JP6494437B2 - Alkyd-modified resole resin and printing ink - Google Patents

Description

  The present invention relates to an alkyd-modified resole resin for printing ink, which has high heat setting properties and emulsification suitability, and excellent printing workability, a printing ink varnish and printing ink containing the alkyd-modified resole resin, and a printed matter obtained by printing the same.

  Conventionally, rosin-modified phenolic resins have been widely used for offset lithographic inks. In the field of lithographic ink, various improvements have been made so far in order to improve the printing speed and the printing work environment, but there has been no drastic change in the resin system, and there are still resins based on rosin-modified phenolic resins. Mainstream (see, for example, Patent Documents 1 and 2). Rosin, which is a raw material, is a natural resource made of pine resin, but it is also used as a raw material for tires and adhesives in addition to printing ink applications, and there is a tendency for supply to be insufficient in response to recent strong demand. On the other hand, the resin obtained from petroleum raw materials is stabilized as excavation of methane hydrate resources progresses, and the supply of vegetable oil by stable cultivation is expected to continue. Under such circumstances, there has been a demand for the development of a resin for printing ink that can exhibit performance equivalent to that of rosin-modified phenolic resin using raw materials abundantly supplied to the market such as petrochemical raw materials and vegetable oils.

Japanese Patent Publication No. 63-030579 JP 2004-175974 A

  Therefore, the problem to be solved by the present invention is a resin for printing ink that has high heat setability and emulsification suitability, and excellent printing workability, varnish and printing ink for printing ink containing the same, and printed matter obtained by printing this. It is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a resole resin modified with an alkyd resin made from fats and oils exhibits printing characteristics equivalent to those of a rosin-modified phenolic resin. The invention has been completed.

  That is, the present invention is obtained by reacting the alkyd resin (A) and the resol resin (B), and the total of the alkyd resin (A) and the resole resin (B) in the reaction raw material is 80% by mass or more. And an alkyd-modified resole resin characterized in that 80% by mass or more of the monobasic acid raw material of the alkyd resin (A) is derived from fat or fatty acid, varnish and printing ink for printing ink using the same, And a printed matter obtained by printing the same.

  ADVANTAGE OF THE INVENTION According to this invention, heat set property and emulsification ability are high, and the resin for printing ink which is excellent in printing workability | operativity, the varnish and printing ink for printing ink containing this, and the printed matter formed by printing this can be provided.

  The alkyd-modified resole resin of the present invention uses alkyd resin (A) and resole resin (B) as main raw materials. The alkyd resin (A) used in the present invention is an alkyd resin obtained by reacting a polybasic acid, an anhydride thereof, a polyhydric alcohol, a monobasic acid raw material such as fat or fatty acid, and the like. 80 mass% or more is derived from fats and oils or fatty acids.

  Examples of the polybasic acid or anhydride thereof 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; (anhydrous) alicyclic dibasic acids such as tetrahydrophthalic acid and (anhydrous) hexahydrophthalic acid; (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, etc. Aromatic dibasic acids; octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, octadecenoic acid, nonadecenoic acid, eicosenoic acid, docosenoic acid, ceracoleic acid Dimer acid and trimer acid obtained by dimerization or trimerization of unsaturated monobasic acids such as linoleic acid; ) 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, aliphatic dibasic acid, alicyclic dibasic acid, and aromatic dibasic acid are preferable from the viewpoint of good reactivity, and aromatic dibasic acid because it becomes an alkyd-modified resole resin having high elasticity and excellent printability. Is particularly preferred.

  The polyhydric alcohol is an aliphatic polyol such as alkylene diol having 2 to 16 carbon atoms, trimethylol ethane, trimethylol propane, glycerin or pentaerythritol; hydroquinone, 2-methylhydroquinone, 1,4-benzenedimethanol, biphenyldiol Aromatic ring-containing polyols such as biphenyldimethanol, bisphenol A, bisphenol F, bisphenol S, naphthalene diol, and naphthalene diethanol; the aliphatic or aromatic ring-containing polyols, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl By ring-opening polymerization with various cyclic ether compounds such as ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Resulting polyether-modified polyol; and the aliphatic or aromatic ring-containing polyols, lactone-modified polyols obtained by polycondensation of a lactone compound such as ε- caprolactone. These may be used alone or in combination of two or more. Among them, since a branched structure is introduced into the resin structure and an alkyd-modified resol resin having high elasticity and excellent printability is obtained, a trifunctional or higher functional polyol is preferable, and a trifunctional or higher aliphatic polyol is more preferable.

  The fat or fatty acid that is a monobasic acid raw material is, for example, linseed oil, tung oil, rice oil, safflower oil, soybean oil, tall oil, rapeseed oil, palm oil, castor oil, palm oil, etc .; Fatty acids; these regenerated fats and oils; higher fatty acids having 12 to 30 carbon atoms such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, and the like. These may be used alone or in combination of two or more. In addition, examples of generally known monobasic acid raw materials include low- and medium-chain fatty acids having less than 12 carbon atoms and rosin. In this invention, as long as 80 mass% or more of monobasic acid raw materials are derived from fats and oils or fatty acids, these other monobasic acid raw materials may be used in combination.

  The method for producing the alkyd resin (A) is not particularly limited. For example, a method of reacting reaction raw materials such as a polybasic acid or an anhydride thereof, a polyhydric alcohol, an oil or fat, a monobasic raw material such as a fatty acid in a lump. Or a method of reacting a monobasic acid raw material such as fat or fatty acid with a polyhydric alcohol and then adding a polybasic acid or anhydride thereof to react, a monobasic acid raw material such as an oil or fatty acid and a polybasic acid or After reacting with the anhydride, a method of reacting by adding a polyhydric alcohol, reacting the polyhydric alcohol with a polybasic acid or its anhydride, and then adding a monobasic acid raw material such as fat or fatty acid The method of making it react is mentioned. The reaction temperature can be monitored by measuring the progress of the reaction at 120 to 300 ° C. by measuring the amount of water distilled by the dehydration reaction, the acid value or the hydroxyl value. Moreover, you may use an esterification catalyst suitably as needed.

  The oil length of the alkyd resin (A) is preferably in the range of 45% to 80% because it is excellent in emulsification suitability and pigment dispersibility, and is excellent in gloss on the printed surface when converted into an ink.

  Further, the mass average molecular weight (Mw) of the alkyd resin (A) is appropriately adjusted depending on the type of printing ink and the desired performance. Particularly, the elastic value suitable for offset printing applications is 10,000 to 100. Is preferably in the range of 30,000, more preferably in the range of 30,000 to 70,000.

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 Corporation “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 monodisperse 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 viscosity of the alkyd resin (A) is appropriately adjusted depending on the type of printing ink and the desired performance, but the value measured with an E-type viscometer is 100 particularly suitable for offset printing applications. It is preferably in the range of ˜300 Pa · s.

  The acid value of the alkyd resin (A) is preferably 30 mgKOH / g or less, and more preferably in the range of 0.1 to 10 mgKOH / g, since it becomes an alkyd-modified resol resin having excellent emulsification ability. Further, the hydroxyl value of the alkyd resin (A) is preferably in the range of 1 to 30 mgKOH / g because it becomes an alkyd-modified resol resin having excellent emulsification ability.

  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 alkylphenols having 1 to 10 carbon atoms such as cresol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, and xylenol in addition to phenol; 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. Of these, alkylphenols are preferred because they provide an alkyd-modified resole resin with an excellent balance between emulsification ability and elasticity.

  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 in 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. The method of making it react for 1 to 5 hours by the temperature conditions of 50-150 degreeC in the presence of a basic catalyst of a grade is 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.

  The resol resin (B) may be modified with a reaction material other than the phenolic compound and the aldehyde compound. Specifically, diene-modified resole resins modified with diene compounds such as dicyclopentadiene and cyclopentadiene, alkoxylated resole resins modified with alcohols such as n-butyl alcohol, isobutyl alcohol, and n-amyl alcohol, etc. Can be mentioned. In the alkyd-modified resole resin of the present invention, it is preferable to use a diene-modified resole resin modified with a diene compound because it has a high glass transition temperature and is highly hydrophobic and elastic.

  Examples of the method for producing the diene resole resin include a method in which the phenolic compound, the aldehyde compound, and the diene compound are reacted at a time. As for the reaction ratio of the phenolic compound and the diene compound, for example, the diene compound is preferably used at a ratio of 0.5 to 1 mol with respect to 1 mol of the phenolic compound.

  The alkyd-modified resole resin of the present invention is obtained by reacting the alkyd resin (A) with the resole resin (B). Since the reaction ratio of the two is an alkyd-modified resol resin having an excellent balance between pigment dispersibility and printability, the alkyd resin (A) and the resole resin (B) mass ratio [(A) / (B)] Is preferably in the range of 1/1 to 1/5, and preferably in the range of 1 / 1.5 to 1/4. Moreover, it is preferable that the reaction temperature at this time is about 100-200 degreeC.

  The alkyd-modified resol resin of the present invention thus obtained is excellent in printability, so that the weight average molecular weight is preferably in the range of 50,000 to 150,000.

  The varnish for printing ink of the present invention contains the alkyd-modified resole resin, a gelling agent, and an organic solvent. The gelling agent is used for the purpose of adjusting the viscoelasticity of the varnish for printing ink. For example, aluminum octylate, aluminum stearate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetyl acetate, Aluminum dibutoxide monoacetyl acetate, aluminum triacetyl acetate, tetraisopropoxy titanium, tetrabutoxy titanium, dipropoxy bis (acetylacetonato) titanium, tetrabutoxy zirconium, tolylene diisocyanate, diphenyl diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, Known materials such as isophorone diisocyanate can be used without particular limitation. These may be used alone or in combination of two or more.

  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 D13” from Exxon Chemical Co., Ltd. ", Exor D160", "Exor D100K", "Exor D120K", "Exor D130K", "Exor D280", "Exor D300", "Exor D320"; "Magisol-40" and "Magisol" manufactured by Maggie Bros. -44 "," Maggie Sol-47 "," Maggi Sol-52 "," Maggi Sol-60 "and the like.

  Among these, the AF solvent is preferable because of the excellent solubility of the alkyd-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.

  Although the varnish for printing ink of this invention can be used for various printing ink uses, when using for an offset ink use, it is preferable to adjust so that the non volatile matter of the varnish for printing ink may be 30-75 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 varnish for printing ink 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 varnish composition for ink from being peeled. 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, and 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, Issuer: 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 in 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 intended printing ink, but is usually preferably 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 Although the blending amount of the drying accelerator varies depending on the type of the printing ink to be used, it is usually preferably in the range of 0.01 to 5 parts by mass in 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-butyl hydroquinone and the like. The amount of the drying inhibitor to be added 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 in 100 parts by mass of the printing ink.

  Various additives added to these printing inks may be added at any stage of 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, alkyd-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, ball mill, attritor, and 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 described more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, “part” and “%” are based on mass unless otherwise specified. Moreover, the various property values of the resin and varnish obtained in each Example and Comparative Example were measured by the following methods.

Measurement of Viscosity Using an E-type viscometer, measurement was performed under the conditions of 0.2 ml of a test sample, spindle R9.7, rotation speed 1 to 10 rpm, and 25 ° C.

Measurement of weight average molecular weight (Mw) It was 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 Corporation “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 monodisperse 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 Alkyd Resin (A-1) A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser with a dehydration trap, and a nitrogen gas introduction device was charged with 784 parts by mass of soybean oil and 70 parts by mass of glycerin. The temperature was raised to 230 ° C. and reacted for 2 hours. Next, the mixture was cooled to 180 ° C., charged with 20 parts by mass of pentaerythritol and 80 parts by mass of glycerin, heated to 220 ° C. over 5 hours, and further reacted for 3 hours. After the generation of condensed water weakened, the temperature was further raised to 240 ° C., and a dehydration reaction was further performed for 6 hours to obtain an alkyd resin (A-1) having an oil length of 74%. The acid value of the obtained alkyd resin (A-1) was 5.0 mgKOH / g, the viscosity measured with an E-type viscometer was 200 Pa · sec, and the weight average molecular weight (Mw) was 50,000. In addition, 100 mass% of alkyd resin (A-1) of a monobasic acid raw material is soybean oil.

Production Example 2 Production of Alkyd Resin (A-2) In the same apparatus as in Production Example 1, 750 parts by mass of soybean oil fatty acid and 240 parts by mass of isophthalic acid were charged, heated to 150 ° C. and stirred for 1 hour. Next, 20 parts by mass of pentaerythritol and 150 parts by mass of glycerin were charged, and the temperature was raised to 220 ° C. over 5 hours, followed by further reaction for 3 hours. After the generation of condensed water weakened, the temperature was further raised to 240 ° C., and the dehydration reaction was further performed for 6 hours to obtain an alkyd resin (A-2) having an oil length of 74%. The acid value of the obtained alkyd resin (A-2) was 5.0 mgKOH / g, the viscosity measured with an E-type viscometer was 200 Pa · sec, and the weight average molecular weight (Mw) was 50,000. In addition, 100 mass% of alkyd resin (A-2) of a monobasic acid raw material is soybean oil fatty acid.

Production Example 3 Production of Resol Resin (B-1) In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction device, 1000 parts by mass of para-tertiary butylphenol, 435 parts by mass of 92% paraformaldehyde, 1000 parts by mass of xylene and 10 parts by mass of 50% sodium hydroxide were charged, heated to 90 ° C., and reacted for 6 hours while maintaining the same temperature. Next, after adding and neutralizing a mixed solution of 300 parts by mass of water and 13 parts by mass of hydrochloric acid, 1000 parts by mass of water was further added, and the supernatant was taken out to obtain a resole resin solution (B-1) having a resin solid content of 58% by mass. Got.

Production Example 4 Production of Resol Resin (B-2) In the same apparatus as in Production Example 3, 1000 parts by mass of para-tert-butylphenol, 440 parts by mass of dicyclopentadiene, 435 parts by mass of paraformaldehyde, 1000 parts by mass of xylene, 50 10 parts by weight of sodium hydroxide was charged, the temperature was raised to 90 ° C., and the reaction was carried out for 6 hours while maintaining the same temperature. Subsequently, after neutralizing by adding a mixed solution of 300 parts by mass of water and 13 parts by mass of hydrochloric acid, 1000 parts by mass of water was further added, the supernatant was taken out, and a resole resin solution (B- 2) was obtained.

Production Example 5 Production of Resol Resin (B-3) In a pressurized reaction kettle equipped with a stirrer and a thermometer, 1000 parts by mass of para-tert-butylphenol was charged and dissolved by heating at 120 ° C. Next, 440 parts by mass of dicyclopentadiene, 434 parts by mass of 92% paraformaldehyde, and 8 parts by mass of calcium hydroxide were added, the temperature was raised to 130 ° C., and the reaction was continued for 2 hours while maintaining the same temperature. )

Example 1 Production of Alkyd Modified Resole Resin (1) 200 parts by mass of the alkyd resin (A-1) was charged into a four-necked flask equipped with a stirrer, thermometer, reflux condenser with dehydration trap, and nitrogen gas introducing device. The temperature was raised to 170 ° C., and 730 parts by mass of the resol resin solution (B-1) was added dropwise using a dropping funnel over 3 hours while maintaining the same temperature. After maintaining the same temperature and further reacting for 5 hours, the solvent was removed under reduced pressure for 30 minutes to obtain an alkyd-modified resole resin (1). The obtained alkyd-modified resole resin (1) had a weight average molecular weight (Mw) of 85,000.

Example 2 Production of Alkyd Modified Resole Resin (2) In the same apparatus as in Example 1, 200 parts by mass of the alkyd resin (A-1) was charged, and the temperature was raised to 170 ° C. while maintaining the same temperature. 865 parts by mass of the resin solution (B-2) was added dropwise using a dropping funnel over 3 hours. After maintaining the same temperature and further reacting for 5 hours, the solvent was removed under reduced pressure for 30 minutes to obtain an alkyd-modified resole resin (2). The obtained alkyd-modified resole resin (2) had a weight average molecular weight (Mw) of 95,000.

Example 3 Production of Alkyd Modified Resole Resin (3) In the same apparatus as in Example 1, 200 parts by mass of the alkyd resin (A-1) and 570 parts by mass of the resol resin (B-3) were charged at 170 ° C. The reaction was carried out for 8 hours to obtain an alkyd-modified resole resin (3). The obtained alkyd-modified resole resin (3) had a weight average molecular weight (Mw) of 92,000.

Example 4 Production of Alkyd Modified Resole Resin (4) In the same apparatus as in Example 1, 200 parts by mass of the alkyd resin (A-2) and 570 parts by mass of the resol resin (B-3) were charged at 170 ° C. Reaction was performed for 8 hours to obtain an alkyd-modified resole resin (4). The obtained alkyd-modified resole resin (4) had a weight average molecular weight (Mw) of 90,000.

Examples 5 to 8 and Comparative Example 1 Adjustment of printing ink and evaluation thereof Printing ink was adjusted in the following manner, and various evaluation tests were performed. The test results are shown in Table 3.

Preparation of printing ink varnish Phenol resin, soybean oil, organic solvent ("AF-solvent 7" manufactured by JX Nippon Mining & Energy Co., Ltd.), gelling agent (aluminum dibutoxide monoacetyl acetate) at the ratios shown in Table 1 The varnish for printing ink was adjusted.

※１）比較用フェノール樹脂として「ＢＥＣＡＣＩＴＥ １１２６ＨＶ」（ＤＩＣ株式会社製、一塩基酸原料の１００質量％がロジンであるロジン変性フェノール樹脂）を用いた。

* 1) “BECACITE 1126HV” (manufactured by DIC Corporation, rosin-modified phenolic resin in which 100% by mass of the monobasic acid raw material is rosin) was used as a comparative phenol resin.

Adjustment of printing ink In the ratio shown in Table 2, a varnish for printing ink, a pigment (“FASTOGENBLUE FA5375” manufactured by DIC Corporation), and calcium carbonate (“Shirashinka TDD” manufactured by Shiroishi Kogyo Co., Ltd.) are blended, and a three-roll mill is used. The kneaded meat was dispersed until the kneading degree (JIS K 5701-1 A value) was 5.0 μm or less. Furthermore, soybean oil, organic solvent (“AF-Solvent No. 7” manufactured by JX Nippon Oil & Energy Corporation), anti-drying agent 2,6-di-tert-butyl-4-cresol (“H” manufactured by Honshu Chemical Industry Co., Ltd.) -BHT ") and blended the printing ink.

Evaluation of heat setting property Conveyor type in which 0.125 ml of the above-mentioned printing ink (1) was developed on OK top-coated paper with a 2-split roll and then kept at 200 ° C. using an RI tester (manufactured by Meisei Seisakusho). The dryer was passed over 5 seconds. The degree of stickiness of the color-extracted product was confirmed by finger touch, and the number of times the color-extracted product was passed through the conveyor before drying was measured. The heat setting property was evaluated based on the number of times the conveyor was passed before drying. The smaller the number of passes, the better the dryness.

Evaluation of Gloss Using an RI tester, 0.15 ml of the printing ink (1) was developed on OK top-coated paper with a two-part roll, and then allowed to stand for 10 seconds in a drier at an ambient temperature of 100 ° C. and dried. The gloss value of the developed product after 24 hours from drying was measured with a 60 ° gloss meter (manufactured by BYK Garder GmbH).

Emulsification suitability Using a lithotronic emulsification tester (manufactured by Novocontrol), 25 g of the printing ink (1), temperature 40 ° C., water addition speed 2 mL / min, stirring speed 1200 rpm, conditioning 5 minutes before starting water addition, The torque (unit mN · m) when water was added to the printing ink was continuously measured under the conditions of a clearance of 1 mm between the stirring blade and the cup and a measurement frequency of 2 times / second. When the torque began to fluctuate in an unstable manner and the standard deviation of the latest 10 measured values exceeded 100, the value calculated by the following equation was taken as the maximum emulsification rate. The specific gravity of water is 1 g / mL.
Maximum emulsification rate (%) = [total dripping amount of water (g) / amount of printing ink (25 g)] × 100

Reprintability Using an R704 printing machine manufactured by Roland, after printing 5000 copies at the same density, it was left as it was for 30 minutes. The number of sheets required until the stain was removed when reprinted was examined and evaluated according to the following criteria.
◎: 59 parts or less ○: 60 parts or more and 79 parts or less ×: on 80 sites

Water Stick Adhesiveness Using a R704 printing machine manufactured by Roland, the adhesion state of the printing ink to the swim roller after printing 5000 copies at the same density was evaluated by touch.
A: No sticking X: There is sticking.

Claims (4)

Obtained by reacting the alkyd resin (A) with the resole resin (B), which is a dicyclopentadiene-modified resole resin, the total of the alkyd resin (A) and the resole resin (B) in the reaction raw material is 80 mass. And 80% by mass or more of the monobasic acid raw material of the alkyd resin (A) is derived from fats and oils, fatty acids derived from fats and oils, recycled fats and oils, or higher fatty acids having 12 to 30 carbon atoms. Characteristic alkyd-modified resole resin. Claim 1 Symbol placement alkyd-modified resole resin, a gelling agent, and printing ink varnish contains an organic solvent. A printing ink comprising a pigment in the printing ink varnish according to claim 2 . A printed matter obtained by printing the printing ink according to claim 3 on a paper substrate.