Rosin-modified resin, active energy ray curable composition, cured product, and laminate

Abstract

To provide rosin-modified resins, active energy ray-curable compositions, cured products, and laminates. [Solution] A rosin-modified resin, which is a disproportionated resin product of a reaction product of raw materials including α,β-unsaturated carboxylic acid-modified rosin, polyol, polybasic acid and / or its anhydride, and conjugated rosin.

Description

Technical Field

[0001] The present disclosure relates to a rosin-modified resin, an active energy ray-curable composition, a cured product, and a laminate.

Background Art

[0002] In active energy ray-curable printing inks, poly(meth)acrylate is widely used as a reactive diluent. Since it has excellent compatibility and curability with poly(meth)acrylate, diallyl phthalate resin is widely used as a binder resin (Patent Document 1, paragraph 0009).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, diallyl phthalate resin does not have polar functional groups (such as hydroxyl groups and carboxyl groups). Therefore, the usage modes of diallyl phthalate resin are limited. In recent years, the demand for resins using a large amount of biomass raw materials has been increasing.

[0005] The problem to be solved by the invention is to provide a rosin-modified resin that can impart good fluidity, anti-mixing property, and thermal stability.

Means for Solving the Problems

[0006] The following items are provided by the present disclosure. (Item 1) A disproportionated product of a resin, which is a reaction product of raw materials containing α,β-unsaturated carboxylic acid-modified rosin, a polyol, a polybasic acid and / or its anhydride, and conjugated rosin. (Item 2) The rosin-modified resin according to claim 1, comprising 25% to 65% by mass of the conjugated rosin with respect to 100% by mass of the raw material. (Item 3) An active energy ray curable composition comprising a rosin-modified resin and a poly(meth)acrylate as described in any one of the above items. (Item 4) A cured product of the active energy ray curable composition described in the above items. (Item 5) A laminate containing the cured material described in the above items. (Item P1) A rosin-modified resin, which is a disproportionated resin containing α,β-unsaturated carboxylic acid-modified rosin units, polyol units, polybasic acids and / or their anhydride units, and conjugated rosin units. (Item P2) The rosin-modified resin described above, comprising 100% by mass of the rosin-modified resin and containing 25% to 65% by mass of the conjugated rosin units.

[0007] In this disclosure, one or more of the features described above may be provided in combinations other than those explicitly stated. [Effects of the Invention]

[0008] The rosin-modified resin of this embodiment can provide good fluidity, misting resistance, and thermal stability. [Modes for carrying out the invention]

[0009] Throughout this disclosure, the ranges of numerical values ​​such as physical properties and content may be set as appropriate (for example, by selecting from the values ​​listed in each of the items below). Specifically, if the numerical value α is such as A3, A2, A1 (A3 > A2 > A1), then the range of the numerical value α may be A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less.

[0010] The components, conditions, numerical values, etc., are not particularly limited, as long as the problems that this invention aims to solve are resolved.

[0011] "αβ amount (A / B)" means the amount of β (α) of A relative to 100α of B. α can be expressed as mass%, mole%, or parts by mass, for example. β amount can be expressed as content, amount used, for example. "Mass% content (A / B)" means the content (mass%) of A relative to 100% mass of B.

[0012] "γ ratio (A / B)" refers to the γ ratio calculated using the formula "A ÷ B". Examples of γ ratios include mass ratios and molar ratios.

[0013] "Non-volatile content" refers to the total mass of components other than organic solvents and water. In one embodiment, "non-volatile content of A" refers to the total mass of components remaining when 1 g of A is heated at 105°C and a constant weight is reached.

[0014] "(meth)acrylic" means "acrylic and / or methacrylic". "(meth)acrylate" means "acrylate and / or methacrylate". "(meth)acryloyl" means "acryloyl and / or methacryloyl".

[0015] "Poly(meth)acrylate" means a compound having two or more (meth)acryloyl groups.

[0016] In a compound (such as a polymer), "A unit" means a unit (portion) derived from A (raw material, monomer).

[0017] [Rosin-modified resin] The present disclosure relates to a disproportionated product of a resin, which is a reaction product of a raw material containing α,β-unsaturated carboxylic acid-modified rosin, polyol, polybasic acid and / or its anhydride, and conjugated rosin, and is a rosin-modified resin.

[0018] <α,β-unsaturated carboxylic acid-modified rosin> The α,β-unsaturated carboxylic acid-modified rosin can be used alone or in combination of two or more.

[0019] "α,β-unsaturated carboxylic acid-modified rosin" means rosin subjected to an addition cyclization reaction.

[0020] (Rosin) Rosin is an amber, amorphous resin obtained from pine. Rosin is obtained as a mixture.

[0021] Examples of rosin pine species include Pinus massoniana, Pinus elliottii, Pinus merkusii, Pinus caribaea, Pinus kesiya, Pinus taeda, and Pinus palustris.

[0022] Examples of rosin include natural rosin, purified rosin, etc. Natural rosin and purified rosin are collectively also referred to as unmodified rosin.

[0023] (Natural rosin) Examples of natural rosin include gum rosin, tall oil rosin, wood rosin, etc.

[0024] Examples of producing regions (natural rosin) include China, Vietnam, Indonesia, and Brazil.

[0025] (Refined rosin) Purified rosin can be obtained using various known purification methods. Examples of purification methods include distillation, extraction, recrystallization, and adsorption.

[0026] Distillation methods include, for example, distilling natural rosin at 200°C to 300°C and a pressure of 0.01 kPa to 3 kPa.

[0027] Extraction methods include, for example, preparing natural rosin as an alkaline aqueous solution, extracting insoluble unsaponifiable matter with an organic solvent, and then neutralizing the aqueous layer.

[0028] Recrystallization methods include, for example, dissolving natural rosin in a good solvent, removing the solvent by distillation to obtain a concentrated solution, and then adding a poor solvent.

[0029] Examples of good solvents include aromatic hydrocarbon solvents (benzene, toluene, xylene, etc.), chlorinated hydrocarbon solvents (chloroform, etc.), lower alcohol solvents, ketone solvents (acetone, etc.), and acetate ester solvents (ethyl acetate, etc.).

[0030] Examples of poor solvents include n-hexane, n-heptane, cyclohexane, and isooctane.

[0031] Adsorption methods include, for example, a method of contacting an unmodified rosin (in a molten state or in a solution state dissolved in an organic solvent) with a porous adsorbent.

[0032] Examples of porous adsorbents include activated carbon, metal oxides, alumina, zirconia, silica, molecular sieves, zeolites, and porous clays with micropores.

[0033] Rosin can be isolated for each diterpene resin acid. Each diterpene resin acid isolated from rosin is also defined as rosin.

[0034] Examples of diterpene resin acids include abietane-type diterpene resin acids, pimarane-type diterpene resin acids, dehydro-type diterpene resin acids, and labdan-type diterpene resin acids.

[0035] Examples of abietane-type diterpene resin acids include abietic acid, neoabietic acid, paraslitrinic acid, and lepopimaric acid.

[0036] Examples of pimaran-type diterpene resin acids include pimaric acid, isopimaric acid, and sandaracopimaric acid.

[0037] Examples of dehydro-type diterpene resin acids include dehydroabietic acid.

[0038] Examples of labdan-type diterpene resin acids include combunic acid and dihydroagatic acid.

[0039] (α,β-unsaturated carboxylic acids or their anhydrides) Examples of α,β-unsaturated carboxylic acids or their anhydrides include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic acid anhydride, maleic acid half-ester, fumaric acid half-ester, itaconic acid half-ester, and 3,4,5,6-tetrahydrophthalic anhydride. In one embodiment, the α,β-unsaturated carboxylic acid or its anhydride is preferably maleic acid, maleic anhydride, or fumaric acid.

[0040] The amount used (α,β-unsaturated carboxylic acid / rosin) is preferably 0.5 to 100 parts by mass, and more preferably 0 to 60 parts by mass.

[0041] The manufacturing temperature (for α,β-unsaturated carboxylic acid-modified rosin) is preferably 160°C to 240°C.

[0042] The manufacturing time (for α,β-unsaturated carboxylic acid-modified rosin) is preferably 1 to 9 hours.

[0043] Examples of catalysts for cycloaddition reactions include Lewis acids (zinc chloride, iron chloride, tin chloride, etc.) and Brønsted acids (p-toluenesulfonic acid, methanesulfonic acid).

[0044] The mass% amount used (addition cycloaddition reaction catalyst / rosin) is preferably 0% to 10% by mass.

[0045] In one embodiment, the α,β-unsaturated carboxylic acid-modified rosin is preferably maleated rosin.

[0046] Examples of mass% content (α,β-unsaturated carboxylic acid modified rosin / raw material) include 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 1% by mass. In one embodiment, the above content is preferably 1% by mass to 85% by mass.

[0047] <Polyol> A "polyol" refers to a compound having two or more hydroxyl groups. Polyols can be used individually or in combination of two or more.

[0048] Examples of polyols include diols, triols, and tetraols.

[0049] Examples of diols include aliphatic diols, alicyclic diols, and polyalkylenediols.

[0050] Aliphatic diols include, for example, 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, and 1,10-decanediol.

[0051] Examples of alicyclic diols include 1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-cycloheptanediol, adamantanediol, and tricyclodecanediol.

[0052] Examples of polyalkylenediols include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol.

[0053] Examples of triols include glycerin, trimethylolethane, trimethylolpropane, and adamantanetriol.

[0054] Examples of tetraols include pentaerythritol, diglycerin, ditrimethylolethane, and ditrimethylolpropane.

[0055] Other polyols besides those mentioned above include, for example, sorbitol, dipentaerythritol, and tripentaerythritol.

[0056] Examples of mass% content (polyol / raw material) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 14% by mass, 12% by mass, 10% by mass, 5% by mass, and 1% by mass. In one embodiment, the above content is preferably 1% by mass to 50% by mass.

[0057] <Polybasic acids and / or their anhydrides> Polybasic acids and / or their anhydrides may be used individually or in combination of two or more.

[0058] Examples of polybasic acids include aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids.

[0059] Examples of aliphatic polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid.

[0060] Examples of alicyclic polycarboxylic acids include 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, hexahydrophthalic acid, 3,4,5,6-tetrahydrophthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0061] Examples of aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 2,3-naphthalenedicarboxylic acid, and 2,4-naphthalenedicarboxylic acid.

[0062] Examples of polybasic acid anhydrides include the polybasic acid anhydrides mentioned above.

[0063] In one embodiment, the polybasic acid and / or its anhydride is preferably succinic acid.

[0064] Examples of mass% content (polybasic acid and / or its anhydride / raw material) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, 5% by mass, 1% by mass, etc. In one embodiment, the above content is preferably 1% by mass to 50% by mass.

[0065] <Conjugated Rosin> Conjugated rosin can be used alone or in combination of two or more types.

[0066] "Conjugated rosin" refers to rosin that has a non-aromatic conjugated system structure in which two carbon-carbon double bonds sandwich one carbon-carbon single bond.

[0067] Examples of conjugated rosins include abietic acid, neoabietic acid, paraslitrinic acid, and lepopimaric acid.

[0068] In one embodiment, the conjugated rosin is disproportionated by a disproportionation catalyst.

[0069] In one embodiment, the mass % content (conjugated rosin / raw material) can be, for example, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, etc. In one embodiment, the above content is preferably 25% by mass to 65% by mass.

[0070] Examples of molar ratios (α,β-unsaturated carboxylic acid / conjugated rosin) include 4, 3, 2, 1, 0.75, 0.5, 0.4, 0.3, 0.25, 0.1, 0.05, and 0.01. In one embodiment, the above molar ratio is preferably 0.01 to 4, and more preferably 0.1 to 1.

[0071] <Disproportionated rosin> Disproportioned rosin can be used alone or in combination of two or more types.

[0072] "Disproportionated rosin" refers to rosin that has been subjected to a disproportionation reaction. "Disproportionation" means that two molecules of rosin react, and two molecules of abietic acid with conjugated double bonds are modified so that one becomes aromatic and the other becomes a molecule with a single double bond.

[0073] The above-mentioned disproportionated rosin can be obtained by heating rosin in the presence of a disproportionation catalyst (disproportionation).

[0074] In this disclosure, disproportionate rosin units in the rosin-modified resin may also arise from the disproportionation of conjugated rosin units contained in the resin before the disproportionation reaction. The disproportionation conditions are as described below.

[0075] Examples of mass% content (disproportionate rosin units / rosin-modified resin) include 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, and 1% by mass. In one embodiment, the above content is preferably 1% by mass to 85% by mass, and more preferably 1% by mass to 80% by mass.

[0076] In one embodiment, the raw materials may optionally include disproportionated rosin.

[0077] Examples of mass % content (disproportionated rosin units / raw material) include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 80% by mass, and more preferably 10% by mass to 40% by mass.

[0078] <monobasic acid> The rosin-modified resin may optionally contain a monobasic acid unit. The monobasic acid may be used alone or in combination of two or more types.

[0079] Examples of monobasic acids include rosin hydrogenates, aromatic monobasic acids, saturated aliphatic monobasic acids, and unsaturated aliphatic monobasic acids.

[0080] "Hydrogenated rosin" refers to rosin that has undergone a hydrogenation reaction.

[0081] The hydrogen pressure is preferably 2 MPa to 20 MPa, and more preferably 5 MPa to 20 MPa.

[0082] The hydrogenation reaction temperature is preferably 100°C to 300°C, and more preferably 150°C to 300°C.

[0083] Examples of hydrogenation catalysts include supported catalysts and metal powders.

[0084] Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, and platinum-carbon.

[0085] Examples of metal powders include nickel powder and platinum powder. In one embodiment, the hydrogenation catalyst is preferably a palladium catalyst, a rhodium catalyst, a ruthenium catalyst, or a platinum catalyst.

[0086] The amount of parts by mass used (hydrogenation catalyst / rosin) is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2 parts by mass.

[0087] The above hydrogenation may be carried out with rosin dissolved in a solvent, if necessary. Examples of hydrogenation solvents include cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, and dioxane. The hydrogenation solvents may be used alone or in combination of two or more.

[0088] The amount used (hydrogenation reaction solvent / rosin non-volatile content) is preferably 10% by mass or more, and more preferably 10% by mass to 70% by mass.

[0089] Examples of aromatic monobasic acids include benzoic acid, methylbenzoic acid, tert-butylbenzoic acid, naphthoic acid, and orthobenzoylbenzoic acid.

[0090] Examples of saturated aliphatic monobasic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, and behenic acid.

[0091] Examples of unsaturated aliphatic monobasic acids include crotonic acid, lindelic acid, tuzic acid, myristoleic acid, palmitoleic acid, undecylenic acid, oleic acid, elaidic acid, gadoleic acid, gondolenic acid, cetoleic acid, erucic acid, brassic acid, linolenic acid, linolenic acid, and arachidonic acid.

[0092] Examples of mass% content (monobasic acid units / raw material) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 9% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass.

[0093] Examples of molar content (one basic acid unit / raw material) include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 9 mol%, 5 mol%, 4 mol%, 2 mol%, 1 mol%, and 0 mol%. In one embodiment, the above content is preferably 0 mol% to 50 mol%, and more preferably 5 mol% to 30 mol%.

[0094] <Other constituent units: Other units> The rosin-modified resin described above may contain units that do not fall under any of the above categories (other units).

[0095] Other units include polymerized rosin units and alcohol (monool) units.

[0096] The parts by mass content (other units / rosin-modified resin) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass.

[0097] The parts by mass content (other units / α,β-unsaturated carboxylic acid modified rosin units) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass.

[0098] The parts by mass content (in other units / polyol units) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass.

[0099] The parts by mass content (other units / polybasic acid and / or its anhydride units) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass.

[0100] The parts by mass content (in other units / conjugated rosin units) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass.

[0101] The parts by mass content (other units / unproportionalized rosin units) is preferably less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or 0 parts by mass.

[0102] <Physical properties, etc. (rosin-modified resin)> Examples of acid values ​​(rosin-modified resin) include 50 mg KOH / g, 45 mg KOH / g, 40 mg KOH / g, 35 mg KOH / g, 30 mg KOH / g, 25 mg KOH / g, 20 mg KOH / g, 15 mg KOH / g, 10 mg KOH / g, 9 mg KOH / g, 5 mg KOH / g, 4 mg KOH / g, 2 mg KOH / g, 1 mg KOH / g, 0.9 mg KOH / g, 0.5 mg KOH / g, 0.1 mg KOH / g, etc. In one embodiment, the above acid values ​​are preferably between 0.1 mg KOH / g and 50 mg KOH / g.

[0103] The acid value is measured according to the method compliant with JIS K5601 (neutralization titration method).

[0104] The hydroxyl value (rosin-modified resin) is, for example, 150 mg KOH / g, 145 mg KOH / g, 140 mg KOH / g, 135 mg KOH / g, 130 mg KOH / g, 125 mg KOH / g, 120 mg KOH / g, 115 mg KOH / g, 110 mg KOH / g, 105 mg KOH / g, 100 mg KOH / g, 95 mg KOH / g, 90 mg KOH / g, 85 mg KOH / g, 80 mg KOH / g, 75 mg KOH / g, 70 mg KOH / g, 65 Examples include mgKOH / g, 60mgKOH / g, 55mgKOH / g, 50mgKOH / g, 45mgKOH / g, 40mgKOH / g, 35mgKOH / g, 30mgKOH / g, 25mgKOH / g, 20mgKOH / g, 15mgKOH / g, 10mgKOH / g, 9mgKOH / g, 5mgKOH / g, 4mgKOH / g, 2mgKOH / g, 1mgKOH / g, 0.9mgKOH / g, 0.5mgKOH / g, 0.1mgKOH / g, etc. In one embodiment, the above hydroxyl value is preferably 0.1mgKOH / g to 150mgKOH / g.

[0105] The hydroxyl value is measured according to the method compliant with JIS K0070 (neutralization titration method).

[0106] Examples of weight-average molecular weights (Mw: rosin-modified resin) include 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 35,000, 34,000, 33,000, 32,000, 31,000, 30,000, 29,000, 28,000, 27,000, 26,000, 25,000, 24,000, 23,000, 22,000, 21,000, 20,000, 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, and 1,000. In one embodiment, the weight-average molecular weight (Mw) is preferably 1,000 to 100,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 80,000.

[0107] Examples of the number-average molecular weight (Mn: rosin-modified resin) include 10,000, 9,000, 8,000, 7,000, 6,000, 5,000, 4,000, 3,000, 2,000, 1,750, 1,500, 1,450, 1,400, 1,300, 1,200, 1,100, 1,050, 1,000, 900, 700, and 500. In one embodiment, the above number-average molecular weight (Mn) is preferably 500 to 10,000, more preferably 800 to 10,000, and even more preferably 1,200 to 10,000.

[0108] Examples of molecular weight distributions (Mw / Mn: rosin-modified resin) include 60, 55, 50, 45, 40, 35, 30, 25, 24, 23, 22, 21, 20, 15, 10, 9, 8, 7, 6, 5, 4, 2, and 1. In one embodiment, the above molecular weight distribution (Mw / Mn) is preferably 1 to 60, more preferably 1 to 50, and even more preferably 1 to 30.

[0109] Measurement conditions (weight-average molecular weight and number-average molecular weight) include, for example, the following conditions. Model: Product name "HLC-8320" (manufactured by Tosoh Corporation) Column: Product name "TSK-GEL" (manufactured by Tosoh Corporation) Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Standard: Monodisperse polystyrene Measurement temperature: 40℃ Detector: RI Polymer concentration: 0.2%

[0110] Examples of softening points (rosin-modified resin) include 150°C, 145°C, 140°C, 135°C, 130°C, 125°C, 120°C, 119°C, 117°C, 115°C, 114°C, 113°C, 112°C, 111°C, 110°C, 109°C, 108°C, 107°C, 106°C, 105°C, 104°C, 100°C, 95°C, 90°C, 85°C, and 80°C. In one embodiment, the softening point is preferably 80°C to 150°C, more preferably 85°C to 150°C, and even more preferably 90°C to 150°C.

[0111] The softening point is measured according to the method conforming to JIS K5601 (ring-sphere method).

[0112] The manufacturing method (rosin-modified resin) includes the following steps. Resin manufacturing process: A group of compounds including α,β-unsaturated carboxylic acid-modified rosin, polyol, polybasic acid and / or its anhydride, and conjugated rosin are reacted to obtain a resin. Disproportionation process: The above resin is disproportionately processed to obtain a rosin-modified resin.

[0113] In the above manufacturing method, the order in which each component is added is not particularly limited. Furthermore, various known devices (such as ultrasonic dispersion devices) can be used as dispersion and mixing means.

[0114] Examples of disproportionation catalysts include supported catalysts (palladium-carbon, rhodium-carbon, platinum-carbon, etc.), metal powders (nickel, platinum, etc.), and iodides (iodine, iron iodide, etc.).

[0115] The amount of parts by mass used (disproportionation catalyst / rosin) is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 1 part by mass.

[0116] The reaction temperature (disproportionation reaction) is preferably 100°C to 300°C, and more preferably 150°C to 290°C.

[0117] The reaction temperature (disproportionation time) is preferably between 1 hour and 70 hours.

[0118] The above-mentioned rosin-modified resin can be used as a rosin-modified resin solution for offset inks.

[0119] [Activated energy ray curable composition: Composition] This disclosure provides an active energy ray curable composition comprising the above-mentioned rosin-modified resin and poly(meth)acrylate.

[0120] Examples of mass% content (rosin-modified resin / non-volatile content of composition) include 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass. In one embodiment, the above content is preferably 5% by mass to 80% by mass.

[0121] <Poly(meth)acrylate> Examples of poly(meth)acrylates include (poly)pentaerythritol poly(alkylene oxide modified or epoxy modified)(meth)acrylate, (poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified)(meth)acrylate, (poly)glycerin poly(alkylene oxide modified or epoxy modified)(meth)acrylate, isocyanurate structure-containing poly(alkylene oxide modified or epoxy modified)(meth)acrylate, (poly)alkylenedi(alkylene oxide modified or epoxy modified)(meth)acrylate, bisphenol A di(alkylene oxide modified or epoxy modified)(meth)acrylate, and the like.

[0122] <(Poly)pentaerythritol poly(alkylene oxide modified or epoxy modified)(meth)acrylate> "(Poly)pentaerythritol poly(alkylene oxide modified or epoxy modified) (meth)acrylate" means "at least one selected from the group consisting of pentaerythritol poly(meth)acrylate, pentaerythritol polyalkylene oxide modified (meth)acrylate, pentaerythritol polyepoxy modified (meth)acrylate, polypentaerythritol poly(meth)acrylate, polypentaerythritol polyalkylene oxide modified (meth)acrylate, and polypentaerythritol polyepoxy modified (meth)acrylate."

[0123] Examples of pentaerythritol poly(meth)acrylate include pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.

[0124] Examples of pentaerythritol polyalkylene oxide-modified (meth)acrylates include pentaerythritol di(ethylene oxide-modified (meth)acrylate), pentaerythritol tri(ethylene oxide-modified (meth)acrylate), pentaerythritol tetra(ethylene oxide-modified (meth)acrylate), pentaerythritol di(propylene oxide-modified (meth)acrylate), pentaerythritol tri(propylene oxide-modified (meth)acrylate), and pentaerythritol tetra(propylene oxide-modified (meth)acrylate).

[0125] Examples of pentaerythritol polyepoxy-modified (meth)acrylates include pentaerythritol diepoxy (meth)acrylate, pentaerythritol triepoxy (meth)acrylate, and pentaerythritol tetraepoxy (meth)acrylate.

[0126] Examples of polypentaerythritol poly(meth)acrylate include dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(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, and tripentaerythritol octa(meth)acrylate.

[0127] Polypentaerythritol polyalkylene oxide-modified (meth)acrylates include, for example, dipentaerythritol di(ethylene oxide-modified (meth)acrylate), dipentaerythritol tri(ethylene oxide-modified (meth)acrylate), dipentaerythritol tetra(ethylene oxide-modified (meth)acrylate), dipentaerythritol penta(ethylene oxide-modified (meth)acrylate), dipentaerythritol hexa(ethylene oxide-modified (meth)acrylate), and dipentaerythritol di(p Tripentaerythritol (ethylene oxide modified (meth)acrylate), dipentaerythritol tri(propylene oxide modified (meth)acrylate), dipentaerythritol tetra(propylene oxide modified (meth)acrylate), dipentaerythritol penta(propylene oxide modified (meth)acrylate), dipentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol di(ethylene oxide modified (meth)acrylate), tripentaerythritol tri(ethylene oxide modified (meth)acrylate) Tripentaerythritol tetra(ethylene oxide modified (meth)acrylate), tripentaerythritol penta(ethylene oxide modified (meth)acrylate), tripentaerythritol hexa(ethylene oxide modified (meth)acrylate), tripentaerythritol hepta(ethylene oxide modified (meth)acrylate), tripentaerythritol octa(ethylene oxide modified (meth)acrylate), tripentaerythritol di(propylene oxide modified (meth)acrylate), tripentaerythritol Examples include pentaerythritol tri(propylene oxide modified (meth)acrylate), tripentaerythritol tetra(propylene oxide modified (meth)acrylate), tripentaerythritol penta(propylene oxide modified (meth)acrylate), tripentaerythritol hexa(propylene oxide modified (meth)acrylate), tripentaerythritol hepta(propylene oxide modified (meth)acrylate), tripentaerythritol octa(propylene oxide modified (meth)acrylate), and others.

[0128] Examples of polypentaerythritol polyepoxy-modified (meth)acrylates include dipentaerythritol diepoxy (meth)acrylate, dipentaerythritol triepoxy (meth)acrylate, dipentaerythritol tetraepoxy (meth)acrylate, dipentaerythritol pentaepoxy (meth)acrylate, dipentaerythritol hexapoxy (meth)acrylate, tripentaerythritol diepoxy (meth)acrylate, tripentaerythritol triepoxy (meth)acrylate, tripentaerythritol tetraepoxy (meth)acrylate, tripentaerythritol pentaepoxy (meth)acrylate, tripentaerythritol hexapoxy (meth)acrylate, tripentaerythritol heptapoxy (meth)acrylate, and tripentaerythritol octapoxy (meth)acrylate.

[0129] <(Poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified)(meth)acrylate> "(Poly)trimethylolpropane poly(alkylene oxide modified or epoxy modified)(meth)acrylate" means "at least one selected from the group consisting of trimethylolpropane poly(meth)acrylate, trimethylolpropane polyalkylene oxide modified(meth)acrylate, trimethylolpropane polyepoxy modified(meth)acrylate, polytrimethylolpropane poly(meth)acrylate, polytrimethylolpropane polyalkylene oxide modified(meth)acrylate, and polytrimethylolpropane polyepoxy modified(meth)acrylate."

[0130] Examples of trimethylolpropane poly(meth)acrylate include trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate.

[0131] Examples of trimethylolpropane polyalkylene oxide-modified (meth)acrylates include trimethylolpropanedi(ethylene oxide-modified (meth)acrylate), trimethylolpropanetri(ethylene oxide-modified (meth)acrylate), trimethylolpropanedi(propylene oxide-modified (meth)acrylate), and trimethylolpropanetri(propylene oxide-modified (meth)acrylate).

[0132] Examples of trimethylolpropane polyepoxy-modified (meth)acrylates include trimethylolpropane diepoxy (meth)acrylate and trimethylolpropane triepoxy (meth)acrylate.

[0133] Examples of polytrimethylolpropane poly(meth)acrylate include ditrimethylolpropanedi(meth)acrylate, ditrimethylolpropanetri(meth)acrylate, and ditrimethylolpropanetetra(meth)acrylate.

[0134] Examples of polytrimethylolpropane polyalkylene oxide-modified (meth)acrylates include ditrimethylolpropanedi (ethylene oxide-modified (meth)acrylate), ditrimethylolpropanetri (ethylene oxide-modified (meth)acrylate), ditrimethylolpropanetetra (ethylene oxide-modified (meth)acrylate), ditrimethylolpropanedi (propylene oxide-modified (meth)acrylate), ditrimethylolpropanetri (propylene oxide-modified (meth)acrylate), and ditrimethylolpropanetetra (propylene oxide-modified (meth)acrylate).

[0135] Examples of polytrimethylolpropane polyepoxy-modified (meth)acrylates include ditrimethylolpropane diepoxy (meth)acrylate, ditrimethylolpropane triepoxy (meth)acrylate, and ditrimethylolpropane tetraepoxy (meth)acrylate.

[0136] <(Poly)glycerin poly(alkylene oxide modified or epoxy modified) (meth)acrylate> "(Poly)glycerin poly(alkylene oxide modified or epoxy modified) (meth)acrylate" means "at least one selected from the group consisting of glycerin poly(meth)acrylate, glycerin polyalkylene oxide modified (meth)acrylate, glycerin polyepoxy modified (meth)acrylate, polyglycerin poly(meth)acrylate, polyglycerin polyalkylene oxide modified (meth)acrylate, and polyglycerin polyepoxy modified (meth)acrylate."

[0137] Examples of glycerin poly(meth)acrylate include glycerin di(meth)acrylate and glycerin tri(meth)acrylate.

[0138] Examples of glycerol polyalkylene oxide-modified (meth)acrylates include glycerol di(ethylene oxide-modified (meth)acrylate), glycerol tri(ethylene oxide-modified (meth)acrylate), glycerol di(propylene oxide-modified (meth)acrylate), and glycerol tri(propylene oxide-modified (meth)acrylate).

[0139] Examples of glycerin polyepoxy-modified (meth)acrylates include glycerin diepoxy (meth)acrylate and glycerin triepoxy (meth)acrylate.

[0140] Examples of polyglycerin poly(meth)acrylates include diglycerin di(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, triglycerin di(meth)acrylate, triglycerin tri(meth)acrylate, triglycerin tetra(meth)acrylate, and triglycerin penta(meth)acrylate.

[0141] Polyglycerin polyalkylene oxide-modified (meth)acrylates include, for example, diglycerin di(ethylene oxide-modified (meth)acrylate), diglycerin tri(ethylene oxide-modified (meth)acrylate), diglycerin tetra(ethylene oxide-modified (meth)acrylate), triglycerin di(ethylene oxide-modified (meth)acrylate), triglycerin tri(ethylene oxide-modified (meth)acrylate), triglycerin tetra(ethylene oxide-modified (meth)acrylate), and triglycerin penta(ethylene oxide-modified (meth)acrylate). Examples include (meth)acrylate) diglycerin di(propylene oxide modified (meth)acrylate), diglycerin tri(propylene oxide modified (meth)acrylate), diglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin di(propylene oxide modified (meth)acrylate), triglycerin tri(propylene oxide modified (meth)acrylate), triglycerin tetra(propylene oxide modified (meth)acrylate), triglycerin penta(propylene oxide modified (meth)acrylate), etc.

[0142] Examples of polyglycerin polyepoxy-modified (meth)acrylates include diglycerin diepoxy (meth)acrylate, diglycerin triepoxy (meth)acrylate, diglycerin tetraepoxy (meth)acrylate, triglycerin diepoxy (meth)acrylate, triglycerin triepoxy (meth)acrylate, triglycerin tetraepoxy (meth)acrylate, and triglycerin pentaepoxy (meth)acrylate.

[0143] <Isocyanurate structure-containing poly(alkylene oxide modified or epoxy modified) (meth)acrylate> "Isocyanurate structure-containing poly(alkylene oxide-modified or epoxy-modified) (meth)acrylate" means "at least one selected from the group consisting of isocyanurate structure-containing poly(meth)acrylate, isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate, and isocyanurate structure-containing polyepoxy-modified (meth)acrylate."

[0144] Examples of isocyanurate structure-containing poly(meth)acrylates include isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate.

[0145] Examples of the above-mentioned isocyanurate structure-containing polyalkylene oxide-modified (meth)acrylate include isocyanuric acid di(ethylene oxide-modified (meth)acrylate) and isocyanuric acid tri(ethylene oxide-modified (meth)acrylate).

[0146] Examples of the above-mentioned isocyanurate structure-containing polyepoxy-modified (meth)acrylate include isocyanuric acid diepoxy-modified (meth)acrylate and isocyanuric acid triepoxy-modified (meth)acrylate.

[0147] <(Poly)alkylenedi (alkylene oxide modified or epoxy modified) (meth)acrylate> "(Poly)alkylenedi(alkylene oxide modified or epoxy modified)(meth)acrylate" means "at least one selected from the group consisting of alkylenedi(meth)acrylate, alkylenedialkylene oxide modified(meth)acrylate, alkylenediepoxy modified(meth)acrylate, polyalkylenedi(meth)acrylate, polyalkylenedialkylene oxide modified(meth)acrylate, and polyalkylenediepoxy modified(meth)acrylate."

[0148] Examples of alkylenedi(meth)acrylates include 1,2-ethylenediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and the like.

[0149] Examples of alkylene dialkylene oxide-modified (meth)acrylates include 1,2-ethylenediol di(ethylene oxide-modified (meth)acrylate), 1,3-propanediol di(ethylene oxide-modified (meth)acrylate), 1,4-butanediol di(ethylene oxide-modified (meth)acrylate), 1,5-pentanediol di(ethylene oxide-modified (meth)acrylate), 1,6-hexanediol di(ethylene oxide-modified (meth)acrylate), 1,7-heptanediol di(ethylene oxide-modified (meth)acrylate), 1,8-octanediol di(ethylene oxide-modified (meth)acrylate), 1,9-nonanediol di(ethylene oxide-modified (meth)acrylate), 1,10-decanediol di(ethylene oxide-modified (meth)acrylate), and neopentyl glycol di(ethylene oxide-modified (meth)acrylate). )acrylate), 1,2-ethylenediol di(propylene oxide modified (meth)acrylate), 1,3-propanediol di(propylene oxide modified (meth)acrylate), 1,4-butanediol di(propylene oxide modified (meth)acrylate), 1,5-pentanediol di(propylene oxide modified (meth)acrylate), 1,6-hexanediol di(propylene oxide modified (meth)acrylate) Examples include 1,7-heptanediol di(propylene oxide modified (meth)acrylate), 1,8-octanediol di(propylene oxide modified (meth)acrylate), 1,9-nonanediol di(propylene oxide modified (meth)acrylate), 1,10-decanediol di(propylene oxide modified (meth)acrylate), neopentyl glycol di(propylene oxide modified (meth)acrylate), etc.

[0150] Examples of alkylene epoxy-modified (meth)acrylates include 1,2-ethylenediol diepoxy(meth)acrylate, 1,3-propanediol diepoxy(meth)acrylate, 1,4-butanediol diepoxy(meth)acrylate, 1,5-pentanediol diepoxy(meth)acrylate, 1,6-hexanediol diepoxy(meth)acrylate, 1,7-heptanediol diepoxy(meth)acrylate, 1,8-octanediol diepoxy(meth)acrylate, 1,9-nonanediol diepoxy(meth)acrylate, 1,10-decanediol diepoxy(meth)acrylate, neopentyl glycol diepoxy(meth)acrylate, and the like.

[0151] Examples of polyalkylene(meth)acrylates include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate.

[0152] Examples of polyalkylene dialkylene oxide-modified (meth)acrylates include diethylene glycol di(ethylene oxide-modified (meth)acrylate), dipropylene glycol di(ethylene oxide-modified (meth)acrylate), triethylene glycol (ethylene oxide-modified (meth)acrylate), and tripropylene glycol (ethylene oxide-modified (meth)acrylate).

[0153] Examples of polyalkylene epoxy-modified (meth)acrylates include diethylene glycol diepoxy (meth)acrylate, dipropylene glycol diepoxy (meth)acrylate, triethylene glycol diepoxy (meth)acrylate, and tripropylene glycol diepoxy (meth)acrylate.

[0154] <Bisphenol A di(alkylene oxide modified or epoxy modified) (meth)acrylate> "Bisphenol A di(alkylene oxide modified or epoxy modified) (meth)acrylate" means "at least one selected from the group consisting of bisphenol A di(meth)acrylate, bisphenol A dialkylene oxide modified (meth)acrylate, and bisphenol A diepoxy modified (meth)acrylate."

[0155] Examples of bisphenol A dialkylene oxide-modified (meth)acrylates include bisphenol A di(ethylene oxide-modified (meth)acrylate) and bisphenol A di(propylene oxide-modified (meth)acrylate).

[0156] Examples of mass% content (poly(meth)acrylate / non-volatile content of active energy ray curable composition) include 99% by mass, 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, and 20% by mass. In one embodiment, the above content is preferably 20% by mass to 99% by mass.

[0157] <Photopolymerization initiator> In one embodiment, the active energy ray curable composition may optionally include a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0158] Examples of photopolymerization initiators include benzophenone, o-benzoyl methyl benzoate, p-dimethylaminobenzoate, p-dimethylacetophenone, thioxanthone, alkylthioxanthone, and amines.

[0159] Examples of mass% content (photopolymerization initiator / non-volatile content of active energy ray curable composition) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 50% by mass.

[0160] When using ionizing radiation other than ultraviolet light as the active energy ray, the photopolymerization initiator does not need to be included.

[0161] <Sensitizer> In one embodiment, the active energy ray curable composition may optionally include a sensitizer. The sensitizer may be used alone or in combination of two or more.

[0162] Sensitizers include, for example, unsaturated ketones (benzophenones, chalcones, dibenzalacetone, etc.), 1,2-diketones (benzyl, camphorquinone, etc.), benzoins, fluorenes, naphthoquinones, anthraquinones, xanthenes, thioxanthenes, xanthones, thioxanthones, coumarins, ketocoumarins, cyanines, merocyanines, polymethine dyes such as oxonols, acridines, azines, thiadins, oxazines, indolines, azulenes, and azulenium. Examples include pyryllium compounds, porphyrins, tetraphenylporphyrins, triarylmethanes, tetrabenzoporphyrins, tetrapyradinoporphyrazines, phthalocyanines, tetraazaporphyrazines, tetraquinoxaliloporphyrazines, naphthalocyanines, subphthalocyanines, pyryllium compounds, thiopyrillium compounds, tetraphyllines, annulenes, spiropyrans, spirooxazines, thiospiropyrans, metal arene complexes, and organic ruthenium complexes.

[0163] Examples of sensitizers include 2,5-bis(4-diethylaminobenzal)cyclopentanone, 2,6-bis(4-dimethylaminobenzal)cyclohexanone, 2,6-bis(4-dimethylaminobenzal)-4-methylcyclohexanone, Michler ketone, 4,4-bis(dimethylamino)chalcone, 4,4-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylvinylene)-isonaphthothiazole, 1,3-bis(4-dimethylaminobenzal)acetone, 1,3-carbonyl-bis(4-diethylaminobenzal)acetone, 3,3-carbonyl-bis(7-diethylaminocoumarin), N-phenyl-N-ethylethanol Examples include nolamine, N-phenylethanolamine, N-tolyldiethanolamine, p-dimethylaminobenzoate methyl ester, p-dimethylaminobenzoate ethyl ester, p-dimethylaminobenzoate butyl ester, p-dimethylaminobenzoate butoxyethyl ester, p-dimethylaminobenzoate isoamyl ester, p-diethylaminobenzoate methyl ester, p-diethylaminobenzoate ethyl ester, p-diethylaminobenzoate isoamyl, thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 4,4'-bis-(diethylamino)benzophenone.

[0164] Examples of commercially available sensitizers include OmniradEMK and OmniradDETX (manufactured by IGM Resins).

[0165] Examples of mass% content (sensitizer / non-volatile content of active energy ray curable composition) include 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 1% by mass, 0.5% by mass, 0.1% by mass, etc. In one embodiment, the above content is preferably 0% by mass to 50% by mass.

[0166] <Pigments> In one embodiment, the active energy ray curable composition may optionally contain a pigment. The pigment may be used alone or in combination of two or more.

[0167] Pigments include, for example, white pigments such as titanium dioxide, zinc oxide, lead white, lithobone, and antimony oxide; black pigments such as aniline black, iron black, and carbon black; yellow pigments such as lead yellow, yellow iron oxide, titanium yellow, Hansa yellow (10G, 5G, 3G, etc.), disazo yellow, benzidine yellow, and permanent yellow; orange pigments such as chrome vermilion, permanent orange, Vulcan first orange, and indanthrene brilliant orange; brown pigments such as iron oxide, permanent brown, and para brown; red iron oxide, cadmium red, antimony vermilion, permanent red, rhodamine lake, alizarin lake, thioindigo red, PV carmine, monolite first red, and quinine. Examples include red pigments such as cudrin-based red pigments, purple pigments such as cobalt purple, manganese purple, first violet, methyl violet lake, indanthrene brilliant violet, and dioxazine violet, blue pigments such as ultramarine, Prussian blue, cobalt blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, copper phthalocyanine blue, induthrene blue, and indigo, and green pigments such as chromium green, chromium oxide, emerald green, naphthol green, green gold, acid green lake, malachite green lake, phthalocyanine green, and polychlorobrom copper phthalocyanine, as well as various fluorescent pigments and metal powder pigments.

[0168] Examples of mass% content (pigment / non-volatile content of active energy ray curable composition) include 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 70% by mass.

[0169] <Gelling agent> In one embodiment, the active energy ray curable composition may optionally include a gelling agent. The gelling agent may be used alone or in combination of two or more.

[0170] Examples of gelling agents include aluminum-based gelling agents, titanium-based gelling agents, and zirconium-based gelling agents.

[0171] Examples of aluminum-based gelling agents include aluminum octylate, aluminum stearate, aluminum ethylate, aluminum isopropylate, aluminum triisopropoxide, aluminum tributoxide, aluminum dipropoxide monoacetylacetate, aluminum dibutoxide monoacetylacetate, and aluminum triacetylacetate.

[0172] Examples of titanium-based gelling agents include tetraisopropyl titanate, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, and titanium lactate.

[0173] Examples of zirconium-based gelling agents include zirconium tetrabutoxide, zirconium acetylacetone, and acetate ethyl zirconium butoxide.

[0174] Examples of the mass % content (gelling agent / non-volatile content of the active energy ray curable composition) include 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 20% by mass.

[0175] <Polymerization inhibitors> In one embodiment, the active energy ray curable composition may optionally include a polymerization inhibitor. The polymerization inhibitor may be used alone or in combination of two or more.

[0176] Polymerization inhibitors include, for example, quinone-based polymerization inhibitors, monoalkylphenol-based polymerization inhibitors, amine-based polymerization inhibitors, and nitrosamine-based polymerization inhibitors.

[0177] Examples of quinone polymerization inhibitors include methoquinone, hydroquinone, methoxyhydroquinone, and benzoquinone.

[0178] Examples of monoalkylphenol polymerization inhibitors include 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, and 2,4,6-tri-t-butylphenol.

[0179] Examples of amine polymerization inhibitors include alkylated diphenylamine, phenothiazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine.

[0180] Examples of nitrosamine polymerization inhibitors include N-nitrosophenylhydroxylamine ammonium salts, 2,4-dinitrophenol, and 2-methyl-N-nitrosoaniline.

[0181] Examples of mass% content (polymerization inhibitor / non-volatile content of active energy ray curable composition) include 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.7% by mass, 0.5% by mass, 0.4% by mass, 0.3% by mass, 0.2% by mass, 0.1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 5% by mass, and more preferably 0% by mass to 3% by mass.

[0182] <organic solvents> In one embodiment, the above composition may optionally include an organic solvent. The organic solvent may be used alone or in combination of two or more.

[0183] Examples of organic solvents include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum-based solvents, haloalkane solvents, and amide solvents.

[0184] Examples of ketone solvents include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

[0185] Examples of aromatic solvents include toluene and xylene.

[0186] Examples of alcoholic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, and t-butanol.

[0187] Examples of glycol solvents include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol.

[0188] Examples of glycol ether solvents include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, and ethylene glycol mono-t-butyl ether.

[0189] Examples of ester solvents include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

[0190] Examples of petroleum-based solvents include Solvesso #100 (manufactured by Exxon Technologies) and Solvesso #150 (manufactured by Exxon Technologies).

[0191] Examples of haloalkane solvents include chloroform.

[0192] Examples of amide solvents include dimethylformamide.

[0193] Examples of mass% content (organic solvent / active energy ray curable composition) include 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, the above content is preferably 0% by mass to 90% by mass.

[0194] <Additives> The above composition may optionally contain, as an additive, any agent not listed above.

[0195] Examples of additives include surface modifiers, defoamers, antioxidants, light stabilizers, and polymerization inhibitors.

[0196] Examples of the parts by mass content (additive / rosin-modified resin) include less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0197] Examples of the parts by mass content (additive / poly(meth)acrylate) include less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc.

[0198] An active energy ray curable composition can be produced by dispersing and mixing the above agents.

[0199] Dispersion and mixing means include, for example, a stirrer, an emulsifier / disperser, an ultrasonic dispersion device, and the like.

[0200] Applications (active energy ray curable compositions) include, for example, active energy ray curable compositions for offset inks.

[0201] [Cured product] This disclosure provides a cured product of the above-mentioned active energy ray curable composition.

[0202] Examples of curing conditions include those described later.

[0203] [Laminates] This disclosure provides a laminate including the cured product described above.

[0204] In one embodiment, the laminate is one in which a cured material is laminated on a substrate.

[0205] Examples of substrates include paper (art paper, cast coated paper, foam paper, PPC paper, high-quality coated paper, kraft paper, polyethylene laminated paper, glassine paper, etc.) and plastic substrates (polyolefin, polycarbonate, polymethacrylate, polyester, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, norbornene-based resin, etc.).

[0206] Coating methods (printing methods) include, for example, offset printing, flexographic printing, screen printing, bar coater coating, Meyer bar coating, air knife coating, and gravure coating.

[0207] The amount of cured material (laminate) is preferably 0.01 g / m². 2 ~30g / m 2 For example, 1 g / m 2 ~20g / m 2 These are some examples.

[0208] Examples of curing methods include electron beams and ultraviolet light.

[0209] Examples of ultraviolet light sources include high-pressure mercury lamps, xenon lamps, metal halide lamps, and UV-LEDs.

[0210] When using a high-pressure mercury lamp, the curing conditions are preferably as follows: Lamp output: 80W / cm~160W / cm Conveying speed: 5m / min to 50m / min [Examples]

[0211] The present invention will be specifically described below through examples and comparative examples. However, the above description and the following examples are not intended to limit the present invention. The present invention is limited only to the claims. Unless otherwise specified below, numerical values ​​such as parts and percentages are based on mass.

[0212] Example 1 73 parts of rosin and 7 parts of maleic acid were placed in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and stirred at 180°C for 1 hour to obtain maleated rosin. Subsequently, 14 parts of trimethylolpropane, 8 parts of succinic acid, and 0.1 parts of TBM-6 were added and the mixture was reacted at 270°C for 24 hours while stirring to obtain a rosin-modified resin.

[0213] Unless otherwise specified, other examples were carried out in the same manner as above, except for the modifications shown in the table below.

[0214] Comparative Example 1 73 parts of rosin and 7 parts of maleic acid were placed in a reaction vessel equipped with a stirrer, a reflux condenser with a water divider, and a thermometer, and stirred at 180°C for 1 hour to obtain maleated rosin. Subsequently, 14 parts of trimethylolpropane and 8 parts of succinic acid were added and the mixture was stirred while reacting at 270°C for 24 hours to obtain a rosin-modified resin.

[0215] Comparative Example 2 In a reaction vessel equipped with a stirrer, reflux condenser with water divider, and thermometer, 23 parts of rosin and 7 parts of maleic acid were placed and stirred at 180°C for 1 hour to obtain maleated rosin. Subsequently, 50 parts of disproportionated rosin, 14 parts of trimethylolpropane, and 8 parts of succinic acid were added and the mixture was stirred while reacting at 270°C for 24 hours to obtain a rosin-modified resin.

[0216] [Table 1] The values ​​in the table represent parts by mass in the raw materials. TBM-6: Lowinox® TBM-6, disproportionation catalyst, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0217] The measurement conditions (weight-average molecular weight and number-average molecular weight) were as follows. Model: Product name "HLC-8320" (manufactured by Tosoh Corporation) Column: Product name "TSK-GEL" (manufactured by Tosoh Corporation) Developing solvent, flow rate: tetrahydrofuran, 1.0 mL / min Standard: Monodisperse polystyrene Measurement temperature: 40℃ Detector: RI Polymer concentration: 0.2%

[0218] The softening point was measured according to the method conforming to JIS K5601 (ring-sphere method).

[0219] Twenty parts of rosin-modified resin and thirty parts of ditrimethylolpropanetetraacrylate as poly(meth)acrylate were mixed. Next, 25 parts of ditrimethylolpropanetetraacrylate, eight parts of photopolymerization initiator (product name "Omnirad 369", manufactured by IGM Resins), one part of photoinitiator (product name "Omnirad EMK", manufactured by IGM Resins), one part of photosensitizer (product name "Omnirad DETX", manufactured by IGM Resins), and fifteen parts of ink pigment (MA-100, manufactured by Mitsubishi Chemical) were added and mixed using a three-roller to prepare an active energy ray curable resin composition.

[0220] <Liquidity> 1.30 mL of the active energy ray-curable resin composition was placed on a glass plate tilted at a 60° angle, and the flow of the active energy ray-curable resin composition was measured after 30 minutes. The evaluation criteria were as follows. ○:30mm or more ×: Less than 30mm

[0221] <Misting resistance> A 13cm x 21cm square piece of OHP film was attached to the wall below the roller of an Incomometer. After adjusting the roller temperature to 40°C, 2.6 mL of an active energy ray-curable resin composition was placed on the roller. The roller was rotated at 1200 rpm for 2 minutes, and the mass of the active energy ray-curable resin composition adhering to the film was weighed. The evaluation criteria are as follows. ○: 100mg or less ×: Greater than 100mg

[0222] <Thermal stability> Thermal stability was evaluated using the following methods and criteria. A reaction vessel equipped with a stirrer and a condenser was charged with 40 parts rosin-modified resin, 60 parts ditrimethylolpropanetetraacrylate, and 0.10 parts methoquinone. The mixture was stirred at 120°C for 1 hour to prepare a varnish composition. The mixture was transferred to a sealable glass container and stored at 80°C. The composition was evaluated by the time it took for the E-type viscosity to increase by 20% or more. ○: More than 24 hours ×: Less than 24 hours

Claims

1. A rosin-modified resin is a disproportionated resin product of a reaction product of raw materials including α,β-unsaturated carboxylic acid-modified rosin, polyol, polybasic acid and / or its anhydride, and conjugated rosin.

2. The rosin-modified resin according to claim 1, comprising 25% to 65% by mass of the conjugated rosin with respect to 100% by mass of the raw material.

3. An active energy ray curable composition comprising the rosin-modified resin and poly(meth)acrylate described in claim 1 or 2.

4. A cured product of the active energy ray curable composition according to claim 3.

5. A laminate comprising the cured product described in claim 4.

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