Rosin-modified alkyd resin, composition for ink, and ink

Abstract

To provide a rosin-modified alkyd resin that has excellent compatibility with various monomers and reactivity with a gelator in the preparation of a composition for ink, and also excels in flowability, misting resistance and emulsification resistance.SOLUTION: A rosin-modified alkyd resin is a product from reaction components containing a rosin (A), a polycarboxylic acid (B), and a polyol (C), and has an acid value of 10 mgKOH / g or less, a hydroxyl value of 30-200 mgKOH / g and a weight average molecular weight of 3,000-30,000.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a rosin-modified alkyd resin, an ink composition, and an ink.

Background Art

[0002] An active energy ray-curable printing ink that cures with active energy rays such as ultraviolet rays and electron beams may contain a reactive diluent, a resin, a photopolymerization initiator, and an additive. As the reactive diluent, polyfunctional acrylates such as dipentaerythritol hexaacrylate and ditrimethylolpropane tetraacrylate are widely used because of their excellent curability and film hardness.

[0003] As the resin used in the above printing ink, a diallyl phthalate resin is known (Patent Document 1). The diallyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer. However, since it does not have a hydroxyl group or a carboxyl group, etc., its usage mode is limited. In addition, since the unreacted diallyl phthalate monomer remaining in the resin is also a substance with high concern about mutagenicity, a substance that can replace the resin is required. As an example, a rosin-modified alkyd resin has been developed (Patent Documents 2 and 3).

[0004] However, in Patent Document 2, since the weight average molecular weight and acid value of the rosin-modified alkyd resin are high, the misting resistance, fluidity, and emulsion resistance are likely to be impaired. In addition, in Patent Document 3, since coconut oil is used as a reaction component, the hydroxyl group of the rosin-modified alkyd resin becomes low. As a result, the compatibility with the monomer blended during the preparation of the ink composition decreases, resulting in turbidity, or it becomes difficult to react with a gelling agent, and it could not be applied as an ink.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

[0006] An object of the present invention is to provide a rosin-modified alkyd resin that is excellent in compatibility with various monomers and reactivity with a gelling agent during the preparation of an ink composition, and is also excellent in fluidity, anti-misting property, and anti-emulsification property. [Means for Solving the Problems]

[0007] The present inventors conducted intensive studies focusing on the acid value, weight-average molecular weight, and hydroxyl value of the rosin-modified alkyd resin, and as a result, found that the above problems can be solved, and thus completed the present invention. That is, the present invention relates to the following rosin-modified alkyd resin, ink composition, and ink.

[0008] 1. A product of reaction components containing rosins (A), polycarboxylic acids (B), and polyols (C), which is a rosin-modified alkyd resin having an acid value of 10 mgKOH / g or less, a hydroxyl value of 30 to 200 mgKOH / g, and a weight-average molecular weight of 3,000 to 30,000.

[0009] 2. The rosin-modified alkyd resin according to item 1 above, wherein the component (A) contains disproportionated rosin and / or hydrogenated rosin.

[0010] 3. The rosin-modified alkyd resin according to item 1 or 2 above, wherein the component (B) contains one or more selected from the group consisting of aromatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic polycarboxylic anhydrides, and alicyclic polycarboxylic anhydrides.

[0011] 4. The rosin-modified alkyd resin according to any one of items 1 to 3 above, wherein the component (C) contains an aliphatic diol and / or an aliphatic triol.

[0012] 5. An ink composition containing the rosin-modified alkyd resin according to any one of the preceding items 1 to 4.

[0013] 6. The ink composition according to item 5 above, further containing an active energy ray curable monomer.

[0014] 7. The ink composition according to item 5 or 6 above, further containing a gelling agent.

[0015] 8. An ink containing the ink composition according to any one of the preceding items 5 to 7.

Advantages of the Invention

[0016] According to the rosin-modified alkyd resin of the present invention, when preparing an ink composition, it is also excellent in compatibility with various monomers and reactivity with a gelling agent. Further, the ink obtained from the resin is also excellent in misting resistance, fluidity, and emulsion resistance.

Embodiments for Carrying Out the Invention

[0017] The rosin-modified alkyd resin of the present invention is a product of reaction components containing rosins (A) (hereinafter referred to as component (A)), polycarboxylic acids (B) (hereinafter referred to as component (B)), and polyols (C) (hereinafter referred to as component (C)).

[0018] (A) component is rosin, and its types are not particularly limited. For example, unmodified rosin such as gum rosin, tall oil rosin, and wood rosin; purified products of unmodified rosin (purified rosin); disproportionated products of unmodified rosin or purified rosin (disproportionated rosin); hydrogenated products of unmodified rosin or purified rosin (hydrogenated rosin); unsaturated carboxylic acid-modified rosin obtained by subjecting unmodified rosin or purified rosin to a Diels-Alder reaction with an unsaturated carboxylic acid; polymerized rosin derived from unmodified rosin; hydrogenated products and disproportionated products of polymerized rosin, etc. are included. Also, these may be used alone or in combination of two or more. Note that "unmodified rosin" includes abietic acid-type resin acids such as abietic acid, neoabietic acid, and levopimaric acid; pimaric acid-type resin acids such as palustric acid and pimaric acid, but may also include other substances such as dihydroabietic acid and communic acid.

[0019] The unsaturated carboxylic acid is not particularly limited. For example, unsaturated monocarboxylic acids such as acrylic acid, acrylic anhydride, methacrylic acid, methacrylic anhydride, crotonic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc. are included. Also, the amount of the unsaturated carboxylic acid used is not particularly limited. Usually, it is about 1 to 30 parts by weight, preferably about 1 to 10 parts by weight, based on 100 parts by weight of the unmodified rosin or polymerized rosin.

[0020] The (A) component may be used alone or in combination of two or more. Among them, when preparing the ink composition, disproportionated rosin and hydrogenated rosin are preferred because the rosin-modified alkyd resin and the active energy ray-curable monomer react gently (gelation does not occur) by heating.

[0021] Examples of the method for producing purified rosin include distillation method, extraction method, recrystallization method, etc. Examples of the distillation method include a method of distilling the unmodified rosin at a temperature of about 200 to 300 °C and a reduced pressure of about 60 to 3000 Pa. In the extraction method, for example, there is a method in which the unmodified rosin is made into an aqueous alkali solution, insoluble unsaponifiable matter is extracted with various organic solvents, and then the aqueous layer is neutralized. In the recrystallization method, for example, there is a method in which the unmodified rosin is dissolved in an organic solvent as a good solvent, then the solvent is distilled off to obtain a concentrated solution, and further an organic solvent as a poor solvent is added.

[0022] As a method for producing disproportionated rosin, for example, there is a method in which raw material unmodified rosin or purified rosin is subjected to a heating reaction in the presence of a disproportionation catalyst. Examples of the disproportionation catalyst include supported catalysts such as palladium-carbon, rhodium-carbon, and platinum-carbon; metal powders such as nickel and platinum; and iodides such as iodine and iron iodide. The amount of the disproportionation catalyst used is usually about 0.01 to 5 parts by weight, preferably about 0.01 to 1 part by weight, based on 100 parts by weight of rosin. The reaction temperature is about 100 to 300°C, preferably about 150 to 290°C.

[0023] As a method for producing hydrogenated rosin, it is possible to hydrogenate unmodified rosin or purified rosin using known hydrogenation conditions. For example, there is a method in which unmodified rosin or purified rosin is heated to about 100 to 300°C under a hydrogen pressure of about 2 to 20 MPa in the presence of a hydrogenation catalyst. The hydrogen pressure is preferably about 5 to 20 MPa, and the reaction temperature is preferably about 150 to 300°C. Examples of the hydrogenation catalyst include supported catalysts, metal powders, iodine, and iodides. Examples of the supported catalyst include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon. Examples of the metal powder include nickel and platinum. Examples of the iodide include iron iodide. Among them, palladium, rhodium, ruthenium, and platinum-based catalysts are preferred because they can increase the hydrogenation rate of unmodified rosin or purified rosin and shorten the hydrogenation time. The amount of the hydrogenation catalyst used is usually about 0.01 to 5 parts by weight, preferably about 0.01 to 2 parts by weight, based on 100 parts by weight of rosins.

[0024] Note that commercially available products may be used as the component (A).

[0025] (Component (B) is a compound having two or more carboxyl groups, and by reacting with component (C), an ester cross-linked structure is formed in the rosin alkyd resin. As a result, the elasticity of the ink composition is enhanced, and the ink exhibits excellent anti-misting property and anti-emulsification property.)

[0026] (Examples of component (B) include aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid; alicyclic polycarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 4-methylhexahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, and hexahydrophthalic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 2,3-naphthalenedicarboxylic acid, and 2,4-naphthalenedicarboxylic acid. Note that as component (B), acid anhydrides of the above polycarboxylic acids may be used. These may be used alone or in combination of two or more. Among them, from the viewpoint of the affinity between the ink composition and various pigments, aromatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic polycarboxylic acid anhydrides, and alicyclic polycarboxylic acid anhydrides are preferred, and phthalic acid, phthalic anhydride, isophthalic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, trimellitic acid, trimellitic anhydride, 1,2,3,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid anhydride, hexahydrophthalic acid, and hexahydrophthalic acid anhydride are more preferred.)

[0027] In addition, the rosin-modified alkyd resin of the present invention may be used in combination with a monocarboxylic acid as component (B). Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, oleic acid, linoleic acid, and linolenic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, 2-methylcyclohexanecarboxylic acid, 3-methylcyclohexanecarboxylic acid, and 4-methylcyclohexanecarboxylic acid; and aromatic monocarboxylic acids such as benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, and naphthalenecarboxylic acid. These may be used alone or in combination of two or more. The amount of the monocarboxylic acid used is preferably 20% by weight or less, more preferably 10% by weight or less, based on 100% by weight of the total of component (B) and the monocarboxylic acid.

[0028] (C) component is a compound having two or more hydroxy groups. By the reaction of component (C) with component (A), an ester bond is formed at the terminal of the rosin alkyd resin. As a result, when preparing the ink, it becomes easy to disperse well with the pigment. In addition, by the reaction of component (C) with component (B), an ester crosslinked structure is formed in the rosin alkyd resin. As a result, the elasticity of the ink composition is increased, and the ink exhibits excellent misting resistance and emulsification resistance.

[0029] (C) components include, for example, aliphatic diols such as ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 2-methylpropanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, methyloctanediol, 1,9-nonanediol, 1,10-decanediol; polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; alicyclic diols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, adamantanediol, tricyclodecandiol; aliphatic triols such as glycerin, trimethylolethane, trimethylolpropane; aliphatic tetraols such as pentaerythritol, diglycerin, ditrimethylolethane, ditrimethylolpropane; sorbitol, dipentaerythritol, tripentaerythritol, adamantanetriol and the like. These may be used alone or in combination of two or more. Among them, aliphatic diols and aliphatic triols are preferred, and ethylene glycol, propylene glycol, and trimethylolpropane are more preferred, because it is easy to adjust physical properties such as the softening point and weight average molecular weight of the rosin-modified alkyd resin to desired values.

[0030] (A) As for the usage ratios of components (B) and (C), since the rosin-modified alkyd resin in the ink composition is well compatible with the active energy ray curable monomer and also easily reacts with the gelling agent, the number of carboxyl groups of component (A) (A COOH ) and the number of carboxyl groups of component (B) (B COOHThe hydroxyl group number of component (C) and (C) OH ) is used, and (C OH ) / {(A COOH ) + (B COOH )} = 1.2 to 2 is preferable, and 1.4 to 1.8 is more preferable.

[0031] The carboxyl group number is calculated as follows, for example, taking the case where 100 parts by weight of isophthalic acid (molecular weight (Mw.): 166.1) is charged. (Carboxyl group number of isophthalic acid) = {(Charged weight of isophthalic acid) / (Molecular weight of isophthalic acid)} × (Number of carboxyl groups per molecule of isophthalic acid) = (100 / 166.1) × 2 ≈ 1.20

[0032] Also, the hydroxyl group number is calculated as follows, for example, taking the case where 100 parts by weight of trimethylolpropane (molecular weight (Mw.): 134.2) is charged. (Hydroxyl group number of trimethylolpropane) = {(Charged weight of trimethylolpropane) / (Molecular weight of trimethylolpropane)} × (Number of hydroxyl groups per molecule of trimethylolpropane) = (100 / 134.2) × 3 ≈ 2.23

[0033] The rosin-modified alkyd resin of the present invention is obtained by reacting components (A) to (C) in the presence of a catalyst. The production method is not particularly limited, and for example, methods (1) to (3) etc. can be mentioned. In the following methods, the addition order of each component is not particularly limited. (1) A method of charging components (A) to (C) all at once and reacting in the presence of a catalyst (2) A method of charging components (A) and (C) all at once, reacting in the presence of a catalyst, and then adding component (B) and reacting (3) A method of charging components (B) and (C) all at once, reacting in the presence of a catalyst, and then adding component (A) and reacting

[0034] Examples of the catalyst include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids such as oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid; organic amines such as triethylamine; metal oxides such as lithium oxide, sodium oxide, magnesium oxide, aluminum oxide, potassium oxide, calcium oxide, and zinc oxide; metal hydroxides such as lithium hydroxide, sodium hydroxide, magnesium hydroxide, aluminum hydroxide, potassium hydroxide, and calcium hydroxide; metal acetates such as lithium acetate, sodium acetate, magnesium acetate, aluminum acetate, calcium acetate, and zinc acetate; and organometallic catalysts such as tetrabutyl zirconate, monobutyltin oxide, and tetrabutyl titanate. These may be used alone or in combination of two or more. The amount of the catalyst used is preferably about 0.01 to 0.10 parts by weight, more preferably about 0.02 to 0.05 parts by weight, per 100 parts by weight of the component (A).

[0035] The production conditions are not particularly limited. Usually, the reaction temperature is about 180 to 280 °C and the reaction time is about 40 to 50 hours.

[0036] The acid value of the rosin-modified alkyd resin obtained by the above production method is 10 mgKOH / g or less. The acid value here is the value measured according to JIS K5601. When the acid value exceeds 10 mgKOH / g, the hydrophilicity of the rosin-modified alkyd resin increases, and the ink is likely to have poor anti-emulsification properties. For the same reason, the acid value is preferably 1 to 8 mgKOH / g, more preferably 1 to 5 mgKOH / g.

[0037] The hydroxyl value of the rosin-modified alkyd resin is 30 to 200 mgKOH / g. The hydroxyl value here is the value measured according to JIS K0070. When the hydroxyl value is less than 30 mgKOH / g, the rosin-modified alkyd resin in the ink composition is less likely to be compatible with the active energy ray-curable monomer and is also less likely to react with the gelling agent. When it exceeds 200 mgKOH / g, the anti-misting property of the ink is likely to decrease. For the same reason, the hydroxyl value is preferably 50 to 180 mgKOH / g, more preferably 70 to 150 mgKOH / g.

[0038] Furthermore, the weight average molecular weight of the rosin-modified alkyd resin is from 3,000 to 30,000. The weight average molecular weight herein is the polystyrene conversion value in gel permeation chromatography. When the weight average molecular weight is less than 3,000, the ink has a low viscosity, and its fluidity and anti-misting property are likely to be impaired. When it exceeds 30,000, there are many linear structures in the rosin-modified alkyd resin. Therefore, the elasticity of the ink composition decreases, and the anti-misting property of the ink is likely to be inferior. The softening point herein is the value measured according to JIS K5601.

[0039] As other physical properties of the rosin-modified alkyd resin, for example, the softening point (JIS K5601) is usually from 90 to 120°C.

[0040] The ink composition of the present invention contains the rosin-modified alkyd resin of the present invention.

[0041] The ink composition of the present invention also contains an active energy ray curable monomer in the rosin-modified alkyd resin.

[0042] Examples of the active energy ray curable monomer include aliphatic mono(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate; alicyclic mono(meth)acrylates such as cyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate; Alkylene di(meth)acrylates such as 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, polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate; Trimethylolpropane poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate; Ditrimethylolpropane poly(meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-modified ditrimethylolpropane tetra(meth)acrylate; Pentaerythritol (meth)acrylates such as pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate or mixtures thereof, ethylene oxide-modified pentaerythritol tetra(meth)acrylate; Dipentaerythritol (meth)acrylates such as dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate or mixtures thereof, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate; Tripentaerythritol mono(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, or a mixture thereof, and tripentaerythritol (meth)acrylate such as ethylene oxide-modified tripentaerythritol octa(meth)acrylate, etc. These may be used alone or in combination of two or more.

[0043] As the content of the active energy ray-curable monomer, based on the total of the rosin-modified alkyd resin and the active energy ray-curable monomer being 100% by weight, about 30 to 90% by weight is preferable, and about 40 to 80% by weight is more preferable.

[0044] The composition for printing ink of the present invention may further contain a gelling agent.

[0045] The gelling agent is not particularly limited. For example, aluminum-based gelling agents such as aluminum octylate, aluminum stearate, aluminum ethoxide, aluminum isopropylate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetylacetate, aluminum dibutoxide monoacetylacetate, aluminum triacetylacetate; titanium-based gelling agents such as tetraisopropyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, titanium lactate; zirconium-based gelling agents such as zirconium tetrabutoxide, zirconium acetylacetone, ethyl acetoacetate zirconium butoxide, etc. These may be used alone or in combination of two or more.

[0046] The content of the gelling agent is about 0.01 to 3 parts by weight, preferably about 0.05 to 1.5 parts by weight, based on 100 parts by weight in total of the rosin-modified alkyd resin and the active energy ray-curable monomer.

[0047] The composition for printing ink of the present invention can be obtained, for example, by mixing a rosin-modified alkyd resin, an active energy ray-curable monomer, and (furthermore a gelling agent) while stirring, and reacting at a reaction temperature of usually about 90 to 120°C for 30 to 60 minutes.

[0048] Further, the ink composition may further contain a polymerization inhibitor. Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as methoquinone, hydroquinone, methoxyhydroquinone, and benzoquinone; monoalkylphenol-based polymerization inhibitors such as 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, and 2,4,6-tri-t-butylphenol; amine-based polymerization inhibitors such as alkylated diphenylamine, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine; N-nitrosophenylhydroxylamine ammonium salt; and nitrosoamine-based polymerization inhibitors such as 2,4-dinitrophenol and 2-methyl-N-nitrosoaniline.

[0049] The content of the polymerization inhibitor is usually 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight in total of the rosin-modified alkyd resin, the active energy ray-curable monomer, and the gelling agent.

[0050] The ink composition may contain additives such as a colorant, a photosensitizer, an antioxidant, a light stabilizer, and a leveling agent.

[0051] The ink of the present invention contains the composition for ink of the present invention. Specifically, it contains a composition for ink, a pigment, and, if necessary, additives such as the aforementioned active energy ray-curable monomer, a photoinitiator, and a surface conditioner, an antifoaming agent, a photosensitizer, an antioxidant, a light stabilizer, and a leveling agent.

[0052] Examples of the pigment include inorganic pigments such as zinc oxide, calcium carbonate, titanium dioxide, cadmium red, carbon black, etc., and organic pigments such as isoindolinone-based, quinacridone-based, phthalocyanine-based, perylene-based, etc. Further, the ink preparation means is not particularly limited, and examples include a three-roll mill.

[0053] Examples of the base material include papers such as art paper, cast coated paper, foam paper, PPC paper, high-quality coated paper, kraft paper, polyethylene laminated paper, glassine paper, etc.; plastics such as polyolefin, polycarbonate, polymethacrylate, polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.

[0054] Examples of the ink coating method include offset printing, flexographic printing, screen printing, roll, bar coater, Mayer bar, air knife, gravure, etc.

[0055] Further, as for the coating amount of the ink, the cured layer of the ink is preferably adjusted to be about 0.1 to 30 g / m 2 more preferably about 1 to 20 g / m 2

[0056] Examples of the ink curing means include electron beam and ultraviolet ray, and examples of the ultraviolet light source include high-pressure mercury lamp, xenon lamp, metal halide lamp, UV-LED, etc. Further, the light amount, light source arrangement, and conveyance speed are not particularly limited. When using a high-pressure mercury lamp, it is preferable that the conveyance speed is about 5 to 50 m / min with respect to one lamp having a light amount of about 80 to 160 W / cm.

Examples

[0057] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" are both based on weight.

[0058] ​ (Acid value) The acid value of the rosin-modified alkyd resin was measured in accordance with JIS K5601.

[0059] (Hydroxyl value) The hydroxyl value of the rosin-modified alkyd resin was measured in accordance with JIS K0070.

[0060] (Weight average molecular weight) The weight average molecular weight of the rosin-modified alkyd resin was measured in terms of polystyrene using a commercially available gel permeation chromatography apparatus (manufactured by Tosoh Corporation, HLC-8320GPC), a commercially available column (TSK-GEL column manufactured by Tosoh Corporation), and tetrahydrofuran as the eluent.

[0061] (Softening point) The softening point of the rosin-modified alkyd resin was measured in accordance with JIS K5601.

[0062] Example 1 100 parts of disproportionated rosin (manufactured by Guangxi Wuzhou Arakawa Chemical Industry Co., Ltd.), 62 parts of phthalic anhydride, 60 parts of trimethylolpropane, 20.8 parts of propylene glycol, and 0.03 part of zinc acetate were added to a reaction vessel equipped with a stirrer, a reflux condenser with a water separator, and a thermometer, and the mixture was reacted at 180 to 270°C for 30 hours with stirring to obtain a rosin-modified alkyd resin. The acid value, hydroxyl value, weight average molecular weight, and softening point of the obtained resin are shown in Table 1 (the same applies hereinafter).

[0063] Examples 2 to 15, Comparative Examples 1 to 8 Rosin-modified alkyd resins were obtained in the same manner as in Example 1 using the compositions and amounts shown in Table 1.

[0064]

Table 1

[0065] <Preparation of Composition (1) for Printing Ink and Ink (1)> Evaluation Examples 1 to 15, Comparative Evaluation Examples 1 to 8 In a reaction vessel equipped with a stirring device and a cooling pipe, 45.0 parts of the rosin-modified alkyd resin of Example 1, 55.0 parts of ditrimethylolpropane tetraacrylate (product name: "Aronix M-408", manufactured by Toagosei Co., Ltd.) (hereinafter referred to as DTMPTA), and 0.10 part of methoquinone (manufactured by Seiko Chemical Co., Ltd.) as a polymerization inhibitor were charged, and stirred at 120 °C for 1 hour to prepare an ink composition (1). Next, 18 parts of phthalocyanine blue as a pigment, 35 to 40 parts of the above ink composition, 37 to 42 parts of DTMPTA, 0.1 part of methoquinone, and 5 parts of Omnirad 907 (manufactured by BASF) as a photoinitiator were kneaded with a three-roll mill so that the tack value was 9.0 ± 0.5 to prepare Ink (1). The same was done for the rosin-modified alkyd resins of Examples 2 to 15 and Comparative Examples 1 to 8 to prepare an ink composition (1) and Ink (1), respectively.

[0066] (Viscosity) Using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the viscosity (unit: Pa·s) of the ink composition adjusted to a temperature of 25 °C was measured. The results are shown in Table 2 (the same applies hereinafter). The results of Comparative Evaluation Example 7 are shown in Table 3, and the results of Comparative Evaluation Example 8 are shown in Table 4, respectively.

[0067] (Flowability) 1.3 ml of ink measured with an ink pipette was extruded onto the upper end of a glass plate with a 60° inclination, and the distance (mm) that the ink flowed after 30 minutes was measured. The longer the distance that the ink flowed, the better the flowability. In this evaluation, 50 mm or more was considered a pass.

[0068] (Anti-misting property) 2.6 ml of ink was spread on an inkometer (manufactured by Toyo Seiki Seisaku-sho, Ltd.), rotated at a roll temperature of 30 °C and 400 rpm for 1 minute, and then at 1200 rpm for 2 minutes, and the degree of ink scattering onto white paper placed directly below the roll was observed and evaluated on a scale of 1 to 5. The larger the numerical value, the better the anti-misting property. (Evaluation criteria) 5: Little ink scattering on white paper 4: Slightly less ink scattering on white paper 3: Slightly more ink scattering on white paper 2: More ink scattering on white paper 1: Very much ink scattering on white paper

[0069] (Gloss) After spreading 0.1 ml of ink on art paper with an RI tester (manufactured by Ishikawa Island Industries Co., Ltd.) and curing it by passing it through a UV irradiator with a light quantity of 38 mJ / cm 2 The 60°-60° reflectance was measured with a gloss meter. The larger the value, the better the gloss.

[0070] (Emulsion resistance) 30.0 g of each ink and 30.0 g of water were added, and emulsification was carried out at 3000 rpm using a homodyne disperser (device name: "T.K.HOMO DISPER", manufactured by Primix Corporation). Water in the aqueous phase was collected from the sample separated into an ink phase (solid) and an aqueous phase (liquid), and its weight (g) was measured. The emulsification rate (%) was calculated using Equation 1. The smaller the value, the better the emulsion resistance. In this evaluation, an emulsification rate of 65% or less was considered qualified. (Equation 1) Emulsification rate (%) = [((amount of water added (30.0 g)) - (weight of water collected after emulsification)) / (amount of ink added (30.0 g))] × 100

[0071]

Table 2

[0072] <Preparation of printing ink composition (2) and ink (2)> Evaluation Example 16, Comparative Evaluation Example 9 In a reaction vessel equipped with a stirring device and a cooling pipe, 45.0 parts of the rosin-modified alkyd resin of Example 1, 55.0 parts of DTMPTA, 0.10 part of methoquinone (manufactured by Seiko Chemical Co., Ltd.) as a polymerization inhibitor, and 0.50 part of aluminum ethyl acetoacetate diisopropylate (trade name: 'ALCH', manufactured by Kawaken Fine Chemicals Co., Ltd.) as a gelling agent were charged, and stirred at 120 °C for 1 hour to obtain an ink composition (2). Next, in the same manner as the above-described method, Ink (2) was prepared. The same was done for the rosin-modified alkyd resin of Comparative Example 7, and Ink Composition (2) and Ink (2) were respectively prepared.

[0073] For Ink (2), in the same manner as the above-described method, viscosity, fluidity, anti-misting property, gloss, and anti-emulsification property were measured. The results are shown in Table 3. In addition, the results of Evaluation Example 1 and Comparative Evaluation Example 7 were also shown for comparison.

[0074]

Table 3

[0075] No difference was observed in the inks of Evaluation Example 1 and Comparative Evaluation Example 7 in which no gelling agent was blended. However, when a gelling agent was added, the reaction hardly proceeded in the ink composition of Comparative Evaluation Example 9, whereas the reaction proceeded rapidly in the ink composition of Evaluation Example 16, and it was found that the ink performance was also good.

[0076] <Preparation of Printing Ink Composition (3) and Ink (3)> Evaluation Example 17, Comparative Evaluation Example 10 In a reaction vessel equipped with a stirring device and a cooling pipe, 30.0 parts of the rosin-modified alkyd resin of Example 3, 70.0 parts of Aronix M-402 (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Co., Ltd.) (hereinafter referred to as DPHA), and 0.10 part of methoquinone (manufactured by Seiko Chemical Co., Ltd.) as a polymerization inhibitor were charged, and stirred at 120 °C for 1 hour to prepare an ink composition (3). Next, ink (3) was prepared in the same manner as the method described above. For the rosin-modified alkyd resin of Comparative Example 8, the same procedure was carried out, but since the ink composition became turbid, it was not subjected to the following evaluation.

[0077] For ink (3), viscosity, fluidity, misting resistance, gloss, and emulsion resistance were measured in the same manner as the method described above. The results are shown in Table 4. The results of Evaluation Example 3 and Comparative Evaluation Example 8 are also shown for comparison.

[0078]

Table 4

[0079] In the inks of Evaluation Example 3 and Comparative Evaluation Example 8 using DTMPTA as the active energy ray curable monomer, no difference was observed. However, when DPHA was used, the ink composition of Comparative Evaluation Example 10 became turbid, while the ink composition of Evaluation Example 17 was compatible with DPHA and the ink performance was also found to be good.

Claims

1. A product of reaction components containing rosin (A), polycarboxylic acid (B), and polyol (C), which is a rosin-modified alkyd resin having an acid value of 10 mg KOH / g or less, a hydroxyl value of 30 to 200 mg KOH / g, and a weight average molecular weight of 3,000 to 30,000.

2. The rosin-modified alkyd resin according to Claim 1, wherein the component (A) contains disproportionated rosin and / or hydrogenated rosin.

3. The rosin-modified alkyd resin according to Claim 1 or 2, wherein the component (B) contains one or more selected from the group consisting of aromatic polycarboxylic acids, alicyclic polycarboxylic acids, aromatic polycarboxylic anhydrides, and alicyclic polycarboxylic anhydrides.

4. The rosin-modified alkyd resin according to any one of Claims 1 to 3, wherein the component (C) contains an aliphatic diol and / or an aliphatic triol.

5. An ink composition containing the rosin-modified alkyd resin according to any one of Claims 1 to 4.

6. The ink composition according to Claim 5, further containing an active energy ray curable monomer.

7. The ink composition according to Claim 5 or 6, further containing a gelling agent.

8. An ink containing the ink composition according to any one of Claims 5 to 7.

Images