JP2011032365A - Active energy ray-curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition with which the deterioration in appearance caused by sebum sticking on the surface of a cured material is suppressed, the removability of the stuck sebum is enhanced, and surface physical properties such as surface hardness are improved. <P>SOLUTION: The active energy ray-curable composition contains (meth)acryl (meth)acrylate, a polyfunctional compound, and a photopolymerization initiator. The (meth)acryl (meth)acrylate is synthesized by reacting a (meth)acrylic resin, which is obtained by polymerizing a monomer mixture comprising ≥30 mass% of a lipophilic monomer having an alkyl group or a cycloalkyl group and a (meth)acrylic monomer having a first reactive functional group, and a monomer having a second reactive functional group reacting with the first reactive functional group and an active energy ray-curable functional group. The hydrophilic-lipophilic balance (HLB) value, calculated by Davies' method, of the alkyl group or the cycloalkyl group of the lipophilic monomer, is ≤4.5. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable composition that can improve the appearance and fingerprint removability when a fingerprint is attached to a transparent substrate such as various transparent resin films, transparent resin plates, and glass plates.

  An active energy ray-curable hard coat material is required as an abrasion resistance imparting agent for resin products such as polycarbonate and polyethylene terephthalate, but the surface of the hard coat material is easily attached with fingerprints and sebum, and the dirt is easily removed. In other words, there is a problem that it cannot be removed, resulting in a loss of aesthetics and transparency of the product.

  In order to solve such a problem, a sheet is known in which the surface is a low energy surface and the surface is repelled by fingerprints and sebum, making it difficult to adhere (see, for example, Patent Document 1). That is, the sheet has a cured film layer of an energy ray curable resin composition containing an antifouling agent and an ultraviolet curable resin on a support. According to this sheet, hard coat properties and antifouling properties can be imparted.

  In addition, there is a known anti-smudge coating that makes the surface water-repellent or oleophilic, improves familiarity with fingerprints and sebum components, and does not stand out even if fingerprints or sebum adheres to the surface (for example, patents) Reference 2). That is, the anti-smudge coating is oleophilic to lipid components derived from living organisms, and when a fingerprint is attached to the coating, the fingerprint wets and spreads on the coating, and a thinner film is formed on the coating. As a result, the fingerprint itself becomes inconspicuous and the contamination of the base material can be prevented.

JP-A-10-104403 (pages 2 and 3) JP 2001-353808 A (2nd and 3rd pages)

  However, in the sheet described in Patent Document 1, when used in a mobile phone, the sebum of hands and face contacts the sheet, and when used in a touch panel, the finger repeatedly contacts the sheet, There was a problem that light adhered to the surface of the sheet due to the sebum adhering to the surface, making it more noticeable. On the other hand, in the dirt noticeable coating described in Patent Document 2, the attached sebum is hardly noticeable, but there is a problem that surface physical properties such as surface hardness are lacking and practicality is low.

  Therefore, the object of the present invention is to reduce the appearance due to sebum adhering to the surface of the cured product, to enhance the removal of the adhering sebum, and to improve the surface physical properties such as surface hardness. The object is to provide a linear curable composition.

  In order to achieve the above object, the active energy ray-curable composition according to claim 1 comprises (meth) acrylic (meth) acrylate having an active energy ray-curable functional group, and a plurality of active energy ray-curable properties. It contains a polyfunctional compound having a functional group and a photopolymerization initiator. The (meth) acrylic (meth) acrylate is a polymerized monomer mixture containing 30% by mass or more of a lipophilic monomer having an alkyl group or a cycloalkyl group and a (meth) acrylic monomer having a first reactive functional group. A (meth) acrylic resin made to react with a monomer having a second reactive functional group that reacts with the first reactive functional group of the (meth) acrylic monomer and an active energy ray-curable functional group, and The hydrophilic / lipophilic balance value (HLB value) calculated by the Davis method of the alkyl group or cycloalkyl group of the lipophilic monomer is 4.5 or less.

  The active energy ray-curable composition according to claim 2 is the invention according to claim 1, wherein the lipophilic monomer has an HLB value calculated by a Davis method of an alkyl group or a cycloalkyl group of −4.0. It is -4.2.

  The active energy ray-curable composition according to claim 3 is the invention according to claim 1 or claim 2, wherein the lipophilic monomer is an alkyl group having 8 to 22 carbon atoms or a cycloalkyl having 6 to 12 carbon atoms. It has a group.

  The active energy ray-curable composition according to claim 4 is the invention according to any one of claims 1 to 3, wherein the content of the lipophilic monomer in the monomer mixture is 50 to 85% by mass. It is characterized by being.

  The active energy ray-curable composition according to claim 5 is the invention according to any one of claims 1 to 4, wherein the first reactive functional group and the second reactive functional group are hydroxyl groups. It is a combination of a group or a glycidyl group and an isocyanate group or a carboxyl group.

According to the present invention, the following effects can be exhibited.
In the active energy ray-curable composition of the present invention, the HLB value calculated by the Davis method of the alkyl group or cycloalkyl group of the lipophilic monomer forming the (meth) acrylic (meth) acrylate is 4.5 or less. . For this reason, the lipophilic monomer can exhibit sufficient lipophilicity. Furthermore, the monomer mixture contains 30% by mass or more of an oleophilic monomer having an alkyl group or a cycloalkyl group, and a sufficient ratio of the oleophilic monomer in the monomer mixture is ensured. Therefore, the hardened | cured material of an active energy ray curable composition can express favorable lipophilicity on the surface. Thus, since this hardened | cured material shows affinity with the sebum adhering to the surface, sebum spreads thinly on the hardened | cured material surface, and it becomes difficult to visually recognize, and it becomes easy to wipe off.

  In addition, (meth) acrylic (meth) acrylate is obtained by polymerizing a monomer mixture containing a (meth) acrylic monomer having a first reactive functional group and the (meth) acrylic monomer. It is formed by reacting a monomer having a second reactive functional group that reacts with one reactive functional group and an active energy ray-curable functional group. Thus, since the active energy ray-curable composition contains (meth) acrylic (meth) acrylate having an active energy ray-curable functional group and a polyfunctional compound, the active energy ray-curable composition is included. When cured by irradiating with active energy rays, the cured product integrally forms a crosslinked structure, and the mechanical properties are enhanced.

  Accordingly, it is possible to suppress a decrease in appearance due to sebum adhering to the surface of the cured product, to improve the removability of the adhering sebum, and to improve surface physical properties such as surface hardness.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
[Active energy ray-curable composition]
The active energy ray-curable composition of the present embodiment includes a (meth) acrylic (meth) acrylate having an active energy ray-curable functional group, a polyfunctional compound having a plurality of active energy ray-curable functional groups, and photopolymerization. Containing an initiator. This active energy ray-curable composition can exhibit good lipophilicity on the surface of the cured product (hereinafter, also simply referred to as a cured product), and suppresses deterioration in appearance due to sebum adhering to the surface of the cured product. At the same time, the sebum removability can be improved, and surface properties such as surface hardness can be improved. Below, the component of an active energy ray curable composition is demonstrated in order.
<(Meth) acrylic (meth) acrylate>
(Meth) acrylic (meth) acrylate is obtained by polymerizing a monomer mixture containing 30% by mass or more of an oleophilic monomer having an alkyl group or a cycloalkyl group and a (meth) acrylic monomer having a first reactive functional group. It is formed by reacting a (meth) acrylic resin with a monomer having a second reactive functional group that reacts with the first reactive functional group of the (meth) acrylic monomer and an active energy ray-curable functional group. Therefore, (meth) acrylic (meth) acrylate has an active energy ray-curable functional group and can be copolymerized with an active energy ray-curable functional group of a polyfunctional compound.

  The lipophilic monomer preferably has an alkyl group having 8 to 22 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms in order to develop good lipophilicity. Examples of the lipophilic monomer having an alkyl group having 8 to 22 carbon atoms include 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, isostearyl methacrylate, hexadecyl methacrylate, and behenyl methacrylate. Examples of the lipophilic monomer having a cycloalkyl group having 6 to 12 carbon atoms include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ortho-phenylphenol (meth) acrylate, 1-adamantyl (meth) acrylate and the like. Can be mentioned.

  The content of the lipophilic monomer in the monomer mixture needs to be 30% by mass or more, and preferably 50 to 85% by mass. When the content of the lipophilic monomer is less than 30% by mass, the lipophilicity based on the lipophilic monomer is insufficient, and it becomes impossible to suppress the deterioration of the appearance due to sebum adhering to the cured product surface.

  The first reactive functional group and the second reactive functional group are preferably a combination of a hydroxyl group or glycidyl group and an isocyanate group or a carboxyl group. Specifically, examples of the (meth) acrylic monomer having a hydroxyl group as the first reactive functional group include hydroxyalkyl (2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and the like ( And (meth) acrylate. Examples of the (meth) acrylic monomer having a glycidyl group as the first reactive functional group include glycidyl methacrylate.

  In that case, examples of the monomer having an isocyanate group as the second reactive functional group include isocyanate ethyl acrylate and isocyanate ethyl methacrylate. Examples of the monomer having a carboxyl group as the second reactive functional group include acrylic acid and methacrylic acid.

  Further, a monomer having an isocyanate group or a monomer having a carboxyl group is used as the first reactive functional group, and a (meth) acrylic monomer having a hydroxyl group or a (meth) acrylic monomer having a glycidyl group as the second reactive functional group Can be used.

  The (meth) acrylic resin may be any of a methacrylic resin based on a methacrylic monomer, an acrylic resin based on an acrylic monomer, or a (meth) acrylic resin based on a methacrylic monomer and an acrylic monomer.

  The hydrophilic / lipophilic balance value (HLB value) for the alkyl group or cycloalkyl group of the lipophilic monomer is set to 4.5 or less, preferably −4.0 to 4.2 in order to develop good lipophilicity. Is set. That is, the HLB value is defined as described above for the substituent X of the lipophilic monomer represented by the following chemical formula (1).

但し、Ｒは水素又はメチル基、置換基Ｘはアルキル基又はシクロアルキル基である。

However, R is hydrogen or a methyl group, and the substituent X is an alkyl group or a cycloalkyl group.

  When two or more types of lipophilic monomers are used, it is necessary that each lipophilic monomer satisfies the above HLB value requirements. Here, the HLB value is a value calculated by the Davis method. That is, the HLB value = Σ (the number of hydrophilic groups) + Σ (the number of lipophilic groups) +7. Where Σ represents the sum. Specific examples of the number of hydrophilic groups and the number of lipophilic groups are shown in Table 1.

（メタ）アクリル（メタ）アクリレートの含有量は、（メタ）アクリル（メタ）アクリレートと多官能化合物との総量に対して２０〜８０質量％であることが好ましい。（メタ）アクリル（メタ）アクリレートの含有量が２０質量％を下回る場合には十分な親油性が発現されなくなり、８０質量％を上回る場合には多官能化合物に基づく表面硬度等の機械的物性が低下する傾向を示す。
＜多官能化合物＞
前記多官能化合物は複数の活性エネルギー線硬化性官能基を有する化合物であり、活性エネルギー線硬化性組成物に活性エネルギー線を照射して硬化させたとき硬化物が架橋構造を形成し、硬化物の表面硬度等の機械的物性を高めることができる。この多官能化合物としては、トリプロピレングリコールジアクリレート等の２官能（メタ）アクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート等の３官能（メタ）アクリレート、ジペンタエリスリトールヘキサアクリレート等の６官能（メタ）アクリレートなどが用いられる。これらの多官能化合物は、１種又は２種以上が適宜選択して使用されるが、１分子中に活性エネルギー線硬化性官能基を３又はそれ以上有する多官能化合物が硬化物の機械的強度を高めることができる点で好ましい。

The content of (meth) acrylic (meth) acrylate is preferably 20 to 80% by mass with respect to the total amount of (meth) acrylic (meth) acrylate and polyfunctional compound. When the content of (meth) acrylic (meth) acrylate is less than 20% by mass, sufficient lipophilicity is not expressed, and when it exceeds 80% by mass, mechanical properties such as surface hardness based on a polyfunctional compound are present. Shows a downward trend.
<Polyfunctional compound>
The polyfunctional compound is a compound having a plurality of active energy ray-curable functional groups, and when the active energy ray-curable composition is irradiated with active energy rays and cured, the cured product forms a crosslinked structure, and the cured product The mechanical properties such as surface hardness can be improved. As this polyfunctional compound, bifunctional (meth) acrylates such as tripropylene glycol diacrylate, trifunctional (meth) acrylates such as trimethylolpropane triacrylate, pentaerythritol triacrylate, and 6 functionals such as dipentaerythritol hexaacrylate ( For example, (meth) acrylate is used. One or more of these polyfunctional compounds are appropriately selected and used, but the polyfunctional compound having 3 or more active energy ray-curable functional groups in one molecule is the mechanical strength of the cured product. It is preferable at the point which can raise.

It is preferable that content of this polyfunctional compound is 20-80 mass% with respect to the total amount of (meth) acryl (meth) acrylate and a polyfunctional compound. When the content of the polyfunctional compound is less than 20% by mass, mechanical properties such as surface hardness based on the polyfunctional compound are not sufficiently exhibited, and when it exceeds 80% by mass, the lipophilicity is not sufficiently exhibited. .
<Photopolymerization initiator>
The photopolymerization initiator is for causing the active energy ray-curable composition to irradiate the active energy ray to cause a curing reaction, and any conventionally known photopolymerization initiator can be used. You may use individually and may use 2 or more types together. Examples of the photopolymerization initiator include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethyl anthraquinone, isoamyl p-dimethylaminobenzoate Ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1 -One, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Jiruhorumeto, and the like.

It is preferable that content of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (meth) acrylic (meth) acrylate and a polyfunctional compound, and is 1-5 mass parts. More preferably. When content of a photoinitiator is less than 0.1 mass part, the sclerosis | hardenability of an active energy ray curable composition falls and it becomes impossible to obtain desired hardened | cured material efficiently. On the other hand, when it exceeds 10 mass parts, superposition | polymerization advances excessively and the physical property of hardened | cured material falls and it is colored, and is unpreferable.
<Use of active energy ray-curable composition>
The active energy ray-curable composition is used, for example, as a coating composition (paint) that covers the surface of an object. The object is not particularly limited, and examples thereof include those that impair the appearance due to fingerprint attachment such as a display, a touch panel, a piano, and luxury furniture, and the material thereof is a base material such as a resin film, a resin plate, or a glass plate. As the coating method for the substrate, any coating such as dip coating method, flow coating method, spin coating method, spray coating method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, etc. The method is adopted.

  And after apply | coating the active energy ray curable composition to the surface of a target object, it dries and forms a coating film, and then forms a cured coating film on the surface of a target object by irradiating an active energy ray. be able to. Active energy rays include ultraviolet rays generated from light sources such as xenon lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps, electron beams from particle accelerators of 20 to 2000 kV, α, β, γ rays. Etc. are used. By using an active energy ray, productivity can be improved and the physical property of a cured coating film can be improved.

The effects exhibited by the above embodiment will be described collectively below.
(1) In the active energy ray-curable composition of the present embodiment, the lipophilic monomer has an HLB value calculated by the Davis method of the alkyl group or cycloalkyl group of 4.5 or less, and has sufficient lipophilicity. Can show. Furthermore, 30% by mass or more of the lipophilic monomer is contained in the monomer mixture, and the ratio of the lipophilic monomer in the monomer mixture is sufficiently ensured. Therefore, the cured product can exhibit good lipophilicity on its surface. Thus, since the cured product has an excellent affinity for sebum adhering to the surface, the sebum is thinly spread on the surface of the cured product and becomes difficult to see at the same time, and can be easily wiped off. .

  In addition, (meth) acrylic (meth) acrylate is obtained by polymerizing a monomer mixture containing a (meth) acrylic monomer having a first reactive functional group and the (meth) acrylic monomer. It is formed by reacting a monomer having a second reactive functional group that reacts with one reactive functional group and an active energy ray-curable functional group. Thus, since the active energy ray curable composition contains (meth) acryl acrylate having an active energy ray curable functional group and a polyfunctional compound, the active energy ray curable composition contains active energy. When cured by irradiating a line, the cured product forms a cross-linked structure together, and mechanical properties such as hardness and strength are enhanced.

  Accordingly, it is possible to suppress a decrease in appearance due to sebum adhering to the surface of the cured product, to improve the removability of the attached sebum, and to improve surface physical properties such as surface hardness.

  (2) The lipophilic monomer has an improved lipophilicity by setting the HLB value calculated by the Davis method of the alkyl group or cycloalkyl group to −4.0 to 4.2, and the surface of the cured product A better affinity can be exhibited for sebum adhering to the surface.

  (3) Since the lipophilic monomer has an alkyl group having 8 to 22 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms, the lipophilicity is enhanced, and the affinity for sebum adhering to the cured product surface is further increased. Can be improved.

  (4) When the content of the lipophilic monomer in the monomer mixture is 50 to 85% by mass, the content of the lipophilic monomer is sufficiently ensured, and the cured product can exhibit high lipophilicity.

  (5) The first reactive functional group and the second reactive functional group are a combination of a hydroxyl group or a glycidyl group and an isocyanate group or a carboxyl group, so that a hydroxyl group or a glycidyl group and an isocyanate group or a carboxyl group are combined. The (meth) acrylic (meth) acrylate can be obtained easily and quickly.

Hereinafter, the embodiment will be described more specifically with reference to synthesis examples, examples, and comparative examples. In each example, parts represent parts by mass and% represents mass%.
(Synthesis Example 1)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 30 parts of methyl methacrylate (MMA), 20 parts of 2-hydroxyethyl methacrylate (HEMA), 70 parts of lauryl methacrylate (LMA) (HLB value 1.3) and 1,1-azobis-1-cyclohexanecarbonitrile 3 6 parts were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain methacrylic resin a. It was. The methacrylic resin a had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
Example 1
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate (AOI) as an addition monomer, and 0.8% of dibutyltin (IV) dilaurate as a catalyst. 012 parts and 0.06 part of a polymerization inhibitor hydroquinone monomethyl ether were charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate A1, trimethylolpropane triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., TMP-A, the same was used in the following examples. ] 10 parts, 10 parts of methyl ethyl ketone, and photopolymerization initiator Irgacure 184 [1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by Ciba Specialty Chemicals Co., Ltd.] 0.45 parts were mixed and formed into a paint as a UV curable composition. A UV curable paint A2 was obtained.
(Comparative Synthesis Example 4)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 30 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of n-butyl methacrylate (BMA) (HLB value 5.1) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile Mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And allowed to react for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin e. It was. The methacrylic resin e had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Comparative Example 4)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin e obtained in Comparative Synthesis Example 4, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor Then, 0.06 part of hydroquinone monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate E1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate E1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 [manufactured by Ciba Specialty Chemicals Co., Ltd.] A UV curable paint E2 was obtained by converting into a paint.
(Comparative Example 1)
Dipentaerythritol penta & hexaacrylate [M-402, manufactured by Toagosei Co., Ltd.] 20 parts, trimethylolpropane EO modified (n≈1) triacrylate [M-350, manufactured by Toagosei Co., Ltd.] 5 parts, methyl ethyl ketone 5 parts and 7.5 parts of photopolymerization initiator Irgacure 184 were mixed to obtain UV curable paint B.
(Comparative Example 2)
Dipentaerythritol penta & hexaacrylate [M-402, manufactured by Toagosei Co., Ltd.] 20 parts, trimethylolpropane EO modified (n≈1) triacrylate [M-350, manufactured by Toagosei Co., Ltd.] 5 parts, BYK A UV curable coating C was obtained by mixing 1.25 parts of -370 (manufactured by BYK Chemie, silicone leveling agent), 5 parts of methyl ethyl ketone and 7.5 parts of photopolymerization initiator Irgacure 184.
(Comparative Example 3)
0.45 parts of methacrylic resin a 10 parts obtained in Synthesis Example 1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and Irgacure 184 photopolymerization initiator were mixed and formed into a paint to obtain UV curable paint D.
(Comparative Synthesis Example 5)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 44 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 40 parts of perfluorooctylethyl methacrylate (PFMA), 16 parts of dicyclopentanyl methacrylate (DCPM) (HLB value 2.25) and 1,1 -3.6 parts of azobis-1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And allowed to react for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin f. It was. The methacrylic resin f had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Comparative Example 5)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Comparative Synthesis Example 5, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor 0.06 part of hydroquinone monomethyl ether was added and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate F1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate F1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint F2. It was.
(Comparative Synthesis Example 6)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 82 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 18 parts of lauryl methacrylate (HLB value 1.3) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And allowed to react for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain methacrylic resin x. It was. The methacrylic resin x had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Comparative Example 6)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Comparative Synthesis Example 6, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor 0.06 part of hydroquinone monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate X1 having an active energy ray-curable functional group.

10 parts of the (meth) acrylic (meth) acrylate X1 obtained, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint X2. It was.
(Synthesis Example 2)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube was charged with 90 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 30 parts of methyl methacrylate, 20 parts of glycidyl methacrylate (GMA), 70 parts of lauryl methacrylate (HLB value 1.3), and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin g. It was. The methacrylic resin g had a solid content of 54.5%.
(Example 2)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 125.6 parts of the methacrylic resin obtained in Synthesis Example 2 and 5.2 parts of acrylic acid (AA) [glycidyl group: carboxyl group = 1: 0.9 (molar ratio) )], 0.7 parts of triphenylphosphine as a catalyst and 0.17 part of a polymerization inhibitor hydroquinone monomethyl ether were charged and reacted at 100 ° C. for 6 hours to obtain a (meth) acrylic (meth) having an active energy ray-curable functional group. Acrylate G1 was obtained. The acid value of (meth) acrylic (meth) acrylate G1 was 2.0 mgKOH / g.

10 parts of the (meth) acrylic (meth) acrylate G1 thus obtained, 11.4 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.51 part of photopolymerization initiator Irgacure 184 were mixed and made into a paint, and UV curable paint G2 Got.
(Synthesis Example 3)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 30 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of cyclohexyl methacrylate (CHMA) (HLB value 4.15) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. . The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin h. . The methacrylic resin h had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 3)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Synthesis Example 3, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate H1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate H1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint H2. It was.
(Synthesis Example 4)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 30 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of dicyclopentanyl methacrylate (HLB value 2.25) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. . The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain methacrylic resin i. . The methacrylic resin i had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
Example 4
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin i obtained in Synthesis Example 4, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate I1 having an active energy ray-curable functional group.

10 parts of the (meth) acrylic (meth) acrylate I1 obtained, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint I2. It was.
(Synthesis Example 5)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of dicyclopentanyl methacrylate (HLB value 2.25), 30 parts of behenyl methacrylate (VMA) (HLB value -3.45) and 1,1-azobis-1 -3.6 parts of cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin j. It was. The methacrylic resin j had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 5)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin j obtained in Synthesis Example 5, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate J1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate J1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint J2. It was.
(Synthesis Example 6)
In a 300 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 40 parts of 40% VPE-0401 [manufactured by Wako Pure Chemical Industries, Ltd.] 50 parts of methyl ethyl ketone solution, 15 parts of methyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate Then, 35 parts of lauryl methacrylate (HLB value 1.3) and 40 parts of methyl ethyl ketone were charged, the temperature was raised to 80 ° C., and the mixture was reacted at 80 ° C. for 5 hours to obtain a methacrylic resin l. The methacrylic resin 1 had a solid content of 53.3% and a hydroxyl value of 28.8 mgKOH / g.
(Example 6)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin 1 obtained in Synthesis Example 6, 7.2 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and polymerization inhibition 0.06 part of hydroquinone monomethyl ether was added and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate L1 having an active energy ray-curable functional group.

10 parts of the (meth) acrylic (meth) acrylate L1 thus obtained, 11.2 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and formed into a paint, and UV curable paint L2 Got.
(Synthesis Example 7)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 30 parts of methyl methacrylate, 20 parts of isocyanate ethyl methacrylate (MOI), 70 parts of lauryl methacrylate (HLB value 1.3) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain methacrylic resin m. It was. The methacrylic resin m had a solid content of 50.2%.
(Example 7)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Synthesis Example 7, 6.2 parts of 2-hydroxyethyl acrylate (HEA), 0.012 of dibutyltin dilaurate (IV) as a catalyst Part, 0.06 part of a polymerization inhibitor hydroquinone monomethyl ether, and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate M1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate M1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint M2. It was.
(Synthesis Example 8)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of dicyclopentanyl methacrylate (HLB value 2.25), 30 parts of stearyl methacrylate (SMA) (HLB value -1.55) and 1,1-azobis-1 -3.6 parts of cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin o. It was. The methacrylic resin o had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 8)
100 parts of methacrylic resin o obtained in Synthesis Example 8, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin dilaurate (IV) as catalyst, and polymerization prohibited in a 200 ml flask equipped with a stirrer, thermometer and condenser 0.06 part of hydroquinone monomethyl ether was added and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate O1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate O1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint O2. It was.
(Synthesis Example 9)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 2-hydroxyethyl methacrylate 20 parts, dicyclopentanyl methacrylate 70 parts (HLB value 2.25), isostearyl methacrylate (iSMA) 30 parts (HLB value -1.55) and 1,1-azobis- 3.6 parts of 1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin p. It was. The methacrylic resin p had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
Example 9
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Synthesis Example 9, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate P1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate P1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint P2. It was.
(Synthesis Example 10)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 20 parts 2-hydroxyethyl methacrylate, 70 parts dicyclopentanyl methacrylate (HLB value 2.25), 30 parts lauryl methacrylate (HLB value 1.3) and 1,1-azobis-1-cyclohexanecarbonitrile 3.6 parts were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin q. It was. The methacrylic resin q had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 10)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin q obtained in Synthesis Example 10, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate Q1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate Q1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint Q2. It was.
(Synthesis Example 11)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. 2. 20 parts of 2-hydroxyethyl methacrylate, 70 parts of cyclohexyl methacrylate (HLB value 4.15), 30 parts of behenyl methacrylate (HLB value -3.45) and 1,1-azobis-1-cyclohexanecarbonitrile 3. 6 parts were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin r. It was. The methacrylic resin r had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 11)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin r obtained in Synthesis Example 11, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate R1 having an active energy ray-curable functional group.

10 parts of the (meth) acrylic (meth) acrylate R1 thus obtained, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint R2. It was.
(Synthesis Example 12)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of 2-ethylhexyl methacrylate (2-EHMA) (HLB value 3.2), 30 parts of methyl methacrylate and 1,1-azobis-1-cyclohexanecarbonitrile 3.6 The parts were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And allowed to react for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin s. It was. The methacrylic resin s had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 12)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin s obtained in Synthesis Example 12, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate S1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate S1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint S2. It was.
(Synthesis Example 13)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 20 parts of 2-hydroxyethyl methacrylate, 70 parts of cetyl methacrylate (CMA) (HLB value -0.6), 30 parts of methyl methacrylate and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. did. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin t. It was. The methacrylic resin t had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 13)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Synthesis Example 13, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate T1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate T1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint T2. It was.
(Synthesis Example 14)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 20 parts of 2-hydroxyethyl methacrylate, 64 parts of methyl methacrylate, 36 parts of behenyl methacrylate (HLB value -3.45), and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin u. It was. The methacrylic resin u had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 14)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin u obtained in Synthesis Example 14, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate U1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate U1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint U2. It was.
(Synthesis Example 15)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 2-hydroxyethyl methacrylate 20 parts, 2-ethylhexyl methacrylate 35 parts (HLB value 3.2), behenyl methacrylate 35 parts (HLB value -3.45), methyl methacrylate 30 parts, 1,1-azobis 3.6 parts of -1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin w. It was. The methacrylic resin w had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 15)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin w obtained in Synthesis Example 15, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate W1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate W1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint W2. It was.
(Example 16)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate A1, 20 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.75 part of photopolymerization initiator Irgacure 184 were mixed and coated to obtain a UV curable coating A3. It was.
(Example 17)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate A1, 5 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.3 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint A4. It was.
(Example 18)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

20 parts of the obtained (meth) acrylic (meth) acrylate A1, 5 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint A5. It was.
(Example 19)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

20 parts of the (meth) acrylic (meth) acrylate A1 obtained, 5 parts of dipentaerythritol hexaacrylate [manufactured by Kyoeisha Chemical Co., Ltd., DPE-6A], 10 parts of methyl ethyl ketone and 0.45 of the photopolymerization initiator Irgacure 184 Partial mixing and conversion into a paint gave UV curable paint A6.
(Example 20)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate A1, 5 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., PE-3A], 10 parts of methyl ethyl ketone and 0.45 part of Irgacure 184 photopolymerization initiator Were mixed and converted into a paint to obtain a UV curable paint A7.
(Example 21)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin a obtained in Synthesis Example 1, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate A1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate A1, dipentaerythritol hexaacrylate [manufactured by Kyoeisha Chemical Co., Ltd., DPE-6A]: tripropylene glycol diacrylate [manufactured by Daicel UCB Co., Ltd., TPGDA ] 5 parts of a mixed solution of 7: 3 (mass ratio) and 0.45 parts of Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint A8.
(Synthesis Example 16)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 50 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 50 parts of dicyclopentanyl methacrylate (HLB value 2.25) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. . The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain a methacrylic resin k. It was. The methacrylic resin k had a solid content of 50.2% and a hydroxyl value of 35.4 mgKOH / g.
(Example 22)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Synthesis Example 16, 8.9 parts of isocyanate ethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and a polymerization inhibitor hydroquinone 0.06 part of monomethyl ether was charged and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate K1 having an active energy ray-curable functional group.

10 parts of the obtained (meth) acrylic (meth) acrylate K1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 parts of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to obtain a UV curable paint K2. It was.
(Synthesis Example 17)
A 300 ml flask equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube was charged with 110 parts of methyl isobutyl ketone and heated to 110 ° C. Separately, 64 parts of methyl methacrylate, 20 parts of isocyanate ethyl methacrylate, 36 parts of lauryl methacrylate (HLB value 1.3) and 3.6 parts of 1,1-azobis-1-cyclohexanecarbonitrile were mixed. The solution was added dropwise over 2 hours and allowed to react for 3 hours, and 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were added dropwise. And reacted for 1 hour. Further, 5 parts of methyl isobutyl ketone, 0.1 part of 1,1-azobis-1-cyclohexanecarbonitrile and 0.1 part of azobis-2-methylbutyronitrile were dropped and reacted for 2 hours to obtain methacrylic resin n. It was. Methacrylic resin n had a solid content of 50.2%.
(Example 23)
In a 200 ml flask equipped with a stirrer, a thermometer and a condenser, 100 parts of the methacrylic resin obtained in Synthesis Example 17, 6.2 parts of 2-hydroxyethyl acrylate, 0.012 part of dibutyltin (IV) dilaurate as a catalyst, and polymerization Inhibitor hydroquinone monomethyl ether (0.06 part) was added and reacted at 70 ° C. for 5 hours to obtain (meth) acrylic (meth) acrylate N1 having an active energy ray-curable functional group.

  10 parts of the obtained (meth) acrylic (meth) acrylate N1, 10 parts of trimethylolpropane triacrylate, 10 parts of methyl ethyl ketone and 0.45 part of photopolymerization initiator Irgacure 184 were mixed and converted into a paint to prepare a UV curable paint N2. Obtained.

  The compositions and HLB values of Comparative Example 3, Comparative Synthesis Examples 4 and 5 and Synthesis Examples 1 to 17 are shown in Table 2.

＜塗料性能評価＞
以下の方法でＵＶ硬化塗料の硬化塗膜を作製して評価した。すなわち、厚さ１００μｍの透明なポリエチレンテレフタレートフィルム〔Ａ４３００、東洋紡（株）製〕上にバーコーターを用いて乾燥後の塗膜の膜厚が６μｍになるように塗布し、８０℃で２分間加熱乾燥後、出力１２０Ｗ／ｃｍの高圧水銀灯で紫外線照射して硬化塗膜を形成した。その硬化塗膜について、透明性（ヘイズ値）、鉛筆硬度、密着性、接触角（水、擬似指紋液）、皮脂外観性、皮脂除去性及び指紋視認性を下記に示す方法で評価し、それらの結果を表３に示した。なお、表３中のＭＡＭＡは（メタ）アクリル（メタ）アクリレートを表し、ＭＦＣは多官能化合物を表す。
(1)透明性：ＪＩＳ Ｋ ７１０５に基づくヘイズ値で評価した。このヘイズ値は、０．５以下であることが好ましい。
(2)鉛筆硬度：ＪＩＳ Ｋ ５４００に準拠して測定し、傷の入らない最も硬い鉛筆の番手で示した。鉛筆硬度は、２Ｈ以上であることが合格レベルである。
(3)密着性：ＪＩＳ Ｋ ５４００に記載の碁盤目法で試験した。そして、全くはがれの生じないものを〇、１０％以下のはがれを生じるものを△、それ以外を×として評価した。
(4)接触角：硬化塗膜に３μｌの純水又は擬似指紋液を滴下し、１秒後の接触角を５箇所測定して平均値を算出した。なお、接触角の測定には協和界面科学（株）製の接触角測定器を用いて測定した（単位；度）。
(5)皮脂外観性：２０号のシリコーンゴム栓に擬似指紋液〔オレイン酸：オリーブ油：ホホバ油：スクアレン＝６．１：２９．３：４７．５：１７．１（質量比）〕を付着させて硬化塗膜にスタンプし、ヘイズ値の増加（ΔＨ）で評価した。ΔＨは小さいほど付着した指紋液が見え難いことを示し、０．７以下が合格レベルである。
(6)皮脂除去性：(5)でスタンプした擬似指紋液を市販のティッシュで１回拭取った後のヘイズ値の変化（除去後のヘイズ値−初期のヘイズ値の差ΔＨ）で評価した。ΔＨは小さいほど付着した指紋液の除去性が良いことを示し、２．０以下が合格レベルである。
(7)指紋視認性（目視評価）：拳を握り、少し湿らした親指を硬化塗膜に垂直に５秒間押しつけ、２４時間後の指紋視認性について次の４段階で目視による官能評価を行った。

<Evaluation of paint performance>
A cured coating film of UV curable paint was prepared and evaluated by the following method. That is, a 100 μm thick transparent polyethylene terephthalate film (A4300, manufactured by Toyobo Co., Ltd.) was applied using a bar coater so that the film thickness after drying was 6 μm and heated at 80 ° C. for 2 minutes. After drying, a cured coating film was formed by irradiating ultraviolet rays with a high-pressure mercury lamp having an output of 120 W / cm. About the cured coating film, transparency (haze value), pencil hardness, adhesion, contact angle (water, pseudo-fingerprint liquid), sebum appearance, sebum removal property and fingerprint visibility were evaluated by the methods shown below. The results are shown in Table 3. In Table 3, MAMA represents (meth) acrylic (meth) acrylate, and MFC represents a polyfunctional compound.
(1) Transparency: The haze value based on JIS K 7105 was evaluated. The haze value is preferably 0.5 or less.
(2) Pencil hardness: Measured in accordance with JIS K 5400 and indicated by the hardest pencil count without scratches. It is a pass level that pencil hardness is 2H or more.
(3) Adhesiveness: Tested by a grid pattern method described in JIS K 5400. Then, the case where no peeling occurred was evaluated as ◯, the case where peeling of 10% or less occurred was evaluated as Δ, and the others were evaluated as ×.
(4) Contact angle: 3 μl of pure water or pseudo-fingerprint solution was dropped onto the cured coating film, and the contact angle after 1 second was measured at five locations to calculate an average value. The contact angle was measured using a contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. (unit: degree).
(5) Appearance of sebum: Pseudo-fingerprint solution [Oleic acid: Olive oil: Jojoba oil: Squalene = 6.1: 29.3: 47.5: 17.1 (mass ratio)] attached to No. 20 silicone rubber stopper The cured coating film was stamped and evaluated by increasing the haze value (ΔH). The smaller ΔH is, the more difficult it is to see the attached fingerprint liquid, and 0.7 or less is a pass level.
(6) Sebum removability: evaluated by change in haze value after wiping the pseudo fingerprint liquid stamped in (5) once with a commercially available tissue (haze value after removal-initial haze value difference ΔH). . The smaller ΔH is, the better the removability of the attached fingerprint liquid is, and an acceptable level is 2.0 or less.
(7) Fingerprint visibility (visual evaluation): Holding a fist and pressing a slightly moistened thumb vertically against the cured coating film for 5 seconds, the fingerprint visibility after 24 hours was subjected to visual sensory evaluation in the following four stages. .

4; The fingerprint is completely invisible; 3; The fingerprint is slightly visible; 2; The fingerprint is thin but clearly visible; 1; The fingerprint is clearly visible.
(8) Fingerprint visibility (incident angle): After holding a fist and attaching a slightly moistened thumb to the cured film by pressing it vertically for 5 seconds, the desired incident angle (the normal of the light receiving surface is in the direction of light) The white fluorescent lamp was applied to the fingerprint at an angle formed with respect to the fingerprint, the specular reflection light was observed, and the evaluation was performed based on the incident angle value at which the fingerprint can be visually confirmed. When the fingerprint visibility is good, the value of the incident angle at which the fingerprint can be visually confirmed increases.

表３に示したように、実施例１〜２３においては硬化塗膜の鉛筆硬度が２Ｈ以上であり、皮脂外観性が０．５以下であると共に、皮脂除去性が２．０以下であって、いずれも優れた結果を示した。一方、比較例１及び２では、親油性モノマーを含む（メタ）アクリル（メタ）アクリレートを用いなかったため、皮脂外観性及び皮脂除去性が発揮されなかった。比較例３では、メタクリル樹脂を（メタ）アクリル化しなかったため、メタクリル樹脂が可塑剤として働き、硬化塗膜の硬度が不足した。比較例４では、親油性モノマーとしてＨＬＢ値が４．５を超えるモノマーを用いた結果、皮脂外観性及び皮脂除去性が悪化した。比較例５では、親油性モノマーとフッ素系モノマーを併用したため撥油性が上がり、指紋視認性やヘイズ値が悪化した。比較例６では、親油性モノマーの含有量がモノマー混合物中に３０質量％を下回ったため、親油性が低下し、指紋視認性やヘイズ値が悪化した。

As shown in Table 3, in Examples 1 to 23, the pencil hardness of the cured coating film is 2H or more, the sebum appearance is 0.5 or less, and the sebum removability is 2.0 or less. Both showed excellent results. On the other hand, in Comparative Examples 1 and 2, since (meth) acrylic (meth) acrylate containing a lipophilic monomer was not used, sebum appearance and sebum removability were not exhibited. In Comparative Example 3, since the methacrylic resin was not (meth) acrylated, the methacrylic resin worked as a plasticizer, and the hardness of the cured coating film was insufficient. In Comparative Example 4, as a result of using a monomer having an HLB value exceeding 4.5 as a lipophilic monomer, the sebum appearance and sebum removal properties deteriorated. In Comparative Example 5, since the lipophilic monomer and the fluorine monomer were used in combination, the oil repellency was improved, and the fingerprint visibility and haze value were deteriorated. In Comparative Example 6, since the content of the lipophilic monomer was less than 30% by mass in the monomer mixture, the lipophilicity was lowered and the fingerprint visibility and haze value were deteriorated.

It should be noted that the present embodiment can be modified as follows.
-An acrylic resin can be prepared using an acrylic monomer as a monomer for forming the (meth) acrylic resin, and a methacrylic monomer can be used as a polyfunctional compound. In this case, it is desirable to use an electron beam for curing the active energy ray-curable composition.

-As the polyfunctional compound, a compound exhibiting lipophilicity can be used to increase the lipophilicity of the cured product.
Further, the technical idea that can be grasped from the embodiment will be described below.

  The active energy ray-curable composition according to claim 5, wherein the first reactive functional group is a hydroxyl group, and the second reactive functional group is an isocyanate group. In this case, in addition to the effect of the invention according to claim 5, the (meth) acrylic resin can be easily prepared, and the hydroxyl group and the second reactive functional group of the (meth) acrylic resin The isocyanate group can be reacted rapidly.

  The active energy ray curing according to any one of claims 1 to 5, wherein the polyfunctional compound is a (meth) acrylate having 3 or more active energy ray-curable functional groups. Sex composition. When comprised in this way, in addition to the effect of the invention which concerns on any one of Claims 1-5, the mechanical strength of hardened | cured material can be raised.

Claims (5)

An active energy ray-curable composition comprising (meth) acrylic (meth) acrylate having an active energy ray-curable functional group, a polyfunctional compound having a plurality of active energy ray-curable functional groups, and a photopolymerization initiator. Because
The (meth) acrylic (meth) acrylate is obtained by polymerizing a monomer mixture containing 30% by mass or more of an oleophilic monomer having an alkyl group or a cycloalkyl group and a (meth) acrylic monomer having a first reactive functional group. The (meth) acrylic resin to be reacted with a monomer having a second reactive functional group that reacts with the first reactive functional group of the (meth) acrylic monomer and an active energy ray-curable functional group, and is lipophilic. An active energy ray-curable composition having a hydrophilic / lipophilic balance value (HLB value) calculated by the Davis method of an alkyl group or a cycloalkyl group of a monomer of 4.5 or less. 2. The active energy ray-curable composition according to claim 1, wherein the lipophilic monomer has an HLB value calculated by a Davis method of an alkyl group or a cycloalkyl group of −4.0 to 4.2. object. The active energy ray-curable composition according to claim 1 or 2, wherein the lipophilic monomer has an alkyl group having 8 to 22 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms. 4. The active energy ray-curable composition according to claim 1, wherein the content of the lipophilic monomer in the monomer mixture is 50 to 85% by mass. 5. The method according to claim 1, wherein the first reactive functional group and the second reactive functional group are a combination of a hydroxyl group or a glycidyl group and an isocyanate group or a carboxyl group. The active energy ray-curable composition described in 1.