Active energy ray curable composition, active energy ray curable ink, active energy ray curable coating material, and article

Abstract

An object of the present invention is to provide an active energy ray-curable composition capable of forming a coating film having excellent adhesion and abrasion resistance. The present invention provides an active energy ray-curable composition containing a fatty acid-modified unsaturated polyester resin (A) and an active energy ray-curable monomer (B), The fatty acid-modified unsaturated polyester resin (A) is an active energy ray-curable composition characterized in that it is a reaction product of raw material components including at least one of fatty acids and fats and oils, α,β-unsaturated dicarboxylic acids as an acid component, and a polyhydric alcohol.

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable composition, an active energy ray-curable ink, an active energy ray-curable coating material, and an article. More specifically, the present invention relates to an active energy ray-curable composition, an active energy ray-curable ink, an active energy ray-curable coating material, which are capable of forming a coating film having excellent adhesion and abrasion resistance to the surface of, for example, a plastic substrate, and an article having a coating film formed using these. [Background technology]

[0002] The active energy ray curable composition contains a binder resin and an active energy ray curable monomer such as an acrylic acid ester compound. When exposed to active energy rays, a crosslinking reaction of the active energy ray curable monomer occurs, and the active energy ray curable composition is instantly cured to form a tough coating.

[0003] In this way, by using an active energy ray-curable composition, a tough coating film can be instantly formed, and therefore, active energy ray-curable compositions have been used in a wide range of fields such as inks, paints, and coating agents.

[0004] For example, the active energy ray-curable composition is used as an active energy ray-curable ink by being mixed with a pigment. In general, the active energy ray-curable ink contains a pigment, a binder resin, an active energy ray-curable monomer such as an acrylic acid ester compound, a photopolymerization initiator, and additives.

[0005] Examples of binder resins used in active energy ray-curable inks include diallyl phthalate resins, polyester resins, and acrylic resins.

[0006] When an active energy ray-curable ink is printed on a plastic film having low polarity, such as polypropylene or polyethylene, and then a coating film is formed by irradiating the film with active energy rays, there is a problem that the coating film may have poor adhesion to the plastic film.

[0007] The main cause of the poor adhesion is that irradiation with active energy rays causes a polymerization reaction of the active energy ray-curable monomer, which causes a sudden volumetric shrinkage of the active energy ray-curable ink, resulting in crazing or cracks in the coating film.

[0008] In addition, acrylic esters are commonly used as active energy ray-curable monomers, but the polarity of acrylic esters is significantly different from the polarity of plastics such as polypropylene and polyethylene, which is also a factor in poor adhesion.

[0009] To address the poor adhesion of active energy ray-curable compositions, binder resins using rosins or fatty acids are used.

[0010] Patent Document 1 discloses a rosin-modified alkyd resin, which is composed of a condensation polymer of an acid component including rosins, fatty acids and polybasic acids, and a polyhydric alcohol, and has a specific acid value and solubility parameter (SP value), as a binder resin in an active energy ray-curable ink.

[0011] However, when the rosin-modified alkyd resin of Patent Document 1 is used as a binder resin for active energy ray-curable ink, a coating film having excellent adhesion to plastic substrates can be formed, but there is a problem in that the abrasion resistance of the coating film decreases.

[0012] Patent Document 2 discloses a reaction product of an addition reaction mixture of rosin acids (A) and an α,β-unsaturated carboxylic acid or its acid anhydride (B), a polyol (C), and a fatty acid (D) as a binder resin for active energy ray-curable ink having excellent printability.

[0013] However, the α,β-unsaturated carboxylic acid or its anhydride (B) is used to form an addition reaction product with rosins via a Diels-Alder reaction, and therefore the final reaction product described in Patent Document 2 does not contain any unsaturated bond derived from the α,β-unsaturated carboxylic acid or its anhydride that is copolymerizable with an acrylic ester compound.

[0014] In addition, Patent Document 2 exemplifies unsaturated fatty acids such as tall oil fatty acid as fatty acids. However, the unsaturated bonds derived from the unsaturated fatty acids have large steric hindrance and cannot be copolymerized instantly with the acrylic acid ester compound upon irradiation with active energy rays.

[0015] Therefore, the binder resin of Patent Document 2 cannot copolymerize with the acrylic acid ester compound when irradiated with active energy rays, and as a result, there is a problem that the adhesion and abrasion resistance of the coating film are insufficient. [Prior art documents] [Patent documents]

[0016] [Patent Document 1] JP 2020-128467 A [Patent Document 2] Patent Publication No. 2022-065754 Summary of the Invention [Problem to be solved by the invention]

[0017] An object of the present invention is to provide an active energy ray-curable composition capable of forming a coating film having excellent adhesion and abrasion resistance. Another object of the present invention is to provide an active energy ray-curable ink containing the active energy ray-curable composition, an active energy ray-curable coating material, and an article having a printed layer printed using the active energy ray-curable ink. [Means for solving the problem]

[0018] Means for Solving the Problems The present inventors have intensively investigated the above-mentioned problems and have found that it is possible to provide an active energy ray-curable composition capable of forming a coating film having excellent adhesion and abrasion resistance by using, as a binder resin, a fatty acid-modified unsaturated polyester resin, which is a reaction product of raw material components containing at least one of fatty acids and fats and oils, an acid component containing α,β-unsaturated dicarboxylic acids, and a polyhydric alcohol.

[0019] Books The invention [1] is an active energy ray-curable composition containing a fatty acid-modified unsaturated polyester resin (A) and an active energy ray-curable monomer (B), The fatty acid-modified unsaturated polyester resin (A) contains at least one of fatty acids and fats and oils, and an α,β-unsaturated dicarboxylic acid as an acid component. and rosins, A reaction product of a raw material component containing a polyhydric alcohol and the law of nature, The polyhydric alcohol includes a trihydric or higher polyhydric alcohol and a dihydric alcohol, The content of the trihydric or higher polyhydric alcohol in the polyhydric alcohol is 40 mol % or more and 60 mol % or less, In the raw material component, a molar equivalent ratio of a hydroxyl group contained in the polyhydric alcohol to 1 molar equivalent of a carboxyl group contained in the raw material component is 0.9 or more and 1.1 or less; The methanol tolerance of the fatty acid-modified unsaturated polyester resin (A) at 25°C is 120 g or less. The active energy ray-curable composition is characterized in that

[0021] The present invention [2] The rosin is at least one selected from the group consisting of disproportionated rosin, hydrogenated rosin, and polymerized rosin. [1] The active energy ray-curable composition according to claim 1,

[0024] The present invention [3] Refer to [1] above or [2] and a pigment.

[0025] The present invention [4] Refer to [1] above or [2]and a pigment.

[0026] The present invention [5] is the above [3] The present invention also includes an article having a printed layer printed using the active energy ray-curable ink described in . The present invention [6] includes the active energy ray-curable composition according to the above [1], wherein the fatty acid-modified unsaturated polyester resin (A) is a reaction product obtained by esterifying an ester of at least one of the fatty acids and the fats and oils, and the trihydric or higher polyhydric alcohol, with the α,β-unsaturated dicarboxylic acids and the dihydric alcohol. Effect of the Invention

[0027] According to the active energy ray-curable composition of the present invention, and further, an active energy ray-curable ink and an active energy ray-curable paint containing the active energy ray-curable composition, a coating film having excellent adhesion and abrasion resistance can be formed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0028] [Active energy ray curable composition] The active energy ray-curable composition of the present invention contains a fatty acid-modified unsaturated polyester resin (A) and an active energy ray-curable monomer (B).

[0029] <Fatty acid modified unsaturated polyester resin (A)> The fatty acid-modified unsaturated polyester resin (A) is a reaction product obtained by reacting raw material components, which essentially include at least one of fatty acids and fats and oils, α,β-unsaturated dicarboxylic acids as acid components, and polyhydric alcohols.

[0030] (Fatty acids and oils) As a raw material component for forming the fatty acid modified unsaturated polyester resin (A), at least one of fatty acids and fats and oils is used.

[0031] In the fatty acid modified unsaturated polyester resin (A), by using at least one of fatty acids and oils and fats as a raw material component, the flexibility of the coating film of the active energy ray curable composition can be appropriately improved. As a result, the active energy ray curable composition can form a coating film having excellent adhesion to the substrate. In addition, by using at least one of fatty acids and oils and fats, when the active energy ray curable composition is applied to an active energy ray curable ink, at least one of fatty acids and oils and fats has a fatty acid skeleton, and therefore, the composition exhibits excellent affinity to the pigment. Therefore, in the active energy ray curable ink, the pigment can be dispersed with excellent dispersibility. Furthermore, the coating film (printed matter) formed by printing the active energy ray curable ink can be imparted with excellent gloss.

[0032] Furthermore, raw material components derived from biomass can be used as raw material components for fatty acids, oils, etc. This can increase the content of biomass components and contribute to solving environmental problems such as global warming and the depletion of fossil resources.

[0033] Fatty acids include saturated fatty acids and unsaturated fatty acids, etc. These fatty acids are acid components that have one carboxy group in one molecule and a monovalent saturated or unsaturated hydrocarbon group linked to the carboxy group.

[0034] The fatty acids are not particularly limited, but preferably have 12 or more carbon atoms.

[0035] Examples of saturated fatty acids include lauric acid (carbon number 12), myristic acid (carbon number 14), palmitic acid (carbon number 16), and stearic acid (carbon number 18). Examples of unsaturated fatty acids include α-linolenic acid (carbon number 18), linoleic acid (carbon number 18), and oleic acid (carbon number 18). Among these fatty acids, saturated fatty acids are preferred, and stearic acid and lauric acid are more preferred, because they have excellent physical properties such as solubility in the active energy ray-curable monomer (B) and curability. The fatty acids may be used alone or in combination of two or more.

[0036] The fatty acids do not need to be purified fatty acids, and may be mixed fatty acids containing two or more fatty acids. The mixed fatty acids may be a mixture of two or more fatty acids. Examples of the mixed fatty acids include fatty acids derived from animal fats and oils, and fatty acids derived from vegetable fats and oils. Fatty acids derived from animal fats and oils and oils are preferred because they contain a large amount of fatty acids having 12 or more carbon atoms.

[0037] Examples of fatty acids derived from animal fats and oils include beef tallow fatty acid, lard fatty acid, fish oil fatty acid, and fatty acids obtained by hydrogenating (hardening) these fatty acids, etc. Examples of fatty acids derived from vegetable fats and oils include tall oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, tung oil fatty acid, coconut oil fatty acid, castor oil fatty acid, etc.

[0038] The iodine value of the fatty acids is preferably 50 or less, more preferably 30 or less, even more preferably 5 or less, and particularly preferably 0. The iodine value of the fatty acids is preferably 0 or more. The iodine value is used as an index of the amount of unsaturated bonds contained in the fatty acids. In addition, when the fatty acids are mixed fatty acids, the iodine value is not the iodine value of each fatty acid contained in the mixed fatty acid, but the iodine value of the entire mixed fatty acid. The less the amount of unsaturated bonds in the fatty acids, the lower the iodine value. The fewer the number of unsaturated double bonds contained in the fatty acids, the more preferable, and the iodine value of the fatty acids is preferably 50 or less, and the fatty acids are particularly preferably saturated fatty acids. By using fatty acids with a small number of unsaturated double bonds in this way, it is possible to reduce the disappearance of the unsaturated bonds of the α,β-unsaturated dicarboxylic acids due to addition reactions such as the Ene reaction and the Diels-Alder reaction between the fatty acids and the α,β-unsaturated dicarboxylic acids. This makes it possible to sufficiently introduce unsaturated double bonds derived from the α,β-unsaturated dicarboxylic acids into the molecular structure of the fatty acid-modified unsaturated polyester resin (A).

[0039] The iodine value of fatty acids can be measured in accordance with JIS K 0070:1992.

[0040] In the present invention, instead of fatty acids, fats and oils can be used as raw material components constituting the fatty acid-modified unsaturated polyester resin (A). As raw material components, only one of fatty acids and fats and oils may be used, or both may be used.

[0041] The fats and oils include triglyceryl esters (triglycerides) of fatty acids and glycerin. The fatty acid moiety constituting the fats and oils can be subjected to an ester exchange reaction with a polyhydric alcohol used as a raw material component, whereby the fatty acid moiety can be introduced into the molecular structure of the fatty acid-modified unsaturated polyester resin (A).

[0042] The oils and fats are not particularly limited, and examples thereof include animal oils and fats, vegetable oils and fats, etc. Among these, oils and fats in which at least one of the three fatty acids constituting the triglyceride has 12 or more carbon atoms are preferred.

[0043] Examples of animal fats and oils include beef tallow, lard, and fish oil. Examples of vegetable fats and oils include soybean oil, linseed oil, tung oil, coconut oil, castor oil, palm oil, and rapeseed oil. As fats and oils, coconut oil is preferred. Recycled oils such as tempura oil that have been used for cooking and then recovered and recycled may also be used. Recycle treatment methods generally include removal of sediments by filtration, decolorization, and the like. The fats and oils may be used alone or in combination of two or more.

[0044] The content of at least one of fatty acids and oils and fats in the raw material components is preferably 3 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 45 parts by mass or less, and even more preferably 15 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the total amount of the raw material components. If the content is less than 3 parts by mass, depending on the combination of raw material components, the coating film (printed layer) of the active energy ray curable composition may not be given appropriate flexibility, and adhesion failure may easily occur. On the other hand, if the content exceeds 50 parts by mass, depending on the combination of raw material components, the coating film of the active energy ray curable composition may become excessively flexible, and the friction resistance (wear resistance) etc. may decrease.

[0045] In the present invention, among the fatty acids and the oils and fats, only the fatty acids may be used, only the oils and fats may be used, or the fatty acids and the oils and fats may be used in combination. When the fatty acids and the oils and fats are used in combination, the total content of the fatty acids and the oils and fats is set to be within the above range.

[0046] (α,β-unsaturated dicarboxylic acids) As a raw material component constituting the fatty acid modified unsaturated polyester resin (A), α,β-unsaturated dicarboxylic acids are used. Examples of α,β-unsaturated dicarboxylic acids include α,β-unsaturated dicarboxylic acids and their anhydrides, and α,β-unsaturated aliphatic dicarboxylic acids and their anhydrides are preferred. In this embodiment, α,β-unsaturated dicarboxylic acids refer to dicarboxylic acids having two carboxy groups in one molecule and having an unsaturated bond between the α-position carbon and the β-position carbon of at least one carboxy group.

[0047] The fatty acid-modified unsaturated polyester resin (A) contains an unsaturated double bond derived from an α,β-unsaturated dicarboxylic acid. This allows the fatty acid-modified unsaturated polyester resin (A) to copolymerize with the active energy ray curable monomer (B) via the unsaturated double bond, forming a three-dimensional network structure in which the molecular chains of the fatty acid-modified unsaturated polyester resin (A) are crosslinked by the active energy ray curable monomer (B). As a result, it is possible to improve the abrasion resistance of the coating film of the active energy ray curable composition.

[0048] Specific examples of α,β-unsaturated dicarboxylic acids include fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, and anhydrides thereof. The α,β-unsaturated dicarboxylic acids may be used alone or in combination of two or more.

[0049] Among the α,β-unsaturated dicarboxylic acids, from the viewpoint of ease of synthesis, fumaric acid, maleic acid and maleic anhydride are preferred, fumaric acid and maleic anhydride are more preferred, and maleic anhydride is even more preferred.

[0050] The content of α,β-unsaturated dicarboxylic acids in the raw material components is, for example, 5 parts by mass or more, preferably 7 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the total amount of the raw material components, and is, for example, 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less. When the content of α,β-unsaturated dicarboxylic acids is less than 5 parts by mass, depending on the combination of the raw material components, the abrasion resistance of the coating film may decrease. When the content of α,β-unsaturated dicarboxylic acids exceeds 50 parts by mass, depending on the combination of the raw material components, the adhesion of the coating film to the substrate may decrease. On the other hand, if the content of α,β-unsaturated dicarboxylic acids is within the above range, an active energy ray curable composition capable of forming a coating film having excellent adhesion and abrasion resistance can be obtained.

[0051] As described above, the raw material components used to obtain the fatty acid-modified unsaturated polyester resin (A) as a reaction product contain at least one of fatty acids and fats and oils, and α,β-unsaturated dicarboxylic acids. Therefore, it is possible to achieve both excellent improvement in adhesion of the coating film to the substrate based on the hydrocarbon group contained in at least one of the fatty acids and fats and oils, and improvement in abrasion resistance of the coating film due to the formation of a three-dimensional network structure based on the unsaturated double bond derived from the α,β-unsaturated dicarboxylic acid.

[0052] (Polyhydric alcohol) A polyhydric alcohol is used as a raw material component for forming the fatty acid modified unsaturated polyester resin (A). In the present embodiment, the polyhydric alcohol refers to a compound (polyol) having two or more hydroxyl groups in one molecule.

[0053] Examples of polyhydric alcohols include trihydric or higher polyhydric alcohols and dihydric alcohols. The polyhydric alcohol preferably contains a trihydric or higher polyhydric alcohol, and may contain, for example, a trihydric or higher polyhydric alcohol alone, but preferably contains a trihydric or higher polyhydric alcohol and a dihydric alcohol in combination.

[0054] Trihydric or higher polyhydric alcohols are compounds having three or more hydroxyl groups in one molecule. Examples of trihydric or higher polyhydric alcohols include trihydric alcohols such as glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane (hereinafter, sometimes simply referred to as "trimethylolpropane"), trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2,3,4-pentanetriol, and 1,2,5-hexanetriol, tetrahydric alcohols such as pentaerythritol, dipentaerythritol, glucose, sucrose, and sorbitol, and further, alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts thereof. The trihydric or higher polyhydric alcohols may be used alone or in combination of two or more.

[0055] Among the trihydric or higher polyhydric alcohols, from the viewpoint of reactivity, trihydric or tetrahydric alcohols are preferred, trihydric alcohols are more preferred, glycerin and trimethylolpropane are more preferred, and glycerin is more preferred. By using a trihydric or higher polyhydric alcohol, a suitable branched structure can be imparted to the fatty acid-modified unsaturated polyester resin (A), and a structure in which both α,β-unsaturated dicarboxylic acids and fatty acids are linked to the trihydric or higher polyhydric alcohol can be formed, thereby improving both the adhesion and abrasion resistance of the coating film of the active energy ray-curable composition.

[0056] The content of the trihydric or higher polyhydric alcohol in the raw material components is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, relative to 100 parts by mass of the total amount of the raw material components. The content of the trihydric or higher polyhydric alcohol in the raw material components is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, relative to 100 parts by mass of the total amount of the raw material components. By making the content of the trihydric or higher polyhydric alcohol 1 part by mass or more and 30 parts by mass or less, a structure in which both α,β-unsaturated dicarboxylic acids and fatty acids are linked to the trihydric or higher polyhydric alcohol is appropriately formed in the fatty acid modified unsaturated polyester resin (A), and the abrasion resistance of the coating film of the active energy ray curable composition can be improved, and the coating film of the active energy ray curable composition can maintain appropriate flexibility and maintain high adhesion to the substrate.

[0057] The polyhydric alcohol preferably further contains a dihydric alcohol (diol). By using a dihydric alcohol, it is possible to impart appropriate flexibility to the coating film of the active energy ray curable composition. This makes it possible for the active energy ray curable composition to form a coating film having better adhesion to the substrate.

[0058] Dihydric alcohols are compounds having two hydroxyl groups in one molecule. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxymethylmethane, diethylene glycol, triethylene glycol, polyethylene glycol (PEG), dipropylene glycol, polytetramethylene glycol (PTMG), polypropylene glycol (PPG), 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, bisphenol A, bisphenol F, and further alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts thereof. The dihydric alcohols may be used alone or in combination of two or more.

[0059] Among the dihydric alcohols, 1,3-propanediol and diethylene glycol are preferred. When diethylene glycol is used as the dihydric alcohol, the fatty acid-modified unsaturated polyester resin (A) has an ether bond due to the diethylene glycol having an ether bond. As a result, in the active energy ray curable composition, the fatty acid-modified unsaturated polyester resin (A) exhibits excellent solubility in the active energy ray curable monomer (B).

[0060] When the raw material contains a dihydric alcohol, the content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the raw material. The content of the dihydric alcohol in the raw material is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. By setting the content of the dihydric alcohol within the above range, the active energy ray curable composition can form a coating film having excellent adhesion to the substrate.

[0061] When the polyhydric alcohol contains a polyhydric alcohol having a valence of 3 or more and a dihydric alcohol, the content of the polyhydric alcohol having a valence of 3 or more in the polyhydric alcohol is preferably 30 mol% or more, more preferably 40 mol% or more. When the polyhydric alcohol contains a polyhydric alcohol having a valence of 3 or more and a dihydric alcohol, the content of the polyhydric alcohol having a valence of 3 or more in the polyhydric alcohol is preferably 60 mol% or less, more preferably 50 mol% or less. By making the content of the polyhydric alcohol having a valence of 3 or more equal to or more than the above lower limit, a structure in which both α,β-unsaturated dicarboxylic acids and fatty acids are linked is frequently formed in the fatty acid modified unsaturated polyester resin (A), and the abrasion resistance of the coating film of the active energy ray curable composition can be further improved. By making the content of the polyhydric alcohol having a valence of 3 or more equal to or less than the above upper limit, the amount of excess hydroxyl groups that are not subjected to the esterification reaction with α,β-unsaturated dicarboxylic acids and fatty acids can be reduced, and the methanol tolerance described later can be set low.

[0062] In the raw material components, the molar equivalent ratio of hydroxyl groups contained in the polyhydric alcohol to 1 molar equivalent of carboxyl groups contained in the raw material components is preferably 0.5 to 2.0, more preferably 0.9 to 1.3, even more preferably 0.95 to 1.15, and particularly preferably 1.0 to 1.1. By setting the molar equivalent ratio within the above range, it is possible to provide an active energy ray-curable composition capable of forming a coating film having an excellent balance between adhesion and abrasion resistance.

[0063] The molar equivalent ratio of hydroxyl groups contained in the polyhydric alcohol to 1 molar equivalent of carboxyl groups contained in the raw material components can be calculated by dividing the total number of moles of hydroxyl groups contained in the polyhydric alcohol by the total number of moles of carboxyl groups contained in the raw material components.

[0064] The total number of moles of hydroxyl groups contained in the polyhydric alcohol can be calculated as follows. The polyhydric alcohol may contain multiple types of polyols, such as trihydric or higher polyhydric alcohols and dihydric alcohols. Therefore, for each polyhydric alcohol, the number of moles of the polyhydric alcohol contained in the raw material is first multiplied by the number of hydroxyl groups in one molecule of the polyhydric alcohol to obtain the number of moles of hydroxyl groups (M OH Next, calculate the number of moles of hydroxyl groups (M OH ) and the value obtained is the "total number of moles of hydroxyl groups contained in the polyhydric alcohol."

[0065] The raw material components contain multiple types of carboxylic acid components, such as fatty acids, α,β-unsaturated dicarboxylic acids, and, if necessary, rosins, which will be described later. Therefore, the total number of moles of carboxy groups contained in the raw material components can be calculated as follows. First, for each carboxylic acid component, the number of moles of the carboxylic acid component contained in the raw material components is multiplied by the number of carboxy groups in one molecule of this carboxylic acid component to obtain the number of moles of carboxy groups (M COOH Next, the mole number of carboxy groups calculated for each carboxylic acid component (M COOH ) and the value obtained is the "total number of moles of carboxy groups contained in the raw material components."

[0066] In addition, in the "total moles of carboxyl groups contained in the raw material components," the moles of carboxyl groups of rosins (M COOH ) is calculated as follows. First, the acid value of the rosins contained in the raw material components is measured to calculate the amount of carboxy groups per unit mass contained in the rosins. The average molecular weight of the rosins is calculated based on this amount of carboxy groups. Then, the number of moles of carboxy groups of the rosins (M COOH The acid value of rosins can be measured in accordance with JIS K5601-2-1 (1999).

[0067] (Monohydric alcohol) The raw material components constituting the fatty acid modified unsaturated polyester resin (A) may contain a monohydric alcohol in addition to the above-mentioned polyhydric alcohol.

[0068] A monohydric alcohol is a compound having one hydroxyl group in one molecule. Examples of the monohydric alcohol include methanol, ethanol, propanol, and isopropanol. The monohydric alcohol may be used alone or in combination of two or more kinds.

[0069] (rosins) The raw material components constituting the fatty acid modified unsaturated polyester resin (A) preferably contain rosins as other acid components (carboxylic acids).

[0070] In the fatty acid modified unsaturated polyester resin (A), by preferably containing rosins as other acid components contained in the raw material components, the abrasion resistance of the coating film of the active energy ray curable composition is improved.

[0071] Examples of rosins include unmodified rosin (unmodified rosin), modified rosin (rosin derivative), etc. The rosins may be used alone or in combination of two or more kinds.

[0072] An example of the unmodified rosin is natural rosin. Natural rosin is a natural resin mainly composed of resin acid. Resin acid is a compound having a carboxyl group derived from a tree. Specific examples of the resin acid include resin acids having conjugated double bonds such as abietic acid, palustric acid, neoabietic acid, and levopimaric acid, and resin acids not having conjugated double bonds such as dehydroabietic acid, dihydroabietic acid, and tetrahydroabietic acid.

[0073] Examples of natural rosins include tall oil rosin, gum rosin, wood rosin, etc. Gum rosin is preferred. The natural rosins may be used alone or in combination of two or more.

[0074] The rosin modified product is a modified product of the above-mentioned unmodified rosin, and examples thereof include acid-modified rosin, stabilized rosin, etc. The rosin modified product may be used alone or in combination of two or more kinds.

[0075] The acid-modified rosin is a modified product obtained by modifying unmodified rosin with an acid. The acid modification is not particularly limited, but for example, it is performed by adding (reacting) a known α,β-unsaturated carboxylic acid to unmodified rosin by Diels-Alder reaction or the like. Examples of the α,β-unsaturated carboxylic acid include α,β-unsaturated carboxylic acid and its anhydride. Specific examples include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, citraconic anhydride, acrylic acid, and methacrylic acid. The α,β-unsaturated carboxylic acid may be used alone or in combination of two or more kinds.

[0076] The stabilized rosin is a modified product obtained by stabilizing the above-mentioned unmodified rosin. The stabilization reduces or eliminates the conjugated double bonds of the resin acid having the conjugated double bonds. Specific examples of the stabilization treatment include hydrogenation, disproportionation, and polymerization, and hydrogenation and disproportionation are preferred.

[0077] Examples of the stabilized rosin include hydrogenated rosin obtained by hydrogenating natural rosin, disproportionated rosin obtained by disproportionating natural rosin, and polymerized rosin obtained by polymerizing natural rosin. The stabilized rosin also includes a hydrogenated product of polymerized rosin. The stabilized rosin may be used alone or in combination of two or more kinds.

[0078] As the stabilized rosin, preferably, hydrogenated rosin and disproportionated rosin are used, and disproportionated rosin is preferred.

[0079] As the rosin, a rosin modified product is preferred, and a stabilized rosin is more preferred. This makes it possible to obtain a fatty acid-modified unsaturated polyester resin (A) having a sufficient number of unsaturated bonds capable of copolymerizing with the active energy ray-curable monomer (B) described later, and to make the coating film of the active energy ray-curable composition exhibit high abrasion resistance.

[0080] Here, if stabilized rosin is not used as the rosin, a Diels-Alder reaction occurs between the abietic acid having the above-mentioned conjugated double bond, which is listed as an example of unmodified rosin, and α,β-unsaturated dicarboxylic acids, and as a result, it may be difficult to leave the double bond derived from the α,β-unsaturated dicarboxylic acids in the fatty acid-modified unsaturated polyester resin (A). As a result, the abrasion resistance of the coating film may be insufficient due to a decrease in the opportunity for copolymerization between the fatty acid-modified unsaturated polyester resin (A) and the active energy ray curable monomer (B).

[0081] In contrast, by using a stabilized rosin as the rosin, it is possible to suppress the Diels-Alder reaction between the stabilized rosin and α,β-unsaturated dicarboxylic acids. Therefore, it is possible to leave the unsaturated double bonds derived from the α,β-unsaturated dicarboxylic acids in the fatty acid-modified unsaturated polyester resin (A). Therefore, it is possible to reliably form a copolymer in which the fatty acid-modified unsaturated polyester resin (A) and the active energy ray-curable monomer (B) are copolymerized, and the abrasion resistance of the coating film (printed layer) is improved.

[0082] The content of the rosin modified product in the rosins is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, and particularly preferably 100% by mass.

[0083] The content of rosins in the raw material components is, relative to 100 parts by mass of the total amount of the raw material components, for example, 5 parts by mass or more, preferably 7 parts by mass or more, preferably 15 parts by mass or more, and for example, 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. By keeping the content of rosins within the above range, the adhesion and abrasion resistance of the coating film (printed layer) can be improved.

[0084] As described later, rosins may contain metal atoms as unavoidable impurities, but when rosins are contained in the raw material components, the content of metal atoms can be prevented from becoming unintentionally high during the production of the fatty acid-modified unsaturated polyester resin (A) by making the content ratio of rosins equal to or less than the above upper limit. Therefore, in the second esterification step described later, it is possible to reduce the occurrence of gelation of the fatty acid-modified unsaturated polyester resin (A) caused by the metal atoms acting as a polymerization catalyst to promote polymerization between α,β-unsaturated dicarboxylic acids.

[0085] (Aromatic carboxylic acids) The raw material components constituting the fatty acid modified unsaturated polyester resin (A) preferably contain aromatic carboxylic acids as other acid components. By using aromatic carboxylic acids, it is possible to impart excellent gloss to the coating film (printed matter).

[0086] Examples of aromatic carboxylic acids include aromatic carboxylic acids and their anhydrides. Examples of aromatic carboxylic acids include benzoic acid, p-tertiary butyl benzoic acid, salicylic acid, naphthoic acid, phthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, and their substituted derivatives in which at least one alkyl group is introduced into the aromatic ring. The aromatic carboxylic acids may be used alone or in combination of two or more.

[0087] The content of aromatic carboxylic acids in the raw material components is, for example, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and for example, preferably 1 part by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of the total amount of the raw material components.

[0088] The raw material components constituting the fatty acid-modified unsaturated polyester resin (A) may contain, as other acid components, aliphatic dicarboxylic acids that do not contain linear unsaturated hydrocarbon chains. Examples of the aliphatic dicarboxylic acids include aliphatic dicarboxylic acids that do not contain linear unsaturated hydrocarbon chains and their anhydrides.

[0089] Examples of the aliphatic dicarboxylic acids include chain-type saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and anhydrides thereof; and cyclic aliphatic dicarboxylic acids such as tetrahydrophthalic acid, cyclopropane-1,1-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, and anhydrides thereof. Among these, adipic acid, tetrahydrophthalic acid, and anhydrides thereof are more preferable. The aliphatic dicarboxylic acids may be used alone or in combination of two or more kinds.

[0090] The content of aliphatic dicarboxylic acids in the raw material components is, for example, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and more preferably 10 parts by mass or less, relative to 100 parts by mass of the total amount of the raw material components, and for example, preferably 1 part by mass or more.

[0091] (Epoxy compounds) Furthermore, the raw material components for obtaining the fatty acid-modified unsaturated polyester resin (A) may contain an epoxy compound.

[0092] Examples of epoxy compounds include allyl glycidyl ether, phenol (EO) 5 glycidyl ether (CAS number: 54140-67-9), lauryl alcohol (EO) 15 glycidyl ether (CAS number: 86630-59-3), glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and epoxy cresol novolac. The epoxy compounds may be used alone or in combination of two or more.

[0093] The content of the epoxy compound in the raw material components may be appropriately set depending on the purpose and application.

[0094] The fatty acid modified unsaturated polyester resin (A) is a reaction product containing unsaturated double bonds derived from α,β-unsaturated dicarboxylic acids contained as raw material components. Therefore, when unsaturated fatty acids or rosins are used, it is preferable that the unsaturated double bonds derived from α,β-unsaturated dicarboxylic acids are not lost due to addition reactions such as Ene reaction and Diels-Alder reaction with unsaturated fatty acids or rosins.

[0095] From this viewpoint, the fatty acid-modified unsaturated polyester resin (A) is preferably a reaction product (polycondensate) obtained by esterifying an ester of at least one of fatty acids and fats and oils, and, if necessary, rosins, aromatic dicarboxylic acids, and aliphatic dicarboxylic acids with a trihydric or higher polyhydric alcohol, with an α,β-unsaturated dicarboxylic acid.

[0096] In the above reaction product, an acid component other than α,β-unsaturated dicarboxylic acids is first reacted with a polyhydric alcohol having a valence of 3 or more, and then α,β-unsaturated dicarboxylic acids are reacted, so that the steric hindrance of the polyhydric alcohol having a valence of 3 or more can suppress the addition reaction between the components containing unsaturated bonds, such as fatty acids and rosins, and the α,β-unsaturated dicarboxylic acids. Therefore, the unsaturated double bonds derived from the α,β-unsaturated dicarboxylic acids can be introduced into the molecular structure of the above reaction product without disappearing.

[0097] In addition, when a dihydric alcohol is further used as the polyhydric alcohol, the fatty acid-modified unsaturated polyester resin (A) is preferably a reaction product obtained by esterifying an ester of at least one of fatty acids and fats and oils, and, if necessary, rosins, aromatic dicarboxylic acids, and aliphatic dicarboxylic acids with a trihydric or higher polyhydric alcohol, with an α,β-unsaturated dicarboxylic acid and a dihydric alcohol.

[0098] In such a reaction product, the unsaturated double bond derived from the α,β-unsaturated dicarboxylic acid can be introduced into the molecular structure of the reaction product without disappearing, as in the above. Furthermore, by reacting a polyhydric alcohol having a valence of 3 or more first and then reacting a dihydric alcohol, it is possible to impart an appropriate branched structure to the finally obtained reaction product. This makes it possible to form a coating film having appropriate flexibility and hardness, and to provide a coating film that is compatible with adhesion to the substrate and abrasion resistance.

[0099] The fatty acid-modified unsaturated polyester resin (A) can impart flexibility to the coating film due to the fatty acids or oils contained in the raw material components, so that the coating film has excellent adhesion. Furthermore, the unsaturated bonds derived from α,β-unsaturated dicarboxylic acids are copolymerized with active energy ray curable monomers when irradiated with active energy rays, so that the coating film has excellent abrasion resistance.

[0100] The fatty acid modified unsaturated polyester resin (A) has a viscosity of 1.01 x 10 at 25°C. 5It is preferable that the fatty acid-modified unsaturated polyester resin (A) is in a liquid state or in a solid state with a softening point of 70° C. or less under Pa (1 atm). The fatty acid-modified unsaturated polyester resin (A) in a liquid state or in a solid state with a low softening point has excellent compatibility with the active energy ray curable monomer (B). Therefore, the content of the active energy ray curable monomer (B) in the active energy ray curable composition can be increased, and a coating film with a high crosslink density can be formed, so that the abrasion resistance of the coating film can be further improved. In addition, since the fatty acid-modified unsaturated polyester resin (A) is in a liquid state or in a solid state with a low softening point, the active energy ray curable composition containing the fatty acid-modified unsaturated polyester resin (A) can be prepared as a liquid with low viscosity. Therefore, when the active energy ray curable composition is supplied onto a substrate, the active energy ray curable composition spreads uniformly on the substrate, so that a coating film with excellent adhesion can be formed.

[0101] When the fatty acid-modified unsaturated polyester resin (A) is solid, the softening point of the fatty acid-modified unsaturated polyester resin (A) is, as described above, preferably 70°C or lower, more preferably 60°C or lower, and also preferably 40°C or higher, more preferably 45°C or higher.

[0102] The softening point of the fatty acid-modified unsaturated polyester resin (A) in a solid state can be measured in accordance with ASTM D6090 (1997). For the above measurement, a measuring device such as "Dropping Point System DP70" manufactured by Mettler Toledo can be used. When using the above measuring device, for example, the softening point can be measured as follows. First, a stainless steel cup having a diameter of 10 mm at the top, a hole having a diameter of 6.35 mm at the bottom, and a depth of 10 mm is filled with the fatty acid-modified unsaturated polyester resin (A), and the cup is set in the measuring device. The temperature is then increased from 40°C at a rate of 3°C / min, and the temperature is measured when the fatty acid-modified unsaturated polyester resin (A) is detected by a detector installed at a position 19 mm vertically below the hole at the bottom of the cup, and this temperature can be taken as the softening point.

[0103] The methanol tolerance of the fatty acid-modified unsaturated polyester resin (A) at 25°C is preferably 120g or less, more preferably 90g or less, and even more preferably 70g or less. When the methanol tolerance of the fatty acid-modified unsaturated polyester resin (A) is equal to or less than the upper limit, it can be said that the methanol tolerance is set low. In contrast, as the substrate to which the active energy ray curable composition is supplied, a substrate having low polarity such as a plastic film composed of polypropylene or polyethylene terephthalate is frequently selected. Therefore, as described above, by setting the methanol tolerance low, the interaction between the coating film formed using the active energy ray curable composition and the substrate is improved, and therefore a coating film having excellent adhesion can be formed on the substrate. In addition, when the raw material components contain both fatty acids and oils and rosins as acid components, it can be said that the fatty acid-modified unsaturated polyester resin (A), which is the reaction product of the raw material components, has a well-balanced ester bond formed between the acid component and the polyhydric alcohol, so that a coating film having excellent adhesion and abrasion resistance can be formed on a substrate. The methanol tolerance of the fatty acid-modified unsaturated polyester resin (A) at 25°C is preferably 25g or more. By making the methanol tolerance 25g or more, it is possible to reduce the penetration of oil into the coating film on the substrate, and therefore the oil resistance (oil repellency) of the coating film can be improved.

[0104] The methanol tolerance of the fatty acid-modified unsaturated polyester resin (A) at 25°C can be measured according to the following procedure. First, 5 g of the fatty acid-modified unsaturated polyester resin (A) is dissolved in 50 mL of toluene in a transparent glass Erlenmeyer flask (volume 100 mL) to obtain a reference solution. While stirring the reference solution at 25°C, methanol is dropped into the reference solution, and the mass (g) of methanol dropped until the reference solution becomes cloudy is determined. This mass (g) of methanol is taken as the methanol tolerance of the fatty acid-modified unsaturated polyester resin (A) at 25°C. Note that when the Erlenmeyer flask is placed on a newspaper and the newspaper and the Erlenmeyer flask are in contact with each other, the character (10 point) printed on the newspaper is visually observed through the reference solution in the Erlenmeyer flask. The point at which the character becomes invisible due to the clouding of the reference solution is judged to be "clouding of the reference solution".

[0105] The acid value of the fatty acid-modified unsaturated polyester resin (A) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and even more preferably 20 mgKOH / g or less. If the acid value of the fatty acid-modified unsaturated polyester resin (A) is within the above range, an active energy ray-curable composition capable of forming a coating film having excellent adhesion can be obtained.

[0106] The acid value of the fatty acid modified unsaturated polyester resin (A) can be measured according to the following procedure. 1 g of the fatty acid modified unsaturated polyester resin (A) is dissolved in 20 mL of a mixed solvent of xylene and ethanol (xylene:ethanol = 2:1 (mass ratio)) to obtain a mixed solution. Then, 3 mL of a 3 mass % phenolphthalein solution is added to the mixed solution as an indicator, and the acid value (mgKOH / g) is determined by neutralization titration with a 0.1 mol / L ethanolic potassium hydroxide solution.

[0107] The weight average molecular weight of the fatty acid modified unsaturated polyester resin (A) is preferably 2,000 or more, more preferably 3,000 or more. The weight average molecular weight of the fatty acid modified unsaturated polyester resin (A) is preferably 50,000 or less, more preferably 20,000 or less, and more preferably 15,000 or less. When the weight average molecular weight of the fatty acid modified unsaturated polyester resin (A) is 2,000 or more, the abrasion resistance of the coating film formed using the fatty acid modified unsaturated polyester resin (A) can be improved. When the weight average molecular weight of the fatty acid modified unsaturated polyester resin (A) is 50,000 or less, gelation and excessively high molecular weight of the fatty acid modified unsaturated polyester resin (A) are reduced, and the solubility of the fatty acid modified unsaturated polyester resin (A) in the active energy ray curable monomer (B) can be improved. As a result, a coating film formed using the active energy ray curable composition can be formed with a high crosslink density, so that the abrasion resistance of the coating film can be further improved.

[0108] The weight average molecular weight of the fatty acid modified unsaturated polyester resin (A) refers to the value obtained by converting the molecular weight measured by gel permeation chromatography (GPC) into polystyrene equivalent. For example, it can be measured under the following measurement conditions. The fatty acid modified unsaturated polyester resin (A) is dissolved in tetrahydrofuran to obtain a measurement sample having a concentration of the fatty acid modified unsaturated polyester resin (A) of 0.5% by mass. Using this measurement sample, the weight average molecular weight of the fatty acid modified unsaturated polyester resin (A) can be measured by a gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID) under the following measurement device and measurement conditions. Measuring device: Showa Denko "shodex GPC-101" Column: Showa Denko "KF-802" + "KF-806L" x 2 Detector: Shodex RI-71 (Differential Refractive Index Detector) Data processing: "480IIXP", Standard polystyrene (Showa Denko Co., Ltd. "S-0.5", "S-1.0", "S-1.2", "S-1.9", "S-2.9", "S-3.1", "S-4.4", "S-5.1", "S-7.2", "S-19.6", "S-49.2", "S-114", "S-257", "S-778", "S-1320", "S-7450") Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1.0mL / min Sample concentration: 0.5% by mass Injection amount: 100μm

[0109] <Method for producing fatty acid modified unsaturated polyester resin (A)> The method for producing the fatty acid-modified unsaturated polyester resin (A) is not particularly limited, and any known method can be used.

[0110] The fatty acid modified unsaturated polyester resin (A) can be produced by mixing and heating raw material components including at least one of fatty acids and fats and oils, α,β-unsaturated dicarboxylic acids as acid components, and polyhydric alcohol, in the presence of a solvent as necessary, to cause an esterification reaction. In the production of the fatty acid modified unsaturated polyester resin (A), it is preferable to set the reaction temperature of the esterification after the introduction of α,β-unsaturated dicarboxylic acids after the esterification reaction between at least one of fatty acids and fats and oils and polyhydric alcohol to 230°C or less. This makes it possible to proceed with the esterification reaction while suppressing the disappearance of the unsaturated double bonds of the α,β-unsaturated dicarboxylic acids due to polymerization between the α,β-unsaturated dicarboxylic acids, and to introduce the unsaturated double bonds derived from the α,β-unsaturated dicarboxylic acids into the fatty acid modified unsaturated polyester resin (A). The reaction temperature of the esterification after the introduction of the α,β-unsaturated dicarboxylic acids is preferably 180°C or more.

[0111] The esterification reaction may be a direct esterification reaction involving dehydration of an acid component and an alcohol component, or a transesterification reaction. The esterification reaction may be appropriately selected depending on the raw material components used.

[0112] The solvent is not particularly limited, but examples thereof include petroleum-based hydrocarbon solvents such as hexane and mineral spirits; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, and propylene glycol monomethyl ether acetate; and organic solvents such as aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and pyridine. The solvent may be used alone or in combination of two or more. The blending ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and application.

[0113] For example, the raw material components can be heated in the presence of a solvent capable of forming an azeotropic distillation with water (e.g., an azeotropic dehydrating agent such as xylene or toluene) to induce an esterification reaction and distill off the water generated by the reaction. After the reaction is completed, the solvent may be removed as necessary. For example, the raw material components can be heated in the absence of a solvent to induce an esterification reaction and distill off the water generated by a known method.

[0114] The reaction of the raw material components is preferably carried out in the presence of an esterification catalyst. The esterification catalyst is not particularly limited, but examples thereof include organic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid, and ethanesulfonic acid; mineral acids such as sulfuric acid and hydrochloric acid; metal catalysts such as tetrabutyl zirconate, tetraisopropyl titanate, tetraisobutyl titanate, aluminum oxide, titanium oxide, magnesium oxide, magnesium hydroxide, magnesium acetate, calcium oxide, calcium hydroxide, calcium acetate, zinc oxide, and zinc acetate; trifluoromethylsulfuric acid, trifluoromethylacetic acid, and the like. The esterification catalyst may be used alone or in combination of two or more. The addition ratio of the esterification catalyst is not particularly limited, and is appropriately set according to the purpose and application.

[0115] The reaction of the raw material components is preferably carried out under atmospheric pressure in an inert gas atmosphere. In the reaction of the raw material components, the heating temperature of the raw material components is preferably 150 to 280° C., and more preferably 200 to 250° C. The heating time is preferably 4 to 20 hours, and more preferably 6 to 15 hours.

[0116] In the reaction of the raw material components, the order in which the raw material components are reacted, i.e., the order in which the raw material components are mixed, is not particularly limited. All the raw material components may be mixed and reacted at the same time, or the raw material components may be mixed and reacted in any order.

[0117] For example, when fatty acids are used among fatty acids and fats and oils, and a polyhydric alcohol having a valence of three or more is used as the polyhydric alcohol, the following production method is preferably used.

[0118] The method for producing the fatty acid-modified unsaturated polyester resin (A) includes the following steps: a first esterification step of directly esterifying fatty acids, and optionally rosins, aromatic dicarboxylic acids, and aliphatic dicarboxylic acids with a trihydric or higher polyhydric alcohol to obtain an esterified product; A preferred example of the method includes a second esterification step in which, after completion of the first esterification step, the above esterified product is directly esterified with an α,β-unsaturated dicarboxylic acid and, if necessary, a dihydric alcohol to obtain a fatty acid-modified unsaturated polyester resin (A).

[0119] In the above method, when the raw material components contain rosins, the esterification reaction of rosins, fatty acids, and trivalent or higher polyhydric alcohols is carried out in the first esterification step, and then the esterification reaction of α,β-unsaturated dicarboxylic acids is carried out in the second esterification step. This reduces the addition of α,β-unsaturated dicarboxylic acids to the resin acid through the Diels-Alder reaction, even when the rosins contain a resin acid having a conjugated double bond, and allows sufficient introduction of unsaturated bonds derived from α,β-unsaturated dicarboxylic acids into the fatty acid-modified unsaturated polyester resin (A).

[0120] In the above method, when the raw material components further contain a dihydric alcohol, the heating temperature during the esterification reaction can be increased by first carrying out the esterification reaction of rosins, fatty acids, and trihydric or higher polyhydric alcohols prior to the reaction of α,β-unsaturated dicarboxylic acids and dihydric alcohols in the first esterification step. This allows the esterification reaction of rosins, fatty acids, and trihydric or higher polyhydric alcohols to proceed sufficiently, and even when the content ratios of rosins and fatty acids are high, the methanol tolerance of the finally obtained fatty acid-modified unsaturated polyester resin (A) can be reduced.

[0121] The reaction temperature in the first esterification step is preferably 210° C. or higher, more preferably 220° C. or higher, and even more preferably more than 230° C. The reaction temperature in the first esterification step is preferably 280° C. or lower, more preferably 250° C. or lower. In order to sufficiently proceed with the esterification reaction, the first esterification step is preferably carried out until the acid value of the esterified product becomes 10 mgKOH / g or lower.

[0122] The reaction temperature of the second esterification step is, for example, preferably 180°C or higher, more preferably 190°C or higher, for example, preferably 230°C or lower. That is, in the second esterification step, the esterified product obtained in the first esterification step is heated with α,β-unsaturated dicarboxylic acids and dihydric alcohol at a relatively low heating temperature, and further esterified to obtain a fatty acid-modified unsaturated polyester resin (A). In this way, when the reaction temperature of the second esterification step is within the above range, even if the system (raw material component) contains rosins (particularly unmodified rosin) as other acid components, the unsaturated bonds (unsaturated double bonds) derived from α,β-unsaturated dicarboxylic acids copolymerizable with the active energy ray curable monomer (B) can be left in the fatty acid-modified unsaturated polyester resin (A) at a high residual rate. The second esterification step is preferably performed until the acid value of the fatty acid-modified unsaturated polyester resin (A) becomes, for example, 30 mgKOH / g or less, and more preferably until it becomes 20 mgKOH / g or less. This allows the esterification reaction to proceed sufficiently in the second esterification step, thereby decreasing the methanol tolerance of the finally obtained fatty acid-modified unsaturated polyester.

[0123] In the second esterification step, although not particularly limited, it is preferable to cool the temperature in the system to 180° C. or less, particularly 150 to 180° C., and then heat the esterified product, α,β-unsaturated dicarboxylic acids, and, if necessary, dihydric alcohol at the above reaction temperature to carry out the esterification reaction. This makes it possible to more significantly exert the above-mentioned effects.

[0124] The acid value of the esterified product obtained in the first esterification step and the acid value of the fatty acid-modified unsaturated polyester resin (A) obtained in the second esterification step can each be measured in accordance with JIS K5601-2-1 (1999).

[0125] When rosins are contained in the raw material components, the rosins may contain rosin metal salts as inevitable impurities. The metal atoms contained in such rosin metal salts can act as a catalyst for the esterification reaction in the first esterification step. On the other hand, in the second esterification step, the metal atoms may act as a polymerization catalyst that promotes the polymerization of α,β-unsaturated dicarboxylic acids. As a result, the fatty acid-modified unsaturated polyester resin (A) may become high molecular weight and gel. Therefore, by using a polymerization inhibitor, the polymerization of α,β-unsaturated dicarboxylic acids in the second esterification step can be suppressed, and the gelation of the fatty acid-modified unsaturated polyester resin (A) can be reduced.

[0126] Examples of the metal atom of the rosin metal salt include at least one of an iron atom, a copper atom, a zinc atom, an aluminum atom, and a magnesium atom. The content of the rosin metal salt in the rosin is extremely small.

[0127] Examples of the polymerization inhibitor include phenol-based polymerization inhibitors such as (alkyl)phenol, p-methoxyphenol, o-isopropylphenol, catechol, resorcin, t-butylcatechol, pyrogallol, dibutylcresol, and guaiacol, nitroso-based polymerization inhibitors such as nitrosobenzene, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, picric acid, cupferron, butyraldoxime, methylethylketoxime, and cyclohexanone oxime, quinone-based polymerization inhibitors such as hydroquinone, t-butylhydroquinone, p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone, and piperidine-based polymerization inhibitors such as phenothiazine. The polymerization inhibitor may be used alone or in combination of two or more.

[0128] The amount of the polymerization inhibitor is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total amount of the raw material components. By setting the amount of the polymerization inhibitor within the above range, polymerization between α,β-unsaturated dicarboxylic acids in the second esterification step can be sufficiently suppressed.

[0129] When a polymerization inhibitor is used in the second esterification step, the fatty acid-modified unsaturated polyester resin (A) obtained by the above-mentioned production method is obtained in the form of a mixture with the polymerization inhibitor. That is, when a polymerization inhibitor is used in the second esterification step, a composition containing the fatty acid-modified unsaturated polyester resin (A) and the polymerization inhibitor is obtained. Then, the active energy ray curable monomer (B), and if necessary, a polymerization initiator and a curing accelerator, etc. are added to this composition to obtain a fatty acid-modified unsaturated polyester composition. In addition, if necessary, a polymerization inhibitor may be further added to the fatty acid-modified unsaturated polyester composition.

[0130] In the method for producing the fatty acid-modified unsaturated polyester resin (A), when fats and oils are used among fatty acids and fats and oils, it is preferable to carry out an ester exchange step instead of the first esterification step described above.

[0131] In the transesterification step, an intermediate reaction product is obtained by transesterifying fats and oils with a trihydric or higher polyhydric alcohol. The transesterification reaction produces an intermediate reaction product in which a fatty acid portion in the fats and oils is introduced into the polyhydric alcohol. A known catalyst can also be used for the transesterification reaction.

[0132] The reaction temperature in the ester exchange step is preferably 220° C. or higher, more preferably 230° C. or higher, and even more preferably 240° C. or higher. The reaction temperature in the ester exchange step is preferably 280° C. or lower, and more preferably 250° C. or lower.

[0133] After the transesterification step is completed, the intermediate reaction product obtained by the transesterification reaction can be regarded as the esterified product obtained in the first esterification step described above, and the second esterification step described above can be carried out.

[0134] After the transesterification step, if necessary, a first esterification step and a second esterification step can be carried out by adding other acid components. For example, the first esterification step can be carried out to obtain an esterified product by directly esterifying the intermediate reaction product obtained in the transesterification step with at least one of rosins, aromatic dicarboxylic acids, and aliphatic dicarboxylic acids. Thereafter, the second esterification step can be carried out in the same manner as above. When the transesterification step is carried out, the reaction temperature in the first esterification step is preferably 180° C. or higher, more preferably 190° C. or higher, and preferably 230° C. or lower. The reaction temperature in the second esterification step and the polymerization inhibitor used in the second esterification step are the same as those described above, and therefore will not be described here.

[0135] However, in general, it may be difficult to adjust the weight average molecular weight during the synthesis of the fatty acid modified unsaturated polyester resin (A). Specifically, as the reaction of the raw material components starts, the molecular weight of the reactants of the raw material components gradually increases, but at the end of the reaction of the raw material components, the molecular weight of the reactants of the raw material components has increased considerably, and the reactants react with each other, which may cause a sudden increase in molecular weight or gelation, making it difficult to obtain a fatty acid modified unsaturated polyester resin (A) with a relatively low weight average molecular weight. However, according to the above-mentioned production method, the occurrence of a sudden increase in molecular weight and gelation can be reduced, and a fatty acid modified unsaturated polyester resin (A) with a relatively low weight average molecular weight can be easily produced. Specifically, a fatty acid modified unsaturated polyester resin (A) with a weight average molecular weight of preferably 50,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less can be easily produced. Therefore, even when a large amount of fatty acid-modified unsaturated polyester resin (A) is produced in a factory or the like, the above-mentioned production method does not require strict control of reaction conditions such as the reaction time of the raw material components, and the burden associated with controlling the reaction conditions can be reduced, making it possible to reproducibly produce a fatty acid-modified unsaturated polyester resin (A) having a relatively low weight average molecular weight.

[0136] <Active energy ray curable monomer (B)> The active energy ray curable composition contains, in addition to the fatty acid-modified unsaturated polyester resin (A), an active energy ray curable monomer (B). The active energy ray curable monomer (B) is a polymerizable functional group-containing compound having one or more polymerizable groups that can be copolymerized with the fatty acid-modified unsaturated polyester resin (A) upon irradiation with active energy rays such as ultraviolet rays.

[0137] The polymerizable group preferably has an ethylenically unsaturated double bond. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a vinyl group, and an allyl group, and an acryloyl group and a methacryloyl group are preferred. The polymerizable group may be used alone or in combination of two or more kinds.

[0138] Examples of the active energy ray curable monomer (B) include a polymerizable monofunctional compound having one polymerizable group in one molecule, and a photopolymerizable multifunctional compound having two or more polymerizable groups in one molecule. In the following, the polymerizable monofunctional compound and the photopolymerizable multifunctional compound are exemplified by those having a (meth)acryloyl group. The (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0139] Examples of the polymerizable monofunctional compound include (meth)acrylic acid ester compounds such as 2-hydroxyethyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isooctyl (meth)acrylate, isomyristyl (meth)acrylate, isostearyl (meth)acrylate, isobornyl (meth)acrylate, ethoxy-diethylene glycol (meth)acrylate, 2-ethylhexyl-carbitol (meth)acrylate, neopentyl glycol benzoate (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, epichlorohydrin (ECH)-modified phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, and paracumylphenol ethylene oxide (EO)-modified (meth)acrylate; vinyl pyrrolidone, vinyl caprolactam, and acryloyl morpholine.

[0140] Examples of the polymerizable multifunctional compound include a polymerizable bifunctional compound having two polymerizable groups in one molecule, a polymerizable trifunctional compound having three polymerizable groups in one molecule, a polymerizable tetrafunctional compound having four polymerizable groups in one molecule, a polymerizable pentafunctional compound having five polymerizable groups in one molecule, and a polymerizable hexafunctional compound having six polymerizable groups in one molecule.

[0141] Examples of the polymerizable bifunctional compound include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dicyclopentadiene di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and dicyclopentanyl di(meth)acrylate; (meth)acrylic acid ester compounds such as bisphenol A ethylene oxide (EO) adduct diacrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate, or alkylene oxide-modified versions thereof, divinylbenzene, butanediol-1,4-divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical under the trade name "AH-600"), and phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical under the trade name "AT-600").

[0142] Examples of the polymerizable trifunctional compound include (meth)acrylic acid ester compounds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(acryloxyethyl)isocyanurate, as well as alkylene oxide modified compounds thereof and tri(meth)acrylates of alkylene oxide modified isocyanuric acid.

[0143] Examples of the polymerizable tetrafunctional compound include (meth)acrylic acid ester compounds such as ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate, and alkylene oxide modified products thereof.

[0144] Examples of the polymerizable pentafunctional compound include (meth)acrylic acid ester compounds such as dipentaerythritol penta(meth)acrylate, and alkylene oxide modified products thereof.

[0145] Examples of the polymerizable hexafunctional compound include (meth)acrylic acid ester compounds such as dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (trade name "UA-306H" manufactured by Kyoeisha Chemical Co., Ltd.), and caprolactone-modified dipentaerythritol hexa(meth)acrylate, or alkylene oxide-modified versions of these compounds.

[0146] The active energy ray-curable monomer (B) may be used alone or in combination of two or more kinds.

[0147] The active energy ray-curable composition is suitably used as an active energy ray-curable ink composition.

[0148] The active energy ray-curable composition can be obtained by mixing, without any particular limitation, the fatty acid-modified unsaturated polyester resin (A) and the active energy ray-curable monomer (B).

[0149] In the active energy ray-curable composition, the content of the fatty acid-modified unsaturated polyester resin (A) is, for example, preferably 15 parts by mass or more, more preferably 25 parts by mass or more, relative to 100 parts by mass of the total amount of the fatty acid-modified unsaturated polyester resin (A) and the active energy ray-curable monomer (B), and is, for example, preferably 80 parts by mass or less, more preferably 75 parts by mass or less.

[0150] In the active energy ray curable composition, the content of the active energy ray curable monomer (B) is, for example, preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and for example, preferably 85 parts by mass or less, more preferably 75 parts by mass or less, based on 100 parts by mass of the total amount of the fatty acid modified unsaturated polyester resin (A) and the active energy ray curable monomer (B). The fatty acid modified unsaturated polyester resin (A) has excellent compatibility with the active energy ray curable monomer (B). Therefore, the content of the active energy ray curable monomer (B) can be increased in the active energy ray curable composition, thereby further improving the abrasion resistance of the coating film.

[0151] In addition, the active energy ray curable composition may contain known additives as necessary. Examples of additives include polymerization inhibitors, photopolymerization initiators, fillers, thickeners, foaming agents, antioxidants, light stabilizers, heat stabilizers, and flame retardants. Polymerization inhibitors are preferred. The additives may be used alone or in combination of two or more. The amount and timing of the additives are not particularly limited and may be appropriately set according to the purpose and application.

[0152] As a method for producing the active energy ray curable composition, a method of mixing the fatty acid modified unsaturated polyester resin (A), the active energy ray curable monomer (B), and additives such as a polymerization inhibitor as necessary while heating is preferably used. This allows the fatty acid modified unsaturated polyester resin (A) to be dissolved in the active energy ray curable monomer (B) to obtain the active energy ray curable composition. The heating temperature is not particularly limited, and is preferably 100 to 240°C.

[0153] The use of the active energy ray curable composition is not particularly limited. The active energy ray curable composition can form a cured film having excellent adhesion to a substrate and excellent abrasion resistance after curing. Therefore, when no pigment is used, the active energy ray curable composition can be suitably used as an uncolored varnish or coating agent (coating agent).

[0154] In addition, when a pigment is used, the active energy ray curable composition can be suitably used as an ink, a paint, etc. Even when the active energy ray curable composition is used as an ink or paint containing a pigment, the fatty acid modified unsaturated polyester resin (A) can form a coating film having excellent adhesion and abrasion resistance after curing. The active energy ray curable composition and the ink containing a pigment (active energy ray curable ink) will be described in detail below.

[0155] [Active energy ray curable ink] The active energy ray-curable ink contains an active energy ray-curable composition and a pigment.

[0156] The pigment is not particularly limited, and examples thereof include inorganic pigments and organic pigments. The pigments may be used alone or in combination of two or more kinds.

[0157] Examples of inorganic pigments include yellow lead, zinc yellow, Prussian blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, alumina white, calcium carbonate, ultramarine, carbon black, graphite, aluminum powder, red iron oxide, etc. The inorganic pigments may be used alone or in combination of two or more.

[0158] Examples of organic pigments include soluble azo pigments such as β-naphthol pigments, β-oxynaphthoic acid pigments, β-oxynaphthoic acid anilide pigments, acetoacetate anilide pigments, and pyrazolone pigments; insoluble azo pigments such as β-naphthol pigments, β-oxynaphthoic acid anilide pigments, acetoacetate anilide monoazo pigments, acetoacetate anilide disazo pigments, and pyrazolone pigments; copper phthalocyanine blue; and halogenated (chlorinated or brominated) copper phthalocyanine. Examples of the organic pigment include polycyclic pigments and heterocyclic pigments such as phthalocyanine pigments, such as phthalocyanine blue, sulfonated copper phthalocyanine blue, and metal-free phthalocyanine, quinacridone pigments, dioxazine pigments, threne pigments (pyranthrone, anthrone, indanthrone, anthrapyrimidine, flavanthrone, thioindigo, anthraquinone, perinone, and perylene pigments), isoindolinone pigments, metal complex pigments, and quinophthalone pigments. The organic pigments may be used alone or in combination of two or more.

[0159] In the active energy ray-curable ink, the content of the active energy ray-curable composition is, for example, preferably 30 parts by mass or more, and more preferably 40 parts by mass or more, relative to 100 parts by mass of the total amount of the active energy ray-curable composition and the pigment, and for example, preferably 95 parts by mass or less, and more preferably 90 parts by mass or less.

[0160] In the active energy ray-curable ink, the content of the pigment, relative to 100 parts by mass of the total amount of the active energy ray-curable composition and the pigment, is, for example, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, and for example, preferably 70 parts by mass or less, and more preferably 60 parts by mass or less.

[0161] The active energy ray-curable ink may further contain the above-mentioned active energy ray-curable monomer (B) as required, which allows the viscosity of the active energy ray-curable ink to be adjusted depending on the application, such as the printing method.

[0162] The amount of the active energy ray-curable monomer mixed when preparing the active energy ray-curable ink is, per 100 parts by mass of the total amount of the active energy ray-curable composition (varnish) and the pigment, for example, 3 parts by mass or more, preferably 5 parts by mass or more, and for example, 45 parts by mass or less, preferably 35 parts by mass or less.

[0163] The active energy ray-curable ink may further contain a photopolymerization initiator, if necessary.

[0164] The photopolymerization initiator is not particularly limited, and examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, and the like. -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one, etc. The photopolymerization initiator may be used alone or in combination of two or more kinds.

[0165] In the active energy ray-curable ink, the content of the photopolymerization initiator, relative to 100 parts by mass of the total amount of the active energy ray-curable composition (varnish) and pigment, is, for example, preferably 0.5 parts by mass or more, and more preferably 1.0 part by mass or more, and for example, preferably 20 parts by mass or less, and more preferably 15 parts by mass or less.

[0166] The active energy ray-curable ink may contain other additives as necessary.

[0167] Examples of additives include curing accelerators (such as cobalt naphthenate), and additives similar to those described above in the active energy ray curable composition (such as fillers, thickeners, foaming agents, antioxidants, light resistance stabilizers, heat resistance stabilizers, and flame retardants). The additives may be used alone or in combination of two or more. The amount and timing of the additives are not particularly limited and are appropriately set according to the purpose and application.

[0168] The active energy ray-curable ink can be produced, for example, by kneading the active energy ray-curable composition, the pigment, and, if necessary, the active energy ray-curable monomer (B), the photopolymerization initiator, and other additives. The kneading can be carried out using known means such as a bead mill, a roll mill, a ball mill, an attritor, or a sand mill.

[0169] The above-mentioned active energy ray-curable composition (varnish) and active energy ray-curable ink contain an active energy ray-curable composition, and therefore are excellent in solubility and misting resistance.

[0170] Therefore, the active energy ray-curable composition (varnish) and the active energy ray-curable ink can be printed using various printing methods.

[0171] More specifically, in printing, an active energy ray-curable composition or an active energy ray-curable ink is applied to a substrate by a known method, and then cured by irradiating with active energy rays. This results in an article having a substrate and a coating film made of a cured product of the active energy ray-curable composition or the active energy ray-curable ink. That is, when the active energy ray-curable ink is applied to a substrate, a printed layer is formed on the substrate by printing using the active energy ray-curable ink.

[0172] The substrate is not particularly limited, and examples thereof include uncoated paper such as fine paper; coated paper such as lightly coated paper, art paper, coated paper, lightly coated paper, and cast coated paper; paperboard such as white paperboard and ball coated paper; synthetic paper, aluminum vapor-deposited paper, and plastic films.

[0173] Generally, active energy ray curable compositions and active energy ray curable inks have difficulty penetrating into plastic films on substrates such as paper, and adhesion is easily reduced. In particular, plastic films containing resins such as polypropylene and polyethylene have low polarity, and therefore the adhesion of active energy ray curable compositions and active energy ray curable inks may be further reduced. However, in the present invention, by using the above-mentioned fatty acid-modified unsaturated polyester resin (A), the active energy ray curable compositions and active energy ray curable inks have appropriate fluidity and excellent wettability to substrates, and thus can exhibit high adhesion not only to substrates such as paper, but also to plastic films. Therefore, plastic films are preferably used as substrates, since they can particularly exhibit the effects of the present invention.

[0174] Examples of plastics constituting the plastic film include olefin resins such as polyethylene and polypropylene; ester resins such as polyethylene terephthalate, polycarbonate, and polylactic acid; styrene resins such as polystyrene, AS resin, and ABS resin; nylon, polyamide, polyvinyl chloride, and polyvinylidene chloride. Among these, olefin resins are preferred, and polyethylene and polypropylene are preferred. Olefin resins have low polarity and therefore tend to have low adhesion, but the active energy ray-curable composition and active energy ray-curable ink of the present invention can exhibit high adhesion even to plastic films containing such olefin resins.

[0175] The application method is not particularly limited, and known printing methods such as screen printing, offset printing, flexographic printing, and roll printing can be used.

[0176] In addition, the active energy ray curable composition and the active energy ray curable ink may be required to have a high viscosity in offset printing, while they may be required to have a low viscosity in flexographic printing. Since the fatty acid modified unsaturated polyester resin (A) has excellent compatibility with the active energy ray curable monomer (B), the mixing ratio of the fatty acid modified unsaturated polyester resin (A) and the active energy ray curable monomer (B) can be adjusted in a wide range, and by adjusting this mixing ratio, the viscosity of the active energy ray curable composition and the active energy ray curable ink can be easily adjusted to a desired range. Therefore, it is easy to adjust the viscosity to a required value depending on the application, and the active energy ray curable composition and the active energy ray curable ink can be used in various printing methods.

[0177] Examples of the active energy rays include ultraviolet rays and electron beams.

[0178] When curing with ultraviolet light, an ultraviolet irradiator having, for example, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like, as a light source is used. The amount of ultraviolet light irradiation, the amount of light from the ultraviolet irradiator, the arrangement of the light source, and the like are appropriately adjusted as necessary. Specifically, when a high-pressure mercury lamp is used, for example, a substrate coated with an active energy ray-curable composition or an active energy ray-curable ink is irradiated with a light intensity of 80 to 1000 W / cm. 2 For one lamp, the substrate is conveyed at a conveying speed of 5 to 50 m / min. When curing is performed by electron beam, the substrate coated with the active energy beam-curable composition or the active energy beam-curable ink is conveyed at a conveying speed of 5 to 50 m / min by an electron beam accelerator having an acceleration voltage of 10 to 300 kV, for example.

[0179] The active energy ray-curable composition or the active energy ray-curable ink is crosslinked and cured by irradiation with ultraviolet light, i.e., active energy rays, resulting in a cured film being obtained on the substrate as a cured product of the active energy ray-curable composition or the active energy ray-curable ink.

[0180] The active energy ray-curable composition or the active energy ray-curable ink is suitably used in printing methods such as lithographic, letterpress, intaglio, and stencil printing to obtain various printed matters, such as printed matters for forms, various printed matters for packaging such as carton paper, various printed matters for plastics, printed matters for seals and labels, art printed matters, and metal printed matters.

[0181] The active energy ray curable composition can also be used as a coating agent. When the active energy ray curable composition is used as a coating agent, the coating agent may contain a photopolymerization initiator and other additives. The explanation of the photopolymerization initiator and other additives is the same as that of the active energy ray curable ink described above, and therefore will not be described here. Then, the coating agent is applied to a substrate in the same manner as above, and then irradiated with active energy rays to cure, thereby forming a coating layer made of a cured product of the coating agent on the substrate.

[0182] Furthermore, the active energy ray curable composition can also be used as an active energy ray curable paint. The active energy ray curable paint includes the active energy ray curable composition and a pigment. The active energy ray curable paint may also include a photopolymerization initiator and other additives. The pigment, photopolymerization initiator and other additives are similar to those of the active energy ray curable ink described above, and therefore detailed description is omitted here. The active energy ray curable paint is applied to a substrate in the same manner as above, and then irradiated with active energy rays to cure, thereby forming a coating layer made of a cured product of the active energy ray curable paint on the substrate. EXAMPLES

[0183] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are based on mass unless otherwise specified. In addition, the specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit value (numeric value defined as "less than or equal to" or "less than") or lower limit value (numeric value defined as "more than or equal to" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention".

[0184] <Example 1: Synthesis of fatty acid modified unsaturated polyester resin 1> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer was charged with 30.8 parts by mass of lauric acid (iodine value 1 or less), 10.1 parts by mass of isophthalic acid, and 13.8 parts by mass of glycerin, and the temperature was raised to 230°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 27.8 parts by mass of maleic anhydride, 17.5 parts by mass of 1,3-propanediol, and 0.1 parts by mass of t-butylhydroquinone (TBHQ) were charged, and the direct esterification reaction was performed until the acid value became 20 mgKOH / g (second esterification step). As a result, a fatty acid-modified unsaturated polyester resin 1 was obtained. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 1 at 25°C was 55g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 1 was measured according to the above-mentioned procedure, and the measurement results are shown in Table 1.

[0185] <Example 2: Synthesis of fatty acid modified unsaturated polyester resin 2> 37.4 parts by mass of lauric acid, 5.2 parts by mass of tetrahydrophthalic anhydride, 5.2 parts by mass of benzoic acid, and 14.9 parts by mass of glycerin were put into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer, and the temperature was raised to 230°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 23.9 parts by mass of maleic anhydride, 13.4 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were put in, and the direct esterification reaction was performed until the acid value became 21 mgKOH / g (second esterification step). This resulted in the fatty acid-modified unsaturated polyester resin 2. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 2 at 25°C was 93 g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 2 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0186] <Example 3: Synthesis of fatty acid modified unsaturated polyester resin 3> 34.6 parts by mass of coconut oil (iodine value 9) and 7 parts by mass of pentaerythritol were put into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer, and an ester exchange reaction was carried out at 250 ° C for 6 hours (ester exchange step). Next, the reaction vessel was cooled to 200 ° C, 10.3 parts by mass of benzoic acid and 5.8 parts by mass of tetrahydrophthalic anhydride were put in, and the temperature was raised to 230 ° C while blowing in nitrogen gas, and the reaction was continued until the acid value was 10 mg KOH / g or less, and a direct esterification reaction was carried out (first esterification step). Next, the reaction vessel was cooled to 200 ° C, and 24.3 parts by mass of maleic anhydride, 18 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were put in, and a direct esterification reaction was carried out until the acid value was 22 mg KOH / g (second esterification step). As a result, a fatty acid modified unsaturated polyester resin 3 was obtained. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 3 at 25° C. was 93 g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 3 was measured according to the above-mentioned procedure, and the measurement results are shown in Table 1.

[0187] <Example 4: Synthesis of fatty acid modified unsaturated polyester resin 4> Stearic acid (iodine value 1 or less) 25.1 parts by mass, disproportionated rosin 25.1 parts by mass, tetrahydrophthalic anhydride 3.1 parts by mass, and glycerin 11.8 parts by mass were put into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 240 ° C. while blowing in nitrogen gas, and the reaction was continued until the acid value was 10 mg KOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200 ° C., and 22.4 parts by mass of maleic anhydride, 12.5 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were put in, and the direct esterification reaction was performed until the acid value was 15 mg KOH / g (second esterification step). As a result, a fatty acid modified unsaturated polyester resin 4 was obtained. The methanol tolerance of the fatty acid modified unsaturated polyester resin 4 at 25 ° C. was 44 g. The weight average molecular weight of fatty acid-modified unsaturated polyester resin 4 was measured according to the above-mentioned procedure, and the measurement results are shown in Table 1.

[0188] <Example 5: Synthesis of fatty acid modified unsaturated polyester resin 5> 25.1 parts by mass of lauric acid, 25.1 parts by mass of disproportionated rosin, 3.1 parts by mass of tetrahydrophthalic anhydride, and 11.8 parts by mass of glycerin were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 240°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 22.4 parts by mass of maleic anhydride, 12.5 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were added, and the direct esterification reaction was performed until the acid value became 19 mgKOH / g (second esterification step). This resulted in the fatty acid-modified unsaturated polyester resin 5. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 5 at 25°C was 58 g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 5 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0189] <Example 6: Synthesis of fatty acid modified unsaturated polyester resin 6> 25.1 parts by mass of lauric acid, 25.1 parts by mass of disproportionated rosin, 3.1 parts by mass of tetrahydrophthalic anhydride, and 11.8 parts by mass of glycerin were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 240°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 230°C, and 22.4 parts by mass of maleic anhydride, 12.5 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were added, and the direct esterification reaction was performed until the acid value became 21 mgKOH / g (second esterification step). This resulted in the fatty acid-modified unsaturated polyester resin 6. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 6 at 25°C was 42 g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 6 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0190] <Example 7: Synthesis of fatty acid modified unsaturated polyester resin 7> 25.1 parts by mass of lauric acid, 25.1 parts by mass of gum rosin, 3.1 parts by mass of tetrahydrophthalic anhydride, and 9.5 parts by mass of glycerin were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 240°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 22.4 parts by mass of maleic anhydride, 14.8 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were added, and the direct esterification reaction was performed until the acid value became 25 mgKOH / g (second esterification step). This resulted in the fatty acid-modified unsaturated polyester resin 7. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 7 at 25°C was 40 g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 7 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0191] <Example 8: Synthesis of fatty acid modified unsaturated polyester resin 8> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer was charged with 5.2 parts by mass of lauric acid, 41 parts by mass of disproportionated rosin, 5 parts by mass of tetrahydrophthalic anhydride, 5 parts by mass of benzoic acid, and 11.4 parts by mass of glycerin, and the temperature was raised to 240°C while blowing in nitrogen gas, and the reaction was continued until the acid value was 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 20.1 parts by mass of maleic anhydride, 12.3 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were charged, and the direct esterification reaction was performed until the acid value was 23 mgKOH / g (second esterification step). As a result, a fatty acid-modified unsaturated polyester resin 8 was obtained. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 8 at 25°C was 80g. The weight average molecular weight of the fatty acid modified unsaturated polyester resin 8 was measured according to the above-mentioned procedure, and the measurement results are shown in Table 1.

[0192] <Example 9: Synthesis of fatty acid modified unsaturated polyester resin 9> 24.8 parts by mass of lauric acid, 6.5 parts by mass of tetrahydrophthalic anhydride, 8 parts by mass of benzoic acid, and 16 parts by mass of glycerin were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 250°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 25 parts by mass of maleic anhydride, 19.7 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were added, and the direct esterification reaction was performed until the acid value became 18 mgKOH / g (second esterification step). This resulted in the production of fatty acid-modified unsaturated polyester resin 9. The methanol tolerance of fatty acid-modified unsaturated polyester resin 9 at 25°C was 135g. The weight average molecular weight of fatty acid-modified unsaturated polyester resin 9 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0193] <Example 10: Synthesis of fatty acid modified unsaturated polyester resin 10> 32.8 parts by mass of lauric acid, 21.8 parts by mass of adipic acid, 12.8 parts by mass of isophthalic acid, and 13.3 parts by mass of glycerin were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 230°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 6 parts by mass of maleic anhydride, 13.3 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were added, and the direct esterification reaction was performed until the acid value became 17 mgKOH / g (second esterification step). This resulted in the fatty acid-modified unsaturated polyester resin 10. The methanol tolerance of the fatty acid-modified unsaturated polyester resin 10 at 25°C was 92 g. The weight average molecular weight of the fatty acid-modified unsaturated polyester resin 10 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0194] <Comparative Example 1: Synthesis of fatty acid modified unsaturated polyester resin 11> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, and a thermometer was charged with 49.2 parts by mass of disproportionated rosin, 5 parts by mass of tetrahydrophthalic anhydride, 5 parts by mass of benzoic acid, and 11.4 parts by mass of glycerin, and the temperature was raised to 250°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 18.5 parts by mass of maleic anhydride, 10.9 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were charged, and the direct esterification reaction was performed until the acid value became 15 mgKOH / g (second esterification step). This resulted in the production of fatty acid-modified unsaturated polyester resin 11. The methanol tolerance of fatty acid-modified unsaturated polyester resin 11 at 25°C was 58 g. The weight average molecular weight of fatty acid-modified unsaturated polyester resin 11 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0195] <Comparative Example 2: Synthesis of fatty acid modified unsaturated polyester resin 12> 32.8 parts by mass of lauric acid, 12.8 parts by mass of isophthalic acid, and 10.3 parts by mass of glycerin were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, and the temperature was raised to 230°C while blowing in nitrogen gas, and the reaction was continued until the acid value became 10 mgKOH / g or less to perform a direct esterification reaction (first esterification step). Next, the reaction vessel was cooled to 200°C, and 27.8 parts by mass of adipic acid, 16.3 parts by mass of 1,3-propanediol, and 0.1 parts by mass of TBHQ were added, and the direct esterification reaction was performed until the acid value became 20 mgKOH / g (second esterification step). This resulted in the production of fatty acid-modified unsaturated polyester resin 12. The methanol tolerance of fatty acid-modified unsaturated polyester resin 12 at 25°C was 58 g. The weight average molecular weight of fatty acid-modified unsaturated polyester resin 12 was measured according to the above-mentioned procedure, and the measurement results were as shown in Table 1.

[0196] Example 1 60 parts by mass of the obtained fatty acid modified unsaturated polyester resin 1, 20 parts by mass of EO modified trimethylolpropane triacrylate (EO modified TMPTA), 20 parts by mass of hexanediol diacrylate (HDDA), and 0.1 parts by mass of hydroquinone (HQ) were mixed and dissolved by heating at about 110°C to obtain active energy ray curable ink composition 1 (hereinafter referred to as varnish 1).

[0197] Next, 50 parts by mass of the obtained varnish 1, 20 parts by mass of neutral carbon black (CB, pigment, Mitsubishi Chemical Corporation product name "RCF # 52"), 25 parts by mass of hexanediol diacrylate (HDDA), and 5 parts by mass of photopolymerization initiator (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, BASF Japan Ltd. product name "Irgacure 907") were mixed and milled with a three-roll mill (Inoue Seisakusho Co., Ltd. S-4 3 / 4 × 11) to disperse the pigment so that the maximum particle diameter was 7.5 μm or less. This resulted in the active energy ray curable ink 1 (hereinafter referred to as ink 1).

[0198] (Examples 2 to 10 and Comparative Examples 1 to 2) Except for using fatty acid-modified unsaturated polyester resins 2 to 12 instead of fatty acid-modified unsaturated polyester resin 1, active energy ray-curable ink compositions 2 to 12 (hereinafter referred to as "varnishes 2 to 12", respectively) were obtained in the same manner as in Example 1. Furthermore, active energy ray-curable inks 2 to 12 (hereinafter referred to as "inks 2 to 12", respectively) were obtained in the same manner as in Example 1, except that varnish 1 was replaced with varnishes 2 to 12, respectively.

[0199] Tables 1 to 3 show the raw material components used in the synthesis of the above-mentioned fatty acid-modified unsaturated polyester resin, and the blending amounts of each component used in the production of the active energy ray-curable ink composition (also simply referred to as "varnish") and the active energy ray-curable ink (also simply referred to as "ink"). In Tables 1 and 2, fatty acid-modified unsaturated polyester resins 1 to 12 are simply described as "resins 1 to 12", respectively. In the raw material components of fatty acid-modified unsaturated polyester resins 1 to 12, the molar equivalent ratio of the hydroxyl group contained in the polyhydric alcohol to 1 molar equivalent of the carboxyl group contained in the raw material components is shown in the "molar equivalent ratio [OH / COOH]" column in Table 1.

[0200] In addition, for fatty acid modified unsaturated polyester resins 1 to 12, the 5 The state (liquid or solid) of the substance under 1 Pa (1 atm) is shown in Table 1. 5 At 1 Pa (1 atm), the fatty acid modified unsaturated polyester resin 8 was in a solid state with a softening point of 65°C, and the fatty acid modified unsaturated polyester resin 11 was in a solid state with a softening point of 79°C.

[0201] (evaluation) The inks obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Table 1.

[0202] (Adhesion evaluation) 0.5 mL of the ink was applied to a polypropylene sheet (manufactured by Okamoto Corporation, product name "Clear C") using a full-surface RI tester roll. After that, the ink was exposed to a metal halide lamp of 80 W / cm using an ultraviolet irradiation device (manufactured by Eye Graphics Corporation, product name "ESC-4011GX"). 2 The ink spread on the polypropylene sheet was cured by irradiating it with ultraviolet light at a conveyor speed of 50 m / min to obtain a printed layer.

[0203] The adhesion of the printed layer was evaluated according to the cross-cut method of JIS K5600-5-6 (1999). Specifically, first, a grid-like cut was made in the printed layer at intervals of 1 mm to form 100 square meshes. Next, an adhesive tape was evenly applied onto the printed layer and then peeled off, and the remaining rate [%] of the printed layer (the ratio of the number of remaining meshes out of 100) was evaluated based on the following evaluation criteria. Note that if the remaining rate was 70% or more, i.e., the following evaluation criteria was 3 or more, it was determined that the product was practical. <Evaluation criteria> 5: The survival rate was 90% or more. 4: The residual rate was 80% or more but less than 90%. 3: The residual rate was 70% or more but less than 80%. 2: The residual rate was 60% or more but less than 70%. 1: The survival rate was 60% or less.

[0204] (Abrasion resistance evaluation) The ink was applied to art paper in a volume of 0.25 mL using an RI tester (manufactured by Tester Sangyo Co., Ltd.). Then, the ink was exposed to a metal halide lamp of 80 W / cm using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., product name "ESC-4011GX"). 2 The ink spread on the art paper was cured by irradiating it with ultraviolet light at a conveyor speed of 50 m / min to form a printed layer, and a test specimen was obtained.

[0205] A test piece was used to carry out a rub resistance test using a Gakushin type rub fastness tester (manufactured by Tester Sangyo Co., Ltd., load 500g 50 times, paper: high quality paper), and the scratches on the ink-spread surface of the test piece, i.e., the surface of the printed layer, were evaluated based on the following evaluation criteria. Note that a rating of 3 or higher on the following criteria is considered to be at a level that is acceptable for practical use. <Evaluation criteria> 5: No scratches at all 4: The damaged area is less than 10% 3: The area of ​​the scratch is 10% or more but less than 30% 2: The damaged area is 30% or more but less than 50% 1: The damaged area is 50% or more

[0206] [Table 1]

[0207] [Table 2]

[0208] [Table 3]

[0209] In the active energy ray curable composition of the present invention, by using the fatty acid modified unsaturated polyester resin (A), it is possible to form a coating film having excellent adhesion to a substrate and excellent abrasion resistance. It has been demonstrated by the examples that such effects can be similarly exhibited even when the active energy ray curable composition is used as an ink containing the composition together with a pigment (active energy ray curable ink), but it can be said that the active energy ray curable composition of the present invention can exhibit the above effects even if it does not contain a pigment. [Industrial Applicability]

[0210] According to the present invention, by using the fatty acid-modified unsaturated polyester resin (A), it is possible to provide an active energy ray-curable composition capable of forming a coating film having excellent adhesion to a substrate and excellent abrasion resistance.

Claims

1. An active energy ray-curable composition comprising a fatty acid-modified unsaturated polyester resin (A) and an active energy ray-curable monomer (B), the fatty acid-modified unsaturated polyester resin (A) is a reaction product of raw material components including at least one of fatty acids and fats and oils, α,β-unsaturated dicarboxylic acids and rosins as acid components, and a polyhydric alcohol; The polyhydric alcohol includes a trihydric or higher polyhydric alcohol and a dihydric alcohol, The content of the trihydric or higher polyhydric alcohol in the polyhydric alcohol is 40 mol % or more and 60 mol % or less, In the raw material component, a molar equivalent ratio of a hydroxyl group contained in the polyhydric alcohol to 1 molar equivalent of a carboxyl group contained in the raw material component is 0.9 or more and 1.1 or less; 2. An active energy ray-curable composition, wherein the fatty acid-modified unsaturated polyester resin (A) has a methanol tolerance of 120 g or less at 25° C.

2. 2. The active energy ray-curable composition according to claim 1, wherein the rosin is at least one selected from the group consisting of disproportionated rosin, hydrogenated rosin, and polymerized rosin.

3. 2. An active energy ray-curable ink comprising the active energy ray-curable composition according to claim 1 and a pigment.

4. An active energy ray-curable coating material comprising the active energy ray-curable composition according to claim 1 and a pigment.

5. An article comprising a printed layer printed using the active energy ray-curable ink described in claim 3.

6. The active energy ray-curable composition according to claim 1, characterized in that the fatty acid-modified unsaturated polyester resin (A) is a reaction product obtained by esterifying an ester of at least one of the fatty acids and the oils and fats, and the trivalent or higher polyhydric alcohol, with the α,β-unsaturated dicarboxylic acids and the dihydric alcohol.

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