JP2023106324A - Active energy ray-curable resin and active energy ray-curable antifogging resin composition, and cured product of the same and article - Google Patents

Abstract

To provide an active energy ray-curable resin and an active energy ray-curable antifogging resin composition which enable formation of a cured coating film that prevents lowering of antifogging property and adhesion under high temperature environment and does not impair its appearance, and a cured product of the same and an article.SOLUTION: There are provided an active energy ray-curable resin which contains a copolymer (A) having a hydroxyl group and an isocyanate compound (B) having a (meth)acryloyl group as essential reaction raw materials, wherein the copolymer (A) contains N-acryloyl morpholine, and a (meth)acrylate compound having a hydroxyl group as essential copolymer components; an active energy ray-curable antifogging resin composition which contains the active energy ray-curable resin and a (meth)acrylate compound (C); a cured product of the active energy ray-curable antifogging resin composition; and an article having a coating film composed of the cured product.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable resin, an active energy ray-curable anti-fogging resin composition, a cured product, and an article.

In recent years, automotive headlamps, virtual reality (VR) displays, and the like are required to have high antifogging properties to prevent fogging. Clouding here is a phenomenon that occurs when water droplets adhering to the surface cause irregular reflection of light. Antifogging methods for preventing such fogging generally include a method of reducing the contact angle of water, a method of absorbing moisture adhering to the surface, a method of imparting water repellency to the surface to repel water, and the like. Are known. Among these methods, the method of reducing the contact angle of water is often used because it is simple and has good antifogging performance.

As a method for reducing the contact angle of water, an attempt has been made to form an antifogging coating film by applying an antifogging resin composition to the surface of a glass or plastic substrate. Therefore, as a resin for anti-fogging paint that can form a coating film that is excellent in anti-fogging properties and does not leave dripping marks, it is known that a mixture containing multiple types of acrylamide monomers is subjected to living radical polymerization (for example, , Patent Document 1).
Further, in Patent Document 2, as an antifog agent composition curable under low temperature conditions for a short time, a plurality of types of acrylamide-based monomers, a plurality of types of (meth)acrylic acid esters, and a hydroxyl group-containing (meth) A composition is disclosed comprising a copolymer obtained from a mixture of acrylates, an acid catalyst and a surfactant.
On the other hand, long-term use of the anti-fogging resin composition may cause the surfactant to bleed out, resulting in a decrease in anti-fogging properties and deterioration of the coating film appearance. Accordingly, there is a demand for an antifogging resin or composition with high heat resistance that can withstand long-term use.

JP 2019-266669 A Japanese Patent Application Laid-Open No. 2019-6881

However, in the inventions described in Patent Documents 1 and 2, tests on anti-fogging properties, adhesion, and yellowness after long-term heating at an ultra-high temperature of 100 degrees or more are not conducted. The heat resistance of the described composition could not be confirmed sufficiently.

The present invention has been made in view of the above problems. An object of the present invention is to provide an energy ray-curable antifogging resin composition, a cured product, and an article.

As a result of investigations by the present inventors, it was found that the active energy ray-curable resin (I) comprising a copolymer (A) having a hydroxyl group and an isocyanate compound (B) having a (meth)acryloyl group as essential reaction raw materials is the above The inventors have found that the problem can be solved, and completed the present invention.

That is, the present invention provides the following inventions.
[1] An active energy ray-curable resin containing a copolymer (A) having a hydroxyl group and an isocyanate compound (B) having a (meth)acryloyl group as essential reaction raw materials, wherein the copolymer (A) is An active energy ray-curable resin comprising N-acryloylmorpholine and a (meth)acrylate compound (A-1) having a hydroxyl group as essential copolymer components.
[2] The active energy ray-curable resin of [1], wherein the copolymer (A) further comprises a compound (A-2) represented by the following general formula (1) as an essential copolymer component.

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 1 to 20 carbon atoms, or a functional group in which —CH ₂ — in a hydrocarbon group is substituted with an oxygen atom or —NH— as long as it is discontinuous. )
[3] The active energy ray-curable resin of [2], wherein R ² is a hydrocarbon group having 1 to 6 carbon atoms in general formula (1).
[4] The content of the structure derived from N-acryloylmorpholine is in the range of 20 to 65% by mass in the copolymer (A), and the content of the structure derived from the compound (A-2) is in the copolymer The active energy ray-curable resin of [2] or [3], which is in the range of 20 to 65% by mass in (A).
[5] The activation energy of any one of [1] to [4], wherein the isocyanate group in the isocyanate compound (B) has a substance amount of 0.2 mol or more per 1 mol of the hydroxyl group in the compound (A-1). Line curing resin.
[6] The active energy ray-curable resin according to any one of [1] to [5] and at least one selected from the group consisting of urethane (meth)acrylates, ester (meth)acrylates and epoxy (meth)acrylates. (Meth)acrylate compound (C) and an active energy ray-curable antifogging resin composition.
[7] The (meth)acrylate compound (C) is a urethane (meth)acrylate having a polycarbonate polyol-derived structure in one molecule, and the content of the (meth)acrylate compound (C) is 1 to 1 in the solid content. The active energy ray-curable antifogging resin composition of [6], wherein the content is in the range of 50% by mass.
[8] Urethane (meth)acrylate is a reaction product of a polycarbonate polyol compound, an isocyanate compound, and a (meth)acrylate having a hydroxyl group,
The polycarbonate polyol compound is a polycarbonate polyol compound obtained as an essential reaction component of either one or both of 1,6-hexanediol and 1,5-pentanediol,
The isocyanate compound is either or both of isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate),
The active energy ray-curable antifogging resin composition of [7], wherein the (meth)acrylate having a hydroxyl group is one or both of pentaerythritol tri(meth)acrylate and 2-hydroxyethyl (meth)acrylate.
[9] The active energy ray-curable antifogging resin composition of any one of [6] to [8], further containing a non-reactive surfactant (D).
[10] A cured product of the active energy ray-curable antifogging resin composition of any one of [6] to [9].
[11] An article having a coating film made of the cured product of [10].

The active-energy-ray-curable resin (I) and the active-energy-ray-curable antifogging resin composition of the present invention have excellent antifogging properties, and prevent deterioration of the antifogging properties and adhesion after high-temperature heating. It is possible to form a cured coating film that does not spoil the appearance. Since this cured coating exhibits excellent antifogging properties even when exposed to high-temperature environments, the active energy ray-curable resin (I) and the active energy ray-curable antifogging resin composition of the present invention can be suitably used as a hard coat for resin materials in automobile applications and display applications.

In this specification, the copolymer (A) is referred to as "component (A)", and the other components (B) to (D) are also referred to in the same way. Further, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate", and "acryloyl" and "methacryloyl" are collectively referred to as "(meth)acryloyl".

<Active energy ray-curable resin (I)>
The active energy ray-curable resin (I) of the present invention (hereinafter sometimes simply referred to as "resin (I)") comprises a copolymer (A) having a hydroxyl group and an isocyanate compound having a (meth)acryloyl group ( B) is synthesized as an essential reaction raw material. A compound having a hydroxyl group that does not correspond to component (A) may also be used as an arbitrary reaction raw material for resin (I).

[(A) Component]
Component (A) is a copolymer having a hydroxyl group, specifically a copolymer comprising N-acryloylmorpholine and a (meth)acrylate compound (A-1) having a hydroxyl group as essential copolymer components. be.
Generally, to develop antifogging properties, it is necessary to lower the surface tension of water droplets adhering to the substrate surface and form a clean water film. Therefore, a water film can be formed in a short time by forming a coating film containing a hydrophilic resin such as the copolymer (A) having a hydroxyl group on the substrate surface. Among them, a composition containing a copolymer having N-acryloylmorpholine as a constitutional unit can form a rigid coating film and can prevent deterioration after heating at a high temperature.

Specifically, the (meth)acrylate compound (A-1) having a hydroxyl group includes dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth) ) acrylate, ditrimethylolpropane tri (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, polyethylene glycol- or polypropylene glycol-modified hydroxy mono (meth) acrylate, and the like. These commercially available products include various trade names "Aronix" (registered trademark) manufactured by Toagosei Co., Ltd. (M-400, M-403, M-404, M-405, M-406, M-306, M-305 , M-303, M-452, M-450, etc.), Daicel's trade name "Plaxel (registered trademark) FA-2D", "Plaxel (registered trademark) FA-4DT", Daicel's trade name "HEMAC" (registered trademark), trade names “Blemmer (registered trademark) AE-200”, “Blemmer (registered trademark) AE-400”, and “Blemmer (registered trademark) AP-400” manufactured by NOF Corporation can be used.

Among the above, compounds having one (meth)acryloyl group in one molecule are preferable from the viewpoint of antifogging properties, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl ( More preferred are meth)acrylates, and particularly preferred is 2-hydroxyethyl (meth)acrylate.

Component (A) may be a copolymer comprising, in addition to N-acryloylmorpholine and compound (A-1), a compound (A-2) represented by the following general formula (1) as an essential copolymer component. . However, compound (A-2) is a compound that does not correspond to compound (A-1).

In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 1 to 20 carbon atoms. Alternatively, R ² may be a functional group in which —CH ₂ — in a hydrocarbon group is substituted with an oxygen atom or —NH—, provided that nitrogen atoms, oxygen atoms, and a nitrogen atom and an oxygen atom are not continuous. do.

Specific examples of the compound (A-2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate and the like. Among them, from the viewpoint of antifogging property after high-temperature heating and adhesion to substrates, compounds in which R ² in general formula (1) is a hydrocarbon group having 1 to 6 carbon atoms are more preferable, and R ² is carbon. Compounds that are linear alkyl groups having 1 to 6 atoms are more preferred, and methyl (meth)acrylate, ethyl (meth)acrylate and n-butyl (meth)acrylate are particularly preferred.

In summary, component (A) is N-acryloylmorpholine, 2-hydroxyethyl (meth)acrylate as compound (A-1), and methyl (meth)acrylate and ethyl (meth)acrylate as compound (A-2). A copolymer containing acrylate or n-butyl (meth)acrylate as an essential copolymer component is most preferred. However, it is possible to solve the problems of the present invention with a copolymer having another compound as an essential copolymerization component, or a copolymer that does not have the compound (A-2) as an essential copolymerization component, and is limited to this. not to be

The method for synthesizing the copolymer (A) is not particularly limited, and examples thereof include known production methods such as radical polymerization, cationic polymerization, cationic living polymerization, and anionic living polymerization. Radical polymerization is particularly preferred from the viewpoint of industrial productivity. Examples of the radical polymerization method include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and the like, and the solution polymerization method is particularly preferable.

Specifically, for example, a radical polymerization initiator, the essential copolymerization components, and a mixture of various monomers as optional components are added dropwise to an organic solvent, and a polymerization reaction is performed at 100 ° C. to synthesize. can. Known radical polymerization initiators such as commonly used organic peroxides and azo compounds can be used. Examples of the organic peroxide include benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-hexanoate, t-butylperoxypivalate, t- and hexyl peroxypivalate. Examples of the azo compound include 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. At least one of the radical polymerization initiators may be used, and two or more of them may be used in combination. As the polymerization solvent, commonly used organic solvents can be used, excluding alcohol solvents. In particular, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran and dioxane, and , methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, ethyl lactate and the like, and propylene glycol monomethyl ether acetate. At least one of the polymerization solvents may be used, and two or more of them may be used in combination.

That is, component (A) may have a structure derived from N-acryloylmorpholine, a structure derived from (meth)acrylate compound (A-1) having a hydroxyl group, and a structure derived from compound (A-2). do not have. In that case, the content of the N-acryloylmorpholine-derived structure in the copolymer (A) is preferably in the range of 5 to 90% by mass, more preferably 10 to 80% by mass, from the viewpoint of antifogging properties and adhesion. % range is more preferred, and a range of 20 to 65 mass % is particularly preferred.
The content of the structure derived from the (meth)acrylate compound (A-1) having a hydroxyl group is preferably in the range of 1 to 50% by mass in the copolymer (A), and is preferably in the range of 5 to 30% by mass. More preferably, it is particularly preferably in the range of 10 to 20% by mass.
The content of the structure derived from the compound (A-2) is preferably in the range of 5 to 90% by mass, more preferably in the range of 10 to 80% by mass, in the copolymer (A). A range of up to 65% by mass is particularly preferred.

As the component (A), one compound may be used alone, or two or more compounds may be used in combination.

[(B) component]
Component (B) is an isocyanate compound having an acryloyl group in one molecule. For example, (meth)acryloyl isocyanate, 2-isocyanatoethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, 2-([1′-methylpropylideneamino]carboxyamino)ethyl (Meth)acryloyl group-containing monomonomers such as (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, and 2-(2-(meth)allyloyloxyethyl)ethyl isocyanate isocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, methylenebis(cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, One isocyanate group of diisocyanate such as cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate and norbornane diisocyanate and a hydroxyl group-containing (meth)acrylate are urethane-bonded (reacted by urethane reaction), and the like. be done. Among them, from the viewpoint of suppressing yellowing due to high temperature heating, aliphatic isocyanate compounds are more preferable, 2-isocyanatoethyl (meth) acrylate, 2-(2-(meth) allyloyloxyethyl) ethyl isocyanate is more preferable, 2- Particular preference is given to isocyanatoethyl (meth)acrylate.

As the component (B), one compound may be used alone, or two or more compounds may be used in combination.

As described above, the active energy ray-curable resin (I) of the present invention is obtained by reacting the (A) component, the (B) component, and optionally the compound having a hydroxyl group other than the (A) component. Specifically, the hydroxyl groups of component (A) and optional components react with the isocyanate groups of component (B) to synthesize an active energy ray-curable resin (I) having urethane bonds. Therefore, the molar ratio (OH:NCO) of the hydroxyl groups contained in the component (A) and optional components and the isocyanate groups contained in the component (B) in the raw material of the active energy ray-curable resin (I) is Although not limited, it is preferably about 1:0.05 to 1:1.5, particularly preferably about 1:0.2 to 1:1, from the viewpoint of antifogging properties and heat resistance. When a compound (optional component) having a hydroxyl group other than the component (A) is not included as a reaction raw material for the resin (I), and among the copolymerization components of the component (A), the compound having a hydroxyl group is the compound (A -1), the amount of hydroxyl group contained in component (A) is equal to the amount of hydroxyl group contained in compound (A-1).

The method for producing the active energy ray-curable resin (I) having a urethane bond includes component (A), which is a copolymer having a hydroxyl group, component (B), which is an isocyanate compound, and, if necessary, components other than component (A). is not particularly limited as long as it is a method of reacting an optional component having a hydroxyl group, and various known production methods are exemplified. Specifically, for example, component (A), component (B), and optionally any component having a hydroxyl group other than component (A) are reacted at an appropriate reaction temperature (eg, 60 to 90° C.) in the presence of a catalyst. ) and the like. In addition, the order in which the components (A), (B) and an optional component having a hydroxyl group are reacted is not particularly limited, and a method of optionally mixing and reacting them, or a method of reacting by mixing all components at once. methods and the like.

<Active energy ray-curable anti-fogging resin composition>
The active energy ray-curable anti-fog resin composition of the present invention (hereinafter sometimes simply referred to as "composition") contains at least the above-mentioned active energy ray-curable resin (I) and optionally other compounds. is a composition containing as appropriate. When the composition contains a compound other than resin (I), the content of resin (I) in the composition is preferably in the range of 50 to 99.9% by mass, more preferably in the range of 60 to 95% by mass. A range of 75 to 90% by weight is particularly preferred.

Any compound other than the resin (I) in the composition may be used as long as it does not interfere with the solution of the problems of the present invention.

[(C) component]
Component (C) is a (meth)acrylate compound that is at least one selected from the group consisting of urethane (meth)acrylates, ester (meth)acrylates and epoxy (meth)acrylates.

Examples of urethane (meth)acrylates include compounds synthesized using either polycarbonate polyol or polyalkylene glycol, an isocyanate compound, and a (meth)acrylate having a hydroxyl group as raw materials.
Commercially available products of polycarbonate polyols include, for example, Ube Industries' product name "ETERNACOLL" (registered trademark) series (UH-50, UH-100, UH-200, UH-300, PH-50, PH-100, PH -200, PH-300, UC-100, UM-90, UHC50-100, UP-50, UP-100 and UP-200, etc.), Mitsubishi Chemical Corporation's product name "BENEBiOL" (registered trademark) grades (NL1010DB, NL2010DB, NL3010DB, NL1005B, NL2005B, NL1030B, HS0830B, HS0840B, HS0840B and HS0850H, etc.), Kuraray products under the trade name "Kuraray Polyol" (C-590, C-1090, C-2090, etc.), etc. can be used. Among them, straight-chain polycarbonate polyols tend to agglomerate more easily than branched polycarbonate polyols, so that urethane (meth)acrylates synthesized using them as raw materials have improved heat resistance and substrate adhesion. Therefore, reaction products of 1,6-hexanediol and dimethyl carbonate (trade name "ETERNACOLL" (registered trademark) series UH-50, UH-100, UH-200, UH-300 manufactured by Ube Industries, Ltd.), and Reaction products of 1,6-hexanediol, 1,5-pentanediol and carbonate ester (trade name "ETERNACOLL" series PH-50, PH-100, PH-200, PH-300 manufactured by Ube Industries, Ltd.) are more preferred.
Commercial products of polyalkylene glycol include, for example, Sanyo Chemical Industries, Ltd. trade name "PEG" series (PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2000, PEG-4000), "Newpol ” PP series (PP-200, PP-400, PP-600, PP-1000 and PP-2000), grades of the trade name “PTMG” manufactured by Mitsubishi Chemical Corporation (PTMG-650, PTMG-1000, PTMG-2000 etc.) can be used. Among them, polyethylene glycol having a number average molecular weight of 200 to 4000 (trade name "PEG" series manufactured by Sanyo Chemical Industries, Ltd. PEG-200, PEG-400, PEG-600, PEG-1000, PEG-2000, PEG-4000 is more preferable. .
Examples of isocyanate compounds include aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate; Aliphatic isocyanates such as trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, norbornane diisocyanate, hydrogenated xylene alicyclic isocyanates such as diisocyanate, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and the like; Alternatively, dimers and trimers (isocyanurate, biuret, allophanate, etc.) of these isocyanate compounds may be used. Among these, isophorone diisocyanate and 4,4'-methylenebis(cyclohexyl isocyanate) are more preferred.
Examples of (meth)acrylates having a hydroxyl group include dipentaerythritol penta(meth)acrylate, pentaerythritol tri(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, polyethylene glycol or polypropylene glycol-modified hydroxy mono (meth) acrylate, and the like. be done. These commercially available products include various trade names "Aronix" (registered trademark) manufactured by Toagosei Co., Ltd. (M-400, M-403, M-404, M-405, M-406, M-306, M-305 , M-303, M-452, M-450, etc.), Daicel's product name "PLAXEL (registered trademark) FA-2D", Daicel's product name "HEMAC" (registered trademark), NOF Corporation's product The names "Blemmer (registered trademark) AE-200", "Blemmer (registered trademark) AP-400" and the like can be used. Among these, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are more preferred.

Examples of ester (meth)acrylates include dehydration condensates of polyester polyols and (meth)acrylic acid.
Polyester polyols include, for example, condensation polymers of polyhydric alcohols and polycarboxylic acids or anhydrides thereof; ring-opening polymers of cyclic esters (lactones); polyhydric alcohols, polycarboxylic acids or anhydrides thereof, and cyclic Reaction products by three kinds of components of ester, etc. are mentioned.
Polyhydric alcohols are, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol. , 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, tri Examples include methylolpropane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, etc.), bisphenols (bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.).
The polyvalent carboxylic acid or its anhydride is, for example, malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedioic acid; Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid and trimellitic acid, or their anhydrides things, etc.
Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, ε-caprolactone and the like.
Examples of commercially available ester (meth)acrylates include various products (M6100, M6250, M6500, M7100, M7300K, M-8030, etc.) under the trade name “Aronix” (registered trademark) manufactured by Toagosei Co., Ltd., and the like. Among them, in the present invention, bifunctional polyester acrylates (in the case of commercial products, various trade names "Aronix" (registered trademark) manufactured by Toagosei Co., Ltd. (M6100, M6250, and M6500, etc.), etc.) are more preferable, and "Aronix (registered Trademark M6250" is particularly preferred.

Epoxy (meth)acrylates are obtained by reacting (meth)acrylic acid with epoxy groups of epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and the like. What can be done is mentioned. Commercially available epoxy acrylates include, for example, DIC's product name "LUXYDIR (registered trademark) V-5500".

Among the above, from the viewpoint of adhesion after heating to a high temperature, the component (C) is particularly preferably a urethane (meth)acrylate having a structure derived from a polycarbonate polyol, specifically a compound represented by the following general formula (2) is more preferred.

In the above formula, X represents a structure derived from a polycarbonate polyol, Y ₁ and Y ₂ each independently represent a structure derived from a (meth)acrylate having a hydroxyl group, α represents a structure derived from an isocyanate compound, and a plurality of may be the same or different, and the average repetition number n1 is an integer of 1-10. As used herein, the term "structure derived from polycarbonate polyol" refers to a structure obtained by removing terminal hydrogen atoms from a polycarbonate polyol compound, and the term "structure derived from (meth)acrylate having a hydroxyl group" refers to a (meth)acrylate having a hydroxyl group. The term "structure derived from an isocyanate compound" refers to a structure obtained by removing all isocyanate groups from an isocyanate compound.

Accordingly, the reaction raw material for component (C) is not particularly limited, but examples thereof include polycarbonate polyol compounds, isocyanate compounds, and (meth)acrylates having hydroxyl groups. Furthermore, the number average molecular weight of the polycarbonate polyol compound as a reaction raw material is more preferably in the range of 500 to 1000, and is a reaction product of 1,6-hexanediol, 1,5-pentanediol and a carbonate ester (for example, Trade names of "ETERNACOLL (registered trademark) PH50" and "ETERNACOLL (registered trademark) PH-100" manufactured by Ube Industries, Ltd.) are particularly preferred.
The isocyanate compound as a reaction raw material is preferably an aliphatic diisocyanate compound, more preferably isophorone diisocyanate or 4,4′-methylenebis(cyclohexyl isocyanate).
Although the (meth)acrylate having a hydroxyl group as a reaction raw material is not particularly limited, it is more preferable to use, for example, pentaerythritol tri(meth)acrylate or 2-hydroxyethyl (meth)acrylate.

From the standpoint of easy availability, the component (C) may be a commercially available urethane (meth)acrylate having a structure derived from polycarbonate polyol. etc. may be used.

The content of component (C) is preferably in the range of 0.1 to 90% by mass based on the total solid content contained in the composition, from the viewpoint of antifogging property and heat resistance, and 0.5 to 90% by mass. It is more preferably in the range of 70% by mass, still more preferably in the range of 1 to 50% by mass, and particularly preferably in the range of 5 to 30% by mass.

As the component (C), one type of compound may be used alone, or two or more types may be used in combination.

The active energy ray-curable antifogging resin composition of the present invention may further contain, for example, the component (D) described below.

[(D) Component]
Component (D) is a non-reactive surfactant selected from anionic surfactants, cationic surfactants and nonionic surfactants. Here, "non-reactive" refers to not causing addition polymerization due to the polymerization reaction of vinyl monomers, and "non-reactive surfactant" refers to a surfactant that does not have a (meth)acryloyl group in the molecule. Point.
In the present invention, by adding the component (D), more suitable hydrophilicity can be imparted to the surface of the base material, and the antifogging property and heat resistance are improved.

As the anionic surfactant, all conventionally known surfactants can be used. For example, fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfate esters such as sodium lauryl sulfate and ammonium lauryl sulfate; dodecyl Alkylbenzenesulfonates and alkylnaphthalenesulfonates such as sodium benzenesulfonate, sodium alkylnaphthalenesulfonate; dialkylnaphthalenesulfonate salts, naphthalenesulfonate formalin condensate salts, dialkylsulfosuccinates, dialkylphosphate salts, polyoxyethylene Examples include polyoxyethylene sulfate salts such as sodium alkylphenyl ether sulfate. Examples of the anionic surfactant include fluorine-containing anionic surfactants such as perfluoroalkylcarboxylates, perfluoroalkylsulfonates, and perfluoroalkylphosphates. The anionic surfactant is preferably a dialkyl sulfosuccinate or a dialkyl phosphate salt from the viewpoint of excellent antifogging performance.

As the cationic surfactant, all conventionally known ones can be used. Alkyltrimethylammonium salts such as trimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride; didecyldimethylammonium chloride, dilauryldimethylammonium chloride, dicetyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and dialkyldimethylammonium salts such as stearyldimethylbenzylammonium chloride. Examples of the cationic surfactant include fluorine-containing cationic surfactants such as perfluoroalkyltrimethylammonium salts. From the viewpoint of antifogging performance, the cationic surfactant is preferably an alkyltrimethylammonium salt or a dialkyldimethylammonium salt.

As the nonionic surfactant, all conventionally known surfactants can be used. Examples include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene octylphenol; Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol; Polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate; Polypropylene glycol ethylene oxide adducts, Polyoxyethylene sorbitan monolaurate, Polyoxyethylene sorbitan mono polyoxyethylene sorbitan fatty acid esters such as stearates; phosphate esters such as alkyl phosphates and polyoxyethylene alkyl ether phosphates; sugar esters, cellulose ethers and the like. Examples of nonionic surfactants include perfluoroalkylamine oxides, perfluoroalkylethylene oxide adducts, oligomers having a perfluoroalkyl group and a hydrophilic group, and oligomers having a perfluoroalkyl group and a lipophilic group. , an oligomer having a perfluoroalkyl group and a lipophilic group, and an oligomer having a perfluoroalkyl group and a hydrophilic group and a lipophilic group. The nonionic surfactant is preferably polyoxyethylene higher alcohol ethers from the viewpoint of antifogging performance.

Component (D) is not particularly limited, but from the viewpoint of anti-fogging properties and heat resistance, an ether-type nonionic surfactant (for example, Noigen (registered trademark) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) XL-140" and trade name "DKS (registered trademark) NL-30", etc.), quaternary ammonium salts (for example, trade name "Lebon (registered trademark) TM-16" manufactured by Sanyo Chemical Co., Ltd., manufactured by Sanyo Chemical Co., Ltd. The product name “Lebon (registered trademark) TM-18”, the product name “Lipocard (registered trademark) 12W-37” manufactured by Lion Specialty Chemicals, the product name “Cation DSV” manufactured by Sanyo Chemical Co., Ltd., Tetrabutylammonium bromide , tetrapropylammonium bromide, etc.), or dimethylaminopropyl amide stearate (e.g., trade name "Cathiogen (registered trademark) TMP" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), sodium linear alkylbenzene sulfonate or sodium alpha olefin sulfonate (For example, the trade name "Neogen (registered trademark) S-20F" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), sodium dioctyl sulfosuccinate (for example, the trade name "Aerosol (registered trademark) OT-100" manufactured by Solvay), Fluorine-containing surfactants (for example, the product name "Futergent (registered trademark) 100" manufactured by Neos, the product name "Surflon (registered trademark) 211" manufactured by AGC Seichemical Co., Ltd., the product name manufactured by AGC Seichemical Co. " Surflon (registered trademark) 221", etc.) is preferably used.

Component (D) can be used alone or in combination of two or more.

From the viewpoint of antifogging properties and heat resistance, the amount of component (D) to be blended is in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the solid content of the active energy ray-curable antifogging resin composition. is preferred, the range of 0.3 to 20 parts by weight is more preferred, and the range of 0.5 to 15 parts by weight is particularly preferred.

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

[Photoinitiator]
Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 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- one, 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, with respect to 100 parts by mass of the solid content of the active energy ray-curable antifogging resin composition. is more preferable, and 1 to 5 parts by mass is particularly preferable. When the content of the photopolymerization initiator is 0.1 parts by mass or more, the curing reaction proceeds favorably, and a cured product having high hardness can be obtained, which is preferable. On the other hand, when the content of the photopolymerization initiator is 10 parts by mass or less, yellowing or the like is less likely to occur, and a cured product having high transparency can be obtained, which is preferable.

In addition, the active energy ray-curable antifogging resin composition of the present invention may contain a solvent. By containing 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, 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; Aromatic solvents and the like are included.

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

The content of the solvent is preferably 0 to 300 parts by mass, more preferably 0 to 150 parts by mass, relative to 100 parts by mass of the solid content of the active energy ray-curable antifogging resin composition. preferable. When the content of the solvent is 300 parts by mass or less, it is preferable because the film thickness can be easily controlled. A solvent content of 10 parts by mass or more is preferable because various coating methods such as spray coating and flow coating can be employed.

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

[Other ingredients]
Typical examples of other components include reactive compounds, various resins, fillers, ultraviolet absorbers, and leveling agents. Furthermore, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants other than component (D), stabilizers, flow modifiers, coupling agents, dyes, rheology control agents, antioxidants, It may contain a plasticizer or the like.

As the reactive compound, a (meth)acrylate compound other than the components (A) to (C) or a compound having a double bond such as a vinyl group may be blended. (Meth)acryloyl compounds include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

Monofunctional (meth)acrylates include, for example, acryloylmorpholine, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (for example, Daicel Co., Ltd. trade name "PLAXEL" (registered trademark)), reaction products of phthalic anhydride or succinic anhydride and hydroxyalkyl (meth)acrylates, mono(meth)acrylates of polyester diols obtained from succinic acid and ethylene glycol, succinic acid and propylene glycol Polyester diol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-(meth) acryloyloxypropyl (meth) acrylate, acrylamide, dimethyl acrylamide , diethylacrylamide, amino (meth)acrylate, and (meth)acrylate containing an ionic group such as a sulfonic acid group or a quaternary ammonium salt.

Polyfunctional (meth)acrylates include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di( meth)acrylate, ethylene oxide-modified glycerol tri(meth)acrylate, propylene oxide-modified glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, hydroxypivalic acid-modified trimethylolpropane tri(meth)acrylate , ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-modified phosphoric acid tri(meth)acrylate, pentaerythritol ethoxytetra(meth) Acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra (meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra( meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, propylene oxide-modified dipentaerythritol hexa(meth)acrylate, isocyanate compound and alcohol Examples include urethane (meth)acrylate compounds obtained by reacting a system compound.

A liquid organic polymer may also be used for viscosity adjustment. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction. Kyoei Chemical Co., Ltd.), special modified phosphate amine salt (HIPLAAD (registered trademark) ED-251: manufactured by Kusumoto Kasei Co., Ltd.), modified acrylic block copolymer (DISPERBYK (registered trademark) 2000; manufactured by BYK Chemie), etc. mentioned.

Thermosetting resins and thermoplastic resins can be used as various resins.
A thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means of heat, radiation, a catalyst, or the like. As a specific example, a thermosetting resin is a resin that has the property of being substantially insoluble and infusible when cured by means of heat, radiation, a catalyst, or the like. 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, ketone resin, and xylene. 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 singly or in combination of two or more.

A thermoplastic resin is a resin that can be melt-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 Resins, polysulfone resins, polyphenylene sulfide resins, polyetherimide resins, polyethersulfone resins, polyarylate resins, thermoplastic polyimide resins, polyamideimide resins, polyetheretherketone resins, polyketone resins, liquid crystal polyester resins, fluororesins, synth otakutic polystyrene resins, cyclic polyolefin resins, and the like. These thermoplastic resins can be used singly or in combination of two or more.

As a filler, for example, silica can be blended for the purpose of improving hard coat properties.
Silica is not limited, and known fine silica particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdery silica fine particles include Aerosil (registered trademark) 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121 and H122 manufactured by AGC, and E220A and E220 manufactured by Nippon Silica Kogyo Co., Ltd. , SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.
Further, as commercially available colloidal silica, for example, Nissan Chemical Industries, Ltd. 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 and the like can be mentioned.

Silica may be reactive silica. Examples of reactive silica include reactive compound-modified silica. Examples of the reactive compound include 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.
Examples of commercially available powdery silica modified with a compound having a (meth)acryloyl group include Aerosil (registered trademark) RM50 and R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth)acryloyl group. Examples thereof include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z and MEK-AC-2140Z manufactured by Nissan Chemical Industries. In addition, after modification with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane, a silica obtained by addition reaction with acrylic acid, or a compound having 3-isocyanatopropyltriethoxysilane, a hydroxyl group and a (meth)acryloyl group is used as a urethane. Reactive silicas also include silicas modified with chemical reactions.

The shape of the silica fine particles is not particularly limited, and may be spherical, hollow, porous, rod-like, plate-like, fibrous, or amorphous. For example, Silinax (registered trademark) manufactured by Nittetsu Mining Co., Ltd. can be used as commercially available hollow silica fine particles.
Also, the primary particle size is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the inorganic fine particles are sufficiently dispersed in the composition, and when it is 200 nm or less, sufficient strength of the cured product can be maintained.

Examples of fillers other than silica include inorganic fillers and organic fillers. The shape of the filler is not limited, and examples include particulate, plate-like, and fibrous fillers.
Fillers with excellent heat resistance include alumina, magnesia, titania, zirconia, etc.; Fillers with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; As those excellent in barrier properties, metal fillers and / or metal-coated fillers using single metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); Excellent ones include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, potassium titanate, magnesium sulfate, sepiolite, xonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, oxide Zinc, magnesium hydroxide; high refractive index barium titanate, zirconia oxide, titanium oxide, etc.; photocatalytic titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon , sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, photocatalyst metals such as lead, composites of the above metals, their oxides; Metals such as zirconia and magnesium oxide, and their composites and oxides; those with excellent conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; those with excellent UV shielding include titanium oxide , zinc oxide and the like.
These inorganic fine particles may be appropriately selected depending on the application, and may be used alone or in combination of multiple types. In addition, since the inorganic fine particles have various properties other than the properties listed as examples, they may be appropriately selected according to the intended use.

Examples of inorganic fibers include inorganic fibers such as carbon fiber, glass fiber, boron fiber, alumina fiber, silicon carbide fiber, carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber, 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, proteins, polypeptides, and regenerated fibers such as alginic acid.

The amount of filler compounded is preferably 0 to 60% by mass in 100% by mass of the composition.

An ultraviolet absorber may be added to the composition of the present invention for the purpose of improving light resistance. Examples of UV absorbers include benzophenone-based, benzotriazole-based, cyclic iminoester-based, cyanoacrylate-based, and polymer-type UV absorbers.

A light stabilizer may be added to the composition of the present invention for the purpose of improving light resistance. Light stabilizers include hindered amine light stabilizers (HALS) and the like.

Various surface modifiers may be added to the composition of the present invention for the purpose of improving the leveling property during application, or for the purpose of improving the slipperiness of the cured film to improve the scratch resistance. As the surface modifier, various additives that modify surface physical properties and are commercially available under the names of surface conditioners, leveling agents, slipperiness imparting agents, antifouling agents and the like can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
Specifically, silicone-based polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone-based polymers and oligomers having silicone chains and polyester chains, fluorine-based polymers and oligomers having perfluoroalkyl groups and polyalkylene oxide chains, fluorine-based polymers 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 the lubricity, one containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL (registered trademark) 350 (manufactured by Daicel Ornex), BYK (registered trademark)-333 (manufactured by BYK-Chemie Japan), BYK-377 (manufactured by BYK-Chemie Japan), 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 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 ( DIC), OPTOOL (registered trademark) DAC-HP (Daikin), ZX-058-A (T&K TOKA), ZX-201 (T&K TOKA), ZX-202 (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 Co., Ltd.), X-22-164A (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd.) Chemical Industry Co., Ltd.), X-22-164C (Shin-Etsu Chemical Co., Ltd.), X-22-164E (Shin-Etsu Chemical Co., Ltd.), X-22-174DX (Shin-Etsu Chemical Co., Ltd.), etc. can.

The active energy ray-curable antifogging resin composition of the present invention is suitable as a cured coating film that imparts antifogging properties to a substrate by applying an active energy ray to at least one surface of various materials and then irradiating it with an active energy ray. can be used for The cured coating film made of the composition of the present invention can be used for a long period of time in a harsh high-temperature and high-humidity environment or outdoors because it does not impair the appearance while suppressing the deterioration of anti-fogging properties and adhesion in a high-temperature environment. It exhibits excellent effects when used as an anti-fogging coating film for the material used.

<Hardened products/articles>
(Composition/Material)
The article of the present invention has a coating film made of a cured product of the active energy ray-curable antifogging resin composition of the present invention, and a substrate.
The base material is not particularly limited, and may be appropriately selected according to the application. Examples include plastic, glass, wood, metal, metal oxide, paper, silicone, modified silicone, etc., which are obtained by bonding different materials. It may be a base material.
The shape of the substrate is also not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having a curvature over its entire surface or part thereof. Moreover, 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. 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 mixture of a plurality of resins, and may have a single-layer structure or a laminated structure of two or more layers. These plastic substrates may also 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, Known additives such as crystal nucleating agents and lubricants may be included.

The article of the present invention may further have a second substrate on top of the substrate and cured coating. 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 is a base material obtained by bonding different materials. good too. The shape of the substrate is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape having curvature over its entire surface or part thereof. Moreover, 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 substances, it can be preferably used as an interlayer material for dissimilar 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, deposited films (CVD, PVD, sputtering), magnetic films, reflective films, Ni, Cu, Cr, Fe, stainless steel, and the like. Metal, 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 metals, and insulating substrates silicon-based substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon;

(Production method)
The article of the present invention is obtained by applying the composition of the present invention to the substrate surface and then curing it.
Application to the substrate can be carried out by a method in which the composition is directly applied to the substrate or directly molded and cured.
In the case of direct coating, the coating method is not particularly limited, and includes 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, A screen printing method, an inkjet method, and the like can be mentioned.
Direct molding includes in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, and the like.
Alternatively, the article of the present invention may be obtained by laminating a cured product of the composition on a substrate. When the cured product of the composition is laminated, the semi-cured cured product may be laminated on the substrate and then completely cured, or the completely cured 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 irradiation with 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 preferred from the viewpoint of curability and convenience.
Here, when ultraviolet rays are used as active energy rays, devices for irradiating the ultraviolet rays include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps and the like. Using these, it is possible to obtain a cured coating film or a cured product by irradiating a coated or molded composition with ultraviolet rays having a wavelength of about 180 to 400 nm. The irradiation amount of ultraviolet rays is appropriately selected according to the type and amount of the photopolymerization initiator used.

(Application)
Since the cured product of the composition of the present application has excellent anti-fogging properties and heat resistance, it is used in safety equipment such as helmet visors, face shields, and goggles, and in automobiles such as headlamps, windshields, glasses, side mirrors, etc. It can be suitably used for applications such as cameras, canopies, roofs, and cockpit instruments. In addition, window glass, plastic mirrors, various mirrors for bathroom vanities, lights, digital signage, head-up displays, virtual reality (VR) displays, GPS navigation devices, electronic control panels, freezer cases for food , freezers for commercial use, binoculars, surveillance cameras, surgical cameras, sunglasses, eyeglasses, anti-fog film for automobile glass, anti-fog film for window glass, mirrors and showcases, infectious disease control partitions, monitor covers, sensor covers, etc. It can also be suitably used for applications.

EXAMPLES The present invention will be described in more detail below using Examples and Comparative Examples, but the present invention is not limited to the following embodiments. In addition, "parts" and "%" in the examples are based on mass unless otherwise specified.

(Synthesis Example 1: Synthesis of active energy ray-curable resin (1))
Propylene glycol monomethyl ether acetate (50 parts by mass) was added to a 1-liter flask equipped with a stirrer, gas inlet tube, condenser and thermometer, and the temperature was raised to 110°C. Acryloylmorpholine (trade name “ACMO” (registered trademark), manufactured by KJ Chemicals) (80 parts by mass), 2-hydroxyethyl acrylate (20 parts by mass), tertiary butyl peroxy-2-ethylhexanoate (3 parts by mass) part) and propylene glycol monomethyl ether (30 parts by mass) were added to the dropping funnel and added dropwise over 4 hours under a nitrogen atmosphere. After dropping, the mixture was stirred for 8 hours while maintaining the temperature at 110°C, and cooled to 70°C. Switch to an air atmosphere, tert-butyl hydroxytoluene (0.28 parts by mass), methoxyhydroquinone (0.028 parts by mass), dibutyltin diacetate (0.028 parts by mass), 2-acryloyloxyethyl isocyanate (24.3 parts by mass) parts by mass) was added, and the temperature was raised to 85°C. The mixture was stirred at 85° C. until the infrared absorption spectrum at 2250 cm ⁻¹ indicating the isocyanate group disappeared to obtain an active energy ray-curable resin (1).

(Synthesis Examples 2 to 21: Synthesis of Acrylic Resins (2) to (21) Having a Hydroxyl Group)
Active energy ray-curable resins (2) to (21) of each example were obtained in the same manner as in Synthesis Example 1 except that the raw materials shown in Tables 1 and 2 were used.

Each number in Tables 1 and 2 represents parts by mass of each compound.
Further, "OH:NCO=1:x" in Tables 1 and 2 represents hydroxyl groups contained in component (A) of the raw material of resin (I) and isocyanate groups contained in component (B) of the raw material of resin (I). and the values in the table correspond to x.

The abbreviations shown in Tables 1 and 2 above refer to the following compounds.
Acrylate 1: Acryloylmorpholine, trade name “ACMO” (registered trademark), manufactured by KJ Chemicals [(meth)acrylate compound having a hydroxyl group (A-1)]
HEA: Hydroxyethyl acrylate, trade name "HEA", manufactured by Osaka Organic Chemical Industry Co., Ltd. [Compound (A-2) represented by general formula (1)]
MMA: methyl methacrylate, R ² in formula (1) is a hydrocarbon group with 1 carbon atom EA: ethyl acrylate, R ² in formula (1) is a hydrocarbon group with 2 carbon atoms nBA: n-butyl acrylate, formula R ² in (1) is a hydrocarbon group with 4 carbon atoms nBMA: n-butyl methacrylate, R ² in formula (1) is a hydrocarbon group with 4 carbon atoms iBMA: isobutyl methacrylate, R ² in formula (1) is a hydrocarbon group having 4 carbon atoms tBMA: t-butyl methacrylate, R ² in formula (1) is a hydrocarbon group having 4 carbon atoms CHA: cyclohexyl acrylate, R ² in formula (1) is 6 carbon atoms Hydrocarbon group EHA: 2-ethylhexyl acrylate, R ² in formula (1) is a hydrocarbon group with 8 carbon atoms LA: Lauryl acrylate, R ² in formula (1) is a hydrocarbon group with 12 carbon atoms [other ( Copolymerization component of component A]
Amide 1: dimethylacrylamide, trade name "DMAA" (registered trademark), manufactured by KJ Chemicals Amide 2: hydroxyethylacrylamide, trade name "HEAA" (registered trademark), manufactured by KJ Chemicals [Component (B)]
AOI: 2-isocyanatoethyl acrylate, trade name "Karenzu (registered trademark) AOI", manufactured by Showa Denko K.K.

(Synthesis Example 22: Synthesis of urethane acrylate compound UA1 (PC))
189.11 parts by mass of isophorone diisocyanate (trade name “IPDI”, Covestro Polymer Co., Ltd.), 2,6-di-tert- 1 part by mass of butyl-4-methylphenol, 0.10 parts by mass of methoxyhydroquinone, and 0.10 parts by mass of dibutyltin diacetate were added, the temperature was raised to 70° C., and "HEA" 98.0 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was added. 79 parts by mass and polycarbonate polyol (reaction product of 1,6-hexanediol, 1,5-pentanediol and carbonate ester, number average molecular weight: about 500, trade name “ETERNACOLL PH-50”, manufactured by Ube Industries, Ltd.) 210.90 parts by mass was charged in portions over 1 hour. After the preparation, the reaction was carried out at 80° C. until the infrared absorption spectrum at 2250 cm −1 indicating the isocyanate group disappeared to obtain a urethane acrylate compound UA1 (PC) having a structure derived from polycarbonate polyol. As used herein, the term "structure derived from polycarbonate polyol" refers to a structure obtained by removing terminal hydrogen atoms from a polycarbonate polyol.

(Synthesis Example 23: Synthesis of urethane acrylate compound UA2 (PC))
133 parts by mass of isophorone diisocyanate (trade name “IPDI”, Covestro Polymer Co., Ltd.), 2,6-di-tert-butyl- 1 part by mass of 4-methylphenol, 0.10 parts by mass of methoxyhydroquinone, and 0.10 parts by mass of dibutyltin diacetate were added, heated to 70° C., and 70 parts by mass of “HEA” manufactured by Osaka Organic Chemical Industry Co., Ltd. 295 parts by mass of polycarbonate polyol (reaction product of 1,6-hexanediol, 1,5-pentanediol and carbonate ester, number average molecular weight: about 1000, trade name “ETERNACOLL PH-100”, manufactured by Ube Industries, Ltd.) 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 a urethane acrylate compound UA2 (PC) having a structure derived from polycarbonate polyol.

(Synthesis Example 24: Synthesis of urethane acrylate compound UA3 (PC))
60.31 parts by mass of isophorone diisocyanate (trade name “IPDI”, Covestro Polymer Co., Ltd.), 2,6-di-tert- 1 part by mass of butyl-4-methylphenol, 0.10 parts by mass of methoxyhydroquinone, and 0.10 parts by mass of dibutyltin diacetate were added, the temperature was raised to 70° C., and "HEA" 31.Osaka Organic Chemical Industry Co., Ltd. was added. 51 parts by mass and 407.00 parts by mass of polycarbonate polyol (reaction product of 1,6-hexanediol and dimethyl carbonate, number average molecular weight: about 3000, trade name "ETERNACOLL UH-300", manufactured by Ube Industries) for 1 hour. I prepared it in parts. 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 a urethane acrylate compound UA3 (PC) having a structure derived from polycarbonate polyol.

(Synthesis Example 25: Synthesis of urethane acrylate compound UA4 (PEG))
133 parts by mass of isophorone diisocyanate (trade name “IPDI”, Covestro Polymer Co., Ltd.), 2,6-di-tert-butyl- 1 part by mass of 4-methylphenol, 0.1 part by mass of methoxyhydroquinone, and 0.1 part by mass of dibutyltin diacetate were added, the temperature was raised to 70 ° C., and hydroxyethyl acrylate (trade name "HEA", Osaka Organic Chemical Industry Co., Ltd. 70 parts by weight of polyethylene glycol (trade name “PEG-1000” manufactured by Sanyo Chemical Industries, Ltd.) were added over 1 hour. Stirring was carried out at 80° C. until the infrared absorption spectrum at 2250 cm −1 indicating an isocyanate group disappeared to obtain a urethane acrylate compound UA4 (PEG) having a structure derived from polyethylene glycol. The term "polyethylene glycol-derived structure" as used herein refers to a structure obtained by removing a terminal hydrogen atom from polyethylene glycol.

(Example 1)
Active energy ray-curable resin (1) 100 parts by mass, photopolymerization initiator 3 parts by mass (Omnirad 2959 (manufactured by IGM) 1.5 parts by mass, Omnirad 819 (manufactured by IGM) 1.5 parts by mass)), and propylene glycol 154.5 parts by mass of monomethyl ether was blended and uniformly mixed so that the solid content was 40 wt % to prepare an active energy ray-curable anti-fogging resin composition (1).

(Examples 2 to 35, Comparative Examples 1 to 5)
Active energy ray-curable antifogging resin compositions (2) to (35) and (R1) to (R5) of each example were prepared in the same manner as in Example 1 except that the compositions were changed to those shown in Tables 3 to 6. got

[Preparation of evaluation sample]
The active energy ray-curable anti-fogging resin composition of each example was applied to a polycarbonate substrate (“Carboglass (registered trademark) Polish Clear” manufactured by AGC, thickness: 2 mm, area: 10 cm × 10 cm), and the film thickness was 5 μm. and dried at 80° C. for 4 minutes, and irradiated with ultraviolet rays under the conditions of 200 mW/cm ² and 1000 mJ/cm ² with a high-pressure mercury lamp. It was used as a test piece.

[Evaluation of initial anti-fogging property]
At a height of 2 cm from the water surface of a warm water bath maintained at 80 ° C, the test piece was placed with the coating surface facing down, and the coating film was continuously irradiated with steam from the warm water bath for 10 seconds. The time until film formation was measured. 10 seconds or less is regarded as passing.

[Evaluation of antifogging property after high temperature heating]
After allowing the test piece to stand at 120°C for 240 hours, the test piece was placed at a height of 2 cm from the surface of the water in a warm water bath maintained at 50°C, with the coating surface facing down. The coating film was continuously irradiated with steam from the evaporator for 60 seconds, and the time required to form a water film was measured. 60 seconds or less was regarded as passing. Also, when a water film is not formed even after a certain period of time has elapsed, it is marked as x.

[Evaluation of adhesion after high temperature heating]
The cured product of the test piece was cut with a cutter in a grid pattern of 10×10 with a width of 1 mm, and the coated plate was allowed to stand at 120°C. After a certain period of time had passed, cellophane tape ("CT-24" manufactured by Nichiban Co., Ltd.) was attached to the grid-like portion and removed, and the time until the tape was removed was measured. 120 hours or more is regarded as passing.

[Evaluation of Appearance after High Temperature Heating]
The lower the yellowness index (YI value) of the test piece, the higher the transparency of the laminate, which tends to improve the visibility when used for the front plate of a display device, for example. Therefore, the lower the yellowness, the better the appearance.
Specifically, after the test piece was left to stand at 120 ° C. for 240 hours, the yellowness (YI value) of the test piece was measured in accordance with JIS K 7373: 2006, a color difference manufactured by Nippon Denshoku Industries Co., Ltd. It was measured using a meter "Color meter ZE6000". After performing background measurement without a test piece, set the optical film in the sample holder, perform transmission measurement, obtain the tristimulus values (X, Y, Z), and calculate the YI value based on the following formula. Calculated. A YI value of 3 or less is accepted.
YI=100×(1.2985X−1.1335Z)/Y

Active energy ray-curable antifogging resin compositions (1) to (35) obtained in Examples 1 to 35, and active energy ray curable antifogging resin compositions ( The compositions and evaluation results of R1) to (R5) are shown in Tables 3 to 6.

The abbreviations shown in Tables 3-6 refer to the following compounds.
UA1 (PC): Urethane acrylate compound having a structure derived from polycarbonate polyol synthesized in Synthesis Example 22 UA2 (PC): Urethane acrylate compound having a structure derived from polycarbonate polyol synthesized in Synthesis Example 23 UA3 (PC): Synthesis Example 24 Urethane acrylate compound UA4 (PEG) having a structure derived from polycarbonate polyol synthesized in Synthesis Example 25: Urethane acrylate compound UA5 (PC) having a structure derived from polyethylene glycol synthesized in Synthesis Example 25: Urethane acrylate having a structure derived from polycarbonate polyol Average molecular weight: about 5000, trade name “Shiko (registered trademark) UV-3310B”, Mitsubishi Chemical Corporation M6250: Bifunctional polyester acrylate, trade name “Aronix (registered trademark) M6250”, Toagosei Co., Ltd. V-5500: Epoxy acrylate, trade name “LUXYDIR (registered trademark) V-5500”, manufactured by DIC XL140: Ether-type nonionic surfactant, trade name “Noigen (registered trademark) XL-140”, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. NL-30: Ether-type nonionic surfactant, trade name "DKS (registered trademark) NL-30", Daiichi Kogyo Seiyaku Co., Ltd. TM-16: cetyltrimethylammonium chloride, trade name "Lebon (registered trademark) TM-16", OT-100 manufactured by Sanyo Chemical Industries Co., Ltd.: Sodium dioctylsulfosuccinate, trade name "Aerosol OT-100", Photopolymerization initiator manufactured by Solvay: 1-[4-(2-hydroxyethoxy)phenyl]- 2-hydroxy-2-methyl-1-propan-1-one (trade name "Omnirad2959", manufactured by IGM) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name "Omnirad819", IGM) A mixture containing 50% each of

It can be confirmed that the cured coating film of the active energy ray-curable antifogging resin composition of the present invention prevents deterioration of antifogging properties and adhesion after heating at high temperatures, and does not impair the appearance (low yellowness). rice field.
On the other hand, in Comparative Examples 1 and 2, in which the component (B) is not used as the reaction raw material of the active energy ray-curable resin (I), the antifogging property after high-temperature heating, the adhesion to the substrate, and the appearance are impaired. was In Comparative Examples 3 and 4, in which component (A), which does not have N-acryloylmorpholine as a copolymerization component, was used as a reaction raw material for active energy ray-curable resin (I), the antifogging property and appearance after high-temperature heating were impaired. rice field. Similarly, in Comparative Example 5, in which both the urethane acrylate having a polycarbonate structure and the urethane acrylate having a polyethylene glycol-derived structure were used instead of using the active energy ray-curable resin (I) of the present invention, the high temperature The antifogging properties and appearance after heating were impaired.

Claims (11)

An active energy ray-curable resin containing a copolymer (A) having a hydroxyl group and an isocyanate compound (B) having a (meth)acryloyl group as essential reaction raw materials,
An active energy ray-curable resin, wherein the copolymer (A) comprises N-acryloylmorpholine and a (meth)acrylate compound (A-1) having a hydroxyl group as essential copolymer components. 2. The active energy ray-curable resin according to claim 1, wherein the copolymer (A) further contains a compound (A-2) represented by the following general formula (1) as an essential copolymer component.

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a hydrocarbon group having 1 to 20 carbon atoms, or —CH ₂ — in the hydrocarbon group is an oxygen atom as long as it is not continuous.) Or represents a functional group substituted with -NH-.) 3. The active energy ray-curable resin according to claim 2, wherein R ² in the general formula (1) is a hydrocarbon group having 1 to 6 carbon atoms. The content of the structure derived from N-acryloylmorpholine is in the range of 20 to 65% by mass in the copolymer (A), and the content of the structure derived from the compound (A-2) is in the copolymer (A). 3. The active energy ray-curable resin according to claim 2, which is in the range of 20 to 65% by mass in coalescence (A). 2. The active energy ray-curable resin according to claim 1, wherein the amount of isocyanate groups in said isocyanate compound (B) is 0.2 mol or more per 1 mol of hydroxyl groups in said compound (A-1). The active energy ray-curable resin according to any one of claims 1 to 5 and one or more selected from the group consisting of urethane (meth)acrylate, ester (meth)acrylate and epoxy (meth)acrylate (meth ) an active energy ray-curable antifogging resin composition comprising an acrylate compound (C). The (meth)acrylate compound (C) is a urethane (meth)acrylate having a polycarbonate polyol-derived structure in one molecule, and the content of the (meth)acrylate compound (C) is 1 to 50 in the solid content. The active energy ray-curable antifogging resin composition according to claim 6, which is in the range of % by mass. The urethane (meth)acrylate is a reaction product of a polycarbonate polyol compound, an isocyanate compound, and a (meth)acrylate having a hydroxyl group,
The polycarbonate polyol compound is a polycarbonate polyol compound obtained by using either one or both of 1,6-hexanediol and 1,5-pentanediol as essential reaction components,
The isocyanate compound is either or both of isophorone diisocyanate and 4,4′-methylenebis(cyclohexyl isocyanate),
8. The active energy ray-curable antifogging resin composition according to claim 7, wherein the (meth)acrylate having a hydroxyl group is one or both of pentaerythritol tri(meth)acrylate and 2-hydroxyethyl (meth)acrylate. thing. 7. The active energy ray-curable antifogging resin composition according to claim 6, further comprising a non-reactive surfactant (D). A cured product of the active energy ray-curable antifogging resin composition according to claim 6 . An article comprising a coating film comprising the cured product according to claim 10.