KR20240048541A - Active energy ray-curable undercoat agent, undercoat layer, laminate, and metal film attachment substrate - Google Patents

Abstract

An active energy ray-curable undercoat agent for forming an undercoat layer in a metal film-attached substrate comprising a base material, an undercoat layer, and a metal film in this order, having three or more (meth)acryloyl groups. It includes a first compound, a second compound, and a photopolymerization initiator, wherein the second compound is a compound having a silsesquioxane skeleton, a metal compound having an organic group, a triazinethiol compound, and two or more alkoxy It contains at least one kind selected from the group consisting of a silyl group and a silane coupling agent having two or more reactive functional groups, and the content of the first compound is 100% by mass of the non-volatile content of the active energy ray-curable undercoat agent, It is an active energy ray-curable undercoat agent containing 70% by mass or more.

Description

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

One embodiment of the present invention is an active energy ray-curable undercoat agent for forming an undercoat layer in a metal film-attached substrate comprising a base material, an undercoat layer, and a metal film in this order, an undercoat layer, It relates to a laminate and a metal film-attached substrate.

Transparent conductive films made by laminating a transparent conductive material on a transparent plastic film substrate are used in 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. It is widely used in fields such as:

As a transparent conductive material, the main ingredient is indium tin oxide (ITO/Indium Tin Oxide) (hereinafter abbreviated as ITO), an indium-based oxide, due to its high visible light transmittance, relatively low surface resistance, and excellent environmental characteristics. is widely used. However, the lower limit of the surface resistance value of ITO is 50Ω/□, and it is said to be unsuitable for use as an electrode for large displays due to insufficient responsiveness. In addition, the ITO film is weak and has poor bending resistance, and its surface resistance value when bending is high, making it difficult to respond to flexible displays.

Therefore, a metal film made of a metal material such as silver, copper, or aluminum alloy is formed by a method such as physical vapor deposition (PDV/Physical Vapor Deposition) such as vacuum deposition or sputtering, or chemical vapor deposition (CVD/Chemical Vapor Deposition). 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 it on a substrate and performing fine patterning, or conductive ink in which metal is nano-dispersed.

However, the metal film-attached substrate provided with a metal film as an ITO substitute has poor adhesion when the metal film is formed directly on the substrate, and peeling of the metal film is likely to occur, so primer treatment is usually required for the substrate. Therefore, techniques for improving the adhesion between the substrate and the metal film are being investigated by using an active energy ray-curable undercoat agent containing an organic material and/or an inorganic material with excellent affinity for the metal material as a primer treatment (e.g. For example, patent documents 1-3).

Japanese Patent Publication No. 2016-069653 Japanese Patent Publication No. 2015-199946 Japanese Patent Publication No. 2021-147493

However, while treatment with such a conventional undercoat agent improves the adhesion between the metal film and the substrate, it often reduces the surface hardness of the undercoat layer. Therefore, scratches (scratch resistance) of the undercoat layer during manufacturing processes, processing processes, etc. have become a problem. Furthermore, the current situation is that the hardness, transparency, and alkali resistance of the undercoat layer cannot be satisfied.

Accordingly, one embodiment of the present invention aims to provide an undercoat agent capable of forming an undercoat layer having excellent adhesion to a metal film and excellent surface scratch resistance.

As a result of extensive research to solve the above problems, the present inventor has arrived at the following invention.

That is, one embodiment of the present invention is an active energy ray-curable undercoat agent for forming an undercoat layer in a metal film-attached substrate comprising a base material, an undercoat layer, and a metal film in this order,

A first compound having three or more (meth)acryloyl groups, a second compound, and a photopolymerization initiator,

The second compound is selected from the group consisting of compounds having a silsesquioxane skeleton, metal compounds having an organic group, triazinethiol compounds, and silane coupling agents having two or more alkoxysilyl groups and two or more reactive functional groups. Contains at least one type of

The content of the first compound is 70% by mass or more based on 100% by mass of non-volatile matter of the active energy ray-curable undercoat agent.

In another embodiment of the present invention, the second compound includes a compound having a silsesquioxane skeleton,

The compound having the silsesquioxane skeleton relates to the active energy ray-curable undercoat agent, which includes a compound having the silsesquioxane skeleton and a (meth)acryloyl group.

In another embodiment of the present invention, the second compound includes a metal compound having the organic group,

The metal compound having an organic group relates to the active energy ray-curable undercoat agent, which contains at least one kind selected from the group consisting of a metal alkoxide compound, a metal chelate compound, and a metal acylate compound.

In another embodiment of the present invention, the second compound includes a metal compound having the organic group,

It relates to the active energy ray-curable undercoat agent in which the metal of the metal compound having the organic group contains titanium, zirconium, or aluminum.

In another embodiment of the present invention, the second compound includes the triazinethiol compound,

The triazine thiol compound relates to the active energy ray-curable undercoat agent containing a triazine thiol compound having an active energy ray-curable functional group.

In another embodiment of the present invention, the second compound includes a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups,

The silane coupling agent,

It relates to the above active energy ray-curable undercoat agent, which contains a silane coupling agent having two or more alkoxysilyl groups and two or more (meth)acryloyl groups and having an organic structure in the main chain.

Another embodiment of the present invention relates to the active energy ray-curable undercoat agent in which the first compound contains a compound having three or more (meth)acryloyl groups and a nitrogen atom.

In another embodiment of the present invention, the compound having three or more (meth)acryloyl groups and a nitrogen atom is a compound having three or more (meth)acryloyl groups and a nurate ring skeleton. It relates to the active energy ray-curable undercoat agent containing.

Another embodiment of the present invention relates to the active energy ray-curable undercoat agent, wherein the content of the second compound is 1 to 30% by mass based on 100% by mass of non-volatile matter of the active energy ray-curable undercoat agent. will be.

Another embodiment of the present invention relates to an undercoat layer formed from the above active energy ray-curable undercoat agent.

Another embodiment of the present invention relates to a laminate having a base material and the undercoat layer.

Another embodiment of the present invention relates to a metal film-attached base material comprising a base material, the undercoat layer, and a metal film in this order.

According to one embodiment of the present invention, it becomes possible to provide an undercoat agent capable of forming an undercoat layer having excellent adhesion to a metal film and excellent surface scratch resistance.

Furthermore, it becomes possible to provide a laminate with high scratch resistance on the surface of the undercoat layer and a metal film-attached base material with excellent adhesion between the base material and the metal film and excellent hardness, transparency, and alkali resistance.

Hereinafter, embodiments of the present invention will be described. First, terms used in this specification will be described.

Meanwhile, in this specification, when “(meth)acrylic,” “(meth)acryloyl,” and “(meth)acrylate” are used, unless otherwise specified, “acrylic or methacrylic,” respectively. It shall represent “acryloyl or methacryloyl” and “acrylate or methacrylate”.

Unless otherwise noted, the various components described in this specification may be used individually, individually, or in combination of two or more types.

《Active energy ray curable undercoat agent》

The active energy ray-curable undercoat agent (hereinafter also referred to as undercoat agent) of one embodiment of the present invention is used as an undercoat agent in a metal film-attached base material comprising a base material, an undercoat layer, and a metal film in this order. It is an active energy ray-curable undercoat agent for forming a coat layer.

The undercoat agent of one embodiment of the present invention includes a first compound (hereinafter also referred to as compound (A)) and a second compound (hereinafter also referred to as compound (B)) having three or more (meth)acryloyl groups. described) and a photopolymerization initiator (hereinafter also referred to as photopolymerization initiator (C)), and the second compound is a compound having a silsesquioxane skeleton, a metal compound having an organic group, a triazinethiol compound, and It contains one type selected from the group consisting of silane coupling agents having two or more alkoxysilyl groups and two or more reactive functional groups, and the content of the first compound is 100% by mass of the non-volatile content of the active energy ray-curable undercoat agent. Among them, it is more than 70% by mass.

By using such an undercoat agent, even when the metal film is thick, the formed undercoat layer can achieve both adhesion to the metal film and scratch resistance. Furthermore, it becomes possible to form an excellent undercoat layer with good transparency, hardness, and alkali resistance.

<Compound (A)>

Compound (A) is a compound having three or more (meth)acryloyl groups. However, the case of the above silane coupling agent is excluded.

Compound (A) is classified into a compound having a nitrogen atom (hereinafter also referred to as compound (a1)) and a compound (a2) without a nitrogen atom (hereinafter also referred to as compound (a2)), and compound (a1) ) is further divided into compound (a1x) having a nurate ring skeleton (hereinafter also referred to as compound (a1x)) and compounds (a1y) other than compound (a1x) (hereinafter also referred to as compound (a1y)). Can be classified.

From the viewpoint of adhesion to the metal film and alkali resistance, the compound (A) is preferably a compound (a1) having a nitrogen atom, and is more preferably a compound (a1x) having a nurate ring skeleton. When the compound (A) is compound (a1), an undercoat layer with more excellent adhesion to the metal film and alkali resistance is 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, a reaction occurs, and compound (B) is produced. It is preferable because it can exhibit excellent adhesion to metal films and alkali resistance due to the synergistic effect of both affinities.

Specifically as compound (A), for example, among compound (a1) having a nitrogen atom,

As compound (a1x), tris(2-acryloxyethyl)isocyanurate, EO-modified tris(2-acryloxyethyl)isocyanurate, PO-modified tris(2-acryloxyethyl)isocyanurate, and Trimers (isocyanurates) of (meth)acrylates having an isocyanato group such as ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate;

Examples of the compound (a1y) include urethane acrylate, polyacrylic poly(meth)acrylate having nitrogen atoms other than the nurate ring skeleton, etc.;

As a compound (a2) that does not have a nitrogen atom, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and pentaerythritol penta(meth)acrylate. polyol poly(meth)acrylate compounds such as erythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate;

In addition, polyacrylates of polymer polyols having three or more (meth)acryloyl groups, such as polyacryl poly(meth)acrylate and polyester (meth)acrylate;

polyepoxy (meth)acrylate; These may be mentioned, but are not limited to these.

Commercially available products of compound (a1x) include, for example, urethane acrylate (such as Miramer MU9800 manufactured by MIWON), which has three or more (meth)acryloyl groups and a nurate ring skeleton, and tris (2-acryloxy). Ethyl) isocyanurate (FANCRYL FA-731A manufactured by Showa Denko Materials Co., Ltd., NEW FRONTIER TEICA (GX-8430) manufactured by Jeil Industrial Pharmaceutical Co., Ltd., etc.), EO-modified tris(2-acryloxyethyl)isocyanurate Rate (Aronics M-313, M-315 manufactured by Dong-A Synthetic Co., Ltd., NK Ester A-9300 manufactured by Shin Nakamura Chemical Co., Ltd., SARTOMER SR-368 manufactured by ARKEMA Co., Ltd., etc.), PO-modified tris(2-acryloxyethyl)isocytamine. Commercially available products such as anurate and ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate (NK Ester A-9300-1CL, manufactured by Shin Nakamura Chemical Co., Ltd., etc.) may be mentioned, but are not limited to these.

Commercially available products of compound (a1y) include, for example, commercial products such as urethane acrylate (such as Miramer PU610 manufactured by MIWON) which does not have a nurate ring skeleton and has three or more (meth)acryloyl groups, and nurate ring. Examples include polyacrylic poly(meth)acrylate, which has nitrogen atoms other than the skeleton and has three or more (meth)acryloyl groups, but is not limited to these.

Commercially available products of compound (a2) include, for example, trimethylolpropane tri(meth)acrylate (Miwon M300, etc.), glycerin tri(meth)acrylate (Aronics M-930, etc. manufactured by Dong-A Synthetic Co., Ltd.), Dipentaerythritol penta(meth)acrylate (SR399, etc., manufactured by Sartomer), dipentaerythritol hexa(meth)acrylate (Miramer M600, etc., manufactured by MIWON), pentaerythritol tri(meth)acrylate (Miramer M340, etc., manufactured by MIWON), and polyol poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate (Light Acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd., etc.).

In addition, polyacrylic poly(meth)acrylate (KRM8912, manufactured by Daicel/Cytech Co., Ltd., etc.), which has three or more (meth)acryloyl groups and no nitrogen atom, and three or more (meth)acryloyl groups. Polyacrylates of polymer polyols such as polyester (meth)acrylate (EBECRYL800, manufactured by Daicel/Cytech Co., Ltd., etc.);

Polyepoxy (meth)acrylate (EBECRYL3603 manufactured by Daicel/Cytech Co., Ltd., etc.); These may be mentioned, but are not limited to these.

The content of compound (A) is 70% by mass or more out of 100% by mass of non-volatile matter of the active energy ray-curable undercoat agent. The upper limit of the content of compound (A) is less than 100% by mass, and is preferably 98% by mass or less.

From the point of obtaining an undercoat layer with excellent hardness and scratch resistance, it is preferably 72.5% by mass or more, and more preferably 75% by mass or more.

<Compound (B)>

Compound (B) is a compound having a silsesquioxane skeleton (hereinafter also referred to as compound (B1) or compound (B1) having a silsesquioxane skeleton), a metal compound having an organic group (hereinafter referred to as a metal compound having an organic group) (also referred to as compound (B2) or metal compound (B2)), a triazinethiol compound (hereinafter also referred to as triazinethiol compound (B3)), and a compound having two or more alkoxysilyl groups or two or more reactive functional groups. It is at least one of silane coupling agents (hereinafter also referred to as silane coupling agent (B4)). Here, the metal compound (B2) excludes those containing any one of a silsesquioxane skeleton, a triazine thiol ring, and an organosilicon group as an organic group. The triazinethiol compound (B3) excludes those containing either a silsesquioxane skeleton or an organosilicon group. The silane coupling agent (B4) excludes those containing a silsesquioxane skeleton.

(Compound having a silsesquioxane skeleton (B1))

The silsesquioxane skeleton is a rigid skeleton, and has good alkali resistance due to the silsesquioxane skeleton, and does not reduce the scratch resistance of the undercoat layer, and through interaction with oxygen atoms or some remaining silanol groups. Adhesion between the undercoat layer and the metal film improves.

Compound (B1) having a silsesquioxane skeleton is a network polymer having a structure of (RSiO1.5)n obtained by hydrolyzing and condensing silsesquioxane, that is, a trifunctional silane, or a polyhedral cluster structure. There is no particular limitation as long as it is a compound, and a compound having a silsesquioxane skeleton of a known and commonly used structure such as a random structure, a ladder structure, a complete basket structure, and an incomplete basket structure can be used. (RSiO1.5) Among n, 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 still more preferable. Moreover, in (RSiO1.5)n, R is preferably an organic group such as methyl group, ethyl group, phenyl group, or (meth)acryloyl group.

Compound (B1) having a silsesquioxane skeleton is a compound having a silsesquioxane skeleton and a (meth)acryloyl group, in which at least part of R in (RSiO1.5)n is a (meth)acryloyl group ( It is preferable that it is b1). By having a (meth)acryloyl group, a decrease in the scratch resistance of the undercoat layer can be further suppressed, and not only the scratch resistance is high, but also the alkali resistance and adhesion to the metal film can be improved.

On the other hand, when it has a silsesquioxane skeleton, it is classified as a compound (B1) having a silsesquioxane skeleton even if it has three or more (meth)acryloyl groups.

Commercially available compounds (B1) having a silsesquioxane skeleton include Compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group, for example, AC-SQ TA-, manufactured by Dong-A Synthetic Co., Ltd. 100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20, MAC-SQ HDM, etc.

Other commercially available compounds having a silsesquioxane skeleton include, for example, SR-21, SR-23, SR-13, SR-33, SO-04, manufactured by Konishi Chemical Industries, Ltd., and Arakawa Chemical Industries, Ltd. Examples include SQ107, SQ109, SQ506, OX-SQ TX-100, OX-SQ SI-20, and OX-SQ HDX manufactured by Dong-A Synthetic Co., Ltd.

The content of the compound (B1) having a silsesquioxane skeleton is preferably 1 to 30% by mass, more preferably 3 to 27% by mass, based on 100% by mass of non-volatile matter of the active energy ray-curable undercoat agent. , it is more preferable that it is 5 to 25 mass%.

This content range is preferable because the adhesion and alkali resistance between the undercoat layer and the metal film become good even when the metal film has a large film thickness.

(Metal compound having an organic group (B2) and triazinethiol compound (B3))

The metal compound (B2) and the triazinethiol compound (B3) having an organic group are compounds that have a functional group that can interact with an organic material and a functional group that can interact with an inorganic material in the same molecule. As for the metal compound (B2) having an organic group, for example, the coordination site of the chelate ligand of the metal chelate compound (B2y) may interact with organic and inorganic materials. In the triazine thiol compound (B3), the triazine skeleton can interact with organic materials and the thiol group can interact with inorganic materials.

The metal compound (B2) and triazinethiol compound (B3) having an organic group are capable of forming a stable and uniform composition with other organic materials constituting the undercoat agent, and an undercoat agent containing them Ensures good adhesion to the metal film laminated directly on the undercoat layer formed by curing.

The content of the metal compound (B2) or triazinethiol compound (B3) having an organic group is 1 to 100% by mass of the non-volatile content of the active energy ray-curable undercoat agent from the viewpoints of hardness, scratch resistance, and metal film adhesion. It is preferable that it is 30 mass %, it is more preferable that it is 3-25 mass %, and it is still more preferable that it contains 5-15 mass %.

[Metal compound with organic group (B2)]

The metal compound (B2) having an organic group has, for example, an M-C bond between a metal atom (M) and a carbon atom (C) or an M-O-C bond through an oxygen atom, M(-R)n, M(-OR )n, or M(-OCOR)n, etc., and is a compound having a metal atom (M) and an organic group (R).

Examples of the organic group (R) include an alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, alkoxy group, acetoxy group, and carboxyl group, but are not particularly limited to these.

Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and benzyl group.

Examples of the alkenyl group include ethylene group, propylene group, butylene group, pentylene group, hexene group, and phenylene group.

Examples of the alkynyl group include ethynyl group, propynyl group, butynyl group, pentynyl group, and hexynyl group.

Examples of the aryl group include phenyl group, tolyl group, xylyl group, and naphthyl group.

Examples of the acyl group include acetyl group, propionyl group, stearoyl group, oxalyl group, malonyl group, benzoyl group, cinnamoyl group, acryloyl group, and methacryloyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, and phenoxy group.

Examples of the metal compound (B2) include a metal alkoxide compound (B2x), a metal chelate compound (B2y), or a metal acylate compound (B2z).

Specifically, the metal alkoxide compound (B2x) is a compound represented by the general formula M(OR)n, and the metal chelate compound (B2y) contains the donor valence, covalent bond, and It is a compound formed through coordination, and the metal acylate compound (B2z) is a compound represented by the general formula M(OCOR)n.

Here, M represents a metal atom, R represents an organic group, and n represents an integer of 1 or more.

Among these, from the viewpoint of reactivity, if it is a metal alkoxide compound (B2x), the adhesion between the metal and the undercoat layer can be further improved, and if it is a metal chelate compound (B2y) from the viewpoint of stability, the transparency of the coating film can be further improved. It is desirable because it is possible.

In addition, the metal contained in the metal compound (B2) includes, for example, a Group 4 metal, a Group 13 metal, and a Group 14 metal in the periodic table. Among these, organometallic compounds having metals with small periodic numbers are highly active and, from the viewpoint of excellent crosslinking properties, those containing metals of Group 4 or Group 13 of the periodic table are preferable.

Metals specifically include, for example, aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, boron, cobalt, manganese, selenium, chromium, ruthenium, gallium, cadmium, etc. of polyvalent metals. Among these, titanium, zirconium, and aluminum are preferable, and titanium or zirconium is more preferable from the viewpoint of reactivity with the organic component contained in the undercoat agent and adhesion with the metal film directly laminated on the undercoat layer.

That is, from the viewpoint of adhesion to the metal film, an organotitanium compound, an organoaluminum compound, or an organozirconium compound is preferable, and an organotitanium compound or an organozirconium compound is more preferable.

(Metal alkoxide compound (B2x))

The metal alkoxide compound (B2x) is a compound represented by the general formula M(OR)n.

Here, M is a metal atom and R is an organic group having 1 or more carbon atoms.

Examples of the metal alkoxide compound (B2x) include titanium alkoxide compounds, zirconium alkoxide compounds, and aluminum alkoxide compounds, and from the viewpoint of adhesion to the metal film, it is preferable that they are titanium alkoxide compounds or zirconium alkoxide compounds.

Titanium alkoxide compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tetratertiary butyl titanate, tetrastearic titanate, tetra-i-propoxytitanium, tetra Kiss (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate, etc. can be mentioned.

Commercially available products include Orgatics TA-8, TA-21, TA-23, TA-30, TA-12, TA-80, TA-90 manufactured by Matsumoto Fine Chemical Co., Ltd., Plenact 46B manufactured by Ajinomoto Fine Techno Co., Ltd., Examples include 55, 41B, 38S, 338X, 44, 9SA, A-1, TOT, and TOG manufactured by Japan Procurement Corporation.

Examples of the zirconium alkoxide compound include tetranormal propyl zirconate, tetraisopropyl zirconate, normal propyl zirconate, and normal butyl zirconate.

Commercially available products include Orgatics ZA-45, ZA-65, etc. manufactured by Matsumoto Fine Chemical Co., Ltd.

Examples of aluminum alkoxide compounds include aluminum secondary butoxide, aluminum trimethoxide, aluminum triethoxide, and aluminum tripropoxide.

Commercially available products include Orgatics AL-3001 manufactured by Matsumoto Fine Chemicals Co., Ltd.

(Metal chelate compound (B2y))

The metal chelate compound (B2y) is a compound formed by covalent bonding and coordination of the donor atom contained in 1 mole of ligand with respect to 1 mole of metal atom.

Examples of the metal chelate compound (B2y) include a titanium chelate compound, a zirconium chelate compound, and an aluminum chelate compound. From the viewpoint of adhesion to a metal film, a titanium chelate compound or a zirconium chelate compound is preferable.

Chelating agents constituting the chelate ligand include β-diketone, β-keto ester, polyhydric alcohol, alkanolamine, and oxycarboxylic acid, but are not particularly limited to these.

There is no particular limitation on the β-diketone as long as it coordinates as a chelating agent, but specifically, for example, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, and dibenzoylmethane. , thenoyltrifluoroacetone, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, etc.

There is no particular limitation on the β-keto ester, but specifically, for example, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl pivaloyl acetate, methyl isobutyloyl acetate, and capro. Methyl monoacetate, methyl lauroyl acetate, etc. are mentioned.

The polyhydric alcohol is not particularly limited, but includes 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, Glycerin, diethylene glycol, hexylene glycol, etc. can be mentioned.

The alkanolamine is not particularly limited, but includes N,N-dimethylethanolamine, N,N-diethylethanolamine, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, and N-methyldiethanol. Amine, N-ethylethanolamine, N-n-butylethanolamine, N-n-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, triethanolamine, diethanolamine, monoethanolamine, etc. I can hear it.

There is no particular limitation on the oxycarboxylic acid, but examples include glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, and gluconic acid.

Titanium chelate compounds include titanium acetylacetonate, titanium tetraacetylacetonate, titanium octylene glycolate, titanium ethyl acetoacetate, titanium lactate, titanium triethanolaminate, titanium acetylacetonate, di-i-propoxy·bis. (acetylacetonato)titanium, propane dioxy titanium bis(ethylacetoacetate), etc. are mentioned.

Commercially available products include Orgatics TC-120, TC-310, TC-315, TC-400, TC-500, TC-510 manufactured by Matsumoto Fine Chemical Co., Ltd., Plenact 138S and 238S manufactured by Ajinomoto Fine Techno Co., Ltd., and Japanese procurement. Examples include T-50 and T-60 manufactured by a corporation.

Examples of the zirconium chelate compound include zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium tetraacetylcetonate, and zirconium ethyl acetoacetate.

Commercially available products include Orgatics ZC-150, ZC-162, ZC-540, ZC-580, and ZC-700 manufactured by Matsumoto Fine Chemical Co., Ltd.

Examples of the aluminum chelate compound include aluminum trisacetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum trisethylacetoacetate, and alkylacetoacetate aluminum diisopropylate.

Commercially available products include Orgatics AL-3100, AL-3200, and AL-3215 manufactured by Matsumoto Fine Chemical Co., Ltd., and Planact AL-M manufactured by Ajinomoto Fine Techno Co., Ltd.

(Metal acylate compound (B2z))

The metal acylate compound (B2z) is a compound represented by the general formula M(OCOR)n.

Here, M represents a metal atom, R represents an organic group having 1 or more carbon atoms, and n represents an integer of 1 or more.

Examples of the metal acylate compound (B2z) include titanium acylate compounds, zirconium acylate compounds, and aluminum acylate compounds. From the viewpoint of adhesion to the metal film, it is a titanium acylate compound or a zirconium acylate compound. It is desirable.

Titanium acylate compounds include titanium isostearate, tri-n-butoxy titanium monostearate, di-i-propoxy titanium distearate, titanium stearate, and di-i-propoxy titanium diisostearate. , (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium, etc.

Commercially available products include Orgatics TC-800 manufactured by Matsumoto Fine Chemical Co., Ltd., Plenact TTS manufactured by Ajinomoto Fine Techno Co., Ltd., TBSTA, DPSTA-25, S-151, S-152S-181, and TBP manufactured by Nippon Procurement Co., Ltd. I can hear it.

Examples of the zirconium acylate compound include zirconium octylate compounds and zirconium stearate.

Commercially available products include Orgatics ZC-200, ZC-320, etc. manufactured by Matsumoto Fine Chemical Co., Ltd.

Examples of the aluminum acylate compound include titanium isostearate, aluminum stearate, aluminum tristearate, and aluminum diacetate-monostearate.

Commercially available products include Orgatics TC-800 manufactured by Matsumoto Fine Chemical Co., Ltd.

[Triazinethiol compound (B3)]

The triazine thiol compound (B3) is a compound in which at least one thiol group is bonded to the triazine skeleton. The triazine thiol compound (B3) includes a compound (B3x) having an active energy ray-curable functional group (hereinafter also referred to as a triazine thiol compound (B3x)) and a compound (B3y) (hereinafter also referred to as a triazine thiol compound (B3x)) having an active energy ray-curable functional group. , It can be classified as a triazinethiol compound (B3y)). Among these, the compound (B3x) having an active energy ray-curable functional group is preferable from the viewpoint of reactivity with the organic component contained in the undercoat agent and adhesion with the metal film directly laminated on the undercoat layer. By having an active energy ray-curable functional group, it is strongly bonded to the undercoat layer, and adhesion to the metal film layer and alkali resistance are further improved.

Triazinethiol compounds (B3x) having an active energy ray-curable functional group include 6-diallylamino-1,3,5-triazine-2,4-dithiol, 6-(4-vinylbenzyl-n-propyl) Amino-1,3,5-triazine-2,4-diol, 6-(allylamino)-1,3,5-triazine-2,4-dithiol, etc. are mentioned.

Commercially available products include V BATDT manufactured by Kawaguchi Chemical Co., Ltd.; and 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-diol.

Triazinethiol compounds (B3y) that do not have an active energy ray-curable functional group include 1,3,5-triazine-2,4,6-trithiol and 2-(dibutylamino)-1,3,5-tri. Azine-4,6-dithiol, 6-(diisopropylamino)-1,3,5-triazine-2,4-dithiol, 6-(diisobutylamino)-1,3,5-tri Azine-2,4-dithiol, 6-di(2-ethylhexyl)amino-1,3,5-triazine-2,4-dithiol, 6-(butylamino)-1,3,5-tri Azine-2,4-dithiol, etc. can be mentioned.

Commercially available products include TSH manufactured by Kawaguchi Chemical Co., Ltd.; 1,3,5-triazine-2,4,6-triol, BSH; 2-(butylamino)-1,3,5-triazine-4,6-dithiol, IPSH; 6-(diisopropylamino)-1,3,5-triazine-2,4-dithiol, IBSH; 6-(diisobutylamino)-1,3,5-triazine-2,4-dithiol, ESH; and 6-di(2-ethylhexyl)amino-1,3,5-triazine-2,4-dithiol).

(Silane coupling agent (B4))

The alkoxysilyl group in the silane coupling agent (B4) has an alkoxy group on a silicon atom, and includes monoalkoxysilyl group, dialkoxysilyl group, and trialkoxysilyl group, and is preferably a trialkoxysilyl group. Among the trialkoxysilyl groups, trialkoxysilyl group is preferred. A methoxysilyl group, a triethoxysilyl group, or a tripropoxy group is preferable from the viewpoint of hydrolysis reactivity.

On the other hand, the alkoxy group bonded to one silicon may be the same or different, and the alkyl group contained in the alkoxy group may be either a branched or straight-chain alkyl group, and may have a substituent.

Specific examples of the alkoxy group include methoxy group, ethoxy group, and propoxy group.

The silane coupling agent (B4) has two or more alkoxysilyl groups, and preferably has three or more alkoxysilyl groups. Moreover, it is preferable to have two or more reactive functional groups, and to have three or more reactive functional groups.

The upper limit of the number of substituents of the alkoxyalkyl group and the reactive functional group is not limited and can be set appropriately depending on the molecular weight of the resin forming the main skeleton, etc.

Preferably, they are all 100 or less, and more preferably 50 or less.

Examples of reactive functional groups include amino groups, epoxy groups, (meth)acryloyl groups, thiol groups, and isocyanate groups. Among them, (meth)acryloyl groups further suppress the decrease in scratch resistance of the undercoat layer. It is preferable because it not only has high scratch resistance but also improves alkali resistance and adhesion to the metal film layer.

The silane coupling agent (B4) preferably has a main chain and a side chain, and the main chain preferably has an organic structure such as a resin that is a polymer of an organic substance, or a siloxane structure.

Among them, a silane coupling agent whose main chain is an organic structure such as resin is preferable.

On the other hand, the organic structure such as resin is not limited as long as it is a skeleton having a repeating structure, and may be of an oligomer or polymer type.

In the case of an oligomeric or polymer-type silane coupling agent, the weight average molecular weight is preferably 500 to 100,000, and more preferably 700 to 50,000.

At this time, the weight average molecular weight is the weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) measurement.

Oligomers or polymers that are organic structures such as resins are not particularly limited, and include acrylic oligomers or polymers, vinyl-based oligomers or polymers, urethane-based oligomers or polymers, polyester-based oligomers or polymers, olefin-based oligomers or polymers, styrene-based oligomers or polymers, etc. can be mentioned. Among them, acrylic oligomers or polymers are preferable.

Among these, polymer-type silane coupling agent (b4) (hereinafter also referred to as silane coupling agent (b4)) has two or more alkoxysilyl groups and two or more (meth)acryloyl groups, and also has an organic structure in the main chain. This is preferable because it can further suppress a decrease in the scratch resistance of the undercoat layer, and not only have high scratch resistance, but also improve alkali resistance and adhesion to the metal film layer.

The silane coupling agent (B4) may be a synthetic product or a commercially available product.

As a synthesis example, for example, it is obtained by copolymerization of an ethylenically unsaturated monomer having an alkoxysilyl group and an ethylenically unsaturated monomer having a reactive functional group.

In addition, the silane coupling agent (b4) is obtained by adding (meth)acrylic acid in an equimolar amount to the epoxy group 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 an alkoxy group. A method of adding an ethylenically unsaturated monomer having an isocyanate group and an equimolar hydroxyl group to an acrylic polymer obtained by copolymerizing an ethylenically unsaturated monomer having a silyl group and an ethylenically unsaturated monomer having an isocyanate group may be included, but is not limited to this. .

At this time, by adjusting the blending amount of the monomer used, a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups can be obtained.

Commercially available products include, for example, X-12-972F, X-12-981S, X-12-984S, X-12-1154, X-12-59L, and , X-12-1048, and X-12-1050.

Additionally, polymer-type silane coupling agents (b4) having two or more alkoxysilyl groups and two or more (meth)acryloyl groups include X-12-1048 and X-12-1050.

Additionally, commercially available products of silane coupling agent (B4) whose main skeleton is a polymer having a siloxane structure include, for example, KR-517, KR-516, KR-513, and X-41-1805 manufactured by Shin-Etsu Chemical Co., Ltd. , X-41-1810.

The content of the silane coupling agent (B4) may be 1 to 30% by mass, preferably 1% by mass or more and less than 30% by mass, based on 100% by mass of non-volatile matter of the active energy ray-curable undercoat agent. It is more preferable that it is less than 27 mass %, and it is still more preferable that it is 5 mass % or more and less than 25 mass %.

This range is preferable because even when the thickness of the metal film is large, the adhesion and alkali resistance between the undercoat layer and the metal film become good, the scratch resistance does not decrease, and the cost does not increase.

<Photopolymerization initiator (C)>

The photopolymerization initiator (C) includes, for example, a monocarbonyl-based photopolymerization initiator, a dicarbonyl-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, a benzoin ether-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an aminocarbonyl-based photopolymerization initiator. Initiators and the like can be used.

The photopolymerization initiator (C) can also be used in combination with a sensitizer.

For example, benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3',4,4'-tetra(t -Butylperoxycarbonyl)benzophenone, 2-/4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxyl monocarbonyl-based photopolymerization initiators such as thioxanthone;

dicarbonyl-based photopolymerization initiators such as 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene acetate;

2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy -Cyclohexylphenylketone, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-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) Acetophenone-based photopolymerization initiators such as 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-based photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide;

And, ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate ate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzal)cyclopentanone, etc. Aminocarbonyl-based photopolymerization initiator; etc. can be mentioned.

Commercially available products of the photopolymerization initiator (C) include Omnirad184, 651, 500, 907, 127, 369, 784, and 2959 manufactured by IGM-Resins B.V., Esacure One, and Lucirin TPO manufactured by BASF Corporation. In particular, from the viewpoint of yellowing resistance after curing with active energy rays, Omnirad184 and Esacure One are preferable.

The content of the photopolymerization initiator (C) is not limited as long as it contains only an amount that can cure the undercoat layer to the desired physical properties by ultraviolet rays, but from the viewpoint of the self-hardening rate of the undercoat layer and the hardness and scratch resistance. , It is preferable that it is 1-15 mass %, and it is more preferable that it is 3-10 mass % among 100 mass % of non-volatile contents of an active energy ray-curable undercoat agent.

<Other ingredients>

The undercoat agent is obtained by mixing a compound (A) having three or more (meth)acryloyl groups, a compound (B), and a photopolymerization initiator (C). Additionally, if necessary, it may contain other components such as compound (A') having one or two (meth)acryloyl groups (hereinafter also referred to as compound (A')), organic solvent (D), and additives. It may be possible.

Additives include thermosetting resin, polymerization inhibitor, leveling agent, slip agent, anti-foaming agent, surfactant, antibacterial agent, anti-blocking agent, plasticizer, ultraviolet absorber, infrared absorber, antioxidant, silane coupling agent, conductive agent, inorganic filler, and pigment. , dyes, etc.

[Compound (A’)]

Compound (A') is a compound having 1 or 2 (meth)acryloyl groups.

Compound (A') includes, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and diethylene. Di(meth)acrylates such as 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 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, benzyl (meth)acrylate, cyclofentanyl (meth)acrylate, cyclohexyl (meth)acrylate, Mono(meth)acrylates such as dicyclopentenyl (meth)acrylate and isobornyl (meth)acrylate may be mentioned, but are not limited to these.

[Organic solvent (D)]

The undercoat agent may contain an organic solvent (D).

Examples of the organic solvent (D) include aromatic organic solvents such as toluene and xylene; Ketone-based 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-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; Known organic solvents such as glycoether-based organic solvents such as propylene glycol monomethyl ether can be used.

When the undercoat agent contains an organic solvent (D), the content of the organic solvent (D) is preferably in a range such that the non-volatile matter concentration of the undercoat agent is 1 to 60% by mass from the viewpoint of coatability and film forming properties. .

[Metal film attachment base material]

The metal film-coated substrate of one embodiment of the present invention includes a base material, an undercoat layer formed from the undercoat agent of one embodiment of the present invention, and a metal film in this order.

The undercoat agent is used to form a metal film on the surface of a substrate, and as described later, for example, a lamination having an undercoat layer obtained by applying an undercoat agent on a substrate and curing it with active energy rays. By using a sieve and forming a metal film on the undercoat layer of this laminate, it can be used as a metal film-attached base material.

Since the undercoat layer of one embodiment of the present invention has excellent adhesion to the metal film, peeling of the metal film can be suppressed when the undercoat layer and the metal film are directly laminated.

On the other hand, if necessary, another resin layer, etc. may be additionally provided between the base material and the undercoat layer. Other resin layers include, for example, an antistatic resin layer to prevent electrification during the manufacturing process, a hard coat resin layer to further increase the hardness of the laminate of one embodiment of the present invention, a base material, and an embodiment of the present invention. An anchor resin layer for improving adhesion with the undercoat layer of the embodiment may be included, but the present invention is not limited to this.

There is no particular limitation on the base material (also referred to as support), and examples include glass, synthetic resin moldings, and films. Synthetic resin moldings include polymethyl methacrylate resin, copolymer resin containing methyl methacrylate as a main component, polystyrene resin, styrene-methyl methacrylate copolymer resin, styrene-acrylonitrile copolymer resin, polycarbonate resin, Examples include molded products of synthetic resins such as cellulose acetate butyrate resin, polyallyl diglycol carbonate resin, polyvinyl chloride resin, and polyester resin.

In addition, films include, for example, polyester film, polyethylene film, polypropylene film, cellophane film, diacetylcellulose film, triacetylcellulose (TAC) film, acetylcellulose butyrate film, polyvinyl chloride film, and polyvinyl chloride. Riden film, polyvinyl alcohol film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethyl pentether film, polysulfone film, polyether ether ketone film, polyether sulfone film, polyether imide film, poly E Examples include mid film, fluororesin film, nylon film, and acrylic film.

The thickness of the undercoat layer is not particularly limited, but is usually about 0.1 to 5 μm, and is more preferably 0.5 to 3 μm from the viewpoint of hardness and cost.

Metal film-attached substrates are also used as light-reflecting films for liquid crystal displays, decorative films for the back of smartphones, flexible printed wiring boards in which the formed metal film is patterned as a circuit, and antennas for RFID tags. In addition, antennas for the 5th generation mobile communication system are also being reviewed.

Accordingly, in order to improve the optical and electrical properties of a laminate having a metal film, it is required to increase the thickness of the metal film. The optical properties include reflectivity when used as a light reflection film and hiding ability when used as an edible film, and the electrical properties include reception sensitivity when used as an antenna film and response sensitivity when used as a conductive film. can be mentioned. However, conventionally, when the film thickness of the metal film is thickened, the stress generated when forming the metal film becomes much larger than when the film thickness is thin, and the adhesion with the undercoat layer tends to deteriorate further, resulting in lowering of the base material and the metal film. Adhesion is becoming a problem.

Furthermore, when using a metal film-attached base material for decorative films, flexible printed wiring boards, RFID tags, or antenna films for 5th generation mobile communication systems, it is necessary to pattern the formed metal film into a circuit, and during patterning, Alkali resistance is required when immersed in an etching solution (mainly an alkaline solution). In addition, when used as a conductive film, etc., it improves the visibility of displays, and when used as an antenna film, it may be attached to the window of a building or car, and the undercoat layer must also have transparency to improve visibility. there is.

One embodiment of the present invention can provide an undercoat agent capable of forming an undercoat layer excellent in hardness, transparency, and alkali resistance even when the film thickness of the metal film is relatively large.

The thickness of the metal film is not particularly limited as long as it satisfies edible properties, optical properties, and electrical properties, but is usually 0.1 μm or more and 0.5 μm or less. However, depending on the application, it may be used with a film thickness of 0.5 μm or more to improve optical or electrical properties, and since the undercoat agent of one embodiment of the present invention has excellent adhesion, it may be used with a film thickness of 1 μm or more. Even when the thickness of the metal film is relatively thick, a laminate capable of both adhesion and scratch resistance can be obtained. From the viewpoint of manufacturing cost, miniaturization and weight reduction of recent display and antenna films, the thickness of the metal film is preferably 5 μm or less.

Examples of metal films include metal vapor deposition films, metal sputter films, and metal CVD films. The metal film is particularly preferably a metal vapor deposition film or a metal sputter film. Metals constituting the metal film include copper, aluminum, and silver, but are not limited to these. The undercoat agent is particularly effective when copper is used in the metal film.

Furthermore, since the adhesion is excellent even when the metal film is thick, the laminate of one embodiment of the present invention can be suitably used for antenna films that require improvement in reception sensitivity as an electrical characteristic. Additionally, since response sensitivity can be increased, it can be suitably used for conductive films and the like.

Furthermore, since the undercoat layer of one embodiment of the present invention has excellent transparency, the laminate of one embodiment of the present invention can also be suitably used in conductive films and antenna films that require visibility.

In addition, since the undercoat layer of one embodiment of the present invention has excellent alkali resistance, the laminate of one embodiment of the present invention can be used as a decorative film requiring a decorative pattern, a conductive film requiring a circuit pattern, an antenna film, It can also be conveniently used on flexible printed wiring boards, etc.

[Manufacturing method of metal film-attached substrate]

The method for manufacturing the metal film-coated base material of one embodiment of the present invention is not particularly limited. For example, (1) applying an undercoat to the surface of the substrate (for example, one or both sides if the substrate is a film), (2) applying heat to the substrate, and (3) additionally applying activation energy. The laminate is manufactured through a process of forming an undercoat layer by curing it by irradiating a line. (4) An example is manufacturing through a process of forming a metal film on the undercoat layer.

That is, it is preferable to manufacture a laminate having a base material and an undercoat layer through steps (1) to (3), and to form a metal film on the undercoat layer of the laminate to produce a base material with a metal film. .

Since the undercoat layer of one embodiment of the present invention has high scratch resistance, it is possible to prevent scratches in the undercoat layer during the metal film-attached base material manufacturing process and processing process, etc.

Regarding step (1), the conditions for applying the undercoat agent to the surface of the substrate are not particularly limited, and the application means include, for example, spray, roll coater, reverse roll coater, gravure coater, knife coater, Examples include bar coaters and dot coaters. Additionally, the coating amount is not particularly limited, but is usually about 0.01 to 10 g/m ² as dry non-volatile matter.

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

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

Regarding step (4), the means for forming the metal film on the undercoat layer is not particularly limited, but the dry coat method is preferable. Specifically, physical methods such as vacuum deposition or sputtering; Chemical methods such as CVD (chemical vapor reaction) can be mentioned.

Additionally, when the metal film-attached base material is used as an edible film, antenna film, conductive film, or flexible printed wiring board, the metal film can also be patterned into a circuit. The manufacturing method of the metal film-attached base material in this case is also not particularly limited. For example, various resists are applied to the metal film side of the metal film-attached base material obtained in steps (1) to (4), and a circuit pattern is depicted. A method of later immersing in an etching solution (alkaline solution) and removing the resist is included. The shape of the circuit pattern may be in any form, such as fine lines, dots, mesh, and planar shapes.

In this specification, the numerical range indicated using “~” represents a range that includes the numerical values written before and after “~” as the minimum and maximum values, respectively. In the numerical range described in stages in this specification, the upper or lower limit of the numerical range at a certain level can be arbitrarily combined with the upper or lower limit of the numerical range at another level.

The present invention is the subject matter of Japanese Patent Application No. 2021-152749 filed on September 21, 2021, the subject matter of Japanese Patent Application No. 2021-156494 filed on September 27, 2021, and the Japanese Patent Application No. 2021-156494 filed on October 28, 2021 It is related to the subject matter of application number 2021-176214, and the entire disclosure is incorporated herein by reference.

Example

Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the following examples do not limit the technical scope of the present invention at all. Meanwhile, in the examples, “part” means “part by mass” and “%” means “% by mass.”

In addition, the compounding amounts in the table are parts by mass, and values other than solvent are converted to non-volatile matter. Meanwhile, blank spaces in the table indicate that they are not mixed.

≪Experimental Example 1≫

<Manufacture of acrylic copolymer>

Manufacturing Example 1

In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction pipe, 40.8 parts (13.6 mol%) of hydroxyethyl acrylate (HEA), 72.0 parts (27.7 mole) of (methyl methacrylate (MMA)) %), 79.2 parts (23.8 mol%) of butylacrylate (BA), 48.0 parts (about 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate were added, and the reaction system was set to 70°C. , 1.2 parts of 2'-azobis(2,4-dimethylvaleronitrile) (ABN-V) was added, and the mixture was kept at a temperature of around 70°C for 6 hours. Then, 2.4 parts of ABN-V were added, and the reaction system was kept at around the same temperature. The reaction system was then cooled to room temperature to obtain a solution of an acrylic copolymer with a glass transition temperature of 80 mgKOH/g and a non-volatile content of 35.0%. It was determined by potentiometric titration according to K 0070.

(Preparation of undercoat agent)

[Example 1]

As compound (A), 94 parts of Aronics M-403 (manufactured by Dong-A Synthetic Co., Ltd.), 6 parts of MAC-SQ HDM (manufactured by Dong-A Synthetic Co., Ltd.) as compound (B), and Esacure One (DKSH Japan) as photopolymerization initiator (C). 5 parts (manufactured by Co., Ltd.) were mixed well, propylene glycol monomethyl ether as an organic solvent was adjusted to a non-volatile content concentration of 40%, and an undercoat agent was obtained.

[Examples 2 to 13, Comparative Examples 1 to 5]

Undercoat agents with a non-volatile content concentration of 40% were obtained in the same manner as in Example 1, except that each component was changed to the composition and mixing amount (non-volatile content conversion mass part) shown in Table 1.

The details of each material shown in Table 1 are as follows.

<Compound (A)>; Compounds having 3 or more (meth)acryloyl groups

(Compound (a2)); Compounds without nitrogen atoms

·Aronics M-403 (mixture of dipentaerythritol hexaacrylate (number of functional groups: 6): 40 to 50% and dipentaerythritol pentaacrylate (number of functional groups: 5): 50 to 60%; Dong-A Synthetic Co., Ltd. my)

(Compound(a1y)); Compounds with nitrogen atoms other than compound (a1x)

Miramer PU610 (urethane acrylate, weight average molecular weight: 1800, number of functional groups: 6, manufactured by MIWON)

(compound(a1x)); Compounds having a nurate ring skeleton

Miramer MU9800 (urethane acrylate with nurate ring skeleton, weight average molecular weight: 3500, functional group: 9, manufactured by MIWON)

·Aronics M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: 3, manufactured by Dong-A Synthetic Co., Ltd.)

<Compound (A’)>; Compounds having 1 or 2 (meth)acryloyl groups

・NK ester A-DCP (tricyclodecane dimethanol diacrylate, molecular weight: 304, number of acryloyl groups: 2, manufactured by Shinnakamura Chemical Industry Co., Ltd.)

<Inert Resin>

Acrylic copolymer (solution of acrylic copolymer synthesized in Preparation Example 1 with a glass transition temperature of 13°C, hydroxyl value of 80 mgKOH/g, and non-volatile content of 35.0%)

<Compound (B)>

Compound (B1); Compounds with a silsesquioxane skeleton

(etc); Compounds other than compound (b1)

・SR-13 (made by Konishi Chemical Industry Co., Ltd.)

(Compound (b1)); Compounds having a (meth)acryloyl group

AC-SQ SI20 (has an acryloyl group. Manufactured by Dong-A Synthetic Co., Ltd.)

MAC-SQ HDM (having a methacryloyl group. Propylene glycol monobutyl ether solution with non-volatile content concentration of 50%, manufactured by Dong-A Synthetic Co., Ltd.)

<Photopolymerization initiator (C)>

Esacure One (Esacure One, acetophenone-based light polymerization initiator manufactured by DKSH Japan Co., Ltd.)

≪Production of undercoat layer and laminate≫

The undercoat agents obtained in the examples and comparative examples were each applied on a 50 μm thick polyethylene terephthalate (PET) film (“Lumiller U403” manufactured by Toray Co., Ltd.) using a bar coater so that the film thickness after drying was 1.0 μm. After coating as much as possible, ultraviolet rays of 500 mJ/cm ² were irradiated with a high-pressure mercury lamp to form an undercoat layer, thereby producing a laminate.

≪HZ[%]; Measurement of haze value≫

With respect to the above-produced laminate, the haze value (HZ) of the undercoat layer surface was measured using a “Haze Meter SH7000” manufactured by Nippon Seoncho Kogyo Co., Ltd. The evaluation criteria are as follows, and if it is less than 2.0%, there is no practical problem.

[Evaluation standard]

·Maximum: less than 1.0%

·Amount: 1.0 or more but less than 2.0%

·Defect: 2.0% or more

≪Pencil hardness≫

For the manufactured laminate, in accordance with JIS K5600-5-4, pencils of various hardnesses were applied to the surface of the undercoat layer of the laminate at an angle of 45°, and a scratch test was performed by applying a load to obtain the most scratch-free product. The hardness of a hard pencil was referred to as pencil hardness.

The harder the pencil hardness, the better, and if it is H or higher, it can be used without any practical problems. If it is F or lower, there is a risk that defects such as marks may occur, so it cannot be used in practice.

≪Scratch resistance≫

The produced laminate was evaluated for scratch resistance using a "Hakjin type friction fastness tester" manufactured by Tester Industry Co., Ltd. Steel wool #0000 was mounted on a friction element (surface area: 1 cm ² ) equipped with a load of 200 g, and the surface of the undercoat layer (1 cm × 15 cm) was rotated 10 times. After that, the number of scratches on the surface of the undercoat layer was counted and evaluated based on the following criteria. It is better if the number of scratches is small, and if it is 10 or less, it can be used without any practical problems.

[Evaluation standard]

·3: No scratches (0)

2: 1 to 10 scratches

·1: 11 or more scratches

≪Copper adhesion≫

On the undercoat layer of the produced laminate, copper was sputtered to a thickness of 0.5 μm, 1 μm, and 2 μm using “Magtron Sputter MSP-30T” manufactured by Vacuum Devices Co., Ltd. to form a copper film. The adhesion between the copper film and the undercoat layer is determined by making scratches in the copper film with a cutter in a checkerboard pattern at 1 mm intervals, forming a grid pattern of 100 scales, and then attaching cellophane tape to cover all of the scratches in the checkerboard pattern. was peeled off, the peeling state of the copper film was observed with the naked eye, and evaluated based on the following criteria. The less peeling, the better, and if it is 3 or higher in the evaluation standard, it can be used without any practical problems.

[Evaluation standard]

5: The area around the lines of the scratches is completely smooth, and there is no peeling in any grid.

·4: Small peeling of the copper film is observed around the intersection of the scratches, but the total peeled off area is less than 5% of the checkerboard pattern.

· 3: The copper film is peeling off along the edge direction of the flaw, or the copper film is peeling off at the intersection of the flaw, and the total peeled area is 5% to 15% of the checkerboard pattern.

·2: The total area peeled off is 15% to 35% of the checkerboard pattern.

·1: The total area peeled off is between 35% and less than 80% of the checkerboard pattern.

·0: The total peeling area is 80% or more of the checkerboard pattern, and peeling is also observed on the outside of the checkerboard pattern-shaped scratches.

≪Alkali resistance≫

A laminate with a copper film (thickness of 500 nm and 1 μm) that was not evaluated for copper adhesion was immersed in a 5% sodium hydroxide aqueous solution heated to 40°C for 5 minutes, thoroughly washed with water, and then placed in an oven heated to 100°C. After drying for 15 minutes to remove moisture, alkali resistance was evaluated in the same manner as the copper adhesion evaluation method described above. The less peeling, the better. However, if it is 3 or higher in the evaluation standard, it can be used without any practical problems.

[Table 1]

As shown in Table 1, by using the undercoat agent of one embodiment of the present invention, it is possible to achieve both adhesion and scratch resistance between the formed undercoat layer and the metal film, and is also excellent in transparency, hardness, and alkali resistance. I was able to confirm. Accordingly, it can be seen that the obtained metal film-attached substrate is excellent in adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance.

Among them, since it has good adhesion even when the thickness of the metal film is as thick as 1 μm or more, it can be said to be suitable for use in applications that improve the optical and electrical properties of thick metal films, which are recently required. You can.

≪Experimental Example 2≫

<Manufacture of acrylic copolymer>

Preparation Example 1A

In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction pipe, 40.8 parts (13.6 mol%) of hydroxyethyl acrylate (HEA), 72.0 parts (27.7 mole) of (methyl methacrylate (MMA)) %), 79.2 parts (23.8 mol%) of butylacrylate (BA), 48.0 parts (about 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate were added, and the reaction system was set to 70°C. , 1.2 parts of 2'-azobis(2,4-dimethylvaleronitrile) (ABN-V) was added, and the mixture was kept at a temperature of around 70°C for 6 hours. Then, 2.4 parts of ABN-V were added, and the reaction system was kept at around the same temperature. The reaction system was then cooled to room temperature to obtain a solution of an acrylic copolymer with a glass transition temperature of 80 mgKOH/g and a non-volatile content of 35.0%. It was determined by potentiometric titration according to K 0070.

(Preparation of undercoat agent)

[Example 1A]

As compound (A), 94 parts of Aronics M-403 (manufactured by Dong-A Synthetic Co., Ltd.), as compound (B) Orgatics TA-30 (titanium tetra-2-ethylhexoxide, non-volatile component: 99 wt% or more (2-propanol) Solution), 6 parts (manufactured by Matsumoto Fine Chemicals Co., Ltd.), and 5 parts of Esacure One (manufactured by DKSH Japan Co., Ltd.) as a photopolymerization initiator (C) are mixed well, and propylene glycol monomethyl ether is added as an organic solvent to a non-volatile content concentration of 40%. By adjusting, an undercoat agent was obtained.

[Examples 2A to 30A, Comparative Examples 1A to 8A]

Undercoat agents with a non-volatile content concentration of 40% were obtained in the same manner as in Example 1A, except that each component was changed to the composition and mixing amount (part by mass converted to non-volatile content) shown in Tables 2 and 3.

The details of each material shown in Tables 2 and 3 are as follows.

<Compound (A)>; Compounds having 3 or more (meth)acryloyl groups

(Compound (a2)); Compounds without nitrogen atoms

·Aronics M-403 (mixture of dipentaerythritol hexaacrylate (number of functional groups: 6): 40 to 50% and dipentaerythritol pentaacrylate (number of functional groups: 5): 50 to 60%; Dong-A Synthetic Co., Ltd. my)

(Compound(a1y)); Compounds with nitrogen atoms other than compound (a1x)

Miramer PU610 (urethane acrylate, weight average molecular weight: 1800, number of functional groups: 6, manufactured by MIWON)

(compound(a1x)); Compounds having a nurate ring skeleton

Miramer MU9800 (urethane acrylate with nurate ring skeleton, weight average molecular weight: 3500, functional group: 9, manufactured by MIWON)

·Aronics M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: 3, manufactured by Dong-A Synthetic Co., Ltd.)

<Compound (A’)>; Compounds having 1 or 2 (meth)acryloyl groups

・NK ester A-DCP (tricyclodecane dimethanol diacrylate, molecular weight: 304, number of acryloyl groups: 2, manufactured by Shinnakamura Chemical Industry Co., Ltd.)

<Inert Resin>

Acrylic copolymer (solution of acrylic copolymer synthesized in Preparation Example 1A with a glass transition temperature of 13°C, a hydroxyl value of 80 mgKOH/g, and a non-volatile content of 35.0%)

<Compound (B)>

[Metal compound having an organic group (B2))

(Metal alkoxide compound (B2x))

TA-21 (titanium alkoxide compound; titanium tetranormal butoxide, non-volatile component: 99 wt% or more (1-butanol solution), manufactured by Matsumoto Fine Chemicals Co., Ltd.)

ZA-65 (zirconium alkoxide compound; zirconium tetranormal butoxide, non-volatile component: 87 wt% (1-butanol solution), manufactured by Matsumoto Fine Chemicals Co., Ltd.)

AL-3001 (aluminum alkoxide compound; aluminum trisecondary butoxide, non-volatile component: 99 wt% or more, manufactured by Matsumoto Fine Chemicals)

(Metal chelate compound (B2y))

TC-401 (titanium chelate compound; titanium tetraacetylacetonate, non-volatile component: 65 wt% (2-propanol solution), manufactured by Matsumoto Fine Chemical Co., Ltd.)

·ZC-700 (zirconium chelate compound; zirconium tetraacetylacetonate, non-volatile component: 20 wt% (toluene, methyl alcohol, acetylacetone solution), manufactured by Matsumoto Fine Chemical Co., Ltd.)

AL-3200 (aluminum chelate compound; aluminum bisethylacetoacetate monoacetylacetonate, non-volatile component: 76 wt% or more (2-propanol solution), manufactured by Matsumoto Fine Chemicals Co., Ltd.)

(Metal acylate compound (B2z))

TC-800 (titanium acinate compound; titanium isostearate, non-volatile component: 77 wt% (isostearic acid solution), manufactured by Matsumoto Fine Chemical Co., Ltd.)

·ZC-320 (zirconium acylate compound; zirconium stearate, non-volatile component: 81 wt% (1-butanol solution), manufactured by Matsumoto Fine Chemical Co., Ltd.)

[Triazinethiol compound (B3)]

(Triazinethiol compound (B3x) having an active energy ray-curable functional group)

·V BATDT (6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol, manufactured by Kawaguchi Chemical Co., Ltd.)

(Triazinethiol compound (B3y) without an active energy ray-curable functional group)

·ESH (6-di(2-ethylhexyl)amino-1,3,5-triazine-2,4-dithiol, manufactured by Kawaguchi Chemical Industry Co., Ltd.)

<Photopolymerization initiator (C)>

Esacure One (Esacure One, acetophenone-based light polymerization initiator manufactured by DKSH Japan Co., Ltd.)

≪Production of undercoat layer and laminate≫

The undercoat agents obtained in the examples and comparative examples were each applied on a 50 μm thick polyethylene terephthalate (PET) film (“Lumiller U403” manufactured by Toray Co., Ltd.) using a bar coater so that the film thickness after drying was 1.0 μm. After coating as much as possible, ultraviolet rays of 500 mJ/cm ² were irradiated with a high-pressure mercury lamp to form an undercoat layer, thereby producing a laminate.

≪HZ[%]; Measurement of haze value≫

With respect to the above-produced laminate, the haze value (HZ) of the undercoat layer surface was measured using a “Haze Meter SH7000” manufactured by Nippon Seoncho Kogyo Co., Ltd. The evaluation criteria are as follows, and if it is less than 2.0%, there is no practical problem.

[Evaluation standard]

·Maximum: less than 1.0%

·Amount: 1.0 or more but less than 2.0%

·Defect: 2.0% or more

≪Pencil hardness≫

For the manufactured laminate, in accordance with JIS K5600-5-4, pencils of various hardnesses were applied to the surface of the undercoat layer of the laminate at an angle of 45°, and a scratch test was performed by applying a load to obtain the most scratch-free product. The hardness of a hard pencil was referred to as pencil hardness.

The harder the pencil hardness, the better, and if it is H or higher, it can be used without any practical problems. If it is F or lower, there is a risk that defects such as marks may occur, making it impossible to use in practice.

≪Scratch resistance≫

The produced laminate was evaluated for scratch resistance using a "Hakjin type friction fastness tester" manufactured by Tester Industry Co., Ltd. Steel wool #0000 was mounted on a friction element (surface area: 1 cm ² ) equipped with a load of 200 g, and the surface of the undercoat layer (1 cm × 15 cm) was rotated 10 times. After that, the number of scratches on the surface of the undercoat layer was counted and evaluated based on the following criteria. It is better if the number of scratches is small, and if it is 10 or less, it can be used without any practical problems.

[Evaluation standard]

·3: No scratches (0)

2: 1 to 10 scratches

·1: 11 or more scratches

≪Copper adhesion≫

On the undercoat layer of the produced laminate, copper was sputtered to a thickness of 0.5 μm, 1 μm, and 2 μm using “Magtron Sputter MSP-30T” manufactured by Vacuum Devices Co., Ltd. to form a copper film. The adhesion between the copper film and the undercoat layer is determined by making scratches in the copper film with a cutter in a checkerboard pattern at 1 mm intervals, forming a grid pattern of 100 scales, and then attaching cellophane tape to cover all of the scratches in the checkerboard pattern. was peeled off, the peeling state of the copper film was observed with the naked eye, and evaluated based on the following criteria. The less peeling, the better, and if it is 3 or higher in the evaluation standard, it can be used without any practical problems.

[Evaluation standard]

5: The area around the lines of the scratches is completely smooth, and there is no peeling in any grid.

4: Small peeling of the copper film is observed around the intersection of the scratches, but the total peeled off area is less than 5% of the checkerboard pattern.

· 3: The copper film is peeling off along the edge direction of the flaw, or the copper film is peeling off at the intersection of the flaw, and the total peeled area is 5% to 15% of the checkerboard pattern.

·2: The total area peeled off is 15% to 35% of the checkerboard pattern.

·1: The total area peeled off is between 35% and less than 80% of the checkerboard pattern.

·0: The total peeling area is 80% or more of the checkerboard pattern, and peeling is also observed on the outside of the checkerboard pattern-shaped scratches.

≪Alkali resistance≫

A laminate with a copper film (thickness of 500 nm and 1 μm) that was not evaluated for copper adhesion was immersed in a 5% sodium hydroxide aqueous solution heated to 40°C for 5 minutes, thoroughly washed with water, and then placed in an oven heated to 100°C. After drying for 15 minutes to remove moisture, alkali resistance was evaluated in the same manner as the copper adhesion evaluation method described above. The less peeling, the better. If it is 3 or higher in the evaluation standard, it can be used without any practical problems.

[Table 2]

[Table 3]

As shown in Tables 2 and 3, by using the undercoat agent of one embodiment of the present invention, it is possible to achieve both adhesion and scratch resistance between the formed undercoat layer and the metal film, and in addition, transparency, hardness, and alkali resistance are also achieved. I was able to confirm that it was excellent. Accordingly, it can be seen that the obtained metal film-attached substrate is excellent in adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance.

Among them, since it has good adhesion even when the thickness of the metal film is as thick as 1 μm or more, it can be said to be suitable for use in applications that improve the optical and electrical properties of thick metal films, which are recently required. You can.

≪Experimental Example 3≫

<Manufacture of acrylic copolymer>

Production Example 1B

In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction pipe, 40.8 parts (13.6 mol%) of hydroxyethyl acrylate (HEA), 72.0 parts (27.7 mole) of (methyl methacrylate (MMA)) %), 79.2 parts (23.8 mol%) of butylacrylate (BA), 48.0 parts (about 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate were added, and the reaction system was set to 70°C. , 1.2 parts of 2'-azobis(2,4-dimethylvaleronitrile) (ABN-V) was added, and the mixture was kept at a temperature of around 70°C for 6 hours. Then, 2.4 parts of ABN-V were added, and the reaction system was kept at around the same temperature. The reaction system was then cooled to room temperature to obtain a solution of an acrylic copolymer with a glass transition temperature of 80 mgKOH/g and a non-volatile content of 35.0%. It was determined by potentiometric titration according to K 0070.

<Manufacture of silane coupling agent (B4)>

Production example 2

In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction pipe, 3.20 parts (22.5 mmol) of n-butyl methacrylate (BMA), 3-methacryloxypropyltrimethoxysilane (MPTMS) Reaction achieved by dissolving 1.24 parts (5 mmol), 3.20 parts (22.5 mmol) of glycidyl methacrylate (GMA), and 0.784 parts (4 mmol) of γ-mercaptopropyltrimethoxysilane as a chain transfer agent in 8.46 parts of toluene. A solution prepared by dissolving 0.025 parts (0.15 mmol) of azobisisobutyronitrile in 3 parts of toluene was added dropwise to the solution under a nitrogen stream and allowed to react at 70°C for 2 hours. Thereafter, the reaction system was cooled to room temperature and the solid content was adjusted to 40% using toluene to obtain a solution of silane coupling agent (B4-1) having two or more alkoxysilyl groups and two or more epoxy groups (weight average molecular weight 1000). .

Production example 3

In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen introduction pipe, 3.20 parts (22.5 mmol) of n-butyl methacrylate (BMA), 3-methacryloxypropyltrimethoxysilane (MPTMS) Reaction achieved by dissolving 1.24 parts (5 mmol), 3.20 parts (22.5 mmol) of glycidyl methacrylate (GMA), and 0.784 parts (4 mmol) of γ-mercaptopropyltrimethoxysilane as a chain transfer agent in 8.46 parts of toluene. A solution prepared by dissolving 0.025 parts (0.15 mmol) of azobisisobutyronitrile in 3 parts of toluene was added dropwise to the solution under a nitrogen stream and allowed to react at 70°C for 2 hours. Accordingly, a polymer with a weight average molecular weight of 1000 was obtained. 3 parts of methanol and 1.62 parts of acrylic acid were dissolved in the obtained polymer, reacted at 70°C for 2 hours under a nitrogen stream, then the reaction system was cooled to room temperature, the solid content was adjusted to 40% using toluene, and two or more alkoxy A solution of a silane coupling agent (B4-2) having a silyl group and two or more acryloyl groups was obtained (weight average molecular weight 1300).

(Preparation of undercoat agent)

[Example 1B]

As compound (A), 94 parts of Aronics M-403 (manufactured by Dong-A Synthetic Co., Ltd.), 6 parts of Five parts (manufactured by DKSH Japan Co., Ltd.) were mixed well, and propylene glycol monomethyl ether as an organic solvent was adjusted to a non-volatile content concentration of 40% to obtain an undercoat agent.

[Examples 2B to 16B, Comparative Examples 1B to 5B]

Undercoat agents with a non-volatile content concentration of 40% were obtained in the same manner as in Example 1B, except that each component was changed to the composition and mixing amount (part by mass converted to non-volatile content) shown in Table 4.

The details of each material shown in Table 4 are as follows.

<Compound (A)>; Compounds having 3 or more (meth)acryloyl groups

(Compound (a2)); Compounds without nitrogen atoms

·Aronics M-403 (mixture of dipentaerythritol hexaacrylate (number of functional groups: 6): 40 to 50% and dipentaerythritol pentaacrylate (number of functional groups: 5): 50 to 60%; Dong-A Synthetic Co., Ltd. my)

(Compound(a1y)); Compounds with nitrogen atoms other than compound (a1x)

Miramer PU610 (urethane acrylate, weight average molecular weight: 1800, number of functional groups: 6, manufactured by MIWON)

(compound(a1x)); Compounds having a nurate ring skeleton

Miramer MU9800 (urethane acrylate with nurate ring skeleton, weight average molecular weight: 3500, functional group: 9, manufactured by MIWON)

·Aronics M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: 3, manufactured by Dong-A Synthetic Co., Ltd.)

<Compound (A’)>; Compounds having 1 or 2 (meth)acryloyl groups

・NK ester A-DCP (tricyclodecane dimethanol diacrylate, molecular weight: 304, number of acryloyl groups: 2, manufactured by Shinnakamura Chemical Industry Co., Ltd.)

<Inert Resin>

Acrylic copolymer (solution of acrylic copolymer with a glass transition temperature of 13°C, hydroxyl value of 80 mgKOH/g, and non-volatile content of 35.0%, synthesized in Preparation Example 1B)

<Compound (B)>

Silane coupling agent (B4); Silane coupling agents having two or more alkoxysilyl groups and two or more reactive functional groups (other silane coupling agents (B4)); Silane coupling agent (B4) other than silane coupling agent (b4)

·X-12-981S

(manufactured by Shin-Etsu Chemical Co., Ltd., 2 or more alkoxysilyl groups (triethoxy groups), 2 or more epoxy groups)

·KR-513

(manufactured by Shin-Etsu Chemical Co., Ltd., 2 or more alkoxysilyl groups (methoxy groups), 2 or more acryloyl groups, main chain is polysiloxane structure)

(Silane coupling agent (b4)); A polymer-type silane coupling agent 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 is 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 is organic structure)

<Other silane coupling agents>

·KBM-5103

(manufactured by Shin-Etsu Chemical Co., Ltd., alkoxysilyl group 1, acryloyl group 1)

<Photopolymerization initiator (C)>

Esacure One (Esacure One, acetophenone-based light polymerization initiator manufactured by DKSH Japan Co., Ltd.)

≪Production of undercoat layer and laminate≫

The undercoat agents obtained in the examples and comparative examples were each applied on a 50 μm thick polyethylene terephthalate (PET) film (“Lumiller U403” manufactured by Toray Co., Ltd.) using a bar coater so that the film thickness after drying was 1.0 μm. After coating as much as possible, ultraviolet rays of 500 mJ/cm ² were irradiated with a high-pressure mercury lamp to form an undercoat layer, thereby producing a laminate.

≪HZ[%]; Measurement of haze value≫

With respect to the above-produced laminate, the haze value (HZ) of the undercoat layer surface was measured using a “Haze Meter SH7000” manufactured by Nippon Seoncho Kogyo Co., Ltd. The evaluation criteria are as follows, and if it is less than 2.0%, there is no practical problem.

[Evaluation standard]

·Maximum: less than 1.0%

·Amount: 1.0 or more but less than 2.0%

·Defect: 2.0% or more

≪Pencil hardness≫

For the manufactured laminate, in accordance with JIS K5600-5-4, pencils of various hardnesses were applied to the surface of the undercoat layer of the laminate at an angle of 45°, and a scratch test was performed by applying a load to obtain the most scratch-free product. The hardness of a hard pencil was referred to as pencil hardness.

The harder the pencil hardness, the better, and if it is H or higher, it can be used without any practical problems. If it is F or lower, there is a risk that defects such as marks may occur, making it impossible to use in practice.

≪Scratch resistance≫

The produced laminate was evaluated for scratch resistance using a "Hakjin type friction fastness tester" manufactured by Tester Industry Co., Ltd. Steel wool #0000 was mounted on a friction element (surface area: 1 cm ² ) equipped with a load of 200 g, and the surface of the undercoat layer (1 cm × 15 cm) was rotated 10 times. After that, the number of scratches on the surface of the undercoat layer was counted and evaluated based on the following criteria. It is better if the number of scratches is small, and if it is 10 or less, it can be used without any practical problems.

[Evaluation standard]

·3: No scratches (0)

2: 1 to 10 scratches

·1: 11 or more scratches

≪Copper adhesion≫

On the undercoat layer of the produced laminate, copper was sputtered to a thickness of 200 nm, 500 nm, 1 μm, and 2 μm using “Magtron Sputter MSP-30T” manufactured by Vacuum Devices Co., Ltd. to form a copper film. The adhesion between the copper film and the undercoat layer is determined by making scratches in the copper film with a cutter in a checkerboard pattern at 1 mm intervals, forming a grid pattern of 100 scales, and then attaching cellophane tape to cover all of the scratches in the checkerboard pattern. was peeled off, the peeling state of the copper film was observed with the naked eye, and evaluated based on the following criteria. The less peeling, the better, and if it is 3 or higher in the evaluation standard, it can be used without any practical problems.

[Evaluation standard]

5: The area around the lines of the scratches is completely smooth, and there is no peeling in any grid.

4: Small peeling of the copper film is observed around the intersection of the scratches, but the total peeled off area is less than 5% of the checkerboard pattern.

· 3: The copper film is peeling off along the edge direction of the flaw, or the copper film is peeling off at the intersection of the flaw, and the total peeled area is 5% to 15% of the checkerboard pattern.

·2: The total area peeled off is 15% to 35% of the checkerboard pattern.

·1: The total area peeled off is between 35% and less than 80% of the checkerboard pattern.

·0: The total peeling area is 80% or more of the checkerboard pattern, and peeling is also observed on the outside of the checkerboard pattern-shaped scratches.

≪Alkali resistance≫

A laminate with a copper film (thickness of 500 nm and 1 μm) that has not been evaluated for copper adhesion is immersed in a 5% sodium hydroxide aqueous solution heated to 40°C for 5 minutes, then thoroughly washed with water, and then placed in an oven heated to 100°C. After drying for 15 minutes to remove moisture, alkali resistance was evaluated in the same manner as the copper adhesion evaluation method described above. The less peeling, the better. However, if it is 3 or higher in the evaluation standard, it can be used without any practical problems.

[Table 4]

As shown in Table 4, by using the undercoat agent of one embodiment of the present invention, it is possible to achieve both adhesion and scratch resistance between the formed undercoat layer and the metal film, and is also excellent in transparency, hardness, and alkali resistance. I was able to confirm. Accordingly, it can be seen that the obtained metal film-attached substrate is excellent in adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance.

Among them, since it has good adhesion even when the thickness of the metal film is as thick as 1 μm or more, it can be said to be suitable for use in applications that improve the optical and electrical properties of thick metal films, which are recently required. You can.

Claims (12)

An active energy ray-curable undercoat agent for forming an undercoat layer in a metal film-attached substrate comprising a base material, an undercoat layer, and a metal film in this order,
A first compound having three or more (meth)acryloyl groups, a second compound, and a photopolymerization initiator,
The second compound is selected from the group consisting of compounds having a silsesquioxane skeleton, metal compounds having an organic group, triazinethiol compounds, and silane coupling agents having two or more alkoxysilyl groups and two or more reactive functional groups. Contains at least one type of
An active energy ray-curable undercoat agent in which the content of the first compound is 70% by mass or more based on 100% by mass of non-volatile matter of the active energy ray-curable undercoat agent. According to paragraph 1,
The second compound includes a compound having a silsesquioxane skeleton,
An active energy ray-curable undercoat agent, wherein the compound having the silsesquioxane skeleton includes a compound having the silsesquioxane skeleton and a (meth)acryloyl group. According to paragraph 1,
The second compound includes a metal compound having the organic group,
An active energy ray-curable undercoat agent, wherein the metal compound having the organic group includes at least one selected from the group consisting of a metal alkoxide compound, a metal chelate compound, and a metal acylate compound. According to claim 1 or 3,
The second compound includes a metal compound having the organic group,
An active energy ray-curable undercoat agent in which the metal of the metal compound having an organic group contains titanium, zirconium, or aluminum. According to any one of paragraphs 1, 3, and 4,
The second compound includes the triazinethiol compound,
The triazine thiol compound is an active energy ray-curable undercoat agent comprising a triazine thiol compound having an active energy ray-curable functional group. According to paragraph 1,
The second compound includes a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups,
The silane coupling agent,
An active energy ray-curable undercoat agent containing a silane coupling agent having two or more alkoxysilyl groups and two or more (meth)acryloyl groups, and having an organic structure in the main chain. According to any one of claims 1 to 6,
The first compound is an active energy ray-curable undercoat agent containing a compound having three or more (meth)acryloyl groups and a nitrogen atom. In clause 7,
The compound having three or more (meth)acryloyl groups and a nitrogen atom is an active energy ray-curable underbody, including compounds having three or more (meth)acryloyl groups and a nurate ring skeleton. Coatje. According to any one of claims 1 to 8,
An active energy ray curable undercoat agent wherein the content of the second compound is 1 to 30 mass% based on 100 mass% of non-volatile matter of the active energy ray curable undercoat agent. An undercoat layer formed from the active energy ray-curable undercoat agent according to any one of claims 1 to 9. A laminate having a base material and the undercoat layer according to claim 10. A metal film-attached base material comprising a base material, the undercoat layer according to claim 10, and a metal film in this order.