JP5428686B2 - Active energy ray-curable resin composition - Google Patents

Description

  The present invention has excellent storage stability, forms a tack-free coating film before irradiation with active energy rays, has excellent hardness and scratch resistance after irradiation with active energy rays, and is difficult to cure and shrink (hereinafter referred to as low curing) The present invention relates to an active energy ray-curable resin composition from which a cured film may be abbreviated. Specifically, paint materials for plastics, wood, glass, metal, etc., protective layers for various film bases, protective layers for transfer materials, flat panel displays, electronic substrates and optical materials such as photoresists, active energy ray curable type The present invention relates to an active energy ray-curable resin composition that can be used as a resin for ink.

  In recent years, as a method for forming a protective layer by coating the surface of a molded article by irradiation with active energy rays such as ultraviolet rays and electron beams, there are, for example, a coating method and a transfer method, and an active energy ray curable resin used as a protective layer. Active development of the composition is underway. However, since many active energy ray-curable resin compositions are low molecular weight compounds collectively referred to as oligomers such as epoxy acrylate, urethane acrylate, and polyester acrylate, the coating before photocuring by irradiation with active energy rays It is in an undried state having a liquid state or a tack, and dust or dust may adhere to the coating film before irradiation with active energy rays to cause poor appearance, resulting in deterioration of production efficiency. Furthermore, since the molecular weight is low, volume shrinkage tends to occur during active energy ray curing, the cured film cures and shrinks, and the coating film of the coated material is cracked or applied to the film substrate. Causes problems such as curling.

In order to solve these problems, a relatively high molecular weight design is possible, and an active energy ray-curable resin composition having low curing shrinkage has been developed as a compound called acrylic acrylate (for example, Patent Documents 1, 2, and 3). However, in order to obtain tack-free properties and low cure shrinkage, higher molecular weight is required. However, there is a problem that storage stability deteriorates and gelation occurs during synthesis. Even if high molecular weight can be achieved, the introduction amount of acryloyl group or methacryloyl group, which is a functional group that is cured by irradiation of active energy rays, is limited in order to avoid problems of storage stability and gelation. There was a problem that the hardness and scratch resistance of the coating film after irradiation with active energy rays were inferior.

Japanese Patent Laid-Open No. 9-290491 WO2004 / 039856 JP 2008-69303 A

The present invention has a high molecular weight and excellent storage stability, forms a tack-free coating surface before irradiation with active energy rays, has excellent hardness and scratch resistance after irradiation with active energy rays, and has low cure shrinkage. It is a technical problem to provide an active energy ray-curable resin composition for obtaining a cured resin film.

As a result of intensive studies, the inventors of the present invention have added a α, β-unsaturated carboxylic acid to a polymer of an ethylenically unsaturated compound containing an epoxy group in the molecule, and has a (meth) acryl equivalent of 200. An active energy ray-curable resin composition obtained by containing a reaction product having a weight average molecular weight of 50,000 to 200,000 and a saturated organic monocarboxylic acid component is high molecular weight and stable in storage To form a tack-free coating surface before irradiation with active energy rays, and to obtain a cured film having excellent hardness and scratch resistance after irradiation with active energy rays and having low curing shrinkage. The headline has led to the present invention.

That is, the present invention
(1) An (meth) acrylic equivalent of 200 to 500 g / eq obtained by adding an α, β-unsaturated carboxylic acid (B) to a polymer (A) of an ethylenically unsaturated compound containing an epoxy group in the molecule. An active energy ray-curable resin composition (Invention 1), comprising a reaction product (C) having a weight average molecular weight of 50,000 to 200,000 and a saturated organic monocarboxylic acid component (D),
(2) The active energy ray-curable resin composition according to (1) above, containing 2.5 parts by mass or less of the saturated organic monocarboxylic acid component (D) with respect to 100 parts by mass of the reaction product (C) (Invention 2) ),
(3) The active energy ray-curable resin composition according to (1) or (2) (Invention 3), wherein the saturated organic monocarboxylic acid component (D) is at least one selected from formic acid, acetic acid, and propionic acid.
I will provide a.

According to the present invention, an active energy ray-curable resin composition having a high molecular weight and excellent storage stability can be provided. In addition, the active energy ray-curable resin composition according to the present invention has a high molecular weight and an acryloyl group that is a functional group that is cured by irradiation with an active energy ray, compared to a conventional general active energy ray-curable resin. Since the amount of methacryloyl group is large, a tack-free coating film is formed before irradiation with active energy rays, and a cured film having excellent hardness and scratch resistance and low curing shrinkage is obtained after irradiation with active energy rays. I can do it.

The configuration of the present invention will be described in more detail as follows.
<Polymer (A) of ethylenically unsaturated compound containing epoxy group in molecule>
The polymer (A) of an ethylenically unsaturated compound containing an epoxy group in the molecule used in the present invention is not particularly limited as long as it is a polymer of an ethylenically unsaturated compound containing an epoxy group. Can be used. As an ethylenically unsaturated compound-based polymer containing an epoxy group, for example, a copolymer of an ethylenically unsaturated compound containing an epoxy group or an ethylenically unsaturated compound containing an epoxy group can be polymerized. The copolymer which consists of an ethylenically unsaturated compound which does not contain an epoxy group is mentioned.

Examples of the ethylenically unsaturated compound containing an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexyl (meth) acrylate, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types. In particular, glycidyl methacrylate is preferable because it is easily available.

Examples of the ethylenically unsaturated compound that does not contain a polymerizable epoxy group include, for example, methyl acrylate, methyl methacrylate, and ethyl acrylate, which are esters with linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms. , Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-methacrylate -Butyl, 2-butyl acrylate, 2-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-acrylate -Octyl, n-octyl methacrylate, (Meth) acrylate monomers such as n-dodecyl crylate, n-dodecyl methacrylate, n-octadecyl acrylate, n-octadecyl methacrylate, styrene monomers such as styrene, α-methylstyrene, divinylbenzene, ethylene Olefins such as propylene and butene, alkadienes such as butadiene and isoprene, vinyl esters such as vinyl acetate and vinyl propionate, isobutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and the like. In addition to these monomers, acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylamide, diester of unsaturated dibasic acid, and the like can also be used. These may be used individually by 1 type, and may be used in combination of 2 or more types. In particular, the (meth) acrylic acid ester monomer having 1 to 8 carbon atoms and the styrene monomer have good copolymerizability with an ethylenically unsaturated compound containing an epoxy group, and the active energy ray-curable resin composition is tacky. It is preferable for forming a free coating film surface.

The amount of the ethylenically unsaturated compound that does not contain an epoxy group is the total amount of the ethylenically unsaturated compound that contains an epoxy group and the ethylenically unsaturated compound that does not contain an epoxy group in order not to inhibit the effects of the present invention. When it is 100 parts by mass, it is preferably 65 parts by mass or less. When the amount used is more than 65 parts by mass, the (meth) acrylic equivalent of the active energy ray-curable resin composition is 500 or more, and the hardness and scratch resistance after irradiation with active energy rays may be inferior.

  The polymer (A) of an ethylenically unsaturated compound containing an epoxy group used in the present invention is obtained by radical polymerization. The radical polymerization can be performed by a known method. For example, the method of superposing | polymerizing by heating using a polymerization initiator in a solvent is mentioned. The solvent is not particularly limited and a known solvent can be used. Specifically, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as isopropyl alcohol and t-butyl alcohol can be used. These solvents may be used alone or in combination of two or more. In addition, it is preferable from the point which is easy to adjust the molecular weight of an active energy ray hardening-type resin composition that the usage-amount of a solvent is 50 to 150 mass parts with respect to 100 mass parts of total amounts of an ethylenically unsaturated compound. . Further, the solvent may be distilled off after the polymerization reaction.

As the polymerization initiator, inorganic peroxides such as ammonium persulfate and potassium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 An azo compound such as' -azobis (2-methylbutyronitrile), an organic peroxide such as dibenzoyl peroxide, and t-butylperoxy-2-ethylhexanoate can be used. In particular, an azo compound is preferable in order to ensure the storage stability of the active energy ray-curable resin composition. In addition, it is easy to adjust the molecular weight of the active energy ray-curable resin composition that these polymerization initiators are 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of the ethylenically unsaturated compound. To preferred.

The weight average molecular weight of the polymer (A) of the ethylenically unsaturated compound containing an epoxy group in the molecule thus obtained is 40,000 to 150,000. It is preferable for preparing the molecular weight of the reaction product (C) obtained by adding the acid (B) to 50,000 to 200,000.

<Α, β-unsaturated carboxylic acid (B)>
The α, β-unsaturated carboxylic acid (B) used in the present invention may be any carboxylic acid having an unsaturated double bond, and examples thereof include acrylic acid, methacrylic acid, and crotonic acid. In particular, when acrylic acid is used, it is preferable because the curability of the active energy ray-curable resin composition is excellent.

<Reaction product (C)>
The reaction product (C) used in the present invention is obtained by adding an α, β-unsaturated carboxylic acid (B) to a polymer (A) of an ethylenically unsaturated compound containing an epoxy group in the molecule. . The amount of α, β-unsaturated carboxylic acid (B) used is not particularly limited, but it should be such that the equivalent ratio of carboxyl group to epoxy group in the molecule is 0.95 to 1.1. It is preferable in order to ensure gelation suppression and storage stability during synthesis.

The addition reaction of the α, β-unsaturated carboxylic acid (B) to the polymer (A) of an ethylenically unsaturated compound containing an epoxy group in the molecule can be carried out by a known method. For example, it can be obtained by heating in the presence of a catalyst.

Examples of the catalyst used in the addition reaction include phosphines such as triphenylphosphine, quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium bromide and tetrabutylammonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide and the like. And amines such as quaternary phosphonium salts, triethylamine, and tributylamine. These may be used individually by 1 type, and may be used in combination of 2 or more types. In particular, a quaternary phosphonium salt is preferable from the viewpoint of catalytic activity and side reaction suppression. Although the usage-amount of a catalyst is not specifically limited, It is preferable that they are 5 mass parts or more and 25 mass parts or less with respect to 100 mass parts of usage-amounts of (alpha), (beta)-unsaturated carboxylic acid (B). If the amount used is less than 5 parts by mass, the addition reaction may not proceed sufficiently. When the amount used is more than 25 parts by mass, side reactions may occur and gelation may occur during the reaction, or the storage stability of the active energy ray-curable resin composition may deteriorate.

A solvent or a polymerization inhibitor can also be used during the addition reaction. The solvent may be any solvent that does not react with the epoxy group and the carboxyl group. For example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, tertiary grades such as t-butyl alcohol and diacetone alcohol Examples include alcohol. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Although the usage-amount of a solvent is not specifically limited, It is 100 with respect to 100 mass parts of total amounts of the polymer (A) of the ethylenically unsaturated compound containing an epoxy group in a molecule | numerator, and (alpha), (beta) -unsaturated carboxylic acid (B). It is preferable for it to be at least part by mass in order to suppress gelation during the addition reaction.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, t-butylhydroquinone, phenothiazine and the like.

Although the usage-amount of a polymerization inhibitor is not specifically limited, with respect to 100 mass parts of total amounts of the polymer (A) of the ethylenically unsaturated compound which contains an epoxy group in a molecule | numerator, and (alpha), (beta)-unsaturated carboxylic acid (B). 1 mass part or less is preferable because it is difficult to inhibit the curability of the active energy ray-curable resin composition.

Although there is no restriction | limiting in particular in reaction temperature, 80 to 110 degreeC is preferable. When the reaction temperature is lower than 80 ° C., the addition reaction may not proceed sufficiently. When reaction temperature is higher than 110 degreeC, a side reaction may arise and it may gelatinize in the middle of reaction, and the storage stability of an active energy ray hardening-type resin composition may deteriorate.

In order to prevent polymerization of the α, β-unsaturated carboxylic acid (B) and the reaction product (C) during the addition reaction, it is possible to take measures such as introducing air into the reaction system.

The reaction product (C) thus obtained has a (meth) acryl equivalent of 200 to 500 g / eq and a weight average molecular weight of 50,000 to 200,000. It is preferable from the viewpoint that a cured film having a low curing shrinkage can be obtained without reducing the hardness or scratch resistance after irradiation with active energy rays.

<Saturated organic monocarboxylic acid component (D)>
The saturated organic monocarboxylic acid component (D) used in the present invention may be an organic monocarboxylic acid having a carboxyl group that does not have an unsaturated bond. Specifically, formic acid, acetic acid, propionic acid, butyric acid, pentane An acid etc. are mentioned. In particular, formic acid, acetic acid, and propionic acid are preferable because they have a low boiling point and are likely to volatilize, and thus hardly remain in the coating film after active energy ray curing. These may be used alone or in combination of two or more.

The amount of the saturated organic monocarboxylic acid component (D) used is preferably 2.5 parts by mass or less with respect to 100 parts by mass of the reaction product (C). More preferably, they are 0.5 mass part or more and 2 mass parts or less. When the amount used is less than 0.5 parts by mass, the contribution to improving the storage stability of the active energy ray-curable resin composition is small, and when the amount used is more than 2 parts by mass, the coating film is used. The saturated organic monocarboxylic acid component (D) tends to remain, and an odor may be generated from the coating film. Moreover, the sclerosis | hardenability of an active energy ray hardening-type resin composition may be inhibited.

The saturated organic monocarboxylic acid component (D) can be added at an arbitrary timing. For example, when the α, β-unsaturated carboxylic acid (B) is added to the polymer (A) of an ethylenically unsaturated compound containing an epoxy group in the molecule for addition reaction, it may be added in advance or dividedly. You may add to the reaction product (C) after an addition reaction.

The active energy ray-curable resin composition thus obtained includes, for example, coating materials for plastics, wood, glass, metals, etc., protective layers for various film substrates, protective layers for transfer materials, flat panel displays, photoresists, etc. It can be used as a resin for electronic substrates, optical related materials, active energy ray curable inks, and the like.

The active energy ray-curable resin composition of the present invention includes a photopolymerization initiator, an active energy ray-curable oligomer, a reactive monomer having an unsaturated bond, a solvent, a colorant, a curing agent, and a reaction accelerator as necessary. Etc. can be used in combination. These substances to be blended may be used alone or in combination of two or more as required.

For the purpose of imparting functionality to the cured film, a lubricant, an organic filler, an inorganic filler, an antistatic agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a flame retardant, and the like can be blended and used. These substances to be blended may be used alone or in combination of two or more in order to impart functionality.

The means for forming a cured film (protective layer) using the active energy ray-curable resin composition of the present invention is not particularly limited, and a known method can be used. For example, there is a method in which an active energy ray-curable resin composition is applied to an object to be coated and cured by irradiating active energy rays. The means for applying is not particularly limited, and examples thereof include brush coating, roller coating, air spray coating, gravure coating, roll coating, lip coating and other coating methods, gravure printing, screen printing and other printing methods. .

The thickness of the cured film is preferably 0.5 to 30 μm, more preferably 2 to 10 μm.

Examples of the active energy rays to be irradiated include electron beams and ultraviolet rays. The means for irradiating is not particularly limited, and a known method can be used. The irradiation amount of the active energy ray can be appropriately adjusted depending on the type and thickness of the active energy ray-curable resin composition, and is, for example, about 50 to 1000 mJ / cm ² .

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these examples. In each table, all parts are parts by mass unless otherwise specified.

(Synthesis Example 1)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 1000 parts by mass of methyl ethyl ketone (hereinafter sometimes abbreviated as MEK) was placed, and the flask was stirred while stirring in a nitrogen atmosphere. Is heated to 80 ° C., 900 parts by weight of glycidyl methacrylate (hereinafter sometimes abbreviated as GMA), 100 parts by weight of methyl methacrylate (hereinafter sometimes abbreviated as MMA), 4 parts by mass of 2,2′-azobis (2-methylbutyronitrile) (hereinafter sometimes abbreviated as ABN-E) was added dropwise over 3 hours. It was made to react for 2 hours after completion | finish of dripping. Thereafter, 2 parts by mass of ABN-E was added and reacted for 2 hours, and further 2 parts by mass of ABN-E were added, followed by reaction at 80 ° C. for 5 hours. The weight average molecular weight of the obtained resin was 57,000. Then, it is cooled to 40 ° C., the nitrogen gas introduction pipe is switched to the air introduction pipe, and while carrying out air bubbling, 479 parts by mass of acrylic acid (hereinafter sometimes abbreviated as AA), 1895 parts by mass of MEK, Phenyl phosphonium bromide (hereinafter abbreviated as PPh4 · Br) 83.6 parts by mass and 2,6-di-t-butyl-4-methylphenol (hereinafter abbreviated as BHT) After adding 7.4 parts by mass and raising the temperature to 80 ° C. while stirring, the reaction was carried out for 12 hours, after the reaction was completed, the mixture was cooled to room temperature, and then 21 parts by mass of formic acid was added. The resulting active energy ray-curable resin composition (A1) was found to have an acrylic equivalent of 230 g / eq and a weight average molecular weight of 86,500. The amount is a value obtained by measurement using gel permeation chromatography (manufactured by Tosoh Corporation: HPL-8120GPC, standard polystyrene) (hereinafter the same), and the obtained active energy ray-curable resin composition. Table 2 shows the solid content and product viscosity of the product (A1).

(Synthesis Examples 2 to 11)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, the organic solvent 1 was added so as to have the ratio shown in Table 2, and the flask was heated to 80 ° C. while stirring in a nitrogen atmosphere. After raising the temperature so that the ethylenically unsaturated compound containing an epoxy group shown in Table 1 and the ethylenically unsaturated compound containing no epoxy group and ABN-E (total use of ABN-E shown in Table 2) The amount obtained by subtracting 4 parts by mass from the amount) was added dropwise over 3 hours. It was made to react for 2 hours after completion | finish of dripping. Thereafter, 2 parts by mass of ABN-E was added and reacted for 2 hours, and further 2 parts by mass of ABN-E were added, followed by reaction for 5 hours under reflux of the solvent. The weight average molecular weight of the obtained resin is shown in Table 2. Then, it cools to 40 degreeC, a nitrogen gas introduction pipe | tube is switched to an air introduction pipe | tube, (alpha), beta-unsaturated carboxylic acid shown in Table 1, the organic solvent 2 shown in Table 2, addition reaction catalyst, implementing air bubbling And a polymerization inhibitor were added, and the mixture was heated to reflux under organic solvent with stirring, and then reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, added with saturated organic monocarboxylic acid shown in Table 1, and stirred for 30 minutes to obtain an active energy ray-curable resin composition. Table 1 shows the (meth) acryl equivalents and weight average molecular weights of the obtained active energy ray-curable resin compositions (A2) to (A11), and Table 2 shows the solid content and product viscosity.

(Comparative Synthesis Example 1)
After putting 1500 parts by mass of MEK into a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, the temperature was raised to 80 ° C. while stirring in a nitrogen atmosphere. , 600 parts by mass of GMA, 350 parts by mass of MMA, 50 parts by mass of n-butyl acrylate and 8 parts by mass of ABN-E were added dropwise over 3 hours. It was made to react for 2 hours after completion | finish of dripping. Thereafter, 2 parts by mass of ABN-E was added and reacted for 2 hours, and further 2 parts by mass of ABN-E were added, followed by reaction at 80 ° C. for 5 hours. The weight average molecular weight of the obtained resin was 22,800. Then, it cools to 40 degreeC, a nitrogen gas introduction pipe | tube is switched to an air introduction pipe | tube, AA 304 mass part, MEK 1020 mass part, PPh4 * Br 53.1 mass part, and BHT 6.5 mass are implemented, implementing air bubbling. Part was added and the temperature was raised to 80 ° C. with stirring, followed by reaction for 12 hours. After completion of the reaction, it was cooled to room temperature. Thereafter, 12.7 parts by mass of acetic acid was added and stirred at room temperature for 30 minutes. The obtained active energy ray-curable resin composition (B1) had an acrylic equivalent of 309 g / eq and a weight average molecular weight of 31,400. The solid content and product viscosity of the obtained active energy ray-curable resin composition (B1) are shown in Table 2.

(Comparative Synthesis Examples 2 to 4)
In a 5000 mL Separa flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, the organic solvent 1 was added so as to have the ratio shown in Table 2, and the flask was heated to 80 ° C. while stirring in a nitrogen atmosphere. After raising the temperature so that the ethylenically unsaturated compound containing an epoxy group shown in Table 1 and the ethylenically unsaturated compound containing no epoxy group and ABN-E (total use of ABN-E shown in Table 2) The amount obtained by subtracting 4 parts by mass from the amount) was added dropwise over 3 hours. It was made to react for 2 hours after completion | finish of dripping. Thereafter, 2 parts by mass of ABN-E was added and reacted for 2 hours, and further 2 parts by mass of ABN-E were added, followed by reaction for 5 hours under reflux of the solvent. The weight average molecular weight of the obtained resin is shown in Table 2. Then, it cools to 40 degreeC, a nitrogen gas introduction pipe | tube is switched to an air introduction pipe | tube, (alpha), beta-unsaturated carboxylic acid shown in Table 1, the organic solvent 2 shown in Table 2, addition reaction catalyst, implementing air bubbling And a polymerization inhibitor were added, and the mixture was heated to reflux under organic solvent with stirring, and then reacted for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, added with saturated organic monocarboxylic acid shown in Table 1, and stirred for 30 minutes to obtain an active energy ray-curable resin composition. Table 1 shows the acrylic equivalent and weight average molecular weight of the obtained active energy ray-curable resin compositions (B2) to (B4), and Table 2 shows the solid content and product viscosity.

(Confirmation of storage stability)
The active energy ray-curable resin compositions (A1 to A11 and B1 to B4) obtained in Synthesis Examples 1 to 11 and Comparative Synthesis Examples 1 to 4 are placed in a sealed container and left to stand at 60 ° C. for gel. Confirmed the number of days until conversion. In the case where gelation has not occurred after 30 days, gelation is performed in less than 30 days, and the number of days until gelation is described. That is, when there is a numerical value, it indicates that the storage stability is poor. Table 1 shows the results of confirmation of storage stability.
<Preparation of hard coat paint using active energy ray-curable resin composition>
Hard coat paints were prepared using the active energy ray-curable resin compositions (A1) to (A11), (B1), and (B4) obtained in the above synthesis examples and comparative synthesis examples.
Since Comparative Synthesis Examples 2 and 3 were poor in storage stability, no hard coat paint was prepared.

Example 1
To 100 parts by mass of the active energy ray-curable resin composition (A1) obtained in Synthesis Example 1, 2.5 parts of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is blended, and MEK is mixed. The non-volatile content was adjusted to 30%.

(Examples 2 to 11)
For each 100 parts by mass of the active energy ray-curable resin compositions (A2) to (A11) obtained in Synthesis Examples 2 to 11, 2 Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator was used. .5 parts was blended and prepared using MEK so that the nonvolatile content was 30%.

(Comparative Example 1)
To 100 parts by mass of the active energy ray-curable resin composition (B1) obtained in Comparative Synthesis Example 1, 2.5 parts of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is blended, and MEK Was prepared so that the non-volatile content was 30%.

(Comparative Example 2)
2.5 parts of photopolymerization initiator Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is blended with 100 parts by mass of the active energy ray-curable resin composition (B4) obtained in Comparative Synthesis Example 4. MEK Was prepared so that the non-volatile content was 30%.

<Preparation of hard coat paint film>
38 μm PET film (trade name AT-38, manufactured by Unitika) so that the film thickness of the hard coat paint prepared in Examples 1 to 11 and Comparative Examples 1 and 2 is about 8 μm using a # 12 bar coater. And then dried at 140 ° C. for 30 seconds. The obtained hard coat paint film was used for a tack-free test.

<Production of hard coat paint cured coating film>
The hard coat paint film obtained by the above-described method was cured in air under the conditions of a metal halide lamp (lamp output 1.5 Kw), an irradiation distance of 15 cm, a belt speed of 4 m / min, and a total irradiation amount of 600 mJ / cm ² . The obtained hard coat paint cured coating film was used for an abrasion resistance test, a coating hardness test, and a low cure shrinkage test.

(Tack-free test)
Cut each hard coat paint film into 5cm x 5cm, put the same size PET film on top of each other, apply a load of 2Kg, store at 60 ° C for 24 hours, take out, adhere and roughen the film surface The condition was confirmed. The film was peeled off without any resistance and the film surface was not rough. The film was peeled without resistance. The film surface was partially rough. The film surface was resistant to peeling and the film surface was rough. . The results are shown in Table 3.

(Abrasion resistance test)
Each hard coat paint cured coating film was used, and the cured coating surface was rubbed 20 times with a load of 500 g against # 10 mm × 10 mm # 0000 steel wool, and the degree of scratches on the cured coating surface was visually evaluated. The case where no scratch was found was rated as ◎, the case where there were no more than 10 scratches as ◯, the case where there were 11 to 20 scratches as Δ, and the case where there were 20 or more scratches as X. The results are shown in Table 3.

(Film hardness test)
Using each hard coat paint cured film, according to JIS-K5600, the film hardness of the hard coat paint cured film was evaluated by a scratch strength test (pencil method) with a load of 750 g. It shows that the larger the numerical value before H, the better. The results are shown in Table 3.

(Low cure shrinkage test)
Each hard coat paint cured coating film was cut to a size of 10 cm × 10 cm, placed on a flat table, and the warp height (mm) of the four corners of the film from the table surface was measured. The lower the value, the better, and it is practically necessary that it is 0. Table 3 shows the average values of the warp heights at the four corners.

As abbreviations in Table 1, GMA represents glycidyl methacrylate, MMA represents methyl methacrylate, BA represents n-butyl acrylate, AA represents acrylic acid, and MAA represents methacrylic acid.

As abbreviations in Table 2, MEK is methyl ethyl ketone, PPh4 · Br is tetraphenylphosphonium bromide, PPh3 is triphenylphosphine, TBAB is tetrabutylammonium bromide, PBu4 · Br is tetrabutylphosphonium bromide, and ABN-E is 2,2 '. -Azobis (2-methylbutyronitrile), BHT represents 2,6-di-t-butyl-4-methylphenol. In addition, the usage-amount described in ABN-E has shown the total amount used for a synthesis example.

As can be seen from Tables 1 to 3, the examples were superior in storage stability than the comparative examples, and formed a tack-free coating surface before irradiation with active energy rays, and were excellent after irradiation with active energy rays. It can be seen that a cured film having hardness and scratch resistance and low cure shrinkage can be obtained.

Claims (2)

(Meth) acrylic equivalent 200 to 500 g / eq, weight average obtained by adding α, β-unsaturated carboxylic acid (B) to polymer (A) of an ethylenically unsaturated compound containing an epoxy group in the molecule It contains a reaction product (C) having a molecular weight of 50,000 to 200,000 and a saturated organic monocarboxylic acid component (D), and 100 parts by mass of the reaction product (C), a saturated organic monocarboxylic acid component ( An active energy ray-curable resin composition containing 2.5 parts by mass or less of D) . 2. The active energy ray-curable resin composition according to claim 1 , wherein the saturated organic monocarboxylic acid component (D) is at least one selected from formic acid, acetic acid, and propionic acid.