JP6160870B2 - Hydroxyl group-containing polymerizable copolymer, method for producing the same, active energy ray-curable resin composition, and cured product - Google Patents

Description

  The present invention relates to a hydroxyl group-containing polymerizable copolymer having both a hydroxyl group and a polymerizable carbon-carbon double bond in the molecule, a method for producing the same, an active energy ray-curable resin composition containing the copolymer, and a method thereof. It relates to a cured product.

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

  As the reactive diluent, polyfunctional acrylates such as dipentaerythritol hexaacrylate and trimethylolpropane tetraacrylate are widely used because of the excellent curability and film hardness of the active energy ray-curable resin composition. . 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, diallyl phthalate resin is easily miscible with water, and an active energy ray-curable resin composition containing this resin has poor 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 drawback that it cannot be further modified because it does not have a functional group such as a hydroxyl group in the molecule.

JP 2000-80326 A (paragraph [0003] etc.) JP2010-1000082 (paragraph [0003] etc.)

  An object of the present invention is to provide a copolymer that can be substituted for diallyl phthalate resin. That is, since it has a hydroxyl group, it can be modified in various ways, and is compatible with various reactive diluents in the same manner as diallyl phthalate resin, and also contains an active energy ray-curable resin composition containing the reactive diluent. The main object is to provide a novel copolymer that imparts excellent curability and emulsification resistance.

  The present invention further provides a novel active energy ray-curable resin composition that exhibits good curability in a film state and is excellent in emulsification resistance, and a cured product obtained from the resin composition. It becomes the problem to become.

  As a result of intensive studies, the present inventor can replace diallyl phthalate resin with a hydroxyl group-containing polymerizable copolymer obtained by polymerizing various cyclic acid anhydrides and radically polymerizable glycidyl compounds in the presence of a predetermined catalyst. The present inventors have found that a sufficient copolymer can be sufficient and have completed the present invention.

  That is, the present invention is obtained by polymerizing a cyclic acid anhydride (A) and a glycidyl compound (B) having a polymerizable carbon-carbon double bond in the molecule in the presence of triphenylphosphine (C). Hydroxyl group-containing polymerizable copolymer; polymerization reaction of cyclic acid anhydride (A) and glycidyl compound (B) having a polymerizable carbon-carbon double bond in the molecule in the presence of triphenylphosphine (C) A method for producing a hydroxyl group-containing polymerizable copolymer; an active energy ray-curable resin composition containing the copolymer and a polyfunctional acrylate; and curing the active energy ray-curable resin composition. It relates to a cured product.

  The copolymer 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 the active energy ray-curable resin composition. Moreover, the emulsification resistance of the active energy ray-curable resin composition can be improved as compared with diallyl phthalate resin. Moreover, since the copolymer of this invention has a hydroxyl group, the further modification | denaturation of resin using it is possible.

  Since the hydroxyl group-containing polymerizable copolymer of the present invention has a hydroxyl group, it can be variously modified. Moreover, since it is well compatible with various reactive diluents as in the case of diallyl phthalate resin, an active energy ray-curable resin composition having no insoluble matter and excellent in curability and emulsification resistance is provided. The copolymer can be used in conventional applications for diallyl phthalate resins, such as binder resins for UV curable inks, molding materials and decorative plates. Moreover, since this copolymer has a polymerizable carbon-carbon double bond and a hydroxyl group in the molecule, it can be used for other applications such as a coating agent by using them.

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

  The hydroxyl group-containing polymerizable copolymer according to the present invention (hereinafter sometimes simply referred to as a copolymer) has a cyclic acid anhydride (A) (hereinafter referred to as component (A)) and a polymerizable within the molecule. A glycidyl compound (B) having a carbon-carbon double bond (hereinafter referred to as component (B)) is polymerized (opened) in the presence of triphenylphosphine (C) (hereinafter referred to as component (C)). It is a high molecular weight substance having both a hydroxyl group and a polymerizable carbon-carbon double bond in the molecule, which is obtained by a ring copolymerization reaction).

  As the component (A), various known materials can be used without particular limitation. Specifically, for example, aromatic acids such as phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride Anhydrides, alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, glutaric anhydride, pyromellitic anhydride, adipic anhydride, succinic anhydride, itaconic anhydride and butane-1, Aliphatic acid anhydrides such as 2,3,4-tetracarboxylic dianhydride, polymers made from these acid anhydride compounds (maleic anhydride homopolymer, maleic anhydride-vinyl acetate copolymer, Maleic anhydride-styrene copolymer, maleic anhydride-acrylonitrile copolymer, etc.), which can be used alone or in combination of two or more. That. Of these, aromatic acid anhydrides, particularly phthalic anhydride, are preferred from the viewpoints of compatibility with polyfunctional acrylates and curability.

  As the component (B), various known compounds can be used without particular limitation. Specific examples include vinyl group-containing glycidyl compounds such as allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate, and these can be used alone or in combination of two or more. Among these, allyl glycidyl ether is preferable from the viewpoint of compatibility with polyfunctional acrylate and curability.

  The use weight ratio of the component (A) and the component (B) is not particularly limited, but considering the curability and emulsification resistance of the active energy ray-curable composition of the present invention, the former: latter molar ratio is usually It is about 1: 1 to 1: 2.

  The component (C) is a catalyst used for the reaction of the component (A) and the component (B). In the present invention, triphenylphosphine is used particularly from the viewpoint of emulsification resistance. Moreover, the usage-amount is although it does not restrict | limit, It is 0.01-1.00 weight part with respect to 100 weight part of (A) component, Preferably it is 0.30-0.50 weight part.

  In the present invention, together with the component (C), other catalysts include, for example, 2-methylimidazole, 1-methylimidazole, triethylamine, diphenylamine, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, carbonate Sodium hydrogen, potassium hydrogen carbonate, zinc oxide, zinc octylate and the like can be used in combination. The emulsification resistance of the active energy ray-curable resin composition using the containing polymerizable copolymer tends to be insufficient.

  In addition to the components (A) and (B), the copolymer of the present invention further comprises polyol (D1) (hereinafter referred to as (D1) component), rosin (D2) (hereinafter referred to as (D2) component). ), Polycarboxylic acid (D3) (hereinafter referred to as (D3) component), and glycidyl compound (D4) (hereinafter referred to as (D4) component) having no carbon-carbon double bond in the molecule. At least one selected from the group can be used as a reaction component. These are optional components used for the purpose of adjusting the molecular weight, glass transition point, degree of branching, etc. of the copolymer of the present invention.

  As the component (D1), various known compounds can be used without particular limitation. Specifically, for example, diols such as ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, trimethylpentanediol, bisphenol A and hydrogenated bisphenol A (excluding rosin diol described later) ), Triols such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol and 1,2,4-butanetriol, tetraols such as pentaerythritol and diglycerol, and dipenta Examples include hexaols such as erythritol, and these can be used alone or in combination of two or more.

  As the component (D2) (excluding those forming an anhydrous ring), various known ones can be used without particular limitation. Specifically, for example, natural rosin (gum rosin, tall oil rosin, wood rosin, etc.), natural rosin stabilized by various known methods (hydrogenated rosin, disproportionated rosin, etc.), natural rosin and stabilized Polymerized rosins obtained by treating the treated rosin by various known methods, Diels-Alder reaction products of these rosins with α, β unsaturated carboxylic acids (maleated rosin, maleated rosin hydride, acrylated rosin, acrylated rosin) Hydrides, etc.), rosin diol (see JP-A-5-155972) obtained by reacting the natural rosin or the stabilized rosin with a diepoxy compound such that the diepoxy compound is 2: 1. These can be used alone or in combination of two or more.

  As the component (D3) (excluding those forming an anhydrous ring), various known ones can be used without particular limitation. Specific examples include succinic acid, fumaric acid, maleic acid, sebacic acid, isophthalic acid, terephthalic acid, trimellitic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, and cyclohexanehexacarboxylic acid. These can be used alone or in combination of two or more.

  As the component (D4), various known compounds can be used without particular limitation. Specifically, for example, butylene oxide, glycidyl phenyl ether, glycidyl tolyl ether, cyclohexene oxide, styrene oxide, 1,6-hexanediol diglycidyl ether, adipic acid diglycidyl ester, terephthalic acid glycidyl ester, glycerol glycidyl ether, hydroquinone Examples include diglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol triglycidyl ether, trimethylolpropane polyglycidyl ether, and the like. A combination of the above can be used.

  Although the usage-amount of (D1) component-(D4) component is not specifically limited, Usually, it is about 0.1-50 mol% with respect to the total mol of (A) component and (B) component.

  The conditions for reacting the components (A) and (B) and the components (D1), (D2), (D3) and (D4) used as necessary are not particularly limited, and various known methods are employed. it can. Specifically, these components are usually reacted in the presence of component (C) at about 100 ° C to 210 ° C (preferably 140 to 160 ° C) for about 30 minutes to 5 hours (preferably 1 hour to 3 hours). Just do it. If necessary, the residual monomer may be removed by reducing the pressure of the reaction system.

  The physical properties of the copolymer of the present invention thus obtained are not particularly limited, but are compatible with a reactive diluent (polyfunctional acrylate compound), curability and emulsification resistance when used as an active energy ray curable resin composition. From the viewpoint of safety, the hydroxyl value is usually about 1 to 200 mgKOH / g, the acid value is about 0 to 200 mgKOH / g, the weight average molecular weight is about 500 to 100,000, and the glass transition temperature is about -30 to 100 ° C. .

  The active energy ray-curable resin composition of the present invention is a composition containing the copolymer of the present invention and polyfunctional acrylates which are reactive diluents.

  Various known acrylates 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) ) Acrylates, such as glycerol tri (meth) acrylate, and compounds having at least three (meth) acryloyl groups. An oligomer such as polyurethane poly (meth) acrylate and polyester poly (meth) acrylate; a non-copolymer type material such as an acrylic resin having a plurality of polymerizable functional groups such as (meth) acryloyl groups and hydroxyl groups in the molecule These can be used alone or in combination of two or more. In addition, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Mono (meth) acrylates such as isobornyl (meth) acrylate can also be used in combination.

  The ratio of the copolymer of the present invention and the polyfunctional acrylates is not particularly limited, but considering the balance of compatibility, curability and emulsification resistance of the composition, the former / the latter is usually 20/80 to 80 / It is preferably about 20.

  In addition, when the active energy ray-curable resin composition of the present invention is cured with ultraviolet rays, a photopolymerization initiator can be further included. Examples of the photopolymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl luphenyl ketone, and 2,2-dimethoxy-1,2. -Diphenylethane-1-one, 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, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, etc. are mentioned, and these are used alone or in combination of two or more. Can be used. The amount of the photopolymerization initiator is usually 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.

  Moreover, 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 methyl isobutyl ketone, aromatic hydrocarbons such as toluene, alcohols such as ethyl alcohol and propyl alcohol, ethyl acetate, chloroform, dimethylformamide, and the like. The amount used is a range in which the solid content weight of the active energy ray-curable resin composition of the present invention is usually about 10 to 50% by weight.

  The active energy ray-curable resin composition of the present invention can also contain additives such as a polymerization inhibitor, a pigment, a colorant, a photosensitizer, an antioxidant, a light stabilizer, and a leveling agent. .

  The cured product of the present invention is obtained by applying the active energy ray-curable resin composition of the present invention to various substrates and curing it with active energy rays such as ultraviolet rays and electron beams.

  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.) and plastic substrates (polyolefin, polycarbonate, polymethacrylate) Polyester, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, and the like.

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

  Examples of the ultraviolet light source include a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, and a UV-LED. The amount of light, the light source arrangement, and the conveyance speed are not particularly limited. For example, when a high-pressure mercury lamp is used, the conveyance speed is usually 5 to 50 m / min for one lamp having a light amount of about 80 to 160 W / cm. About minutes.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Synthesis of copolymer>
Production Example 1
100.0 parts of phthalic anhydride and 115.6 parts of allyl glycidyl ether were charged into a reaction vessel equipped with a stirrer, a cooling tube, and a nitrogen introduction tube, and the temperature was raised to 140 ° C. Then, 0.4 part of triphenylphosphine was added and stirred at 150 ° C. for 2 hours and 30 minutes. Thereafter, the temperature was raised to 210 ° C. while reducing the pressure at −0.08 MPa for 45 minutes, and the contents were taken out. Thus, a solid hydroxyl group-containing polymerizable copolymer having an acid value of 0.4 mgKOH / g, a hydroxyl value of 9.2 mgKOH / g, a weight average molecular weight of 37,000, and a glass transition point of 7 ° C. was obtained.

Production Example 2
Charge 100.0 parts of phthalic anhydride, 115.6 parts of allyl glycidyl ether, and 10 parts of hydrogenated maleic anhydride rosin (manufactured by Arakawa Chemical Industries, Ltd.) to the same reaction vessel as in Production Example 1 and raise the temperature to 140 ° C. did. Next, 0.4 part of triphenylphosphine was added and stirred at 150 ° C. for 1 hour and 20 minutes. Thereafter, the temperature was raised to 210 ° C. while reducing the pressure at −0.08 MPa for 30 minutes, and the contents were taken out. Thus, a solid hydroxyl group-containing polymerizable copolymer having an acid value of 4.1 mg KOH / g, a hydroxyl value of 18.0 mg KOH / g, a weight average molecular weight of 11,000, and a glass transition point of 10 ° C. was obtained.

Production Example 3
In a reaction vessel similar to Production Example 1, 100.0 parts of phthalic anhydride, 115.6 parts of allyl glycidyl ether, and 10 parts of rosin diol (product name: Pine Crystal D-6011, manufactured by Arakawa Chemical Industries, Ltd.) The temperature was raised to 140 ° C. Next, 0.4 part of triphenylphosphine was added and stirred at 150 ° C. for 1 hour and 20 minutes. Thereafter, the temperature was raised to 210 ° C. while reducing the pressure at −0.08 MPa for 30 minutes, and the contents were taken out. Thus, a solid hydroxyl group-containing polymerizable copolymer having an acid value of 0.5 mgKOH / g, a hydroxyl value of 16.8 mgKOH / g, a weight average molecular weight of 11,000 and a glass transition point of 14 ° C. was obtained.

Production Example 4
Charge 100.0 parts of phthalic anhydride, 77.1 parts of allyl glycidyl ether, 12.6 parts of ethylene glycol, and 1.8 parts of triphenylphosphine to the same reaction vessel as in Production Example 1, and stir at 100 ° C. for 3 hours. The contents were taken out. Thus, a varnish-like hydroxyl group-containing polymerizable copolymer having an acid value of 8.5 mgKOH / g, a hydroxyl value of 106.6 mgKOH / g, a weight average molecular weight of 1,100, and a glass transition point of −16 ° C. was obtained.

Comparative production example 1
In a reaction vessel similar to Production Example 1, 100.0 parts of phthalic anhydride, 77.1 parts of allyl glycidyl ether, 12.6 parts of ethylene glycol and 0.4 parts of triethanolamine were added and stirred at 100 ° C. for 8 hours. The contents were taken out. Thus, a varnish-like hydroxyl group-containing polymerizable copolymer having an acid value of 35.7 mgKOH / g, a hydroxyl value of 94.2 mgKOH / g, a weight average molecular weight of 1,000, and a glass transition point of −16 ° C. was obtained.

Comparative production example 2
A reaction vessel similar to Production Example 1 was charged with 100.0 parts of phthalic anhydride, 77.1 parts of allyl glycidyl ether, 12.6 parts of ethylene glycol, and 0.9 parts of N, N-dimethylbenzylamine. The contents were removed by stirring for a period of time. Thus, a varnish-like hydroxyl group-containing polymerizable copolymer having an acid value of 17.9 mgKOH / g, a hydroxyl value of 110.7 mgKOH / g, a weight average molecular weight of 1,100, and a glass transition point of −16 ° C. was obtained.

Comparative production example 3
In the same reaction vessel as in Production Example 1, 100.0 parts of phthalic anhydride and 115.6 parts of allyl glycidyl ether were charged, and the temperature was raised to 140 ° C. Next, 0.1 part of sodium hydroxide was added and stirred at 150 ° C. for 1 hour and 20 minutes. However, the reaction system gelled and was not used for later evaluation.

<Preparation of active energy ray-curable resin composition>
Example 1
40.5 parts of the copolymer produced in Production Example 1 in a reaction vessel equipped with a stirrer and a cooling tube, 59.4 parts of dipentaerythritol hexaacrylate (product name: Beam Set 700, manufactured by Arakawa Chemical Industries, Ltd.) In addition, 0.09 part of methoquinone (manufactured by Seiko Chemical Co., Ltd.) is used as a polymerization inhibitor, and 0.05 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) is charged as a polymerization inhibitor at 90 to 95 ° C. The mixture was stirred for 3 hours to obtain an active energy ray-curable resin composition 1. In addition, the external appearance of this composition 1 was transparent, and compatibility was favorable. Next, 5.00 parts of the composition 1, 0.25 parts of Irgacure 907 (manufactured by Ciba Japan Co., Ltd.) as a photopolymerization initiator, and 5.50 parts of methyl ethyl ketone (MEK) as a diluent solvent are mixed well. Then, a composition 1 ′ for preparing a cured film was prepared.

Example 2
In the same reaction vessel as in Example 1, 50.0 parts of the copolymer produced in Production Example 2, 49.9 parts of Beam Set 700, 0.09 part of Metoquinone, and 0.05 part of Q-1301 were charged. It stirred at 90-95 degreeC for 3 hours, and the active energy ray hardening-type resin composition 2 was obtained. Next, 5.00 parts of the composition 2, 0.25 parts of Irgacure 907, and 5.50 parts of MEK were mixed well to prepare a composition 2 ′ for forming a cured film.

Example 3
In the same reaction vessel as in Example 1, 45.5 parts of the copolymer produced in Production Example 3, 54.4 parts of beam set 700, 0.09 part of methoquinone, and 0.05 part of Q-1301 were charged. The mixture was stirred at 90 to 95 ° C. for 3 hours to obtain an active energy ray-curable resin composition 3. Next, 5.00 parts of the composition 3, 0.25 parts of Irgacure 907, and 5.50 parts of MEK were mixed well to prepare a composition 3 ′ for forming a cured film.

Example 4
In the same reaction vessel as in Example 1, 26.4 parts of the copolymer produced in Production Example 4, 73.5 parts of beam set 700, 0.10 parts of methoquinone, and 0.05 parts of Q-1301 were charged. It stirred at 90-95 degreeC for 3 hours, and the active energy ray hardening-type resin composition 4 was obtained. Subsequently, 5.00 parts of the composition 4, 0.25 parts of Irgacure 907, and 5.50 parts of MEK were mixed well to prepare a composition 4 ′ for forming a cured film.

Comparative Example 1
In a reaction vessel similar to that in Example 1, 26.4 parts of diallyl phthalate resin (product name: Daiso Dup A, manufactured by Daiso Chemical Co., Ltd.), 73.5 parts of beam set 700, 0.10 parts of methoquinone, and Q 0.051 part of −1301 was added and stirred at 90 to 95 ° C. for 3 hours to obtain an active energy ray-curable resin composition (A). Next, 5.00 parts of the composition (A), 0.25 parts of Irgacure 907, and 5.50 parts of MEK were mixed well to prepare a composition (A ′) for forming a cured film.

Comparative Example 2
The same reaction vessel as in Example 1 was charged with 26.4 parts of the copolymer obtained in Comparative Production Example 1, 73.5 parts of beam set 700, 0.10 parts of methoquinone, and 0.05 parts of Q-1301. The mixture was stirred at 90 to 95 ° C. for 3 hours to obtain an active energy ray-curable resin composition (I). Next, 5.00 parts of the composition (I), 0.25 parts of Irgacure 907, and 5.50 parts of MEK were mixed well to prepare a composition (I ′) for forming a cured film.

Comparative Example 3
The same reaction vessel as in Example 1 was charged with 26.4 parts of the copolymer obtained in Comparative Production Example 2, 73.5 parts of beam set 700, 0.10 parts of methoquinone, and 0.05 parts of Q-1301. The mixture was stirred at 90 to 95 ° C. for 3 hours to obtain an active energy ray-curable resin composition (U). Next, 5.00 parts of the composition (U), 0.25 parts of Irgacure 907, and 5.50 parts of MEK were mixed well to prepare a composition (U ′) for forming a cured film.

<Preparation of cured film>
The composition 1 ′ obtained in Example 1 was applied to an untreated PET film (Lumirror 75T60) using a bar coater # 4 and heated at 80 ° C. for 30 seconds in a normal air dryer to remove MEK. Thereafter, ultraviolet rays were irradiated with an ultraviolet irradiator (120 W / cm, irradiation distance 25 cm, conveyor speed 50 m / min) to produce a cured film. A cured film was prepared in the same manner for the compositions 2 ′, 3 ′ and 4 ′ and the compositions (a ′), (b ′) and (c ′).

<Performance evaluation>
The following tests were conducted on the compositions of Examples and Comparative Examples.

<Compatibility>
The appearances of the compositions of Examples and Comparative Examples were visually observed, and the compatibility was evaluated according to the following criteria.
○ ・ ・ ・ Insoluble matter cannot be confirmed × ・ ・ ・ Insoluble matter can be confirmed

<Curing speed>
Table 1 shows the dose required for producing the cured film. Even if there is little irradiation amount, what is hardened | cured has favorable curability.

<Emulsification resistance>
Ten parts of composition 1 according to Example 1 were dissolved in 20 parts of xylene. Next, 7.5 parts of the solution was placed in a glass test tube (inner diameter: 18 mm × height: 180 mm, trade name: PYREX TEST18) manufactured by Iwaki Glass Co., Ltd., and 7.5 parts of distilled water was further put into the stopper. Next, this was shaken up and down 20 times, emulsified, allowed to stand still, and the time until the water layer and the organic layer were separated was measured. The results are shown in Table 1. The shorter the separation time, the better the emulsification resistance. The emulsification resistance was similarly evaluated for the compositions 2, 3 and 4 and the compositions (a), (b) and (c).

Claims (6)

Phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Glutaric anhydride, pyromellitic anhydride, adipic anhydride, succinic anhydride, itaconic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, maleic anhydride homopolymer, maleic anhydride-acetic acid One or more cyclic acid anhydrides (A) selected from the group consisting of vinyl copolymers, maleic anhydride-styrene copolymers, and maleic anhydride-acrylonitrile copolymers , allyl glycidyl ether, glycidyl acrylate and polymerizable carbon in one or more molecules selected from the group consisting of glycidyl methacrylate - carbon double Glycidyl compounds having an engagement (B) and the obtained by polymerization reaction in the presence of triphenylphosphine (C), hydroxyl group-containing polymerizable copolymer. The hydroxyl group-containing polymerizable copolymer according to claim 1, wherein the component (A) is phthalic anhydride and the component (B) is allyl glycidyl ether. Furthermore, at least one selected from the group consisting of polyol (D1), rosins (D2), polycarboxylic acid (D3) and glycidyl compound (D4) having no polymerizable carbon-carbon double bond in the molecule is a reaction component. The hydroxyl group-containing polymerizable copolymer according to claim 1 or 2. Hydroxyl group-containing, characterized in that a cyclic acid anhydride (A) and a glycidyl compound (B) having a polymerizable carbon-carbon double bond in the molecule are polymerized in the presence of triphenylphosphine (C) A method for producing a polymerizable copolymer. An active energy ray-curable resin composition comprising the copolymer according to any one of claims 1 to 3 or the hydroxyl group-containing polymerizable copolymer obtained by the production method according to claim 4 and a polyfunctional acrylate. A cured product obtained by curing the active energy ray-curable resin composition according to claim 5.