JP2006063197A - Alkyd resin, printing ink obtained using the same and printed matter thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkyd resin obtained using a polymeric resin acid more simply and at a lower cost, a printing ink using the same, and a printed matter thereof. <P>SOLUTION: The alkyd resin is obtained by reacting at 150-300°C 50-90 wt% of a polymeric resin acid composition (A), obtained by reacting 90-99.9 wt% of a resin acid by 0.01-10 wt% of a sulfonic acid compound as a catalyst at 100-300°C for 0.1-20 hr using no solvents or using a solvent in an amount of 10 wt% or less, 3-50 wt% of a polybasic acid (B) and 3-50 wt% of an alcohol compound (C). The polybasic acid (B) in the alkyd resin can be an α,β-unsaturated carboxylic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an alkyd resin using a multimeric resin acid composition composition, a printing ink using the same, and a printed product thereof.

  Conventionally, resin acids containing rosins have been used as part of resin raw materials as printing ink resins. In addition, resin acids containing dimer resin acids such as polymerized rosin, which is a polymer of resin acids containing rosins, are used as part of the resin raw material to increase the molecular weight of, for example, alkyd resins and polyester resins. Sometimes.

  As a method for producing the multimeric resin acid, the resin acid is reacted with sulfuric acid or the like as a catalyst in a large amount of a chlorine solvent such as trichloroethane or dichlorobenzene or a polar solvent such as acetic acid at room temperature to around 100 ° C. for several hours, and optionally washed with water. Discloses a method for producing the catalyst by removing the catalyst by removing the solvent under reduced pressure. (Disclosed Document Name 1) Ind. Chem. Prod. Res. Developer. Vol. 12, No. 3, 1973, 2) Ind. Chem. Prod. Res. Developer. Vol. 9, No. 1, 60, 1970, 3) Ind. Chem. Prod. Res. Developer. Vol. 11, No. 2, 156, 1972) However, the printing ink industry is also in the maturity stage, and it is desired to reduce the cost of printing ink and the resin that is its raw material.

However, in the above method for producing a multimeric resin acid, a large amount of solvent is used, the reaction time is long, and the catalyst is washed away with water. For example, polymerized rosin, which is a resin acid containing a dimeric resin acid, is a monomer in terms of cost. The market price is twice as high as that of gum rosin, which is one of resin acids, the reaction process is complicated, and the need for a low-cost resin raw material with a simpler reaction process has been desired. .
USP Feb. 22, 1938 (2108928) USP July. 26, 1938 (2124675) USP Nov. 15, 1938 (2136525)

  The present invention relates to an alkyd resin using a simpler, low-cost multimeric resin acid composition composition, a printing ink using the alkyd resin, and a printed material thereof.

  That is, in the present invention, 90 to 99.9% by weight of resin acid is reacted with 0.01 to 10% by weight of sulfonic acid compound as a catalyst at 100 to 300 ° C. for 0.1 to 20 hours with no solvent or 10% by weight or less of solvent. The multimeric resin acid composition (A) is reacted at 50 to 90 wt%, the polybasic acid (B) at 3 to 40 wt%, and the alcohol compound (C) at 3 to 40 wt% at 150 to 300 ° C. The alkyd resin.

Moreover, this invention relates to the said alkyd resin whose polybasic acid (B) is (alpha) and (beta) unsaturated carboxylic acid.
In addition, the present invention relates to the alkyd resin, wherein the alcohol compound (C) is an alcohol compound containing a polyol.
In addition, the present invention relates to the alkyd resin obtained by reacting a part of the reaction process under a reduced pressure of 0 to 70 KPa.
In addition, the present invention relates to a printing ink containing 20 to 60% by weight of the alkyd resin, 1 to 40% by weight of vegetable oil or a fatty acid ester thereof, and 0 to 50% by weight of a solvent for ink.
In addition, the present invention relates to the above printing ink having a volatile content at 110 ° C. of 1% or less.
In addition, the present invention relates to a printed matter obtained by printing the printing ink on a substrate.

  The present invention provides an alkyd resin using a simpler, low-cost multimeric resin acid composition, a printing ink and a printed material using the alkyd 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 a naturally occurring resin acid. 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 natural resins containing these resin acids is preferable for handling, and examples include gum rosin, tall oil rosin, wood rosin, partially disproportionated rosin, partially hydrogenated rosin, partially polymerized rosin, copal, and dammar. The

  The sulfonic acid compound of the present invention is an aliphatic sulfonic acid such as sulfuric acid, methane sulfonic acid or ethane sulfonic acid, (alkyl) aromatic sulfonic acid such as benzene sulfonic acid, (ortho or meta or para) toluene sulfonic acid or xylene sulfonic acid. An acid etc. are illustrated. The amount used is 0.01 to 10% by weight, preferably 0.1 to 1% by weight, based on 90 to 99.9% by weight of resin acid. If the amount is less than 0.01%, the amount of the multimeric resin acid is small, and if it is more than 10% by weight, the amount of the resin acid obtained is also large. However, printing is particularly performed with offset printing inks printed using dampening water. There is a possibility that stains in the inside and rusting of the metal roll of the printing press may occur, which is not preferable. In order to reduce these problems, 0.1 to 1% by weight is more desirable.

  In the method for producing a multimeric resin of the present invention, the reaction temperature is 100 to 300 ° C, preferably 150 to 195 ° C. If it is lower than this, the amount of multimeric resin acid obtained is small, and if it is large, the amount of carboxylic acid decomposed in the resin acid is increased, and the softening point of the resulting resin is lowered. 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.

Since the solvent is expensive, it is not used or even if it is used, 10% or less is desirable.
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. The multimeric resin composition (A) is produced as described above.

  Furthermore, there are α, β-ethylenically unsaturated carboxylic acids or their anhydrides as polybasic acids (B 2), fumaric acid, maleic acid or their anhydrides, itaconic acid or their anhydrides, citraconic acid or their anhydrides, 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 multimeric resin acid (A) and the α, β-ethylenically unsaturated carboxylic acid or its anhydride (B) 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. In the case of using this AF solvent, the weight ratio of the resin acid (A) / 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 between the multimeric resin acid (A) and the 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. The 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 the reaction of trimellitic acid or its anhydride, pyromellitic acid or its anhydride and the like with the alcohol compound (C).

  The alcohol compound (C) of the present invention is a monohydric alcohol of C5 to C30, a monovalent long chain normal, iso, tertiary, multi-branched isomer alcohol and / or a mixture thereof, and / or an ethoxylate thereof. Etc. Specifically, as linear alkyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1- Pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2 -Nonadecanol, 1-Icosanol, Olei Alcohol, Geraniol {(CH3) 2C = CH (CH2) 2C (CH3) = CHCH2OH} Linalol {(CH3) 2 C = CH (CH2) 2 C (CH3) (OH) CH = CH2} Myricyl alcohol ( C30H61OH) and the like. Examples of branched alkyl alcohols include 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2, Examples include 6-dimethyl-4-heptanol, isononyl alcohol, 3,7 dimethyl-3-octanol, 2,4 dimethyl-1-heptanol, 2-heptyl undecanol and the like. Or the alkoxylates of the monohydric alcohols described above are also included. These reactions are addition-reacted with an alkali catalyst by a known method. For example, 1-butanol ethoxylate (C 6 H 13 OC 2 H 4 OH), 2-butanol propoxylate (C 6 H 13 OCH 2 CH (OH) CH 3), 1-octanol ethoxylate, 2-octanol propoxylate, and so on. And propoxylate. Further included are alkoxylates of alkylphenols having C4 to C20 alkyl groups. These reactions are addition-reacted with an alkali catalyst by a known method. C4 to C20 alkylphenols, such as ethoxylates and propoxylates such as butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, hexadecylphenol, nonadecylphenol, icosyl (C20H21) phenol. Specific examples include octylphenol ethoxylate, nonylphenol ethoxylate, dodecylphenol ethoxylate, and the like. Further, C5-C30 non-fat alcohols include cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, norbonol, terpineol, water-added rosin alcohol (trade names: Abitol, Hercules shares Including company).

  Divalent alcohol compounds such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, 1,2hexanediol, 1 , 5-hexanediol, 2,5-hexanediol, 1,7 heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decane Diol, 1,12-dodecanediol, 1,2-dodecanediol, 1,14-tetradecanediol, 1,2-tetradecanediol, 1,16-hexadecanediol, 1,2-hexadecanediol, ne Pentyl glycol, 2 ethylhexyl diol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethylpentane Diol, 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-pentanediol, 2,4 -Diethyl-1,5-pentanediol, xylene glycol, cyclohexane dimethylol, hydroquinone bis (2-hydroxy Roxyethyl) 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, (mono or di or tri) glycerin, (mono or di or tri) trimethylol ethane, (mono Or di or tri) trimethylolpropane, (mono or di or tri) trimethylol alkane, (mono or di or tri) pentaerythritol, sorbitol, etc. Aliphatic polyhydric alcohols, 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.

  Divalent polyols include 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, trivalent polyols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolhexane, trimethyloloctane, etc. Alkanes, tetra- or higher-valent polyols such as pentaerythritol, diglycerin, ditrimethylolpropane, sorbitan, sorbitol, dipen Erythritol, inositol, tripentaerythritol, and the like. Glycerin, trimethylolpropane, trimethylolethane and pentaerythritol are preferred for economic reasons.

  Further, 0.1 to 30 parts by weight of the alcohol compound (C) may be used in combination with an epoxy compound, but if it exceeds 30 parts by weight, the emulsification suitability during offset printing deteriorates, which is not preferable. Examples of the epoxy compound include a bisphenol A type epoxy compound such as Epicoat 828, Epicoat 1001, Epicoat 1004, Epicoat 1007, Epicoat 1009, etc. manufactured by Yuka Shell, and also a diglycidyl ether type polyepoxy compound of bisphenol F and bisphenol S. , Carboxylic acid, cresol, t-butylphenol, octylphenol, nonylphenol, dodecylphenol novolak epoxy compounds, alicyclic epoxy compounds, epoxidized soybean oil, epoxidized linseed oil and the like.

  The reaction ratio of the reaction product of the above (A) and (B) to the alcohol (C) compound is the total molar quantity of the carboxylic acid of (A) and (B) / the total number of hydroxyl groups of (C). The molar quantity 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. In the present invention, the sulfonic acid catalyst remains after the synthesis of the multimeric resin acid, but a catalyst may be used in this esterification reaction. 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 used at a temperature of 200 ° C. or more using 0.01 to 1% by weight in the total resin. 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.

  However, in offset printing using fountain solution, the catalyst is preferably 1% or less in the resin from the viewpoint of smearing during printing.

  In addition, the reaction sequence is often the case where the above (C) is charged to the reaction product of the above (A) and (B), but the above (A) is further reacted with the above reaction product of (B) and (C). Alternatively, (A), (B), and (C) may be charged simultaneously.

The esterification reaction of alkyd is an equilibrium reaction, and the reaction is accelerated by dehydration. Therefore, in order to accelerate the reaction, remove some rosin oil such as terpene generated during the reaction, raise the softening point of the resin, or remove some remaining catalyst, 0.5 to In some cases, the reaction is performed under reduced pressure for about 10 hours. According to the Chemical Dictionary, the boiling point of sulfuric acid is 194.2 ° C / 1.3KPa, 257 ° C / 13KPa, and the boiling point of methanesulfonic acid is 167 ° C / 1.3KPa. It can be considered that removal under reduced pressure is possible.
Therefore, methane sulfonic acid and ethane sulfonic acid increase the catalyst amount to about 1 to 10%, preferably about 1 to 5%, so that the reaction of multimeric resin acid and alkyd resin using the same can be performed at lower temperature and shorter time. The reaction is accelerated by time reaction, and the remaining catalyst can be removed under reduced pressure to an amount that does not cause a problem in offset printing using dampening water (0.5% or less in the case of methanesulfonic acid and ethanesulfonic acid). is there.

  When the resin of the present invention is used as a printing ink, the acid value is 30 or less, the weight average molecular weight is 1 to 200,000 (measured by gel permeation chromatography), the solubility in the printing ink solvent is 130 ° C. or less, and the melting point is 100. C. or higher, preferably 120.degree. C. or higher. In addition, the solubility with the solvent for printing inks is calculated | required with the following method. 2 g of resin, 18 g of printing ink solvent, a specified magnetic stirrer in a test tube, the temperature was raised to 200 ° C. with a fully automatic muddy point measuring device {CHEMOTRONIC, manufactured by NOVOCONTROL), and dissolved gradually. The minimum temperature at which no cooling occurs after cooling. Therefore, the lower the minimum temperature, the better the solubility.

  The vegetable oil, fatty acid ester thereof or modified product 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.

  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. Fatty acid monoesters which are liquid at ˜25 ° C. and have a boiling point of 200 ° C. or higher at normal pressure (101.3 kPa) are preferred. Specific examples of such fatty acid esters include hexyl butyrate and heptyl butyrate as saturated fatty acid monoesters. 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, caprylic acid , Vinyl caprylate, propyl caprylate, isopropyl caprylate, butyl caprylate, amyl caprylate, hexyl caprylate, heptyl caprylate, octyl caprylate, methyl pelargonate, ethyl pelargonate, vinyl pelargonate, propyl pelargonate, Butyl pelargonate, amyl pelargonate, heptyl pelargonate, methyl caprate, ethyl caprate, vinyl caprate, propyl caprate, isopropyl caprate, butyl caprate, hexyl caprate, heptyl caprate, methyl laurate, lauric acid Examples include ethyl, vinyl laurate, propyl laurate, isopropyl laurate, butyl laurate, isoamyl laurate, hexyl laurate, and 2-ethyl-hexyl laurate. Can.

  As unsaturated fatty acid ester, 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-ethylhexyl linoleate, linolenic acid Cyl, 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, methyl arachidonic acid, ethyl arachidonic acid, allyl arachidonic acid, propyl arachidonic acid, isopropyl arachidonic acid, butyl arachidonic acid, isobutyl arachidonic acid, arachidonic acid-tert-butyl, pentyl arachidonic acid, hexyl arachidonic acid, heptyl arachidonic acid, arachidone 2-ethylhexyl acid, methyl eicosenoate, ethyl eicosenoate, allyl eicosenoate, propyl eicosenoate, isopropyl eicosenoate, butyl eicosenoate, Isobutyl senate, eicenoic acid-tert-butyl, eicosenic acid pentyl, eicosenoic acid hexyl, eicosenoic acid heptyl, eicosenoic acid-2-ethylhexyl, eicosapentaenoic acid methyl, eicosapentaenoic acid ethyl, eicosapentaenoic acid allyl, eicosapentaenoic 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, erucic acid methyl, Ethyl erucate, allyl erucate, propyl erucate, isopropyl erucate, butyl erucate, isobutyl erucate, erucic acid-t ert-butyl, pentyl erucate, hexyl erucate, heptyl erucate, 2-ethylhexyl erucate, methyl docosahexaenoate, ethyl docosahexaenoate, allyl docosahexaenoate, propyl docosahexaenoate, isopropyl docosahexaenoate, butyl docosahexaenoate, isobutyl docosahexaenoate , Docosahexaenoic acid-tert-butyl, docosahexaenoate pentyl, docosahexaenoate hexyl, docosahexaenoate heptyl, docosahexaenoate-2-ethylhexyl, methyl ricinoleate, ethyl ricinoleate, allyl ricinoleate, propyl ricinoleate, isopropyl ricinoleate, butyl ricinoleate , Isobutyl ricinoleate, tert-butyl ricinoleate, pentyl ricinoleate, Lumpur hexyl, heptyl ricinoleate, and the like can be exemplified ricinoleic acid 2-ethylhexyl.

  The saturated or unsaturated fatty acid constituting the fatty acid ester in the present invention is actually coconut oil fatty acid, palm oil fatty acid, rapeseed oil fatty acid, soybean oil fatty acid, hydrogenated soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, tall oil. Fatty acids, dehydrated castor oil fatty acids, or fractionated fatty acids by fractional distillation thereof are used, and are obtained as a mixture of the aforementioned saturated or unsaturated fatty acids.

  Further, in recent years, soybean oil or fatty acid esters thereof (soybean oil fatty acid alkyl esters such as soybean oil fatty acid ethyl ester and soybean oil fatty acid butyl ester) are exemplified as environmentally friendly types. These vegetable oils or fatty acid esters thereof comprise 1 to 60% by weight in the printing ink.

  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-butyrate (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, manufactured by 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.) -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, tetreoctyl 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. In general,
Colorant or extender 1-40% by weight
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
Is used in the composition consisting of 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 Β-naphthol-based, β-oxynaphthoic acid-based, β-oxynaphthoic acid-based anilide-based, soluble azo pigments such as acetoacetate anilide-based, pyrazolone-based, β-naphthol-based, β-oxynaphthoic acid-based anilide-based, 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 without using 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. It is possible to improve printability (ink does not adhere to non-image areas).

  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 is providing 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.

Examples of the present invention and comparative examples will be described below. The present invention is expressed in parts by weight.
[Example]
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.

Example resin R1
99.5 parts of Chinese gum rosin and 1 part of methanesulfonic acid are charged into a four-necked flask equipped with a stirrer, a water separation tube and a thermometer, and reacted at 170 ° C. for 2 hours under a nitrogen stream. The weight% of dimer resin acid was 26.5%. {Measured by gel permeation chromatography (hereinafter referred to as GPC by HLC8020) manufactured by Tosoh Corporation. } Subsequently, maleic anhydride 5 was added and 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, 4 parts of adipic acid and 16.3 parts of trimethylolpropane were charged, 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. (The acid value is 20, the weight average molecular weight is 30,000 (the weight average molecular weight is measured with polystyrene by gel permeation chromatography (HLC8020) manufactured by Tosoh Corporation)), AF5 (Nippon Petrochemical Co., Ltd.) ) The solubility in printing ink for allomer-free No. 5 solvent) was 102 ° C. The solubility in the printing ink solvent was determined by the following method: 2 g of resin and 18 g of printing ink solvent. This is the minimum temperature at which a magnetic stirrer is placed in a test tube and the temperature is raised to 200 ° C. with a fully automatic turbid point measuring device {CHEMOTORONIC manufactured by NOVOCONTROL) and then gradually cooled and not clouded. Therefore, the lower the minimum temperature, the better the solubility.
Similarly, the resins of Examples R2 to R5 were reacted as shown in Table 1.

比較例樹脂Ｒ６〜Ｒ８も同様に反応させ、表２に示す。

Comparative resins R6 to R8 were reacted in the same manner and shown in Table 2.

表２中、重合ロジンとは２量体樹脂酸を６７％含む樹脂酸で市販のものを使用した。

In Table 2, as the polymerized rosin, a commercially available resin acid containing 67% of a dimer resin acid was used.

Preparation of Example Varnish 48 parts of Example resin R1, 15 parts of soybean oil, 20 parts of linseed oil, 15.9 parts of AF5 in a four-necked flask equipped with a stirrer, a water separation condenser and a thermometer, ALCH (Kawaken Fine Chemical) 1 part of a gelling agent (manufactured by Co., Ltd.) was charged, 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). Hereinafter, Example varnishes V2 to V5 were similarly prepared and shown in Table 3.

Production of Comparative Example Varnishes Comparative Example Varnishes V6 to V8 were produced in the same manner as described above and 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 at a tack value of 9 to 10/25 ° C.

  The printing ink formulation and properties are shown in Table 6 as Example ink (Table 5) and Comparative 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）
・ 乾燥性：上記インキをＲＩテスター（明製作所製簡易印刷機）で０．３mlのインキ盛りでコート紙（三菱製紙製特両アート紙２５cm＊２０cm）印刷し、朝陽会乾燥試験で常温で測定した。
・ 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。
＊揮発分：その測定方法は熱分析装置にて、１１０℃、１時間、窒素ガス流量１００ｍＬ／分の条件での熱重量測定を行った。また含水率はカールフィッシャー法により求めた。

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)
・ Dryability: The above ink is printed on a coated paper (Mitsubishi Paper's special art paper 25cm * 20cm) with an ink volume of 0.3ml using an RI tester (Meiji Seisakusho), and measured at room temperature in the Chaoyangkai drying test. did.
Gloss test: The gloss meter was used under the condition of 60 degrees made by Murakami Color Research Co., Ltd.
* Volatile content: The measurement method was thermogravimetric measurement under the conditions of 110 ° C. for 1 hour and a nitrogen gas flow rate of 100 mL / min. The water content was determined by the Karl Fischer method.

As shown in Table 2 above, comparative resins R6 to R8, for example, Chinese gum rosin (monomer resin acid) did not reach the weight average molecular weight of 20,000 or more required for printing ink, but polymerized rosin (dimer resin acid) Use of wt% / monomer resin acid wt% = 67/33)) increases the molecular weight. However, the cost of polymerized rosin (market price at the time of filing this patent is ¥ 200 to 300 / Kg) is twice that of Chinese gum rosin (market price at the time of filing this patent is ¥ 100 to 150 / Kg). Example resins in Table 1 maintain almost the same specifications in the ink evaluations in Tables 5 and 6 by producing dimer resin acid using low-cost Chinese gum rosin as a starting material and subsequently producing alkyd resin. Therefore, the alkyd resin of the present invention or printing ink using the alkyd resin can be produced at a lower cost and can contribute to industrial development.

Claims (7)

A polymer formed by reacting 90 to 99.9% by weight of a resin acid with 0.01 to 10% by weight of a sulfonic acid compound as a catalyst at 100 to 300 ° C. for 0.1 to 20 hours with no solvent or 10% by weight or less of the solvent. An alkyd resin obtained by reacting a resin acid composition (A) at 50 to 90% by weight, a polybasic acid (B) at 3 to 40% by weight, and an alcohol compound (C) at 3 to 40% by weight at 150 to 300 ° C. The alkyd resin according to claim 1, wherein the polybasic acid (B) is an α, β unsaturated carboxylic acid. The alkyd resin according to claim 1 or 2, wherein the alcohol compound (C) is an alcohol compound containing a polyol. The alkyd resin according to any one of claims 1 to 3, wherein a part of the reaction process is reacted under a reduced pressure of 0 to 70 KPa. A printing ink comprising 20 to 60% by weight of the alkyd resin according to any one of claims 1 to 4, 1 to 60% by weight of vegetable oil or a fatty acid ester thereof, and 0 to 50% by weight of a solvent for ink. The printing ink according to claim 5, wherein the volatile content at 110 ° C is 1% or less. A printed matter obtained by printing the printing ink according to claim 5 or 6 on a substrate.