the like.

As a general resin design, for example, the rosin (A) is preferably used in the range of 20 to 80% by mass and more preferably in the range of 40 to 70% by mass in the total raw material components of the rosin-modified phenol resin. preferable. The resole resin (B) is preferably used in the range of 10 to 70% by mass and more preferably in the range of 20 to 50% by mass in the total raw material components of the rosin-modified phenol resin. The polyol compound (C) is preferably used in such a ratio that the hydroxyl group contained in the polyol compound (C) is in the range of 0.5 to 1.5 moles relative to 1 mole of the carboxyl group contained in the rosin-modified phenol resin. The fat / oil (D) is preferably used in the range of 0.5 to 30% by mass, more preferably in the range of 1 to 20% by mass, based on the total raw material components of the rosin-modified phenolic resin.

When the petroleum resin (E) is used, it is preferably used in the range of 0.5 to 15% by mass and more preferably in the range of 1 to 10% by mass in the total raw material components of the rosin-modified phenol resin. When the polybasic acid compound (F) is used, it is preferably used in the range of 0.1 to 10% by mass, and in the range of 0.3 to 5% by mass in the total raw material components of the rosin-modified phenol resin. Is more preferable. When the terpene resin (G) is used, it is preferably used in the range of 0.1 to 10% by mass in all raw material components of the rosin-modified phenol resin.

The method for producing a rosin-modified phenolic resin of the present invention comprises a step (α) of reacting rosin (A) with a polyol compound (C), then a step (β) of reacting fat (D), and a resole resin (B). It has the process ((gamma)) made to react. As described above, the most important point in the present invention is that the fat (D) is reacted before the resole resin (B) in the production process of the rosin-modified phenol resin.

Specifically, in the step (α), the rosin (A) and the polyol compound (C) are heated to about 230 to 300 ° C. in the presence of a metal catalyst until the acid value becomes 30 mgKOH / g or less. The method of making it react is mentioned.

Examples of the metal catalyst include zinc oxide, zinc acetate, magnesium oxide, calcium oxide, calcium hydroxide, and lithium hydroxide.

The step (β) is a step of reacting the reaction product obtained in the step (α) with the oil (D) after the step (α). Specifically, the fat (D) is added and reacted in the range of 200 to 280 after the step (α).

The step (γ) is a step of reacting the reaction product obtained in the step (β) with the resole resin (B) after the step (β). Specifically, after the fat (D) is charged in the step (β), the resole resin (B) is added stepwise and reacted. Examples of the end point of the reaction include a method in which the end point of the reaction is controlled by the viscosity of the toluene solution.

The method for producing the rosin-modified phenolic resin of the present invention is not particularly limited in the reaction order of other components as long as it includes the steps (α), (β), and (γ). That is, when reacting raw materials other than the components (A) to (E), specifically, the petroleum resin (F), the polybasic acid compound (G), the terpene resin (H), etc., the timing of reacting them. Is not particularly limited, and may be charged at any timing after the step (α), (β), (γ), or the step (γ).

In the production process of the rosin-modified phenol resin, a petroleum solvent or the like may be used as desired. Examples of the petroleum solvent used here include “No. 1 spindle oil” and “No. 3 solvent” manufactured by JX. ”,“ No. 4 Solvent ”,“ No. 5 Solvent ”,“ No. 6 Solvent ”,“ Naphthezol H ”,“ Alkene 56NT ”,“ Diadol 13 ”,“ Dialen 168 ”manufactured by Mitsubishi Chemical Corporation; “F Oxocol”, “F Oxocol 180” manufactured by JX Corporation; “AF Solvent No. 4”, “AF Solvent No. 5”, “AF Solvent No. 6”, “AF Solvent No. 7” manufactured by JX, DSOL solvent manufactured by ISU, “ Solvent H ”;“ N-paraffin C14-C18 ”manufactured by ISU Corporation;“ Supersol LA35 ”,“ Supersol LA38 ”; Idemitsu Kosan Co., Ltd. “Exor D80”, “Exor D110”, “Exor D120”, “Exor D130”, “Exor D100K”, “Exor D120K”, “Exor D130K”, “Exor D280” , “Exor D300”, “Exor D320”; “Maggie Sol-40”, “Maggi Sol-44”, “Magi Sol-47”, “Magi Sol-52”, “Magi Sol-60” manufactured by Maggie Bros.

The weight average molecular weight (Mw) of the rosin-modified phenol resin of the present invention thus obtained is preferably in the range of 10,000 to 150,000, and preferably in the range of 30,000 to 130,000. Is more preferable.

In the present invention, the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC) under the following conditions.
Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column "HZ-H" manufactured by Tosoh Corporation
+ Tosoh Co., Ltd. “TSK-GEL SuperHZM-H” x 4 detectors: RI (differential refractometer)
Data processing: “GPC-8320 EcoSEC application” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 0.6 ml / min Standard: The following monodispersed polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8320 EcoSEC application”.
(Used polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-380” manufactured by Tosoh Corporation
“F-450” manufactured by Tosoh Corporation
“F-850” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

The rosin-modified phenolic resin of the present invention preferably has a heptane tolerance of 350 or more, more preferably in the range of 350 to 500. In the present invention, heptane tolerance is added when white turbidity occurs when 0.1 ml of heptane is added to 1 g of a solution in which rosin-modified phenolic resin and toluene are mixed at a mass ratio of 1/1 and stirred. The total amount of heptane (ml) × 100.

The printing ink varnish of the present invention contains the rosin-modified phenolic resin, gelling agent, and organic solvent as essential components. The gelling agent is used for the purpose of adjusting the viscoelasticity of the varnish for printing ink, and examples thereof include an organic aluminum compound, an organic titanate compound, an organic zinc compound, and an organic strength lucium compound. One type of gelling agent may be used alone, or two or more types may be used in combination. Of these, organoaluminum compounds are preferred. Examples of organoaluminum compounds include aluminum alcoholates and aluminum chelate compounds. Among them, aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, and ethyl acetoacetate aluminum. Diisopropylate, ethyl acetyl acetate aluminum di-n-butyrate, ethyl acetyl acetate aluminum-n-butyrate, and aluminum trisethyl acetyl acetate are preferred.

The addition amount of the gelling agent can be adjusted according to the target viscoelasticity, but is usually used in the range of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the varnish for printing ink.

Examples of the organic solvent include vegetable oils and petroleum solvents. The vegetable oil is, for example, vegetable oils such as linseed oil, tung oil, rice oil, safflower oil, soybean oil, tall oil, rapeseed oil, palm oil, castor oil, palm oil and fat, and these vegetable oils are used for food processing and the like. In addition to regenerated vegetable oils that were regenerated later, linseed oil fatty acid methyl, soybean oil fatty acid methyl, linseed 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, etc. And monoesters of the vegetable oil fatty acids. These may be used alone or in combination of two or more. Among them, vegetable oils having unsaturated bonds in the molecule such as linseed oil, tung oil, soybean oil, etc. are preferable because they become varnishes for printing inks that are excellent in drying properties, and soybean oil and its regenerated oil are more because it has a low environmental impact. preferable.

Examples of the petroleum solvent include “No. 1 spindle oil”, “No. 3 solvent”, “No. 4 solvent”, “No. 5 solvent”, “No. 6 solvent”, “Naphthezol H”, “Alkene” manufactured by JX. "56NT", Mitsubishi Chemical Corporation "Diadol 13", "Dialen 168"; Nissan Chemical Corporation "F Oxocol", "F Oxocol 180"; JX "AF Solvent No. 4", "AF Solvent No. 5, “AF Solvent No. 6”, “AF Solvent No. 7”, DSOL solvent manufactured by ISU, “Solvent H”; “N-paraffin C14-C18” manufactured by ISU Corporation; “Supersol LA35”, Idemitsu Kosan Co., Ltd. , “Supersol LA38”; “Exor D80”, “Exor D110”, “Exor D120”, “Exor D1” from Exxon Chemical Co., Ltd. "0", "Exor D160", "Exor D100K", "Exor D120K", "Exor D130K", "Exor D280", "Exor D300", "Exor D320"; "Magisol-40", "Maggi Brothers" Examples include Maggie Sol-44, Maggie Sol-47, Maggie Sol-52, and Maggie Sol-60.

Among these, the AF solvent is preferable because of the excellent solubility of the rosin-modified resole resin and the aromatic component is small, and a so-called aroma-free solvent having an aromatic component of 1.0% or less is particularly preferable. More specifically, for example, for the preparation of a varnish for heat drying type offset rotary ink, “AF Solvent No. 4” manufactured by JX, “AF Solvent No. 5” manufactured by JX, “AF Solvent No. 7” manufactured by JX In order to adjust the varnish for osmotic drying type newspaper ink, “AF Solvent No. 6” manufactured by JX and “DSOL300” manufactured by ISU are preferable. For adjusting the varnish for oxidation polymerization type sheet ink, “AF” manufactured by JX “Solvent No. 6” is preferred.

The printing ink varnish of the present invention can be used for various printing ink applications, but when used for an offset ink application, it is preferable to adjust the non-volatile content of the printing ink varnish to 30 to 75% by mass. Moreover, in order to reduce VOC and make an ink with a small environmental load, it is preferable to use only vegetable oil as the organic solvent. On the other hand, when used for ink applications that promote setting by evaporating the solvent component with hot air, such as for web offset printing, there are many cases where petroleum-based solvents are used more than vegetable oils. In the present invention, vegetable oil and petroleum solvent may be used in an appropriate ratio depending on the purpose.

The printing ink varnish of the present invention may contain other additives such as an antioxidant in addition to the gelling agent and the organic solvent. The antioxidant is used for the purpose of preventing the ink varnish composition from being skinned. For example, a known one such as 2,6-di-tert-butyl-4-methylphenol can be used without any particular limitation. . The amount of the antioxidant used is determined in consideration of the storage period and the like, but is usually used in the range of 0.1 to 1.0 part by mass in 100 parts by mass of the varnish for printing ink.

The varnish for printing ink of the present invention can be produced by mixing and stirring the above-mentioned components. When mixing and stirring, these are usually heated to a temperature in the range of 100 ° C to 240 ° C. By doing so, each component is dissolved and mixed.

The printing ink of the present invention is obtained by further blending a pigment or the like with the varnish for printing ink. In addition to the pigment, for example, various additives such as wax, a drying accelerator (dryer), and a drying inhibitor can be used.

Examples of the pigment include organic pigments for printing inks described in “Organic Pigment Handbook (Author: Isao Hashimoto, Publisher: Color Office, 2006 First Edition)”, soluble azo pigments, insoluble azo pigments, condensed azo pigments. Pigment, metal phthalocyanine pigment, metal-free phthalocyanine pigment, quinacridone pigment, perylene pigment, perinone pigment, isoindolinone pigment, isoindoline pigment, dioxazine pigment, thioindigo pigment, anthraquinone pigment, quinophthalone pigment, metal complex pigment, diketopyrrolo A pyrrole pigment, a carbon black pigment, other polycyclic pigments, and the like can be used. In the present invention, inorganic pigments can also be used. For example, in addition to inorganic coloring pigments such as titanium oxide, kraftite, and zinc white, lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth Inorganic extender pigments such as talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, and abrasive powder, silicone, and glass beads. The blending amount of these pigments varies depending on the type of the intended printing ink, but is usually preferably in the range of 5 to 55 parts by mass per 100 parts by mass of the printing ink.

The wax is added for the purpose of improving the friction resistance, anti-blocking property, slipperiness, anti-scratch property, etc. of the ink coating film, such as carnauba wax, wax, lanolin, montan wax, paraffin wax. And natural waxes such as microcrystalline wax; synthetic waxes such as Fischer-Trops wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compound. The blending amount of the wax varies depending on the type of the printing ink to be used, but it is usually preferable to be in the range of 0.1 to 7.0 parts by mass in 100 parts by mass of the printing ink.

The drying accelerator (dryer) is added for the purpose of improving the drying property of the ink coating film. For example, metals such as cobalt, manganese, lead, iron, and zinc and octylic acid, naphthenic acid, neodecanoic acid are used. And metal soaps which are salts with carboxylic acids such as The blending amount of the drying accelerator varies depending on the type of the intended printing ink, but is usually preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the printing ink.

The drying inhibitor is added for the purpose of improving storage stability and suppressing skinning, and examples thereof include hydroquinone, methoquinone, tert-butylhydroquinone, and the like. The amount of the drying inhibitor is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the printing ink, although the blending amount of the drying inhibitor varies depending on the type of the intended printing ink.

These various additives added to the printing ink may be added at any stage of the printing ink production as long as they can be uniformly mixed in the printing ink. Specifically, it may be added at the final stage of printing ink production, or may be added in advance at the production stage of printing ink varnish.

The printing ink of the present invention is, for example, rosin-modified resole resin, gelling agent, organic solvent, pigment and other additives, kneaded and prepared using a known ink manufacturing apparatus such as a roll mill, a ball mill, an attritor, and a sand mill. Can be obtained.

The printing ink of the present invention thus adjusted can be suitably used as an offset ink, a resin letterpress ink, and among them, a heat-drying offset rotary ink, an osmotic drying newspaper ink, and an oxidation polymerization sheet-fed ink. . Moreover, since the printing ink of the present invention exhibits excellent emulsification characteristics as described above, it is particularly suitable for use in obtaining printed matter by offset rotary printing or offset sheet-fed printing, which is a printing method using water such as a PS plate. Can be used.

Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In addition, in an Example, a part and% are a mass part and the mass%, respectively.

In the examples of the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column "HZ-H" manufactured by Tosoh Corporation
+ Tosoh Co., Ltd. “TSK-GEL SuperHZM-H” x 4 detectors: RI (differential refractometer)
Data processing: “GPC-8320 EcoSEC application” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 0.6 ml / min Standard: The following monodispersed polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8320 EcoSEC application”.
(Used polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-380” manufactured by Tosoh Corporation
“F-450” manufactured by Tosoh Corporation
“F-850” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Production Example 1 Production of Resole Resin (B-1) Solution In a pressurized reaction kettle equipped with a stirrer and a thermometer, 1000 parts by mass of para-tertiary butylphenol was charged and heated at 120 ° C. for dissolution. Next, 520 parts by mass of 92% paraformaldehyde and 8 parts by mass of calcium hydroxide were added, the temperature was raised to 130 ° C., the reaction was performed for 2 hours, the pressure was reduced to normal pressure, and the mixture was further stirred for 20 minutes. ) To 800 parts by mass of this resole resin, 200 parts by mass of a petroleum solvent (“AF Solvent No. 7” manufactured by JX Nippon Oil & Energy is added) and stirred at 110 ° C. for 1 hour, and a resole resin (B-1 ) A solution was obtained.

Example 1 Production of rosin-modified phenolic resin (1) A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introducing device was charged with 1000 parts by mass of gum rosin having an acid value of 165 mgKOH / g and heated to 180 ° C. After heating, 60 parts by mass of pentaerythritol, 40 parts by mass of glycerin, and 2 parts by mass of zinc oxide were added, and the temperature was raised to 250 ° C. until the acid value became 20 mgKOH / g or less. After lowering the temperature to 180 ° C., 160 parts by mass of petroleum resin, 340 parts by mass of petroleum solvent (“AF Solvent No. 7” manufactured by JX Nippon Mining & Energy), and 100 parts by mass of soybean oil are obtained. The resole resin (B-1) solution was charged stepwise. When the Gardner viscosity of the 50% toluene solution reached B to C, the charging of the resole resin (B-1) solution was stopped and the mixture was further stirred for 30 minutes to obtain a rosin-modified phenol resin (1). The total amount of the resole resin (B-1) solution added was 520 parts by mass. Moreover, the weight average molecular weight (Mw) of the rosin modified phenolic resin (1) was 60,000.

Comparative Example 1 Production of rosin-modified phenolic resin (2) A four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introducing device was charged with 1000 parts by mass of gum rosin having an acid value of 165 mgKOH / g and heated to 180 ° C. After heating, 60 parts by mass of pentaerythritol, 40 parts by mass of glycerin, and 2 parts by mass of zinc oxide were added, and the temperature was raised to 250 ° C. until the acid value became 20 mgKOH / g or less. After the temperature was lowered to 180 ° C., 160 parts by mass of a petroleum resin and 315 parts by mass of a petroleum solvent (“AF Solvent No. 7” manufactured by JX Nippon Oil & Energy) were added, and the resole resin (B— 1) The solution was added stepwise. The charging was stopped when the Gardner viscosity of the 50% toluene solution became F to G, and the mixture was further stirred for 30 minutes to obtain a rosin-modified phenol resin (2). The total amount of the resole resin (B-1) solution added was 520 parts by mass. Moreover, the weight average molecular weight (Mw) of the rosin modified phenolic resin (2) was 80,000.

Comparative Example 2 Production of rosin-modified phenolic resin (3) In a four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas introducing device, 1000 parts by mass of gum rosin having an acid value of 165 mgKOH / g and 100 parts by mass of soybean oil Parts, and after heating up to 180 ° C., 60 parts by mass of pentaerythritol, 40 parts by mass of glycerin and 2 parts by mass of zinc oxide are added, and the temperature is raised to 250 ° C. until the acid value becomes 20 mgKOH / g or less. Reacted. After the temperature was lowered to 180 ° C., 160 parts by mass of a petroleum resin and 340 parts by mass of a petroleum solvent (“AF Solvent No. 7” manufactured by JX Nippon Oil & Energy) were added, and the resole resin (B-1) obtained in Production Example 1 was added. ) The solution was added stepwise. The charging was stopped when the Gardner viscosity of the 50% toluene solution became F to G, and the mixture was further stirred for 30 minutes to obtain a rosin-modified phenolic resin (3). The total amount of the resole resin (B-1) solution added was 520 parts by mass. Moreover, the weight average molecular weight (Mw) of the rosin modified phenolic resin (3) was 75,000.

Evaluation of solvent solubility The solvent solubility of the rosin-modified phenolic resin obtained in Example 1 and Comparative Examples 1 and 2 and the toluene solution of the varnish for printing ink prepared in the following manner was evaluated by heptane tolerance. The results are shown in Table 2.

1. Evaluation of solvent solubility of rosin-modified phenolic resin To 1 g of a solution in which rosin-modified phenolic resin and toluene were mixed at a mass ratio of 1/1, 0.1 ml of heptane was added and stirred. The total amount of heptane (ml) added at the time when white turbidity (ml) × 100 was taken as the heptane tolerance.

2. Solvent solubility evaluation of varnish for printing ink In the ratio shown in Table 1, rosin-modified phenolic resin and soybean oil are heated and stirred at 200 ° C. for 1 hour, and then petroleum solvent (“AF manufactured by JX Nippon Mining & Energy Corporation” -Solvent 7 ") was added. After the temperature was lowered to 160 ° C., a gelling agent (ethyl acetyl acetate aluminum di-n-butyrate) was added, and the mixture was held at the same temperature for 1 hour to prepare a varnish for printing ink. The amount of soybean oil added is such that the total mass of soybean oil in the rosin modified phenolic resin and post-added soybean oil is about 22% by mass with respect to the total mass of the rosin modified phenolic resin and soybean oil. The amount of the petroleum solvent was adjusted so that the viscosity of the varnish for printing ink was 450 Pa · S.
To 1 g of a solution obtained by mixing the printing ink varnish and toluene at a mass ratio of 1/2, 0.1 ml of heptane was added and stirred. The value of the total amount (ml) of heptane added when white turbidity occurred was defined as heptane tolerance.

Claims (8)

A rosin-modified phenolic resin comprising rosin (A), resole resin (B), polyol compound (C) and fat (D) as essential raw materials, and reacting rosin (A) with polyol compound (C) A rosin-modified phenolic resin produced by a method comprising (α), then a step (β) of reacting fat (D), and a step (γ) of further reacting resole resin (B). The rosin-modified phenol resin according to claim 1, wherein an alkylphenol having an alkyl group having 6 or less carbon atoms is used as a phenolic compound raw material of the resole resin (B). The rosin-modified phenolic resin according to claim 2, wherein 80% by mass or more of the phenolic compound raw material of the resole resin (B) is an alkylphenol having an alkyl group having 6 or less carbon atoms. A rosin-modified phenolic resin obtained by using an alkylphenol having an alkyl group having 6 or less carbon atoms as a phenolic compound raw material, and having a heptane tolerance of 350 or more. A printing ink varnish comprising the rosin-modified phenolic resin according to any one of claims 1 to 4, a gelling agent, and an organic solvent. 6. A printing ink comprising a varnish for printing ink according to claim 5 blended with a pigment. A printed matter obtained by printing the printing ink according to claim 6 on a paper substrate. A rosin-modified phenolic resin comprising rosin (A), resole resin (B), polyol compound (C) and fat (D) as essential raw materials, and reacting rosin (A) with polyol compound (C) A method for producing a rosin-modified phenolic resin, comprising: (α), then a step (β) of reacting fat (D), and further a step (γ) of reacting resole resin (B).