JP2023177576A - Active energy ray-curable hard coat agent, hard coat layer, laminate and base material with inorganic oxide film - Google Patents

Abstract

To provide a hard coat layer which has excellent adhesiveness between the hard coat layer and an inorganic oxide film and excellent hardness and scratch resistance on the surface of a hard coat film and hardly causes curling of the hard coat film and a hard coat agent for forming the hard coat layer.SOLUTION: There is provided an active energy ray-curable hard coat agent for forming a hard coat layer in a base material with an inorganic oxide film, which comprises a base material, a hard coat layer and an inorganic oxide film (excluding a transparent conductive film) in this order, wherein the active energy ray-curable hard coat agent comprises a compound (A) having a (meth)acryloyl group (excluding (B)), a compound (B) having a silsesquioxane skeleton and a photopolymerization initiator (C) and the compound (A) includes a compound (a1) having 6 or more (meth)acryloyl groups and a nurate ring skeleton and a compound (a2) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less.SELECTED DRAWING: None

Description

The present invention provides an active material for forming a hard coat layer in a base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order. The present invention relates to an energy ray-curable hard coat agent, a hard coat layer, a laminate, and an oxide base material with an inorganic oxide film.

Base materials made of plastic such as polyethylene terephthalate resin have excellent transparency and impact resistance, are lightweight, and are easy to process, so they are used in place of glass base materials for various purposes.

However, plastic substrates may have inferior surface properties such as hardness and scratch resistance compared to glass substrates. For this reason, it is common to coat the surface of a plastic substrate with an active energy ray-curable composition to form a hard coat film to improve the surface characteristics of the plastic substrate.

In order to make the surface hardness of a plastic substrate as hard as that of a glass substrate, it is not enough to form a hard coat film; instead, it is necessary to form a laminate in which an inorganic material layer is laminated on a hard coat film. is proposed.

On the other hand, when an inorganic material layer is laminated on a hard coat film using an active energy ray-curable composition, the adhesion between the hard coat film and the inorganic material layer is insufficient. To address this problem, Patent Document 1 discloses that the use of a trifunctional acrylate having a nurate ring and a silsesquioxane compound provides excellent adhesion to the inorganic material layer.

However, the composition of Patent Document 1 does not sufficiently satisfy the hardness of the hard coat film surface, and when the plastic base material is a thin film, there is a problem that the laminate coated with the hard coat film curls. there were. Therefore, it is possible to achieve both the adhesion between the hard coat film and the inorganic material layer and the hardness of the hard coat film surface, and also to prevent the laminate coated with the hard coat film from curling even when using a film-like plastic base material. There is a need for linearly curable compositions.

Japanese Patent Application Publication No. 2013-035274

The present invention has excellent adhesion between the hard coat layer and the inorganic oxide film (excluding the transparent conductive film), and has excellent hardness and scratch resistance on the surface of the hard coat film. The purpose of the present invention is to provide a hard coat layer that does not easily form, and a hard coat agent for forming the hard coat layer.

The present inventors have conducted extensive research to solve the above problems, and as a result, have arrived at the following invention. The present invention provides the following active energy ray-curable hard coat agent, hard coat layer, laminate, and base material with an inorganic oxide film.
[1]: Activity for forming a hard coat layer in a base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order An energy ray curable hard coating agent,
A compound (A) having a (meth)acryloyl group (excluding the compound (B)), a compound (B) having a silsesquioxane skeleton, and a photopolymerization initiator (C),
The compound (A) has 6 or more (meth)acryloyl groups and a compound (a1) (excluding (a2)) having a nurate ring skeleton and 3 or more (meth)acryloyl groups, An active energy ray-curable hard coating agent comprising a compound (a2) having a (meth)acryloyl group equivalent of 115 or less.
[2]: The active energy ray-curable hard coating agent according to [1], wherein the compound (B) is a compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group.
[3]: The content of the compound (B) is 1 to 30% in the total of 100% by mass of the active energy ray-curable hard coating agent, compound (A), compound (B), and photopolymerization initiator (C). The active energy ray-curable hard coating agent according to [1] or [2], which is % by mass.
[4]: A hard coat layer in a base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order,
A compound (A) having a (meth)acryloyl group (excluding the compound (B)) and a compound (B) having a silsesquioxane skeleton,
The compound (A) has 6 or more (meth)acryloyl groups and a compound (a1) (excluding (a2)) having a nurate ring skeleton and 3 or more (meth)acryloyl groups, A hard coat layer comprising a compound (a2) having a (meth)acryloyl group equivalent of 115 or less.
[5]: A laminate comprising a base material having a thickness of 100 μm or less and a hard coat layer according to [4].
[6]: A base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order,
A compound (A) having a (meth)acryloyl group (excluding the compound (B)) and a compound (B) having a silsesquioxane skeleton,
The compound (A) has 6 or more (meth)acryloyl groups and a compound (a1) (excluding (a2)) having a nurate ring skeleton and 3 or more (meth)acryloyl groups, A base material with an inorganic oxide film, comprising a compound (a2) having a (meth)acryloyl group equivalent of 115 or less.

The present invention provides a hard coat layer that has excellent adhesion between the hard coat layer and the inorganic oxide film (excluding the transparent conductive film), has excellent surface hardness and scratch resistance, and is less likely to cause curling of the hard coat layer. It becomes possible to provide a coating layer and a hard coating agent for forming the hard coating layer.

The present invention will be explained in detail below. It goes without saying that other embodiments are also included in the scope of the present invention as long as they meet the spirit of the present invention. Furthermore, in this specification, numerical ranges specified using "~" include the numerical values written before and after "~" as the lower limit and upper limit ranges.

First, the terms used in this specification will be explained.
In this specification, "(meth)acrylic,""(meth)acryloyl," and "(meth)acrylate" are used as "acrylic or methacrylic," respectively, unless otherwise specified. "acryloyl or methacryloyl" and "acrylate or methacrylate".
In addition, "active energy ray-curable hard coating agent" is referred to as "hard coating agent", "(meth)acryloyl group-containing compound (A)" is referred to as "compound (A)", and "(meth)acryloyl group containing 6 or more and a compound (a1) having a nurate ring skeleton, and a compound (a2) having three or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less. "Compound (a2)" and "compound (B) having a silsesquioxane skeleton" may be respectively referred to as "compound (B)."
Unless otherwise noted, the various components appearing in this specification may be used individually or in combination of two or more.

《Hard coat agent》
The hard coat agent of the present invention is an active energy ray-curable hard coat agent for forming a hard coat layer on a base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film in this order. It is a coating agent.
The hard coating agent of the present invention comprises a compound (a1) having 6 or more (meth)acryloyl groups and a nurate ring skeleton, and a (meth)acryloyl group equivalent of 115 or less having 3 or more (meth)acryloyl groups. It contains a compound (A) containing a compound (a2), a compound (B), and a photopolymerization initiator (C).
By using such a hard coating agent, it has excellent adhesion between the hard coat layer and the inorganic oxide film, and also has excellent hardness and scratch resistance on the surface of the hard coat film. It becomes possible to form a hard coat layer that is less prone to curling.

<Compound (A)>
Compound (A) is a compound having a (meth)acryloyl group.
Compound (A) has 6 or more (meth)acryloyl groups and has a nurate ring skeleton and Compound (a1) has 3 or more (meth)acryloyl groups and has a (meth)acryloyl group equivalent of 115 It contains the following compound (a2). By including (a1) and (a2), it is possible to suppress curling properties and ensure sufficient hardness on the surface of the hard coat film.

Compound (a1) has six or more (meth)acryloyl groups and has a nurate ring skeleton. The nurate ring skeleton is a trimer of isocyanate compounds having a nitrogen atom and has a six-membered ring structure. By having six or more (meth)acryloyl groups, the crosslinking density increases, the hard coat film surface has excellent hardness and scratch resistance, and curling of the hard coat film can be suppressed. Although the detailed factors that suppress the curling property are unknown, it is believed that the ring structure of the nurate ring skeleton greatly contributes to stress relaxation.
A compound having three (meth)acryloyl groups and a nurate ring skeleton is also relatively easily available, but it is not suitable because its crosslinking density is low and the hardness and scratch resistance of the hard coat film surface are insufficient.

Specifically, the compound (a1) includes a reaction product of isocyanurate (trimer) of diisocyanate and a poly(meth)acrylate compound having a hydroxyl group, a reaction product of isocyanurate (trimer) of polyisocyanate, a polyol, and a poly(meth)acrylate compound having a hydroxyl group. Examples include reactants with poly or mono(meth)acrylate compounds, but from the viewpoint of improving the hardness and scratch resistance of the hard coat film surface, it is possible to combine an isocyanurate (trimer) compound of diisocyanate with one hydroxyl group and ( A reaction product with a poly(meth)acrylate compound having two or more meth)acryloyl groups is preferred.
Examples of diisocyanates include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate, hydrogenated products of the aromatic isocyanates, and aliphatic diisocyanurates such as isophorone diisocyanate and hexamethylene diisocyanate. is,
Mono(meth)acrylates having one hydroxyl group include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate,
Poly(meth)acrylates having one hydroxyl group include, but are not limited to, (meth)acrylates having a hydroxyl group such as pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate.

Examples of the polyol include, but are not limited to, ethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, cyclohexanediol, cyclohexanedimethanol, and tricyclodecane dimethanol.

The (meth)acryloyl group equivalent of compound (a2) is 115 or less, preferably 110 or less. When the (meth)acryloyl group equivalent is 115 or less, the crosslinked coating film after the curing reaction has a dense three-dimensional structure, and the hardness of the hard coat film can be increased.

Here, the (meth)acryloyl group equivalent is determined by the following formula.
(Meth)acryloyl group equivalent = molecular weight/number of (meth)acryloyl groups in the same molecule

Compound (a2) specifically includes trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and pentaerythritol tri(meth)acrylate. Polyol poly(meth)acrylate compounds such as acrylate and pentaerythritol tetra(meth)acrylate;
In addition, polyacrylates of polymer polyols having three or more (meth)acryloyl groups, such as polyacrylic poly(meth)acrylate, polyurethane poly(meth)acrylate, and polyester(meth)acrylate;
Polyepoxy (meth)acrylate;
etc., but are not limited to these.

Commercially available products of compound (a2) include, for example, trimethylolpropane tri(meth)acrylate (Miramer M300, manufactured by MIWON, etc.), glycerin tri(meth)acrylate (Aronix M-930, manufactured by Toagosei, etc.), and dipentaerythritol. Penta(meth)acrylate (SR399, etc. manufactured by Sartomer), dipentaerythritol hexa(meth)acrylate (Miramer M600, etc. manufactured by MIWON), pentaerythritol tri(meth)acrylate (Miramer M340, etc. manufactured by MIWON), and pentaerythritol tetra Examples include, but are not limited to, polyol poly(meth)acrylate compounds such as (meth)acrylate (Light Acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd., etc.).

The content of compound (A) is 30% by mass or more and less than 99% by mass out of the total 100% by mass of compound (A), compound (B), and photopolymerization initiator (C) of the active energy ray-curable hard coating agent. is preferred.

In order to obtain a hard coat layer with excellent hardness and curling properties, the content of compound (a1) in 100% by mass of compound (A) is preferably 5% by mass or more, more preferably 25% by mass or more, More preferably, it is 40% by mass or more, and the content of compound (a2) in 100% by mass of compound (A) is preferably 5% by mass or more, more preferably 25% by mass or more, and still more preferably 40% by mass. That's all.
Further, the content of compound (a1) in 100% by mass of compound (A) is preferably 95% by mass or less, more preferably 75% by mass or less, even more preferably 60% by mass or less, and the content of compound (A) The content of compound (a2) in 100% by mass is preferably 95% by mass or less, more preferably 75% by mass or less, even more preferably 60% by mass or less.
When the content of compound (a1) is within the above range, curling can be suppressed and excellent scratch resistance can be achieved. Further, by having the content of the compound (a2) within the above range, sufficient hardness and scratch resistance of the hard coat film surface can be achieved.

The hard coating agent of the present invention may contain a compound (A) other than (a1) and (a2), if necessary.
Examples include a compound (a3) having three or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of more than 115, and a compound (a4) having one or two (meth)acryloyl groups.

Examples of the compound (a3) include, but are not limited to, urethane acrylate, polyester acrylate, and epoxy acrylate.

<Urethane acrylate>
Urethane acrylates include, for example, those obtained by reacting diisocyanates with (meth)acrylates having hydroxyl groups, and isocyanate group-containing urethane prepolymers obtained by reacting polyols and polyisocyanates under conditions with an excess of isocyanate groups. There are those obtained by reacting with (meth)acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under conditions with an excess of hydroxyl groups can also be obtained by reacting with (meth)acrylates having isocyanate groups.

Known polyisocyanates can be used as the polyisocyanate, including aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and the like.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, and 1,3-phenylene. Examples include diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate-benzyl chloride.
Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, Examples include methylcyclohexane diisocyanate, norbornane diisocyanate, and dimer diisocyanate obtained by converting the carboxy group of dimer acid into an isocyanate group.

Examples of hydroxyl group-containing (meth)acrylates include trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate (meth)acrylic acid 2- Hydroxyethyl, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxy(meth)acrylate Hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexanedimethanol mono(meth) Acrylic acid ester, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl (meth)acrylate-α-(hydroxymethyl), monofunctional glycerol (meth)acrylate, or these (Meth)acrylate and (meth)acrylic acid ester having a hydroxyl group at the end by ring-opening addition of ε-caprolactone lactone, and alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide for the above hydroxyl group-containing (meth)acrylate. Hydroxyl group-containing (meth)acrylic esters, such as alkylene oxide-added (meth)acrylic esters, which are repeatedly added with . Among these, those containing at least one selected from trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

<Polyester acrylate>
Polyester acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensing a polybasic acid and a polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.
Examples of the polybasic acids mentioned above include aliphatic acids, alicyclic acids, and aromatic acids, each of which can be used without particular limitations. For example, aliphatic polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, Examples include itaconic acid, succinic anhydride, maleic anhydride, and these aliphatic dicarboxylic acids and their anhydrides can be used. Further, acid anhydride derivatives can also be used.

Further, examples of the polyhydric alcohol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5 -Pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (number of moles added is 10 or less) , polyoxypropylene glycol (additional mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol , neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol, etc. Mention may be made of cyclic diols.

Further, polyols containing three or more hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol may be used in part.

Among the above polyhydric alcohols, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 '-Dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, and other branched alkanes have hydroxyl groups. It is preferable that two or more oligomers are introduced in terms of adhesiveness, heat resistance, etc.

Examples of the hydroxyl group-containing (meth)acrylates include those mentioned above, and among them, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta( Those containing at least one selected from meth)acrylates are preferred.

<Epoxy acrylate>
Examples of polyepoxy acrylates include those obtained by esterifying the glycidyl group of an epoxy resin with (meth)acrylic acid to form a (meth)acrylate group as a functional group.

Examples of the compound (a4) include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and diethylene glycol di(meth)acrylate. acrylate, di(meth)acrylates such as neopentyl glycol di(meth)acrylate and ethylene oxide-modified di(meth)acrylate of bisphenol A, oligomers such as polyurethane poly(meth)acrylate and polyester poly(meth)acrylate, and 2 - Ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, benzyl (meth)acrylate, cyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobonyl ( Examples include, but are not limited to, mono(meth)acrylates such as meth)acrylate.

<Compound (B)>
Compound (B) is a compound having a silsesquioxane skeleton. Due to the rigid skeleton of the silsesquioxane skeleton, the hard coat layer and the inorganic oxide film adhere to each other through interaction with oxygen atoms and some remaining silanol groups without reducing the hardness or scratch resistance of the hard coat layer. The properties become better.
Compound (B) may be a silsesquioxane, that is, a network polymer having a structure of (RSiO _1.5 ) _n obtained by hydrolyzing and condensing a trifunctional silane or a compound having a polyhedral cluster structure. There are no particular limitations, and compounds having a silsesquioxane skeleton with a known and commonly used structure such as a random structure, a ladder structure, a complete cage structure, an incomplete cage structure, etc. can be used. (RSiO _1.5 ) In _n , n is an integer of 2 or more. n is preferably an integer of 2 to 200, more preferably 2 to 150, even more preferably 2 to 100. Further, in (RSiO _1.5 ) _n , R is preferably an organic group such as a methyl group, an ethyl group, a phenyl group, or a (meth)acryloyl group.

Compound (B) is a compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group in which at least a part of R is a (meth)acryloyl group in (RSiO _1.5 ) _n , and a compound (b1) in which R is a (meth)acryloyl group. It is divided into compounds (b2) having a silsesquioxane skeleton that is not a (meth)acryloyl group. The compound (B) is preferably a compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group. By having a (meth)acryloyl group, the deterioration of the scratch resistance of the hard coat layer can be further suppressed, and not only the scratch resistance is high, but also the alkali resistance and the adhesion with the inorganic oxide film layer can be improved.
In addition, when it has a silsesquioxane skeleton, it is classified as a compound (B) even if it has a (meth)acryloyl group.

Commercial products of the compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group include AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, and MAC manufactured by Toagosei. -SQ SI-20, MAC-SQ HDM, etc.
Commercially available compounds (b2) having a silsesquioxane skeleton in which R is not a (meth)acryloyl group include SR-21, SR-23, SR-13, SR-33, SO-04, manufactured by Konishi Chemical Industry Co., Ltd. Examples include SQ107, SQ109, and SQ506 manufactured by Arakawa Chemical Industries, and OX-SQ TX-100, OX-SQ SI-20, and OX-SQ HDX manufactured by Toagosei.

The content of the compound (B) having a silsesquioxane skeleton is 1% by mass in the total of 100% by mass of the active energy ray-curable hard coating agent compound (A), compound (B), and photopolymerization initiator (C). The content is preferably 30 to 30% by mass, more preferably 3 to 27% by mass, and even more preferably 5 to 25% by mass.
The above content is preferable because the adhesion between the hard coat layer and the inorganic oxide film is good even when the inorganic oxide film is thick.

<Photopolymerization initiator (C)>
Examples of the photopolymerization initiator (C) include monocarbonyl photopolymerization initiators, dicarbonyl photopolymerization initiators, acetophenone photopolymerization initiators, benzoin ether photopolymerization initiators, and acylphosphine oxide photopolymerization initiators. agent, aminocarbonyl photopolymerization initiator, etc. can be used.
The photopolymerization initiator (C) may be used in combination with a sensitizer.

For example, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, Monocarbonyl photopolymerization initiators such as 2-/4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone;
Dicarbonyl photopolymerization initiators such as 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene acetate;
2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenyl ketone , diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[ 4-(Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 1-phenyl-1,2-propane Acetophenone photopolymerization initiator such as dione-2-(o-ethoxycarbonyl)oxime;
Benzoin ether photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether;
Acyl phosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide;
Also, ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, 4,4' - Aminocarbonyl photopolymerization initiators such as bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, and 2,5′-bis(4-diethylaminobenzal)cyclopentanone;
etc.

As a commercially available photopolymerization initiator (C), IGM-Resins B. V. Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, Esacure One manufactured by BASF Corporation, Lucirin TPO manufactured by BASF Corporation, and the like. In particular, Omnirad 184 and Esacure One are preferred from the viewpoint of yellowing resistance after curing with active energy rays.

The content of the photopolymerization initiator (C) is not limited as long as it contains an amount that allows the hard coat layer to be cured by ultraviolet rays to achieve predetermined physical properties. From the viewpoint of scratch resistance, it is preferable that the active energy ray-curable hard coating agent contains 1 to 15% by mass of the total of 100% by mass of compound (A), compound (B), and photopolymerization initiator (C), It is more preferable to contain 3 to 10% by mass.

<Other ingredients>
The hard coating agent of the present invention may contain an organic solvent (D), additives, and other compounds (E) such as a resin component having no (meth)acryloyl group, as necessary.
Additives include thermosetting resins, polymerization inhibitors, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, anti-blocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, Examples include silane coupling agents, conductive agents, inorganic fillers, pigments, and dyes.

[Organic solvent (D)]
The hard coating agent of the present invention may also contain an organic solvent (D).
Examples of the organic solvent (D) include aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, ester organic solvents, methanol, Known organic solvents can be used, such as alcohol-based organic solvents such as ethanol, n-propanol, isopropanol, and n-butanol, and glycoether-based organic solvents such as propylene glycol monomethyl ether.

When containing an organic solvent (D), the content of the organic solvent (D) is within a range such that the nonvolatile content concentration of the hard coating agent of the present invention is 1 to 70% by mass from the viewpoint of coating properties and film forming properties. It is preferable that there be.

<Hard coat layer>
The hard coat layer can be obtained by curing the hard coat agent of the present invention with active energy rays. Examples of active energy rays include ultraviolet rays and electron beams. Examples of sources of ultraviolet rays include high-pressure mercury lamps and metal halide lamps, and the irradiation energy thereof is usually about 100 to 2,000 mJ/cm ² . Examples of electron beam supply methods include scanning electron beam irradiation and curtain electron beam irradiation, and the irradiation energy is usually about 10 to 200 kGy.

<Laminated body>
The laminate of the present invention includes a base material having a thickness of 100 μm or less and a hard coat layer.
The base material (also referred to as support) is not particularly limited, and examples thereof include glass, synthetic resin moldings, films, and the like. Synthetic resin molded products include polymethyl methacrylate resin, copolymer resin whose main component is methyl methacrylate, polystyrene resin, styrene-methyl methacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, and cellulose acetate butylene resin. Examples include molded products of synthetic resins such as rate resins, polyallyl diglycol carbonate resins, polyvinyl chloride resins, and polyester resins.

Examples of films include polyester film, polyethylene film, polypropylene film, cellophane film, diacetyl cellulose film, triacetyl cellulose (TAC) film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, and polyvinyl alcohol. Film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentyl film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film , acrylic film, etc.

A laminate can be obtained by applying the hard coat agent of the present invention onto a base material and forming a hard coat layer cured by active energy rays. The conditions for applying the hard coating agent to the surface of the substrate (for example, one side or both sides if the substrate is in the form of a film) are not particularly limited, and the application means include, for example, spraying, a roll coater, and a reverse roll coater. , a gravure coater, a knife coater, a bar coater, a dot coater, and the like. The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 30 μm, more preferably 5 to 25 μm.

<Substrate with inorganic oxide film>
The base material with an inorganic oxide film of the present invention includes an inorganic oxide film on the hard coat layer side of the laminate. However, the inorganic oxide film excludes the transparent conductive film.
Since the hard coat layer of the present invention has excellent adhesion to the inorganic oxide film, it is possible to suppress peeling of the inorganic oxide film when the hard coat layer and the inorganic oxide film are directly laminated.
Note that, if necessary, another resin layer or the like may be further provided between the base material and the hard coat layer. Other resin layers include, for example, an antistatic resin layer to prevent static electricity during the manufacturing process, a hard coat resin layer to further increase the hardness of the laminate of the present invention, and a layer between the base material and the hard coat layer of the present invention. Examples include, but are not limited to, an anchor resin layer for improving adhesion.

The inorganic oxide film is formed by a dry film forming method, and examples thereof include an inorganic oxide vapor-deposited film, an inorganic oxide sputtered film, and an inorganic oxide CVD film. A material sputtered film is preferable.

The thickness of the inorganic oxide film layer is not particularly limited as long as it satisfies physical, optical, and electrical properties, but is usually 0.01 to 0.5 μm.

Examples of elements constituting the inorganic oxide film include, but are not limited to, Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, Zr, Sn, and Ta. The hard coating agent of the present invention is particularly effective when silicon oxide is used in the inorganic oxide film.

[Method for manufacturing base material with inorganic oxide film]
The method for producing the inorganic oxide film-coated base material of the present invention is not particularly limited. For example, (1) the hard coating agent of the present invention is applied to the surface of the substrate (for example, on one or both sides if the substrate is in the form of a film), (2) after applying heat to the substrate, ( 3) A laminate is manufactured through a step of further curing by irradiating active energy rays to form a hard coat layer. (4) An embodiment in which the product is manufactured through a step of forming an inorganic oxide film on the hard coat layer is mentioned.
That is, by steps (1) to (3), a laminate having a base material and a hard coat layer of the present invention is manufactured, and an inorganic oxide film is formed on the hard coat layer of the laminate. Preferably, the method is a method for manufacturing a base material.
Since the hard coat layer of the present invention has high scratch resistance, it is possible to prevent the hard coat layer from being scratched during the manufacturing process of the inorganic oxide film-coated substrate, the processing process, and the like.

Regarding step (1), the conditions for applying the hard coat agent to the surface of the substrate (on one side or both sides if the substrate is in the form of a film, for example) are not particularly limited, and the application means include, for example, spraying, Examples include a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater, and a dot coater. Further, the coating amount is not particularly limited, but is usually about 0.01 to 10 g/m ² as dry nonvolatile content.

Regarding step (2), the conditions for applying heat to the base material are not particularly limited, but usually the temperature is about 80 to 150°C and the time is about 10 seconds to 2 minutes.

Regarding step (3), the conditions for irradiating active energy rays are not particularly limited. Examples of active energy rays include ultraviolet rays and electron beams. Examples of sources of ultraviolet rays include high-pressure mercury lamps and metal halide lamps, and the irradiation energy thereof is usually about 100 to 2,000 mJ/cm ² . Examples of electron beam supply methods include scanning electron beam irradiation and curtain electron beam irradiation, and the irradiation energy is usually about 10 to 200 kGy.

Regarding step (4), the means for forming the inorganic oxide film on the hard coat layer is not particularly limited, but a dry coating method is preferred. Specifically, for example, a physical method such as a vacuum evaporation method or a sputtering method, and a chemical method (chemical vapor phase reaction, etc.) such as CVD may be used.

Furthermore, when the base material with an inorganic oxide film is used as a decorative film, an antenna film, a conductive film, or a flexible printed wiring board, the inorganic oxide film may be formed into a circuit pattern. In this case, the manufacturing method of the base material with an inorganic oxide film is not particularly limited, and for example, various resists are applied to the inorganic oxide film side of the base material with an inorganic oxide film obtained in steps (1) to (4). However, after drawing the circuit pattern, the resist is immersed in an etching solution (alkaline solution) to remove the resist. The shape of the circuit pattern may be any shape, such as a thin line shape, a dot shape, a mesh shape, or a planar shape.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the following Examples do not limit the technical scope of the present invention. In the examples, "parts" means "parts by mass" and "%" means "% by mass."
Further, the blending amounts in the table are parts by mass, and values other than the solvent are nonvolatile content equivalent values. In addition, a blank column in the table indicates that it is not blended.

<Production of compound (a1) having 6 or more (meth)acryloyl groups and having a nurate ring skeleton>
(Synthesis Example 1) (a1-1): In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, add Aronix M305 (manufactured by Toagosei Co., Ltd., pentaerythritol trifluoride having a molecular weight of 298). 1325.6 parts by mass of pentaerythritol polyacrylate) containing 67.5% by mass of acrylate (PE-3A) and 32.5% by mass of pentaerythritol tetraacrylate (PE-4A) having a molecular weight of 352, and neostane U-810 ( After adding 0.1 part by mass of tin catalyst (manufactured by Nitto Kasei Co., Ltd.) and bringing the liquid temperature to 50°C, add Desmodur Z4470BA (manufactured by Sumika Covestro Co., Ltd., isophorone diisocyanate (manufactured by Sumika Covestro Co., Ltd., with a molecular weight of 667 relative to the nonvolatile content). IPDI) 1109.8 parts by mass of polyisocyanate containing 85.8% by mass of trimer, NCO content 11.9%, non-volatile content 70% by mass (volatile component butyl acetate) having nurate rings was added from the dropping funnel for 30 minutes. dripped.
After the temperature rise subsided, the temperature was raised to 80°C and reacted for 3 hours. After confirming that the peak of isocyanate groups disappeared on FT-IR, the temperature was lowered to room temperature and the non-volatile components had a weight average molecular weight of 1600. 74.3% by mass of urethane acrylate (a1-1) having 9 acryloyl groups, 20.5% by mass of pentaerythritol tetraacrylate (PE-4A) (a2-1), and others without (meth)acryloyl groups A solution containing 5.2% by mass of compound (e-1) and a nonvolatile content of 86.3% by mass was obtained.

(Synthesis Example 2) (a1-2): In a 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, add Aronix M305 (manufactured by Toagosei Co., Ltd., pentaerythritol trichloride with a molecular weight of 298). 1325.6 parts by mass of pentaerythritol polyacrylate) containing 67.5% by mass of acrylate (PE-3A) and 32.5% by mass of pentaerythritol tetraacrylate (PE-4A) having a molecular weight of 352, and neostane U-810 ( After adding 0.1 part by mass of tin catalyst (manufactured by Nitto Kasei Co., Ltd.) and bringing the liquid temperature to 50°C, add Duranate TPA-100 (manufactured by Asahi Kasei Corp., hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation) with a molecular weight of 505 based on the non-volatile content). HDI) 571.7 parts by mass of polyisocyanate containing 88.3% by mass of trimer, 23.1% NCO content and nurate rings with 100% by mass of non-volatile content (volatile content: butyl acetate) was added from the dropping funnel for 30 minutes. dripped.
After the temperature rise subsided, the temperature was raised to 80°C and reacted for 3 hours. After confirming that the peak of isocyanate groups disappeared on FT-IR, the temperature was lowered to room temperature and the non-volatile components had a weight average molecular weight of 1400. 73.8% by mass of urethane acrylate (a1-2) having 9 acryloyl groups, 22.7% by mass of pentaerythritol tetraacrylate (PE-4A:) (a2-1), and no (meth)acryloyl group A mixture containing 3.5% by mass of other compound (e-2) and a nonvolatile content of 100% by mass was obtained.

(Synthesis Example 3) (a1-3): In a 4-necked flask equipped with a stirrer, reflux condenser, nitrogen introduction tube, thermometer, and dropping funnel,
Desmodur Z4470BA (manufactured by Sumika Covestro Co., Ltd., contains 85.8% by mass of isophorone diisocyanate (IPDI) trimer with a molecular weight of 667 based on nonvolatile content, NCO content 11.9%, nonvolatile content 70% by mass (volatile content) 4439.0 parts by mass of polyisocyanate having a nurate ring (butyl acetate), 432.6 parts by mass of cyclohexyl dimethanol (manufactured by Co., Ltd., molecular weight 144, hydroxyl value 389 mgKOH/g), Neostan U-810 (Nitto Kasei) Co., Ltd., tin catalyst) was added, the temperature was raised to 80°C, and the reaction was carried out for 3 hours. After confirming that the peak of isocyanate groups was 50% on FT-IR, 4- Add 865.0 parts by mass of hydroxybutyl acrylate (molecular weight 144, hydroxyl value 389 mgKOH/g), further react at 80°C for 3 hours, and after confirming that the isocyanate group peak has disappeared on FT-IR, heat to room temperature. Lower the temperature, and in the nonvolatile matter, 90.0% by mass of urethane acrylate (a1-3) having 6 acryloyl groups with a weight average molecular weight of 4000, and other compounds (e-3) having no (meth)acryloyl groups 10 A solution with a non-volatile content of 76.8% by weight was obtained, containing .0% by weight.

Details of the abbreviations in Tables 1 and 2 are as follows.
<Compound (A)>
a2-1: Pentaerythritol tetraacrylate (PE-4A) contained in the mixture obtained in Synthesis Example 1 or Synthesis Example 2 (number of functional groups: 4, acroyl group equivalent: 88)
a2-2: Aronix M-403 (dipentaerythritol hexaacrylate (number of functional groups: 6, acryloyl group equivalent: 96): 40 to 50% and dipentaerythritol pentaacrylate (number of functional groups: 5, acryloyl group equivalent: 105) ): 50-60% mixture; manufactured by Toagosei Co., Ltd.)
a3-1: Miramer PU610 (urethane acrylate, weight average molecular weight: 1800, number of functional groups: 6, acryloyl group: equivalent weight 300, manufactured by MIWON)
a3-2: Aronix M315 (isocyanuric acid EO modified diacrylate (number of functional groups: 2, acryloyl group: equivalent weight 185) 8% and isocyanuric acid EO modified triacrylate (number of functional groups: 3, acryloyl group: equivalent weight 141) 92% (Mixture with Toagosei Co., Ltd.)
a4: Viscoat #230 (1,6-hexanediol diacrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Compound (B)>
b1-1: MAC-SQ HDM (having a methacryloyl group. Propylene glycol monobutyl ether solution with a non-volatile concentration of 50%, manufactured by Toagosei Co., Ltd.)
b1-2: AC-SQ SI20 (has an acryloyl group. Manufactured by Toagosei Co., Ltd.)
b2: SR-13 (silsesquioxane without (meth)acryloyl group. Manufactured by Konishi Chemical Industry)
<Photopolymerization initiator (C)>
・Esacure One (acetophenone photopolymerization initiator manufactured by DKSH Japan Co., Ltd.)
<Other ingredients>
x-1: PGM-AC-2140Y (Silica fine particles whose surface is modified with acrylate, manufactured by Nissan Chemical Co., Ltd.)

[Example 1]
≪Preparation of hard coating agent≫
In a flask with a stirrer, add 45 parts of compound (a1-1), 12.4 parts of pentaerythritol tetraacrylate (a2-1), and 3.1 parts of other compound (e-1) in terms of nonvolatile content. , the solution obtained in Synthesis Example 1 was added, and 32.6 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.) was added as compound (a2-2), and MAC-SQ HDM (manufactured by Toagosei Co., Ltd.) was added as compound (B). ) and 5 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.) as a photopolymerization initiator (C) were thoroughly mixed, and methyl ethyl ketone was used as an organic solvent to adjust the nonvolatile content concentration to 60% to form a hard coat. obtained the drug.
<<Preparation of hard coat layer and laminate>>
The hard coating agent obtained above was coated on an 80 μm thick triacetyl cellulose (TAC) film using a bar coater so that the film thickness after drying was 15 μm, and then 500 mJ was applied using a high pressure mercury lamp. / ^cm2 ultraviolet rays were irradiated to form a hard coat layer to produce a laminate.

[Example 4]
In a flask equipped with a stirrer, add 45 parts of compound (a1-2), 13.8 parts of pentaerythritol tetraacrylate (a2-1), and 2.1 parts of other components (e-2) in terms of nonvolatile content. , the solution obtained in Synthesis Example 2 was added, and 31.2 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.) was added as compound (a2-2), and MAC-SQ HDM (manufactured by Toagosei Co., Ltd.) was added as compound (B). ) and 5 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.) as a photopolymerization initiator (C) were thoroughly mixed, and methyl ethyl ketone was used as an organic solvent to adjust the nonvolatile content concentration to 60% to form a hard coat. obtained the drug.
Further, a laminate was produced in the same manner as in Example 1.

[Example 5]
The solution obtained in Synthesis Example 3 was added to a flask equipped with a stirrer so that the amount of compound (a1-3) was 45 parts and the other component (e-3) was 5 parts in terms of nonvolatile content, and then compound (a2-3) was added to the flask with a stirrer. 2) 45 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.), 10 parts of MAC-SQ HDM (manufactured by Toagosei Co., Ltd.) as the compound (B), and Esacure One (DKSH Japan (manufactured by DKSH Japan) as the photopolymerization initiator (C). Co., Ltd.) were thoroughly mixed, and methyl ethyl ketone was used as an organic solvent to adjust the nonvolatile content concentration to 60% to obtain a hard coat agent.
Further, a laminate was produced in the same manner as in Example 1.

[Examples 2, 3, 6 to 24, Comparative Example 1]
A hard coat agent having a nonvolatile content concentration of 60% was obtained in the same manner as in Example 1, except that each component had the composition and blending amount (parts by mass in terms of nonvolatile content) shown in Tables 1 and 2.
Further, a laminate was produced in the same manner as in Example 1 except that the films and the film thicknesses after drying were as shown in Tables 1 and 2.

[Comparative Examples 2 to 5]
Each component was blended in the composition shown in Table 2, mixed well, and methyl ethyl ketone was used as an organic solvent to adjust the nonvolatile content concentration to 60% to obtain a hard coat agent.
Further, a laminate was produced in the same manner as in Example 1.

≪HZ [%]; Measurement of haze value≫
Regarding the laminate produced above, the haze value (HZ) of the surface of the hard coat layer was measured using "Hazemeter SH7000" manufactured by Nippon Denshoku Industries. There is no practical problem if it is less than 1.5%.
[Evaluation criteria]
・Less than 1.0%: Very good ・1.0 or more and less than 1.5%: No practical problem
・1.5% or more: Not practical

≪Pencil hardness≫
The produced laminate was subjected to a scratch test in accordance with JIS K5600-5-4 by applying a pencil of various hardness to the surface of the hard coat layer of the laminate at an angle of 45° and applying a load. The hardness of a hard pencil was defined as pencil hardness.
The harder the pencil hardness is, the better it is, and if it is 5H or higher, it can be used practically without any problems. If it is less than 4H, defects such as dent marks may occur, making it impractical.

≪Abrasion resistance≫
The produced laminate was evaluated for scratch resistance using a "Gakushin type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. Steel wool #0000 was attached to a friction element (surface area 1 cm ² ) to which a load of 1000 g was attached, and the surface of the hard coat layer (1 cm×15 cm) was moved back and forth 10 times. Thereafter, the number of scratches on the surface of the hard coat layer was counted and evaluated according to the following criteria. The fewer the number of scratches, the better; if the number is 10 or less, it can be used without any problem in practical use.
[Evaluation criteria]
・3: No scratches (0): Very good ・2: 1 to 10 scratches: No practical problem ・1: 11 or more scratches: Not practical

≪Curling property≫
The curling properties of the produced laminates were evaluated by the method described below. The laminate was cut into a size of 10 cm x 10 cm, and the average height of the four corners was calculated.
[Evaluation criteria]
・3: Less than 5 mm: Very good ・2: 5 mm or more and less than 10 mm: No practical problem ・1: 10 mm or more: Not practical

<Preparation of base material with inorganic oxide film>
On the hard coat layers of Examples 1 to 24 and Comparative Examples 1 to 5 prepared above, silicon oxide was applied to a thickness of 0.01 μm, 0.1 μm, and 0.1 μm, respectively, using “Magtron Sputter MSP-30T” manufactured by Vacuum Devices. A silicon oxide film was formed by sputtering to a thickness of .5 μm, and a base material with an inorganic oxide film was produced.

≪Adhesion of inorganic oxide film≫
The adhesion between the silicon oxide film and the hard coat layer was determined after making scratches with a cutter in a checkerboard pattern at 1 mm intervals on the silicon oxide film of the base material with the inorganic oxide film to form a 100-square grid pattern. A cellophane tape was attached so as to cover the entire checkerboard-shaped scratches, and then peeled off.The state of peeling of the silicon oxide film was visually observed and evaluated according to the following criteria. The less peeling, the better, and if it is 3 or higher according to the evaluation criteria, it can be used practically without any problems.
[Evaluation criteria]
・4: The area around the scratch line is completely smooth, and there is no peeling on any of the grids. : Very good ・3: Small peeling of the silicon oxide film is observed around the intersection of scratches, but the total peeled area is less than 5% of the grid. : Good ・2: The silicon oxide film is peeled off along the edge direction of the scratch, or the silicon oxide film is peeled off at the intersection of the scratches, and the total peeled area is 5% or more and less than 15% of the grid. : No practical problem. ・1: Total peeled area is 15% or more of the grid. :Not practical

As shown in Tables 1 and 2, by using the hard coat agent of the present invention, it is possible to achieve both adhesion and scratch resistance between the formed hard coat layer and the inorganic oxide film, as well as transparency, hardness, It was confirmed that the curling property was also excellent. This shows that the obtained base material with an inorganic oxide film has excellent adhesion between the base material and the inorganic oxide film, transparency, hardness, and curling property.

Claims (6)

Active energy ray curability for forming a hard coat layer in a base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order A hard coating agent,
A compound (A) having a (meth)acryloyl group (excluding the compound (B)), a compound (B) having a silsesquioxane skeleton, and a photopolymerization initiator (C),
The compound (A) has 6 or more (meth)acryloyl groups and a compound (a1) (excluding (a2)) having a nurate ring skeleton and 3 or more (meth)acryloyl groups, An active energy ray-curable hard coating agent comprising a compound (a2) having a (meth)acryloyl group equivalent of 115 or less. The active energy ray-curable hard coating agent according to claim 1, wherein the compound (B) includes a compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group. The content of the compound (B) is 1 to 30% by mass in the total of 100% by mass of the active energy ray-curable hard coating agent, compound (A), compound (B), and photopolymerization initiator (C). , the active energy ray-curable hard coating agent according to claim 1. A hard coat layer in a base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order,
A compound (A) having a (meth)acryloyl group (excluding the compound (B)) and a compound (B) having a silsesquioxane skeleton,
The compound (A) has 6 or more (meth)acryloyl groups and a compound (a1) (excluding (a2)) having a nurate ring skeleton and 3 or more (meth)acryloyl groups, A hard coat layer comprising a compound (a2) having a (meth)acryloyl group equivalent of 115 or less. A laminate comprising a base material having a thickness of 100 μm or less and a hard coat layer according to claim 4. A base material with an inorganic oxide film comprising a base material, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order,
The hard coat layer contains a compound (A) having a (meth)acryloyl group (excluding the compound (B)) and a compound (B) having a silsesquioxane skeleton,
The compound (A) has 6 or more (meth)acryloyl groups and a compound (a1) (excluding (a2)) having a nurate ring skeleton and 3 or more (meth)acryloyl groups, A base material with an inorganic oxide film, comprising a compound (a2) having a (meth)acryloyl group equivalent of 115 or less.