JP2023131972A - Active energy ray-curable composition and film - Google Patents

Abstract

To provide an active energy ray-curable composition capable of forming a hard coat layer which can give a film surface hardness and can maintain its adhesion when exposed to hot water or light, and provide a film including a cured coating of the composition.SOLUTION: An active energy ray-curable composition is provided that includes a compound (A) with a (meth)acryloyl group and a compound (B) with a triazine or triazole structure. There is also provided a film that includes a cured coating of the active energy ray-curable composition.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable composition and a film.

Flat panel displays (FPD) such as liquid crystal displays (LCDs), organic EL displays (OLEDs), and plasma displays (PDPs) are used as display devices for various electronic devices such as computers, televisions, mobile phones, and electronic dictionaries. There is. Further, display elements inside the display, touch panels (touch sensors), and the like are provided with electrodes made of a conductive electrode material such as indium tin oxide (ITO).

Various resin films are used for various purposes such as scratch prevention films for display surfaces, protective films for electrodes inside displays and touch panels, decorative films (sheets) for the interior and exterior of automobiles, low-reflection films for windows, and heat ray blocking films. It is used. However, since the surface of a resin film may have low hardness and light resistance, in order to compensate for these, a hard coat agent made of a UV curable composition is applied to the film surface and cured to form a hard coat layer on the film surface. It is common practice to provide The hard coat layer is also required to have high adhesion to the resin film (substrate), and in particular, for protective films of electrodes inside displays and touch panels, adhesion is required to prevent moisture and salt from entering the electrodes and protective films. becomes important.

Therefore, from the viewpoint of being usable in a variety of applications, there is a need for a hard coat layer that has good hardness, light resistance, and adhesion to substrates.

As a composition with high adhesiveness, a composition containing 2% by mass or more of an active energy ray-curable component having a tertiary amino group and a cured coating film thereof are known. (For example, see Patent Document 1.)
Furthermore, Patent Document 2 discloses a cured coating film of a composition containing a polymerizable monomer having an isocyanurate skeleton and a polymerizable monomer having an oxyethylene group, which exhibits high heat-resistant water adhesion. ing.

However, the invention described in Patent Document 1 does not test for water intrusion between the base material and the cured coating film, and the invention described in Patent Document 2 does not conduct a light resistance test. Therefore, it has been difficult to realize a composition that satisfies hardness, light resistance, and adhesion to a substrate.

JP2020-197737A Re-table No. 2019-235206

The problem to be solved by the present invention is an active energy ray-curable composition that can form a hard coat layer with excellent hardness, hot water-resistant adhesion, and light-resistant adhesion on the film surface, and a film using a cured coating film of the composition. The goal is to provide the following.

The present invention provides an active energy ray-curable composition containing a compound (A) having a (meth)acryloyl group and a compound (B) having a triazine structure or triazole structure. The present invention also provides a film having a cured coating film of the active energy ray-curable composition.

（式（Ｉ）中、Ｒ_１は下記式（ａ）～（ｅ）のいずれか１つで表される基を示し、Ｒ_２は下記式（ｆ）～（ｈ）のいずれか１つで表される基を示し、同一分子中の複数のＲ_２は同一でも異なっていてもよい。）

（式（ａ）中、＊は結合手である。）

（式（ｂ）中、＊は結合手である。）

（式（ｃ）中、＊は結合手であり、Ｒ_３は炭素数１～１０のアルキル基である。）

（式（ｄ）中、＊は結合手である。）

（式（ｅ）中、＊は結合手である。）

（式（ｆ）中、＊は結合手であり、Ｒ_４は水素原子、メチル基、及びフェニル基のいずれかであり、同一分子中の複数のＲ_４は同一でも異なっていてもよい。）

（式（ｇ）中、＊は結合手である。）

（式（ｈ）中、＊は結合手であり、Ｒ_５は炭素数１～８のアルキル基である。）
［７］前記化合物（Ｂ）の含有量が樹脂固形分１００質量部に対して、０．５～６質量部である［１］～［６］のいずれかの活性エネルギー線硬化性組成物。
［８］アクリル樹脂（Ｃ）をさらに含有する［１］～［７］のいずれかの活性エネルギー線硬化性組成物。
［９］前記アクリル樹脂（Ｃ）の重量平均分子量が５０００～３００００の範囲であり、二重結合当量が２００～４５０の範囲である［８］の活性エネルギー線硬化性組成物。
［１０］前記アクリル樹脂（Ｃ）が、下記式（ＩＩ）又は式（ＩＩＩ）で表される構造を有する［８］又は［９］の活性エネルギー線硬化性組成物。

（式（ＩＩ）及び式（ＩＩＩ）中、Ｒ_６は水素原子またはメチル基を示し、繰り返し数ｎは任意の自然数である。式（ＩＩ）中、Ｒ_７は炭素数１～８のアルキル基、及び式(ｉ)で表される基のいずれかを示す。式（ＩＩＩ）中、Ｒ_８は炭素数１～８のアルキル基、及び式(ｊ)で表される基のいずれかを示し、繰り返し数ｍは２～４のいずれかである。同一分子中の複数のＲ_６、Ｒ_７、Ｒ_８、ｍは同一でも異なっていてもよく、式(ｉ)及び式（ｊ）中、＊は結合手であり、Ｒ_９及びＲ_１０は水素基またはメチル基を示す。）
［１１］前記アクリル樹脂（Ｃ）の含有量が樹脂固形分１００重質量部に対して、５～６０質量部である［８］～［１０］のいずれかの活性エネルギー線硬化性組成物。
［１２］無機粒子（Ｄ）をさらに含有する［１］～［１１］のいずれか記載の活性エネルギー線硬化性組成物。
［１３］前記無機粒子（Ｄ）の粒子径が２００ｎｍ以下であり、前記無機粒子（Ｄ）の含有量が樹脂固形分１００重質量部に対して、５～６５質量部である［１２］記載の活性エネルギー線硬化性組成物。
［１４］前記無機粒子（Ｄ）が反応性基を有する表面修飾剤で修飾された無機酸化物である［１２］又は［１３］の活性エネルギー線硬化性組成物。
［１５］［１］～［１４］のいずれか一項記載の組成物を硬化させた硬化塗膜を有することを特徴とするフィルム。
［１６］前記硬化塗膜表面のぬれ張力が３５～６０ｍＮ／ｍの範囲である［１５］記載のフィルム。 That is, the present invention provides the following inventions.
[1] An active energy ray-curable composition containing a compound (A) having a (meth)acryloyl group and a compound (B) having a triazine structure or a triazole structure.
[2] Active energy ray curability of [1], wherein the compound (A) has four or more (meth)acryloyl groups in the molecule and has a double bond equivalent in the range of 80 g/mol to 160 g/mol. Composition.
[3] Compound (A-1) in which the compound (A) does not have a urethane bond in the molecule and has a (meth)acryloyl group, and a compound (A-1) in which the compound (A) has a urethane bond and a (meth)acryloyl group in the molecule. -2) The active energy ray-curable composition of [1] or [2] containing either one or both.
[4] The compound (A-1) may contain either or both of a compound (A-1-1) containing a hydroxyl group in the molecule and a compound (A-1-2) not containing a hydroxyl group in the molecule. The active energy ray-curable composition of [3] containing the active energy ray-curable composition.
[5] The compound (A) contains the compound (A-1) and the compound (A-2), and the compounding ratio of the compound (A-2) to the compound (A-1) [(A -1)/(A-2)] is in the range of 1/10 to 40/1 in the active energy ray-curable composition of [3] or [4].
[6] The active energy ray-curable composition according to any one of [1] to [5], wherein the compound (B) is a compound represented by the following formula (I).

(In formula (I), R ₁ represents a group represented by any one of the following formulas (a) to (e), and R ₂ represents any one of the following formulas (f) to (h). (Indicates the group represented, and multiple _R2s in the same molecule may be the same or different.)

(In formula (a), * is a bond.)

(In formula (b), * is a bond.)

(In formula (c), * is a bond, and R ₃ is an alkyl group having 1 to 10 carbon atoms.)

(In formula (d), * is a bond.)

(In formula (e), * is a bond.)

(In formula (f), * is a bond, R ₄ is a hydrogen atom, a methyl group, or a phenyl group, and multiple R _4s in the same molecule may be the same or different.)

(In formula (g), * is a bond.)

(In formula (h), * is a bond, and R ₅ is an alkyl group having 1 to 8 carbon atoms.)
[7] The active energy ray-curable composition according to any one of [1] to [6], wherein the content of the compound (B) is 0.5 to 6 parts by mass based on 100 parts by mass of the resin solid content.
[8] The active energy ray-curable composition according to any one of [1] to [7], further containing an acrylic resin (C).
[9] The active energy ray-curable composition of [8], wherein the acrylic resin (C) has a weight average molecular weight in the range of 5,000 to 30,000 and a double bond equivalent in the range of 200 to 450.
[10] The active energy ray-curable composition of [8] or [9], wherein the acrylic resin (C) has a structure represented by the following formula (II) or formula (III).

(In formula (II) and formula (III), R ₆ represents a hydrogen atom or a methyl group, and the repeating number n is any natural number. In formula (II), R ₇ is an alkyl group having 1 to 8 carbon atoms. , and a group represented by formula (i).In formula (III), R ₈ represents either an alkyl group having 1 to 8 carbon atoms or a group represented by formula (j). , the repeating number m is either 2 to 4. Plural R ₆ , R ₇ , R ₈ , m in the same molecule may be the same or different, and in formula (i) and formula (j), * is a bond, and R ₉ and R ₁₀ represent a hydrogen group or a methyl group.)
[11] The active energy ray-curable composition according to any one of [8] to [10], wherein the content of the acrylic resin (C) is 5 to 60 parts by weight based on 100 parts by weight of the resin solid content.
[12] The active energy ray-curable composition according to any one of [1] to [11], further containing inorganic particles (D).
[13] The particle size of the inorganic particles (D) is 200 nm or less, and the content of the inorganic particles (D) is 5 to 65 parts by weight based on 100 parts by weight of the resin solid content [12] Active energy ray curable composition.
[14] The active energy ray-curable composition of [12] or [13], wherein the inorganic particles (D) are inorganic oxides modified with a surface modifier having a reactive group.
[15] A film comprising a cured coating film obtained by curing the composition according to any one of [1] to [14].
[16] The film according to [15], wherein the cured coating surface has a wetting tension in the range of 35 to 60 mN/m.

By coating and curing the active energy ray-curable composition of the present invention on the surface of a resin film, it can impart high hardness to the film surface and form a hard coat layer with excellent light-resistant adhesion and hot water-resistant adhesion. can do.

Therefore, the active energy ray-curable composition of the present invention can be used as a display device for various electronic devices such as personal computers, televisions, mobile phones, and electronic dictionaries, such as liquid crystal displays (LCDs), organic EL displays (OLEDs), and plasma displays (PDPs). ) and other flat panel displays (FPD), protective films for the display elements and electrodes of touch panels (touch sensors) inside these displays and touch panels, decorative films (sheets) for the interior and exterior of automobiles, low-temperature coatings for windows, etc. It can be widely used in various applications such as reflective films and heat ray cutting films, and is particularly suitable for use as a hard coating agent for protective films of electrodes inside touch panels.

In this specification, the compound represented by formula (I) is referred to as "compound (I)", and the compounds represented by other formulas are also referred to in the same manner.
Furthermore, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate," and "(meth)acryloyl" and "acryloyl" are collectively referred to as "(meth)acryloyl."
The compound (A) having a (meth)acryloyl group is referred to as "component (A)", and the other components (B) to (D) are also referred to in the same manner.

<Active energy ray curable composition>
The active energy ray-curable composition of the present invention has components (A) and (B) as essential components, and optionally contains components (C) to (D) or other compounds.
As an evaluation method of the present invention, the hardness of a coating film obtained by curing the composition was tested. Furthermore, the adhesion to the substrate was tested after the coating was immersed in boiling water or exposed to ultraviolet rays. In the case of a coating film that easily absorbs water, its volume increases and its adhesion to the substrate decreases.
Therefore, when this test result is excellent, it is considered that the hot water resistant adhesion and light resistant adhesion are excellent.

[(A) Component]
Component (A) is a compound having one or more (meth)acryloyl groups in the molecule, and a mixture thereof.
Furthermore, component (A) includes a compound (A-1) having no urethane bond and a (meth)acryloyl group in the molecule, and a compound (A-2) having a urethane bond and a (meth)acryloyl group in the molecule. ).

[Compound (A-1)]
Compound (A-1) contains either or both of a compound (A-1-1) containing a hydroxyl group in the molecule and a compound (A-1-2) not containing a hydroxyl group in the molecule.
Since the compound containing a hydroxyl group (A-1-1) has a hydroxyl group, it improves the reactivity of the (meth)acryloyl group through intermolecular interaction, and improves the hardness of the cured coating film and the adhesion to the substrate. It can be done. Furthermore, for the compound (A-1-2) that does not contain a hydroxyl group, the viscosity of the composition and the concentration of each compound can be adjusted as appropriate.

Specifically, the compound (A-1-1) containing a hydroxyl group in the molecule includes ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and dipentaerythritol. Examples include tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and the like. These may be used alone or in combination.

Specifically, the compound (A-1-2) containing no hydroxyl group in the molecule includes 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1 , 6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol Di(meth)acrylate of dihydric alcohol such as di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; Diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A. Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripenta Erythritol octa(meth)acrylate, polypentaerythritol poly(meth)acrylate, (poly)ethylene glycol dipentaerythritol hexa(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)ethylene glycol (meth)acrylate , (poly)propylene glycol dipentaerythritol (meth)hexaacrylate, (poly)propylene glycol di(meth)acrylate, (poly)propylene glycol (meth)acrylate, ethoxylated dipentaerythritol poly(meth)acrylate, neopentyl glycol Diol di(meth)acrylate obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, etc. Examples include acrylates having an alkylene oxide structure; acrylates having an amine skeleton such as amine-modified polyether tetraacrylate; and polyfunctional (meth)acrylates such as acrylates having a thiol group such as ethanedithiol-modified poly(meth)acrylate. These may be used alone or in combination.

[Compound (A-2)]
The synthesis method of compound (A-2) is not particularly limited as long as it has at least a urethane bond and a (meth)acryloyl group in the molecule, but it can be synthesized by combining a compound having an isocyanate group with a hydroxyl group and a (meth)acryloyl group. Examples include compounds obtained by dehydration condensation reaction with a compound having
Further, since compound (A-2) has a urethane bond, it improves the reactivity of the (meth)acryloyl group through intermolecular interaction, and improves the hardness and hot water resistant adhesion of the cured coating film.

Examples of compounds having an isocyanate group that can be used as raw materials for compound (A-2) include aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate; 1,6-hexamethylene diisocyanate, 1,4-butane diisocyanate, 2,2,4 - Aliphatic isocyanates such as trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-bis( Alicyclic isocyanate compounds such as isocyanatomethyl)cyclohexane, norbornane diisocyanate, hydrogenated xylene diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc. . Alternatively, dimers or trimers (isocyanurate, biuret, allophanate, etc.) of these isocyanate compounds may be used. These may be used alone or in combination.

Examples of compounds having a hydroxyl group and a (meth)acryloyl group that can be used as raw materials for compound (A-2) include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy mono(meth)acrylate (e.g. Daicel) Polycarbonate-modified hydroxy mono(meth)acrylate (for example, Daicel's product name "HEMAC" (registered trademark), etc.), polyethylene glycol or Examples include polypropylene glycol-modified hydroxy mono(meth)acrylates (for example, trade names "Blenmar (registered trademark) AE-200", "Blenmar (registered trademark) AP-400" manufactured by NOF Corporation), and the like. These may be used alone or in combination.

Among the above, it is more preferable that component (A) has a compound having four or more (meth)acryloyl groups in the molecule.
Specifically, as compound (A-1-1), dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, etc. are more preferable.
As the compound (A-1-2), pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are more preferable.
Examples of the compound (A-2) include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, a dimer of 1,6-hexamethylene diisocyanate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. More preferred.
By using four or more (meth)acryloyl compounds in the molecule as component (A) in this way, the crosslinking density when curing the composition is improved and the hardness is increased. Furthermore, the cured coating film becomes less likely to absorb moisture, and its heat-resistant water adhesion properties are also improved.

The compound used as component (A) preferably has a double bond equivalent in the range of 20 to 300 g/mol, more preferably in the range of 50 to 250 g/mol, and more preferably in the range of 80 to 160 g/mol. Particularly preferred are compounds where The double bond equivalent herein refers to the mass of a compound divided by the amount of double bonds in the compound.
By using a compound having a double bond equivalent within these ranges, the crosslinking density becomes optimal, and hardness, hot water resistant adhesion, and light resistant adhesion can be improved in a well-balanced manner.

When component (A) contains both compound (A-1) and compound (A-2), the blending ratio of compound (A-2) to compound (A-1) [(A-1)/ (A-2)] is preferably in the range of 1/100 to 100/1, more preferably in the range of 1/40 to 60/1, and more preferably in the range of 1/10 to 40/1. It is particularly preferable. By setting it as these ranges, light resistance adhesion improves.

When the compound (A-1) component contains both a compound (A-1-1) containing a hydroxyl group in the molecule and a compound (A-1-2) not containing a hydroxyl group in the molecule, the compound ( The blending ratio of the compound (A-1-2) to A-1-1) [(A-1-1)/(A-1-2)] is preferably in the range of 20/80 to 95/5, The range of 30/70 to 90/10 is more preferred, and the range of 50/50 to 80/20 is particularly preferred. By setting it within these ranges, the hydrophilicity of compound (A-1) can be adjusted to an optimal range, and the hot water resistant adhesion is improved.

[(B) Component]
Component (B) is a compound having a triazine structure or a triazole structure in its molecule. Component (B) can weaken the water absorption of the cured coating film of the composition and increase the heat-resistant water adhesion. Furthermore, since it can absorb ultraviolet rays, light-resistant adhesion can also be improved.

Specifically, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-( 1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol ], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-( Examples include benzotriazoles such as 2-hydroxy-5-t-butylphenyl)-2H-benzotriazole; or triazines represented by the following formula (I).

In formula (I), R ₁ represents a group represented by any one of the following formulas (a) to (e), and R ₂ represents a group represented by any one of the following formulas (f) to (h). R ₂ in the same molecule may be the same or different.

In formula (c), R ₃ is an alkyl group having 1 to 10 carbon atoms.

R ₄ is a hydrogen atom, a methyl group, or a phenyl group, and multiple R _4s in the same molecule may be the same or different.

R ₅ is an alkyl group having 1 to 8 carbon atoms.

In the above formulas (a) to (h), * is a bond.

Among the above-mentioned components (B), 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole or the compound (I ) is more preferred, and a compound in which R ₁ in compound (I) is (b), R ₂ is (f), and R ₄ in (f) is a hydrogen atom is particularly preferred.

Component (B) may be used alone or in combination of two or more.

The content of compound (B) is preferably in the range of 0.1 to 20 parts by mass, and preferably in the range of 0.3 to 8 parts by mass, based on 100 parts by mass of the total resin solid content in the composition. More preferably, the amount is particularly preferably 0.5 to 6.0 parts by mass. By setting it as these ranges, a composition will harden|cure without a problem, the water absorption power of a cured coating film can also be reduced, and light resistance is also improved. Therefore, hot water-resistant adhesion and light-resistant adhesion are improved.

The composition of the present invention may further contain component (C) if necessary.

[(C) Component]
Component (C) is an acrylic resin, that is, a polymer of acrylic ester or methacrylic ester. When the composition of the present invention contains component (C), the cured coating film becomes moderately easy to deform. Therefore, even if the volume of the base material increases, the shape of the cured coating film can change to match the base material, improving adhesion to the base material.

The weight average molecular weight of the acrylic resin that can be used as component (C) is preferably in the range of 1,000 to 50,000, more preferably in the range of 2,000 to 40,000, particularly preferably in the range of 5,000 to 30,000. preferable. By setting it as these ranges, hot water-resistant adhesion and light-resistant adhesion will improve.

Furthermore, the acrylic resin that can be used as component (C) preferably has a double bond equivalent in the range of 100 to 700 g/mol, more preferably in the range of 150 to 600 g/mol, and more preferably in the range of 200 to 450 g/mol. A range of /mol is particularly preferred. By setting it as these ranges, hot water-resistant adhesion and light-resistant adhesion will improve.

Specifically, as component (C), it is preferable to use a compound having a structure represented by the following formula (II) or the following formula (III).

In formula (II) and formula (III), R ₆ represents a hydrogen atom or a methyl group, and the repeating number n is an arbitrary natural number. In formula (II), R ₇ represents either an alkyl group having 1 to 8 carbon atoms or a group represented by formula (i). In formula (III), R ₈ represents either an alkyl group having 1 to 8 carbon atoms or a group represented by formula (j), and the repeating number m is 2 to 4. A plurality of R ₆ , R ₇ , R ₈ and m in the same molecule may be the same or different.

In formula (i) or formula (j), * is a bond, and R ₉ and R ₁₀ represent a hydrogen group or a methyl group.

The content of the acrylic resin (C) is preferably in the range of 1 to 90 parts by weight, and preferably in the range of 3 to 80 parts by weight, based on 100 parts by weight of the total resin solid content in the composition. More preferably, the amount is in the range of 5 to 60 parts by mass. By setting it as these ranges, the shape can be changed moderately while maintaining a high crosslinking density of the cured coating film.
Therefore, the water absorption of the coating film can be reduced and the shape change of the base material can be followed, so that the hot water resistant adhesion is improved.

The composition of the present invention may further contain component (D) if necessary.

[(D) Component]
Component (D) is an inorganic particle. By containing the inorganic particles (D) in the composition, volume shrinkage during curing of the composition can be suppressed. Therefore, stress strain is less likely to occur between the base material and the cured coating film, and hot water-resistant adhesion and light-resistant adhesion are improved.

Specific examples of inorganic particles (D) include silica, alumina, magnesia, titania, zirconia, etc.; examples of those having excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, etc.; Examples of materials with excellent conductivity include metal fillers and/or metal-coated fillers using metals or alloys (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); barriers; Examples of minerals with excellent properties include mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, and barium sulfate. , zinc oxide, magnesium hydroxide; those with a high refractive index include barium titanate, zirconia oxide, titanium oxide, etc.; those exhibiting photocatalytic properties include titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, etc. , photocatalytic metals such as carbon, sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, and lead, composites of the above metals, oxides thereof, etc.; Those with excellent wear resistance include: Metals such as alumina, zirconia, magnesium oxide, and their composites and oxides, etc.; Those with excellent conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; Those with excellent ultraviolet shielding include: Titanium oxide, zinc oxide, etc. can be used. These inorganic fine particles may be appropriately selected depending on the intended use, and may be used alone or in combination.

For example, when using silica as component (D), there is no particular limitation, and known fine silica particles such as powdered silica and colloidal silica can be used. Commercially available powdered silica particles include, for example, the "Aerosil (registered trademark)" series (50, 200, etc.) manufactured by Nippon Aerosil Co., Ltd., and the "Sildex" series (H31, H32, H32, etc.) manufactured by AGC Co., Ltd. H51, H52, H121, H122, etc.), product name "E220A" or "E220" manufactured by Tosoh Silica Co., Ltd., product name "SYLYSIA (registered trademark) 470" manufactured by Fuji Silysia Chemical Co., Ltd., product name manufactured by Nippon Sheet Glass Co., Ltd. Examples include "SG flakes".
In addition, commercially available colloidal silica includes, for example, the product names "Methanol Silica Sol", "IPA-ST", "MEK-ST", "PGM-ST", "NBA-ST", and "Methanol Silica Sol" manufactured by Nissan Chemical Industries, Ltd. XBA-ST”, “DMAC-ST”, “ST-UP”, “ST-OUP”, “ST-20”, “ST-40”, “ST-C”, “ST-N”, “ST- Examples include "O", "ST-50", "ST-OL", etc.

Reactive silica may be used as the silica. Examples of the reactive silica include reactive compound-modified silica. From the viewpoint of lowering the water absorption of the cured coating film, the reactive compounds include, for example, a reactive silane coupling agent having a hydrophobic group, a compound having a (meth)acryloyl group, a compound having a maleimide group, and a compound having a glycidyl group. are preferred, and from the viewpoint of compatibility with component (A) and other components, silica modified with a compound having a (meth)acryloyl group is particularly preferred.
Commercially available powdered silica modified with a compound having a (meth)acryloyl group includes (meth)acryloyl Commercially available colloidal silica modified with a compound having a group includes the product names "MIBK-SD", "MIBK-SD-L", "MIBK-AC-2140Z", and "MEK-AC-2140Z" manufactured by Nissan Chemical Industries, Ltd. ” etc. In addition, silica modified with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then subjected to an addition reaction with acrylic acid, or 3-isocyanatepropyltriethoxysilane and a compound having a hydroxyl group and a (meth)acryloyl group can be used as urethane. Reactive silica also includes silica modified with chemical reaction.

The method for producing silica that can be used in the present invention is not particularly limited, but for example, silica produced by a wet method can be used. In addition, although precipitation methods and gel methods are known as wet methods, silica produced by either method can be used. Furthermore, in both the precipitation method and the gel method, by adjusting the reaction conditions (pH, raw material concentration, reaction temperature, etc.) between sodium silicate, which is the raw material for silica particles, and mineral acids such as sulfuric acid, the primary average particle size of silica can be improved. The diameter and secondary average particle diameter may be adjusted.

It is preferable that silica particles having a primary average particle size are crushed into secondary agglomerates (the particle size after crushing is defined as the secondary average particle size), and the equipment used for crushing silica particles is as follows: A ball mill, bead mill, rod mill, SAG mill, high-pressure grinding roll, vertical axis impactor (VSI) mill, colloid mill, conical mill, disk mill, edge mill, hammer mill, mortar, jet mill, etc. can be used.

Furthermore, when pulverizing silica particles, a wetting and dispersing agent or a silane coupling agent may be added to modify the surface of the silica particles with an organic group at the same time as pulverization. Examples of the wetting and dispersing agent and silane coupling agent include DISPERBYK-103 and DISPERBYK-106.
, DISPERBYK-161, DISPERBYK-2152, DISPERBYKP104, 3-(meth)acryloylpropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Can be used.

The inorganic particles (D) preferably have a secondary average particle diameter in the range of 10 to 300 nm, more preferably in the range of 20 to 250 nm, and particularly preferably in the range of 50 to 200 nm. Within these ranges, the transparency of the cured coating film can be maintained.

The blending amount of the inorganic particles (D) is preferably in the range of 0 to 90 parts by mass, more preferably in the range of 3 to 80 parts by mass, and more preferably in the range of 5 to 65 parts by mass, based on 100 parts by mass of the total resin solid content in the composition. Particularly preferred is a range of 50%. By setting it as these ranges, it is possible to reduce the water absorption of the cured coating film while suppressing shrinkage during curing of the composition. That is, since it is difficult to form a space between the base material and the cured coating film, hot water-resistant adhesion and light-resistant adhesion are improved.

Moreover, the active energy ray-curable composition of the present invention may contain a photopolymerization initiator.

[Photopolymerization initiator]
Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and the like.

The above photopolymerization initiators can be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the solid content of the active energy ray-curable composition. , 1 to 5 parts by mass is particularly preferred. It is preferable that the content of the photopolymerization initiator is 0.1 part by mass or more because the curing reaction proceeds suitably and a cured coating film having high hardness can be obtained. On the other hand, it is preferable that the content of the photopolymerization initiator is 10 parts by mass or less because yellowing and the like are less likely to occur and a cured coating film having high transparency can be obtained.

Moreover, the active energy ray-curable composition of the present invention may contain a solvent. By including a solvent, the viscosity of the composition can be adjusted.

[solvent]
Examples of the solvent include alcohol solvents such as methanol, ethanol, 1-propanol, t-butanol, and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Alcohol ether solvents such as monoethyl ether, carbitol, and cellosolve; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; toluene, xylene, dibutylhydroxytoluene, etc. Examples include aromatic solvents.

The above-mentioned solvents can be used alone or in combination of two or more.

The content of the solvent is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the solid content of the active energy ray-curable composition. It is preferable that the content of the solvent is 300 parts by mass or less because the film thickness can be easily controlled. In addition, it is preferable that the content of the solvent is 10 parts by mass or more, since various coating methods such as spray coating and flow coating can be employed.

Furthermore, the active energy ray-curable composition of the present invention may contain other additives as necessary.

[Other ingredients]
Typical other components include, for example, reactive compounds, various resins, fillers, ultraviolet absorbers, and leveling agents. However, these do not fall under components (A) to (D).
It also contains inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, stabilizers, fluidity regulators, coupling agents, dyes, rheology control agents, antioxidants, plasticizers, etc. You can leave it there.

As the reactive compound and resin, a compound having a double bond such as a (meth)acrylate compound or a vinyl group other than the component (A) and the component (C) may be blended.

Liquid organic polymers may be used to adjust the viscosity. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and includes, for example, carboxyl group-containing polymer modified products (Floren G-900, NC-500: Kyoei Kagaku Kogyo Co., Ltd.), acrylic polymers (Floren WK-20: Kyoei Kagaku Kogyo Co., Ltd.), special modified phosphoric acid ester amine salt (HIPLAAD (registered trademark) ED-251: Kusumoto Kasei Co., Ltd.), modified acrylic block copolymer (DISPERBYK (registered trademark) 2000; Byk Chemie Co., Ltd.), etc. can be mentioned.

As various resins, thermosetting resins and thermoplastic resins can be used.
A thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means such as heating, radiation, or a catalyst. As a specific example, a thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means such as heating, radiation, or a catalyst. Specific examples include phenolic resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin. Examples include resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene-maleic anhydride (SMA) resins, and the like. These thermosetting resins can be used alone or in combination of two or more.

Thermoplastic resin refers to resin that can be melt-molded by heating. Specific examples include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndication Examples include tactic polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

As the filler, things other than component (D) can be used, such as inorganic fibers or organic fibers.

Inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, and silicon carbide fiber, as well as carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber, and silicon carbide fiber (silicon carbide fiber). ), ceramic fibers, alumina fibers, natural fibers, mineral fibers such as basalt, boron fibers, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

Organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylenebenzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, polyarylate, cellulose, pulp, Examples include natural fibers such as cotton, wool, and silk, and regenerated fibers such as proteins, polypeptides, and alginic acid.

Examples of the ultraviolet absorber include benzophenone type, cyclic iminoester type, cyanoacrylate type, and polymer type ultraviolet absorber.

A light stabilizer can also be used in the composition of the present invention for the purpose of improving light resistance. Examples of the light stabilizer include hindered amine stabilizers (HALS).

Various surface modifiers may be added to the composition of the present invention for the purpose of increasing the leveling property during coating, the sliding property of the cured film, and the scratch resistance, etc. As the surface modifier, various additives that modify surface physical properties, which are commercially available under the names of surface conditioners, leveling agents, slippery agents, antifouling agents, etc., can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
Specifically, silicone polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone polymers and oligomers having silicone chains and polyester chains, fluorine polymers and oligomers having perfluoroalkyl groups and polyalkylene oxide chains, Examples include fluoropolymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains. One or more of these may be used. For the purpose of increasing the durability of slipperiness, a material containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL (registered trademark) 350 (manufactured by Daicel Allnex), BYK-333 (manufactured by BYK-Chemie Japan), BYK-377 (manufactured by BYK-Chemie Japan), and BYK-378 (manufactured by BYK-Chemie Japan). BYK-UV3500 (manufactured by BYK-Chemie Japan), BYK-UV3505 (manufactured by BYK-Chemie Japan), BYK-UV3576 (manufactured by BYK-Chemie Japan), Megafac (registered trademark) RS-75 (manufactured by BYK-Chemie Japan) (manufactured by DIC), Megafac (registered trademark) RS-76-E (manufactured by DIC), Megafac (registered trademark) RS-72-K (manufactured by DIC), Megafac (registered trademark) RS-76-NS (manufactured by DIC), Megafac (registered trademark) RS-90 (manufactured by DIC), Megafac (registered trademark) RS-91 (manufactured by DIC), Megafac (registered trademark) RS-55 (manufactured by DIC) , Optool (registered trademark) DAC-HP (manufactured by Daikin), ZX-058-A (manufactured by T&K TOKA), ZX-201 (manufactured by T&K TOKA), ZX-202 (manufactured by T&K TOKA), ZX-212 (manufactured by T&K TOKA) ), ZX-214-A (manufactured by T&K TOKA), X-22-164AS (manufactured by Shin-Etsu Chemical), X-22-164A (manufactured by Shin-Etsu Chemical), X-22-164B (manufactured by Shin-Etsu Chemical) (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd.), and X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.).

The active energy ray-curable composition of the present invention is applied to at least one surface of various materials and then irradiated with active energy rays, thereby imparting hardness and light resistance to the substrate and forming a cured coating film with high adhesion. It can be suitably used as The cured coating film made of the composition of the present invention can impart hardness and light resistance to the film surface, and can also form a hard coat layer with excellent hot water resistant adhesion, so it can be used in harsh high temperature and high humidity environments. It exhibits particularly excellent effects when used as a hard coat for materials that will be used outdoors for long periods of time.

<Cured coating/film>
(Composition/Materials)
The film of the present invention has a coating film made of a cured product of the active energy ray-curable composition of the present invention, and a base material.
There are no particular limitations on the base material, and it may be selected as appropriate depending on the application. Examples include plastic, glass, wood, metal, metal oxide, paper, silicon, or modified silicon, and the base material can be obtained by joining different materials. It may also be a base material.
The shape of the base material is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape having curvature on the entire surface or a part thereof. Furthermore, there are no restrictions on the hardness, thickness, etc. of the base material.

The plastic base material is not particularly limited as long as it is made of resin, and for example, the above-mentioned thermosetting resin or thermoplastic resin may be used. The material may be a base material containing a single resin or a combination of resins, and may have a single layer or a laminated structure of two or more layers. Moreover, these plastic base materials may be fiber reinforced (FRP).

In addition, the base material may include known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, etc., within a range that does not impede the effects of the present invention. It may contain known additives such as crystal nucleating agents and lubricants.

The film of the present invention may further have a second base material on the base material and the cured coating film. The material of the second base material is not particularly limited, and examples thereof include glass, wood, metal, metal oxide, plastic, paper, silicon, modified silicon, etc., and the second base material is a base material obtained by joining different materials. Good too. The shape of the base material is not particularly limited, and may be any shape depending on the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape having curvature on the entire surface or a part thereof. Furthermore, there are no restrictions on the hardness, thickness, etc. of the base material.

Since the cured coating film of the present invention has high adhesion to both plastics and inorganic materials, it can be preferably used as an interlayer material for different materials. Particularly preferably, the base material is plastic and the second base material is an inorganic layer. Examples of inorganic layers include quartz, sapphire, glass, optical films, ceramic materials, inorganic oxides, vapor deposited films (CVD, PVD, sputtering), magnetic films, reflective films, Ni, Cu, Cr, Fe, stainless steel, etc. Metal, paper, SOG (Spin On Glass), SOC (Spin On Carbon), plastic layers such as polyester, polycarbonate, polyimide, TFT array substrates, PDP electrode plates, conductive substrates such as ITO and metals, insulating substrates Examples include silicon-based substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon.

The surface wetting tension of the cured coating film of the present invention is preferably in the range of 35 to 60 mN/m, more preferably in the range of 40 to 55 mN/m. In addition, the said wetting tension is the value measured based on JIS test method K6768:1999.

(Production method)
The film of the present invention can be obtained by applying the composition of the present invention to the surface of a substrate and then curing the composition.
Application to the substrate can be carried out by directly applying the composition to the substrate or by directly molding and curing the composition.
In the case of direct coating, there are no particular limitations on the coating method, including spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, Examples include screen printing method, inkjet method, and the like.
In the case of direct molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, and the like.
Alternatively, the film of the present invention may be obtained by laminating a cured product of the composition on a substrate. When laminating cured products of the composition, a semi-cured cured product may be laminated on the base material and then completely cured, or a completely cured cured product may be laminated on the base material.

Since the composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiation with active energy rays.
Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet (UV) rays are particularly preferred in terms of curability and convenience.
Here, when ultraviolet rays are used as active energy rays, examples of devices for irradiating the ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Examples include black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, and LED lamps. By using these materials and irradiating the coated or molded composition with ultraviolet rays having a wavelength of about 180 to 400 nm, it is possible to obtain a cured coating film or a cured product. The amount of ultraviolet ray irradiation is appropriately selected depending on the type and amount of the photopolymerization initiator used.

(Application)
The cured coating film of the composition of the present application has high hardness and excellent hot water-resistant adhesion and light-resistant adhesion, so it can maintain high adhesion while protecting the object from external impact, moisture, and light. , film for preventing scratches on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), and plasma displays (PDP), display elements inside displays, touch panels (touch sensors), etc. It can be suitably used as a protective film for an electrode made of a conductive electrode material. It can also be suitably used for various purposes such as decorative films (sheets) for the interior and exterior of automobiles, low-reflection films for windows, and heat ray-cutting films.

Hereinafter, the present invention will be explained more specifically using Examples and Comparative Examples, but the present invention is not limited to the following embodiments. Furthermore, in the present examples, "parts" and "%" are based on mass unless otherwise specified.

(Synthesis Example 1: Synthesis of urethane acrylate compound (1))
In a 1 liter flask equipped with a stirrer, gas inlet tube, condenser, and thermometer, add Covestro's "Desmodur H" (168.2 parts by mass) and 2,6-di-tert-butyl-4-methyl. Phenol (1.05 parts by mass), methoxyhydroquinone (0.11 parts by mass) and dibutyltin diacetate (0.11 parts by mass) were added, the temperature was raised to 70°C, and pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd.) was added. Aronix M-306 (trade name) containing about 30% by mass of pentaerythritol tetraacrylate (356.9 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80° C. until the infrared absorption spectrum at 2250 cm ⁻¹ indicating the isocyanate group disappeared, to obtain urethane acrylate compound (1) (containing about 20.4% pentaerythritol tetraacrylate).

(Synthesis Example 2: Synthesis of urethane acrylate compound (2))
In a 1 liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "IPDI" manufactured by Covestro (222.3 parts by mass), 2,6-di-tert-butyl-4-methylphenol ( 1.16 parts by mass), methoxyhydroquinone (0.12 parts by mass), and dibutyltin diacetate (0.12 parts by mass) were heated to 70°C, and pentaerythritol triacrylate (trade name manufactured by Toagosei Co., Ltd.) was added. "Aronix M-306" (containing about 30% by mass of pentaerythritol tetraacrylate) (356.9 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80° C. until the infrared absorption spectrum at 2250 cm ⁻¹ indicating an isocyanate group disappeared, to obtain urethane acrylate compound (2) (containing about 18.5% pentaerythritol tetraacrylate).

(Synthesis Example 3: Synthesis of urethane acrylate compound (3))
In a 1 liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "IPDI" manufactured by Covestro (222.3 parts by mass), 2,6-di-tert-butyl-4-methylphenol ( 1.49 parts by mass), methoxyhydroquinone (0.15 parts by mass), and dibutyltin diacetate (0.15 parts by mass) were added, the temperature was raised to 70°C, and "MIRAMER M500" manufactured by MIWON (524 parts by mass) was added. was prepared in portions over 1 hour. After charging, the reaction was carried out at 80° C. until the infrared absorption spectrum at 2250 cm ⁻¹ indicating the isocyanate group disappeared, to obtain urethane acrylate compound (3).

(Synthesis Example 4: Synthesis of urethane acrylate compound (4))
In a 1-liter flask equipped with a stirrer, a gas inlet tube, a condenser, and a thermometer, "Basnonat HB100" manufactured by BASF (186.67 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.09 parts by mass), methoxyhydroquinone (0.11 parts by mass), and dibutyltin diacetate (0.11 parts by mass) were added, and the temperature was raised to 70°C. Aronix M-306 (containing about 30% by mass of pentaerythritol tetraacrylate) (356.87 parts by mass) was charged in portions over 1 hour. After charging, the reaction was carried out at 80° C. until the infrared absorption spectrum at 2250 cm ⁻¹ indicating an isocyanate group disappeared to obtain urethane acrylate compound (4) (containing about 19.7% pentaerythritol tetraacrylate).

(Synthesis Example 5: Synthesis of acrylic resin (1))
254 parts by mass of methyl isobutyl ketone was charged into a high-pressure sealed reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised with stirring until the system temperature reached 150°C. 229 parts by mass of acrylate, 153 parts by mass of methyl methacrylate, 46 parts by mass of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 1,1'-bis-(t-butyl A mixed solution consisting of 24 parts by mass of cyclohexane (peroxy)cyclohexane ("Perhexa C" manufactured by NOF Corporation) was added dropwise from the dropping funnel over a period of 3 hours, and then maintained at 150° C. for 2 hours. Next, after lowering the temperature to 90°C, 0.1 part by mass of methoquinone and 118 parts by mass of acrylic acid were added, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110°C to give an acid value of 3 mgKOH/g. It was confirmed that the following conditions were met, and an acrylic acrylate resin (ACAC-1) was obtained. The properties of the acrylic acrylate resin (ACAC-1) were as follows. Weight average molecular weight (Mw): 10,000, double bond equivalent: 305.34.

(Synthesis Example 6: Synthesis of acrylic resin (2))
254 parts by mass of methyl isobutyl ketone was charged into a high-pressure sealed reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised with stirring until the system temperature reached 150°C. 283 parts by mass of acrylate, 73 parts by mass of methyl methacrylate, 43 parts by mass of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 1,1'-bis-(t-butyl A mixed solution consisting of 21.5 parts by mass of (peroxy)cyclohexane ("Perhexa C" manufactured by NOF Corporation) was added dropwise from the dropping funnel over a period of 3 hours, and then maintained at 150° C. for 2 hours. Next, after lowering the temperature to 90°C, 0.1 part by mass of methoquinone and 144 parts by mass of acrylic acid were added, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110°C to give an acid value of 3 mgKOH/g. It was confirmed that the following conditions were met, and an acrylic acrylate resin (ACAC-2) was obtained. The properties of the acrylic acrylate resin (ACAC-2) were as follows. Weight average molecular weight (Mw): 10,000, double bond equivalent: 250.21.

(Synthesis Example 7: Synthesis of acrylic resin (3))
254 parts by mass of methyl isobutyl ketone was charged into a high-pressure sealed reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised with stirring until the system temperature reached 150°C. 165 parts by mass of acrylate, 251 parts by mass of methyl methacrylate, 43 parts by mass of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 1,1'-bis-(t-butyl A mixed solution consisting of 21.5 parts by mass of (peroxy)cyclohexane ("Perhexa C" manufactured by NOF Corporation) was added dropwise from the dropping funnel over a period of 3 hours, and then maintained at 150° C. for 2 hours. Next, after lowering the temperature to 90°C, 0.1 part by mass of methoquinone and 84 parts by mass of acrylic acid were added, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110°C to give an acid value of 3 mgKOH/g. It was confirmed that the following conditions were met, and an acrylic acrylate resin (ACAC-3) was obtained. The properties of the acrylic acrylate resin (ACAC-3) were as follows. Weight average molecular weight (Mw): 10,000, double bond equivalent: 428.93.

(Synthesis Example 8: Synthesis of acrylic resin (4))
254 parts by mass of methyl isobutyl ketone was charged into a high-pressure sealed reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised with stirring until the system temperature reached 150°C. 283 parts by mass of acrylate, 73 parts by mass of methyl methacrylate, 30 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 1,1'-bis-(t-butyl A mixed solution consisting of 15 parts by mass of cyclohexane (peroxy)cyclohexane ("Perhexa C" manufactured by NOF Corporation) was added dropwise from the dropping funnel over a period of 3 hours, and then maintained at 150° C. for 2 hours. Next, after lowering the temperature to 90°C, 0.1 part by mass of methoquinone and 144 parts by mass of acrylic acid were added, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110°C to give an acid value of 3 mgKOH/g. It was confirmed that the following conditions were met, and an acrylic acrylate resin (ACAC-4) was obtained. The properties of the acrylic acrylate resin (ACAC-4) were as follows. Weight average molecular weight (Mw): 30,000, double bond equivalent: 250.28.

(Synthesis Example 9: Synthesis of acrylic resin (5))
254 parts by mass of methyl isobutyl ketone was charged into a high-pressure sealed reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised with stirring until the system temperature reached 150°C. 165 parts by mass of acrylate, 251 parts by mass of methyl methacrylate, 30 parts by mass of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 1,1'-bis-(t-butyl A mixed solution consisting of 15 parts by mass of cyclohexane (peroxy)cyclohexane ("Perhexa C" manufactured by NOF Corporation) was added dropwise from the dropping funnel over a period of 3 hours, and then maintained at 150° C. for 2 hours. Next, after lowering the temperature to 90°C, 0.1 part by mass of methoquinone and 84 parts by mass of acrylic acid were added, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110°C to give an acid value of 3 mgKOH/g. It was confirmed that the following conditions were met, and an acrylic acrylate resin (ACAC-5) was obtained. The properties of the acrylic acrylate resin (ACAC-5) were as follows. Weight average molecular weight (Mw): 30,000, double bond equivalent: 428.93.

(Synthesis Example 10: Synthesis of acrylic resin (6))
254 parts by mass of methyl isobutyl ketone was charged into a high-pressure sealed reaction apparatus equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen introduction tube, and the temperature was raised with stirring until the system temperature reached 150°C. 153 parts by mass of acrylate, 229 parts by mass of methyl methacrylate, 56 parts by mass of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 1,1'-bis-(t-butyl A mixed solution consisting of 28 parts by mass of peroxy)cyclohexane ("Perhexa C" manufactured by NOF Corporation) was added dropwise from the dropping funnel over a period of 3 hours, and then maintained at 150° C. for 2 hours. Next, after lowering the temperature to 90°C, 0.1 part by mass of methoquinone and 118 parts by mass of acrylic acid were added, and after adding 3 parts by mass of triphenylphosphine, the temperature was further raised to 110°C to give an acid value of 3 mgKOH/g. It was confirmed that the following conditions were met, and an acrylic acrylate resin (ACAC-6) was obtained. The properties of the acrylic acrylate resin (ACAC-6) were as follows. Weight average molecular weight (Mw): 5,000, double bond equivalent: 305.34

(Example 1)
Solid content: 100 parts by mass of dipentaerythritol pentaacrylate (containing 50% dipentaerythritol hexaacrylate "MIRAMER M400" manufactured by MIWON), 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole ("Tinuvin PS" manufactured by BASF Japan) and 5 parts by mass of Omnirad 184 (manufactured by IGM) were blended, and the solid content was 40 wt in a mixed solvent of propylene glycol monomethyl ether/methyl ethyl ketone = 50/50 wt%. % to prepare an active energy ray-curable composition (1).

(Examples 2 to 51, Comparative Examples 1 to 2)
Active energy ray-curable compositions of each example were obtained in the same manner as in Example 1, except that the solid content compositions shown in Tables 2 to 6 were changed.

[Preparation of evaluation sample]
The active energy ray-curable composition of each example is applied to a polyethylene terephthalate (PET) base material (trade name "Lumirror UH-13" manufactured by Toray Industries, Inc., thickness: 50 μm) so that the film thickness is 1.25 μm. The sample was dried at 60°C for 1 minute, and irradiated with ultraviolet light using a high-pressure mercury lamp at 120 mW/cm ² and 250 mJ/cm ² . The resulting laminate of the PET base material and cured coating film was used as a test piece. .

[Measurement of pencil hardness]
The pencil hardness of the surface of the cured coating film of the evaluation sample obtained above was measured under a load of 500 g in accordance with JIS K5600-5-4 (1999). Each hardness was measured five times, and the hardness for which no scratches were observed four or more times was defined as the surface hardness of the laminated film. In addition, the hardness of the pencil is 2H, H, F, HB, and B in descending order of hardness, and a grade of H or higher is considered to be a pass.

[Measurement of wetting tension]
Wet tension was measured on the cured coating surface of the evaluation sample obtained above using a wet tension test mixture (manufactured by Wako Pure Chemical Industries, Ltd.) under an environment of 23°C and humidity of 50RH%. . It was measured in accordance with JIS test method K6768:1999, and a range of 35 mN/m or more and 60 mN/m or less was considered to be a pass.

[Boiling water resistance test]
・Adhesion Adjust hot water at 100°C in a constant temperature water bath (Thomas Scientific T-104NA), soak the evaluation sample obtained above for a certain period of time, take it out, leave it at room temperature for 24 hours, and then test. A grid cut of 100 squares was made near the center of the sample for later evaluation, and cellophane tape was attached to the cut portion and quickly peeled off to check whether peeling occurred.
Tables 1 to 6 list the immersion time when peeling occurs, and those exceeding 2.5 minutes were considered acceptable.

[Light resistance test]
・Adhesion The evaluation sample obtained above was irradiated with ultraviolet rays for a certain period of time under the conditions of 300 mW/cm ² and 500 mJ/cm ² using a high-pressure mercury lamp, and after standing at room temperature for 24 hours, the evaluation sample after the test was A grid cut of 100 squares was made near the center, and cellophane tape was pasted on the cut portion and quickly peeled off to check whether peeling occurred.
Tables 1 to 6 list the irradiation doses when peeling occurs, and those exceeding 250 mJ/cm ² or more were considered to be acceptable. Note that the irradiation amount is determined by 500 mJ/cm ² × ultraviolet irradiation time.

Compositions of active energy ray curable compositions (1) to (51) obtained in Examples 1 to 48 and active energy ray curable compositions (C1) to (C2) obtained in Comparative Examples 1 to 2 and the evaluation results are shown in Tables 1 to 6.

The abbreviations shown in Tables 1 to 6 refer to the following compounds.
・M400: Mixture of 50% dipentaerythritol pentaacrylate and 50% dipentaerythritol hexaacrylate, trade name "Miramer M400", manufactured by MIWON ・M403: 40% dipentaerythritol pentaacrylate, 60% dipentaerythritol hexaacrylate Mixture, trade name "Miramer M403", manufactured by MIWON Co., Ltd. M404: Mixture of 60% dipentaerythritol pentaacrylate and 40% dipentaerythritol hexaacrylate, trade name "Miramer M404", manufactured by MIWON Co., Ltd. M405: Dipentaerythritol Mixture of 80% pentaacrylate and 20% dipentaerythritol hexaacrylate, trade name "Miramer M405", manufactured by MIWON DPHA: Dipentaerythritol hexaacrylate, trade name "Miramer M600", manufactured by MIWON, double bond equivalent 96 .4g/mol
・PETA: Pentaerythritol tetraacrylate, double bond equivalent 88.1 g/mol
・TEMPTA: Trimethylolpropane triacrylate, trade name "Miramer M300", manufactured by MIWON, double bond equivalent 98.7 g/mol
・EO-modified TEMPTA: Trimethylolpropane EO-modified triacrylate, trade name "Miramer M3190", manufactured by MIWON, double bond equivalent 392.1 g/mol
・A9300: Tris-(2-acryloxyethyl) isocyanurate, trade name "NK Ester A9300", manufactured by Shin Nakamura Chemical Co., Ltd. ・Urethane acrylate (1): Hexamethylene diisocyanate and pentaerythritol triacrylate obtained in Synthesis Example 1 reaction product (mass fraction excluding pentaerythritol tetraacrylate is listed in the table), double bond equivalent 127.5 g/mol
- Urethane acrylate (2): reaction product of isophorone diisocyanate and pentaerythritol triacrylate obtained in Synthesis Example 2 (mass fraction excluding pentaerythritol tetraacrylate is listed in the table), double bond equivalent: 136. 5g/mol
- Urethane acrylate (3): reaction product of isophorone diisocyanate and dipentaerythritol pentaacrylate obtained in Synthesis Example 3, double bond equivalent 127.1 g/mol
・Urethane acrylate (4): reaction product of biuret type hexamethylene diisocyanate obtained in Synthesis Example 4 and pentaerythritol triacrylate (mass fraction excluding pentaerythritol tetraacrylate is listed in the table), double bond Equivalent weight 152.6g/mol
・TinuvinPS: 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, trade name "Tinuvin PS", manufactured by BASF Japan ・Tinuvin405: R ₁ in formula (I) is (a), A structure in which all R ₂ are represented by (f), a structure in which all R ₄ in (f) are methyl groups, product name "Tinuvin 405", manufactured by BASF Japan, LA-46: in formula (I) A group in which R ₁ is represented by (b) and all R ₂ are represented by (f), a structure in which all R ₄ in (f) are hydrogen atoms, product name "ADEKA STAB LA-46", manufactured by ADEKA, Tinuvin 479: In formula (I), R ₁ is a group represented by (c) and R ₂ are all represented by (f), R ₄ in the para position to the internal bond of R ₄ in (f) is a phenyl group, and Structure in which all other atoms are hydrogen atoms, product name "Tinuvin 479", manufactured by BASF Japan Co., Ltd. Tinuvin 460: Structure in which R ₁ in formula (I) is a group represented by (d) and all R ₂ are groups represented by (g) , trade name "Tinuvin 460", manufactured by BASF Japan, Tinuvin 152: structure in which R ₁ in formula (I) is a group represented by (e) and all R ₂ are represented by (h), product name "Tinuvin 152" , manufactured by BASF Japan Co., Ltd. Acrylic resin (1): Acrylic resin obtained in Synthesis Example 5, having a structure in which R ₆ in formula (II) is a methyl group, R ₇ is a methyl group, or (i), Double bond equivalent 305.3g/mol
- Acrylic resin (2): Acrylic resin obtained in Synthesis Example 6, having a structure in which R ₆ in formula (II) is a methyl group, R ₇ is a methyl group, or (i), double bond equivalent 250 .2g/mol
- Acrylic resin (3): Acrylic resin obtained in Synthesis Example 7, having a structure in which R ₆ in formula (II) is a methyl group, R ₇ is a methyl group, or (i), double bond equivalent 428 .9g/mol
- Acrylic resin (4): Acrylic resin obtained in Synthesis Example 8, having a structure in which R ₆ in formula (II) is a methyl group, R ₇ is a methyl group, or (i), double bond equivalent 250 .2g/mol
- Acrylic resin (5): Acrylic resin obtained in Synthesis Example 9, having a structure in which R ₆ in formula (II) is a methyl group, R ₇ is a methyl group, or (i), double bond equivalent 428 .9g/mol
- Acrylic resin (6): acrylic resin obtained in Synthesis Example 10, having a structure in which R ₆ in formula (II) is a methyl group, R ₇ is a methyl group, or (i), double bond equivalent 305 .3g/mol
・Methacryloyl-modified nanosilica: Product name “Aerosil R7200” manufactured by Evonik

It was confirmed that the cured coating film of the active energy ray-curable composition of the present invention exhibited high hardness and wetting tension, and was excellent in hot water-resistant adhesion and light-resistant adhesion.
On the other hand, it was confirmed that in Comparative Examples 1 and 2, which did not contain the component (B), the hardness, hot water resistant adhesion, and light resistant adhesion were reduced.

Claims (16)

An active energy ray-curable composition containing a compound (A) having a (meth)acryloyl group and a compound (B) having a triazine structure or a triazole structure. The active energy ray-curable composition according to claim 1, wherein the compound (A) has four or more (meth)acryloyl groups in the molecule and has a double bond equivalent in the range of 80 g/mol to 160 g/mol. . A compound (A-1) in which the compound (A) does not have a urethane bond in the molecule and has a (meth)acryloyl group, and a compound (A-2) in which the compound (A) has a urethane bond and a (meth)acryloyl group in the molecule. The active energy ray-curable composition according to claim 1 or 2, containing one or both of the following. A claim that the compound (A-1) contains one or both of a compound (A-1-1) containing a hydroxyl group in the molecule and a compound (A-1-2) not containing a hydroxyl group in the molecule. Item 3. Active energy ray-curable composition. The compound (A) contains the compound (A-1) and the compound (A-2),
Claim 3 or 4, wherein the blending ratio of the compound (A-2) to the compound (A-1) [(A-1)/(A-2)] is in the range of 1/10 to 40/1. Active energy ray curable composition. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the compound (B) is a compound represented by the following formula (I).

(In formula (I), R ₁ represents a group represented by any one of the following formulas (a) to (e), and R ₂ represents any one of the following formulas (f) to (h). (Indicates the group represented, and multiple _R2s in the same molecule may be the same or different.)

(In formula (a), * is a bond.)

(In formula (b), * is a bond.)

(In formula (c), * is a bond, and R ₃ is an alkyl group having 1 to 10 carbon atoms.)

(In formula (d), * is a bond.)

(In formula (e), * is a bond.)

(In formula (f), * is a bond, R ₄ is a hydrogen atom, a methyl group, or a phenyl group, and multiple R _4s in the same molecule may be the same or different.)

(In formula (g), * is a bond.)

(In formula (h), * is a bond, and R ₅ is an alkyl group having 1 to 8 carbon atoms.) The active energy ray-curable composition according to any one of claims 1 to 6, wherein the content of the compound (B) is 0.5 to 6 parts by mass based on 100 parts by mass of the resin solid content. The active energy ray-curable composition according to any one of claims 1 to 7, further comprising an acrylic resin (C). The active energy ray-curable composition according to claim 8, wherein the acrylic resin (C) has a weight average molecular weight in the range of 5,000 to 30,000 and a double bond equivalent in the range of 200 to 450. The active energy ray-curable composition according to claim 8 or 9, wherein the acrylic resin (C) has a structure represented by the following formula (II) or formula (III).

(In formula (II) and formula (III), R ₆ represents a hydrogen atom or a methyl group, and the repeating number n is any natural number. In formula (II), R ₇ is an alkyl group having 1 to 8 carbon atoms. , and a group represented by formula (i).In formula (III), R ₈ represents either an alkyl group having 1 to 8 carbon atoms or a group represented by formula (j). , the repeating number m is either 2 to 4. Plural R ₆ , R ₇ , R ₈ , m in the same molecule may be the same or different, and in formula (i) and formula (j), * is a bond, and R ₉ and R ₁₀ represent a hydrogen group or a methyl group.) The active energy ray-curable composition according to any one of claims 8 to 10, wherein the content of the acrylic resin (C) is 5 to 60 parts by weight based on 100 parts by weight of the resin solid content. The active energy ray-curable composition according to any one of claims 1 to 11, further comprising inorganic particles (D). The particle size of the inorganic particles (D) is 200 nm or less,
The active energy ray-curable composition according to claim 12, wherein the content of the inorganic particles (D) is 5 to 65 parts by weight based on 100 parts by weight of the resin solid content. The active energy ray-curable composition according to claim 12 or 13, wherein the inorganic particles (D) are inorganic oxides modified with a surface modifier having a reactive group. A film comprising a cured coating film obtained by curing the composition according to any one of claims 1 to 14. The film according to claim 15, wherein the wetting tension of the cured coating film surface is in the range of 35 to 60 mN/m.