Active energy ray-curable hard coat agent, hard coat layer, and substrate with inorganic oxide film

Abstract

To provide: a hard coat layer that is excellent in adhesion between the hard coat layer and an inorganic oxide film (excluding transparent conductive films) even when the inorganic oxide film is thick, and has excellent surface hardness and scratch resistance of the hard coat film; a hard coat agent for forming the hard coat layer; and a substrate having attached an inorganic oxide film with the hard coat layer.SOLUTION: An active energy ray-curable hard coat agent comprises a compound (A) having a (meth)acryloyl group (excluding compound (B)), a compound (B) having a silsesquioxane skeleton, and a photopolymerization initiator (C). The compound (A) includes a urethane (meth)acrylate (a1) including at least 10 (meth)acryloyl groups and having a weight-average molecular weight of 5000 or less (excluding (a2)), and a compound (a2) including at least 3 (meth)acryloyl groups and having a (meth)acryloyl group equivalent of at most 115.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray curable hard coat agent for forming a hard coat layer, a hard coat layer, and an oxide substrate with an inorganic oxide film in a substrate with an inorganic oxide film provided with a substrate, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order.

Background Art

[0002] Substrates made of plastics such as polyethylene terephthalate resin are excellent in transparency and impact resistance, lightweight, and easy to process, and thus are used in various applications instead of glass substrates.

[0003] However, plastic substrates may be inferior to glass substrates in surface properties such as hardness and scratch resistance. 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 and improve the surface properties of the plastic substrate.

[0004] Making the surface hardness of a plastic substrate comparable to that of a glass substrate is not sufficient only by forming a hard coat film, and it has been proposed to form a laminate in which an inorganic substance layer is laminated on the hard coat film.

[0005] On the other hand, when an inorganic substance 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 substance layer is insufficient. Further, when the inorganic substance layer is thickened to improve the hardness, the adhesion between the hard coat layer and the inorganic substance layer tends to deteriorate. Regarding the problem of the adhesion between the hard coat film and the inorganic substance layer, Patent Document 1 discloses that excellent adhesion can be obtained by using a trifunctional acrylate and a silsesquioxane compound.

[0006] However, in the composition of Patent Document 1, the hardness of the surface of the hard coat film is insufficient. As a result of investigations by the present inventors, there was a problem with the adhesion between the hard coat layer and the inorganic substance layer when the inorganic substance layer was thickened. Thus, there is a need for an active energy ray-curable composition that achieves both hardness and adhesion to the inorganic substance layer and has excellent adhesion even when a thick inorganic substance layer is formed on the hard coat layer.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] An object of the present invention is to provide a hard coat layer having excellent adhesion between a hard coat layer and an inorganic oxide film (excluding a transparent conductive film), and excellent hardness and scratch resistance on the surface of the hard coat film, a hard coat agent for forming the hard coat layer, and a substrate with an inorganic oxide film having the hard coat layer. Further, an object of the present invention is to provide a hard coat layer having excellent adhesion even when a thick inorganic substance layer is formed on the hard coat layer, a hard coat agent for forming the hard coat layer, and a substrate with an inorganic oxide film having the hard coat layer.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have arrived at the following invention. The present invention provides the following active energy ray-curable hard coat agent, hard coat layer, laminate, and substrate with an inorganic oxide film. [1]: An active energy ray-curable hard coat agent for forming a hard coat layer in a substrate with an inorganic oxide film having a substrate, 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 compound (B)), a compound (B) having a silsesquioxane skeleton, and a photopolymerization initiator (C), The active energy ray-curable hard coat agent according to claim 1, wherein the compound (A) contains a urethane acrylate (a1) having 10 or more (meth)acryloyl groups and a weight average molecular weight of 5000 or less (excluding (a2)) and a compound (a2) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less. [2]: The active energy ray-curable hard coat agent according to [1], wherein the compound (B) contains a compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group. [3]: The active energy ray-curable hard coat agent according to [1] or [2], wherein the content of the compound (B) is 1 to 30% by mass in 100% by mass in total of the compound (A) and the compound (B). [4] A hard coat layer formed by a cured film of the hard coat agent according to any one of [1] to [3]. [5] A substrate with an inorganic oxide film, comprising a substrate, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order, wherein the hard coat layer is the hard coat layer according to [4]. [Effect of the Invention]

[0010] According to the present invention, it is possible to provide a hard coat layer excellent in adhesion between the hard coat layer and an inorganic oxide film (excluding a transparent conductive film) and excellent in surface hardness and scratch resistance, a hard coat agent for forming the hard coat layer, and a substrate with an inorganic oxide film having the hard coat layer. Furthermore, even when a thick inorganic substance layer is formed on the hard coat layer, it is possible to provide a hard coat layer excellent in adhesion, a hard coat agent for forming the hard coat layer, and a substrate with an inorganic oxide film having the hard coat layer. [Embodiments for Carrying Out the Invention]

[0011] Hereinafter, the present invention will be described in detail. Needless to say, other embodiments are also included in the scope of the present invention as long as they are consistent with the gist of the present invention. In addition, the numerical range specified by using "~" in this specification shall include the numerical values described before and after "~" as the range of the lower limit value and the upper limit value.

[0012] First, the terms used in this specification will be explained. In addition, in this specification, when expressed as "(meth)acryl", "(meth)acryloyl", and "(meth)acrylate", unless otherwise specified, they respectively represent "acryl or methacryl", "acryloyl or methacryloyl", and "acrylate or methacrylate". Also, "active energy ray curable hard coat agent" may be referred to as "hard coat agent", "(meth)acryloyl group-containing compound (A)" may be referred to as "compound (A)", "urethane acrylate (a1) having 10 or more (meth)acryloyl groups and a weight average molecular weight of 5000 or less" may be referred to as "compound (a1)", "(meth)acryloyl group-containing compound (a2) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less" may be referred to as "compound (a2)", and "compound (B) having a silsesquioxane skeleton" may be referred to as "compound (B)". Unless otherwise noted, each of the various components appearing in this specification may be used independently alone or in combination of two or more.

[0013] 《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 substrate with an inorganic oxide film, which is provided with a substrate, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order. The hard coat agent of the present invention contains a compound (A) containing a urethane acrylate (a1) having 10 or more (meth)acryloyl groups and a weight average molecular weight of 5000 or less and a compound (a2) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less, a compound (B), and a photopolymerization initiator (C). By being such a hard coat agent, it becomes possible to form a hard coat layer that 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.

[0014] <Compound (A)> Compound (A) is a compound having a (meth)acryloyl group. Compound (A) contains urethane acrylate (a1) having 10 or more (meth)acryloyl groups and a weight average molecular weight of 5000 or less, and compound (a2) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less. By containing (a1) and (a2), it has sufficient hardness on the surface of the hard coat film and excellent adhesion even when a thick inorganic oxide film is formed on the hard coat layer.

[0015] Since compound (a1) has 10 or more (meth)acryloyl groups, containing compound (a1) increases the crosslinking density and the hardness and scratch resistance on the surface of the hard coat film are excellent. In the present invention, even a urethane acrylate having 10 or more (meth)acryloyl groups and a weight average molecular weight of 5000 or less, if the (meth)acryloyl group equivalent is 115 or less, is classified as compound (a2). The weight average molecular weight is a value in terms of polystyrene measured by the gel permeation chromatography (GPC) method. Details will be described in the examples.

[0016] Specific examples of compound (a1) include those obtained by reacting a polyisocyanate with a mono(meth)acrylate or poly(meth)acrylate having a hydroxyl group, and those obtained by reacting a polyol and a polyisocyanate under conditions of an excess of isocyanate groups to form an isocyanate group-containing urethane prepolymer and then reacting it with a mono(meth)acrylate or poly(meth)acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl group-excess conditions can also be obtained by reacting it with (meth)acrylates having isocyanate groups.

[0017] The production method of compound (a1) is shown below. However, this is only an example and is not limited thereto. For example, urethane (meth)acrylate (a1) can be obtained by stirring a polyisocyanate and a hydroxyl group-containing (meth)acrylate in the presence of a suitable urethanization catalyst under an oxygen atmosphere at 60 to 100 °C for 4 to 8 hours. Specific examples of the urethanization catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo[2.2.2]octane, 2,6,7-trimethyl-1,4-diazabicyclo[2.2.2]octane, etc. Among these, dibutyltin dilaurate and the like are particularly preferred.

[0018] Examples of the polyisocyanate include aliphatic diisocyanates, aromatic diisocyanates, etc. Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Examples of the aromatic diisocyanate include toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, etc. The bonding position of the isocyanate group to the aromatic group can be any of the ortho, meta, and para positions. Further, the diisocyanate may form an isocyanurate ring as a trimer. Among them, from the viewpoint of suppressing yellowing when assuming optical applications, aliphatic diisocyanates are preferred.

[0019] The weight average molecular weight of compound (a1) can be adjusted by combining a polyol, a polyisocyanate, and a hydroxyl group-containing mono(meth)acrylate or poly(meth)acrylate.

[0020] As the hydroxyl group-containing (meth)acrylate, from the viewpoint of hardness and scratch resistance of the hard coat film surface, a (meth)acrylic acid ester having five or more (meth)acrylolyl groups is preferred. Specifically, dipentaerythritol penta(meth)acrylate is preferred.

[0021] Examples of urethane acrylates (a1) whose molecular weight and number of acryloyl groups are published in a catalog or the like include Shikoh UV1700B (molecular weight 2000, number of acryloyl groups 10) and MU9500 (molecular weight 3200, number of acryloyl groups 10) manufactured by Mitsubishi Chemical Corporation, KAYARAD DPHA-40H (molecular weight 2000, number of acryloyl groups 10), UN-3320HC (molecular weight 1500, number of acryloyl groups 15, volatile content 5%) and UN-904 (molecular weight 4900, number of acryloyl groups 10) manufactured by Nippon Kayaku Co., Ltd., but are not limited to these.

[0022] Compound (a2) is a compound having three or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of not more than 115. The (meth)acryloyl group equivalent is preferably not more than 110. When the (meth)acryloyl group equivalent is not more than 115, 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.

[0023] Here, the (meth)acryloyl group equivalent is a value obtained by dividing the molecular weight of a compound by the number of (meth)acryloyl groups in the same molecule, and is calculated by the following formula. (Meth)acryloyl group equivalent = molecular weight / number of (meth)acryloyl groups in the same molecule The molecular weight of a compound is the formula weight in the case of a monomer, and the weight average molecular weight in the case of a polymer.

[0024] As the compound (a2), specifically, polyol poly(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; In addition, polyacrylates of polymer polyols such as polyacryl poly(meth)acrylate, polyurethane poly(meth)acrylate, and polyester (meth)acrylate, which have three or more (meth)acryloyl groups; Polyepoxy (meth)acrylate; Examples include, but are not limited to, these.

[0025] Examples of commercially available products of the compound (a2) include, for example, polyol poly(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate (Miramer M300 manufactured by MIWON Co., Ltd.), glycerin tri(meth)acrylate (Aronix M-930 manufactured by Toagosei Co., Ltd.), dipentaerythritol penta(meth)acrylate (SR399 manufactured by Sartomer Co., Ltd.), dipentaerythritol hexa(meth)acrylate (Miramer M600 manufactured by MIWON Co., Ltd.), pentaerythritol tri(meth)acrylate (Miramer M340 manufactured by MIWON Co., Ltd.), and pentaerythritol tetra(meth)acrylate (Light Acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd.); examples include, but are not limited to, these.

[0026] The content of the compound (A) is preferably 70 to 99% by mass, more preferably 73 to 97% by mass, and even more preferably 75 to 95% by mass in a total of 100% by mass of the compound (A) and the compound (B).

[0027] In order to obtain a hard coat layer with excellent hardness, the content of compound (a1) in 100% by mass of compound (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more. The content of compound (a2) in 100% by mass of compound (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more. Also, the content of compound (a1) in 100% by mass of compound (A) is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. The content of compound (a2) in 100% by mass of compound (A) is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. By the content of compound (a1) being within the above range, excellent scratch resistance can be satisfied. Also, by the content of compound (a2) being within the above range, sufficient hardness of the hard coat film surface and scratch resistance can be satisfied.

[0028] The hard coat agent of the present invention may contain a compound (A) other than (a1) and (a2) as necessary. As an example, a compound (a3) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent greater than 115, or a compound (a4) having 1 or 2 (meth)acryloyl groups can be mentioned.

[0029] Examples of compound (a3) include, but are not limited to, urethane acrylate, polyester acrylate, epoxy acrylate, and acrylate having a nurate ring skeleton having 3 to 9 (meth)acryloyl groups.

[0030] The 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 or the like. As the above polybasic acids, aliphatic, alicyclic, and aromatic acids can be mentioned, and each can be used without particular limitation. For example, as aliphatic polybasic acids, 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, itaconic acid, succinic anhydride, maleic anhydride, etc. can be mentioned, and these aliphatic dicarboxylic acids and their anhydrides can be used. Also, derivatives of acid anhydrides can be used.

[0031] Further, as the above polyhydric alcohols, for example, 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 (addition mole number 10 or less), polyoxypropylene glycol (addition 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, and other aliphatic or alicyclic diols can be mentioned.

[0032] Also, polyols containing three or more hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol may be partially used.

[0033] Among the above polyhydric alcohols, those with two or more hydroxyl groups introduced into branched alkanes such as 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, etc. are preferable in terms of adhesiveness, heat resistance, etc.

[0034] Examples of the hydroxyl group-containing (meth)acrylate include the same ones as above. Among them, at least one selected from trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate is preferable.

[0035] Examples of the polyepoxy acrylate include those obtained by esterifying the glycidyl group of an epoxy resin with (meth)acrylic acid to convert the functional group into a (meth)acrylate group.

[0036] Examples of the acrylate having an isocyanurate ring skeleton include the reaction product of an isocyanurate (trimer) of diisocyanate and a poly(meth)acrylate compound having a hydroxyl group, and the reaction product of an isocyanurate (trimer) of polyisocyanate and a polyol and a poly or mono(meth)acrylate compound having a hydroxyl group.

[0037] Examples of the compound (a4) include di(meth)acrylates such as 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and ethylene oxide-modified di(meth)acrylate of bisphenol A; oligomers such as polyurethane di(meth)acrylate and polyester di(meth)acrylate; and mono(meth)acrylates such as 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, benzyl (meth)acrylate, cyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate. However, the examples are not limited thereto.

[0038] <Compound (B)> Compound (B) is a compound having a silsesquioxane skeleton. Due to the rigid skeleton of the silsesquioxane skeleton, the hardness and scratch resistance of the hard coat layer are not reduced, and the adhesion between the hard coat layer and the inorganic oxide film is improved by the interaction with oxygen atoms and partially remaining silanol groups. Compound (B) is not particularly limited as long as it is a network polymer having a structure of (RSiO 1.5 ) n or a compound having a polyhedral cluster structure, and a compound having a silsesquioxane skeleton with a known and commonly used structure such as a random structure, a ladder structure, a complete cage structure, or an incomplete cage structure can be used. (RSiO 1.5 ) n In this formula, n is an integer of 2 or more. As n, an integer of 2 to 200 is preferable, an integer of 2 to 150 is more preferable, and an integer of 2 to 100 is even more preferable. 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.

[0039] Compound (B) is (RSiO 1.5 ) n Among them, the compounds (b1) are classified into a compound having a silsesquioxane skeleton and a (meth)acryloyl group, in which at least a part of R is a (meth)acryloyl group, and a compound (b2) is classified into a compound having a silsesquioxane skeleton and a (meth)acryloyl group, in which R 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 is suppressed, and not only the scratch resistance is high, but also the alkali resistance and the adhesion to the inorganic oxide film layer can be improved. In addition, when a compound has a silsesquioxane skeleton, it is classified as compound (B) even if it has a (meth)acryloyl group.

[0040] Commercially available examples 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, MAC-SQ SI-20, and MAC-SQ HDM, manufactured by Toagosei Co., Ltd. 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, and SO-04 manufactured by Konishi Chemical Industry Co., Ltd., SQ107, SQ109, and SQ506 manufactured by Arakawa Chemical Industry Co., Ltd., and OX-SQ TX-100, OX-SQ SI-20, and OX-SQ HDX manufactured by Toagosei Co., Ltd.

[0041] The content of the compound (B) having a silsesquioxane skeleton is preferably 1 to 30 mass%, more preferably 3 to 27 mass%, and even more preferably 5 to 25 mass%, in 100 mass% in total of the compound (A) and the compound (B). The above content is preferable because it ensures good adhesion between the hard coat layer and the inorganic oxide film even when the inorganic oxide film is thick.

[0042] <Photopolymerization initiator (C)> As the photoinitiator (C), for example, monocarbonyl photoinitiators, dicarbonyl photoinitiators, acetophenone photoinitiators, benzoin ether photoinitiators, acylphosphine oxide photoinitiators, aminocarbonyl photoinitiators, etc. can be used. The photoinitiator (C) may be used in combination with a sensitizer.

[0043] For example, monocarbonyl photoinitiators such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3’,4,4’-tetra(t-butylperoxycarbonyl)benzophenone, 2- / 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone; Dicarbonyl photoinitiators such as 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzenacetate; Acetophenone photoinitiators such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenylketone, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-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-propanedione-2-(o-ethoxycarbonyl)oxime; Benzoin ether photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether; Acylphosphine oxide-based photoinitiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide; And aminocarbonyl-based photoinitiators such as ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzal)cyclopentanone; And the like.

[0044] Commercially available products of the photoinitiator (C) include Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, Esacure One manufactured by IGM-Resins B.V., Lucirin TPO manufactured by BASF Corporation, and the like. In particular, from the viewpoint of yellowing resistance after active energy ray curing, Omnirad 184 and Esacure One are preferable.

[0045] The content of the photoinitiator (C) is not limited as long as it contains an amount that can cure the hard coat layer to have predetermined physical properties by ultraviolet rays. However, from the viewpoints of the curing rate of the hard coat layer, hardness, and scratch resistance, it is preferably contained in an amount of 1 to 15% by mass, more preferably 3 to 10% by mass, based on 100% by mass in total of the compound (A), compound (B), and photoinitiator (C) of the active energy ray curable hard coat agent.

[0046] <Other components> The hard coat agent of the present invention may contain, if necessary, other compounds such as organic solvents, additives, and resin components having no (meth)acryloyl group. Examples of additives include thermosetting resins, polymerization inhibitors, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, dyes, and the like.

[0047] [Organic solvent] The hard coat agent of the present invention may contain an organic solvent (D). As the organic solvent, known organic solvents such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, and isobutyl acetate, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, and glycol ether organic solvents such as propylene glycol monomethyl ether can be used.

[0048] When an organic solvent is included, the content of the organic solvent is preferably in the range such that the nonvolatile content concentration of the hard coat agent of the present invention is 1 to 70% by mass from the viewpoints of coatability and film formability.

[0049] <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 the active energy rays include ultraviolet rays and electron beams. Examples of the ultraviolet ray source include a high-pressure mercury lamp and a metal halide lamp, and the irradiation energy is usually about 100 to 2,000 mJ / cm 2 or so. Examples of the electron beam supply method include a scanning electron beam irradiation and a curtain-type electron beam irradiation method, and the irradiation energy is usually about 10 to 200 kGy.

[0050] <Substrate with inorganic oxide film> The substrate with an inorganic oxide film of the present invention includes a substrate, a hard coat layer, and an inorganic oxide film in this order. However, the inorganic oxide film excludes a 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. In addition, if necessary, another resin layer or the like may be further provided between the base material and the hard coat layer. Examples of the other resin layer include an antistatic resin layer for preventing charging in the manufacturing process, a hard coat resin layer for further increasing the hardness of the laminate of the present invention, and an anchor resin layer for improving the adhesion between the base material and the hard coat layer of the present invention, but the present invention is not limited thereto.

[0051] The base material (also referred to as a support) is not particularly limited, and examples thereof include glass, synthetic resin moldings, and films. Examples of the synthetic resin molding include moldings of synthetic resins such as polymethyl methacrylate resin, copolymer resin mainly composed of methyl methacrylate, polystyrene resin, styrene-methyl methacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, cellulose acetate butyrate resin, polyallyl diglycol carbonate resin, polyvinyl chloride resin, and polyester resin.

[0052] Examples of the film 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, polyvinyl alcohol film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyether imide film, polyimide film, fluororesin film, nylon film, and acrylic film.

[0053] The inorganic oxide film is formed by a dry film-forming method, and examples thereof include an inorganic oxide vapor deposition film, an inorganic oxide sputtered film, and an inorganic oxide CVD film, but an inorganic oxide vapor deposition film or an inorganic oxide sputtered film is preferable.

[0054] The thickness of the inorganic oxide film layer is not particularly limited as long as physical properties, optical properties, and electrical properties are satisfied, but it is usually 0.5 to 1.0 μm.

[0055] Examples of the 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 coat agent of the present invention exhibits particularly effective effects when silicon oxide is used for the inorganic oxide film.

[0056] [Method for manufacturing a substrate with an inorganic oxide film] The method for manufacturing a substrate with an inorganic oxide film of the present invention is not particularly limited. For example, (1) the hard coat agent of the present invention is applied to the surface of the substrate (one side or both sides if the substrate is, for example, in the form of a film), (2) heat is applied to the substrate, and then (3) the hard coat layer is formed by curing by irradiating active energy rays. A mode of manufacturing a laminate through a process of forming an inorganic oxide film on the hard coat layer is mentioned. (4) That is, it is preferable that the method for manufacturing a substrate with an inorganic oxide film is a method for manufacturing a substrate and a laminate having the hard coat layer of the present invention by steps (1) to (3), and forming an inorganic oxide film on the hard coat layer of the laminate. Since the hard coat layer of the present invention has high scratch resistance, it is possible to prevent damage to the hard coat layer in the process of manufacturing a substrate with an inorganic oxide film, a processing process, or the like.

[0057] Regarding step (1), the conditions for applying the hard coat agent to the surface of the substrate (if the substrate is, for example, in the form of a film, one side or both sides) are not particularly limited. As the coating means, for example, spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, and dot coater, etc. can be mentioned. Also, the coating amount is not particularly limited, but usually, it is about 0.01 to 10 g / m as the dry non-volatile content. 2 is the extent.

[0058] Regarding step (2), the conditions when applying heat to the substrate are not particularly limited either, but usually, the temperature is about 80 to 150 °C and the time is about 10 seconds to 2 minutes.

[0059] Regarding step (3), the conditions when irradiating with active energy rays are not particularly limited. Examples of the active energy rays include ultraviolet rays and electron beams. Examples of the ultraviolet ray supply source include high-pressure mercury lamps and metal halide lamps, etc., and the irradiation energy is usually about 100 to 2,000 mJ / cm. 2 is the extent. Examples of the electron beam supply method include scan type electron beam irradiation, curtain type electron beam irradiation method, etc., and the irradiation energy is usually about 10 to 200 kGy.

[0060] Regarding step (4), the means for forming the inorganic oxide film on the hard coat layer is not particularly limited, but the dry coating method is preferred. Specifically, for example, physical methods such as vacuum evaporation method or sputtering method, and chemical methods such as CVD (chemical vapor reaction, etc.) can be mentioned.

[0061] In addition, when using a substrate with an inorganic oxide film as a decorative film, an antenna film, a conductive film, or a flexible printed wiring board, the inorganic oxide film may be patterned into a circuit pattern. The manufacturing method of the substrate with an inorganic oxide film in this case is not particularly limited. For example, various resists are applied to the inorganic oxide film side of the substrate with an inorganic oxide film obtained by steps (1) to (4), a circuit pattern is drawn, and then it is immersed in an etching solution (alkali solution) to remove the resist. The shape of the circuit pattern may be in any form such as a thin wire shape, a dot shape, a mesh shape, and a planar shape.

Examples

[0062] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the following Examples do not limit the technical scope of the present invention in any way. In the Examples, "parts" means "parts by mass", and "%" means "% by mass". In addition, the compounding amounts in the table are in parts by mass, and those other than the solvent are in terms of non-volatile content. Note that the blanks in the table indicate that they are not compounded.

[0063] Table 1 shows the abbreviated names, chemical names, molecular weights, and functional group numbers of the compounds used in the synthesis examples, examples, and comparative examples.

[0064]

Table 1

[0065] Table 2 shows the raw material names, manufacturers, chemical names, chemical compositions, non-volatile content, functional group content rates, functional group numbers, and molecular weights used in the synthesis examples, examples, and comparative examples. When there is a range in the catalog value, the average value of the lower limit value and the upper limit value is shown.

[0066]

Table 2

[0067] Tables 3 and 4 show the synthetic compounding compositions of the synthesis examples. The slight mass difference between the polyisocyanate compounding amount calculated from the isocyanate group content and the compounding amount calculated from the molecular weight was shown as an isocyanate condensate having no isocyanate groups.

[0068] (Measurement of weight-average molecular weight) The weight-average molecular weight was measured using gel permeation chromatography "HLC-8220GPC" manufactured by Tosoh Corporation, with separation columns: "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK-GEL SUPER H3000", and "TSK-GEL SUPER H2000" manufactured by Tosoh Corporation connected in series. Using tetrahydrofuran at a temperature of 40 °C as the mobile phase, the polystyrene-equivalent weight-average molecular weight was measured at a flow rate of 0.6 ml / min.

[0069] (Production of urethane acrylate mixture (X1)) (Synthesis Example 1): In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 1153.9 parts by mass of Purchase DPPA (dipentaerythritol pentaacrylate manufactured by Molekula, molecular weight 524) and 0.1 part by mass of Neostan U-810 (tin catalyst manufactured by Nitto Kasei Co., Ltd.) were placed. After raising the liquid temperature to 50 °C, 223.2 parts by mass of VESTANAT IPDI (isophorone diisocyanate (IPDI) with a molecular weight of 222 based on the non-volatile content, NCO content 37.7%, polyisocyanate with a non-volatile content of 100% by mass) manufactured by EVONIC was added dropwise from the dropping funnel over 30 minutes. After the temperature rise subsided, the temperature was raised to 80 °C and reacted for 3 hours. After confirming that the peak of the isocyanate group disappeared on FT-IR, the temperature was lowered to room temperature, and a urethane acrylate mixture (X1) with a non-volatile content of 100.0% by mass, containing 92.3% by mass of urethane acrylate (a1-1) having 10 acryloyl groups with a weight-average molecular weight of 1300 and 7.6% by mass of dipentaerythritol pentaacrylate (a2-1) was obtained.

[0070] (Synthesis Example 2) to (Synthesis Example 8), (Synthesis Example 13), (Synthesis Example 14), (Synthesis Example 17), (Synthesis Example 19), (Synthesis Example 20): Similar to (Synthesis Example 1), according to the formulation in Table 3, urethane acrylate mixtures (X2) to (X8), (X13), (X14), (X17), (X19), and (X20) were obtained.

[0071] (Synthesis Example 9): In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 669.6 parts by mass of VESTANAT IPDI (isophorone diisocyanate (IPDI) with a molecular weight of 222 based on non-volatile matter, NCO content of 37.7%, polyisocyanate with a non-volatile matter of 100% by mass) manufactured by EVONIC, 288.4 parts by mass of cyclohexyl dimethanol (manufactured by [company name], molecular weight 144, hydroxyl value 389 mgKOH / g), and 0.1 part by mass of Neostan U-810 (tin catalyst manufactured by Nitto Kasei Co., Ltd.) were added. The temperature was raised to 80°C and reacted for 3 hours. After confirming that the peak of the isocyanate group on FT-IR had decreased by 30%, 1907.2 parts by mass of Aronix M403 (pentaerythritol polyacrylate containing 55% by mass of dipentaerythritol pentaacrylate (DPPA) with a molecular weight of 524 and 45% by mass of dipentaerythritol tetraacrylate (DPHA) with a molecular weight of 352, manufactured by Toagosei Co., Ltd.) was added, and the reaction was further continued at 80°C for 3 hours. After confirming that the peak of the isocyanate group on FT-IR had disappeared, the temperature was lowered to room temperature, and a urethane acrylate mixture X9 with a non-volatile matter of 100% containing 69.9% by mass of urethane acrylate (a1-2) having 10 acryloyl groups with a weight average molecular weight of 2000 and 30.0% by mass of dipentaerythritol hexaacrylate (a2-2) was obtained.

[0072] (Synthesis Example 10) to (Synthesis Example 12), (Synthesis Example 15), (Synthesis Example 16), and (Synthesis Example 18): Similar to (Synthesis Example 9), according to the formulation in Table 3, urethane acrylate mixtures (X10) to (X12), (X15), (X16), and (X18) were obtained.

[0073]

Table 3

[0074]

Table 4

[0075] The details of the abbreviations described in Tables 3 to 10 are as follows. <Compound (A)>

[0076] · (a1-1): Urethane acrylate obtained in (Synthesis Example 1) to (Synthesis Example 8), (Synthesis Example 17) (weight average molecular weight: 1300, number of acryloyl groups: 10) · (a1-2): Urethane acrylate obtained in (Synthesis Example 9) (weight average molecular weight: 2000, number of acryloyl groups: 10) · (a1-3): Urethane acrylate obtained in (Synthesis Example 10) (weight average molecular weight: 3500, number of acryloyl groups: 10) · (a1-4): Urethane acrylate obtained in (Synthesis Example 11) (weight average molecular weight: 4900, number of acryloyl groups: 10) · (a1-5): Urethane acrylate obtained in (Synthesis Example 12) (weight average molecular weight: 2500, number of acryloyl groups: 10) · (a1-6): Urethane acrylate obtained in (Synthesis Example 13) (weight average molecular weight: 2200, number of acryloyl groups: 10) · (a1-7): Urethane acrylate obtained in (Synthesis Example 14) (weight average molecular weight: 1200, number of acryloyl groups: 10) · (a1-8): Urethane acrylate obtained in (Synthesis Example 15) (weight average molecular weight: 2400, number of acryloyl groups: 10) · (a1-9): Urethane acrylate obtained in (Synthesis Example 16) (weight average molecular weight: 2300, number of acryloyl groups: 10)

[0077] ·(a2-1): The dipentaerythritol pentaacrylate (DPPA) (number of acryloyl groups: 5, acryloyl group equivalent: 105) derived from Aronix M403 used in (Synthesis Example 1) to (Synthesis Example 3), (Synthesis Example 8), or the mixture (X1) to the mixture (X3), or the mixture (X8), or (Comparative Example 5) ·(a2-2): The dipentaerythritol hexaacrylate (DPHA) (number of acryloyl groups: 6, acryloyl group equivalent: 97) derived from Aronix M403, Aronix M400, Aronix M471, Aronix M405 used in (Synthesis Example 4) to (Synthesis Example 16), (Synthesis Example 18), or the mixture (X4) to the mixture (X16), or the mixture (X18), or (Comparative Example 2), (Comparative Example 5), (Comparative Example 6) ·(a2-3): Pentaerythritol triacrylate contained in Aronix M306 used in (Synthesis Example 19) (number of acryloyl groups 3, acryloyl equivalent: 99) ·(a2-4): Pentaerythritol tetraacrylate (PE-4A) contained in the mixture (X19) obtained in (Synthesis Example 19) (number of acryloyl groups 4, acryloyl equivalent: 88)

[0078] ·(a3-1): Urethane acrylate contained in the mixture X18 obtained in (Synthesis Example 18) (weight average molecular weight: 5300, number of acryloyl groups: 10) ·(a3-2): Urethane acrylate contained in the mixture X19 obtained in (Synthesis Example 19) (weight average molecular weight: 1600, number of acryloyl groups: 9) ·(a3-3): Urethane acrylate contained in the mixture X19 obtained in (Synthesis Example 20) (weight average molecular weight: 1100, number of acryloyl groups: 3) <Compound (B)> ·(b1-1): MAC-SQ HDM (a compound having a silsesquioxane skeleton and a methacryloyl group, a propylene glycol monobutyl ether solution with a non-volatile content concentration of 50%, manufactured by Toagosei Co., Ltd.) ·(b1-2): AC-SQ SI20 (a compound having a silsesquioxane skeleton and an acryloyl group, manufactured by Toagosei Co., Ltd.) ·(b2-1): SR-13 (Silsesquioxane skeleton compound without (meth)acryloyl group, manufactured by KONISHI CHEMICAL INDUSTRY CO., LTD.) <Photoinitiator (C)> ·Esacure One (Esacure One, acetophenone-based photoinitiator, manufactured by DKSH JAPAN CO., LTD.)

[0079] [Example 1] ≪Preparation of Hard Coating Agent≫ Into a flask equipped with a stirrer, 100.1 parts by mass of urethane acrylate mixture (X1), 22.22 parts by mass of MAC-SQ HDM (manufactured by TOAGOSEI CO., LTD., propylene glycol monobutyl ether solution with a non-volatile content concentration of 50% of silsesquioxane having a methacryloyl group), and 5.85 parts by mass of Esacure One (manufactured by DKSH JAPAN CO., LTD.) as the photoinitiator (C) were thoroughly mixed, and methyl ethyl ketone was adjusted as an organic solvent to a non-volatile content concentration of 60% to obtain a hard coating agent. ≪Preparation of Substrate with Hard Coating Layer≫ The hard coating agent obtained above was applied onto an 80-μm-thick triacetyl cellulose (TAC) film using a bar coater so that the film thickness after drying would be 15 μm, and then irradiated with ultraviolet rays of 500 mJ / cm 2 to form a hard coating layer, thereby producing a substrate with a hard coating layer.

[0080] [Example 2] to [Example 28], [Comparative Example 1] to [Comparative Example 6] In the same manner as in Example 1, a hard coating agent was adjusted according to the formulations in Tables 5 to 10 to obtain a substrate with a hard coating layer.

[0081]

Table 5

[0082]

Table 6

[0083]

Table 7

[0084] ≪Pencil Hardness≫ For the produced substrate with a hard coat layer, in accordance with JIS K5600-5-4, pencils of various hardnesses were applied to the surface of the hard coat layer of the laminate at an angle of 45°, a load was applied, and a scratch test was conducted. The hardness of the hardest pencil that did not get scratched was taken as the pencil hardness. A higher pencil hardness is better. If it is 8H or higher, it can be used without practical problems. If it is 7H or lower, there is a risk of defects such as indentation marks, and it is not practical for use.

[0085] ≪Scratch Resistance≫ For the produced substrate with a hard coat layer, the scratch resistance was evaluated using a "Gakushin-type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. A friction pad with a load of 1000 g (surface area 1 cm 2 ) was attached with steel wool #0000, and the surface of the hard coat layer (1 cm × 15 cm) was reciprocated 30 times. Then, 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 it is 10 or less, it can be used without practical problems. [Evaluation Criteria] ·3: No scratches (0): Very good ·2: 1 or more and 10 or less scratches: No practical problems ·1: 11 or more scratches: Not practical for use

[0086] <Fabrication of Substrate with Inorganic Oxide Film> On the hard coat layer of the substrate with a hard coat layer fabricated above, silicon oxide was sputtered to a thickness of 0.5 μm, 0.8 μm, and 1.0 μm respectively using a "Magnetron Sputter MSP-30T" manufactured by Vacuum Device Co., Ltd. to form a silicon oxide film, and substrates with inorganic oxide films were fabricated respectively.

[0087] ≪Adhesion of Inorganic Oxide Film≫ The adhesion between the silicon oxide film and the hard coat layer was evaluated as follows: On the silicon oxide film of the substrate with the prepared inorganic oxide film, cuts were made with a cutter in a grid pattern at 1-mm intervals to form a 100-cell grid pattern. Then, cellophane tape was attached to cover the entire grid pattern of cuts, peeled off, and the peeling state of the silicon oxide film was visually observed and evaluated according to the following criteria. The less peeling, the better. If the evaluation criterion is 2 or more, it can be used without practical problems. [Evaluation Criteria] ·4: The area around the lines of the cuts is completely smooth, and there is no peeling in any grid. : Very good ·3: The total area of the peeled silicon oxide film is less than 5% of the grid. : Good ·2: The total area of the peeled silicon oxide film is 5% or more and less than 15% of the grid. : No practical problems ·1: The total area of the peeled silicon oxide film is 15% or more of the grid. : Not practical

[0088]

Table 8

[0089]

Table 9

[0090]

Table 10

Claims

1. An active energy ray curable hard coat agent for forming a hard coat layer on a substrate with an inorganic oxide film, which comprises a substrate, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order, comprising a compound (A) having a (meth)acryloyl group (excluding compound (B)), a compound (B) having a silsesquioxane skeleton, and a photopolymerization initiator (C), wherein the compound (A) contains a urethane (meth)acrylate (a1) having 10 or more (meth)acryloyl groups and a weight average molecular weight of 5000 or less (excluding (a2)) and a compound (a2) having 3 or more (meth)acryloyl groups and a (meth)acryloyl group equivalent of 115 or less. The active energy ray curable hard coat agent is characterized by this.

2. The active energy ray curable hard coat agent according to Claim 1, wherein the compound (B) contains a compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group.

3. The active energy ray curable hard coat agent according to Claim 1, wherein the content of the compound (B) is 1 to 30% by mass in a total of 100% by mass of the compound (A) and the compound (B).

4. A hard coat layer formed by a cured film of the hard coat agent according to any one of Claims 1 to 3.

5. A substrate with an inorganic oxide film, which comprises a substrate, a hard coat layer, and an inorganic oxide film (excluding a transparent conductive film) in this order, and wherein the hard coat layer is the hard coat layer according to Claim 4.

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