JP6548018B2 - Modified rosin ester resin, active energy ray curable resin composition and cured product - Google Patents

Description

  The present invention relates to a modified rosin ester resin, an active energy ray-curable resin composition and a cured product.

  A resin composition (hereinafter referred to as an active energy ray-curable resin composition) which is cured by active energy rays such as ultraviolet rays and electron beams is usually composed of a reactive diluent, a resin, a photopolymerization initiator and additives. It is provided as an energy-saving industrial material in applications such as coating agents, paints and printing inks.

  As reactive diluents, polyfunctional acrylates such as dipentaerythritol hexaacrylate and trimethylolpropane tetraacrylate are widely used because the curability of the active energy ray-curable resin composition and the film hardness are excellent. . Moreover, as a resin, a diallyl phthalate resin may be used by the point which is excellent in compatibility with the said polyfunctional acrylate (refer patent document 1 and 2).

  However, the diallyl phthalate resin is easily miscible with water, and the active energy ray-curable resin composition containing the same is poor in emulsification resistance such as forming a stable emulsion for a long time. The diallyl phthalate resin is obtained by polymerizing a diallyl phthalate monomer, but has a disadvantage that it can not be further modified because it has no functional group such as a hydroxyl group in the molecule.

Japanese Patent Laid-Open No. 2000-80326 (Paragraph [0003], etc.) Unexamined-Japanese-Patent No. 2010-10082 (paragraph [0003] etc.)

  An object of the present invention is to provide a copolymer that can replace the diallyl phthalate resin. That is, since it has a hydroxyl group, various modifications are possible, and similarly to the diallyl phthalate resin, it is compatible with various reactive diluents, and an active energy ray-curable resin composition containing the reactive diluent. It is a main object to provide a modified rosin ester resin which imparts excellent curability and emulsion resistance.

  The present invention has been found that the modified rosin ester resin of the present invention is a modified resin which is compatible with the reactive diluent as well as the diallyl phthalate resin and imparts excellent curability and emulsification resistance. It came to complete.

  That is, according to the present invention, rosin esters (A) which are reaction products of rosins (a1) and polyalcohols (a2), polyvalent carboxylic acid anhydrides (B), and polymerizable double bonds in the molecule Modified rosin ester resin obtained by reacting glycidyl compound (C) having the same; active energy ray-curable resin composition containing the modified rosin ester resin and a reactive diluent; curing the active energy ray-curable resin composition It relates to the cured product.

  The modified rosin ester resin of the present invention is excellent in compatibility with various reactive diluents, particularly polyfunctional acrylates such as dipentaerythritol hexaacrylate. Therefore, it is useful as a reactive viscosity modifier in an active energy ray-curable resin composition. In addition, the emulsification resistance of the active energy ray-curable resin composition can be enhanced as compared to the diallyl phthalate resin. Further, since the modified rosin ester resin of the present invention has a hydroxyl group, further modification using it is possible.

  Since the modified rosin ester resin of the present invention is well compatible with various reactive diluents, there is no insoluble matter, and an active energy ray-curable resin composition excellent in curability and emulsification resistance is obtained. Therefore, it can be used for conventional applications for diallyl phthalate resins, for example, materials such as binder resins and molding materials for decorative UV-curable inks and decorative plates. In addition, since the modified rosin ester resin of the present invention has a polymerizable double bond and a hydroxyl group in the molecule, they can be used for other applications such as coating agents.

  The active energy ray-curable resin composition of the present invention has good curability and resistance to emulsification, and is therefore suitable as a binder resin composition such as an ultraviolet curable ink as an application utilizing these attributes.

The modified rosin ester resin according to the present invention is
Rosin esters (A) (hereinafter referred to as component (A)) which are reaction products of rosins (a1) (hereinafter referred to as component (a1)) and polyols (a2) (hereinafter referred to as component (a2))
Polyvalent carboxylic acid anhydride (B) (hereinafter referred to as component (B)) and
It is obtained by reacting allyl glycidyl ether (C) (hereinafter, referred to as component (C)).

  Specific examples of the component (A) include reaction products of rosins (a1) (hereinafter referred to as component (a1)) and polyols (a2) (hereinafter referred to as component (a2)).

  As the component (a1), various known ones can be used without particular limitation. Specifically, for example, natural rosin (gum rosin, tall oil rosin, wood rosin, etc.), rosin obtained by stabilizing natural rosin by various known methods (hydrogenated rosin, disproportionated rosin, etc.), natural rosin or stabilization Polymerized rosins obtained by treating the treated rosins by various known methods, Diels-Alder reaction products of these rosins with α, β-unsaturated carboxylic acids (maleated rosins, hydrogenated maleated rosins, acrylated rosins, acrylated rosins And the like, and these can be used alone or in combination of two or more.

  As the component (a2), various known polyols can be used without particular limitation. Specifically, aliphatic polyols, aromatic polyols and alicyclic polyols are mentioned. Examples of aliphatic polyols include aliphatic diols such as ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol and trimethylpentanediol; glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1, Aliphatic triols such as 2,4-butanetriol; aliphatic tetraols such as pentaerythritol and diglycerol; and aliphatic hexaols such as dipentaerythritol. Examples of the aromatic polyol include bisphenol A and the like, and examples of the alicyclic polyol include 1,4-cyclohexanediol, hydrogenated bisphenol A and the like. These can be used 1 type or in combination of 2 or more types. Among these, aliphatic polyalcohols are preferable, aliphatic triols and / or aliphatic tetraols are more preferable, and glycerin and pentaerythritol are preferable, from the viewpoint of the compatibility between the modified rosin ester resin and the reactive diluent and the curability. Particularly preferred.

  The use ratio of the component (a1) and the component (a2) is not particularly limited, but from the viewpoint of the compatibility between the modified rosin ester resin and the reactive diluent and the resistance to emulsification, the total equivalent number of hydroxyl groups of the component (a2) The ratio (OH / COOH) of the total number of carboxyl group equivalents (COOH) of the (OH) component and the (a1) component (OH / COOH) is usually about 0.5 to 1.5.

  The method for producing the component (A) is not particularly limited, but the components (a1) and (a2) may be reacted at a temperature of about 200 to 300 ° C. for about 1 to 20 hours in the presence or absence of a known catalyst. good. Further, as the catalyst, various known ones can be used without particular limitation, and, for example, mineral acids such as hydrochloric acid and sulfuric acid, sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid and dodecylbenzenesulfonic acid, oxidation Metal oxides such as zinc oxide, magnesium oxide and calcium oxide, metal hydroxides such as magnesium hydroxide and calcium hydroxide, acetates such as calcium acetate, magnesium acetate and zinc acetate, etc. More than species can be used in combination. The amount of the catalyst used is not particularly limited, but is usually about 0.01 to 5% by weight with respect to 100% by weight in total of the components (a1) and (a2).

  The physical properties of the component (A) thus obtained are not particularly limited, but from the viewpoint of the compatibility and curability of the modified rosin ester resin and the reactive diluent, the weight average molecular weight is usually about 100 to 30,000, and the acid value is usually The softening point is about 80 to 170 ° C., and the hydroxyl value is about 5 to 100 mg KOH / g.

  In addition, as the component (A), commercially available products can also be used without particular limitation. For example, ester gum AA-V, ester gum A, ester gum AT, ester gum H, pencel C, pencel D-125, pencel KK (above, Arakawa Chemical Industries Co., Ltd. product), Harrier Star TF, Neotol 125HK (above, Harima Chemicals Co., Ltd. product), etc. are mentioned.

As the component (B), various known polyvalent carboxylic acid anhydrides can be used without particular limitation. Specifically, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride and benzophenone tetracarboxylic acid dianhydride, etc. Cycloaliphatic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic anhydride, adipic anhydride, succinic anhydride, itaconic anhydride and 1,2,3,4- Aliphatic acid anhydrides, such as tetracarboxylic acid dianhydride, etc. are mentioned, These can be combined 1 type or 2 types or more. Among these, aromatic acid anhydrides, in particular phthalic anhydride, are preferable from the viewpoint of the compatibility between the modified rosin ester resin and the reactive diluent and the curability.

Component (C) is a A Li glycidyl ether, viewpoint et preferred compatibility and curable with denatured rosin ester resin with a reactive diluent.

  The amount of the component (A), the component (B) and the component (C) to be used is not particularly limited, but from the viewpoint of the compatibility between the modified rosin ester resin and the reactive diluent and the curability, the component (A) is usually selected. The amount of each of (B) component and (C) component is 5 to 1000 parts by weight, preferably 10 to 700 parts with respect to 100 parts by weight.

  In the present invention, a glycidyl compound (D2) other than the component (A), the component (B) and the component (C) together with the polyvalent carboxylic acid (D1) (hereinafter referred to as the component (D1)) and the component (C) Hereinafter, at least one selected from the group consisting of (D2) components can be reacted. These can be used for the purpose of adjusting the weight average molecular weight, glass transition point, softening point, degree of branching, etc. of the modified rosin ester resin of the present invention.

  As component (D1), for example, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid and sebacic acid; fumaric acid, maleic acid, itaconic acid, citraconic acid, alkenyl succinic acid, alkadienyl succinic acid and the like Aliphatic unsaturated dicarboxylic acids; aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid; aromatic polyvalent carboxylic acids such as trimellitic acid; 4-methylhexahydrophthalic acid, hexahydrophthalic acid, cyclohexanehexacarboxylic acid and the like Alicyclic polyhydric carboxylic acid is mentioned, and these can combine two or more sorts.

  As the component (D2), for example, bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, butylene oxide, glycidyl phenyl ether, glycidyl triethyl ether, cyclohexene oxide, styrene oxide-1,6- Hexanediol diglycidyl ether, hydroquinone diglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, etc. Two or more of these can be combined.

  Although the usage-amount (solid content conversion) of (D1) and (D2) component is not specifically limited, All are normally about 1-500 weight part with respect to 100 weight part of (A) component.

  The order and conditions for reacting (A) component, (B) component and (C) component, and (D1) component and / or (D2) component as required are not particularly limited, and various known methods can be adopted. . Specifically, after reacting the component (A), the component (B) and the component (C), a method of further reacting the component (D1) and / or the component (D2) may be mentioned. The reaction conditions are, for example, about 100 ° C. to 210 ° C., and the reaction time is about 30 minutes to 5 hours (preferably about 1 to 3 hours). The reaction system may be depressurized to remove the residual monomer, if necessary.

  Moreover, various well-known catalysts can be used in the case of the said reaction. Specifically, for example, triphenylphosphine, 2-methylimidazole, 1-methylimidazole, triethylamine, diphenylamine, sodium hydrogencarbonate, potassium hydrogencarbonate, calcium hydroxide, magnesium hydroxide and the like can be mentioned, and one or two kinds thereof can be mentioned. The above can be combined. The amount thereof to be used is not particularly limited, but generally 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, per 1 part by weight of the component (A).

  Although the detailed mechanism is not clear, the modified rosin ester resin of the present invention thus obtained has the hydroxyl group in the component (A) as the starting point, and the components (B) and (C) repeat alternate ring-opening copolymerization, I speculate that it has grown. In addition, since the modified rosin ester resin of the present invention has a polymerizable double bond and a hydroxyl group in the side chain, it can be used for various applications utilizing these reaction points.

  The modified rosin ester resin of the present invention is not particularly limited, but from the viewpoints of compatibility with a reactive diluent and curability and emulsification resistance when made into an active energy ray-curable resin composition, the acid value is usually 0. .01 to 50 mg KOH / g, hydroxyl value about 1 to 200 mg KOH / g, polymerizable double bond equivalent about 100 to 2000 eq / g, weight average molecular weight about 500 to 100,000, glass transition temperature -20 to 20 It is about 100 ° C.

  The active energy ray-curable resin composition of the present invention contains the modified rosin ester resin of the present invention and a reactive diluent.

  The reactive diluent is not particularly limited, and known ones can be used, and examples thereof include monofunctional acrylates and polyfunctional acrylates.

  Examples of the monofunctional acrylate include 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentanyl (meth) acrylate and cyclohexyl (meth) acrylate And phenol ethylene oxide modified acrylate, nonyl phenol ethylene oxide modified acrylate, dicyclopentenyl (meth) acrylate and the like. These can be used alone or in combination of two or more.

  As the polyfunctional acrylates, various known ones can be used without particular limitation. Specifically, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, Di (meth) acrylates such as neopentyl glycol di (meth) acrylate, ethylene oxide modified di (meth) acrylate of bisphenol A; trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, Propylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) ester ) Compounds having at least three (meth) acryloyl groups such as acrylate and glycerol tri (meth) acrylate; oligomers such as polyurethane poly (meth) acrylate and the above polyester poly (meth) acrylate; and polymerizability such as (meth) acryloyl group Non-copolymer type materials, such as an acrylic resin which has a functional group and multiple hydroxyl groups in a molecule | numerator, etc. are mentioned, These can be used individually or in combination of 2 or more types. Moreover, it can also be used in combination with the said monofunctional acrylate.

  The ratio by weight of the modified rosin ester resin and the reactive diluent is not particularly limited, but in consideration of the balance of compatibility and curability, the former and the latter usually have a ratio of 20/80 to 80/20, preferably 20/80 to 20. It is preferably 60/40.

  Further, the active energy ray-curable resin composition of the present invention may further contain a photopolymerization initiator. Specifically, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenyl Ethan-1-one, 1-cyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy Examples thereof include -2-methyl-1-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone and the like, and two or more types can be combined. Although the usage-amount of a photoinitiator is not specifically limited, Usually, it is about 1 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition of the present invention.

  In addition, the active energy ray-curable resin composition of the present invention may further contain a radical polymerization inhibitor. Specifically, for example, quinone polymerization inhibitors such as methoquinone, hydroquinone, methoxyhydroquinone and benzoquinone, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-t-butyl-4 Alkylphenol-based polymerization inhibitors such as 2,6-dimethylphenol and 2,4,6-tri-t-butylphenol; amine compounds such as alkylated diphenylamine, phenothiazine and 4-hydroxy-2,2,6,6-tetramethylpiperidine Polymerization inhibitors, N-nitrosophenylhydroxylamine ammonium salts, 2,4-dinitrophenol, nitrosamine type polymerization inhibitors such as 2-methyl-N-nitrosoaniline, and the like can be mentioned, and two or more thereof can be combined. The amount of the radical polymerization inhibitor used is not particularly limited, but it is usually about 0.01 to 10 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition of the present invention.

  In the active energy ray-curable resin composition of the present invention, a pigment and a colorant. Additives such as photosensitizers, antioxidants, light stabilizers, and leveling agents can also be contained.

  The active energy ray-curable resin composition of the present invention can be used as a solution of various known organic solvents. Examples of the organic solvent include lower ketones of methyl ethyl ketone and isobutyl ketone, aromatic hydrocarbons such as toluene, alcohols such as ethyl alcohol and propyl alcohol, ethyl acetate, chloroform, dimethylformamide and the like. Can be used alone or in combination of two or more.

  The cured product of the present invention is obtained by curing the active energy ray-curable resin composition of the present invention. For example, the resin composition is applied to various substrates, and active energy such as ultraviolet light or electron beam is applied. Those cured by a wire are included.

  As the substrate, various known materials can be used without particular limitation. Specifically, for example, paper (art paper, cast coated paper, foam paper, PPC paper, high quality coated paper, kraft paper, polyethylene laminated paper, glassine paper, etc.), as well as plastic substrates (polyolefin, polycarbonate, polymethacrylate) And polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin and the like).

Examples of the coating method include offset printing, flexo printing, screen printing bar coater coating, mayer bar coating, air knife coating, and gravure coating. Although the coating amount is not particularly limited, the weight after drying is usually about 0.1 to 30 g / m ² , preferably about 1 to ²⁰ g / m ² .

  As a curing means, an electron beam or an ultraviolet ray is mentioned, for example. As a light source of an ultraviolet-ray, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, UV-LED etc. are mentioned, for example. The amount of light, the arrangement of light sources, and the transfer speed are not particularly limited. For example, when using a high pressure mercury lamp, the transfer speed is usually 5 to 50 m / per one lamp having a light amount of about 80 to 160 W / cm. It is about a minute.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, "parts" means "parts by weight" unless otherwise noted.

  The following physical properties of the modified resins of Production Examples 1 and 2 were measured.

<Acid number>
It measured according to JIS K 5601.

<Hydroxyl number>
It measured according to JIS K 0070.

<Polymerizable double bond equivalent>
The polymerizable double bond equivalent is a value representing the mass (g) of the modified rosin ester resin per equivalent (eq) of the polymerizable double bond.

<Weight average molecular weight>
It measured by the polystyrene calibration curve using gel permeation chromatography (GPC) (made by Tosoh Co., Ltd.).

<Glass transition point>
The temperature was measured at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc.).

<Production example of rosin ester>
100 parts of rosin was charged into a reaction vessel equipped with a stirrer, a cooling pipe and a nitrogen introducing pipe and dissolved, then 14 parts of pentaerythritol and 1 part of glycerin were added and reacted at 250 ° C to 280 ° C for 5 hours. Thus, a rosin ester (A-1) having a weight average molecular weight of 840, an acid value of 22.7 mg KOH / g, a hydroxyl value of 40 mg KOH / g and a softening point of 101.0 ° C. was obtained.

<Synthesis of Modified Rosin Ester Resin>
Production Example 1
100 parts of the rosin esters (A-1) obtained as described above, 500 parts of phthalic anhydride, 500 parts of allyl glycidyl ether are charged in a reaction vessel equipped with a stirrer, a cooling pipe and a nitrogen introducing pipe, 140 ° C. The temperature rose to the end. Then, 0.1 part of 2-methylimidazole was added and allowed to react at 150 ° C. for 3 hours. Thereafter, the pressure was reduced to -0.08 Pa · s. Thus, a modified rosin ester resin having an acid value of 0.3 mg KOH / g, a hydroxyl value of 22 mg KOH / g, a polymerizable double bond equivalent of 251 g / eq, a weight average molecular weight of 9,700 and a glass transition temperature of 9.5 ° C was obtained.

Production Example 2
100 parts of rosin ester (A-1), 40 parts of phthalic anhydride and 40 parts of allyl glycidyl ether were charged into a reaction vessel equipped with a stirrer, a cooling pipe and a nitrogen introducing pipe, and the temperature was raised to 140 ° C. Then, 0.1 part of triphenyl phosphine was added and allowed to react at 150 ° C. for 2 hours. Thereafter, the pressure was reduced to -0.08 Pa · s. Thus, a modified rosin ester resin having an acid value of 0.2 mg KOH / g, a hydroxyl value of 59 mg KOH / g, a polymerizable double bond equivalent of 514 g / eq, a weight average molecular weight of 1,700 and a glass transition temperature of 11.6 ° C. was obtained.

<Preparation of Active Energy Ray-Curable Resin Composition>
Example 1
In a reaction vessel equipped with a stirrer and a cooling pipe, 46.5 parts of the modified rosin ester resin of Production Example 1, 53.4 parts of dipentaerythritol polyacrylate (product name: Beam set 700, manufactured by Arakawa Chemical Industries, Ltd.), Charge 0.1 parts of methoquinone (Seiko Chemical Co., Ltd.) and 0.05 parts of Q-1301 (Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor, stir at 90 to 95 ° C. for 3 hours, and then activate energy A line-curable resin composition was obtained. In addition, since the insoluble matter was not confirmed for the external appearance of this composition, compatibility was made into (circle).

Example 2
Into a reaction container equipped with a stirrer and a cooling pipe, 49.0 parts of modified rosin ester resin of Production Example 2, 50.8 parts of Beam Set 700, 0.1 parts of methoquinone and 0.05 parts of Q-1301 are charged, The mixture was stirred at 95 ° C. for 3 hours to obtain an active energy ray-curable resin composition. In addition, since the insoluble matter was not confirmed for the external appearance of this composition, compatibility was made into (circle).

Comparative Example 1
In a reaction vessel equipped with a stirrer and a condenser, 25.0 parts of diallyl phthalate resin (product name: Daisodapu A, manufactured by Daiso Corporation), 75.0 parts of beam set 700, methoquinone as a polymerization inhibitor (SEIKO CHEMICAL 0.1 part and Q-1301 0.05 part were prepared, and it stirred at 90-95 degreeC for 3 hours, and obtained the active energy ray curable resin composition. In addition, since the insoluble matter was not confirmed for the external appearance of this composition, compatibility was made into (circle).

<Preparation of a composition for producing a cured product>
A composition for producing a cured product by thoroughly mixing 5.0 parts of the active energy ray-curable resin composition obtained in Examples and Comparative Examples, 0.25 parts of Irgacure 907 (manufactured by BASF), and 5.5 parts of methyl ethyl ketone Was prepared.

<Preparation of cured product>
The composition for producing a cured product was applied to an untreated PET film (Lumirror (registered trademark) 75T60) using a bar coater # 4, and heated at 80 ° C. for 30 seconds in a forward air dryer to remove methyl ethyl ketone. Then, it irradiated with an ultraviolet ray with an ultraviolet irradiation machine (80 W / cm, irradiation distance 25 cm, conveyor speed 50 m / min), and hardened | cured material was produced.

<Performance evaluation>
The following tests were done about each composition of an example and a comparative example.

<Compatibility>
The appearance of each composition of the examples and comparative examples was observed, and the compatibility was evaluated based on the following criteria.
○ · · · · · · · · · · · · · · · · · · insolubles can not be confirmed × · · insolubles can be confirmed

<Curing speed>
The dose required for producing a cured product is shown in Table 1. Even if the amount of irradiation is small, those which are cured have good curability.

Emulsification resistance
Ten parts of the active energy ray-curable resin composition of Example 1 were dissolved in 20 parts of xylene. Next, 7.5 parts of the solution is placed in a glass test tube (inner diameter 18 mm × height 180 mm, trade name: PYREX (registered trademark) TEST 18 manufactured by Iwaki Glass Co., Ltd.), and then 7.5 parts of ultrapure water is placed. I plugged it. After shaking this up and down 20 times and making it emulsify, it left still and time until an aqueous layer and an organic layer isolate | separate was measured. The results are shown in Table 1. The shorter the separation time, the better the emulsification resistance. With respect to the active energy ray-curable resin compositions of Example 2 and Comparative Example 1, the emulsification resistance was evaluated in the same manner.

Claims (12)

Modified rosin ester resin obtained by reacting rosin esters (A), polyvalent carboxylic acid anhydride (B) and allyl glycidyl ether (C) which are reaction products of rosins (a1) and polyols (a2) . The modified rosin ester resin according to claim 1, wherein the component (a2) is an aliphatic polyol. The modified rosin ester resin according to claim 1 or 2, wherein the component (a2) is an aliphatic triol and / or an aliphatic tetraol. The modified rosin ester resin according to any one of claims 1 to 3, wherein the component (B) is phthalic anhydride. The modified rosin ester resin according to any one of claims 1 to 4 , which further comprises at least one selected from the group consisting of polyhydric carboxylic acids (D1) and glycidyl compounds (D2) other than component (C). The modified rosin ester resin according to any one of claims 1 to 5 , which has an acid value of 0.01 to 50 mg KOH / g. The modified rosin ester resin according to any one of claims 1 to 6 , which has a hydroxyl value of 1 to 200 mg KOH / g. The modified rosin ester resin according to any one of claims 1 to 7 , which has a polymerizable double bond equivalent of 100 to 2,000 g / eq. The modified rosin ester resin according to any one of claims 1 to 8 , which has a weight average molecular weight of 500 to 100,000. The modified rosin ester resin according to any one of claims 1 to 9 , which has a glass transition temperature of -20 to 100 ° C. An active energy ray-curable resin composition comprising the modified rosin ester resin according to any one of claims 1 to 10 and a reactive diluent. Claim 1 1 of the active energy ray curable resin composition cured product obtained by curing the.