Active energy ray-curable undercoat agent, undercoat layer, laminate, and substrate with metal film

Abstract

To provide an undercoat layer which has excellent adhesion to a metal film and does not reduce the scratch resistance of the surface even when the film thickness of the metal film is thick and to provide an undercoat agent for forming the undercoat layer.SOLUTION: There is provided an active energy ray-curable undercoat agent for forming an undercoat layer in a base material with a metal film having a base material, an undercoat layer, and a metal film in this order, which comprises a compound (A) having three or more (meth)acryloyl groups, a silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups and a photopolymerization initiator (C), wherein the content rate of the compound (A) is 70 mass% or more in 100 mass% of the non-volatile content of the active energy ray-curable undercoat agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an active energy ray-curable undercoating agent for forming an undercoat layer in a metal film-coated substrate having a substrate, an undercoat layer, and a metal film in this order, an undercoat layer, a laminate, and a metal film-coated substrate. [Background technology]

[0002] Transparent conductive films, which are formed by laminating a transparent conductive material onto a transparent plastic film substrate, are widely used in fields such as flat panel displays such as liquid crystal displays and electroluminescence (hereinafter abbreviated as EL) displays, touch panels, lighting, solar cells, and electrical and electronic devices.

[0003] Transparent conductive materials primarily composed of indium tin oxide (ITO / IndiumTinOxide) (hereafter abbreviated as ITO), an indium-based oxide, are widely used due to their high visible light transmittance, relatively low surface resistance, and excellent environmental properties. However, the lower limit of ITO's surface resistance is 50 Ω / □, making it unsuitable for use as an electrode in large displays due to its insufficient response. In addition, ITO films are brittle and have poor bending resistance, and their surface resistance when bent is high, making them difficult to adapt to flexible displays.

[0004] For this reason, materials and technologies to replace ITO are being developed, such as metal mesh that makes the electrode pattern invisible to the naked eye by forming a metal film made of metal materials such as silver, copper, or aluminum alloys on a substrate using methods such as physical vapor deposition (PDV) methods such as vacuum deposition and sputtering, or chemical vapor deposition (CVD), and then applying fine patterning, as well as conductive inks with nano-dispersed metals.

[0005] However, when a metal film is formed directly on a substrate, the adhesion is poor and the metal film is prone to peeling, so the substrate usually needs to be treated with a primer. Therefore, a technology has been investigated for improving the adhesion between the substrate and the metal film by using an active energy ray-curable undercoat agent containing an organic material and / or an inorganic material that has excellent affinity with metal materials in the primer treatment (for example, Patent Documents 1 to 3).

[0006] Furthermore, in recent years, metal film substrates have also been used in applications such as light-reflecting films for liquid crystal displays, decorative films for the backs of smartphones, flexible printed circuit boards with circuit patterns made from formed metal films, and antennas for RFID tags. In recent years, they have also been considered for use in antennas for fifth-generation mobile communication systems.

[0007] Therefore, in order to improve the optical and electrical properties of laminates containing metal films, it is necessary to increase the thickness of the metal film. Optical properties include reflectance when used as a light-reflecting film and concealment when used as a decorative film, while electrical properties include reception sensitivity when used as an antenna film and response sensitivity when used as a conductive film. However, when the thickness of the metal film is increased, the stress generated during the formation of the metal film becomes much greater than when the film is thin, which tends to further reduce adhesion with the undercoat layer, creating problems with adhesion between the substrate and the metal film.

[0008] Furthermore, when metal film-coated substrates are used for decorative films, flexible printed wiring boards, RFID tags, or antenna films for fifth-generation mobile communication systems, the formed metal film must be patterned into a circuit, and alkali resistance is required when immersed in etching solutions (mainly alkaline solutions) during patterning. Furthermore, when used as conductive films, etc., they are sometimes applied to the windows of buildings or automobiles to improve the visibility of displays, and the undercoat layer must also be transparent to improve visibility. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-069653 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-199946 [Patent Document 3] Patent Publication No. 2021-147493 Summary of the Invention [Problem to be solved by the invention]

[0010] However, while such conventional undercoat treatments improve adhesion between the metal film and the substrate, they often reduce surface hardness, resulting in problems such as scratches (scratch resistance) on the undercoat layer during manufacturing and processing, and also failing to satisfy the requirements for hardness, transparency, and alkali resistance.

[0011] Therefore, an object of the present invention is to provide an undercoat layer that has excellent adhesion to a metal film and does not reduce the scratch resistance of the surface, even when the metal film is thick, and an active energy ray-curable undercoat agent for forming the undercoat layer. Furthermore, the undercoat layer of the present invention provides a laminate with high surface scratch resistance, thereby providing a substrate with a metal film that is also excellent in adhesion between the substrate and the metal film, hardness, transparency, and alkali resistance. [Means for solving the problem]

[0012] The present inventors have conducted extensive research to solve the above problems and have arrived at the following invention. That is, the first invention relates to an active energy ray-curable undercoating agent for forming an undercoat layer in a metal film-coated substrate having a substrate, an undercoat layer, and a metal film in this order, the active energy ray-curable undercoating agent comprising a compound (A) having three or more (meth)acryloyl groups, a silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups, and a photopolymerization initiator (C), wherein the content of compound (A) is 70 mass% or more in 100 mass% of the non-volatile content of the active energy ray-curable undercoating agent.

[0013] The second invention relates to the active energy ray-curable undercoating agent, wherein the compound (A) is a compound (a1) having three or more (meth)acryloyl groups and a nitrogen atom.

[0014] The third invention relates to the active energy ray-curable undercoating agent, wherein the compound (a1) is a compound (a1x) having three or more (meth)acryloyl groups and a nurate ring skeleton.

[0015] In addition, a fourth invention is a polymer-type silane coupling agent (b1) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups and having an organic structure in the main chain, The active energy ray-curable undercoating agent according to any one of claims 1 to 3.

[0016] The fifth invention relates to the active energy ray-curable undercoating agent, wherein the content of the compound (B) is 1% by mass or more and less than 30% by mass, based on 100% by mass of the nonvolatile content of the active energy ray-curable undercoating agent.

[0017] The sixth invention relates to an undercoat layer formed from the active energy ray-curable undercoat agent.

[0018] The seventh invention relates to a laminate having a substrate and the undercoat layer.

[0019] Furthermore, an eighth aspect of the present invention relates to a metal film-coated substrate comprising a substrate, the undercoat layer, and a metal film in this order. [Effects of the Invention]

[0020] The present invention makes it possible to provide an undercoat layer that has excellent adhesion to a metal film and does not reduce the scratch resistance of the surface, even when the metal film is thick, and an undercoat agent that can form the undercoat layer. Furthermore, it is possible to provide a laminate having a highly scratch-resistant undercoat layer surface, and a substrate with a metal film that has excellent adhesion between the substrate and the metal film, as well as excellent hardness, transparency, and alkali resistance. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, embodiments of the present invention will be described, but first, terms used in this specification will be explained. In this specification, unless otherwise specified, the terms "(meth)acrylic", "(meth)acryloyl", and "(meth)acrylate" mean "acrylic or methacrylic", "acryloyl or methacryloyl", and "acrylate or methacrylate", respectively. In addition, "active energy ray-curable undercoating agent" is referred to as "undercoating agent," "compound (A) having three or more (meth)acryloyl groups" is referred to as "compound (A)," "silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups" is referred to as "silane coupling agent (B)," "polymer-type silane coupling agent (b1) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups and having an organic structure in the main chain" is referred to as "silane coupling agent (b1)," and "(meth)acryloyl" is referred to as "silane coupling agent (b1)." A compound (a1) having three or more (meth)acryloyl groups and a nitrogen atom may be referred to as a compound (a1), a compound (a2) having three or more (meth)acryloyl groups and no nitrogen atom may be referred to as a compound (a2), a compound (a1x) having three or more (meth)acryloyl groups and a nurate ring skeleton may be referred to as a compound (a1x), a compound (a1y) other than compound (a1x) may be referred to as a compound (a1y), and a compound (A') having one or two (meth)acryloyl groups may be referred to as a compound (A'). Unless otherwise noted, the various components appearing in this specification may be used independently as a single type or as a mixture of two or more types.

[0022] <Undercoating agent> The undercoating agent of the present invention is an active energy ray-curable undercoating agent for forming an undercoat layer in a metal film-coated substrate having a substrate, an undercoat layer, and a metal film in this order. The undercoating agent of the present invention comprises a compound (A) having three or more (meth)acryloyl groups, a silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups, and a photopolymerization initiator (C), and the content of the compound (A) is 70 mass% or more in 100 mass% of the nonvolatile content of the active energy ray-curable undercoating agent. By using such an undercoating agent, the formed undercoat layer can achieve both adhesion to the metal film and scratch resistance, even when the metal film is thick.Furthermore, it is possible to form an excellent undercoat layer that is also good in transparency, hardness, and alkali resistance.

[0023] <Compound (A)> The compound (A) is a compound having three or more (meth)acryloyl groups. However, this does not apply when the agent is a silane coupling agent (B). Compound (A) is classified into compounds (a1) having a nitrogen atom and compounds (a2) not having a nitrogen atom, and compound (a1) having a nitrogen atom can be further classified into compounds (a1x) having a nurate ring skeleton and compounds (a1y) other than compound (a1x).

[0024] From the viewpoints of adhesion to metal films and alkali resistance, the compound (A) is preferably a compound (a1) having a nitrogen atom, and more preferably a compound (a1x) having a nurate ring skeleton. When the compound (A) is the compound (a1), an undercoat layer having excellent adhesion to metal films and alkali resistance can be obtained. The nurate structure is a trimer of an isocyanate compound having a nitrogen atom, and has a six-membered ring structure. Therefore, polymerization of the (meth)acryloyl group proceeds around the rigid six-membered ring, causing a reaction, which is preferable because it can exhibit excellent adhesion to the metal film and alkali resistance due to a synergistic effect with the affinity of both the silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups and the metal film.

[0025] Specific examples of the compound (A) include: for example, Among the compounds (a1) having a nitrogen atom, As the compound (a1x), Trimers (isocyanurates) of (meth)acrylates having an isocyanato group, such as tris(2-acryloxyethyl) isocyanurate, EO-modified tris(2-acryloxyethyl) isocyanurate, PO-modified tris(2-acryloxyethyl) isocyanurate, and ε-caprolactone-modified tris(2-acryloxyethyl) isocyanurate; As the compound (a1y), Urethane acrylate, polyacrylic poly(meth)acrylate having nitrogen atoms other than the nurate ring skeleton, etc. As the compound (a2) having no nitrogen atom, 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; Other examples include 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; These include, but are not limited to:

[0026] Commercially available products of the compound (a1x) include, for example, urethane acrylates having a nurate ring skeleton and three or more (meth)acryloyl groups (Miramer MU9800 manufactured by MIWON, etc.), tris(2-acryloxyethyl)isocyanurate (FANCRYL FA-731A manufactured by Hitachi Chemical Co., Ltd., NEW FRONTIER TEICA (GX-8430) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., etc.), EO-modified tris(2-acryloxyethyl)isocyanurate (ARONIX M-313, M-315 manufactured by Toagosei Co., Ltd., NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., SARTOMER SR-368 manufactured by ARKEMA, etc.), PO-modified tris(2-acryloxyethyl)isocyanurate, ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate (NK Ester manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), Examples of commercially available products include, but are not limited to, A-9300-1CL.

[0027] Examples of commercially available products of compound (a1y) include, but are not limited to, urethane acrylates having no nurate ring skeleton and three or more (meth)acryloyl groups (such as Miramer PU610 manufactured by MIWON Corporation), and polyacrylic poly(meth)acrylates having nitrogen atoms and three or more (meth)acryloyl groups.

[0028] Commercially available products of compound (a2) include polyol poly(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate (Miramer M300 manufactured by MIWON Co., Ltd., etc.), glycerin tri(meth)acrylate (Aronix M-930 manufactured by Toagosei Co., Ltd., etc.), dipentaerythritol penta(meth)acrylate (SR399 manufactured by Sartomer Co., Ltd., etc.), dipentaerythritol hexa(meth)acrylate (Miramer M600 manufactured by MIWON Co., Ltd., etc.), pentaerythritol tri(meth)acrylate (Miramer M340 manufactured by MIWON Co., Ltd., etc.), and pentaerythritol tetra(meth)acrylate (Light Acrylate PE-4A manufactured by Kyoeisha Chemical Co., Ltd., etc.). Other examples include polyacrylic poly(meth)acrylates with three or more (meth)acryloyl groups and no nitrogen atoms (KRM8912 manufactured by Daicel-Cytec, etc.), and polyacrylates of polymer polyols such as polyester (meth)acrylates with three or more (meth)acryloyl groups (EBECRYL800 manufactured by Daicel-Cytec, etc.); Polyepoxy (meth)acrylate (e.g., EBECRYL3603 manufactured by Daicel-Cytec Co., Ltd.); These include, but are not limited to:

[0029] The content of compound (A) is 70% by mass or more based on 100% by mass of the nonvolatile content of the active energy ray-curable undercoating agent, and the upper limit of the content of compound (A) is less than 100% by mass. The content is preferably 72.5% by mass or more, and more preferably 75% by mass or more, since this provides an undercoat layer excellent in hardness and scratch resistance.

[0030] <Silane coupling agent (B)> The silane coupling agent (B) is a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups. The alkoxysilyl group has an alkoxy group on a silicon atom, and examples thereof include a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group. A trialkoxysilyl group is preferred, and among trialkoxysilyl groups, a trimethoxysilyl group, a triethoxysilyl group, or a tripropoxy group is preferred from the viewpoint of hydrolysis reactivity. The alkoxy groups bonded to one silicon atom may be the same or different, and the alkyl group carried by the alkoxy group may be either a branched or linear alkyl group and may have a substituent. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

[0031] The silane coupling agent (B) has two or more alkoxysilyl groups, preferably three or more, and two or more reactive functional groups, preferably three or more. There is no upper limit to the number of substituents of the alkoxyalkyl group and the reactive functional group, and it can be set appropriately depending on the molecular weight of the resin that forms the main skeleton, etc. Preferably, each is 100 or less, more preferably 50 or less.

[0032] Examples of reactive functional groups include amino groups, epoxy groups, (meth)acryloyl groups, thiol groups, and isocyanate groups, and among these, (meth)acryloyl groups are preferred because they not only prevent the undercoat layer from decreasing in scratch resistance and have high scratch resistance, but also improve alkali resistance and adhesion to the metal film layer.

[0033] The silane coupling agent (B) has a main chain and side chains, and the main chain preferably has an organic structure such as a resin that is an organic polymer, or a siloxane structure. Among these, a silane coupling agent whose main chain is an organic structure such as a resin is preferred. The organic structure of the resin or the like is not limited as long as it has a skeleton with a repeating structure, and may be either an oligomer or a polymer. In the case of an oligomer or polymer type silane coupling agent, the weight average molecular weight is preferably 500 to 100,000, and more preferably 700 to 50,000. In this case, the weight average molecular weight is a weight average molecular weight calculated in terms of polystyrene, determined by gel permeation chromatography (GPC) measurement.

[0034] The oligomer or polymer, which is an organic structure such as a resin, is not particularly limited, and examples thereof include acrylic oligomers or polymers, vinyl oligomers or polymers, urethane oligomers or polymers, polyester oligomers or polymers, olefin oligomers or polymers, styrene oligomers or polymers, etc. Among these, acrylic oligomers or polymers are preferred.

[0035] Among these, polymeric silane coupling agents (b1) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups and an organic structure in the main chain are preferred because they not only further suppress the deterioration of the scratch resistance of the undercoat layer and have high scratch resistance, but also improve alkali resistance and adhesion to the metal film layer.

[0036] The silane coupling agent (B) may be a synthetic product or a commercially available product. As a synthesis example, it can be obtained by copolymerizing an ethylenically unsaturated monomer having an alkoxysilyl group with an ethylenically unsaturated monomer having a reactive functional group. In addition, the silane coupling agent (b1) may be prepared by adding (meth)acrylic acid in an amount equivalent to the moles of epoxy groups to an acrylic polymer obtained by copolymerizing an ethylenically unsaturated monomer having an alkoxysilyl group and an ethylenically unsaturated monomer having an epoxy group, or by adding an ethylenically unsaturated monomer having a hydroxyl group in an amount equivalent to the moles of isocyanate groups to an acrylic polymer obtained by copolymerizing an ethylenically unsaturated monomer having an alkoxysilyl group and an ethylenically unsaturated monomer having an isocyanate group, but this is not limited thereto. By adjusting the amount of the monomer used in this case, a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups can be obtained.

[0037] Examples of commercially available products include X-12-972F, X-12-981S, X-12-984S, X-12-1154, X-12-1159L, X-12-1242, X-12-1048, and X-12-1050 sold by Shin-Etsu Chemical Co., Ltd. Furthermore, examples of the polymeric silane coupling agent (b1) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups include X-12-1048 and X-12-1050.

[0038] Commercially available silane coupling agents (B) that are polymers whose main skeleton has a siloxane structure include, for example, KR-517, KR-516, KR-513, X-41-1805, and X-41-1810 sold by Shin-Etsu Chemical Co., Ltd.

[0039] The content of the silane coupling agent (B) is preferably 1% by mass or more and less than 30% by mass, more preferably 3% by mass or more and less than 27% by mass, and even more preferably 5% by mass or more and less than 25% by mass, based on 100% by mass of the non-volatile content of the active energy ray-curable undercoating agent. This range is preferable because, even when the thickness of the metal film is thick, the adhesion between the undercoat layer and the metal film and alkali resistance are good, scratch resistance is not reduced, and costs are not increased.

[0040] <Photopolymerization initiator (C)> Examples of the photopolymerization initiator (C) that can be used include monocarbonyl-based photopolymerization initiators, dicarbonyl-based photopolymerization initiators, acetophenone-based photopolymerization initiators, benzoin ether-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and aminocarbonyl-based photopolymerization initiators. The photopolymerization initiator (C) may be used in combination with a sensitizer.

[0041] For example, monocarbonyl photopolymerization initiators 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-oxobenzeneacetate; acetophenone-based photopolymerization initiators such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl 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-propanedione-2-(o-ethoxycarbonyl)oxime; benzoin ether-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether; acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide; and aminocarbonyl photopolymerization initiators 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; etc.

[0042] Commercially available photopolymerization initiators (C) include Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, and Esacure One manufactured by IGM-Resins BV, and Lucirin TPO manufactured by BASF Ltd. In particular, Omnirad 184 and Esacure One are preferred from the viewpoint of yellowing resistance after curing with active energy rays.

[0043] The content of the photopolymerization initiator (C) is not limited as long as it is contained in an amount that allows the undercoat layer to be cured by ultraviolet light to have the desired physical properties. However, from the viewpoints of the purple curing speed, hardness, and scratch resistance of the undercoat layer, the content of the photopolymerization initiator (C) is preferably 1 to 15 mass%, and more preferably 3 to 10 mass%, relative to 100 mass% of the nonvolatile content of the active energy ray-curable undercoat agent.

[0044] <Other ingredients> The undercoating agent of the present invention is obtained by mixing a compound (A) having three or more (meth)acryloyl groups, a silane coupling agent (B), and a photopolymerization initiator (C). If necessary, the undercoating agent may also contain other components such as a compound (A') having one or two (meth)acryloyl groups, an organic solvent (D), and additives. Examples of additives include thermosetting resins, polymerization inhibitors, leveling agents, slip agents, antifoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, and dyes.

[0045] [Compound (A')] The compound (A') is a compound having one or two (meth)acryloyl groups. Examples of the compound (A') include, but are not limited to, 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 poly(meth)acrylate and polyester poly(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.

[0046] [Organic solvent (D)] The undercoating agent of the present invention may contain an organic solvent (D). As the organic solvent (D), known organic solvents can be used, 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 glycoether organic solvents such as propylene glycol monomethyl ether.

[0047] When the organic solvent (D) is contained, the content of the organic solvent (D) is preferably in a range such that the nonvolatile concentration of the undercoating agent of the present invention is 1 to 60 mass %, from the viewpoints of coatability and film-forming property.

[0048] <Substrate with metal film> The substrate with a metal film of the present invention comprises a substrate, an undercoat layer formed from the undercoat agent of the present invention, and a metal film, in this order. The undercoating agent of the present invention is used to form a metal film on the surface of a substrate. As described below, for example, the undercoating agent of the present invention is applied to a substrate, and the undercoating agent is cured by active energy rays to form a laminate having an undercoat layer, and a metal film is formed on the undercoat layer of the laminate, thereby making it possible to obtain a substrate with a metal film. The undercoat layer of the present invention has excellent adhesion to a metal film, and therefore, when the undercoat layer and the metal film are directly laminated together, peeling of the metal film can be suppressed. If necessary, other resin layers may be further provided between the substrate and the undercoat layer, etc. Examples of other resin layers include, but are not limited to, an antistatic resin layer for preventing static buildup during the manufacturing process, a hard coat resin layer for increasing the hardness of the laminate of the present invention, and an anchor resin layer for improving adhesion between the substrate and the undercoat layer of the present invention.

[0049] The substrate (also referred to as a support) is not particularly limited, and examples thereof include glass, synthetic resin moldings, films, etc. Examples of synthetic resin moldings include moldings of synthetic resins such as polymethyl methacrylate resin, copolymer resins containing methyl methacrylate as the main component, 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.

[0050] Examples of films include polyester films, polyethylene films, polypropylene films, cellophane films, diacetyl cellulose films, triacetyl cellulose (TAC) films, acetyl cellulose butyrate films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, ethylene vinyl alcohol films, polyolefin films, polystyrene films, polycarbonate films, polymethylpentel films, polysulfone films, polyether ether ketone films, polyether sulfone films, polyether imide films, polyimide films, fluororesin films, nylon films, and acrylic films.

[0051] The thickness of the undercoat layer is not particularly limited, but is usually about 0.1 to 5 μm. A more preferable range is 0.5 to 3 μm in terms of hardness and cost.

[0052] Examples of metal films include metal vapor deposition films, metal sputtering films, and metal CVD films. Metal vapor deposition films or metal sputtering films are particularly preferred as metal films. The thickness of the metal film layer is not particularly limited as long as it satisfies decorative, optical, and electrical properties, but is typically 0.1 to 0.5 μm. However, depending on the application, a film thickness of 0.5 μm or more may be used to improve optical and electrical properties. Because the undercoating agent of the present invention has excellent adhesion, even when the metal film is relatively thick, such as 1 μm or more, it can be used as a laminate that can achieve both adhesion and scratch resistance. In order to reduce production costs and the recent trend toward smaller and lighter displays and antenna films, a film thickness of 5 μm or less is preferred.

[0053] The metals constituting the metal film include, but are not limited to, copper, aluminum, silver, etc. The undercoating agent of the present patent is particularly effective when copper is used for the metal film. Furthermore, since the laminate of the present invention has excellent adhesion even when the metal film is thick, it can be suitably used for antenna films and the like, which require improved reception sensitivity as an electrical characteristic.In addition, since it can increase response sensitivity, it can also be suitably used for conductive films and the like.

[0054] Furthermore, since the undercoat layer of the present invention has excellent transparency, the laminate of the present invention can be suitably used for conductive films, antenna films, etc., which require visibility. Furthermore, since the undercoat layer of the present invention has excellent alkali resistance, the laminate of the present invention can also be suitably used for decorative films that require decorative patterns, conductive films that require circuit patterns, antenna films, flexible printed wiring boards, etc.

[0055] [Metal Film-Coated Substrate Manufacturing Method] The method for producing the metal film-coated substrate of the present invention is not particularly limited. For example, a laminate is produced by (1) applying the undercoating agent of the present invention to the surface of the substrate (for example, one or both surfaces if the substrate is in the form of a film), (2) applying heat to the substrate, and (3) further irradiating the substrate with active energy rays to cure the undercoat layer, thereby producing the laminate. (4) An embodiment of the present invention includes a method for producing the laminate by (1) applying the undercoat agent of the present invention to the surface of the substrate (for example, one or both surfaces if the substrate is in the form of a film), (2) applying heat to the substrate, and (3) further irradiating the substrate with active energy rays to cure the undercoat layer, thereby producing the laminate. (4) An embodiment of the present invention includes (1) applying the undercoat agent of the present invention to the surface of the substrate (for example, one or both surfaces if the substrate is in the form of a film), (2) applying heat to the substrate, (3) further irradiating the substrate with active energy rays to cure the undercoat layer, thereby producing the laminate. That is, the method for producing a substrate with a metal film is preferably a method for producing a laminate having a substrate and the undercoat layer of the present invention through steps (1) to (3), and forming a metal film on the undercoat layer of the laminate. The undercoat layer of the present invention has high scratch resistance, and therefore can prevent the undercoat layer from being scratched during the manufacturing process or processing of the metal film-coated substrate.

[0056] Regarding step (1), the conditions for applying the undercoating agent to the surface of the substrate (for example, one or both surfaces if the substrate is in the form of a film) are not particularly limited, and examples of the application method include a spray, a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater, and a dot coater. The amount of coating is also not particularly limited, but is usually 0.01 to 10 g / m2 in terms of dry nonvolatile content. 2 That's about it.

[0057] Regarding step (2), the conditions for applying heat to the substrate are not particularly limited, but typically the temperature is about 80 to 150° C. and the time is about 10 seconds to 2 minutes.

[0058] Regarding step (3), the conditions for irradiating with 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 is usually 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.

[0059] Regarding step (4), the method for forming the metal film on the undercoat layer is not particularly limited, but a dry coating method is preferred.Specific examples include physical methods such as vacuum deposition and sputtering, and chemical methods (chemical vapor phase reaction, etc.) such as CVD.

[0060] Furthermore, when the metal film-coated substrate is used as a decorative film, an antenna film, a conductive film, or a flexible printed wiring board, the metal film may be patterned into a circuit. The method for producing the metal film-coated substrate in this case is not particularly limited, and examples include a method in which various resists are applied to the metal film side of the metal film-coated substrate obtained by steps (1) to (4), a circuit pattern is drawn, and then the substrate is immersed in an etching solution (alkaline solution) to remove the resist. The shape of the circuit pattern may be any shape, such as fine lines, dots, meshes, or planes. [Example]

[0061] The present invention will be described in more detail below with reference to examples and comparative examples, but the following examples are not intended to limit the technical scope of the present invention in any way. In the examples, "parts" means "parts by mass" and "%" means "% by mass." The blend amounts in the table are in parts by mass, and values ​​other than the solvent are calculated as non-volatile content. Note that blank spaces in the table indicate that no blend was made.

[0062] The "weight average molecular weight" is a value measured using a gel permeation chromatograph "HLC-8220GPC" manufactured by Tosoh Corporation. The polystyrene-equivalent weight average molecular weight was measured using four separation columns connected in series: "TSK-GEL SUPER H5000," "TSK-GEL SUPER H4000," "TSK-GEL SUPER H3000," and "TSK-GEL SUPER H2000" manufactured by Tosoh Corporation, using tetrahydrofuran at a temperature of 40°C as the mobile phase at a flow rate of 0.6 ml / min.

[0063] <Production of acrylic copolymer> Manufacturing Example 1 Stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube A reaction vessel equipped with a pressure cooker was charged with 40.8 parts (13.6 mol%) of hydroxyethyl acrylate (HEA), 72.0 parts (27.7 mol%) of methyl methacrylate (MMA), 79.2 parts (23.8 mol%) of butyl acrylate (BA), 48.0 parts (approximately 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate, and the reaction system was set to 70°C. Next, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (ABN-V) was charged and the temperature was maintained at around 70°C for 6 hours. Next, 2.4 parts of ABN-V was charged, and the reaction system was maintained at around the same temperature for an additional 6 hours. The reaction system was then cooled to room temperature, yielding a solution of an acrylic copolymer having a glass transition temperature of 13°C, a hydroxyl value of 80 mgKOH / g, and a non-volatile content of 35.0%.

[0064] <Production of Silane Coupling Agent (B)> Manufacturing Example 2 A reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube was charged with 3.20 parts (22.5 mmol) of n-butyl methacrylate (BMA), 1.24 parts (5 mmol) of 3-methacryloxypropyltrimethoxysilane (MPTMS) and 3.20 parts (22.5 mmol) of glycidyl methacrylate (GMA), and 0.784 parts (4 mmol) of γ-mercaptopropyltrimethoxysilane as a chain transfer agent, dissolved in 8.46 parts of toluene. A solution of 0.025 parts (0.15 mmol) of azobisisobutyronitrile dissolved in 3 parts of toluene was added dropwise under a nitrogen stream, and the reaction was carried out at 70 ° C. for 2 hours. The reaction system was then cooled to room temperature and adjusted to a solids content of 40% using toluene to obtain a solution of silane coupling agent (B-1) having two or more alkoxysilyl groups and two or more epoxy groups (weight average molecular weight 1000).

[0065] Manufacturing Example 3 A reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was charged with 3.20 parts (22.5 mmol) of n-butyl methacrylate (BMA), 1.24 parts (5 mmol) of 3-methacryloxypropyltrimethoxysilane (MPTMS), 3.20 parts (22.5 mmol) of glycidyl methacrylate (GMA), and 0.784 parts (4 mmol) of γ-mercaptopropyltrimethoxysilane as a chain transfer agent dissolved in 8.46 parts of toluene. A solution of 0.025 parts (0.15 mmol) of azobisisobutyronitrile dissolved in 3 parts of toluene was added dropwise under a nitrogen stream, and the mixture was allowed to react at 70°C for 2 hours. This produced a polymer with a weight-average molecular weight of 1,000. Three parts of methanol and 1.62 parts of acrylic acid were dissolved in the obtained polymer, and the mixture was reacted at 70°C for 2 hours under a nitrogen stream. The reaction system was then cooled to room temperature, and the solid content was adjusted to 40% using toluene, yielding a solution of a silane coupling agent (B-2) having two or more alkoxysilyl groups and two or more acryloyl groups (weight average molecular weight 1300).

[0066] (Preparation of Undercoating Agent) [Example 1] An undercoating agent was obtained by thoroughly mixing 94 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.) as compound (A), 6 parts of X-12-981S (manufactured by Shin-Etsu Chemical Co., Ltd.) as compound (B), and 5 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.) as photopolymerization initiator (C), and adjusting propylene glycol monomethyl ether as an organic solvent to a nonvolatile concentration of 40%.

[0067] [Examples 2 to 13, Comparative Examples 1 to 5] Undercoating agents with a nonvolatile content of 40% were obtained in the same manner as in Example 1, except that the compositions and blending amounts (parts by mass converted into nonvolatile content) of each component were as shown in Table 1.

[0068] Details of each material shown in Table 1 are as follows: <Compound (A)>: a compound having three or more (meth)acryloyl groups (Compound (a2)); a compound having no nitrogen atom Aronix M-403 (a mixture of 40-50% dipentaerythritol hexaacrylate (functional groups: 6) and 50-60% dipentaerythritol pentaacrylate (functional groups: 5); manufactured by Toagosei Co., Ltd.) (Compound (a1y)); Compounds containing a nitrogen atom other than compound (a1x) Miramer PU610 (urethane acrylate, weight average molecular weight: 1800, number of functional groups: 6, manufactured by MIWON) (Compound (a1x)); a compound having a nurate ring skeleton Miramer MU9800 (urethane acrylate with nurate ring structure, weight average molecular weight: 3500, functional groups: 9, manufactured by MIWON) Aronix M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: 3, manufactured by Toagosei Co., Ltd.) <Compound (A')>: a compound having one or two (meth)acryloyl groups NK Ester A-DCP (tricyclodecane dimethanol diacrylate, molecular weight: 304, number of acryloyl groups: 2, manufactured by Shin-Nakamura Chemical Co., Ltd.) <Inert resin> Acrylic copolymer (a solution of acrylic copolymer synthesized in Production Example 1, with a glass transition temperature of 13°C, a hydroxyl value of 80 mgKOH / g, and a non-volatile content of 35.0%)

[0069] <Silane coupling agent (B)>: A silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups. [Other silane coupling agents (B)]; silane coupling agents (B) other than the silane coupling agent (b1) X-12-981S (Shin-Etsu Chemical Co., Ltd., alkoxysilyl groups (triethoxy groups) 2 or more, epoxy groups 2 or more) KR-513 (Manufactured by Shin-Etsu Chemical Co., Ltd., contains two or more alkoxysilyl groups (methoxy groups), two or more acryloyl groups, and has a polysiloxane main chain) [Silane coupling agent (b1)]: A polymeric silane coupling agent (b1) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups. X-12-1048 (Manufactured by Shin-Etsu Chemical Co., Ltd., 2 or more alkoxysilyl groups (trimethoxy groups), 2 or more acryloyl groups, main chain has an organic structure) X-12-1050 (Manufactured by Shin-Etsu Chemical Co., Ltd., 2 or more alkoxysilyl groups (trimethoxy groups), 2 or more acryloyl groups, main chain has an organic structure)

[0070] <Other silane coupling agents> KBM-5103 (Shin-Etsu Chemical Co., Ltd., 1 alkoxysilyl group, 1 acryloyl group) <Photopolymerization initiator (C)> Esacure One (acetophenone-based photopolymerization initiator, manufactured by DKSH Japan Co., Ltd.)

[0071] <<Preparation of Undercoat Layer and Laminate>> The undercoating agents obtained in the examples and comparative examples were each applied to a 50 μm thick polyethylene terephthalate (PET) film ("Lumirror U403" manufactured by Toray Industries, Inc.) using a bar coater so that the film thickness after drying would be 1.0 μm. Then, the undercoating agents were applied to the film using a high-pressure mercury lamp at 500 mJ / cm. 2 The laminate was irradiated with ultraviolet light of 1000 kJ / cm 2 to form an undercoat layer, thereby producing a laminate.

[0072] <HZ [%]; Haze value measurement> The haze value (HZ) of the undercoat layer surface of the laminate produced above was measured using a haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd. If it is less than 2.0%, there is no practical problem. [Evaluation criteria] Best: Less than 1.0% Good: 1.0 or more and less than 2.0% ·Defect: 2.0% or more

[0073] ≪Pencil hardness≫ The prepared laminate was subjected to a scratch test in accordance with JIS K5600-5-4 by applying pencils of various hardness to the surface of the undercoat layer of the laminate at a 45° angle and applying a load, and the hardness of the hardest pencil that did not cause a scratch was recorded as the pencil hardness. The harder the pencil hardness, the better, and if it is H or higher, it can be used without any problems in practice. If it is F or lower, there is a risk of defects such as dents, making it unusable.

[0074] ≪Scratch resistance≫ The scratch resistance of the prepared laminate was evaluated using a Gakushin-type friction fastness tester manufactured by Tester Sangyo Co., Ltd. A friction element (surface area 1 cm) with a load of 200 g was attached. 2 Steel wool #0000 was attached to the undercoat layer and the surface (1 cm x 15 cm) of the undercoat layer was rubbed back and forth 10 times. After that, the number of scratches on the surface of the undercoat layer was counted and evaluated according to the following criteria. The fewer the number of scratches, the better, and if there were 10 or fewer scratches, the product could be used without any problems in practice. [Evaluation criteria] 3: No scratches (0 pieces) ·2: 1 to 10 scratches 1: 11 or more scratches

[0075] <Copper adhesion> Copper films were formed on the undercoat layer of the prepared laminate by sputtering copper to thicknesses of 200 nm, 500 nm, 1 μm, and 2 μm using a Magtron Sputter MSP-30T manufactured by Vacuum Devices Co., Ltd. The adhesion between the copper film and the undercoat layer was evaluated by scratching the copper film in a checkerboard pattern at 1 mm intervals with a cutter to form a 100-square grid pattern, then applying cellophane tape to cover the entire checkerboard scratch, peeling it off, and visually inspecting the copper film for peeling. The adhesion was evaluated according to the following criteria: the absence of peeling indicates good adhesion, and a rating of 3 or higher indicates practical use without any problems. [Evaluation criteria] 5: The area around the scratch line is completely smooth and there is no peeling of any of the grids. 4: Small areas of copper film peeling are observed around the intersections of scratches, but the total peeled area is less than 5% of the grid. 3: The copper film peels off along the edges of the scratches or at the intersections of the scratches, and the total peeled area is between 5% and 15% of the grid. 2: The total peeled area is 15% or more but less than 35% of the grid. 1: The total peeled area is 35% or more but less than 80% of the grid. 0: The total peeled area is 80% or more of the grid, and peeling is observed outside the grid scratches.

[0076] <Alkali resistance> Laminates with copper films (thicknesses of 500 nm and 1 μm) that had not been evaluated for copper adhesion were immersed in a 5% aqueous solution of sodium hydroxide heated to 40°C for 5 minutes, then thoroughly washed with water, and then dried in an oven heated to 100°C for 15 minutes to remove moisture, after which copper adhesion was evaluated in the same manner as above. The less peeling there was, the better, but a rating of 3 or higher was sufficient for practical use.

[0077] [Table 1]

[0078] As shown in Table 1, it was confirmed that by using the undercoating agent of the present invention, it is possible to achieve both adhesion between the formed undercoat layer and the metal film and scratch resistance, and furthermore, excellent transparency, hardness, and alkali resistance were also achieved. This shows that the obtained substrate with metal film is also excellent in adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance. In particular, since the adhesion is good even when the metal film is thick, such as 1 μm or more, it can be said that it can be suitably used for applications requiring thick metal films to improve the optical and electrical properties, which are in demand in recent years.

Claims

1. An active energy ray-curable undercoating agent for forming an undercoat layer in a metal film-attached substrate having a substrate, an undercoat layer, and a metal film in this order, comprising: The composition includes a compound (A) having three or more (meth)acryloyl groups, a silane coupling agent (B) having two or more alkoxysilyl groups and two or more reactive functional groups, and a photopolymerization initiator (C), The content of the compound (A) is 70% by mass or more based on 100% by mass of the nonvolatile content of the active energy ray-curable undercoating agent.

2. 2. The active energy ray-curable undercoating agent according to claim 1, wherein the compound (A) is a compound (a1) having three or more (meth)acryloyl groups and a nitrogen atom.

3. 3. The active energy ray-curable undercoating agent according to claim 1, wherein the compound (A) is a compound (a1x) having three or more (meth)acryloyl groups and a nurate ring skeleton.

4. The silane coupling agent (B) is a silane coupling agent (b1) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups and having an organic structure in the main chain; The active energy ray-curable undercoating agent according to any one of claims 1 to 3.

5. The active energy ray-curable undercoating agent according to any one of claims 1 to 4, wherein the content of the compound (B) is 1 mass% or more and less than 30 mass% based on 100 mass% of the non-volatile content of the active energy ray-curable undercoating agent.

6. An undercoat layer in a metal film-coated substrate comprising a substrate, an undercoat layer, and a metal film in this order, said undercoat layer being formed from an active energy ray-curable undercoat agent according to any one of claims 1 to 5.

7. A laminate comprising a substrate and the undercoat layer according to claim 6.

8. A metal film-coated substrate comprising a substrate, the undercoat layer according to claim 6, and a metal film, in this order.

Images