JP2007056188A - Reaction-produced composition and printing ink containing the same, and printed matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a reaction-produced composition good in solubility, fluidity and gloss, to provide a printing ink containing the same, and to provide printed matter therewith. <P>SOLUTION: The composition is obtained by transesterification between animal/vegetable oil and a polyhydric alcohol followed by esterification with a monobasic acid (except acrylic acid and methacrylic acid); wherein the animal/vegetable oil consists of recovered and recycled oil, and the esterification catalyst is either one of 0-5 wt.% alkali metal compound-, alkaline earth metal compound-, titanium compound-, zirconium compound- and sulfonic acid compound-based ones. The printing ink contains 0.1-30 wt.% of the above composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a reaction product composition having good solubility, fluidity, and gloss, which is obtained by subjecting animal and vegetable oils and polyhydric alcohols to esterification with a single basic acid (excluding acrylic acid and methacrylic acid) after transesterification. The present invention relates to ink and its printed matter.

Conventionally, rosin phenol resin using resin acid containing rosin is used as resin for printing ink, but rosin phenol resin uses formaldehyde in the reaction process and does not use formaldehyde from the viewpoint of work environment etc. Rosin alkyd resins and the like using resin acids containing rosins are being studied. In recent years, paraffin, olefin, and naphthene-based allomer-free solvents (AF solvents) with an aromatic component of 1% or less have been used as printing ink solvents from the viewpoint of the environment. These AF solvents often deteriorate in solubility with printing ink resins such as rosin phenol resin, rosin alkyd resin, and petroleum resin. Therefore, in parallel with the development of resins that dissolve in these solvents, it has been desired to develop materials that compensate for the lack of solubility of the resin and the solvent.
None.

  The present invention is a reaction product composition having good solubility, fluidity, and gloss, which is obtained by subjecting animal and vegetable oils and polyhydric alcohols to esterification with a single basic acid (excluding acrylic acid and methacrylic acid) after transesterification. The present invention relates to ink and its printed matter.

That is, the present invention relates to a reaction product composition obtained by subjecting animal and vegetable oils and polyhydric alcohols to esterification with monobasic acid (excluding acrylic acid and methacrylic acid) after transesterification.
In addition, the present invention relates to the reaction product composition as described above, wherein the animal and vegetable oil is a recovered regenerated oil.
In addition, the present invention relates to the reaction product composition as described above, wherein the animal and vegetable oils are soybean oil, linseed oil and tung oil.
In addition, 0-5% by weight of an alkali metal compound, alkaline earth metal compound, titanium compound, zirconium compound, or sulfonic acid compound based transesterification catalyst or esterification catalyst is added. It relates to the reaction product composition described above.
In addition, the present invention relates to a printing ink containing 0.1 to 30% by weight of the reaction product composition described above.
In addition, it relates to a printing ink as described above comprising 1-50% by weight rosin phenolic resin and / or 1-50% by weight rosin alkyd resin and / or 1-50% by weight petroleum resin alkyd.
In addition, the present invention relates to a printed matter obtained by printing the above-described printing ink on a substrate.

  According to the present invention, it is possible to provide a printing ink excellent in solubility, fluidity and gloss, and environmentally friendly, and a printed matter thereof.

  The animal and vegetable oils and fatty acid monoesters thereof used in the present invention will be described. First, vegetable oil is triglyceride in which at least one fatty acid is a fatty acid having at least one carbon-carbon unsaturated bond in triglyceride of glycerin and fatty acid. Real oil, linseed oil, eno oil, oil deer oil, olive oil, cacao oil, kapok oil, kayak oil, mustard oil, kyounin oil, kiri oil, kukui oil, walnut oil, poppy oil, sesame oil, safflower oil, radish seed oil , Soybean oil, Daifucho oil, Camellia oil, Corn oil, Rapeseed oil, Niger oil, Nuka oil, Palm oil, Castor oil, Sunflower oil, Grape seed oil, Gentia oil, Pine seed oil, Cottonseed oil, Palm oil, Peanut oil And dehydrated castor oil. Further preferred vegetable oils are vegetable oils having an iodine value of at least 100 or more (in parentheses indicate the oil and fat chemical product manual: the iodine value quoted from the Nikkan Kogyo Shimbun), Asa oil (149 or more), Linseed oil (over 170), Eno oil (over 192), deer oil (over 140), Kapok oil (85-102), kaya oil (over 130), mustard oil (over 101), Kyonin oil (97-109) , Kiri oil (145 or higher), kukui oil (136 or higher), walnut oil (143 or higher), poppy oil (131 or higher), sesame oil (104 or higher), safflower oil (130 or higher), radish seed oil (98 to 112) ), Soybean oil (117 or more), large fusose oil (101), corn oil (109 or more), rapeseed oil (97 to 107), niger oil (126 or more), nuka oil (92 to 1) 5), sunflower oil (125 or more), grape seed oil (124 or more), gentian oil (93 to 105), pine seed oil (146 or more), cottonseed oil (99 to 113), peanut oil (84 to 102), dehydrated Castor oil (147 or more) is preferably used, and more preferably a vegetable oil having an iodine value of 120 or more. By setting the iodine value to 120 or more, it is possible to further improve the drying property by oxidative polymerization of the curable composition. Furthermore, fish oil such as squid oil and sama oil, animal oil such as beef tallow oil, horse oil, whale oil and sheep oil are exemplified.

  In addition, in this invention, the regenerated vegetable oil collect | recovered / regenerated after using for edibles, such as tempura oil, can also be used. The regenerated vegetable oil is preferably an oil that has been regenerated with a water content of 0.3% by weight or less, an iodine value of 100 or more, and an acid value of 3 or less. Impurities that affect the emulsification behavior of the ink, such as contained salt, can be removed, and by regenerating the iodine value as 100 or more, it becomes possible to make the dryness, that is, the oxidative polymerization good, Furthermore, by selecting and regenerating vegetable oil having an acid value of 3 or less, the acid value of the regenerated vegetable oil can be lowered, and overemulsification of the ink can be suppressed. As a method for regenerating the recovered vegetable oil, methods such as filtration, removal of precipitates by standing, and decolorization by activated clay are taken.

  Next, examples of the fatty acid ester in the present invention include fatty acid monoesters obtained by ester reaction of saturated or unsaturated fatty acids obtained by hydrolysis of vegetable oils and saturated or unsaturated alcohols. A monoester of a fatty acid monohydric alcohol having a boiling point of 200 ° C. or more at a normal pressure (101.3 kPa) and a normal pressure (101.3 kPa). Specific examples of such a fatty acid ester include a saturated fatty acid monoester, butyric acid Hexyl, heptyl butyrate, hexyl butyrate, octyl butyrate, butyl caproate, acyl caproate, hexyl caproate, heptyl caproate, octyl caproate, nonyl caproate, propyl enanthate, butyl enanthate, amyl enanthate, hexyl enanthate , Heptyl enanthate, octyl enanthate , Ethyl caprylate, vinyl caprylate, propyl caprylate, isopropyl caprylate, butyl caprylate, amyl caprylate, hexyl caprylate, heptyl caprylate, octyl caprylate, methyl pelargonate, ethyl pelargonate, vinyl pelargonate, pelargon Propyl acid, butyl pelargonate, amyl pelargonate, heptyl pelargonate, methyl caprate, ethyl caprate, vinyl caprate, propyl caprate, isopropyl caprate, butyl caprate, hexyl caprate, heptyl caprate, methyl laurate , Ethyl laurate, vinyl laurate, propyl laurate, isopropyl laurate, butyl laurate, isoamyl laurate, hexyl laurate, 2-ethyl-hexyl laurate And the like.

  As unsaturated fatty acid monohydric alcohol monoester, ethyl oleate, propyl oleate, butyl oleate, allyl oleate, isoamyl oleate, heptyl oleate, 2-ethylhexyl oleate, methyl elaidate, ethyl elaidate, Propyl elaidate, allyl elaidate, butyl elaidate, isobutyl elaidate, tert-butyl elaidate, isoamyl elaidate, 2-ethylhexyl elaidate, methyl linoleate, ethyl linoleate, allyl linoleate, propyl linoleate Isopropyl linoleate, butyl linoleate, isobutyl linoleate, tert-butyl linoleate, pentyl linoleate, hexyl linoleate, heptyl linoleate, 2-ethyl linoleate Sil, methyl linolenate, ethyl linolenate, allyl linolenate, propyl linolenate, isopropyl linolenate, butyl linolenate, isobutyl linolenate, tert-butyl linolenate, pentyl linolenate, hexyl linolenate, heptyl linolenate, linolenic acid 2-ethylhexyl acid, methyl arachidonic acid, ethyl arachidonic acid, allyl arachidonic acid, propyl arachidonic acid, isopropyl arachidonic acid, butyl arachidate, isobutyl arachidonic acid, tert-butyl arachidonic acid, pentyl arachidonic acid, hexyl arachidonic acid Heptyl acid, 2-ethylhexyl arachidonate, methyl eicosenoate, ethyl eicosenoate, allyl eicosenoate, propyl eicosenoate, isopropyl eicosenoate, eico Butylate, isobutyl eicenoate, tert-butyl eicosenoate, pentyl eicosenoate, hexyl eicosenoate, heptyl eicosenoate, 2-ethylhexyl eicosenoate, methyl eicosapentaenoate, ethyl eicosapentaenoate, allyl eicosapentaenoate, e Icosapentaenoic acid propyl, eicosapentaenoic acid isopropyl, eicosapentaenoic acid butyl, eicosapentaenoic acid isobutyl, eicosapentaenoic acid-tert-butyl, eicosapentaenoic acid pentyl, eicosapentaenoic acid hexyl, eicosapentaenoic acid heptyl, eicosapentaenoic acid-2-ethylhexyl, Methyl erucate, ethyl erucate, allyl erucate, propyl erucate, isopropyl erucate, butyl erucate, isobu erucate Til, tert-butyl erucate, pentyl erucate, hexyl erucate, heptyl erucate, 2-ethylhexyl erucate, methyl docosahexaenoate, ethyl docosahexaenoate, allyl docosahexaenoate, propyl docosahexaenoate, isopropyl docosahexaenoate, docosahexaenoic acid Butyl, docosahexaenoate isobutyl, docosahexaenoate-tert-butyl, docosahexaenoate pentyl, docosahexaenoate hexyl, docosahexaenoate heptyl, docosahexaenoate-2-ethylhexyl, ricinoleate, ethyl ricinoleate, allyl ricinoleate, ricinoleate, ricinoleic acid Isopropyl, butyl ricinoleate, isobutyl ricinoleate, tert-butyl ricinoleate, ricinole Acid pentyl, hexyl ricinoleate, heptyl ricinoleate, and the like can be exemplified ricinoleic acid 2-ethylhexyl.

  As a polyhydric alcohol compound, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, 1, 2 hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7 heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2- Xadecanediol, neopentyl glycol, 2 ethylhexyl diol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2 , 4-Dimethylpentanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane (Mitsubishi Chemical), 2-ethyl-1,3-hexanediol 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentane Diol, 2,4-diethyl-1,5-pentanediol, xylene glycol, cyclohexanedimethylol, Idroquinone bis (2-hydroxyethyl) ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, nepentyl glycol, branched alkyl diols such as butyl, ethyl, propanediol, tricyclodecane dimethylol, dicyclopentadiene diallyl alcohol Copolymer, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, hydrogenated catechol, hydrogenated resorcin, hydrogenated hydroquinone, tri- or higher alcohol compound (mono or di or tri) glycerin, (mono or di or Tri) trimethylolethane, (mono or di or tri) trimethylol propane, (mono or di or tri) trimethylol alkane, (mono or di or tri) penta Risurito - le, aliphatic polyhydric alcohols such as sorbitol, tris (2-hydroxyethyl) isocyanurate, inositol, cyclic polyhydric alcohol such as cellulose and the like. Furthermore, compounds obtained by the reaction of polyhydric alcohols, polyhydric phenols, amine-based active hydrogen compounds with alkylene oxides such as ethylene oxide and propylene oxide, such as bisphenol A diethylene oxide adducts, catechol or resorcin or Examples include hydroquinone diethylene oxide adducts and triethanolamine triethylene oxide adducts.

  A transesterification catalyst composed of at least one of an alkali metal compound system, an alkaline earth metal compound system, a titanate compound system, a zirconium compound system, and a sulfonic acid compound system will be described. For alkali metal compounds, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, alkali metal hydroxide compounds, for alkaline earth metal compounds, beryl hydroxide, magnesium hydroxide, water Alkali earth metal compounds such as calcium oxide, strontium hydroxide and barium hydroxide, alkoxy titanate compounds such as tetrabutoxy titanate for titanate compounds, alkoxy zirconium compound such as tetrabutoxy zirconium for zirconium compounds Examples of the sulfonic acid compound system include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid and the like.

  The transesterification method is based on 0.1 mol to 10 mol of polyhydric alcohol per 1 mol (880 to 900 parts by weight) of the above-mentioned animal and vegetable oils, and 0.001 to 5% by weight, preferably 0 to 100% by weight of the total amount of the transesterification catalyst charged. The transesterification is carried out at 0.01 to 0.5 wt% at 100 ° C to 300 ° C, preferably 150 ° C to 250 ° C for 0.5 hours to 5 hours, preferably 1 to 2 hours. The end point of the transesterification is the point where the distribution changed by the transesterification reaction with respect to the molecular weight distribution before the reaction in GPC (gel permeation chromatography) becomes a steady state.

  Furthermore, as one basic acid, acetic acid, propionic acid, butyric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, eicosenoic acid, erucic acid The above-mentioned animal and vegetable oil fatty acids such as docosahexaene, ricinoleic acid, soybean oil fatty acid, linseed oil fatty acid, and tung oil fatty acid can be exemplified. Further examples include benzoic acid, methylbenzoic acid, t-butylbenzoic acid, the following rosins, o-benzoylbenzoic acid, and naphthenic acid.

  The reaction ratio between the residual hydroxyl group of the transesterification reaction product and the monobasic acid compound is such that the molar ratio of the residual hydroxyl group of the product to the carboxylic acid of the polybasic oxidation compound is 1 / 0.5 to 1 / 1.2, preferably Is 1 / 0.8 to 1 / 1.2. The esterification reaction is carried out at 180 to 270 ° C. until the acid value reaches 5 to 15 positions. The esterification reaction is uncatalyzed or acid catalysts include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, trifluoromethylsulfuric acid, Examples include fluoromethylacetic acid, Lewis acid, etc., metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkalis such as magnesium oxide, calcium oxide and zinc oxide, oxides of alkaline earth metals, metal salt catalysts, etc. Is done. These catalysts are reacted using 0 to 1% by weight in the total resin. The reaction solvent is not used or toluene, xylene, MIBK, anone or the like is used. Further, the solvent is removed under reduced pressure of 0 to 75 KPa. However, since the reactant is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. may be used in combination. Light yellow or brown liquid oil-modified alkyd having an acid value of 0.1 to 15, a weight average molecular weight of 0.1 to 50,000, preferably 0.5 to 15,000 and a viscosity of 1 to 100 Pa · s / 25 ° C. A resin is obtained.

Usually the printing ink composition is
0.1 to 30% by weight of the reaction product composition of the present invention
Resin varnish or resin gel varnish 10-70% by weight
1 to 60% by weight of vegetable oil or fatty acid ester thereof
0-50% by weight of solvent for ink
Other additives 0-10% by weight
Colorant or extender 1-40% by weight
Is used in the composition consisting of A resin acid (rosins) phenol resin, resin acid (rosins) alkyd resin, or petroleum resin alkyd having a weight average molecular weight of 0.5 to 200,000 is used as a printing ink resin. The resin acid of the present invention is not particularly limited as long as it is an organic acid present as a free or ester contained in naturally occurring rosins. Examples include abietic acid, neoabietic acid, d-pimaric acid, iso-d-pimaric acid, podocarp acid, agatendicarboxylic acid, danmarol acid, benzoic acid, cinnamic acid, and p-oxycinnamic acid. Use in the form of a natural resin containing these resin acids is preferable for handling. Gum rosin, tall oil rosin, wood rosin, partially disproportionated rosin, partially hydrogenated rosin, partially polymerized rosin, copal, dammar and other gum rosin, wood rosin , Tall oil rosin and polymerized rosin. However, since these resins are solid at room temperature, they are used as resin varnishes prepared by adding vegetable oils or their fatty acid esters and ink solvents. In order to make the viscosity of the resin varnish easy to prepare a printing ink composition (100 to 200 Pa · s), resin / vegetable oil or its fatty acid ester / ink solvent = 30-60 parts by weight / 1-60 parts by weight / 0 The resin is dissolved in 30 minutes to 1 hour in an air stream at 150 to 200 ° C. Further, in order to obtain a resin gel varnish, 0.1 to 3 parts by weight of a gelling agent is added to the dissolved resin varnish and reacted at 100 to 120 ° C. for 30 minutes to 1 hour.

  As rosin-modified phenolic resins, phenols such as carboxylic acid, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, (tertiary) butylphenol, (tertiary) octylphenol, nonylphenol, dodecylphenol, hexylphenol and mixtures thereof are condensed with formaldehyde A weight-average molecular weight of 0.5 to 200,000 obtained by subjecting the resin acid containing a reacted resole or novolak phenol resin and rosins to a chromanization reaction and further esterifying a polyol such as glycerin, trimethylolpropane, pentaerythritol, and the like. A resin having a softening point of 80 to 180 ° C. (mainstream is 130 to 170 ° C.) is used as a reaction method.

  Further examples include rosin alkyd resins and petroleum resin alkyds.

  Resin acid alkyd resin using resin acid such as rosins, 50 to 90 wt% resin acid, 3 to 50 wt% polybasic acid, 3 to 50 wt% alcohol compound, 0.01 to 10 wt% if necessary A rosin alkyd resin that is reacted at 150 to 300 ° C. using a% sulfonic acid compound as a catalyst will be described.

  The resin acid is exemplified by the above resin acids. Further, α, β-ethylenically unsaturated carboxylic acid or its anhydride is included as polybasic acid, fumaric acid, maleic acid or its anhydride, itaconic acid or its anhydride, citraconic acid or its anhydride, crotonic acid, cinnamic acid , (Meth) acrylic acid, 2,4-hexadienic acid (sorbic acid) and the like. Particularly preferred is maleic acid or its anhydride. The reaction between the resin acid and the α, β-ethylenically unsaturated carboxylic acid or its anhydride is a Diels Alder or polymerization reaction, and can be performed by a known method. For example, the Diels-Alder reaction temperature is 120 to 300 ° C, preferably 180 to 260 ° C, and the reaction time is 1 to 4 hours. Disproportionated rosin, dimer or higher rosin in polymerized rosin, hydrogenated rosin (converted rosins) are less susceptible to Diels-Alder reaction, such unmodified rosin is Diels-Alder reaction Acid modified with Currently, a printing ink solvent (aromatic free solvent, hereinafter referred to as AF solvent) having an aromatic component of 3% by weight or less is used as an environmentally friendly printing ink. When this AF solvent is used, the weight ratio of resin acid / α, β-ethylenically unsaturated carboxylic acid or anhydride thereof is 80/15 to 97/3, preferably 88/12 to 97/3. Accordingly, if the amount of α, β-ethylenically unsaturated carboxylic acid or its anhydride is large, the solubility of the resin in the printing ink solvent is deteriorated, and if it is small, an appropriate molecular weight for printing ink cannot be obtained. Furthermore, in the polymerization reaction of a resin acid with an α, β-ethylenically unsaturated carboxylic acid or an anhydride thereof, a case where polymerization is performed at 80 to 150 ° C. using a peroxide such as benzoyl peroxide as a polymerization catalyst is exemplified. In addition, other polybasic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenyl succinic anhydride, pentadecenyl succinic acid, etc. Acid, (anhydrous) maleic acid, o-phthalic acid or its anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid or its anhydride, hexahydrophthalic acid or its anhydride, (methyl) hymic acid or its anhydride And trimellitic acid or its anhydride, pyromellitic acid or its anhydride, and the like.

Further, the α and β reactants are reacted with an alcohol compound.
Examples of the polyhydric alcohol compound are the same as above.

  The reaction ratio between the α and β reaction products and the alcohol compound is such that the total molar quantity of carboxylic acids in the α and β reaction products / the total molar quantity of hydroxyl groups in the alcohol compound is 1 / 0.5 to 1/1. 2, preferably 1 / 0.8 to 1 / 1.2. The esterification reaction is carried out at 180 to 270 ° C. until the acid value reaches 15 to 30 positions. Further, the reaction is performed under reduced pressure of 0 to 75 KPa as necessary. Acid catalysts include sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid and ethanesulfonic acid, mineral acids such as sulfuric acid and hydrochloric acid, trifluoromethylsulfuric acid, trifluoromethylacetic acid, Lewis acid, etc. Furthermore, metal complexes such as tetrabutyl zirconate and tetraisopropyl titanate, alkalis such as magnesium oxide, calcium oxide and zinc oxide, oxides of alkaline earth metals, metal salt catalysts and the like are exemplified. These catalysts are reacted using 0.01 to 1% by weight in the total resin. Further, the reaction is performed under reduced pressure of 0 to 75 KPa as necessary. However, since the reactant is easily colored under such conditions, a reducing agent such as hypophosphorous acid, triphenyl phosphite, triphenyl phosphate, etc. may be used in combination. A resin having a weight average molecular weight of 0.5 to 200,000 and a softening point of 80 to 180 ° C. (mainstream is 130 to 170 ° C.) is obtained.

  Further, 90-99.9% by weight of resin acid is reacted with 0.01-10% by weight of sulfonic acid compound as a catalyst at 100-300 ° C. for 0.1-20 hours with no solvent or 10% by weight or less of solvent. The body resin acid composition will be described.

  With respect to the method for producing a multimeric resin of the present invention, the reaction temperature is preferably 100 to 300 ° C., preferably 150 to 195 ° C. The amount increases, and the softening point of the resulting resin decreases. In particular, when the reaction temperature exceeds 200 ° C., the softening point becomes close to normal temperature (25 ° C.), and when used in printing ink, the drying property deteriorates.

  The reaction time is 0.1 to 24 hours, preferably 1 to 8 hours. When the amount is less than this, the amount of the multimeric resin acid obtained is small, and when the amount is large, the multimeric resin acid obtained is expensive.

Multimers are mainly composed of dimers, but of course, it is desirable that the amount of multimers produced is large. However, in the case of the present invention, it is sufficient to produce 10 to 70% of the multimer with respect to the charged amount. If more than 10% is obtained, it is not always desirable because the reaction time is increased or the catalyst is increased. A multimeric resin composition is produced as described above.
The catalyst conforms to the catalyst used in the synthesis of the rosin phenol resin.

  Furthermore, it describes about petroleum resin alkyd. Petroleum resins and the like are obtained by cation, anion or radical polymerization of the C5 fraction or C9 fraction obtained by naphtha decomposition. Petroleum resin containing a C5 fraction is a cyclopentadiene, methylcyclopentadiene, a dimer or pentamer thereof, a cyclopentadiene monomer such as a co-multimer, or a cyclopentadiene monomer. It is obtained by thermally polymerizing a mixture with a polymerizable comonomer in the presence of a catalyst or without a catalyst. As the catalyst, a Friedel-Craft type Lewis acid catalyst, for example, boron trifluoride and its complex with phenol, ether, acetic acid and the like are usually used. The copolymerization ratio of the cyclopentadiene monomer and the comonomer copolymerizable therewith in the hydrocarbon resin of the present invention needs to be at least 5 mol% of the cyclopentadiene monomer. . Examples of the comonomer used include diisobutylene obtained by dimerizing ethylene, propylene, propene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene and isobutylene with an acid catalyst ( 2,4,4-trimethylpentene-1 and 2,4,4-trimethylpentene-2), 1-hexene, 2-hexene, 1-octene, 2-octene, 4-octene, 1-decene, etc. Chain conjugated dienes such as 1,3-butadiene, 1,3-pentadiene (piperylene), isoprene, 1,3-hexadiene, 2,4-hexadiene, styrene, α- Methylstyrene, β-methylstyrene, isopropenyltoluene, p-tert-butylstyrene, p-hydroxystyrene, vinyltoluene, dibi And vinyl aromatics such as nylbenzene, and aromatic unsaturated compounds such as indene, methylindene, coumarone (benzofuran), and methylcoumarone (2-methylbenzofuran). Petroleum resin containing C9 fraction is obtained by the above thermal polymerization of the above vinyl aromatics, aromatic unsaturated compounds and the like.

  Below, Maruzen Petroleum Co., Ltd. C5 series Marcarets M510A, Marcarets M845A, Marcarets M905A, Marcarets M100A, Marcarets # 8011, Marcarets T-100A, Marcarets R-100B, Marcarets S100A, Marcarets H505, Marcarets H700F, 25 The Furthermore, Nippon Petrochemical Co., Ltd. Nisseki Neoresin 540, Nisseki Neoresin 580, Nisseki Neoresin EP-80, Nisseki Neoresin EP-110, Nisseki Neoresin EP-140, Nisseki Neoresin PH-105, Nisseki Neoresin NB-90, Nisseki Neopolymer S, Nisseki Neopolymer 80, Nisseki Neopolymer L-90, Nisseki Neopolymer 100, Nisseki Neopolymer 110, Nisseki Neopolymer 120, Nisseki Neopolymer 130, Nisseki Neopolymer E-100, Nisseki Neopolymer E-130, Nisseki Neopolymer E-130S, Nisseki Neopolymer M, Nisseki Neopolymer S-110, Nisseki Neopolymer E-100 Nisseki Neopolymer GS, Japan Examples of the stone neopolymer 170S, TO-90, and TO-100. Further, C5 series quinton 1000 series (1325, 1345, 1500, 1522, 1700), quinton QTN1100, quinton QTN1345H, quinton RI-201 manufactured by Nippon Zeon Co., Ltd. are exemplified. Furthermore, Toho Chemical Co., Ltd. Toho High Resin (# 60, # 90, # 90S, #NX, # 120, # 130, # 140, # 120S, RS-9, RS-21, # 2100, Super # 110, Super # 110T, PA-140), COPEREX2100, etc. are exemplified. Furthermore, ESCOREZ 1100 series, 1200 series, 1300 series, 2000 series, 5000 series, 8000 series, etc. manufactured by Tonex Co., Ltd. are exemplified. In addition, C9 Petcole (hereinafter, grades LX, LX-HS, 100-T, 120, 120HV, 130, 140, 140HM, 140HM3, 150) manufactured by Tosoh Corp., C9 rich C9 / C5 mixed petro Tack (70, 90) etc. are illustrated. Further, C5 Picotac (95, B), Pico Pale 100, C9 modified C5 Hercotac 1149, C9 Endex 155, Crystallex (hereinafter each grade # 1120, 3085, 3100, 5140, F100), Hercolite, manufactured by Hercules Co., Ltd. (Hereinafter each grade # 240, 290) picolastic (hereinafter each grade A5, A75, 100, LC), hydrogenated C9-based Ligalite Y (hereinafter each grade R1010, R1090, R1100, R1125, S5100, R7100) and the like are exemplified. The

  In addition, the above α, β ethylenically unsaturated carboxylic acids or their anhydrides are available. Currently, printing ink solvents (allomer-free solvents, hereinafter referred to as AF solvents) with aromatic components of 3% by weight or less are used as environmentally friendly printing inks. Has been. When this AF solvent is used, the weight ratio of hydrocarbon resin / α, β ethylenically unsaturated carboxylic acid or anhydride thereof is 80/15 to 97/3, preferably 88/12 to 97/3. Accordingly, if the amount of α, β-ethylenically unsaturated carboxylic acid or its anhydride is large, the solubility of the resin in the printing ink solvent is deteriorated, and if it is small, an appropriate molecular weight for printing ink cannot be obtained. Further, in the polymerization reaction of resin acid and hydrocarbon resin with α, β ethylenically unsaturated carboxylic acid or anhydride thereof, there is exemplified the case of polymerization at 80 to 150 ° C. using peroxide such as benzoyl peroxide as a polymerization catalyst. . In addition, other polybasic acids such as succinic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, dodecenyl succinic anhydride, pentadecenyl succinic acid, etc. Acid, (anhydrous) maleic acid, o-phthalic acid or its anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid or its anhydride, hexahydrophthalic acid or its anhydride, (methyl) hymic acid or its anhydride And trimellitic acid or its anhydride, pyromellitic acid or its anhydride, and the like.

Further, the reaction method of the petroleum resin α, β-ethylenically unsaturated carboxylic acid modified product and the alcohol compound is in accordance with the reaction method of the resin acid alkyd resin.
Furthermore, an alkyd modified product of an α, β ethylenically unsaturated carboxylic acid modified product in which resin acid and petroleum resin are used in combination with resin acid / petroleum resin = 1 to 99% by weight / 1 to 99% by weight is exemplified. The reaction method is based on the reaction method of the above resin acid alkyd and petroleum resin alkyd. A resin having a weight average molecular weight of 0.5 to 200,000 and a softening point of 80 to 180 ° C. (mainstream is 130 to 170 ° C.) is obtained.

  In addition to the reaction product composition of the present invention, the above-exemplified animal and vegetable oils and fatty acid monoesters thereof are used as printing inks.

Furthermore, the varnish, vegetable oil or fatty acid monoester at the time of ink preparation, and the reaction product composition of the present invention using it as a raw material are used.
Vegetable oil or fatty acid monoesters are the same as described above.

  The printing ink solvent of the present invention includes, for example, Nippon Oil Co., Ltd. No. 1 spindle oil, No. 3-8 Solvent, Naphthezol H, Alkene 56NT, Mitsubishi Chemical Corporation Diadol 13, Dairen 168, Nissan Chemical Co., Ltd. Examples thereof include Foxocol, Foxocol 180 and the like. The printing ink solvent with the aromatic component reduced to 3% or less is a petroleum solvent having the same boiling point range, and the weight ratio of aromatic component / naphthene component / paraffin component is 0-3 / 0-100 / 100- It is a solvent of 0 and sometimes contains an olefinic component. Specifically, AF Solvents 4-8, No. 0 Solvent H manufactured by Nippon Oil Co., Ltd., N-paraffin C14-C18 manufactured by ISU Corporation, Supersol LA35, LA38 manufactured by Idemitsu Kosan Co., Ltd., Exxon Chemical ( Ex.) Exol D80, D110, D120, D130, D160, D100K, D120K, D130K, D280, D300, D320 etc., Maggie Sol-40, -44, -47, -52, -60, etc. manufactured by Maggie Bros. Is done. The aniline point is preferably 60 to 115 ° C. If a solvent with an aniline point higher than 115 ° C. is used, the solvent with the resin used in the ink composition will be insufficient and the fluidity of the ink will be insufficient, resulting in poor leveling on the printing medium and gloss. You can only get prints with no. Further, ink using a solvent having an aniline point lower than 60 ° C. is poor in detachment of the solvent from the ink film at the time of drying and causes drying deterioration.

  Further, the varnish can be made into a gel varnish using a gelling agent. As the gelling agent, usually an aluminum complex compound can be mentioned. Cyclic aluminum compounds such as cyclic aluminum oxide octate (Algomer 800 manufactured by Kawaken Fine Chemical Co., Ltd.), cyclic aluminum oxide stearate (Algomer 1000S manufactured by Kawaken Fine Chemical Co., Ltd.), and the like, as aluminum alcoholates, aluminum ethylate, aluminum isopropylate (river AIPD) manufactured by Ken Fine Chemical Co., Ltd., aluminum sec-butylate (ASPD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum isopropylate mono-sec-butylate (AMD manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum alkyl acetates such as aluminum di-n -Butoxide-ethyl acetoacetate (Chelope-Al-EB2 manufactured by Hope Pharmaceutical), aluminum-di-iso-butoxide Methyl acetoacetate (Chelope-Al-MB12 manufactured by Hope Pharmaceutical), Aluminum-di-iso-butoxide-ethyl acetoacetate (Chelope-Al-EB102 manufactured by Hope Pharmaceutical), Aluminum-di-iso-butoxide-ethyl acetoacetate (Hope Pharmaceutical) (Chelope-Al-EB2), Aluminum-di-iso-propoxide-ethyl acetoacetate (Chelope-Al-EP12, Hope Pharmaceutical Co., Ltd., ALch manufactured by Kawaken Fine Chemicals), Aluminum-Tris (acetylacetonate) (Kawaken Fine Chemicals) ALCH-TR), aluminum-tris (acetylacetoacetate) (Aluminum chelate-A, manufactured by Kawaken Fine Chemicals), aluminum-bis (ethylacetylacetonate) ) -Monoacetylacetonate (Aluminum chelate D manufactured by Kawaken Fine Chemical Co., Ltd.), aluminum chelate M (produced by Kawaken Fine Chemical Co., Ltd.), aluminum chelate NB-15 (manufactured by Hope Pharmaceutical Co., Ltd.), Kerope S (manufactured by Hope Pharmaceutical Co., Ltd.) Kerope ACS -2 (manufactured by Hope Pharmaceutical Co., Ltd., liquid Olype AOO (manufactured by Hope Pharmaceutical Co., Ltd.), liquid oil AOS (manufactured by Hope Pharmaceutical Co., Ltd.), aluminum stearate (manufactured by Nippon Oil & Fats Co., Ltd.), aluminum oleate, Examples thereof include aluminum naphthonate, aluminum urate, and aluminum acetylacetonate, and these gelling agents are used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of varnish. As a gelling agent, it can gel cyclic dipeptides and organic liquids Bisamides such as tylene bis (12-hydroxyoctadecanoic acid) amide, Al-Mg-hydroxycaprylate, Al-Mg-hydroxymyristate, Al-Mg-hydroxypalmitate, Al-Mg-hydroxybehenate, etc. A powdery aluminum-magnesium compound is exemplified. Further examples include organic titanates such as tetraisopropyl titanate, tetra n-butyl titanate, tertreoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate, and titanium lactate ethyl ester. Furthermore, organic zirconium such as zirconium tetrabutoxide, zirconium acetylacetone, zirconium acetylacetone, zirconium acetylacetone, acetylacetone zirconium butoxide, ethyl acetoacetate butoxide, and the like are exemplified. Preparation of gel varnish is usually obtained by charging 0.1 to 3 parts by weight of a gelling agent and reacting in a temperature range of 100 to 200 ° C. for 30 minutes to 2 hours.

  Next, the usage form as a printing ink composition in this invention is demonstrated. The printing ink composition in the present invention is usually used in the form of a lithographic printing ink. Further, since the resin is solid at room temperature, it is used as a resin varnish prepared by adding vegetable oil or a fatty acid ester thereof, and an ink solvent. In order to make the viscosity of the resin varnish easy to prepare a printing ink composition (100 to 200 Pa · s), resin / vegetable oil or its fatty acid ester / ink solvent = 30-60 parts by weight / 1-60 parts by weight / 0 The resin is dissolved in 30 minutes to 1 hour in an air stream at 150 to 200 ° C. Further, in order to obtain a resin gel varnish, 0.1 to 3 parts by weight of a gelling agent is added to the dissolved resin varnish and reacted at 100 to 120 ° C. for 30 minutes to 1 hour.

  The printing ink of the present invention comprises a printing ink composition component such as a pigment, a resin varnish and / or a gel varnish thereof, a vegetable oil or a fatty acid ester thereof, an ink solvent and other additives at a temperature between room temperature and 100 ° C. Manufactured using kneaded meat, mixing and adjusting machines such as three rolls, attritor, sand mill, and gate mixer.

There are pigments as colorants, and inorganic pigments and organic pigments including extender pigments can be shown. Inorganic pigments such as yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, petal, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, bengara etc. as organic pigments Are soluble azo pigments such as β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide, pyrazolone, β-naphthol, β-oxynaphthoic acid anilide, Insoluble azo pigments such as acetoacetanilide monoazo, acetoacetanilide disazo and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated (chlorinated or brominated) copper phthalocyanine blue, sulfonated copper phthalocyanine blue, metal-free phthalocyanine , Quinacridone, geo Polycyclics such as sazine, selenium (pyrantron, anthanthrone, indanthrone, anthrapyrimidine, flavantron, thioindigo, anthraquinone, perinone, perylene), isoindolinone, metal complex, quinophthalone Various publicly known pigments such as pigments and heterocyclic pigments can be used.
Furthermore, the polymerization inhibitors exemplified above are used.

  Furthermore, other additives can be used in the printing ink as required. For example, anti-friction agents, anti-blocking agents, slip agents, anti-scratch agents include carnauba wax, wax, lanolin, montan wax, paraffin wax, microcrystalline wax and other natural waxes, Fischer-Trops wax, polyethylene wax, polypropylene Synthetic waxes such as wax, polytetrafluoroethylene wax, polyamide wax, and silicone compound can be exemplified.

  The printing ink of the present invention is also applied to offset printing using fountain solution, but is also applied to waterless printing that does not use fountain solution, that is, dry lithographic printing.

  For example, in the present invention, a solvent containing a paraffinic component such as No. 0 solvent, N-paraffin C14-C18 manufactured by ISU Co., Ltd., or an olefinic component such as dialen 168 may be used. In particular, the present dry lithographic printing ink composition comprises 1 to 30% by weight of 5 to 1 million, preferably 5 to 150,000 weight average molecular weight resin and 0.1 to 10% by weight of paraffin and olefin solvent. The dry lithographic plate is formed by adjusting the solubility with the material and forming a weak boundary layer "WFBL (Week Fluid Boundary Layer) in this technical field" between the dry lithographic plate and the ink, which has a very weak bonding force due to the solvent. Printability (ink does not adhere to non-image areas) can be improved.

  Furthermore, by combining 0.1 to 10% by weight of the organopolysiloxane in the dry lithographic printing ink composition, the poor solubility of this material is utilized, and after printing, the organopolysiloxane appears on the surface of the ink composition. A weak boundary layer that has a very weak binding force at the interface between the ink and the plate, and the organopolysiloxane appears on the surface of the ink composition after printing. In the technical field, it is possible to improve the suitability of dry lithographic printing (ink does not adhere to the non-image area) by forming “WFBL” (Week Fluid Boundary Layer). Examples of the organopolysiloxane of the present invention include dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane. For example, TSF451-10, TSF451-20, TSF451-30, TSF451-50, TSF451-100, TSF451-200, TSF451-300, TSF451-350, TSF451-500, TSF451-1000, TSF451- manufactured by Toshiba Silicon Corporation 3000, TSF451-5000, TSF451-6000, TSF451-1M, TSF451-3M, TSF451-5M, TSF451-6M, TSF451-10M, TSF451-20M, TSF451-30M, TSF451-50M, TSF456-100, TSF456-200, TSF456-1000, TSF456-2000, TSF456-1M, TSF410, TSF411, TSF4421, XF42-A3161, TSF 84, TSF431, YF33-100, YF33-3000, YF33-1M, TSF458-50, TSF433, TSF404, TSF405, TSF4045, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451- 1000A, TSF451-5000A, TSF437, TSF4440, TSF433, TSF404, TSF405, TSF4045, TSF451-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451-1000A, TSF451-5000, F TSF433, TSF404, TSF405, TSF4045, TSF4 1-5A, TSF451-10A, TSF451-50A, TSF451-100A, TSF451-350A, TSF451-1000A, TSF451-5000A, TSF437, TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460, TSF4600, TSF4700, TSF4701 TSF4703, TSF4704, TSF4705, TSF4706, TSF4707, TSF4708, TSF4709, TSF4450, TSF4730, XF42-B0970, FQF501, etc. are illustrated. Further, Pentide A, Pentide H, Pentide M, Pentide Q, Pentide Q-N, Pentide S, Pentide 7, Pentide E-10, Pentide 29, Pentide 31, Pentide 32, Pentide 51, Pentide 54, manufactured by Dow Corning Asia Co., Ltd. Pentide 56, Pentide 57, DCZ-6018, DKQ8-8011, and the like. Furthermore, KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF are used as non-reactive silicone oils manufactured by Shin-Etsu Silicon Co., Ltd. -618, KF-6011, KF-6015, KF-6004, X-22-4272, X-22-4925, X-22-6266, KF-410 as methylstill modified silicone oil, KF-412 as alkyl modified silicone oil , KF-413, KF-414, KF-910, X-22-715 as higher fatty acid ester-modified silicone oil, KF-3935 as higher fatty acid-containing silicone oil, FL-5, FL-10, X as fluorine-modified silicone oil -22-821, X-22-822, FL100, etc. It is.

  Furthermore, this invention can provide the printed matter which does not use volatile organic compounds (VOCS), such as a petroleum solvent. By the present invention, it is possible to limit the thermal weight loss to 1% or less (excluding water) in the VOC measurement method Metyod24 (110 ° C., heating residue measurement by heating for 1 hour) proposed by the US Environmental Protection Agency. Thus, it becomes possible to provide VOC-free ink and printed matter.

  In addition, as an environmental measure, petroleum-based components contained in offset ink, soybean oil ink in which part of dry oil is replaced with soybean oil or its modified products, and ink that has cleared ASA (American Soybean Association) certification standards It is also possible to satisfy the required criteria according to the present invention.

Hereinafter, the present invention will be described with reference to production examples. The present invention is expressed in parts by weight.
Next, the present invention will be described with reference to specific examples. In the examples, “parts” means parts by weight.
Specific examples will be shown below.
Examples of reaction product compositions of the present invention

  A four-necked flask equipped with a stirrer, a water separator, and a thermometer was charged with 880 parts of soybean oil KT (collected and regenerated soybean oil manufactured by Kaneda Corp.), 124 parts of ethylene glycol, and 3 parts of p-toluenesulfonic acid. The end point of transesterification was confirmed by confirming that the molecular weight distribution in GPC (gel permeation chromatography) was in a steady state by an exchange reaction. Thereafter, at 115 ° C., 218 parts of acetic acid and 50 parts of toluene are charged and reacted. When the dehydration stopped, the temperature was gradually raised and the reaction was carried out at 130 ° C. for 10 hours. The acid value became 10 or less, and the solvent was removed under reduced pressure at the same temperature. A liquid having an acid value of 9.8, brown color, and a viscosity of 0.1 Pa · s / 25 ° C. was obtained. (Example reaction product composition (E1))

  A four-necked flask equipped with a stirrer, a water separator, and a thermometer was charged with 880 parts of soybean oil KT (collected recycled soybean oil manufactured by Kaneda Corp.), 124 parts of ethylene glycol, and 0.3 part of sodium hydroxide at 190 ° C. for 2 hours. The transesterification reaction was performed, and it was confirmed that the molecular weight distribution in GPC (gel permeation chromatography) was in a steady state. Thereafter, 333 parts of benzoic acid and 50 parts of xylene are charged and reacted at 180 ° C. Thereafter, the temperature was raised and the reaction was carried out for 10 hours. The acid value became 10 or less, and the solvent was removed under reduced pressure at the same temperature. A liquid having an acid value of 9.8, a brown color, and a viscosity of 0.5 Pa · s / 25 ° C. was obtained. (Example reaction product composition (E2))

  A four-necked flask equipped with a stirrer, water separation tube and thermometer was charged with 880 parts of soybean oil KT (collected and regenerated soybean oil manufactured by Kaneda Corp.), 124 parts of glycerin and 3 parts of p-toluenesulfonic acid, and transesterified at 190 ° C for 2 hours. After the reaction, it was confirmed that the molecular weight distribution in GPC (gel permeation chromatography) was in a steady state, and was used as the end point of transesterification. Thereafter, at 115 ° C., 218 parts of acetic acid and 50 parts of toluene are charged and reacted. When dehydration stopped, the temperature was gradually raised and the reaction was carried out at 130 ° C. for 10 hours. The acid value became 10 or less, and the solvent was removed under reduced pressure at the same temperature. A liquid having an acid value of 9.8, brown color, and a viscosity of 0.1 Pa · s / 25 ° C. was obtained. (Example reaction product composition (E3))

  A four-necked flask equipped with a stirrer, a water separator, and a thermometer was charged with 880 parts of soybean oil KT (collected and regenerated soybean oil manufactured by Kaneda Co., Ltd.), 124 parts of glycerin, and 0.3 part of sodium hydroxide. After the reaction, it was confirmed that the molecular weight distribution in GPC (gel permeation chromatography) was in a steady state, and was used as the end point of transesterification. Thereafter, 333 parts of benzoic acid and 50 parts of xylene are charged and reacted at 180 ° C. Thereafter, the temperature was raised and the reaction was carried out for 10 hours. The acid value became 10 or less, and the solvent was removed under reduced pressure at the same temperature. A liquid having an acid value of 9.8, a brown color, and a viscosity of 0.5 Pa · s / 25 ° C. was obtained. (Example reaction product composition (E4))

  A four-necked flask equipped with a stirrer, a water separator, and a thermometer was charged with 680 parts of soybean oil KT (collected and regenerated soybean oil manufactured by Kaneda Corp.), 200 parts of linseed oil, 122 parts of glycerin, and 3 parts of p-toluenesulfonic acid. The transesterification reaction was carried out at 200 ° C. for 2 hours, and it was confirmed that the molecular weight distribution in GPC (gel permeation chromatography) was in a steady state, and was used as the end point of transesterification. Thereafter, 317 parts of butyric acid and 50 parts of toluene were added at 150 ° C., the temperature was raised from 150 ° C., and the reaction was carried out for 10 hours at 160. The acid value became 10 or less, and the solvent was removed under reduced pressure at the same temperature. A liquid having an acid value of 9.8, a brown color, and a viscosity of 10 Pa · s / 25 ° C. was obtained. (Example reaction product composition (E5))

  Stirrer, water separator, four-neck flask with thermometer, 780 parts soybean oil white extract (Nisshin Oilio Co., Ltd.), 100 parts paulownia oil (Nisshin Oilio Co., Ltd.) 178 parts trimethylolpropane, p -3 parts of toluene sulfonic acid was charged and subjected to a transesterification reaction at 200 ° C. for 2 hours to confirm that the molecular weight distribution in GPC (gel permeation chromatography) was in a steady state, and was used as an end point of transesterification. Thereafter, 250 parts of propionic acid and 50 parts of toluene were added at 120 ° C., and the mixture was gradually reacted at 140 ° C. for 10 hours to cause the acid value to be 10 or less. A liquid having an acid value of 10 and a viscosity of 0.1 Pa · s / 25 ° C. was obtained. (Example reaction product composition (E6))

Synthesis example of rosin phenol resin (Production Example 1)
(Synthesis of resol type phenol resin)
A four-necked flask equipped with a stirrer, reflux condenser, and thermometer was charged with 206 parts of p-octylphenol, 203 parts of 37% formalin and 250 parts of xylene, heated and stirred while blowing nitrogen gas, and calcium hydroxide 2.0 at 50 ° C. Parts were dispersed in 10 parts of water, the dispersion was added, the temperature was raised to 95 ° C., and the reaction was carried out at the same temperature for 3.5 hours. Then, it cooled, neutralized with sulfuric acid, and washed with water. The resole xylene solution layer and the aqueous layer were allowed to stand and separate. This resol type phenol resin is used as a resol solution.
(Synthesis of rosin phenol resin)
While blowing nitrogen gas into a four-necked flask equipped with a stirrer, water separator and a thermometer, 120 parts of rosin was charged and stirred with heating, and 80 parts of resole liquid (80 parts in terms of solid content) at 200 ° C. Charged over about 2 hours while dripping, while reacting while collecting water and xylene. After completion of the charge, the temperature was raised and 6.0 parts of glycerin and 0.6 part of p-toluenesulfonic acid were charged at 250 ° C. for 12 hours. It was made to react, and since the acid value became 20 or less, it pumped out.
The weight average molecular weight of this resin was 45,000 and the softening point was 160 ° C. (Production Example Resin R1)
Note) * Resol solution that reacts with rosin indicates parts by weight of solid content.
* The weight average molecular weight was measured by gel permeation chromatography (HLC8020) manufactured by Tosoh Corporation and the standard sample for the calibration curve was measured by polystyrene.

Production Example Resin 2 (Rosin Alkyd Resin)
A four-necked flask equipped with a stirrer, a water separator, and a thermometer was charged with 200 parts of polymerized rosin (dimer resin acid 67%), and then 16 parts of maleic anhydride, and measured by GPC reacted at 170 ° C. for 1 hour. It was confirmed that there was no unreacted maleic acid and the Diels-Alder reaction was completed. Furthermore, 40 parts of trimethylolpropane and 0.3 part of ethanesulfonic acid were added, and the temperature was gradually raised and reacted at 240 ° C. for 15 hours to obtain an acid value of 20 and a weight average molecular weight of 30,000. (Example resin R2)

Production Example Resin 3 (Rosin Alkyd Resin)
A four-necked flask equipped with a stirrer, a water separation tube, and a thermometer is charged with 198 parts of Chinese gum rosin and 1.8 parts of p-toluenesulfonic acid and allowed to react at 190 ° C. for 6 hours under a nitrogen stream. The weight% of dimer resin acid was 30.5%. {Measured by gel permeation chromatography (hereinafter referred to as GPC by HLC8020) manufactured by Tosoh Corporation. } Then, maleic anhydride 10 was charged and measured by GPC reacted at 170 ° C. for 1 hour. As a result, it was confirmed that there was no unreacted maleic anhydride and the Diels-Alder reaction was completed. Further, 8 parts of adipic acid and 32.6 parts of trimethylolpropane were added, and the temperature was gradually raised and reacted at 240 ° C. for 10 hours, and then reacted at a reduced pressure of 13 KPa for 5 hours. An acid value of 20 and a weight average molecular weight of 30,000 were obtained and pumped out. (Example resin R3)

Production Example Resin 4 (Petroleum Resin Alkyd)
470 parts of Quinton 1345 (Nippon Zeon Co., Ltd. dicyclopentagen resin) and 30 parts of maleic anhydride were charged into a stirrer, reflux condenser and flask equipped with a thermometer, and heated with heating while blowing nitrogen gas. The reaction was performed at 0 ° C. for 3 hours to obtain maleic anhydride-modified DCPD resin (MD resin). Next, 200 parts of MD resin, 13.3 parts of butylethylpropanediol (BEPD) and 0.2 part of ethanesulfonic acid were charged into a stirrer, a reflux condenser with a water separator, and a flask with a thermometer, and nitrogen gas was blown into them. While heating at 250 ° C. for 3 hours, a resin having an acid value of 10, a melting point of 140 ° C., and a weight average molecular weight (hereinafter referred to as Mw) of 44,000 in gel permeation chromatography (hereinafter referred to as GPC) is pumped out. It was. (Example resin R4)

Production Example Resin 5 (Rosin and Petroleum Resin Alkyd)
A four-necked flask equipped with a stirrer, a water separation tube and a thermometer was charged with 106 parts of gum rosin, 80 parts of Quinton 1345 (dicyclopentagen resin manufactured by Nippon Zeon Co., Ltd.), 14 parts of maleic anhydride, and 180 parts under a nitrogen stream. The Diels-Alder reaction is performed at 1 ° C. for 1 hour. Thereafter, 31 parts of trimethylolpropane, 23.6 parts of butylethylpropanediol and 0.6 part of p-toluenesulfonic acid were added, and the temperature was gradually raised and reacted at 250 ° C. until the acid value was 25 or less. Pumped out 50,000 resins. (Example resin R5)

Solubility test In addition, the solubility with the solvent for printing inks is calculated | required with the following method. 2 g of resin or 1.5 g of resin + 0.5 g of resin acid ester of the present invention and 18 g of solvent for printing ink, a specified magnetic stirrer is placed in a test tube, and a fully automatic muddy point measuring device {device name NOVOCONTROL's Chemotronic ( CHEMOTORONIC)} is the lowest temperature at which the temperature is raised to 200 ° C. and dissolved and then gradually cooled to prevent clouding. Therefore, the lower the minimum temperature, the better the solubility.

Comparative Example Solubility Test

Example Solubility test
Preparation of varnish Manufacture example Resin R1 48 parts, Esterified product E1 16 parts, Soybean oil 10 parts, Linseed oil 19 parts, AF5 5.9 in a four-necked flask with a stirrer, water separation condenser, thermometer 1 part of ALCH (manufactured by Kawaken Fine Chemical Co., Ltd.) and dissolved at 190 ° C. under a nitrogen stream, and after 1 hour, the viscosity was adjusted to 200 Pa · S / 25 ° C. Thereafter, the mixture was cooled to 160 ° C., and 0.1 part of BHT (di-t-butyl-hydroxytoluene) was charged and pumped out. (Example varnish V1). Comparative examples varnishes CV1 to CV5 are shown in Table 3, and Example varnishes V1 to V6 are shown in Table 4.

Example of production of printing ink The printing ink was prepared by a conventional method with three rolls according to the printing ink composition. The ink was prepared to have a tack value of 9 to 10 / room temperature of 25 ° C. (roll temperature of 30 ° C.).

  The printing ink formulation and properties are shown in Table 5 for the comparative example ink and Table 6 for the example ink.

インキ試験法
＊タック値：インコメター４００ＲＰＭ、室温２５℃、ロール温度３０℃、 規格のインキ量で一分後の値。
・ フロー値：規格平行板粘度計で２５℃、一分後のインキの流動半径値（ミ リメートル）
・ 光沢試験：光沢計は村上色彩研究所（株）製６０度の条件で使用した。

Ink test method * Tack value: Incometa 400 RPM, room temperature 25 ° C., roll temperature 30 ° C., value after 1 minute with standard ink amount.
・ Flow value: Flow radius value of ink after 1 minute at 25 ° C with standard parallel plate viscometer (millimeter)
Gloss test: The gloss meter was used under the condition of 60 degrees made by Murakami Color Research Co., Ltd.

Claims (7)

A reaction product composition obtained by subjecting animal and vegetable oils and polyhydric alcohols to esterification with 1 basic acid (excluding acrylic acid and methacrylic acid) after transesterification. The reaction product composition according to claim 1, wherein the animal and vegetable oil is a recovered regenerated oil. The reaction product composition according to claim 1 or 2, wherein the animal or vegetable oil is at least one of soybean oil, linseed oil and tung oil. Claims obtained by adding 0 to 5% by weight of an ester exchange catalyst or esterification catalyst comprising at least one of an alkali metal compound system, an alkaline earth metal compound system, a titanium compound system, a zirconium compound system and a sulfonic acid compound system Item 4. The reaction product composition according to any one of Items 1 to 3. A printing ink comprising 0.1 to 30% by weight of the reaction product composition according to any one of claims 1 to 4 in the total amount of the ink. 6. The printing according to claim 1, further comprising 1 to 50% by weight of rosin phenolic resin and / or 1 to 50% by weight of rosin alkyd resin and / or 1 to 50% by weight of petroleum resin alkyd in the total amount of ink. ink. A printed matter obtained by printing the printing ink according to any one of claims 1 to 6 on a substrate.