Polyester resin, lithographic ink composition, printed matter, and method for producing printed matter

Abstract

The polyester resin of the present invention is a polycondensate of a polyol mixture (A) containing an epoxidized vegetable oil and a rosin adduct, a polycarboxylic acid (B), and a plant-derived polyol (C), wherein the mass ratio of the rosin to the epoxidized vegetable oil (rosin / epoxidized vegetable oil) is 2 or more and 10 or less, and the biomass degree is 80% or more. The polyester resin can obtain an ink composition for lithographic printing having excellent scratch resistance and abrasion resistance, and the proportion of components derived from biomass is high.

Description

Technical Field

[0001] The present invention relates to a polyester resin, an ink composition for lithographic printing, a printed matter, and a method for producing the printed matter. Background Art

[0002] In recent years, all walks of life are carrying out activities to reduce environmental load, but the ultimate goal is to protect the global environment. The printing ink industry has also been promoting activities to reduce environmental load from various perspectives, and various certification marks are attached to products that meet the purpose of such activities. As such certification marks, there are NL regulatory marks, plant marks, GP marks, environmental protection printing marks, etc. In this case, the Japan Printing Ink Industry Association recently established a new INK GREEN mark (hereinafter referred to as the IG mark) system. The IG mark is a system that mainly uses the proportion of components from biomass in the various components that constitute the ink composition as an indicator, and classifies the environmental protection level of the ink composition into three levels according to its degree. That is, it can also be considered that the characteristic of this system is to promote the use of raw materials from biomass instead of raw materials from petrochemical resources to reduce environmental load.

[0003] In addition, recently, a printing method has gradually become popular in various printing fields, which is to irradiate active energy rays such as ultraviolet rays or electron beams to the printed matter that has just been printed, so that the ink composition on the surface of the printed matter is instantly dried. The ink composition used in the printing contains a photopolymerization initiator that generates free radicals or cations by irradiation with active energy rays, and a monomer or oligomer that is polymerized by reacting with these free radicals or cations. By irradiating the active energy rays, the ink composition on the surface of the printed matter becomes a film-like hardened product and becomes a dry state. Among such ink compositions, products of the type that are hardened by ultraviolet rays are called UV inks. In particular, various products have been proposed in the field of lithography that performs high-speed printing. For example, an active energy ray-hardening type lithographic printing ink composition such as Patent Document 1 is known.

[0004] In the field of UV ink, as with other ink compositions, products that can be dried by irradiating less ultraviolet rays or energy-saving products that can be dried by light from light-emitting diodes (LEDs) that consume less power are being sold, thereby expanding actions to reduce environmental load. However, since UV inks must use a large amount of monomers or oligomers as their components, it is considered difficult to use a large amount of components derived from biomass. Therefore, the current situation is that the proportion of components derived from biomass is not included in the recognition criteria of the IG mark, and instead, environmental characteristics such as recycling adaptability or energy-saving responsiveness are used as indicators.

[0005] On the other hand, it is socially useful to increase the proportion of components derived from biomass in the field of UV inks, which is of great significance. For example, Patent Document 2 discloses a polyester resin used in a lithographic ink composition that can increase the proportion of components derived from biomass.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2014-173070

[0009] Patent Document 2: Japanese Patent Application Publication No. 2018-65912 Summary of the invention

[0010] [Problems to be solved by the invention]

[0011] On the other hand, the lithographic printing ink composition containing the polyester resin as described above is required to have excellent scratch resistance or abrasion resistance from the viewpoint that printed materials using the ink composition are used as packaging for commercial products or the like.

[0012] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a polyester resin having a high ratio of a biomass-derived component and capable of obtaining a lithographic printing ink composition having excellent scratch resistance and abrasion resistance.

[0013] Another object of the present invention is to provide a lithographic printing ink composition containing the polyester resin, a printed article having a printed layer formed of the ink composition, and a method for producing the printed article.

[0014] [Methods of solving the problem]

[0015] That is, the present invention relates to a polyester resin, which is a polycondensate of a polyol mixture (A) containing an epoxidized vegetable oil and a rosin adduct, a polycarboxylic acid (B), and a plant-derived polyol (C), wherein the mass ratio of the rosin to the epoxidized vegetable oil (rosin / epoxidized vegetable oil) is greater than 2 and less than 10, and the biomass degree is greater than 80%.

[0016] The present invention also relates to a lithographic printing ink composition comprising the polyester resin.

[0017] The present invention also relates to a printed article having a printed layer formed from the lithographic printing ink composition.

[0018] The present invention also relates to a method for producing a printed article, comprising the step of performing printing using the lithographic printing ink composition.

[0019] [Effects of the Invention]

[0020] The detailed mechanism of action of the effect of the polyester resin of the present invention is partially unclear, but is presumed as follows. However, the present invention can be interpreted without being limited to the above mechanism of action.

[0021] The polyester resin of the present invention is a polycondensate of a polyol mixture (A) containing an epoxidized vegetable oil and a rosin adduct, a polycarboxylic acid (B), and a plant-derived polyol (C), wherein the mass ratio of the rosin to the epoxidized vegetable oil (rosin / epoxidized vegetable oil) is 2 or more and 10 or less, and the biomass degree is 80% or more. Since the polyol mixture (A) containing an epoxidized vegetable oil and a rosin adduct and the plant-derived polyol (C) are raw materials with a high biomass degree, the polyester resin of the present invention is a resin with a high proportion of components derived from biomass and a small amount of unreacted components and a sufficiently high molecular weight, and therefore, by using the polyester resin of the present invention, an ink composition for lithographic printing having excellent scratch resistance and abrasion resistance can be obtained. DETAILED DESCRIPTION

[0022] The polyester resin of the present invention is a polycondensate of a polyol mixture (A) containing an epoxidized vegetable oil and a rosin adduct, a polycarboxylic acid (B), and a plant-derived polyol (C), wherein the mass ratio of the rosin to the epoxidized vegetable oil (rosin / epoxidized vegetable oil) is greater than 2 and less than 10, and the biomass degree is greater than 80%.

[0023] <Epoxidized vegetable oil>

[0024] The epoxidized vegetable oil of the present invention is usually obtained by epoxidizing at least a part of the carbon-carbon double bonds (C=C) of the vegetable oil with peracetic acid, perbenzoic acid, etc. to modify the carbon-carbon double bonds (C=C) of the vegetable oil into epoxy groups (epoxy modification). The vegetable oil used as the starting material includes, for example, hemp seed oil, perilla oil, auti oil, cocoa butter, kapok seed oil, torreya seed oil, mustard oil, apricot kernel oil, kuju oil, walnut oil, poppy seed oil, radish seed oil, cycas oil, camellia oil, soap stock oil, grape seed oil, almond oil, pine nut oil, peanut oil, rice bran oil, sesame oil, coconut oil, castor oil, palm oil, almond oil, cashew nut oil, hazelnut oil, pine nut oil, dehydrated castor oil, tung oil, linseed oil, sunflower seed oil, rosehip oil, perilla oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, sesame oil, corn oil, olive oil, cocoa butter, etc. At least one of the above-mentioned vegetable oils may be used, or two or more of them may be used in combination.

[0025] Examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized safflower oil, epoxidized sunflower oil, epoxidized palm oil, epoxidized cottonseed oil, epoxidized olive oil, epoxidized cocoa butter, epoxidized rice bran oil, and the like. In addition, these epoxidized vegetable oils may be obtained by epoxidizing "used edible oils" that are waste materials used in household or commercial applications (tempura, deep-fried foods, etc.), and the epoxidation may be performed using a well-known treatment method. Among these, epoxidized soybean oil and epoxidized linseed oil are preferred from the viewpoint of ease of commercial acquisition. At least one of the epoxidized vegetable oils may be used, or two or more of them may be used in combination.

[0026] <Rosin>

[0027] The rosins are non-volatile components of pine oil collected from pine plants with rosin acid and its isomers as the main components. Any rosin can be used as long as it has a carboxyl group. Examples include raw rosins such as rosin gum, tall oil rosin, and natural rosin such as wood rosin. In addition, the rosins include purified rosin obtained by purifying the raw rosin, hydrogenated rosin obtained by hydrogenating the raw rosin, disproportionated rosin obtained by disproportionating the raw rosin, polymerized rosin derived from the raw rosin, and unsaturated carboxylic acid-modified rosin as a reaction product of the raw rosin and unsaturated carboxylic acids. Among them, disproportionated rosin and polymerized rosin are preferred. In addition, the acid value of the rosins is preferably 100 to 200 mgKOH / g. At least one of the rosins can be used, and two or more of them can also be used in combination.

[0028] <Polyol mixture (A)>

[0029] The polyol mixture (A) of the present invention is a mixture containing a polyol (adduct) obtained by an addition reaction of the epoxidized vegetable oil and the rosin. The addition reaction can be carried out by reacting the epoxy group of the epoxidized vegetable oil with the carboxyl group of the rosin at a temperature of about 130 to 185° C. under an inert gas environment using a known reaction catalyst. The reaction can be terminated when the acid value of the reaction mixture stops decreasing.

[0030] In the addition reaction of the epoxidized vegetable oil and the rosins, the mass ratio of the rosins to the epoxidized vegetable oil (rosins / epoxidized vegetable oil) is 2 or more and 10 or less. In the addition reaction of the epoxidized vegetable oil and the rosins, the mass ratio of the rosins to the epoxidized vegetable oil (rosins / epoxidized vegetable oil) is preferably 2 or more and 8 or less, and more preferably 3 or more and 6 or less, from the viewpoint of reducing unreacted components as much as possible.

[0031] <Polycarboxylic acid (B)>

[0032] The polycarboxylic acid (B) of the present invention is a compound having a plurality of carboxyl groups, and is a component for increasing the molecular weight by polycondensation with a polyol component.

[0033] As the polycarboxylic acid (B), known polycarboxylic acids can be used, for example, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, trimellitic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexenedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclohexenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexenedicarboxylic acid, hexahydrophthalic anhydride, 5-sodium sulfonate The polycarboxylic acid (B) may be 1,2-cyclohexene dicarboxylic acid, ...

[0034] <Plant-derived polyols (C)>

[0035] The plant-derived polyol (C) of the present invention is a compound having a plurality of hydroxyl groups, and is a component for increasing the molecular weight by polycondensation with a polycarboxylic acid component.

[0036] The plant-derived polyol (C) may be a well-known polyol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 2-methyl-1,4-butylene glycol, glycerol, 2,5-dihydroxymethylfuran, castor oil, cardanol-modified polyol, etc. At least one plant-derived polyol (C) may be used, and two or more plant-derived polyols may be used in combination.

[0037] The polyester resin of the present invention is a polycondensate obtained by polycondensing a polyol mixture (A) containing the epoxidized vegetable oil and rosin adduct, the polycarboxylic acid (B), and the plant-derived polyol (C).

[0038] The polycondensation reaction can be carried out by a well-known and conventional method, for example, the reaction can be carried out at a temperature of about 170 to 250° C. under an inert gas environment. The reaction time is usually about 5 to 25 hours, but is not particularly limited. Regarding the judgment of the end of the reaction, the reaction can be terminated at the time when the acid value of the reaction mixture stops decreasing. The polycondensation reaction can be carried out in a shorter time by distilling the water produced by the polycondensation to the outside of the system or using a reaction catalyst. As reaction catalysts, for example, tetrabutyl zirconate, monobutyl tin oxide, zirconium cyclohexaneate, tetrabutyl titanate, etc. can be listed.

[0039] From the viewpoint of the molecular weight and acid value of the obtained polyester resin, the polycarboxylic acid (B) is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 2 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total of the epoxidized vegetable oil and the rosins.

[0040] From the viewpoint of the molecular weight and acid value of the obtained polyester resin, the plant-derived polyol (C) is preferably at least 1 part by mass and at most 30 parts by mass, and more preferably at least 2 parts by mass and at most 20 parts by mass, relative to 100 parts by mass of the total of the epoxidized vegetable oil and the rosins.

[0041] The biomass degree of the polyester resin is 80% or more. When the polyester resin is used in an ink composition for lithographic printing, the biomass degree of the polyester resin is preferably 85% or more, and more preferably 90% or more, from the viewpoint of increasing the proportion of components derived from biomass. In addition, the biomass degree of the polyester resin can be calculated according to the following formula.

[0042] Biomass content (%) = (added mass of biomass component) × 100 / total added mass

[0043] When the polyester resin is used in an active energy ray-curable lithographic printing ink composition, the solubility parameter sp value obtained by turbidity titration is preferably 9.0 to 11.0 (cal / cm 3 ) 1 / 2 , more preferably 9.0 to 10.0 (cal / cm 3 ) 1 / 2 .

[0044] Here, the calculation of the solubility parameter sp value by turbidity titration is described. The value can be measured by turbidity titration as a simple measurement method, and is calculated according to the following formula of KWSUH, JMCORBETT. In addition, for the calculation of the sp value by the method, refer to J.Appl.Polym.Sci.1968,12,2359.

[0045] sp value = (V ml 1 / 2 ·δH+V mh 1 / 2 ·δD) / (V ml 1 / 2 +V mh 1 / 2 )

[0046] In the turbidity titration, 0.5 g of a sample is dissolved in 10 mL of toluene or 10 mL of trimethylolpropane triacrylate (TMPTA) as a good solvent, and n-hexane as a poor solvent with a low sp value is added, and the titration amount H (mL) at the turbidity point is read. Similarly, the titration amount D (mL) at the turbidity point when ethanol as a poor solvent with a high sp value is added to the toluene solution is read, and these are applied to the following formula to calculate V ml 、V mh , δH, and δD, and substitute them into the above formula.

[0047] In addition, the molar volume or sp value of each solvent used in the turbidity point titration is as follows.

[0048] Molar volume of good solvent φ0 Toluene: 106.28 mL / mol, TMPTA: 279.55 mL / mol

[0049] Molar volume of low sp value poor solvent φl n-hexane: 131.61mL / mol

[0050] Molar volume of high sp value poor solvent φh ethanol: 58.39mL / mol

[0051] The sp values ​​of each solvent are toluene: 9.14, TMPTA: 9.88, n-hexane: 7.28, ethanol: 12.58

[0052] V ml =(φO·φl) / {(1-VH)·φl+VH·φO}

[0053] V mh =(φO·φh) / {(1-VD)·φh+VD·φO}

[0054] VH=H / (M+H)

[0055] VD=D / (M+D)

[0056] δH=(δO·M) / (M+H)+(δl·H) / (M+H)

[0057] δD=(δO·M) / (M+D)+(δl·D) / (M+D)

[0058] δO: sp value of good solvent

[0059] δl: sp value of low sp value poor solvent

[0060] δh: sp value of high sp value poor solvent

[0061] H: Titration of low sp value poor solvent (mL)

[0062] D: Titration of high sp value poor solvent (mL)

[0063] M: Amount of good solvent (mL)

[0064] VH: Volume fraction of low sp value poor solvent titration (%)

[0065] VD: Volume fraction of high sp value poor solvent titration (%)

[0066] When the polyester resin is used in an ink composition for lithographic printing, the acid value is preferably 1 to 50 mgKOH / g, more preferably 1 to 25 mgKOH / g, and even more preferably 1 to 10 mgKOH / g, from the viewpoint of being able to suppress problems such as abnormal emulsification in the ink composition. The acid value is a value measured in accordance with JIS K5601-2-1.

[0067] The weight average molecular weight of the polyester resin is preferably 25,000 or more, more preferably 30,000 or more, from the viewpoint of excellent dispersibility of the pigment contained in the lithographic ink composition and good viscoelasticity being imparted to the ink composition. Furthermore, the weight average molecular weight of the polyester resin is preferably 60,000 or less, more preferably 50,000 or less, from the viewpoint of good solubility and excellent operability.

[0068] The weight average molecular weight can be measured by gel permeation chromatography (GPC). For example, Water 2690 (manufactured by Waters Corporation) can be used as a GPC device, PLgel, 5 μm, MIXED-D (manufactured by Polymer Laboratories) can be used as a column, and tetrahydrofuran can be used as a developing solvent, a column temperature of 25° C., a flow rate of 1 ml / min, an RI detector, a sample injection concentration of 10 mg / ml, and an injection volume of 100 μl. Under the conditions, the chromatography is performed to obtain the weight average molecular weight converted to polystyrene.

[0069] <Lithographic printing ink composition>

[0070] The lithographic ink composition of the present invention contains the polyester resin. The polyester resin has a biomass degree of 80% or more, so the proportion of biomass-derived components in the lithographic ink composition containing the polyester resin can be increased. Therefore, the lithographic ink composition reduces environmental load and becomes a product suitable for receiving various environmental certifications such as IG mark certification.

[0071] In the lithographic ink composition, the content of the polyester resin is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, from the viewpoint of being able to impart good scratch resistance or abrasion resistance to a printed coating film using the ink composition. Furthermore, from the viewpoint of the printability or viscoelasticity of the ink composition, the content of the polyester resin is preferably 70% by mass or less, more preferably 60% by mass or less.

[0072] In addition, the polyester resin is preferably used as a constituent component of an active energy ray-curable lithographic ink composition. The active energy ray-curable lithographic ink composition generally contains a compound having an ethylenically unsaturated bond (monomer or oligomer, etc.) and a photopolymerization initiator. When irradiated with active energy rays, free radicals generated from the photopolymerization initiator convert the compound having an ethylenically unsaturated bond into a high molecular weight, thereby curing.

[0073] The active energy rays can break chemical bonds in the photopolymerization initiator to generate free radicals, and examples thereof include ultraviolet rays, electron beams, etc. As the irradiation device for the active energy rays, examples thereof include metal halide lamps, high pressure mercury lamps, excimer lamps sealed with rare gas, ultraviolet light emitting diodes (LEDs), etc.

[0074] Examples of the monomer include monofunctional monomers having one ethylenically unsaturated bond in the molecule, and difunctional or higher monomers having two or more ethylenically unsaturated bonds in the molecule. The difunctional or higher monomers can crosslink molecules when the ink composition hardens, thereby helping to accelerate the hardening speed or form a strong film. Although the monofunctional monomer does not have the crosslinking ability as described above, on the other hand, it helps to reduce the hardening shrinkage caused by crosslinking. The monomers can be used in combination with various monomers as needed.

[0075] Examples of the monofunctional monomer include alkyl acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, and dodecyl (meth)acrylate; (meth)acrylic acid, (meth)acrylate of ethylene oxide adduct, (meth)acrylate of propylene oxide adduct, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecane monohydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and propylene oxide adduct. The monofunctional monomers include 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-methoxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, β-carboxyethyl (meth)acrylate, (meth)acrylic acid dimer, ω-carboxypolycaprolactone mono(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N-vinylpyrrolidone, N-vinylformamide, (meth)acryloylmorpholine, etc. The monofunctional monomers may be used alone or in combination of two or more.

[0076] Examples of the difunctional or higher-functional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, pentylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivaloyl hydroxypivalate di(meth)acrylate, hydroxypivaloyl hydroxypivalate dicaprolactone di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. Ester, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate 1,2-hexadecanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl-2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dihydroxymethyloctane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate ) acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,2-hexanediol di(meth)acrylate, 1,5-hexanediol di(meth)acrylate, 2,5-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,2-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-Dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,2-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,2-hexadecanediol di(meth)acrylate, 2-methyl-2,4-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2-methyl-2-propyl-1,3-propanediol di(meth)acrylate, 2,4-dimethyl 2,4-pentanediol di(meth)acrylate, 2,2-diethyl-1,3-propanediol di(meth)acrylate, 2,2,4-trimethyl-1,3-pentanediol di(meth)acrylate, dimethylol octane di(meth)acrylate, 2-ethyl-1,3-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 2,4-diethyl-1,5-Pentanediol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tricyclodecane dimethylol dicaprolactone di(meth)acrylate, bisphenol A tetraethylene oxide adduct di(meth)acrylate, bisphenol F tetraethylene oxide adduct di(meth)acrylate, bisphenol S tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol A tetraethylene oxide adduct di(meth)acrylate, hydrogenated bisphenol F tetraethylene oxide adduct di(meth)acrylate Bifunctional monomers such as acrylate, hydrogenated bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, bisphenol A tetraethylene oxide adduct dicaprolactone di(meth)acrylate, bisphenol F tetraethylene oxide adduct dicaprolactone di(meth)acrylate; glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tricaprolactone tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolhexane tri(meth)acrylate trifunctional monomers such as trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetracaprolactone tetra(meth)acrylate, diglycerol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, di-trimethylolpropane tetracaprolactone tetra(meth)acrylate, di-trimethylolethane tetra(meth)acrylate Acid ester, di-trimethylolbutane tetra(meth)acrylate, di-trimethylolhexane tetra(meth)acrylate, di-trimethyloloctane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol polyoxyalkylene heptath(meth)acrylate and the like tetrafunctional or higher monomers, etc. Among them, trimethylolpropane triacrylate (TMPTA; trifunctional), di-trimethylolpropane tetraacrylate (DITMPTA; tetrafunctional), dipentaerythritol hexaacrylate (DPHA; hexafunctional), glycerol propoxy triacrylate (GPTA; trifunctional), hexanediol diacrylate (HDDA; difunctional) and the like are preferred. The difunctional or higher monomers can be used alone or in combination of two or more. ,

[0077] In addition, as one of the monomers, there is epoxidized vegetable oil acrylate obtained by modifying epoxidized vegetable oil with acrylic acid. It is a compound obtained by ring-opening addition polymerization of (meth) acrylic acid and the epoxy group of "epoxidized vegetable oil obtained by epoxidizing the double bonds of unsaturated vegetable oil using an oxidizing agent such as peracetic acid and perbenzoic acid". Unsaturated vegetable oil refers to a triglyceride in which at least one fatty acid has at least one carbon-carbon unsaturated bond, and examples thereof include hemp seed oil, linseed oil, perilla oil, auti oil, olive oil, cocoa oil, kapok seed oil, torreya seed oil, mustard oil, apricot kernel oil, tung oil, kuju oil, walnut oil, poppy seed oil, sesame oil, safflower oil, radish seed oil, soybean oil, cycas oil, camellia oil, corn oil, rapeseed oil, soap stock oil, rice bran oil, palm oil, castor oil, sunflower seed oil, grape seed oil, almond oil, pine nut oil, cottonseed oil, coconut oil, peanut oil, dehydrated castor oil, etc. Such monomers are derived from vegetable oils and thus contribute to increasing the amount of biomass components in the ink composition. Since various commercial products of epoxidized vegetable oil acrylates are available, such commercial products may also be used.

[0078] Although the oligomer is a component that has been polymerized to a high molecular weight as described above, it is also used to impart appropriate viscosity or elasticity to the ink composition because of its relatively high molecular weight. As oligomers, the following oligomers can be cited: epoxy-modified (meth)acrylates, which are esters of (meth)acrylic acid with hydroxyl groups generated by ring-opening epoxy groups contained in epoxy compounds such as epoxy resins with acid or alkali; rosin-modified epoxy acrylates; polyester-modified (meth)acrylates, which are esters of (meth)acrylic acid with terminal hydroxyl groups of condensates of dibasic acids and diols; polyether-modified (meth)acrylates, which are esters of (meth)acrylic acid with terminal hydroxyl groups of polyether compounds; and urethane-modified (meth)acrylates, which are esters of (meth)acrylic acid with terminal hydroxyl groups in condensates of polyisocyanate compounds and polyol compounds. Such oligomers are commercially available, for example, products called Ebecryl series manufactured by Daicel-Cytec Co., Ltd.; products called CN and SR series manufactured by Sartomer Co., Ltd.; products called ARONIX M-6000 series, 7000 series, 8000 series, ARONIX M-1100, ARONIX M-1200, ARONIX M-1600 manufactured by Toagosei Co., Ltd.; products called NK Oligo manufactured by Shin-Nakamura Chemical Co., Ltd., etc. The above oligomers can be used alone or in combination of two or more.

[0079] As a constituent component of the active energy ray-curable lithographic ink composition, a polymer having an ethylenically unsaturated bond may also be used. The polymer having an ethylenically unsaturated bond is a component that is high in molecular weight together with the monomer or oligomer, and since it has a large molecular weight before being irradiated with active energy rays, it is a component that helps to improve the viscoelasticity of the ink composition. This type of polymer is used, for example, in a state of being dissolved or dispersed in a monomer that is a low-viscosity liquid. Examples of the polymer having an ethylenically unsaturated bond include polydiallyl phthalate, an acrylic resin having an unreacted unsaturated group, an acrylic modified phenol resin, and the like.

[0080] In the active energy ray-curable lithographic printing ink composition, the compound having an ethylenically unsaturated bond is preferably 5 to 60% by mass, more preferably 8 to 40% by mass, and further preferably 10 to 30% by mass, from the viewpoint of achieving both good curability and good printing suitability. In addition, in the active energy ray-curable lithographic printing ink composition, the polymer having an ethylenically unsaturated bond is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 15% by mass, from the viewpoint of providing the ink composition with appropriate viscoelasticity to suppress the occurrence of fogging and the like, and ensuring good curability of the ink composition.

[0081] The photopolymerization initiator is not particularly limited as long as it generates radicals when irradiated with active energy rays. Examples of the photopolymerization initiator include benzophenone, diethylthioxanthone, 2-methyl-1-(4-methylthio)phenyl-2-morpholinopropane-1-one, 4-benzoyl-4′-methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, bis-2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2,2-dimethyl-2-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, and 2-benzyl-2-dimethylamino-1-(morpholinophenyl)-butane-1-one. Photopolymerization initiators are commercially available, for example, Irgacure 907, Irgacure 369, Irgacure 184, Irgacure 379, Irgacure 819, TPO, etc. are available from BASF, or DETX, etc. are available from Lamberti. The photopolymerization initiators may be used alone or in combination of two or more.

[0082] In the active energy ray-curable lithographic printing ink composition, the photopolymerization initiator is preferably contained in an amount of 1 to 20% by mass, and more preferably 2 to 15% by mass, from the viewpoint of ensuring sufficient curability and good internal curability.

[0083] A coloring component may be added to the lithographic ink composition as needed. The coloring component is a component added to impart coloring power or hiding power to the ink composition, and examples thereof include coloring pigments, white pigments, metal powders, and the like. Examples of such coloring components include organic and / or inorganic pigments that have been used in ink compositions in the past without particular limitation. In addition, when the lithographic ink composition does not contain a coloring component, it is preferably used for coating purposes, and the like.

[0084] Examples of the coloring component include yellow pigments such as disazo yellow (Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 1) and Hansa yellow; magenta pigments such as Brilliant Carmine 6B, Red Lake C, and Uchinoin; cyan pigments such as phthalocyanine blue, phthalocyanine green, and basic blue; black pigments such as carbon black; white pigments such as titanium oxide; and metal powders such as aluminum paste and bronze powder.

[0085] In the lithographic ink composition, the coloring component is about 1 to 30% by mass, but is not particularly limited. In addition, when preparing a colored ink composition, a coloring component of another color may be used as a complementary color, or an ink composition of another color may be added.

[0086] In addition to the above-mentioned components, other components may be added to the lithographic ink composition as needed. Examples of other components include: extender pigments; resin components; polymerization inhibitors; dispersants; salts such as phosphates; waxes such as polyethylene waxes, olefin waxes, and Fischer-Tropsch waxes; and alcohols.

[0087] The extender pigment is a component used to impart appropriate printing adaptability or viscoelasticity and other properties to the ink composition, and various extenders commonly used in the preparation of the ink composition can be used. Examples of extenders include clay, kaolinite (kaolin), barium sulfate, magnesium sulfate, calcium carbonate, silicon oxide (silicon dioxide), bentonite, talc, mica, titanium oxide, etc. In the lithographic ink composition, the extender pigment is about 0 to 30% by mass, but is not particularly limited.

[0088] The resin component is a component that helps to impart appropriate printing adaptability or viscoelasticity and other properties to the ink composition. As the resin component, for example, various resins used in the ink composition for printing can be cited, and preferably a resin component having compatibility with the monomer or oligomer can be cited, including: styrene-acrylic resin, acrylic resin, alkyd resin, rosin-modified phenol resin, rosin-modified maleic acid resin, rosin-modified alkyd resin, rosin-modified petroleum resin, rosin ester resin, petroleum resin-modified phenol resin, vegetable oil-modified alkyd resin, petroleum resin, etc.

[0089] In the case of adding the resin component to the ink composition, in the lithographic ink composition, the resin component is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less, based on the viewpoint that it can not only impart appropriate viscoelasticity to the ink composition to suppress the occurrence of phenomena such as fogging, but also ensure good curability of the ink composition.

[0090] The polymerization inhibitor can inhibit the polymerization reaction during storage to thicken the ink composition. Preferred examples of the polymerization inhibitor include phenolic compounds such as butylated hydroxytoluene, vitamin E acetate, nitrosamine, benzotriazole, hindered amines, etc., among which butylated hydroxytoluene is more preferred. The content of the polymerization inhibitor in the ink composition is about 0.01 to 1% by mass.

[0091] The dispersant is used to disperse the coloring component or extender pigment contained in the ink composition in a good state. There are various commercially available dispersants, for example, DISPERBYK (trade name) series manufactured by BYK-Chemie Japan Co., Ltd. and the like.

[0092] When the lithographic ink composition of the present invention is prepared using the above components, a conventionally known method can be applied. In this case, the polyester resin can be dissolved in an oil component such as a vegetable oil or a mineral oil to form a varnish, or can be dissolved in a compound having an ethylenically unsaturated bond to form a varnish. Regarding the viscosity of the ink composition, the value measured at 25° C. using a Layley viscometer can be 10 to 70 Pa·s, but is not particularly limited.

[0093] <Printed matter and method for producing the same>

[0094] The printed matter of the present invention is provided with a printing layer formed by the above-mentioned lithographic ink composition. In addition, the method for producing the printed matter of the present invention includes the step of printing using the above-mentioned lithographic ink composition. Printing is carried out using a general lithographic printing technique, and lithographic printing can be a water-based printing method using dampening water or a waterless printing method using a dedicated lithographic printing plate without dampening water.

[0095] Example

[0096] Hereinafter, the present invention will be described with reference to Examples and the like, but the present invention is not limited to these Examples.

[0097] <Example 1>

[0098] <Manufacturing of polyester resin>

[0099] In a reaction vessel equipped with a stirrer, a reflux cooler, and a thermometer, 50 parts by mass of epoxidized soybean oil (manufactured by ADEKA, trade name: "O-130P"), 150 parts by mass of disproportionate rosin (manufactured by Wako Pure Chemical Industries, Ltd., trade name: "DEHYDROABIETICACID", acid value 136 mgKOH / g), and 0.5 parts by mass of triphenylphosphine as a catalyst were added, and reacted at 180°C for 5 hours to perform an addition reaction, thereby obtaining a mixture containing a polyol (adduct). Furthermore, 10 parts by mass of 1,2-cyclohexenedicarboxylic acid was added, and the temperature was raised to 250°C and heated for 2 hours, and then 10 parts by mass of glycerol was added, and the temperature was maintained at 250°C for further 8 hours to perform a polycondensation (dehydration condensation) reaction, thereby obtaining a polyester resin of Example 1. The obtained polyester resin had a weight average molecular weight of 35,000, an acid value of 7.6 mgKOH / g, an sp value measured by turbidity titration method of 9.10, and a biomass degree of 94.3%.

[0100] <Preparation of Lithographic Printing Ink Composition>

[0101] 80 parts by mass of the polyester resin obtained above, 19 parts by mass of di-trimethylolpropane triacrylate (DI-TMPTA), and 1 part by mass of butylated hydroxytoluene (BHT) were added to a reaction kettle equipped with a cooling tube, and heated and stirred at 100° C. for 1 hour to prepare a varnish. Next, 70 parts by mass of the obtained varnish, 15 parts by mass of carbon black (manufactured by Mitsubishi Chemical Co., Ltd., trade name: "#60"), 7 parts by mass of Irgacure 907 (manufactured by BASF), and 3 parts by mass of 4,4'-bis(diethylamino)benzophenone (EAB) were mixed, and milled using a three-roll mill at a roll temperature of 40° C. until the particle size became 5.0 μm or less, and 5 parts by mass of trimethylolpropane triacrylate (TMPTA) was added to prepare an active energy ray-curable lithographic printing ink composition.

[0102] <Production of printed materials>

[0103] 0.1 cc of the above-obtained lithographic ink composition was applied to Aurora Coat paper using an RI color spreader (two-split roll, manufactured by Mei Seisakusho Co., Ltd.), and then immediately irradiated with ultraviolet light (metal halide lamp, irradiation dose: 36 mJ / cm 2 ), thereby producing a printed matter.

[0104] <Example 2-10, Comparative Example 1-6>

[0105] In each example and each comparative example, except that the raw materials of the polyester resin used were changed to the raw materials and the blending amounts described in Table 1, the same operation as in Example 1 was carried out to prepare the polyester resin of each example and each comparative example, and then prepare the ink composition for lithographic printing and produce the printed matter.

[0106] The printed matter obtained above was evaluated for each item according to the following evaluation method. The results are shown in Table 1.

[0107] [Scratch resistance]

[0108] The printed coating film of the printed material was scratched with a fingernail, and the number of times the coating film was scratched and thinned was evaluated according to the following criteria.

[0109] 5: It is not chipped even after being scratched 10 times.

[0110] 4: Scrape 8 to 9 times and become thinner.

[0111] 3: Scrape 5 to 7 times and become thinner.

[0112] 2: Scrape 2 to 4 times to be thinned.

[0113] 1: It becomes thinner after being scratched once.

[0114] [Abrasion resistance]

[0115] The printed coating film of the printed material was evaluated for the residual rate of the printed coating film after the test by visual inspection using a Gakushin type friction fastness tester (manufactured by Yasuda Seiki Co., Ltd.) under test conditions (500 g×10 times, backing paper: Aurora Coat paper) according to the following criteria.

[0116] 5: The coating does not fall off.

[0117] 4: The coating is slightly peeled off.

[0118] 3: Half of the coating falls off.

[0119] 2: The coating almost peels off.

[0120] 1: The coating film is completely peeled off.

[0121]

[0122] In Table 1, epoxidized soybean oil (biomass degree: 95%) indicates a product named "O-130P" (manufactured by ADEKA Corporation);

[0123] Epoxidized linseed oil (biomass content: 95%) refers to a product named "O-180A" (manufactured by ADEA);

[0124] Bisphenol A type epoxy resin (biomass content: 0%) refers to a product named "EP-4100" (manufactured by ADEKA Corporation);

[0125] Disproportionated rosin (biomass content: 100%) refers to a product called "DEHYDROABIETIC ACID" (manufactured by Wako Pure Chemical Industries, Ltd.);

[0126] The polymerized rosin (biomass content: 100%) was a product called "Ardyme R-95" (manufactured by Arakawa Chemical Industries, Ltd.).

Claims

1. A lithographic ink composition, characterized in that: The polyester resin is a polycondensate of a polyol mixture (A) containing an epoxidized vegetable oil and a rosin adduct, a polycarboxylic acid (B), and a plant-derived polyol (C), and The mass ratio of the rosin to the epoxidized vegetable oil (rosin / epoxidized vegetable oil) is 2 or more and 10 or less, The biomass degree of the polyester resin is above 80%, The biomass degree (%) = (added mass of biomass component) × 100 / total added mass.

2. The lithographic ink composition according to claim 1, characterized in that The acid value of the polyester resin is 1 to 50 mgKOH / g.

3. The lithographic ink composition according to claim 1 or 2, characterized in that: The solubility parameter sp value of the polyester resin measured by turbidity point titration method is 9.0 to 11.0 (cal / cm 3 ) 1 / 2 .

4. The lithographic printing ink composition according to claim 1 or 2, characterized in that: The weight average molecular weight of the polyester resin is 25,000 to 60,000.

5. The lithographic ink composition according to claim 1 or 2, characterized in that: It is an active energy ray hardening type.

6. A printed matter, characterized in that: A printing layer formed of the lithographic printing ink composition according to claim 1 or 2 is provided.

7. A method for producing a printed matter, characterized in that: The method comprises the step of performing printing using the lithographic printing ink composition according to claim 1 or 2.

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