TWI837832B - Active energy ray-curable primers, primers, laminates, and metal film-coated substrates - Google Patents

Abstract

An active energy ray-curable primer is used to form a primer layer in a metal film substrate which includes a substrate, a primer layer, and a metal film in sequence. The active energy ray-curable primer includes: a first compound having three or more (meth)acryl groups, a second compound, and a photopolymerization initiator, the second compound including at least one selected from the group consisting of a compound having a silsesquioxane skeleton, a metal compound having an organic group, a triazine thiol compound, and a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups, and the content of the first compound is 70% by mass or more in 100% by mass of the non-volatile components of the active energy ray-curable primer.

Description

Active energy ray-hardening primer, primer layer, laminate and substrate with metal film

One embodiment of the present invention relates to an active energy ray-hardening primer, a primer layer, a laminate, and a substrate with a metal film for forming a primer layer in a substrate with a metal film that sequentially includes a substrate, a primer layer, and a metal film.

Transparent conductive films formed by laminating transparent conductive materials on transparent plastic film substrates are widely used in flat panel displays such as liquid crystal displays and electroluminescence (EL) displays, touch panels, lighting, solar cells, electrical electronics, and other fields.

As a transparent conductive material, materials with indium oxide, indium tin oxide (ITO/Indium Tin Oxide) (hereinafter referred to as ITO) as the main component are widely used due to its high visible light transmittance, relatively low surface resistance and excellent environmental characteristics. However, the lower limit of the surface resistance of ITO is 50Ω/□, which is not suitable for use as an electrode for large displays due to its insufficient responsiveness. In addition, the ITO film is brittle and has poor bending resistance, and the surface resistance is high when bent, so it is difficult to cope with the flexibility of the display.

Therefore, the following materials and technologies have been developed: using vacuum evaporation, sputtering and other physical evaporation methods (PVD/Physical Vapor Deposition), chemical evaporation (CVD/Chemical Vapor Deposition) and other methods to form a metal film containing metal materials such as silver, copper, aluminum alloy, etc. on the substrate, and implement fine patterning, thereby using a metal mesh with invisible electrode pattern, or conductive ink made by nano-dispersing metal to replace ITO materials and technologies.

However, regarding the metal film substrate including the metal film as such an ITO substitute, if the metal film is directly formed on the substrate, the adhesion is poor and the metal film is easily peeled off, so the substrate is usually required to be primed. Therefore, the following technology is studied: as a primer treatment, an active energy ray-curable primer containing an organic material and/or an inorganic material having excellent affinity with the metal material is used to improve the adhesion between the substrate and the metal film (for example, Patent Documents 1 to 3).

[Prior art literature]

[Patent Literature]

Patent document 1: Japanese Patent Publication No. 2016-069653

Patent document 2: Japanese Patent Publication No. 2015-199946

Patent document 3: Japanese Patent Publication No. 2021-147493

However, most of the existing treatments using primers improve the adhesion between the metal film and the substrate while reducing the surface hardness of the primer layer. Therefore, damage (abrasion resistance) of the primer layer during the manufacturing and processing steps becomes a problem. Furthermore, the current situation is that the hardness, transparency, and alkali resistance of the primer layer cannot be satisfied.

Therefore, an embodiment of the present invention aims to provide a primer that can form a primer layer having excellent adhesion to a metal film and excellent surface abrasion resistance.

In order to solve the above problem, the inventor has repeatedly conducted diligent research and completed the following invention.

That is, one embodiment of the present invention is related to an active energy ray-curable primer, which is used to form a primer layer in a metal film substrate including a substrate, a primer layer, and a metal film in sequence, wherein the active energy ray-curable primer comprises: a first compound having three or more (meth)acryl groups, a second compound, and a photopolymerization initiator, wherein the second compound comprises at least one selected from the group consisting of a compound having a silsesquioxane skeleton, a metal compound having an organic group, a triazine thiol compound, and a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups, and the content of the first compound is 70% by mass or more in 100% by mass of the non-volatile components of the active energy ray-curable primer.

Another embodiment of the present invention is related to the active energy ray-curable primer, wherein the second compound includes a compound having a silsesquioxane skeleton, and the compound having a silsesquioxane skeleton includes a compound having the silsesquioxane skeleton and a (meth)acryl group.

Another embodiment of the present invention is related to the active energy ray-hardening primer, wherein the second compound includes the metal compound having an organic group, and the metal compound having an 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.

Another embodiment of the present invention is related to the active energy ray-hardening primer, wherein the second compound includes the metal compound having an organic group, and the metal of the metal compound having an organic group includes titanium, zirconium, or aluminum.

Another embodiment of the present invention is related to the active energy ray-hardening primer, wherein the second compound includes the triazine thiol compound, and the triazine thiol compound includes a triazine thiol compound having an active energy ray-hardening functional group.

Another embodiment of the present invention is related to the active energy ray-curable primer, wherein the second compound includes a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups, and the silane coupling agent includes a silane coupling agent having two or more alkoxysilyl groups and two or more (meth)acryl groups and having an organic structure in the main chain.

Another embodiment of the present invention is related to the active energy ray-curable primer, wherein the first compound includes a compound having three or more (meth)acryl groups and a nitrogen atom.

Another embodiment of the present invention is related to the active energy ray-hardening primer, wherein the compound having three or more (meth)acryl groups and a nitrogen atom includes a compound having three or more (meth)acryl groups and a urate ring skeleton.

Another embodiment of the present invention is related to the active energy ray-curable primer, wherein the content of the second compound is 1 mass % to 30 mass % in 100 mass % of the non-volatile components of the active energy ray-curable primer.

Another embodiment of the present invention relates to a primer layer formed by the active energy ray-hardening primer.

Another embodiment of the present invention relates to a laminate having a substrate and the base coating layer.

Another embodiment of the present invention relates to a substrate with a metal film, which sequentially comprises a substrate, the base coating layer, and a metal film.

According to one embodiment of the present invention, a primer can be provided that can form a primer layer having excellent adhesion to a metal film and excellent surface abrasion resistance.

Furthermore, it is possible to provide a laminate having a high scratch resistance on the surface of the base coating layer, and a metal film substrate having excellent adhesion between the substrate and the metal film, and also excellent hardness, transparency, and alkali resistance.

The following describes the implementation of the present invention, and first describes the terms used in this specification.

Furthermore, in this specification, when "(meth)acrylic acid", "(meth)acryl", and "(meth)acrylate" are expressed, unless otherwise specified, they are assumed to represent "acrylic acid or methacrylic acid", "acryl or methacryl", and "acrylate or methacrylate", respectively.

Unless otherwise specified, the various ingredients listed in this manual can be used individually or in combination of two or more.

《Active energy ray-hardening primer》

An active energy ray-hardening primer (hereinafter also referred to as a primer) of one embodiment of the present invention is an active energy ray-hardening primer for forming a primer layer in a metal film substrate including a substrate, a primer layer, and a metal film in sequence.

The primer of one embodiment of the present invention comprises a first compound having three or more (meth)acryloyl groups (hereinafter, also described as compound (A)), a second compound (hereinafter, also described as compound (B)), and a photopolymerization initiator (hereinafter, also described as photopolymerization initiator (C)), wherein the second compound comprises at least one selected from the group consisting of a compound having a silsesquioxane skeleton, a metal compound having an organic group, a triazine thiol compound, and a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups, and the content of the first compound is 70% by mass or more in 100% by mass of the non-volatile components of the active energy ray-curable primer.

By using this kind of primer, even when the metal film is thick, the primer layer formed can take into account both the adhesion with the metal film and the scratch resistance. Furthermore, it is possible to form an excellent primer layer with good transparency, hardness, and alkali resistance.

<Compound (A)>

Compound (A) is a compound having three or more (meth)acryloyl groups. Except for the case where it is the above-mentioned silane coupling agent.

Compound (A) is classified into compounds having a nitrogen atom (hereinafter, also referred to as compound (a1)) and compounds (a2) not having a nitrogen atom (hereinafter, also referred to as compound (a2)). Compound (a1) can be further classified into compounds having a urate ring skeleton (a1x) (hereinafter, also referred to as compound (a1x)) and compounds other than compound (a1x) (hereinafter, also referred to as compound (a1y)).

From the perspective of adhesion and alkali resistance to metal films, compound (A) is preferably compound (a1) having a nitrogen atom, and more preferably compound (a1x) having a urate ring skeleton. By using compound (A) as compound (a1), a base coating with better adhesion and alkali resistance to metal films can be obtained.

The urate structure is a trimer of an isocyanate compound having a nitrogen atom. Since it is a six-membered ring structure, (meth)acrylic groups are polymerized around its straight six-membered ring to cause a reaction. The synergistic effect of affinity with both the compound (B) and the metal film can show excellent adhesion to the metal film and alkali resistance, so it is preferred.

As the compound (A), specifically, for example, among the compounds (a1) having a nitrogen atom, the compound (a1x) includes trimers (isocyanurates) of (meth)acrylates having an isocyanate group such as tris(2-acryloxyethyl)isocyanurate, ethylene oxide (EO)-modified tris(2-acryloxyethyl)isocyanurate, propylene oxide (PO)-modified tris(2-acryloxyethyl)isocyanurate, and ε-caprolactone-modified tris(2-acryloxyethyl)isocyanurate; the compound (a1y) includes urethane acrylate, polyacrylic acid poly(meth)acrylate having a nitrogen atom other than a urate ring skeleton, and the like; the compound (a2) not having a nitrogen atom includes trihydroxymethylpropane tri(meth)acrylate, glycerol tri(meth)acrylate, and the like. Polyol poly(meth)acrylate compounds such as tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; in addition, polyacrylates of polymer polyols such as polyacrylic acid poly(meth)acrylates and polyester (meth)acrylates having three or more (meth)acryloyl groups; and polyepoxy (meth)acrylates, etc., but are not limited to these.

Examples of commercially available products of compound (a1x) include urethane acrylates having three or more (meth)acryloyl groups and a urethane ring skeleton (such as Miramer MU9800 manufactured by MIWON Co., Ltd.), tris(2-acryloxyethyl)isocyanurate (FANCRYL FA-731A manufactured by Showa Denko Materials Co., Ltd., NEW FRONTIER TEICA (GX-8430) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), EO-modified tris(2-acryloxyethyl)isocyanurate (Aronix M-313 and M-315 manufactured by Toagosei Co., Ltd., NK ester (NK-316 manufactured by Shin-Nakamura Chemical Co., Ltd.), and EO-modified tris(2-acryloxyethyl)isocyanurate (Aronix M-313 and M-315 manufactured by Toagosei Co., Ltd., and NK ester (NK-316 manufactured by Shin-Nakamura Chemical Co., Ltd.). Ester) A-9300, SARTOMER SR-368 manufactured by ARKEMA Co., Ltd., etc.), PO modified tris(2-acryloyloxyethyl) isocyanurate, ε-caprolactone modified tris(2-acryloyloxyethyl) isocyanurate (NK Ester A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), etc., but not limited to these.

Commercially available products of compound (a1y) include, for example, urethane acrylates having no urethane ring skeleton and having three or more (meth)acryloyl groups (such as Miramer PU610 manufactured by MIWON), polyacrylic acid poly(meth)acrylates having nitrogen atoms other than the urethane ring skeleton and having three or more (meth)acryloyl groups, etc., but are not limited to these.

Examples of commercially available products of compound (a2) include trihydroxymethylpropane tri(meth)acrylate (such as Miramer M300 manufactured by Miwon Co., Ltd.), glycerol tri(meth)acrylate (such as Aronix M-930 manufactured by Toagosei Co., Ltd.), dipentaerythritol penta(meth)acrylate (such as SR399 manufactured by Sartomer Co., Ltd.), dipentaerythritol hexa(meth)acrylate (such as Miramer M600 manufactured by Miwon Co., Ltd.), pentaerythritol tri(meth)acrylate (such as Miramer M340 manufactured by Miwon Co., Ltd.), and pentaerythritol tetra(meth)acrylate (such as Light Acrylate manufactured by Kyoeisha Chemical Co., Ltd.). acrylate) PE-4A, etc.); in addition, polyacrylic acid poly(meth)acrylates having three or more (meth)acryloyl groups and no nitrogen atom (such as KRM8912 manufactured by Daicel-Cytec Co., Ltd.), polyester (meth)acrylates having three or more (meth)acryloyl groups, etc., polyacrylates of polymer polyols (such as EBECRYL 800 manufactured by Daicel-Cytec Co., Ltd.); and polyepoxy (meth)acrylates (such as EBECRYL 3603 manufactured by Daicel-Cytec Co., Ltd.), etc., but are not limited to these.

The content of compound (A) is 70% by mass or more in 100% by mass of the non-volatile components of the active energy ray-curable primer. The upper limit of the content of compound (A) is less than 100% by mass, preferably less than 98% by mass.

In terms of obtaining a base coat with excellent hardness and abrasion resistance, it is preferably 72.5% by mass or more, and more preferably 75% by mass or more.

<Compound (B)>

The compound (B) is at least one of a compound having a silsesquioxane skeleton (hereinafter, also described as a compound having a silsesquioxane skeleton (B1) or compound (B1)), a metal compound having an organic group (hereinafter, also described as a metal compound having an organic group (B2) or metal compound (B2)), a triazinethiol compound (hereinafter, also described as a triazinethiol compound (B3)), and a silane coupling agent having two or more alkoxysilyl groups or two or more reactive functional groups (hereinafter, also described as a silane coupling agent (B4)). Here, the metal compound (B2) excludes compounds containing any one of a silsesquioxane skeleton, a triazinethiol ring, and an organic silyl group as an organic group. The triazinethiol compound (B3) excludes compounds containing any one of a silsesquioxane skeleton and an organic silyl group. Silane coupling agents (B4) exclude compounds containing a silsesquioxane skeleton.

(Compound (B1) having a silsesquioxane skeleton)

The silsesquioxane skeleton is a straight skeleton. The silsesquioxane skeleton has good alkali resistance, and the adhesion between the base coating and the metal film is improved by the interaction with oxygen atoms or some residual silanol groups without reducing the scratch resistance of the base coating.

The compound (B1) having a silsesquioxane skeleton is not particularly limited if it is a network polymer having a structure of silsesquioxane, that is, (RSiO _1.5 ) _n obtained by hydrolyzing and condensing trifunctional silane, or a compound having a polyhedral cluster structure, and a compound having a silsesquioxane skeleton having a known conventional structure such as a random structure, a ladder structure, a complete cage structure, an incomplete cage structure, etc. can be used. In (RSiO _1.5 ) _n , n is an integer greater than 2. As n, an integer of 2 to 200 is preferred, an integer of 2 to 150 is more preferred, and an integer of 2 to 100 is further preferred. In (RSiO _1.5 ) _n , R is preferably an organic group such as a methyl group, an ethyl group, a phenyl group, or a (meth)acryl group.

The compound (B1) having a silsesquioxane skeleton is preferably a compound (b1) having a silsesquioxane skeleton in which at least a portion of R in (RSiO _1.5 ) _n is a (meth)acryl group and a (meth)acryl group. By having a (meth)acryl group, the reduction in the scratch resistance of the base coating can be further suppressed, and not only the scratch resistance is high, but also the alkali resistance and the adhesion to the metal film can be improved.

Furthermore, in the case of having a silsesquioxane skeleton, even if it has three or more (meth)acryloyl groups, it is classified as a compound having a silsesquioxane skeleton (B1).

Commercially available products of the compound (B1) having a silsesquioxane skeleton include, for example, the compound (b1) having a silsesquioxane skeleton and a (meth)acryloyl group: AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20, MAC-SQ HDM, etc. manufactured by Toagosei Co., Ltd.

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

The content of the compound (B1) having a silsesquioxane skeleton is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 27% by mass, and even more preferably 5% by mass to 25% by mass in 100% by mass of the non-volatile components of the active energy ray-curable primer.

If the content is within this range, even if the metal film is thick, the adhesion and alkali resistance between the base coating and the metal film are good, so it is preferred.

(Metal compound having an organic group (B2) and triazine thiol compound (B3))

The metal compound (B2) and triazine thiol compound (B3) having an organic group are compounds having 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. In the metal compound (B2) having an organic group, for example, the coordination site of the chelate ligand of the metal chelate compound (B2y) can interact with both organic and inorganic materials. In the triazine thiol compound (B3), the triazine skeleton can interact with an organic material, and the thiol group can interact with an inorganic material.

The metal compound (B2) and triazine thiol compound (B3) having an organic group can form a stable and uniform composition with the organic materials constituting other components of the primer, and also have good adhesion to the metal film directly laminated on the primer layer formed by hardening the primer containing them.

From the viewpoint of hardness, scratch resistance, and metal film adhesion, the content of the metal compound (B2) or triazine thiol compound (B3) having an organic group is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, and further preferably 5% by mass to 15% by mass in 100% by mass of the non-volatile components of the active energy ray-curable primer.

[Metal compound with organic group (B2)]

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

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

As alkyl groups, there are: methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, etc.

As alkenyl groups, there are: vinyl, propenyl, butenyl, pentenyl, hexenyl, phenylene, etc.

Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, etc.

As aromatic groups, there are: phenyl, tolyl, xylyl, naphthyl, etc.

As acyl groups, there can be listed: acetyl, propionyl, stearyl, oxalyl, propadienyl, benzoyl, cinnamyl, acryl, methacryl, etc.

Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and phenoxy.

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

Specifically, the metal alkoxide compound (B2x) is a compound represented by the general formula M(OR)n, the metal chelate compound (B2y) is a compound formed by covalent bonding and coordination bonding of donor atoms contained in 1 mol of ligands relative to 1 mol of metal atoms, 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 greater than 1.

Among these, from the perspective of reactivity, metal alkoxide compounds (B2x) can further improve the adhesion between the metal and the base coating layer, and from the perspective of stability, metal chelate compounds (B2y) can further improve the transparency of the coating film, so they are preferred.

In addition, the metal contained in the metal compound (B2) includes, for example, metals of Group 4, Group 13, and Group 14 of the periodic table. Among these, organic metal compounds containing metals with small period numbers are highly active and have excellent crosslinking properties, and preferably contain metals of Group 4 or Group 13 of the periodic table.

As metals, specifically, for example, polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, boron, cobalt, manganese, selenium, ruthenium, gallium, and cadmium can be listed. Among these, titanium, zirconium, and aluminum are preferred from the viewpoint of reactivity with organic components contained in the primer and adhesion with the metal film directly deposited on the primer, and titanium or zirconium is more preferred.

That is, from the perspective of adhesion to the metal film, organic titanium compounds, organic aluminum compounds, or organic zirconium compounds are preferred, and organic titanium compounds or organic zirconium compounds are more preferred.

(Metal alkoxide compounds (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 with 1 or more carbon atoms.

As the metal alkoxide compound (B2x), titanium alkoxide compounds, zirconium alkoxide compounds, or aluminum alkoxide compounds can be listed. From the viewpoint of adhesion with the metal film, titanium alkoxide compounds or zirconium alkoxide compounds are preferred.

As titanium alcohol compounds, there are: tetraisopropyl titanium ester, tetra-n-butyl titanium ester, butyl titanium ester dimer, tetraoctyl titanium ester, tetra-tert-butyl titanium ester, tetrastearyl titanium ester, tetra-isopropoxy titanium, tetra(2-ethylhexyloxy) titanium, isopropoxy octyl glycolic acid titanium, etc.

As commercially available products, there are: ORGATIX TA-8, TA-21, TA-23, TA-30, TA-12, TA-80, TA-90 manufactured by Matsumoto Fine Chemical Co., Ltd., Plenact 46B, 55, 41B, 38S, 338X, 44, 9SA manufactured by Ajinomoto Fine-Techno Co., Ltd., A-1, TOT, TOG manufactured by Nippon Soda Co., Ltd., etc.

As zirconium alcohol compounds, there are tetra-n-propyl zirconate, tetra-isopropyl zirconate, n-propyl zirconate, n-butyl zirconate, etc.

Examples of commercially available products include ORGATIX ZA-45 and ZA-65 manufactured by Matsumoto Fine Chemical Co., Ltd.

As aluminum alcohol compounds, there are: aluminum 2-butoxide, aluminum trimethoxide, aluminum triethoxide, aluminum tripropoxide, etc.

Examples of commercially available products include ORGATIX AL-3001 manufactured by Matsumoto Fine Chemical Co., Ltd.

(Metal chelate compound (B2y))

The metal chelate compound (B2y) is a compound formed by covalent bonding and coordination bonding of donor atoms contained in one mole of ligands relative to one mole of metal atoms.

Examples of the metal chelate compound (B2y) include titanium chelate compounds, zirconium chelate compounds, and aluminum chelate compounds. From the perspective of adhesion to the metal film, titanium chelate compounds and zirconium chelate compounds are preferred.

As chelating agents constituting chelate ligands, β-diketones, β-ketoesters, polyols, alkanolamines, and hydroxycarboxylic acids can be cited, but are not particularly limited to these.

As β-diketone, there is no particular limitation if it is coordinated as a chelating agent. For example, specifically, it can be 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, diphenylmethane, thiophenecarbonyltrifluoroacetone, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, etc.

There is no particular limitation on the β-ketoester, and specific examples thereof include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl trimethylacetoacetate, methyl isobutyryl acetate, methyl hexanoyl acetate, methyl lauryl acetate, etc.

There is no particular limitation on the polyols, and examples thereof include: 1,2-ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,2-pentanediol, 2,3-butylene glycol, 2,3-pentanediol, glycerol, diethylene glycol, hexanediol, etc.

There is no particular limitation on the alkanolamines, and examples thereof include: N,N-dimethylethanolamine, N,N-diethylethanolamine, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-n-butylethanolamine, N-n-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, triethanolamine, diethanolamine, monoethanolamine, etc.

The hydroxy carboxylic acid is not particularly limited, and examples thereof include glycolic acid, lactic acid, tartaric acid, citric acid, apple acid, gluconic acid, etc.

As titanium chelate compounds, there are: titanium acetylacetonate, titanium tetraacetylacetonate, titanium octyl glycolate, titanium ethylacetylacetate, titanium lactate, titanium triethanolaluminate, di-isopropoxy. bis(acetylacetonate)titanium, propanedioxybis(ethylacetylacetate)titanium, etc.

As commercially available products, there are: ORGATIX TC-120, TC-310, TC-315, TC-400, TC-500, TC-510 manufactured by Matsumoto Fine Chemical Co., Ltd., Plenact 138S, 238S manufactured by Ajinomoto Fine-Techno Co., Ltd., T-50, T-60 manufactured by Nippon Soda Co., Ltd., etc.

Examples of zirconium chelate compounds include: zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetylacetate, etc.

Examples of commercially available products include: ORGATIX ZC-150, ZC-162, ZC-540, ZC-580, ZC-700, etc. manufactured by Matsumoto Fine Chemical Co., Ltd.

As aluminum chelate compounds, there are: aluminum triacetylacetonate, aluminum diethylacetylacetate monoacetylacetonate, aluminum triethylacetylacetate, aluminum diisopropionate, etc.

Examples of commercially available products include: ORGATIX AL-3100, AL-3200, AL-3215 manufactured by Matsumoto Fine Chemical Co., Ltd., and Plenact AL-M manufactured by Ajinomoto Fine-Techno Co., Ltd.

(Metal acetate 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 with a carbon number of 1 or more, and n represents an integer of 1 or more.

As the metal acylate compound (B2z), titanium acylate compounds, zirconium acylate compounds, or aluminum acylate compounds can be listed. From the viewpoint of adhesion with the metal film, titanium acylate compounds or zirconium acylate compounds are preferred.

As titanium acylate compounds, there can be listed: titanium isostearate, tri-n-butoxy titanium monostearate, di-isopropoxy titanium distearate, titanium stearate, di-isopropoxy titanium diisostearate, (2-n-butoxycarbonylbenzoyloxy)tributoxy titanium, etc.

As commercially available products, there are: ORGATIX 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, TBP, etc. manufactured by Nippon Soda Co., Ltd.

Examples of zirconium acylate compounds include zirconium octanoate compounds, zirconium stearate, etc.

Examples of commercially available products include ORGATIX ZC-200 and ZC-320 manufactured by Matsumoto Fine Chemical Co., Ltd.

As aluminum acylate compounds, there are: titanium isostearate, aluminum stearate, aluminum tristearate, aluminum diacetate-monostearate, etc.

Examples of commercially available products include ORGATIX TC-800 manufactured by Matsumoto Fine Chemical Co., Ltd.

[Triazine thiol compound (B3)]

The triazine thiol compound (B3) is a compound having at least one thiol group bonded to a triazine skeleton. The triazine thiol compound (B3) can be classified into a compound (B3x) having an active energy ray-hardening functional group (hereinafter, also described as a triazine thiol compound (B3x)) and a compound (B3y) not having an active energy ray-hardening functional group (hereinafter, also described as a triazine thiol compound (B3y)). Among these, the compound (B3x) having an active energy ray-hardening functional group is preferred from the viewpoint of reactivity with the organic component contained in the primer and adhesion with the metal film directly deposited on the primer. By having an active energy ray-hardening functional group, the compound is firmly bonded in the primer, and the adhesion with the metal film and alkali resistance are further improved.

Examples of triazine thiol compounds (B3x) having an active energy ray-hardening functional group include 6-diallylamino-1,3,5-triazine-2,4-dithiol, 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithiol, and 6-(allylamino)-1,3,5-triazine-2,4-dithiol.

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

Examples of triazinethiol compounds (B3y) that do not have an active energy ray-hardening functional group include 1,3,5-triazine-2,4,6-trithiol, 2-(dibutylamino)-1,3,5-triazine-4,6-dithiol, 6-(diisopropylamino)-1,3,5-triazine-2,4-dithiol, 6-(diisobutylamino)-1,3,5-triazine-2,4-dithiol, 6-di(2-ethylhexyl)amino-1,3,5-triazine-2,4-dithiol, and 6-(butylamino)-1,3,5-triazine-2,4-dithiol.

Commercially available products include: TSH manufactured by Kawaguchi Chemical Industry Co., Ltd.; 1,3,5-triazine-2,4,6-trithiol, 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; 6-di(2-ethylhexyl)amino-1,3,5-triazine-2,4-dithiol, etc.

(Silane coupling agent (B4))

The alkoxysilyl group in the silane coupling agent (B4) has an alkoxy group on the silicon atom, and can be monoalkoxysilyl, dialkoxysilyl, or trialkoxysilyl, preferably trialkoxysilyl. Among the trialkoxysilyl groups, trimethoxysilyl, triethoxysilyl, or tripropoxysilyl is preferred from the viewpoint of hydrolysis reactivity.

Furthermore, the alkoxy groups bonded to one silicon can be the same or different, and the alkyl group possessed by the alkoxy group can be either a branched alkyl group or a straight-chain alkyl group, and can also have a substituent.

Specifically, the alkoxy group includes methoxy, ethoxy, propoxy, etc.

The silane coupling agent (B4) has two or more alkoxysilyl groups, preferably three or more alkoxysilyl groups. In addition, it has two or more reactive functional groups, preferably three or more reactive functional groups.

There is no upper limit on the number of substituents of the alkoxyalkyl group and the reactive functional group, and it can be appropriately set according to the molecular weight of the resin that becomes the main skeleton, etc.

It is better to be below 100, and more preferably below 50.

As reactive functional groups, for example, there can be listed: amino group, epoxy group, (meth)acryl group, thiol group, isocyanate group, among which (meth)acryl group is preferred because it further suppresses the reduction of the scratch resistance of the base coating layer, not only has high scratch resistance, but also can improve alkali resistance and adhesion with metal film.

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

Among them, the preferred ones are silane coupling agents with organic structures such as resins as the main chain.

Furthermore, the organic structure of resins, etc., is not limited as long as it has a skeleton with a repeating structure, and can be either an oligomer type or a polymer type.

When used as an oligomer silane coupling agent or a polymer silane coupling agent, the weight average molecular weight is preferably 500~100000, and more preferably 700~50000.

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

The organic structure oligomers or polymers as resins are 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 them, acrylic oligomers or polymers are preferred.

Among these, the polymer type silane coupling agent (b4) (hereinafter also described as silane coupling agent (b4)) having two or more alkoxysilyl groups and two or more (meth)acryl groups and having an organic structure in the main chain is preferred because it further suppresses the reduction of the scratch resistance of the base coating layer, not only has high scratch resistance, but also can improve alkali resistance and adhesion to the metal film.

The silane coupling agent (B4) can be a synthetic product or a commercial product.

As a synthesis example, it can be obtained by copolymerizing an ethylenically unsaturated monomer having an alkoxysilyl group and an ethylenically unsaturated monomer having a reactive functional group.

In addition, regarding the silane coupling agent (b4), there can be cited a method of adding a molar amount of (meth)acrylic acid such as an 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 a method of adding a molar amount of an ethylenically unsaturated monomer having a hydroxyl group such as an isocyanate group to an acrylic polymer obtained by copolymerizing an ethylenically unsaturated monomer having an alkoxysilyl group and an ethylenically unsaturated monomer having an isocyanate group, etc., but the present invention is not limited thereto.

By adjusting the amount of monomer used at this time, a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups can be prepared.

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 manufactured by Shin-Etsu Chemical Co., Ltd.

In addition, as polymer-type silane coupling agents (b4) having two or more alkoxysilyl groups and two or more (meth)acryl groups, there are: X-12-1048, X-12-1050.

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

The content of the silane coupling agent (B4) can be 1% to 30% by mass in 100% by mass of the non-volatile components of the active energy ray-curable primer, 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.

By setting the range to this, even when the metal film is thick, the adhesion and alkali resistance between the base coating and the metal film are improved, the scratch resistance is not reduced, and the cost is not increased, so it is better.

<Photopolymerization initiator (C)>

As the photopolymerization initiator (C), for example, a monocarbonyl photopolymerization initiator, a dicarbonyl photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin ether photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, an aminocarbonyl photopolymerization initiator, etc. can be used.

Photopolymerization initiator (C) can be used together with sensitizer.

For example, monocarbonyl photopolymerization initiators such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2-/4-iso-propylthioanthrone, 2,4-diethylthioanthrone, 2,4-dichlorothioanthrone, and 1-chloro-4-propoxythioanthrone can be listed; 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxythioanthrone can be listed; Dicarbonyl series such as phenylacetic acid esters Photopolymerization initiators; 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenyl ketone, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-pyroline Acetophenone-based photopolymerization initiators such as 1-phenyl-1,2-propanedione-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-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 n-butyl ether; 2,4,6-trimethylbenzyldiphenylphosphine oxide, and 4-n-propylphenyl-bis(2,6-dichlorobenzyl)phosphine oxide; ) phosphine oxide and other acyl phosphine oxide-based photopolymerization initiators; and ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isopentyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethylbenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, and 2,5'-bis(4-diethylaminobenzylidene)cyclopentanone and other aminocarbonyl-based photopolymerization initiators, etc.

Commercially available products of photopolymerization initiators (C) include: Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, Esacure one manufactured by IGM-Resins B.V., and Lucirin TPO manufactured by BASF. In particular, Omnirad 184 or Esacure one is preferred from the perspective of yellowing resistance after active energy ray curing.

The content of the photopolymerization initiator (C) is not limited as long as it includes an amount that allows the primer layer to be cured by ultraviolet rays to have predetermined physical properties. From the perspective of the curing speed, hardness, and scratch resistance of the primer layer, it is preferably 1% to 15% by mass, and more preferably 3% to 10% by mass, based on 100% by mass of the non-volatile components of the active energy ray-curable primer.

<Other ingredients>

The primer can be obtained by mixing a compound (A) having three or more (meth)acrylic groups, a compound (B), and a photopolymerization initiator (C). In addition, if necessary, other components such as a compound (A') having one or two (meth)acrylic groups (hereinafter also referred to as compound (A')), an organic solvent (D), and an additive may also be contained.

As additives, we can cite: thermosetting resins, polymerization inhibitors, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, anti-adhesive agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, dyes, etc.

[Compound (A')]

Compound (A') is a compound having one or two (meth)acryloyl groups.

Examples of compound (A') include: di(meth)acrylates such as 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and bisphenol A ethylene oxide-modified di(meth)acrylate; 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, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate, but are not limited to these.

[Organic solvent (D)]

The primer may also contain an organic solvent (D).

As the organic solvent (D), the following can be used: 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, isobutyl acetate; alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol; glycol ether organic solvents such as propylene glycol monomethyl ether, and other well-known organic solvents.

When the primer contains an organic solvent (D), the content of the organic solvent (D) is preferably such that the concentration of the non-volatile components of the primer is in the range of 1 mass % to 60 mass % from the viewpoint of coating properties and film-forming properties.

[Substrate with metal film]

A metal film-bearing substrate in an embodiment of the present invention sequentially comprises: a substrate, a base coating layer formed by a base coating agent in an embodiment of the present invention, and a metal film.

The primer is used to form a metal film on the surface of the substrate. For example, as described below, the primer is applied on the substrate and hardened by active energy rays to obtain a primer layer, and a laminate having a primer layer is made. A metal film is formed on the primer layer of the laminate, thereby making a substrate with a metal film.

Since the base coating layer of one embodiment of the present invention has excellent adhesion with the metal film, it is possible to suppress the peeling of the metal film when the base coating layer and the metal film are directly laminated.

Furthermore, if necessary, other resin layers may be further provided between the substrate and the primer layer. Examples of other resin layers include: an antistatic resin layer for preventing charging during the manufacturing process, a hard coating resin layer for further improving the hardness of the laminate of an embodiment of the present invention, and a tackifying resin layer for improving the adhesion between the substrate and the primer layer of an embodiment of the present invention, but are not limited thereto.

The substrate (also called a support) is not particularly limited, and examples thereof include glass, synthetic resin moldings, and films. Examples of synthetic resin moldings include polymethyl methacrylate resins, copolymer resins containing methyl methacrylate as a main component, polystyrene resins, styrene-methyl methacrylate copolymer resins, styrene-acrylonitrile copolymer resins, polycarbonate resins, cellulose acetate butyrate resins, polyallyl diglycol carbonate resins, polyvinyl chloride resins, polyester resins, and other synthetic resin moldings.

In addition, as the film, for example, there can be listed: polyester film, polyethylene film, polypropylene film, cellophane film, diacetyl cellulose film, triacetyl cellulose (TAC) film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, polyolefin film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film, acrylic film, etc.

The thickness of the base coating is not particularly limited, but is usually around 0.1μm~5μm. From the perspective of hardness and cost, it is preferably 0.5μm~3μm.

The metal film substrate can also be used in the light reflection film of liquid crystal display, the decorative film for the back of smart phones, etc., the flexible printed wiring board formed by patterning the formed metal film circuit, and the antenna of the radio frequency identification (RFID) tag, etc., and has also been studied in the antenna of the fifth generation mobile communication system, etc.

Therefore, in order to improve the optical and electrical properties of the laminate with metal film, it is required to increase the thickness of the metal film. As optical properties, the reflectivity when used as a light reflective film and the concealment when used as a decorative film can be listed, and as electrical properties, the receiving sensitivity when used as an antenna film and the response sensitivity when used as a conductive film can be listed. However, in the past, if the thickness of the metal film was increased, the stress generated when the metal film was formed became significantly larger than that of a thin film, and the adhesion with the base coating tended to be further reduced, and the adhesion between the substrate and the metal film became a problem.

Furthermore, when the metal film substrate is used in decorative films, flexible printed wiring boards, RFID tags, or antenna films for fifth-generation mobile communication systems, the formed metal film circuit needs to be patterned, and during patterning, alkaline resistance is required when immersed in an etching solution (mainly an alkaline solution). In addition, when used as a conductive film, the visibility of the display needs to be improved. When used as an antenna film, it is sometimes attached to a building or a car window. In order to make the visibility good, the base coating needs to have transparency.

One embodiment of the present invention can provide a primer that can form a primer layer with excellent hardness, transparency, and alkali resistance even when the metal film is relatively thick.

The thickness of the metal film is not particularly limited as long as it satisfies the decorative, optical, and electrical properties, and is usually greater than 0.1 μm and less than 0.5 μm. However, depending on the application, the film thickness is sometimes set to 0.5 μm or more to improve the optical or electrical properties. The primer of one embodiment of the present invention has excellent adhesion, so even if the film thickness of the metal film is relatively thick, such as 1 μm or more, a laminate that can take into account both adhesion and scratch resistance can be made. From the perspective of manufacturing cost and the miniaturization and lightweight of displays and antenna films in recent years, the thickness of the metal film is preferably less than 5 μm.

As metal films, for example, metal evaporation films, metal sputtering films, and metal CVD films can be listed. As metal films, metal evaporation films or metal sputtering films are particularly preferred. As metals constituting the metal film, copper, aluminum, silver, etc. can be listed, but are not limited to these. The primer is particularly effective when copper is used as the metal film.

Furthermore, even if the metal film is thick, the laminate of one embodiment of the present invention can be suitably used in antenna film applications that require improved reception sensitivity as an electrical characteristic, due to its excellent adhesion. In addition, since the response sensitivity can be improved, it can also be suitably used in conductive films, etc.

Furthermore, since the base coating 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 base coating of one embodiment of the present invention has excellent alkali resistance, the laminate of one embodiment of the present invention can also be suitably used in decorative films requiring decorative patterns and conductive films, antenna films, flexible printed wiring boards, etc. requiring circuit patterns.

[Method for manufacturing a substrate with a metal film]

The method for manufacturing a metal film substrate in one embodiment of the present invention is not particularly limited. For example, the following can be cited: (1) applying a primer on the surface of a substrate (for example, if the substrate is a film-like substrate, one side or both sides), (2) applying heat to the substrate, and (3) further irradiating the substrate with active energy rays to harden it to form a primer layer to manufacture a laminate; and (4) forming a metal film on the primer layer to manufacture a metal film substrate.

That is, it is preferred to manufacture a laminate having a substrate and a base coating layer by steps (1) to (3), and to form a metal film on the base coating layer of the laminate to manufacture a substrate with a metal film.

Since the base coating layer of one embodiment of the present invention has high abrasion resistance, it is possible to prevent damage to the base coating layer during the manufacturing and processing steps of the metal film substrate.

Regarding step (1), the conditions for applying the primer on the surface of the substrate are not particularly limited. Examples of the application method include spraying, roller coating, reverse roller coating, gravure coating, doctor blade coating, rod coating, and spot coating. In addition, the application amount is not particularly limited, but is generally about 0.01 g/ ^m2 to 10 g/ ^m2 in terms of dry non-volatile components.

Regarding step (2), there is no particular limitation on the conditions for applying heat to the substrate, but the temperature is usually around 80°C to 150°C and the time is around 10 seconds to 2 minutes.

Regarding step (3), the conditions for irradiating the active energy ray are not particularly limited. Examples of the active energy ray include ultraviolet rays and electron beams. Examples of the supply source of ultraviolet rays include high-pressure mercury lamps and metal halide lamps, and the irradiation energy thereof is generally about 100 mJ/ ^cm2 to 2,000 mJ/ ^cm2 . Examples of the supply method of electron beams include scanning electron beam irradiation and curtain electron beam irradiation, and the irradiation energy thereof is generally about 10 kGy to 200 kGy.

Regarding step (4), there is no particular limitation on the method of forming a metal film on the base coating layer, and dry coating is preferred. Specifically, for example, physical methods such as vacuum evaporation or sputtering; chemical methods such as CVD (chemical vapor deposition), etc. can be cited.

In addition, when the metal film substrate is used as a decorative film, antenna film, conductive film, or flexible printed wiring board, the metal film circuit can also be patterned. The manufacturing method of the metal film substrate at this time is also not particularly limited. For example, the following method can be listed: various anti-etching agents are applied to the metal film side of the metal film substrate obtained by steps (1) to (4), and after drawing the circuit pattern, it is immersed in an etching solution (alkaline solution) to remove the anti-etching agent. The shape of the circuit pattern can be any form such as thin lines, dots, meshes, and surfaces.

In this manual, the numerical range represented by "~" indicates a range that includes the numerical values recorded before and after "~" as the minimum and maximum values, respectively. In the numerical range recorded in stages in this manual, the upper limit or lower limit of the numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of the numerical range of another stage.

This invention is related to 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 subject matter of Japanese Patent Application No. 2021-176214 filed on October 28, 2021, and all the disclosures thereof are incorporated into this specification by reference.

[Implementation example]

The present invention is described in more detail below by using examples and comparative examples, but the following examples do not limit the technical scope of the present invention in any way. Furthermore, in the examples, "parts" refers to "parts by mass", and "%" refers to "% by mass".

In addition, the amounts in the table are in parts by mass, and are converted to non-volatile components except for solvents. In addition, blank columns in the table indicate that no ingredients are mixed.

《Experimental Example 1》

<Manufacturing of acrylic copolymer>

Manufacturing example 1

In a reaction vessel including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, 40.8 parts (13.6 mol%) of hydroxy ethyl 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 (about 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate were placed, and the reaction system was set to 70°C. Then, 1.2 parts of 2,2'-azobis(2,4-dimethyl valeronitrile) (ABN-V) was added, and the temperature was kept at about 70°C for 6 hours. Next, 2.4 parts of ABN-V were added, and the reaction system was further kept at a temperature near that temperature for 6 hours. After that, by cooling the reaction system to room temperature, 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 component of 35.0% was obtained. The hydroxyl value was determined by potentiometric titration in accordance with Japanese Industrial Standards (JIS) K 0070.

(Preparation of primer)

[Implementation Example 1]

94 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.) as compound (A), 6 parts of MAC-SQ HDM (manufactured by Toagosei Co., Ltd.) as compound (B), and 5 parts of Esacure one (manufactured by DKSH Co., Ltd., Japan) as photopolymerization initiator (C) were fully mixed, and propylene glycol monomethyl ether as an organic solvent was adjusted to a non-volatile component concentration of 40% to obtain a primer.

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

Except that the composition and mixing amount of each component were set to those shown in Table 1 (converted to mass parts of non-volatile components), a primer with a non-volatile component concentration of 40% was obtained in the same manner as in Example 1.

The 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 without a nitrogen atom

． Aronix M-403 (a mixture of dipentaerythritol hexaacrylate (number of functional groups: six): 40%~50% and dipentaerythritol pentaacrylate (number of functional groups: five): 50%~60%; manufactured by Toa Gosei Co., Ltd.)

(Compound (a1y)): A compound having a nitrogen atom other than compound (a1x)

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

(Compound (a1x)): A compound having a urate ring skeleton

． Miramer MU9800 (urethane acrylate with urethane ring skeleton, weight average molecular weight: 3500, number of functional groups: nine, manufactured by MIWON)

． Aronix M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: three, manufactured by Toa Gosei Co., Ltd.)

<Compound (A')>: A compound having one or two (meth)acryloyl groups

．NK Ester A-DCP (tricyclodecanedimethanol diacrylate, molecular weight: 304, number of acryloyl groups: two, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Inert resin>

． Acrylic copolymer (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%)

<Compound (B)>

Compound (B1): a compound having a silsesquioxane skeleton

(Others): Compounds other than compound (b1)

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

(Compound (b1)): Compound having a (meth)acryloyl group

．AC-SQ SI20 (with acryloyl group; manufactured by Toa Gosei Co., Ltd.)

. MAC-SQ HDM (containing methacrylic acid group; propylene glycol monobutyl ether solution with a non-volatile component concentration of 50%, manufactured by Toa Gosei Co., Ltd.)

<Photopolymerization initiator (C)>

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

《Production of base coat and layered bodies》

The primers obtained in the examples and comparative examples were applied onto 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 was 1.0 μm, and then irradiated with ultraviolet rays of 500 mJ/ ^cm2 using a high-pressure mercury lamp to form a primer layer, thereby producing a laminate.

《HZ[%]: Determination of haze value》

For the laminated body produced as described above, the haze value (HZ) of the base coating surface was measured using the "Haze meter SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. The evaluation criteria are as follows. If it is less than 2.0%, there is no problem in practical use.

[Evaluation criteria]

． Best: less than 1.0%

． Good: 1.0% or more and less than 2.0%

．Defective: more than 2.0%

《Pencil Hardness》

For the manufactured laminate, pencils of various hardnesses were made to touch the surface of the base coating layer of the laminate at an angle of 45° in accordance with JIS K5600-5-4, and a load was applied to perform a scratch test. The hardness of the hardest pencil that was not damaged was set as the pencil hardness.

The harder the pencil hardness, the better. If it is H or above, it can be used without any problems in practical use. If it is F or below, it may have defects such as scratches and cannot be used in practice.

《Abrasion resistance》

The abrasion resistance of the produced laminate was evaluated using the "Gakushin type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. Steel wool #0000 was mounted on a friction piece (surface area 1 cm ² ) with a load of 200g, and it was moved back and forth 10 times on the surface of the base coating (1cm×15cm). Afterwards, the number of scratches on the surface of the base coating was counted and evaluated according to the following criteria. The fewer the number of scratches, the better. If there are 10 or less, it can be used without any problem in practical use.

[Evaluation criteria]

． 3: No scratches (0)

．2: There are more than 1 scratch and less than 10 scratches

． 1: More than 11 scratches

《Copper Adhesion》

On the base coat of the produced laminate, copper was sputtered to a thickness of 0.5μm, 1μm, and 2μm using a "Magnetron sputter MSP-30T" manufactured by Vacuum Device Co., Ltd. to form a copper film. Regarding the adhesion between the copper film and the base coat, scratches were made on the copper film in a checkerboard pattern with a cutter at intervals of 1mm to form a 100-mesh grid pattern. Then, a cellophane tape was attached to cover the entire checkerboard scratches and removed. The peeling state of the copper film was visually observed and evaluated according to the following criteria. The less peeling, the better. If it is 3 or above on the evaluation standard, it can be used without any practical problems.

[Evaluation criteria]

．5: The area around the scratched line is completely smooth, and no grid has peeled off.

．4: Small peeling of the copper film was observed around the intersections of the scratches, but the total peeling area was less than 5% of the chessboard.

．3: The copper film peels off along the edge of the scratch, or the copper film peels off at the intersection of the scratch, or the total peeling area is more than 5% and less than 15% of the chessboard.

． 2: The total area of the peeled pieces is greater than 15% and less than 35% of the board.

． 1: The total area of the peeled pieces is more than 35% and less than 80% of the chessboard.

. 0: The total area of the peeling is more than 80% of the checkerboard pattern, and peeling is also observed outside the checkerboard pattern.

《Alkali resistance》

The laminate with a copper film (thickness 500nm and 1μm) that has not been evaluated for copper adhesion was immersed in a 5% sodium hydroxide aqueous solution heated to 40°C for 5 minutes and then fully washed with water. It was then dried in an oven heated to 100°C for 15 minutes to remove moisture, and then evaluated for alkali resistance in the same way as the copper adhesion evaluation method. The less peeling, the better. If it is 3 or above, it can be used without any problems in practice.

As shown in Table 1, it can be confirmed that: by using a primer of an embodiment of the present invention, the adhesion and abrasion resistance of the formed primer layer and the metal film can be taken into account, and the transparency, hardness, and alkali resistance are also excellent. It can be seen that the obtained metal film substrate is a metal film substrate with excellent adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance.

Among them, even when the metal film is as thick as 1μm or more, the good adhesion makes it suitable for applications requiring thick metal films and improved optical and electrical properties in recent years.

《Experimental Example 2》

<Manufacturing of acrylic copolymer>

Manufacturing Example 1A

In a reaction vessel including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, 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 (about 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate were placed, and the reaction system was set to 70°C. Then, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (ABN-V) was added, and the temperature was kept at about 70°C for 6 hours. Then, 2.4 parts of ABN-V were added, and the reaction system was further kept at about the same temperature for 6 hours. After that, by cooling the reaction system to room temperature, 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 component of 35.0% was obtained. The hydroxyl value was determined by the potentiometric titration method in accordance with JIS K 0070.

(Preparation of primer)

[Example 1A]

94 parts of Aronix M-403 (manufactured by Toagosei Co., Ltd.) as compound (A), 6 parts of ORGATIX TA-30 (titanium tetra-2-ethylhexanolate, non-volatile component: 99 wt% or more (2-propanol solution), manufactured by Matsumoto Fine Chemical Co., Ltd.) as compound (B), and 5 parts of Esacure one (manufactured by DKSH Co., Ltd., Japan) as photopolymerization initiator (C) were fully mixed, and propylene glycol monomethyl ether as an organic solvent was adjusted so that the concentration of non-volatile components became 40% to obtain a primer.

[Example 2A~Example 30A, Comparative Example 1A~Comparative Example 8A]

Except that the composition and mixing amount (non-volatile component converted to mass parts) of each component are set as shown in Table 2 and Table 3, a primer with a non-volatile component concentration of 40% is obtained in the same manner as Example 1A.

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

<Compound (A)>: A compound having three or more (meth)acryloyl groups

(Compound (a2)): A compound without a nitrogen atom

． Aronix M-403 (a mixture of dipentaerythritol hexaacrylate (number of functional groups: six): 40%~50% and dipentaerythritol pentaacrylate (number of functional groups: five): 50%~60%; manufactured by Toa Gosei Co., Ltd.)

(Compound (a1y)): A compound having a nitrogen atom other than compound (a1x)

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

(Compound (a1x)): A compound having a urate ring skeleton

． Miramer MU9800 (urethane acrylate with urethane ring skeleton, weight average molecular weight: 3500, number of functional groups: nine, manufactured by MIWON)

． Aronix M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: three, manufactured by Toa Gosei Co., Ltd.)

<Compound (A')>: A compound having one or two (meth)acryloyl groups

．NK Ester A-DCP (tricyclodecanedimethanol diacrylate, molecular weight: 304, number of acryloyl groups: two, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Inert resin>

． Acrylic copolymer (solution of acrylic copolymer synthesized in Production 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 with organic group (B2)]

(Metal alkoxide compounds (B2x))

. TA-21 (titanium alcohol compound; titanium tetra-n-butoxide, non-volatile content: more than 99wt% (1-butanol solution), manufactured by Matsumoto Fine Chemical Co., Ltd.)

． ZA-65 (zirconia alcohol compound; zirconium tetra-n-butoxide, non-volatile content: 87wt% (1-butanol solution), manufactured by Matsumoto Fine Chemical Co., Ltd.)

． AL-3001 (aluminum alcohol compound; aluminum tri-butyl alcohol, non-volatile content: more than 99wt%, manufactured by Matsumoto Fine Chemical Co., Ltd.)

(Metal chelate compound (B2y))

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

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

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

(Metal acetate compound (B2z))

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

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

[Triazine thiol compound (B3)]

(Triazine thiol compound (B3x) having an active energy ray-hardening functional group)

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

(Triazine thiol compound (B3y) without active energy ray-hardening functional group)

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

<Photopolymerization initiator (C)>

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

《Production of base coat and layered bodies》

The primers obtained in the examples and comparative examples were applied onto a 50 μm thick polyethylene terephthalate (PET) film ("Lumirror U403" manufactured by Toray Industries, Ltd.) using a bar coater so that the film thickness after drying was 1.0 μm, and then irradiated with ultraviolet rays of 500 mJ/ ^cm2 using a high-pressure mercury lamp to form a primer layer, thereby producing a laminate.

《HZ[%]: Determination of haze value》

For the laminated body produced as described above, the haze value (HZ) of the hard coating surface was measured using the "Haze meter SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. The evaluation criteria are as follows. If it is less than 2.0%, there is no problem in practical use.

[Evaluation criteria]

． Best: less than 1.0%

． Good: 1.0% or more and less than 2.0%

．Defective: more than 2.0%

《Pencil Hardness》

For the manufactured laminate, pencils of various hardnesses were made to touch the surface of the base coating layer of the laminate at an angle of 45° in accordance with JIS K5600-5-4, and a load was applied to perform a scratch test. The hardness of the hardest pencil that was not damaged was set as the pencil hardness.

The harder the pencil hardness, the better. If it is H or above, it can be used without any problems in practical use. If it is F or below, it may have defects such as scratches and cannot be used in practice.

《Abrasion resistance》

The abrasion resistance of the produced laminate was evaluated using the "Gakushin type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. Steel wool #0000 was mounted on a friction piece (surface area 1 cm ² ) with a load of 200g, and it was moved back and forth 10 times on the surface of the base coating (1cm×15cm). Afterwards, the number of scratches on the surface of the base coating was counted and evaluated according to the following criteria. The fewer the number of scratches, the better. If there are 10 or less, it can be used without any problem in practical use.

[Evaluation criteria]

． 3: No scratches (0)

．2: There are more than 1 scratch and less than 10 scratches

． 1: More than 11 scratches

《Copper Adhesion》

On the base coat of the produced laminate, copper was sputtered to a thickness of 0.5μm, 1μm, and 2μm using a "Magnetron sputter MSP-30T" manufactured by Vacuum Device Co., Ltd. to form a copper film. Regarding the adhesion between the copper film and the base coat, scratches were made on the copper film in a checkerboard pattern with a cutter at intervals of 1mm to form a 100-mesh grid pattern. Cellophane tape was then attached to cover the entire checkerboard scratches and removed. The peeling state of the copper film was visually observed and evaluated according to the following criteria. The less peeling, the better. If it is 3 or above on the evaluation standard, it can be used without any practical problems.

[Evaluation criteria]

．5: The area around the scratched line is completely smooth, and no grid has peeled off.

．4: Small peeling of the copper film was observed around the intersections of the scratches, but the total peeling area was less than 5% of the chessboard.

．3: The copper film peels off along the edge of the scratch, or the copper film peels off at the intersection of the scratch, or the total peeling area is more than 5% and less than 15% of the chessboard.

． 2: The total area of the peeled pieces is greater than 15% and less than 35% of the board.

． 1: The total area of the peeled pieces is more than 35% and less than 80% of the chessboard.

. 0: The total area of the peeling is more than 80% of the grid, and peeling is also observed outside the grid-shaped scratches.

《Alkali resistance》

The laminate with a copper film (thickness 500nm and 1μm) that has not been evaluated for copper adhesion was immersed in a 5% sodium hydroxide aqueous solution heated to 40°C for 5 minutes and then fully washed with water. It was then dried in an oven heated to 100°C for 15 minutes to remove moisture, and then evaluated for alkali resistance in the same way as the evaluation method for copper adhesion. The less peeling, the better. If it is 3 or above, it can be used without any problems in practice.

As shown in Table 2 and Table 3, it can be confirmed that: by using a primer of an embodiment of the present invention, the adhesion and abrasion resistance of the formed primer layer and the metal film can be taken into account, and the transparency, hardness, and alkali resistance are also excellent. It can be seen that the obtained metal film substrate is a metal film substrate with excellent adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance.

Among them, even when the metal film is as thick as 1μm or more, the good adhesion makes it suitable for applications requiring thick metal films and improved optical and electrical properties in recent years.

《Experimental Example 3》

<Manufacturing of acrylic copolymer>

Manufacturing Example 1B

In a reaction vessel including a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, 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 (about 34.9 mol%) of acrylonitrile (AN), and 445.7 parts of ethyl acetate were placed, and the reaction system was set to 70°C. Then, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (ABN-V) was added, and the temperature was kept at about 70°C for 6 hours. Then, 2.4 parts of ABN-V were added, and the reaction system was further kept at about the same temperature for 6 hours. After that, by cooling the reaction system to room temperature, 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 component of 35.0% was obtained. The hydroxyl value was determined by the potentiometric titration method in accordance with JIS K 0070.

<Manufacturing of silane coupling agent (B4)>

Manufacturing Example 2

In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen inlet tube, a solution prepared by dissolving 0.025 parts (0.15 mmol) of azobisisobutyronitrile in 3 parts of toluene was dropwise added under a nitrogen stream to a reaction solution prepared by dissolving 3.20 parts (22.5 mmol) of n-butyl methacrylate (BMA), 1.24 parts (5 mmol) of 3-methacryloxypropyltrimethoxy silane (MPTMS) and 3.20 parts (22.5 mmol) of glycidyl methacrylate (GMA) and 0.784 parts (4 mmol) of γ-butylpropyltrimethoxysilane as a chain transfer agent in 8.46 parts of toluene, and the mixture was reacted at 70° C. for 2 hours. The reaction system was then cooled to room temperature and adjusted to a solid content of 40% using toluene, thereby obtaining a solution of a silane coupling agent (B4-1) having two or more alkoxysilyl groups and two or more epoxy groups (weight average molecular weight 1000).

Manufacturing Example 3

In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen inlet tube, a solution prepared by dissolving 0.025 parts (0.15 mmol) of azobisisobutyronitrile in 3 parts of toluene was added dropwise under a nitrogen flow to a reaction solution prepared by dissolving 3.20 parts (22.5 mmol) of n-butyl methacrylate (BMA), 1.24 parts (5 mmol) of 3-methacryloyloxypropyltrimethoxysilane (MPTMS), 3.20 parts (22.5 mmol) of glycidyl methacrylate (GMA), and 0.784 parts (4 mmol) of γ-butylpropyltrimethoxysilane as a chain transfer agent in 8.46 parts of toluene, and the mixture was reacted at 70°C for 2 hours. A polymer having 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, and reacted at 70°C for 2 hours under a nitrogen flow. The reaction system was then cooled to room temperature and adjusted to a solid content of 40% using toluene, thereby obtaining a solution of a silane coupling agent (B4-2) having two or more alkoxysilyl groups and two or more acryl groups (weight average molecular weight 1300).

(Preparation of primer)

[Example 1B]

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 Co., Ltd., Japan) as photopolymerization initiator (C) were fully mixed, and propylene glycol monomethyl ether as an organic solvent was adjusted to a non-volatile component concentration of 40% to obtain a primer.

[Example 2B~Example 16B, Comparative Example 1B~Comparative Example 5B]

Except that the composition and mixing amount of each component are set to those shown in Table 4 (converted to mass parts of non-volatile components), a primer with a non-volatile component concentration of 40% is obtained in the same manner as in Example 1B.

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

<Compound (A)>: A compound having three or more (meth)acryloyl groups

(Compound (a2)): A compound without a nitrogen atom

． Aronix M-403 (a mixture of dipentaerythritol hexaacrylate (number of functional groups: six): 40%~50% and dipentaerythritol pentaacrylate (number of functional groups: five): 50%~60%; manufactured by Toa Gosei Co., Ltd.)

(Compound (a1y)): A compound having a nitrogen atom other than compound (a1x)

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

(Compound (a1x)): A compound having a urate ring skeleton

． Miramer MU9800 (urethane acrylate with urethane ring skeleton, weight average molecular weight: 3500, number of functional groups: nine, manufactured by MIWON)

． Aronix M-315 (isocyanuric acid ethylene oxide modified triacrylate, number of functional groups: three, manufactured by Toa Gosei Co., Ltd.)

<Compound (A')>: A compound having one or two (meth)acryloyl groups

．NK Ester A-DCP (tricyclodecanedimethanol diacrylate, molecular weight: 304, number of acryloyl groups: two, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Inert resin>

． Acrylic copolymer (solution of acrylic copolymer synthesized in Production Example 1B 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)>

Silane coupling agent (B4): a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups

(Other silane coupling agents (B4)): Silane coupling agents (B4) other than silane coupling agents (b4)

． X-12-981S

(Made by Shin-Etsu Chemical Co., Ltd., with two or more alkoxysilyl (triethoxy) groups and two or more epoxy groups)

．KR-513

(Made by Shin-Etsu Chemical Co., Ltd., with two or more alkoxysilyl (methoxy) groups, two or more acryl groups, and a main chain of polysiloxane structure)

(Silane coupling agent (b4)): A polymer-type silane coupling agent having two or more alkoxysilyl groups and two or more (meth)acryl groups

． X-12-1048

(Made by Shin-Etsu Chemical Co., Ltd., with two or more alkoxysilyl (trimethoxy) groups, two or more acryl groups, and an organic main chain)

． X-12-1050

(Made by Shin-Etsu Chemical Co., Ltd., with two or more alkoxysilyl (trimethoxy) groups, two or more acryl groups, and an organic main chain)

<Other silane coupling agents>

． KBM-5103

(Made by Shin-Etsu Chemical Co., Ltd., one alkoxysilyl group, one acryl group)

<Photopolymerization initiator (C)>

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

《Production of base coat and layered bodies》

The primers obtained in the examples and comparative examples were applied onto a 50 μm thick polyethylene terephthalate (PET) film ("Lumirror U403" manufactured by Toray Industries, Ltd.) using a bar coater so that the film thickness after drying was 1.0 μm, and then irradiated with ultraviolet rays of 500 mJ/ ^cm2 using a high-pressure mercury lamp to form a primer layer, thereby producing a laminate.

《HZ[%]: Determination of haze value》

For the laminated body produced as described above, the haze value (HZ) of the base coating surface was measured using the "Haze meter SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. The evaluation criteria are as follows. If it is less than 2.0%, there is no problem in practical use.

[Evaluation criteria]

． Best: less than 1.0%

． Good: 1.0% or more and less than 2.0%

．Defective: more than 2.0%

《Pencil Hardness》

For the manufactured laminate, pencils of various hardnesses were made to touch the surface of the base coating layer of the laminate at an angle of 45° in accordance with JIS K5600-5-4, and a load was applied to perform a scratch test. The hardness of the hardest pencil that was not damaged was set as the pencil hardness.

The harder the pencil hardness, the better. If it is H or above, it can be used without any problems in practical use. If it is F or below, it may have defects such as scratches and cannot be used in practice.

《Abrasion resistance》

The abrasion resistance of the produced laminate was evaluated using the "Gakushin type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. Steel wool #0000 was mounted on a friction piece (surface area 1 cm ² ) with a load of 200g, and it was moved back and forth 10 times on the surface of the base coating (1cm×15cm). Afterwards, the number of scratches on the surface of the base coating was counted and evaluated according to the following criteria. The fewer the number of scratches, the better. If there are 10 or less, it can be used without any problem in practical use.

[Evaluation criteria]

． 3: No scratches (0)

．2: There are more than 1 scratch and less than 10 scratches

． 1: More than 11 scratches

《Copper Adhesion》

On the base coat of the produced laminate, copper was sputtered to a thickness of 200nm, 500nm, 1μm, and 2μm using a "Magnetron sputter MSP-30T" manufactured by Vacuum Device Co., Ltd., to form a copper film. Regarding the adhesion between the copper film and the base coat, scratches were made on the copper film in a checkerboard pattern with a cutter at intervals of 1mm to form a 100-mesh grid pattern. Cellophane tape was then attached to cover the entire checkerboard scratches and removed. The peeling state of the copper film was visually observed and evaluated according to the following criteria. The less peeling, the better. If it is 3 or above on the evaluation standard, it can be used without any practical problems.

[Evaluation criteria]

．5: The area around the scratched line is completely smooth, and no grid has peeled off.

．4: Small peeling of the copper film was observed around the intersections of the scratches, but the total peeling area was less than 5% of the chessboard.

．3: The copper film peels off along the edge of the scratch, or the copper film peels off at the intersection of the scratch, or the total peeling area is more than 5% and less than 15% of the chessboard.

． 2: The total area of the peeled pieces is greater than 15% and less than 35% of the board.

． 1: The total area of the peeled pieces is more than 35% and less than 80% of the chessboard.

. 0: The total area of the peeling is more than 80% of the grid, and peeling is also observed outside the grid-shaped scratches.

《Alkali resistance》

The laminate with a copper film (thickness 500nm and 1μm) that has not been evaluated for copper adhesion was immersed in a 5% sodium hydroxide aqueous solution heated to 40°C for 5 minutes and then fully washed with water. It was then dried in an oven heated to 100°C for 15 minutes to remove moisture, and then evaluated for alkali resistance in the same way as the copper adhesion evaluation method. The less peeling, the better. If it is 3 or above, it can be used in practice without any problems.

As shown in Table 4, it can be confirmed that: by using a primer of an embodiment of the present invention, the adhesion and abrasion resistance of the formed primer layer and the metal film can be taken into account, and the transparency, hardness, and alkali resistance are also excellent. It can be seen that the obtained metal film substrate is a metal film substrate with excellent adhesion between the substrate and the metal film, transparency, hardness, and alkali resistance.

Among them, even when the metal film is as thick as 1μm or more, the good adhesion makes it suitable for applications requiring thick metal films and improved optical and electrical properties in recent years.

Claims (12)

An active energy ray-curable primer is used to form a primer layer in a metal film substrate which sequentially includes a substrate, a primer layer, and a metal film, the active energy ray-curable primer comprising: a first compound having three or more (meth)acryl groups, a second compound, and a photopolymerization initiator, wherein the second compound comprises a compound having a silsesquioxane skeleton, a metal compound having an organic group, a triazine thiol compound, and a first compound having two or more alkoxysilyl groups and two or more reactive functional groups. At least one of the groups composed of silane coupling agents, the metal compound having an organic group is a compound having an M-C bond between a metal atom (M) and a carbon atom (C) or an M-O-C bond via an oxygen atom, represented by M(-R)n, M(-OR)n, or M(-OCOR)n, etc., and having a metal atom (M) and an organic group (R), the content of the first compound is 70% by mass or more in 100% by mass of the non-volatile components of the active energy ray-curable primer, and the metal film is copper. The active energy ray-curable primer as described in claim 1, wherein the second compound includes a compound having a silsesquioxane skeleton, and the compound having a silsesquioxane skeleton includes a compound having the silsesquioxane skeleton and a (meth)acryl group. The active energy ray-curable primer as described in claim 1, wherein the second compound includes the metal compound having an organic group, and the metal compound having an 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. The active energy ray-hardenable primer as described in claim 1 or claim 3, wherein the second compound comprises the metal compound having an organic group, and the metal of the metal compound having an organic group comprises titanium, zirconium, or aluminum. An active energy ray-curable primer as described in claim 1 or claim 3, wherein the second compound includes the triazine thiol compound, and the triazine thiol compound includes a triazine thiol compound having an active energy ray-curable functional group. The active energy ray-curable primer as described in claim 1, wherein the second compound comprises a silane coupling agent having two or more alkoxysilyl groups and two or more reactive functional groups, and the silane coupling agent comprises a silane coupling agent having two or more alkoxysilyl groups and two or more (meth)acryl groups and having an organic structure in the main chain. An active energy ray-curable primer as described in any one of claims 1 to 3, wherein the first compound comprises a compound having three or more (meth)acryl groups and a nitrogen atom. The active energy ray-curable primer as described in claim 7, wherein the compound having three or more (meth)acryl groups and having a nitrogen atom includes a compound having three or more (meth)acryl groups and having a urate ring skeleton. An active energy ray-curable primer as described in any one of claim 1 to claim 3, wherein the content of the second compound is 1 mass % to 30 mass % in 100 mass % of the non-volatile components of the active energy ray-curable primer. A primer layer formed by an active energy ray-hardening primer as described in any one of claims 1 to 9. A laminate having a substrate and a base coating as described in claim 10. A substrate with a metal film, comprising, in sequence, a substrate, a base coating as described in claim 10, and a metal film.