KR20230133216A - Active energy ray-curable composition and film - Google Patents

Abstract

The present invention provides an active energy ray-curable composition capable of imparting hardness to the film surface and forming a hard coat layer with excellent heat-resistant water adhesion and light-resistant adhesion, and a film using a cured coating film of the composition, (Meta ) A film characterized by having a cured coating film obtained by curing an active energy ray curable composition/active energy ray curable composition containing a compound (A) having an acryloyl group and a compound (B) having a triazine structure or a triazole structure. It's about.

Description

ACTIVE ENERGY RAY-CURABLE COMPOSITION AND FILM}

The present invention relates to active energy ray-curable compositions and films.

Flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), and plasma displays (PDP) are used as display devices for various electronic devices such as PCs, televisions, mobile phones, and electronic dictionaries. . Additionally, electrodes made of a conductive electrode material such as indium tin oxide (ITO) are installed on display elements or touch panels (touch sensors) inside the display.

Various resin films are used for various purposes, such as films to prevent damage to the display surface, 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 cut films. It is becoming. However, since the resin film surface may have low hardness and light resistance, in order to compensate for these, it is common to apply a hard coat agent made of a UV curable composition, etc. to the film surface and cure it to provide a hard coat layer on the film surface. is being done. The hard coat layer is also required to have high adhesion to the resin film (base material), and especially for the protective film of the electrode inside the display or touch panel, adhesion becomes important for the purpose of preventing moisture or salt from entering the electrode or protective film. .

Therefore, from the viewpoint of being usable for various purposes, a hard coat layer that combines hardness, light resistance, and substrate adhesion is required.

As a composition with high adhesion, 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).

Additionally, 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 hydrothermal adhesion resistance.

However, in the invention described in Patent Document 1, penetration of water between the base material and the cured coating film was not tested, and in the invention described in Patent Document 2, a light resistance test was not performed. Therefore, it has been difficult to realize a composition that sufficiently satisfies hardness, light resistance, and substrate adhesion.

Japanese Patent Publication No. 2020-197737 Official Gazette of the State of Japan No. 2019-235206

The problem that the present invention seeks to solve is to provide an active energy ray curable composition capable of forming a hard coat layer with excellent hardness, heat resistance and light resistance on the film surface, and a film using a cured coating film of the composition.

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 a triazole structure. Additionally, the present invention provides a film having a cured coating film of the active energy ray-curable composition.

That is, the present invention provides the following invention.

[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] In [1],

An active energy ray-curable composition in which the compound (A) has four or more (meth)acryloyl groups in the molecule and has a double bond equivalent weight in the range of 80 g/mol to 160 g/mol.

[3] In [1] or [2],

The compound (A) is one of compound (A-1), which has no urethane bond in the molecule and a (meth)acryloyl group, and compound (A-2), which has a urethane bond and a (meth)acryloyl group in the molecule. An active energy ray-curable composition containing either or both.

[4] In [3],

The compound (A-1) contains either or both of the compound (A-1-1) containing a hydroxyl group in the molecule and the compound (A-1-2) that does not contain a hydroxyl group in the molecule, and the active energy Pre-curable composition.

[5] In [3] or [4],

The compound (A) contains the compound (A-1) and the compound (A-2), and the mixing ratio of the compound (A-2) to the compound (A-1) [(A-1) )/(A-2)] is an active energy ray-curable composition in the range of 1/10 to 40/1.

[6] In any one of [1] to [5],

An active energy ray-curable composition wherein the compound (B) is a compound represented by the following formula (I).

(In formula (I), R ₁ represents a group represented by any of the following formulas (a) to (e), and R ₂ represents a group represented by any of the following formulas (f) to (h), and in the same molecule A plurality of R ₂ 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 one of a hydrogen atom, a methyl group, and a phenyl group, and multiple R ₄ 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] In any one of [1] to [6],

An active energy ray-curable composition 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] In any one of [1] to [7],

An active energy ray-curable composition further containing an acrylic resin (C).

[9] In [8],

An active energy ray-curable composition in which the weight average molecular weight of the acrylic resin (C) is in the range of 5,000 to 30,000 and the double bond equivalent is in the range of 200 to 450.

[10] In [8] or [9],

An active energy ray-curable composition in which 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 an arbitrary natural number. In formula (II), R ₇ represents an alkyl group having 1 to 8 carbon atoms, and formula ( It represents any one of the groups represented by i).In formula (III), R ₈ represents any one of an alkyl group having 1 to 8 carbon atoms and 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, and in formulas (i) and (j), * is a bond, and R ₉ and R ₁₀ are hydrogen. group or methyl group.)

[11] According to any one of [8] to [10],

An active energy ray-curable composition wherein the content of the acrylic resin (C) is 5 to 60 parts by mass based on 100 parts by mass of the resin solid content.

[12] According to any one of [1] to [11],

An active energy ray-curable composition further containing inorganic particles (D).

[13] In [12],

An active energy ray-curable composition in which 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 mass with respect to 100 parts by mass of the resin solid content.

[14] In [12] or [13],

An active energy ray-curable composition, wherein the inorganic particles (D) are inorganic oxides modified with a surface modifier having a reactive group.

[15] A film characterized by having a cured coating film obtained by curing the composition according to any one of [1] to [14].

[16] In [15],

A film wherein the wetting tension of the surface of the cured coating film is in the range of 35 to 60 mN/m.

The active energy ray-curable composition of the present invention can provide high hardness to the surface of a resin film by coating and curing it, and can form a hard coat layer with excellent light-resistant adhesiveness and heat-resistant water adhesiveness.

Therefore, the active energy ray curable composition of the present invention is used as display devices for various electronic devices such as PCs, televisions, mobile phones, electronic dictionaries, liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), etc. Damage prevention film for the surface of flat panel displays (FPDs), protective films for display elements or electrodes of touch panels (touch sensors) inside these displays or touch panels, decorative films (sheets) for the interior and exterior of automobiles, and anti-reflective films for windows. It can be widely used in various applications, such as hot cut films, and can be particularly suitably used as a hard coat agent for a protective film for electrodes inside a touch panel.

In this specification, the compound represented by formula (I) is referred to as “compound (I)”, and the same applies to compounds represented by other formulas.

Additionally, “acrylate” and “methacrylate” are collectively referred to as “(meth)acrylate”, and “(meth)acryloyl” and “acryloyl” are collectively referred to as “(meth)acryloyl”. It is said.

Compound (A) having a (meth)acryloyl group is referred to as “(A) component,” and other compounds (B) to (D) components are referred to in the same manner.

<Active energy ray curable composition>

The active energy ray-curable composition of the present invention contains component (A) and component (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 the coating film obtained by curing the composition was tested. Additionally, we are testing the adhesion of the coating film to the substrate after immersing it in boiling water or irradiating it with ultraviolet rays. In the case of a coating film that easily absorbs moisture, the volume increases and the adhesion to the substrate decreases.

Therefore, if the test result is excellent, the heat-resistant water adhesion and light-resistant adhesion are considered excellent.

[(A) component]

(A) Components are compounds having one or more (meth)acryloyl groups in the molecule, and mixtures thereof.

In addition, component (A) includes compound (A-1) having a (meth)acryloyl group without a urethane bond in the molecule, and compound (A-2) having a urethane bond and a (meth)acryloyl group in the molecule. Contains one or both of the following.

[Compound (A-1)]

Compound (A-1) contains one or both of compound (A-1-1) containing a hydroxyl group in the molecule and compound (A-1-2) that does not contain a hydroxyl group in the molecule.

Since the hydroxyl group-containing compound (A-1-1) has a hydroxyl group, it can improve the reactivity of the (meth)acryloyl group through intermolecular interaction and improve the hardness and substrate adhesion of the cured coating film. . In addition, the compound (A-1-2) that does not contain a hydroxyl group can appropriately adjust the viscosity of the composition and the concentration of each compound.

The compound (A-1-1) containing a hydroxyl group in the molecule specifically includes ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol (meth)acrylate, tripentaerythritol hepta(meth)acrylate, etc. are mentioned. It does not matter whether you use one type or two or more types.

Compound (A-1-2) that does not contain a hydroxyl group in the molecule, specifically, 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 -Di(meth)acrylates of dihydric alcohols such as propanediol di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; Diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri( Meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, polypentaerythritol poly(meth)acrylate, (poly)ethylene glycoldi Pentaerythritol 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, obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol. Acrylates having an alkylene oxide structure such as diol di(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, and propylene oxide modified trimethylolpropane tri(meth)acrylate; 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. It does not matter whether you use one type or two or more types.

[Compound (A-2)]

Compound (A-2) is a compound that has at least a urethane bond and a (meth)acryloyl group in the molecule, and the synthesis method is not particularly limited. It includes a compound having an isocyanate group, and a compound having a hydroxyl group and a (meth)acryloyl group. A compound obtained by carrying out a dehydration condensation reaction can be mentioned.

In addition, since compound (A-2) has a urethane bond, it improves the reactivity of the (meth)acryloyl group through intermolecular interaction, thereby improving the hardness and hot water resistance of the cured coating film.

Examples of compounds having an isocyanate group that can be used as a raw material 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-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, etc. aliphatic isocyanates; Isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate, hydrogenated xylene diisocyanate, 2-methyl-1,3 -Alicyclic isocyanate compounds such as diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane can be mentioned. Alternatively, dimers or trimers (isocyanurate, biuret, allophanate, etc.) of these isocyanate compounds may be used. It does not matter whether you use one type or two or more types.

Compounds having a hydroxyl group and a (meth)acryloyl group that can be used as a raw material for compound (A-2) include pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and 2-hydroxyethyl ( Meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, capro Lactone-modified hydroxymono(meth)acrylate (e.g., product name “Fraxel (registered trademark) FA-2D” manufactured by Daicel, etc.), polycarbonate-modified hydroxymono(meth)acrylate (e.g. , trade name “HEMAC” (registered trademark) manufactured by Daicel, etc.), polyethylene glycol or polypropylene glycol-modified hydroxymono(meth)acrylate (for example, trade name “Blemmer (registered trademark) AE manufactured by Nichiyu Corporation) -200”, “Blemmer (registered trademark) AP-400”, etc.). It does not matter whether you use one type or two or more types.

Among those mentioned 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 compound (A-1-2), pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are more preferable.

Compound (A-2) includes 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dimer of 1,6-hexamethylene diisocyanate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acryl. Rate reactants, etc. are more preferable.

In this way, by using four or more (meth)acryloyl compounds in the molecule as component (A), the crosslinking density during curing of the composition improves, and hardness increases. Additionally, it becomes difficult for the cured coating film to absorb moisture, and heat-resistant water adhesion also improves.

Additionally, the compound used as component (A) is preferably a compound having a double bond equivalent weight in the range of 20 to 300 g/mol, more preferably a compound in the range of 50 to 250 g/mol, and a compound having a double bond equivalent weight in the range of 80 to 160 g/mol. Compounds are particularly preferred. The double bond equivalent in this specification is defined as the mass of the compound divided by the amount of double bond in the compound.

By using a compound with a double bond equivalent within this range, the crosslinking density becomes optimal, and hardness, heat-resistant water adhesion, and light-resistant adhesion can be improved in a good balance.

When component (A) contains both compound (A-1) and compound (A-2), the mixing ratio of the compound (A-2) to the 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 especially in the range of 1/10 to 40/1. desirable. By setting it to this range, light-resistant adhesiveness 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) that does not contain a hydroxyl group in the molecule, the compound (A The mixing ratio [(A-1-1)/(A-1-2)] of the compound (A-1-2) to -1-1) is preferably in the range of 20/80 to 95/5. , the range of 30/70 to 90/10 is more preferable, and the range of 50/50 to 80/20 is particularly preferable. By setting this range, the hydrophilicity of compound (A-1) can be adjusted to the optimal range, and heat-resistant water adhesion is improved.

[(B) Ingredient]

Component (B) is a compound having a triazine structure or a triazole structure in the molecule. Component (B) can weaken the water absorption of the cured coating film of the composition and increase heat-resistant water adhesion. Additionally, 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-tetramethyl butyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methyl Benzotriazoles such as phenol and 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole; Or a triazine represented by the following formula (I), etc.

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

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

R ₄ is one of a hydrogen atom, a methyl group, and 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 components (B) mentioned above, from the viewpoint of weakening the absorption power of the cured coating film and maintaining substrate adhesion, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole or compound (I) This is more preferable, 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 preferable.

(B) The component may be used as one type or in combination of two or more types.

The content of compound (B) is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.3 to 8 parts by mass, and particularly preferably 0.5 to 6.0 parts by mass, based on 100 parts by mass of the total resin solid content in the composition. By setting it within this range, the composition can be cured without problems, the absorption power of the cured coating film can be reduced, and light resistance is also improved. Therefore, heat-resistant water adhesion and light-resistant adhesion improve.

The composition of the present invention may further contain component (C) as needed.

[(C) component]

Component (C) is an acrylic resin, that is, a polymer of acrylic acid ester or methacrylic acid ester. When the composition of the present invention contains component (C), it becomes easy for the cured coating film to be appropriately deformed. Therefore, even if the volume of the base material increases, the shape of the cured coating film can also change to match the base material, thereby improving adhesion to the base material.

The acrylic resin that can be used as the component (C) preferably has a weight average molecular weight of 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 5,000 to 30,000. By setting it within this range, heat-resistant water adhesion and light-resistant adhesion improve.

In addition, the acrylic resin that can be used as component (C) preferably has a double bond equivalent weight in the range of 100 to 700 g/mol, more preferably in the range of 150 to 600 g/mol, and 200 to 450 g/mol. It is particularly preferable that By setting it within this range, heat-resistant water adhesion and light-resistant adhesion improve.

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

In formulas (II) and (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 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 any of 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), * represents 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 mass, more preferably in the range of 3 to 80 parts by mass, and 5 to 60 parts by mass, based on 100 parts by mass of the total resin solid content in the composition. This is particularly desirable. By setting this range, the shape can be appropriately changed while maintaining the high crosslink density of the cured coating film.

Therefore, the water absorption of the coating film can be reduced and the heat-resistant water adhesion is improved because it can follow the shape change of the base material.

The composition of the present invention may further contain component (D) as needed.

[(D) component]

(D) The component is an inorganic particle. When the composition contains the inorganic particles (D), volumetric shrinkage during curing of the composition can be suppressed. Therefore, stress strain is less likely to occur between the substrate and the cured coating film, and heat-resistant water adhesion and light-resistant adhesion are improved. In addition, the wetting tension of the coating film surface is also improved by exposing the inorganic particles to the coating film surface.

Specific examples of the inorganic particles (D) include silica, alumina, magnesia, titania, and zirconia; Examples of excellent heat conduction include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, etc.; Examples of excellent conductivity include metal fillers and/or metal-coated fillers using metal substances or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); Examples of those with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, xonotlite, aluminum borate, calcium carbonate, titanium oxide, and sulfuric acid. Barium, zinc oxide, magnesium hydroxide; Examples of those having a high refractive index include barium titanate, zirconia, titanium oxide, etc.; Examples of photocatalysts include titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, tellurium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc. Metals, complexes of said metals, their oxides, etc.; Examples of those having excellent wear resistance include metals such as alumina, zirconia, and magnesium oxide, and their composites and oxides; Examples of those having excellent conductivity include metals such as silver and copper, tin oxide, and indium oxide; Titanium oxide, zinc oxide, etc. can be used as materials that are excellent in blocking ultraviolet rays. These inorganic fine particles may be selected appropriately depending on the intended use, and may be used individually or in combination of multiple types.

For example, when using silica as component (D), there is no particular limitation, and known silica fine particles such as powdered silica or colloidal silica can be used. Commercially available powdery silica fine particles include, for example, the “Aerosil (registered trademark)” series (50, 200, etc.) manufactured by Nippon Aerosil Corporation and the “Sildex” series (H31, H32, H51) manufactured by AGC Corporation. , H52, H121, H122, etc.), brand name "E220A" or "E220" manufactured by Tosoh Silica Corporation, brand name "SYLYSIA (registered trademark) 470" manufactured by Fuji Silicia Chemicals Co., Ltd., brand name "SG Flake" manufactured by Nippon Itagalas Corporation. 」etc.

In addition, commercially available colloidal silica includes, for example, those manufactured by Nissan Chemical Industries, Ltd. under the brand names "Methanol Silica Sol", "IPA-ST", "MEK-ST", "PGM-ST", "NBA-ST", " "XBA-ST", "DMAC-ST", "ST-UP", "ST-OUP", "ST-20", "ST-40", "ST-C", "ST-N", "ST- O”, “ST-50”, “ST-OL”, etc.

As silica, reactive silica may be used. Examples of reactive silica include reactive compound-modified silica. As the reactive compound, from the viewpoint of lowering the water absorption of the cured coating film, 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 preferable. , Among these, silica modified with a compound having a (meth)acryloyl group is particularly preferable from the viewpoint of compatibility with component (A) and other components.

Commercially available powdered silica modified with a compound having a (meth)acryloyl group includes (meth)acrylate, brand names “Aerosil (registered trademark) RM50” and “Aerosil (registered trademark) R711” manufactured by Nippon Aerosil Corporation. As commercially available colloidal silica modified with a compound having a loyl group, the product names "MIBK-SD", "MIBK-SD-L", "MIBK-AC-2140Z", and "MEK-AC-2140Z" manufactured by Nissan Chemical Industries, Ltd. etc. can be mentioned. In addition, silica obtained by addition reaction with acrylic acid after modification with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane, or a compound having a hydroxyl group and a (meth)acryloyl group with 3-isocyanatepropyltriethoxysilane. Silica modified by urethanization can also be cited as reactive silica.

The method for producing silica that can be used in the present invention is not particularly limited, but for example, one produced by a wet method can be used. In addition, as wet methods, sedimentation method and gel method are known, and silica produced by any method can be used. In addition, by adjusting the reaction conditions (pH, raw material concentration, reaction temperature, etc.) of sodium silicate, which is the raw material of silica particles, and inorganic acids such as sulfuric acid, along with the precipitation method and gel method, the primary average particle diameter and secondary average particle diameter of silica can be changed. It doesn't matter if you adjust it.

It is preferable that silica particles having a primary average particle diameter are pulverized by secondary agglomeration (the particle diameter after pulverization is set as the secondary average particle diameter). Examples of devices used for pulverizing silica particles include a ball mill, a bead mill, and a rod. Mills, SAG mills, high pressure grinding rolls, vertical impactor (VSI) mills, colloid mills, conical mills, disk mills, edge mills, hammer mills, mortar mills, jet mills, etc. can be used.

Additionally, when pulverizing silica particles, a wet dispersant or a silane coupling agent may be added, and the surface of the silica particles may be modified with an organic group simultaneously with pulverization. Examples of the wet dispersant and silane coupling agent include DISPERBYK-103, DISPERBYK-106, DISPERBYK-161, DISPERBYK-2152, DISPERBYKP104, 3-(meth)acryloylpropyltrimethoxysilane, and 3-glycidoxy. Propyltrimethoxysilane, 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 especially preferably in the range of 50 to 200 nm. By maintaining these ranges, the transparency of the cured coating film is 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 especially preferably in the range of 5 to 65 parts by mass, with respect to 100 parts by mass of the total resin solid content in the composition. do. By setting it within these ranges, the water absorption of the cured coating film can be reduced while suppressing shrinkage during curing of the composition. That is, since it is difficult for a space to be created between the base material and the cured coating film, heat-resistant water adhesion and light-resistant adhesion can be improved, and the wetting tension of the coating film surface can also be improved.

Additionally, 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, and 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc. there is.

The above-mentioned photopolymerization initiator may be used individually or may be used in combination of two or more types.

The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass, relative to 100 parts by mass of solid content of the active energy ray-curable composition. It is preferable that the content of the photopolymerization initiator is 0.1 parts by mass or more because the curing reaction proceeds appropriately and a cured coating film with 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 unlikely to occur and a cured coating film with high transparency can be obtained.

Additionally, 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.

[menstruum]

Examples of the solvent include alcohol solvents such as methanol, ethanol, 1-propanol, t-butanol, and diacetone alcohol; alcohol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol 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; Aromatic solvents such as toluene, xylene, and dibutylhydroxytoluene can be mentioned.

The above-mentioned solvents may be used individually or two or more types may be used in combination.

The content of the solvent is preferably 0 to 300 parts by mass, and more preferably 0 to 100 parts by mass, based on 100 parts by mass of 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 it is easy to control the film thickness. Additionally, it is preferable that the solvent content is 10 parts by mass or more because various coating methods such as spray coating and flow coating can be adopted.

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

[Other ingredients]

Representative examples of other ingredients include reactive compounds, various resins, fillers, ultraviolet absorbers, and leveling agents. However, these shall not correspond to components (A) to (D).

Additionally, it may contain inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, stabilizers, flow regulators, coupling agents, dyes, rheology control agents, antioxidants, plasticizers, etc.

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

Liquid organic polymers may be used to adjust viscosity. Liquid organic polymers are liquid organic polymers that do not directly contribute to the curing reaction, for example, carboxyl group-containing polymer modified products (Flolene G-900, NC-500: Kyoei Chemical Industry Co., Ltd.), acrylic polymers (Flolene WK- 20: manufactured by Kyoei Chemical Industry Co., Ltd.), amine salt of specially modified phosphoric acid ester (HIPLAAD (registered trademark) ED-251: manufactured by Kusumoto Chemical Co., Ltd.), modified acrylic block copolymer (DISPERBYK (registered trademark) 2000; manufactured by Beek Chemistry Co., Ltd. ), etc.

As various resins, thermosetting resins and thermoplastic resins can be used.

A thermosetting resin is a resin that has properties that can change from being substantially insoluble to infusible when cured by means such as heating, radiation, or a catalyst. Specific examples thereof include phenol 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, and ketone resin. , xylene resin, thermosetting polyimide resin, benzoxazine resin, activated ester resin, aniline resin, cyanate ester resin, styrene/maleic anhydride (SMA) resin, etc. These thermosetting resins can be used one type or in combination of two or more types.

Thermoplastic resin refers to a resin that can be melted and molded by heating. Specific examples thereof 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, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluorine resin, syndiotactic polystyrene resin, cyclic polyolefin resin, etc. These thermoplastic resins can be used one type or in combination of two or more types.

As a filler, things other than component (D) can be used, for example, inorganic fibers or organic fibers can be used.

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, silicon carbide fiber (silicon carbide fiber), Examples include 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 fiber include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.

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

Examples of ultraviolet absorbers include benzophenone-based, cyclic iminoester-based, cyanoacrylate-based, and polymer-type ultraviolet absorbers.

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

Various surface modifiers may be added to the composition of the present invention for the purpose of improving leveling properties during application, improving the slipperiness of the cured film and improving scratch resistance, etc. As the surface modifier, various additives that modify surface properties, which are commercially available under names such as surface regulator, leveling agent, slipperiness imparting agent, and antifouling agent, can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are suitable.

Specifically, silicone-based polymers and oligomers having a silicon chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicon chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, purple and fluorine-based polymers and oligomers having a fluoroalkyl ether chain and a polyalkylene oxide chain. You may use one or more of these. For purposes such as increasing the durability of slipperiness, one containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL (registered trademark) 350 (manufactured by Daicel Allnex Co., Ltd.), BYK-333 (manufactured by Beek Chemi Japan Co., Ltd.), BYK-377 (manufactured by Beek Chemi Japan Co., Ltd.), BYK-378 (by Beek Chemical Japan Co., Ltd.) (manufactured by BYK Chemi Japan), BYK-UV3500 (manufactured by BYK Chemi Japan), BYK-UV3505 (manufactured by BYK Chemi Japan), BYK-UV3576 (manufactured by Beek Chemi Japan), Megapak (registered trademark) RS -75 (manufactured by DIC Corporation), Megapark (registered trademark) RS-76-E (manufactured by DIC Corporation), Megapark (registered trademark) RS-72-K (manufactured by DIC Corporation), Megapark (registered trademark) RS- 76-NS (manufactured by DIC Corporation), MegaPac (registered trademark) RS-90 (manufactured by DIC Corporation), MegaPac (registered trademark) RS-91 (manufactured by DIC Corporation), MegaPac (registered trademark) RS-55 (DIC) (manufactured by T&K TOKA), Offtool (registered trademark) DAC-HP (manufactured by Daikin Corporation), 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), (manufactured by Shin-Etsu Chemical), X-22-164C (manufactured by Shin-Etsu Chemical), X-22-164E (manufactured by Shin-Etsu Chemical), and

The active energy ray-curable composition of the present invention can be suitably used as a cured coating film with high adhesion by applying hardness and light resistance to a substrate by applying it to at least one surface of various materials and then irradiating it with active energy rays. The cured coating film made of the composition of the present invention can impart hardness and light resistance to the film surface, and can form a hard coat layer with excellent heat-resistant water adhesion, making it a material that can be used outdoors for long periods of time even in harsh high-temperature and high-humidity environments. It is particularly effective when used as a hard coat.

＜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 is no particular limitation on the substrate, and it may be selected appropriately depending on the application. Examples include plastic, glass, wood, metal, metal oxide, paper, silicon, or modified silicon, and may be a substrate obtained by bonding different materials. .

There are no particular restrictions on the shape of the base material, and it may be any shape according to the purpose, such as a flat plate, a sheet shape, or a three-dimensional shape with curvature on the entire surface or part of it. Additionally, there are no restrictions on the hardness, thickness, etc. of the base material.

There is no particular limitation as to the plastic base material as long as it is made of resin. For example, the thermosetting resin or thermoplastic resin described above may be used. The substrate may be a single resin or a mixture of multiple types of resin, or may have a single-layer or two- or more-layer laminated structure. Additionally, this plastic substrate may be fiber reinforced (FRP).

In addition, the base material may include known antistatic agents, anti-fog agents, anti-blocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, light stabilizers, crystal nucleating agents, lubricants, etc., to the extent that they do not impair the effect of the present invention. It may contain known additives.

The film of the present invention may further have a second base material on the base material and the cured coating film. There is no particular limitation on the material of the second substrate, and examples thereof include glass, wood, metal, metal oxide, plastic, paper, silicon, or modified silicon, and may be a substrate obtained by bonding different materials. 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 with curvature on the entire surface or a portion thereof. Additionally, 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 also be suitably used as an interlayer material for dissimilar materials. Preferably, the substrate is a plastic and the second substrate is an inorganic layer, or the substrate is a plastic and the second substrate is an adhesive or a curable resin coating film. Examples of the inorganic layer include quartz, sapphire, glass, optical film, ceramic material, inorganic oxide, vapor deposition film (CVD, PVD, sputtering), magnetic film, reflective film, metal such as Ni, Cu, Cr, Fe, stainless steel, etc. Paper, SOG (Spin On Glass), SOC (Spin On Carbon), plastic layers such as polyester, polycarbonate, and polyimide, TFT array substrates, PDP electrode plates, conductive substrates such as ITO and metal, insulating substrates, and silicon. , silicon-based substrates such as silicon nitride, polysilicon, silicon oxide, and amorphous silicon.

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

(manufacturing method)

The film of the present invention is obtained by applying the composition of the present invention to the surface of a substrate and then curing it.

Application to the substrate can be performed by directly applying or directly molding the composition to the substrate and curing it.

When applying directly, there is no particular limitation on the coating method, including spray method, spin coat method, dip method, roll coat method, blade coat method, doctor roll method, doctor blade method, curtain coat method, slit coat method, screen printing method, and inkjet method. Examples include laws, etc.

In the case of direct molding, examples include in-mold molding, insert molding, vacuum molding, extrusion laminate molding, and press molding.

Additionally, the film of the present invention may be obtained by laminating the cured product of the composition on a substrate. When laminating the cured product of the composition, the semi-cured product may be laminated on the substrate and then fully cured, or the fully cured product may be laminated on the substrate.

Since the composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiating active energy rays.

Active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Among these, ultraviolet rays (UV) are particularly preferable in terms of curability and convenience.

Here, when using ultraviolet rays as active energy rays, examples of devices that irradiate 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, solar lights, and LED lamps. Using these, it is possible to obtain a cured coating film or cured product by irradiating the coated or molded composition with ultraviolet rays with a wavelength of about 180 to 400 nm. The irradiation amount of ultraviolet rays is appropriately selected depending on the type and amount of the photopolymerization initiator used.

(Usage)

The cured coating film of the composition of the present application has high hardness and excellent heat-resistant water adhesion and light-resistant adhesion, so it can maintain high adhesion while protecting the object from external impact, moisture, and light, and can be used for liquid crystal displays (LCDs), organic Film for preventing damage to the surface of flat panel displays (FPD) such as EL displays (OLED) and plasma displays (PDP), protective films for electrodes made of conductive electrode materials for display elements inside displays and touch panels (touch sensors), etc. It can be used suitably for purposes. In addition, it can be suitably used for various purposes, such as decorative films (sheets) for the interior and exterior of automobiles, low-reflection films exclusively for windows, and heat cut films.

Example

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to the following aspects. In addition, in this example, “part” 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 introduction tube, condenser, and thermometer, "Desmodure H" (168.2 parts by mass) manufactured by Covestro, 2,6-di-tert-butyl-4-methylphenol ( 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 (trade name “Aronics M-, manufactured by Toa Chemical Co., Ltd.) was added. 306”, containing about 30% by mass of pentaerythritol tetraacrylate) (356.9 parts by mass) was injected in portions over 1 hour. After injection, reaction was performed at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and urethane acrylate compound (1) (containing about 20.4% of pentaerythritol tetraacrylate) was obtained.

(Synthesis Example 2: Synthesis of urethane acrylate compound (2))

In a 1-liter flask equipped with a stirrer, gas introduction tube, condenser, and thermometer, "IPDI" (222.3 parts by mass) manufactured by Covestro, and 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 added, the temperature was raised to 70°C, and pentaerythritol triacrylate (trade name “Aronics M-306” manufactured by Toa Synthetic Co., Ltd., Containing about 30% by mass of pentaerythritol tetraacrylate (356.9 parts by mass) was injected in portions over 1 hour. After injection, reaction was performed at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating an isocyanate group disappeared, and urethane acrylate compound (2) (containing about 18.5% of pentaerythritol tetraacrylate) was obtained.

(Synthesis Example 3: Synthesis of urethane acrylate compound (3))

In a 1 liter flask equipped with a stirrer, gas introduction tube, condenser, and thermometer, "IPDI" (222.3 parts by mass) manufactured by Covestro, and 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” (524 parts by mass) manufactured by MIWON was injected in portions over 1 hour. did. After injection, reaction was performed at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating an isocyanate group disappeared, and urethane acrylate compound (3) was obtained.

(Synthesis Example 4: Synthesis of urethane acrylate compound (4))

In a 1-liter flask equipped with a stirrer, gas introduction tube, condenser, and thermometer, "Basnonat HB100" (186.67 parts by mass) manufactured by BASF, and 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, the temperature was raised to 70°C, and pentaerythritol triacrylate (trade name “Aronix M-306” manufactured by Toa Synthetic Co., Ltd., Containing about 30% by mass of pentaerythritol tetraacrylate (356.87 parts by mass) was injected in portions over 1 hour. After injection, reaction was performed at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and urethane acrylate compound (4) (containing about 19.7% of pentaerythritol tetraacrylate) was obtained.

(Synthesis Example 5: Synthesis of acrylic resin (1))

254 parts by mass of methyl isobutyl ketone was injected into a high-pressure sealed reaction device equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, and the temperature was raised while stirring until the internal temperature of the system reached 150°C. Then, glycidyl 229 parts by mass of methacrylate, 153 parts by mass of methyl methacrylate, 46 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Japan Oil Corporation) and 1,1'-bis-( A mixed solution consisting of 24 parts by mass of t-butylperoxy)cyclohexane (“PerhexaC” manufactured by Japan Oil Corporation) was added dropwise from a dropping funnel over 3 hours, and then maintained at 150°C for 2 hours. Next, after lowering the temperature to 90°C, 0.1 parts by mass of methoquinone and 118 parts by mass of acrylic acid were added, 3 parts by mass of triphenylphosphine were added, and the temperature was further raised to 110°C to confirm that the acid value was 3 mgKOH/g or less, Acrylic acrylate resin (ACAC-1) was obtained. The property values 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 injected into a high-pressure sealed reaction device equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, and the temperature was raised while stirring until the internal temperature of the system reached 150°C. Then, glycidyl 283 parts by mass of methacrylate, 73 parts by mass of methyl methacrylate, 43 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Japan Oil Corporation) and 1,1'-bis-( A mixed solution consisting of 21.5 parts by mass of t-butylperoxy)cyclohexane (“PerhexaC” manufactured by Japan Oil Corporation) was added dropwise from a dropping funnel over 3 hours, and then maintained at 150°C for 2 hours. Next, after lowering the temperature to 90°C, 0.1 parts by mass of methoquinone and 144 parts by mass of acrylic acid were added, 3 parts by mass of triphenylphosphine was added, and the temperature was further raised to 110°C to confirm that the acid value was 3 mgKOH/g or less, Acrylic acrylate resin (ACAC-2) was obtained. The property values 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 injected into a high-pressure sealed reaction device equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, and the temperature was raised while stirring until the internal temperature of the system reached 150°C. Then, glycidyl 165 parts by mass of methacrylate, 251 parts by mass of methyl methacrylate, 43 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Oil Co., Ltd.), and 1,1'-bis-( A mixed solution consisting of 21.5 parts by mass of t-butylperoxy)cyclohexane (“PerhexaC” manufactured by Japan Oil Corporation) was added dropwise from a dropping funnel over 3 hours, and then maintained at 150°C for 2 hours. Next, after lowering the temperature to 90°C, 0.1 parts by mass of methoquinone and 84 parts by mass of acrylic acid were added, 3 parts by mass of triphenylphosphine was added, and the temperature was further raised to 110°C to confirm that the acid value was 3 mgKOH/g or less. Acrylic acrylate resin (ACAC-3) was obtained. The property values 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 injected into a high-pressure sealed reaction device equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, and the temperature was raised while stirring until the internal temperature of the system reached 150°C. Then, glycidyl 283 parts by mass of methacrylate, 73 parts by mass of methyl methacrylate, 30 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Japan Oil Corporation) and 1,1'-bis-( A mixed solution consisting of 15 parts by mass of t-butylperoxy)cyclohexane (“PerhexaC” manufactured by Japan Oil Corporation) was added dropwise from a dropping funnel over 3 hours, and then maintained at 150°C for 2 hours. Next, after lowering the temperature to 90°C, 0.1 parts by mass of methoquinone and 144 parts by mass of acrylic acid were added, 3 parts by mass of triphenylphosphine was added, and the temperature was further raised to 110°C to confirm that the acid value was 3 mgKOH/g or less, Acrylic acrylate resin (ACAC-4) was obtained. The property values 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 injected into a high-pressure sealed reaction device equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, and the temperature was raised while stirring until the internal temperature of the system reached 150°C. Then, glycidyl 165 parts by mass of methacrylate, 251 parts by mass of methyl methacrylate, 30 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Japan Oil Corporation) and 1,1'-bis-( A mixed solution consisting of 15 parts by mass of t-butylperoxy)cyclohexane (“PerhexaC” manufactured by Japan Oil Corporation) was added dropwise from a dropping funnel over 3 hours, and then maintained at 150°C for 2 hours. Next, after lowering the temperature to 90°C, 0.1 parts by mass of methoquinone and 84 parts by mass of acrylic acid were added, 3 parts by mass of triphenylphosphine was added, and the temperature was further raised to 110°C to confirm that the acid value was 3 mgKOH/g or less. Acrylic acrylate resin (ACAC-5) was obtained. The property values 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 injected into a high-pressure sealed reaction device equipped with a stirring device, a cooling pipe, a dropping funnel, and a nitrogen introduction pipe, and the temperature was raised while stirring until the internal temperature of the system reached 150°C. Then, glycidyl 153 parts by mass of methacrylate, 229 parts by mass of methyl methacrylate, 56 parts by mass of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Japan Oil Corporation) and 1,1'-bis-( A mixed solution consisting of 28 parts by mass of t-butylperoxy)cyclohexane (“PerhexaC” manufactured by Japan Oil Corporation) was added dropwise from a dropping funnel over 3 hours, and then maintained at 150°C for 2 hours. Next, after lowering the temperature to 90°C, 0.1 parts by mass of methoquinone and 118 parts by mass of acrylic acid were added, 3 parts by mass of triphenylphosphine were added, and the temperature was further raised to 110°C to confirm that the acid value was 3 mgKOH/g or less. Acrylic acrylate resin (ACAC-6) was obtained. The property values of the acrylic acrylate resin (ACAC-6) were as follows. Weight average molecular weight (Mw): 5,000, double bond equivalent: 305.34

(Example 1)

As a solid content, 100 parts by mass of dipentaerythritol pentaacrylate (“MIRAMER M400” manufactured by MIWON, containing 50% dipentaerythritol hexaacrylate), 2-(2-hydroxy-5-t-butylphenyl)-2H- 0.5 parts by mass of benzotriazole (“Tinuvin PS” manufactured by BASF Japan) and 5 parts by mass of Omnirad 184 (manufactured by IGM) were mixed, and the solid content was adjusted to a mixed solvent of propylene glycol monomethyl ether/methyl ethyl ketone = 50/50 wt%. The active energy ray curable composition (1) was adjusted by uniformly mixing to 40 wt%.

(Examples 2 to 51, Comparative Examples 1 to 2)

The active energy ray-curable compositions of each example were obtained in the same manner as in Example 1, except that the composition of the solid content shown in Tables 2 to 6 was changed.

[Production of evaluation samples]

The active energy ray-curable composition of each example was applied to a polyethylene terephthalate (PET) substrate (Toray Co., Ltd. brand name “Lumirror UH-13” thickness: 50 μm) to a film thickness of 1.25 μm, and incubated at 60°C for 1 minute. It was dried and irradiated with ultraviolet rays using a high-pressure mercury lamp under the conditions of 120 mW/cm ² and 250 mJ/cm ² , and the obtained laminate of the PET base material and the cured coating film was used as a test piece.

[Measurement of pencil hardness]

For the surface of the cured coating film of the evaluation sample obtained above, pencil hardness was measured under a 500 g load condition in accordance with JIS K5600-5-4 (1999). Five measurements were made for one hardness, and the hardness in which there were four or more measurements without damage was taken 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 HB or higher is considered passing.

[Measurement of wetting tension]

For the surface of the cured coating film of the evaluation sample obtained above, the wet tension was measured in an environment of 23°C and 50RH% humidity using a mixed liquid for wet tension test (manufactured by Wako Pure Chemical Industries, Ltd.). Measurements were made based on JIS test method K6768:1999, and the range of 35 mN/m to 60 mN/m was considered acceptable.

[Boiling water resistance test]

·Adhesion

In a constant temperature water tank (T-104NA manufactured by Thomas Science), the hot water is adjusted to 100°C, the evaluation sample obtained above is immersed for a certain period of time, taken out, left to stand at room temperature for 24 hours, and the evaluation sample after the test is A checkerboard cut of 100 squares was made near the center, cellophane tape was attached to the cut portion, and it was quickly peeled off to check whether peeling occurred.

Tables 1 to 6 list the immersion times when peeling occurred, and those exceeding 2.5 minutes were considered acceptable.

[Light fastness 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 250 mJ/cm ² using a high-pressure mercury lamp, and after standing at room temperature for 24 hours, a 100-square checkerboard cut was made near the center of the evaluation sample after the test. Then, cellophane tape was applied to the cut portion and quickly peeled off to check whether peeling occurred.

Tables 1 to 6 list the irradiation amounts when peeling occurred, and those exceeding 250 mJ/cm ² were considered acceptable. Additionally, the irradiation amount can be calculated as 250 mJ/cm ² × ultraviolet ray irradiation time.

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

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

The abbreviations shown in Tables 1 to 6 represent the following compounds.

・M400: mixture of 50% dipentaerythritol pentaacrylate and 50% dipentaerythritol hexaacrylate, brand name “Miramer M400”, manufactured by MIWON.

・M403: mixture of 40% dipentaerythritol pentaacrylate and 60% dipentaerythritol hexaacrylate, brand name “Miramer M403”, manufactured by MIWON.

・M404: mixture of 60% dipentaerythritol pentaacrylate and 40% dipentaerythritol hexaacrylate, brand name “Miramer M404”, manufactured by MIWON.

・M405: mixture of 80% dipentaerythritol pentaacrylate and 20% dipentaerythritol hexaacrylate, brand name “Miramer M405”, manufactured by MIWON.

DPHA: Dipentaerythritol hexaacrylate, brand name “Miramer M600”, manufactured by MIWON, double bond equivalent weight 96.4 g/mol

PETA: Pentaerythritol tetraacrylate, double bond equivalent weight 88.1g/mol

・TEMPTA: Trimethylolpropane triacrylate, brand name “Miramer M300”, manufactured by MIWON, double bond equivalent 98.7 g/mol

EO-modified TEMPTA: Trimethylolpropane EO-modified triacrylate, brand name “Miramer M3190”, manufactured by MIWON, double bond equivalent weight 392.1 g/mol

・A9300: Tris-(2-acryloxyethyl)isocyanurate, brand name “NK Ester A9300”, manufactured by Shinnakamura Chemical Co., Ltd.

-Urethane acrylate (1): reaction product of hexamethylene diisocyanate and pentaerythritol triacrylate obtained in Synthesis Example 1 (mass fractions excluding pentaerythritol tetraacrylate are 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 fractions excluding pentaerythritol tetraacrylate are listed in the table), double bond equivalent 136.5 g/ mol

-Urethane acrylate (3): reaction product of isophorone diisocyanate and dipentaerythritol pentaacrylate obtained in Synthesis Example 3, double bond equivalent weight 127.1 g/mol

Urethane acrylate (4): reaction product of biuret-type hexamethylene diisocyanate and pentaerythritol triacrylate obtained in Synthesis Example 4 (mass fractions excluding pentaerythritol tetraacrylate are listed in the table), double bond equivalent 152.6 g/mol

・TinuvinPS: 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, brand name “Tinuvin PS”, manufactured by BASF Japan.

Tinuvin405: Structure in which R ₁ in formula (I) is (a), R ₂ is a group represented by (f), and R ₄ in (f) is all methyl groups, brand name “Tinuvin 405”, manufactured by BASF Japan.

・LA-46: A structure in which R ₁ in formula (I) is a group in which both (b) and R ₂ are represented by (f), and in (f) all R ₄ are hydrogen atoms, brand name “Adekastabe LA-46” 」, manufactured by ADEKA

Tinuvin479: In formula (I), R ₁ is (c), R ₂ is both a group represented by (f), R ₄ in the para position to the R ₄ bond in (f) is a phenyl group, and the rest are hydrogen. Atomic structure, product name “Tinuvin 479”, manufactured by BASF Japan.

・Tinuvin460: A structure in which R ₁ in formula (I) is both (d) and R ₂ are both (g), product name “Tinuvin 460”, manufactured by BASF Japan.

・Tinuvin152: A structure in which R ₁ in formula (I) is both (e) and R ₂ are both (h), brand name “Tinuvin 152”, manufactured by BASF Japan.

Acrylic resin (1): Acrylic resin obtained in Synthesis Example 5, in formula (II), where R ₆ is a methyl group, R ₇ is a methyl group, or has a structure represented by (i), double bond equivalent weight 305.3 g/mol

Acrylic resin (2): Acrylic resin obtained in Synthesis Example 6, in formula (II), where R ₆ is a methyl group, R ₇ is a methyl group, or has a structure represented by (i), double bond equivalent weight 250.2 g/mol

Acrylic resin (3): Acrylic resin obtained in Synthesis Example 7, in formula (II), where R ₆ is a methyl group, R ₇ is a methyl group, or has a structure represented by (i), double bond equivalent weight 428.9 g/mol

Acrylic resin (4): Acrylic resin obtained in Synthesis Example 8, in formula (II), where R ₆ is a methyl group, R ₇ is a methyl group, or has a structure represented by (i), double bond equivalent weight 250.2 g/mol

Acrylic resin (5): Acrylic resin obtained in Synthesis Example 9, in formula (II), where R ₆ is a methyl group, R ₇ is a methyl group, or has a structure represented by (i), double bond equivalent weight 428.9 g/mol

Acrylic resin (6): Acrylic resin obtained in Synthesis Example 10, in formula (II), where R ₆ is a methyl group, R ₇ is a methyl group, or has a structure represented by (i), double bond equivalent weight 305.3 g/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 exhibits high hardness and wetting tension, and is excellent in heat-resistant water adhesion and light-resistant adhesion.

On the other hand, it was confirmed that in Comparative Examples 1 and 2, which did not contain component (B), the hardness, heat-resistant water adhesion, and light-resistant adhesion decreased.

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. In claim 1,
An active energy ray-curable composition in which the compound (A) has four or more (meth)acryloyl groups in the molecule and has a double bond equivalent weight in the range of 80 g/mol to 160 g/mol. In claim 1,
The compound (A) is one of compound (A-1), which has no urethane bond in the molecule and a (meth)acryloyl group, and compound (A-2), which has a urethane bond and a (meth)acryloyl group in the molecule. An active energy ray-curable composition containing either or both. In claim 3,
The compound (A-1) contains either or both of the compound (A-1-1) containing a hydroxyl group in the molecule and the compound (A-1-2) that does not contain a hydroxyl group in the molecule, and the active energy Pre-curable composition. In claim 3,
The compound (A) contains the compound (A-1) and the compound (A-2),
The active energy ray-curable composition wherein the mixing ratio [(A-1)/(A-2)] of the compound (A-2) to the compound (A-1) is in the range of 1/10 to 40/1. . In claim 1,
An active energy ray-curable composition wherein the compound (B) is a compound represented by the following formula (I).

(In formula (I), R ₁ represents a group represented by any of the following formulas (a) to (e), and R ₂ represents a group represented by any of the following formulas (f) to (h), and in the same molecule A plurality of R ₂ 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 one of a hydrogen atom, a methyl group, and a phenyl group, and multiple R ₄ 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.) In claim 1,
An active energy ray-curable composition 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. In claim 1,
An active energy ray-curable composition further containing an acrylic resin (C). In claim 8,
An active energy ray-curable composition in which the weight average molecular weight of the acrylic resin (C) is in the range of 5,000 to 30,000 and the double bond equivalent is in the range of 200 to 450. In claim 8,
An active energy ray-curable composition in which 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 an arbitrary natural number. In formula (II), R ₇ represents an alkyl group having 1 to 8 carbon atoms, and formula ( It represents any one of the groups represented by i).In formula (III), R ₈ represents any one of an alkyl group having 1 to 8 carbon atoms and 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, and in formulas (i) and (j), * is a bond, and R ₉ and R ₁₀ are hydrogen. group or methyl group.) In claim 8,
An active energy ray-curable composition wherein the content of the acrylic resin (C) is 5 to 60 parts by mass based on 100 parts by mass of the resin solid content. In claim 1,
An active energy ray-curable composition further containing inorganic particles (D). In claim 12,
The particle diameter of the inorganic particles (D) is 200 nm or less,
An active energy ray-curable composition wherein the content of the inorganic particles (D) is 5 to 65 parts by mass based on 100 parts by mass of the resin solid content. In claim 12,
An active energy ray-curable composition, wherein the inorganic particles (D) are inorganic oxides modified with a surface modifier having a reactive group. A film characterized by having a cured coating film obtained by curing the composition according to any one of claims 1 to 14. In claim 15,
A film wherein the wetting tension of the surface of the cured coating film is in the range of 35 to 60 mN/m.