TWI661015B - Primer for base material with copper film, method for manufacturing base material with copper film, base material with copper film, and conductive film - Google Patents

Abstract

The invention provides a novel primer, which can not only make the initial adhesion of a substrate and a copper film excellent, but also treat the copper film substrate with an alkaline solution and an acidic solution, and the adhesion between the substrate and the copper film. Also excellent.

The present invention is a primer for a substrate with a copper film attached, which comprises: an acrylic copolymer (A) having a hydroxyl group, an alkyl ester group, a nitrile group, and a primary amidine group as the case may be; and a polyisocyanate (B), which has at least 3 isocyanate groups; an active energy ray polymerizable compound (C), which has at least 3 carbon-carbon double bond-containing groups; and, a reactive alkoxysilyl compound (D), It is represented by the general formula (1), that is, X ¹ -Si (R ¹ ) _a (OR ² ) _3-a . In the formula (1), X ¹ represents that it contains and is selected from the group consisting of hydroxyl group, isocyanate group and polymer A group of at least one functional group that reacts in a group consisting of radical carbon-carbon double bond groups, R ¹ represents hydrogen or a hydrocarbon group of 1 to 8 carbons, R ² represents a hydrocarbon group of 1 to 8 carbon atoms, a Represents 0, 1, or 2.

Description

Primer for base material with copper film, method for manufacturing base material with copper film, base material with copper film, and conductive film

The invention relates to the following: a primer, which is used to form a copper thin film on the surface of various substrates; a substrate with a copper thin film and a manufacturing method thereof; A layer composed of the primer; and a conductive film formed by using the base material with a copper film attached thereto.

The “substrate with a copper film” in this specification refers to an article made of a copper film formed on the surface of various substrates, such as various plastic substrates or plastic films, metal, and glass , Paper, nanofiber paper, wood, etc. Hereinafter, a film having a conductive layer composed of a copper vapor-deposited film on the surface (hereinafter, also referred to as a copper vapor-deposited plastic film) will be described as an example to explain the prior art. The film is positioned as follows: Tin) is a substitute for a film of a conductive layer (hereinafter also referred to as an ITO film).

The ITO film is used as an electrode film for a touch panel such as a smart phone or a tablet PC (Personal Computer) because of its excellent transparency and conductivity. However, since indium is expensive Rare metals have cost problems. In addition, the ITO layer is generally hard and brittle, so it is difficult to bend or deform, which is a problem to be solved in terms of workability.

Therefore, in this field, attempts have been made to use a film-forming organic conductive polymer (for example, polythiophene, polyaniline, or polypyrrole) as a conductive material instead of ITO. However, since an organic conductive polymer is generally strongly colored, the use of a conductive film or an electrode film as a conductive layer causes problems in terms of color tone. This problem can reduce the amount of organic conductive polymer used to improve the color tone, but the conductivity is lost.

On the other hand, in this field, copper-evaporated plastic films have also been studied instead of ITO films. This is because copper has a lower resistivity than ITO, and exhibits a conductivity that is not inferior to that of ITO film, and also has good processability, and more importantly, is cheap. Therefore, the copper-evaporated plastic film is considered to be useful as an electrode film for various electronic devices. For example, it can contribute to the further enlargement of the touch panel and the effective use of an interactive digital signage.

The copper vapor-deposited plastic film is generally obtained by vacuum-depositing nickel on a film surface provided as a base material and further vacuum-depositing copper on the film surface. This nickel vapor-deposited layer functions as an anchor layer, and is used to make the film and the copper vapor-deposited layer adhere more strongly. Then, a resist is coated on the obtained copper-deposited plastic film, and the electrode pattern is immersed in an etching solution (an alkaline solution and / or an acidic solution) after the electrode pattern is drawn to remove the resist, thereby obtaining an electrode film.

However, in the aforementioned copper vapor-deposited plastic film, since nickel lacks alkali resistance and acid resistance, there is a problem that the copper vapor-deposited layer peels off or falls off from the base film after the etching process.

In addition, although the copper-deposited plastic film is cheaper than the ITO film, the nickel constituting the anchor coating is more expensive than copper, but it is more expensive. Therefore, in this field, a copper vapor-deposited plastic film provided with an anchor coating layer is also considered. The anchor coating layer is made of an organic polymer as a primer (see Patent Document 1).

[Prior technical literature] (Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 5-28835

The main problem to be solved by the present invention is to provide a novel primer, which not only makes the initial adhesion of the substrate and the copper film excellent, but also treats the copper film substrate with an alkaline solution and an acidic solution. The adhesiveness (alkali-resistant adhesion, acid-resistant adhesion) of the material and the copper film is still excellent.

As a result of repeated studies, the present inventors have found that the above-mentioned problem can be solved by a primer having a composition in which a specific hydroxyl-containing acrylic copolymer is used as a main agent and a specific polyisocyanate is used as a hardener. In addition, a specific active energy ray-curable compound and a reactive alkoxysilyl compound are further prepared in the material, and both heat and active energy ray can be used for hardening.

That is, the present invention relates to a primer for a substrate with a copper thin film, which contains an acrylic copolymer (A), which has a hydroxyl group, an alkyl ester group, a nitrile group, and a primary amidine group as the case may be. A polyisocyanate (B) having at least 3 isocyanate groups; an active energy ray polymerizable compound (C) having at least 3 carbon-carbon double bond-containing groups; and a reactive alkoxysilyl compound ( D), which is represented by the general formula (1), that is, X ¹ -Si (R ¹ ) _a (OR ² ) _3-a . In formula (1), X ¹ represents that A functional group that reacts with at least one of a group consisting of a group consisting of a group containing a polymerizable carbon-carbon double bond, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents 1 to 8 carbon atoms A hydrocarbon group, a represents 0, 1 or 2.

The present invention also relates to a substrate with a copper thin film and a method for manufacturing the same. The substrate with a copper thin copper film has a layer composed of the primer; and a conductive film using the same. Base material with copper film attached.

As mentioned above, the primer of the present invention is a type of composition that is hardened by using both heat and active energy rays. According to the present invention, not only the initial adhesion of various substrates such as plastics and copper films is excellent, but the alkali resistance is also excellent. The properties and the acid-resistant adhesiveness are also improved (hereinafter, these properties are collectively referred to as adhesiveness in some cases). Moreover, since this primer contains a component which can be hardened by active energy ray, it can also provide an excellent hardness to a primer coating film.

In addition, the base material with a copper film obtained by using the primer of the present invention is particularly excellent in alkali resistance and acid resistance. So even if The copper thin film-containing substrate is immersed in an etching solution, and the copper thin film is not easily peeled off. In addition, since the copper film-coated substrate can impart excellent hardness to the undercoat layer, in the manufacturing process of the substrate, the scratch resistance of the surface except for the copper film will become good. When it is in a mesh shape, defects are less likely to occur.

The copper thin film plastic film of the present invention can be used in various applications. Among them, a copper vapor-deposited film or a copper ultra-thin film formed by a sputtering method is suitable as an electrode film instead of an ITO film. The electrode film can be supplied to, for example, a smartphone, a tablet terminal, a notebook PC, an all-in-one PC, and a digital signage.

[Form for Implementing Invention]

The primer (hereinafter, also simply referred to as a primer) for a substrate with a copper film attached to the present invention is a non-aqueous composition, and includes: an acrylic copolymer (A) (hereinafter, also referred to as (A Component), which has a hydroxyl group, an alkyl ester group and a nitrile group, and a primary amidine group as the case may be; a polyisocyanate (B) (hereinafter, also referred to as (B) component), which has at least 3 isocyanate groups; Active energy ray polymerizable compound (C) (hereinafter, also referred to as (C) component) having at least three carbon-carbon double bond-containing groups; and a reactive alkoxysilicon represented by a specific general formula Base compound (D) (hereinafter, also referred to as (D) component).

(A) component, because it has a hydroxyl group and a nitrile group as polar groups in the molecule, it will have the aforementioned adhesion, especially the aforementioned acid-resistant adhesion and alkali resistance Contribution to adhesion. In addition, when a primary amido group is further introduced into the component (A), the aforementioned acid-resistant and alkali-resistant adhesion will be further improved.

Although various well-known components can be used as a component (A), it does not specifically limit, It is preferable to use the following components as a reaction component, for example, a hydroxyalkyl (meth) acrylate (a1) (henceforth also called (a1) ) Component.), (Meth) acrylic acid alkyl ester (a2) (hereinafter, also referred to as (a2) component.), And (meth) acrylonitrile (a3) (hereinafter, also referred to as (a3) component. ), And (meth) acrylamide (a4) as required, and the alkyl (meth) acrylate (a2), except for those having a hydroxyl group.

The component (a1) is used to introduce a hydroxyl group into the base component (A), and to specifically react with the component (B) to introduce a crosslinked structure into the undercoat layer. As a result of introducing a crosslinked structure, the undercoat layer can exhibit desired adhesion and hardness.

As a component (a1), if it is a compound which has a (meth) acryl fluorenyl group and a hydroxyalkyl ester group in a molecule | numerator, various well-known compounds can be used without a restriction | limiting in particular. Specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxycyclohexyl (meth) acrylate can be used alone or in combination of two or more. use.

The component (a2) is not particularly limited as long as it is a compound having a (meth) acrylfluorenyl group and an alkyl ester group and having a hydroxyl group in the molecule, and various known compounds can be used. Specifically, it can be enumerated For example: methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, (meth) Tert-butyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, dodecyl (meth) acrylate, ( Octadecyl (meth) acrylate, eicosyl (meth) acrylate, behenyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate , Cyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate, these compounds can be used alone or in combination of two or more. Among these compounds, from the viewpoint of adhesion, the number of carbon atoms of the alkyl ester group is preferably about 1 to 6.

Specific examples of the component (a3) include acrylonitrile and / or methacrylonitrile.

Specific examples of the component (a4) include acrylamide, methacrylamide, N-methylol acrylamide, and N-methylolmethacrylamide.

The amount of each of the components used is not particularly limited, and from the viewpoint of adhesiveness and the like, it can be generally set to the following range.

<When the (a4) component is not used>

(a1) Ingredient: usually about 5 to 35 mole%, preferably about 8 to 25 mole%

(a2) Ingredient: usually about 10 ~ 95 mole%, preferably about 30 ~ 70 mole%

(a3) Ingredient: usually about 5 to 80 mole%, preferably about 15 to 65 mole%

<When using (a4) ingredient>

(a1) Ingredient: usually about 5 to 35 mole%, preferably about 8 to 25 mole%

(a2) Ingredient: usually about 10 ~ 87 mole%, preferably about 30 ~ 70 mole%

(a3) Ingredient: usually about 5 to 80 mole%, preferably about 15 to 65 mole%

(a4) Ingredient: usually about 3 to 55 mole%, preferably about 5 to 40 mole%

In addition, in the present invention, the reaction component of the component (A) can include an ethylene-based monomer other than the components (a1) to (a4). Specific examples include 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, and vinyl Α-olefins such as cyclohexane and 2-methylvinylcyclohexane; (meth) allyl alcohol, 4-pentene-1 alcohol, 1-methyl-3-butene-1-ol, and 5 -Unsaturated alcohols such as hexene-1-ol; styrenes such as styrene, α-methylstyrene and tertiary butylstyrene; phenyl (meth) acrylate, benzyl (meth) acrylate, and Aryl (meth) acrylates such as 4-methylbenzyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ( Dimethylaminopropyl (meth) acrylate and diethylaminopropyl (meth) acrylate, and dialkylaminoalkyl (meth) acrylates and their salts; dimethylaminoethyl (Meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamine, and diethylaminopropyl (methyl) Dialkylaminoalkyl (meth) acrylamides such as acrylamide and their salts; N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, 2- (meth) acrylamide-2-methyl Propanesulfonic acid and chain transfer monomers such as 2- (meth) acrylamido-2-methylpropanecarboxylic acid and its salts; vinylamine, aminoethyl (meth) acrylate, allyl mercaptan, and Other monofunctional monomers such as glycidyl (meth) acrylate; methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, and hexamethylenebis (methyl) ) Bis (meth) acrylamides such as acrylamide; di (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate; adipic acid Divinyl esters such as divinyl ester, divinyl sebacate; diallyl dimethyl ammonium, diallyl phthalate, diallyl chlorendate, and divinylbenzene Monomers; 1,3,5-tripropenylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, triallyl trimellitate, and N, N-diene Trifunctional monomers such as propyl allylamine; tetramethylol tetramethacrylate, benzene Tetrafunctional monomers such as tetraallyl acid and N, N, N ', N'-tetraallyl-1,4-diaminobutane, etc. These compounds can be used alone or in combination of two Use more than one. The amount of these compounds to be used is not particularly limited, but is usually less than 10 mol% relative to the components (a1) to (a4).

The component (A) can be produced by various known methods. Specifically, it can be obtained, for example, by (a1) component, (a2) component, and (a3) component, and (a4) component and other monomers as needed, without a solvent, or In the organic solvent (G) described below, usually in the presence of a radical polymerization initiator, at about 80 to 180 ° C. It is allowed to undergo a copolymerization reaction for about 1 to 10 hours. The amount of the organic solvent (G) used is usually within a range of about 10 to 50% by weight of the solid content of the solution containing the component (A).

Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, tert-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, and 2,2'-coupling. Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azoisobutyric acid dimethyl, etc., these compounds can be used alone, or Use in combination of two or more. The amount used is usually in a range of about 0.1 to 2% by weight based on the total weight of the reaction components constituting the component (A).

(A) The physical properties of the component are not particularly limited. From the viewpoints of initial adhesion, acid resistance, alkali resistance, and coating film hardness, the hydroxyl value is usually about 30 to 150 mgKOH / g, and the glass transition temperature It is preferably about 0 to 100 ° C, particularly preferably a hydroxyl value of about 50 to 100 mgKOH / g, and a glass transition temperature of about 10 to 70 ° C.

The component (B) is a component which functions as a curing agent of the component (A) as a main agent. As long as it is a polyisocyanate having at least three isocyanate groups in the molecule, various known components can be used without particular limitation. The component (B) reacts with a compound having an isocyanate-reactive functional group (such as a hydroxyl group or an amine group) in the components (C) and (D) described later, and is given to the undercoat layer in the present invention. Crosslinked structure.

Specific examples of the component (B) include a biuret body and a urate body selected from the group consisting of a diisocyanate compound. A derivative (b1) (hereinafter, also referred to as (b1) component) in the group consisting of (nurate) and adduct body; a reaction product (b2) of the (b1) component and a diol compound (Hereinafter, also referred to as (b2) component); triisocyanate compound (b3) (except those equivalent to (b1) and (b2) components) (hereinafter, also referred to as (b3) component); and other polyisocyanates At least one of the group consisting of a compound (hereinafter, also referred to as (b4) component).

Examples of the diisocyanate compound as the component (b1) include aromatic diisocyanates such as methylphenyl diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; hexamethylene diisocyanate and trimethyl Aliphatic diisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; and dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate And alicyclic diisocyanates such as hydrogenated methylphenyl diisocyanate.

The bisureton of the diisocyanate is represented by the following structural formula.

(In the formula, R ³ represents the residue of the aforementioned diisocyanate compound.)

The uric acid body of the diisocyanate compound is represented by the following structural formula.

(In the formula, R ⁴ represents a residue of the aforementioned diisocyanate compound.)

The adduct of the diisocyanate compound is represented by the following structural formula.

(In the formula, R ⁵ represents an alkyl group having 1 to 3 carbon atoms or a functional group represented by OCN-R ⁶ -HN-C (= O) -O-CH _2- , and R ⁶ represents a residue of the aforementioned diisocyanate compound. base.)

The diol compound constituting the component (b2) is not particularly limited, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, and 1, 6-hexanediol, octanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc. These compounds can be used alone or in combination of two or more. Among these, the carbon number is particularly preferably about 2 to 20, and more preferably about 4 to 8.

(b2) A component can be manufactured by various well-known methods. Specifically, it can be obtained by subjecting the component (b1) to an amine esterification reaction with the diol compound. The former is an isocyanate group (NCO '). The equivalent ratio of the latter to the hydroxyl group (OH '), that is, NCO' / OH 'is usually set to about 5 to 20, preferably in the range of about 10 to 20, and usually below 40 to 80 ° C, 1 to 5 The reaction takes place in about an hour. The obtained (b2) component has an isocyanate group equivalent of usually about 10 meq / g, and preferably about 3 to 6 meq / g.

Examples of the component (b3) include toluene-2,4,6-triisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, and 1,6,11-undecyl Triisocyanates such as triisocyanate, 1,3,6-hexamethylenetriisocyanate and dicycloheptane triisocyanate, and 6-functional polyisocyanates (product name "Duranate MHG-80B", manufactured by Asahi Kasei Chemical Co., Ltd.).

As the component (B), from the viewpoint of the balance of the initial adhesion, acid resistance, and alkali resistance, the component (b1) is preferably (b1) in which the aliphatic diisocyanate is used as a component. )ingredient.

The usage ratio of the component (A) to the component (B) is not particularly limited. From the viewpoints of adhesion and coating film hardness, the molar ratio of the hydroxyl group in the component (A) to the isocyanate group in the component (B) (NCO / OH) can be generally set to about 0.2 to 5, and preferably in a range of 1 to 2.

The component (C) is not particularly limited as long as it is an active energy ray polymerizable compound having at least three carbon-carbon double bond-containing groups in the molecule. Examples of the carbon-carbon double bond-containing group include a vinyl group, an allyl group, an allyl group, and a methacryl group.

As a preferable specific type of the component (C), an active energy ray polymerizable compound (C1) having 3 to 6 (meth) acrylofluorenyl groups and at least one hydroxyl group in the molecule (hereinafter, also It is called (C1) component.), An active energy ray polymerizable compound (C2) (hereinafter, also referred to as (C2) component) having 3 to 6 (meth) acrylfluorenyl groups in the molecule and having no hydroxyl group. , An active energy ray polymerizable compound (C3) (hereinafter, also referred to as (C3) component) having 3 to 6 allyl groups and at least one hydroxyl group in the molecule, and 3 to 6 alkenes in the molecule At least one of the group consisting of an active energy ray polymerizable compound (C4) (hereinafter, also referred to as (C4) component) which is propyl and does not have a hydroxyl group. Among these compounds, those having a hydroxyl group are more preferable, since the hydroxyl group is chemically bonded to those capable of reacting with the hydroxyl group in the component (B) and the component (D) described later, and then is coated on the primer of the present invention. A crosslinked structure is formed in the layer to increase its hardness.

Examples of the (C1) component include trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, and pentaerythritol monohydroxytri (methyl). Hydroxyl-containing (meth) groups such as acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate Acrylate compounds.

Examples of the (C2) component include trimethylolpropane tri (meth) acrylate, oxyethyl modified trimethylolpropane tri (meth) acrylate, and oxymodified trihydroxy Methylpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bis (trimethylol) propane tetra (Meth) acrylate compounds such as (meth) acrylate and glycerol tri (meth) acrylate which do not contain a hydroxyl group.

Examples of the component (C3) include pentaerythritol monohydroxy triallyl ether; and examples of the (C4) component include vinyl compounds such as triallyl citrate.

The amount of the component (C) used is not particularly limited. Generally, when the component (A) and the component (B) are set to 100 parts by weight (solid content conversion), the amount is usually about 10 to 500 parts by weight, preferably It is a range of about 30 to 300 parts by weight (in either case, the solid content is converted).

In addition, the component (C) can be used in combination with compounds 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 oxyethylene modified bis (methyl) of bisphenol A Di (meth) acrylates such as acrylates; oligomers such as polyurethane poly (meth) acrylates and polyester poly (meth) acrylates; and 2-ethylhexyl (meth) acrylate, ( Isodecyl methacrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate Mono (meth) acrylates such as alkenyl esters and isobornyl (meth) acrylates.

The component (D) is a reactive alkoxysilyl compound, which is represented by the general formula (1), that is, X ¹ -Si (R ¹ ) _a (OR ² ) _3-a . In the formula (1), X ¹ represents a group containing a functional group that reacts with at least one selected from the group consisting of a hydroxyl group, an isocyanate group, and a group containing a polymerizable carbon-carbon double bond; R ¹ represents hydrogen or a carbon number of 1 to 8 R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. .

Examples of the functional group in X ¹ of the general formula (1) as the component (D) include a member selected from the group consisting of an isocyanate group, a thiol group, an amine group, an epoxy group, an acid anhydride group, and a vinyl group. One of the groups.

Examples of compounds in which the functional group in X ¹ is an isocyanate group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-isocyanatepropylmethyl. Dimethoxysilane and 3-isocyanatepropylmethyldiethoxysilane.

Examples of the compound in which the functional group in X ¹ is a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethylformate. Oxysilane and 3-mercaptopropylmethyldiethoxysilane.

Examples of the compound in which the functional group in X ¹ is an amine group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidepropyltrialkoxysilane Wait.

Examples of the compound in which the functional group in X ¹ is an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxy Silane, etc.

Examples of the compound in which the functional group in X ¹ is an acid anhydride group include 3-trimethoxysilylpropylsuccinic anhydride.

Examples of the compound in which the functional group in X ¹ is a vinyl group include vinyl trimethoxysilane, vinyl triethoxysilane, styryltrimethoxysilane, and 3- (meth) acrylic acid. Propylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, and 3- (Meth) acryloxypropyltriethoxysilane and the like.

The amount of the (D) component to be used is not particularly limited. Usually, when the (A) component and the (B) component are set to 100 parts by weight (in terms of solid content conversion), the amount is usually about 5 to 50 parts by weight, preferably A range of about 20 to 40 parts by weight.

The primer of the present invention can contain various known inorganic particles (E) (hereinafter, also referred to as (E) component) as necessary. Specific examples include silicon dioxide, titanium dioxide, aluminum oxide, zinc oxide, tin oxide, zirconium dioxide, ITO (indium tin oxide), ATO (antimony tin oxide), aluminum hydroxide, calcium hydroxide, and hydrogen. Particles such as magnesium oxide, and these inorganic particles can be used alone or in combination of two or more. Among these, silicon dioxide and / or aluminum oxide are particularly preferable. The surface of the component (E) may be subjected to various treatments. The median particle diameter (d50) of the (E) component is not particularly limited, but is usually about 10 nm to 5 μm.

The amount of the (E) component used is not particularly limited. Generally, when the (A) component and the (B) component are set to 100 parts by weight (solid content conversion), The range is usually about 1 to 20 parts by weight, preferably about 5 to 10 parts by weight.

The primer of the present invention can further contain a photopolymerization initiator (F) (hereinafter, also referred to as (F) component).

Specific examples of the (F) component include benzophenone, 4 '-(methylthio) -α-morpholinyl-α-methylphenylacetone, and 2,4,6-trimethyldiacetone. Benzophenone, methyl orthobenzoyl benzoate, 4-phenylbenzophenone, tertiary butyl anthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy- 2-methyl-1-phenylpropane-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone}, benzoin Methyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methylthio) phenyl] -2 -Morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -but-1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, diethylthiaxanthone, isopropylthiaxanthone, ( 2,4,6-trimethylbenzyl) diphenylphosphine oxide, bis (2,6-dimethoxybenzyl) -2,4,4-trimethylpentylphosphine oxide, Bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] Phenyl} -2-methylpropane- 1-ketone, methyl benzamate, methyl phenylglyoxylate, 4,4'-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino 4-morpholinophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-phenyl-2-morpholinylpropane-1-one, 2- Methyl-1- [4- (hexyl) phenyl] -2-morpholinylpropane-1-one and 2-ethyl-2-dimethylamino -1- (4-morpholinylphenyl) -butan-1-one, and the photopolymerization initiators described in Japanese Patent Application Publication No. 2014-1390, etc., these photopolymerization initiators can be used alone, Or you can use it combining two or more types. As the (F) component, commercially available products such as IRGACURE907, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE184, IRGACURE500, IRGACURE1000, IRGACURE149, IRGACURE261, and DAROCUR1173 can be used. These photopolymerization initiators can be used alone or in combination of two or more.

The use amount of the (F) component is not particularly limited. When the (C) component is set to 100 parts by weight (in terms of solid content), it is usually set to about 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight. Left and right range.

The following compounds can be used as auxiliary agents for the component (F): triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4 '-Diethylaminobenzophenone, 2-dimethylamino ethyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoic acid n-butoxy Ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,4-diethylthiaxanthone and 2,4-di Isopropylthioxanthone and the like. These auxiliaries can be used alone or in combination of two or more.

The primer of the present invention can further contain an organic solvent (G) (hereinafter, also referred to as (G) component). Specific examples include lower ketones such as methyl ethyl ketone and methyl isobutyl ketone; and aromatic hydrocarbons such as toluene Alcohols such as ethanol and propanol; propylene glycol monomethyl ether acetate and ether acetate such as ethylcellulose acetate; ethyl acetate, chloroform and dimethylformamide, these organic solvents can be used alone, Or you can use it combining two or more types.

The use amount of the (G) component is not particularly limited, and generally, the solid content concentration of the primer of the present invention is usually in the range of about 1 to 60% by weight.

The primer of the present invention can further contain an amine esterification catalyst. Specifically, examples include organometallic catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, and bismuth octoate; or diazabicyclooctane, dimethylcyclohexylamine, and tetramethylpropanediamine. Organic amine catalysts such as amine, ethylmorphine, dimethylethanolamine, triethylamine, and triethylenediamine can be used alone or in combination of two or more. The amount of the amine esterification catalyst used is not particularly limited. Usually, when the component (A) and the component (B) are 100 parts by weight (in terms of solid content), the amount is usually 0.01 to 0.5 weight. It is preferably in the range of about 0.05 to 0.2 parts by weight.

In addition, the primer of the present invention may contain a polythiol compound as necessary. Specifically, for example, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-three -2,4,6 (1H, 3H, 5H) -trione, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate) ester, tris Polymethylol tris (3-mercaptobutyrate) ester, pentaerythritol tetra (3-mercaptobutyrate) ester, pentaerythritol hexa (3-mercaptobutyrate) ester, etc., these polythiol compounds can be used alone, or Use in combination of two or more. The amount of the polythiol compound to be used is not particularly limited. When the component (A) and the component (B) are usually 100 parts by weight (solid content conversion), the amount is usually about 1 to 20 parts by weight, preferably It is a range of about 5 to 10 parts by weight.

When a polythiol compound is used, in order to increase the life of the primer of the present invention, various known ene-thiol reaction inhibitors can be used. Specific examples include phosphorus compounds such as triphenylphosphine and triphenylphosphite; p-methoxyphenol, dihydroxybenzene, trihydroxybenzene, naphthylamine, tert-butylcatechol, and thionyl chloride Copper, 2,6-di-tertiary-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6tertiary-butylphenol), 2,2'-methylenebis (4 -Methyl-6 tertiary butyl phenol), N-nitrosophenylaluminum aluminum salt and diphenylnitrosoamine radical polymerization inhibitors; benzyldimethylamine, 2- (dimethylamino group) Tertiary amines such as methyl) phenol, 2,4,6-tris (diaminomethyl) phenol and diazabicycloundecene; and 2-methylimidazole, 2-ethyl Imidazoles such as 4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole and 1-cyanoethyl-2-methylimidazole. These reaction inhibitors can be used alone or in combination of two or more.

The primer of the present invention can contain other additives such as a leveling agent, an antioxidant, a polymerization inhibitor, an ultraviolet absorber, and the like.

The substrate with a copper film of the present invention is a composite substrate, which is formed by sequentially laminating an undercoat layer and a copper film layer on the surface of various substrates. The aforementioned undercoat layer is the undercoat of the present invention. The agent is hardened.

Examples of the substrate include polyester, polyvinyl chloride, polyimide, polyimide, polycarbonate, polyethylene, and polypropylene. Plastic materials can also be listed: non-plastic materials such as metal, glass, paper, nanofiber paper and wood. In addition, the shape of the substrate is not particularly limited, and may be, for example, spherical, cylindrical, rectangular parallelepiped, plate, or film; and a part of the surface of the substrate may have unevenness or a curved surface. When the base material with a copper thin film of the present invention is used as a conductive film, the base material may be a plastic film from the viewpoint of heat resistance, optical characteristics, and the like, and a polyester film is particularly preferred. The thickness of the substrate film is not particularly limited, but is usually about 50 to 200 μm.

The thickness of the hardened undercoat layer is not particularly limited, but is usually about 0.1 to 5 μm.

Examples of the copper thin film layer include a copper vapor-deposited film, a copper sputtered film, and a copper CVD (chemical vapor deposition) film. When the copper film-attached film of the present invention is used for an electrode film, as the copper film, a copper vapor-deposited film or a copper sputtered film is particularly preferred. The thickness of the copper thin film layer is not particularly limited, but is usually about 0.1 to 2 μm.

The manufacturing method of the copper film-attached base material of this invention is not specifically limited. Examples include the following aspects: (I) firstly coating the primer of the present invention on the surface of the substrate (such as one or both sides of a film-like substrate), and then (II) applying After the substrate is heated, (III) further forms a hardened undercoat layer by irradiating active energy rays, and then (IV) forms a copper thin film layer on the hardened undercoat layer.

Regarding step (I), the conditions for applying the primer of the present invention to the surface of the substrate (such as one or both sides of a film-like substrate) are not particularly limited, and as a coating means, Examples include: spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, Dot coater and the like. The coating amount is not particularly limited, and the dry solid content is usually about 0.01 to 10 g / m ² .

Regarding step (II), the conditions for heating the substrate are not particularly limited either, but the temperature is usually about 80 to 150 ° C. and the time is about 10 seconds to 2 minutes. When an organic solvent (G) is used, the organic solvent (G) can be volatilized from the semi-hardened undercoat layer by this treatment, and the (A) component and the (B) component can be amine ester in this layer at the same time. Reaction to form a crosslinked structure. In the amine esterification reaction, compounds having, for example, a hydroxyl group or an amine group, a thiol group, an isocyanate group, or the like in the (C) component and the (D) component also participate.

Regarding step (III), the conditions when the semi-hardened undercoat layer is irradiated with active energy rays are also not particularly limited. Examples of the active energy rays include ultraviolet rays and electron beams. Examples of the supply source of ultraviolet rays include a high-pressure mercury lamp or a metal halide lamp, and the irradiation energy is usually about 100 to 2,000 mJ / cm ² . Examples of the electron beam supply method include scanning electron beam irradiation and curtain electron beam irradiation. The irradiation energy is usually about 10 to 200 kGy. With this treatment, in the heat-cured undercoat layer, the (C) components undergo radical polymerization reaction with each other to form a crosslinked structure. In this polymerization reaction, a compound having an active energy ray polymerizable functional group in the component (D) also participates.

Regarding step (IV), a means for forming a copper thin film layer on the hardened undercoat layer is not particularly limited, and a so-called dry coating method is preferred. Specific examples include a physical method such as a vacuum deposition method or a sputtering method, or a chemical method (such as a chemical vapor phase reaction) such as CVD.

The conductive film of this invention is a film using the base material with which the copper thin film of this invention was attached. In particular, a film obtained by copper-evaporating a plastic film or a copper sputter film on the substrate with a copper thin film is very useful as a substitute for an ITO film.

The method for producing the conductive film is not particularly limited, and when it is used as an electrode film, the following methods can be cited: coating various resists on the aforementioned copper vapor-deposited plastic film or copper sputtering film, and then dipping after describing the electrode pattern The resist is removed in an etching solution (alkali solution). The shape of the electrode pattern may be any shape such as a thin line shape, a dot shape, a mesh shape, and a planar shape.

[Example]

Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the scope of the present invention is not limited to these examples. In addition, "part" in an Example shows a basis of weight. The hydroxyl value is a value measured in accordance with JIS-0070. The glass transition temperature is a value measured using a commercially available measuring instrument (trade name "DSC8230B", manufactured by Rigaku Electric Co., Ltd.).

〈Manufacture of (A) component〉

[Manufacturing example 1]

In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, the following components were charged and the reaction system was set 70 ° C: 40.8 parts (13.6 mole%) of hydroxyethyl acrylate (HEA) as component (a1); 72.0 parts (about 27.7 mole%) of methyl methacrylate (MMA) as component (a2) and 79.2 parts (about 23.8 mole%) of butyl acrylate (BA); and 48.0 parts (about 34.9 mole%) of acrylonitrile (AN) as component (a3); and 445.7 parts of acetic acid as component (G) Ethyl ester. Then, 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (ABN-V) was added, and the temperature was maintained at about 70 ° C for 6 hours. Then, 2.4 parts of ABN-V was added, and the reaction system was further maintained at the same temperature for about 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-1) having a glass transition temperature of 13 ° C and a hydroxyl value of 80 mgKOH / g.

[Manufacturing example 2]

In the same reaction vessel as in Production Example 1, the following components were charged and the reaction system was set to 70 ° C: 51.0 parts (13.3 mole%) HEA as (a1) component; 72.0 parts (about 2a) as component (a2) 21.8 mole%) MMA and 102.0 parts (about 24.1 mole%) BA; and 60.0 parts (about 34.3 mole%) AN as the (a3) component; and 15.0 parts (about 6.4) as the (a4) component Moore%) acrylamide (AM); and 557.1 parts of ethyl acetate as a (G) component. Then, 1.5 parts of ABN-V was put in and kept at about 70 ° C for 6 hours. Then, 3.0 parts of ABN-V was added, and the reaction system was further maintained at the same temperature for about 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-2) having a glass transition temperature of 13 ° C and a hydroxyl value of 80 mgKOH / g.

[Manufacturing example 3]

In the same reaction vessel as in Production Example 1, the following components were charged and the reaction system was set to 70 ° C: 59.2 parts (12.5 mole%) of hydroxyethyl methacrylate (HEMA) as (a1) component; and ( a2) 196.8 parts (approximately 54.2 mole%) of MMA as the ingredient; and 64.0 parts (approximately 33.3 mole%) of AN as the (a3) ingredient; and 564.3 parts of ethyl acetate as the (G) ingredient. Then, 3.2 parts of ABN-V was put in and kept at about 70 ° C for 6 hours. Then, 3.2 parts of ABN-V was added, and the reaction system was further maintained at the same temperature for about 6 hours. Thereafter, by cooling the reaction system to room temperature, a solution of the acrylic copolymer (A-3) having a glass transition temperature of 92 ° C. and a hydroxyl value of 80 mgKOH / g was obtained.

[Manufacturing example 4]

In the same reaction vessel as in Production Example 1, the following components were charged and the reaction system was set to 70 ° C: 25.5 parts (6.8 mole%) HEA as the (a1) component; 99.0 parts (approximately) as the (a2) component 30.5 mole%) MMA and 115.5 parts (about 27.8 mole%) BA; and 60.0 parts (about 34.9 mole%) AN as the (a3) component; and 557.1 parts of ethyl acetate as the (G) component . Then, 1.5 parts of ABN-V was put in and kept at about 70 ° C for 6 hours. Then, 3.0 parts of ABN-V was added, and the reaction system was further maintained at the same temperature for about 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-4) having a glass transition temperature of 13 ° C and a hydroxyl value of 40 mgKOH / g.

[Manufacturing example 5]

In the same reaction vessel as in Production Example 1, the following components were put and the reaction system was set to 70 ° C: 76.5 parts (18.1 mole%) HEA as the (a1) component; 37.5 parts (about 2a) as the component (a2) 10.3 mole%) MMA and 81.0 parts (about 17.3 mole%) BA; and, 105.0 parts (about 54.3 mole%) AN as the (a3) component; and 557.1 parts of ethyl acetate as the (G) component . Then, 1.5 parts of ABN-V was put in and kept at about 70 ° C for 6 hours. Then, 3.0 parts of ABN-V was added, and the reaction system was further maintained at the same temperature for about 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of the acrylic copolymer (A-5) having a glass transition temperature of 13 ° C and a hydroxyl value of 120 mgKOH / g.

[Comparative Manufacturing Example 1]

In the same reaction vessel as in Production Example 1, the following components were charged and the reaction system was set to 80 ° C: 40.8 parts (15.1 mole%) HEA as the (a1) component; 192.0 parts (approximately) as the (a2) component 82.5 mole%) MMA and 7.2 parts (approximately 2.4 mole%) BA; and, 445.7 parts of methyl ethyl ketone as the (G) component. Then, 1.2 parts of 2,2'-azobisisobutyronitrile (AIBN) was added, and the temperature was maintained at about 80 ° C for 5 hours. Next, 2.4 parts of AIBN was prepared, and the reaction system was further kept at the same temperature for about 4 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of an acrylic copolymer (A ') having a glass transition temperature of 70 ° C and a hydroxyl value of 80 mgKOH / g.

[Table 1]

<Preparation of Primer>

[Example 1]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of the component (A-1), 25.7 parts of the bisuret of hexamethylene diisocyanate as the component (B) (trade name "Duranate24A-100 ", Manufactured by Asahi Kasei Chemical Co., Ltd.), 50.0 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name" Viscoat # 300 ", manufactured by Osaka Organic Chemical Industry Co., Ltd.) as (C1) ingredients, 40.0 parts 3-isocyanatepropyltriethoxysilane (D) as a component (trade name "KBE-9007", manufactured by Shin-Etsu Silicone Co., Ltd.), 5.0 parts of an alumina particle dispersion as a component (Commercial) The name is "NANOBYK3610", manufactured by BYK Chemie Japan Co., Ltd.) and 2.5 parts of a photopolymerization initiator as a component (F) (trade name "Irg907", manufactured by Chiba Japan Co., Ltd.).

[Example 2]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 25.7 parts of Duranate 24A-100, 100.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907 .

[Example 3]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 25.7 parts of Duranate 24A-100, 150.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 7.5 parts of Irg907 .

[Example 4]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of the (A-1) component, 25.7 parts of the Duranate 24A-100, 150.0 parts of the Viscoat # 300, and 40.0 parts of the 3-mercaptopropyltrimethyl group as the (D) component. Oxysilane (trade name "KBM-803", manufactured by Shin-Etsu Silicone Co., Ltd.), 5.0 parts of NANOBYK3610, and 7.5 parts of Irg907.

[Example 5]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 25.7 parts of Duranate 24A-100, 200.0 parts of Viscoat # 300, 40.0 parts of KBM-803, 5.0 parts of NANOBYK3610, and 10.0 parts of Irg907 .

[Example 6]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-2) of a component solution, 25.7 parts of Duranate 24A-100, 100.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907 .

[Example 7]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of (A-3) ingredients, 25.7 parts of Duranate 24A-100, and 100.0 parts Viscoat # 300, 40.0 parts KBE-9007, 5.0 parts NANOBYK3610, and 5.0 parts Irg907.

[Example 8]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-4) of a component solution, 25.7 parts of Duranate 24A-100, 100.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907 .

[Example 9]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-5) of a component solution, 25.7 parts of Duranate 24A-100, 50.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 2.5 parts of Irg907 .

[Example 10]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 28.4 parts of hexamethylene diisocyanate isocyanurate (trade name "CORONATE HX", Japan Polyurethane Industry Co., Ltd. (Manufactured), 100.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907.

[Example 11]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 25.7 parts of Duranate 24A-100, and 100.0 parts of dipentaerythritol polyacrylate (trade name "NK ester A-9550W", Shin Nakamura Chemical Industry Co., Ltd.), 40.0 copies KBE-9007, 5.0 parts NANOBYK3610, and 5.0 parts Irg907.

[Example 12]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 25.7 parts of Duranate 24A-100, 50.0 parts of NK ester A-9550W, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 2.5 Part Irg907.

[Example 13]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of the (A-1) ingredient, 25.7 parts of the Duranate 24A-100, and 100.0 parts of the trimethylolpropane triacrylate (the product name " Viscoat # 295 ", manufactured by Osaka Organic Chemical Industry Co., Ltd.), 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907.

[Example 14]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A-1) of a component solution, 25.7 parts of Duranate 24A-100, 50.0 parts of Viscoat # 295, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 2.5 parts of Irg907 .

[Example 15]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of the (A-1) component, 25.7 parts of the Duranate 24A-100, 100.0 parts of the Viscoat # 300, and 40.0 parts of the 3-propenyloxy group as the (D) component Propyltrimethoxysilane (trade name "KBM-5103", Shin-Etsu Silicone Co., Ltd.), 5.0 parts NANOBYK3610, and 5.0 parts Irg907.

[Example 16]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of the (A-1) ingredient, 25.7 parts of the Duranate 24A-100, 100.0 parts of the Viscoat # 300, and 40.0 parts of the 3-methacrylic acid as the (D) ingredient Oxypropyltrimethoxysilane (trade name "Sila-Ace S710", manufactured by Chisso Co., Ltd.), 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907.

[Example 17]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts of the solution of the (A-1) component, 25.7 parts of the Duranate 24A-100, 100.0 parts of the Viscoat # 300, and 40.0 parts of the 3-glycidyloxy group as the (D) component. Propyltrimethoxysilane (trade name "Sila-Ace S 510", manufactured by Chisso Co., Ltd.), 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907.

[Comparative Example 1]

The following ingredients were carefully mixed to prepare a primer: 286.0 parts (A ') of a component solution, 25.7 parts of Duranate 24A-100, 100.0 parts of Viscoat # 300, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907.

[Comparative Example 2]

Carefully mix the following ingredients to prepare a primer that does not contain (D): 286.0 parts of the solution of (A-1) ingredients, 25.7 parts of Duranate 24A-100, 150.0 parts of Viscoat # 300, 5.0 parts of NANOBYK3610, and 7.5 parts of Irg907.

[Comparative Example 3]

The following ingredients were carefully mixed to prepare a primer containing no component (D): a solution of 286.0 parts (A-1), 25.7 parts of Duranate 24A-100, 200.0 parts of Viscoat # 300, 5.0 parts of NANOBYK3610, and 10.0 parts Irg907.

〈Production of Copper Evaporated Plastic Film〉

The primer of Example 1 was applied to a commercially available polyester film (trade name "Lumirror U48", manufactured by Toray Co., Ltd., 100 μm thick) so that the dry film thickness became approximately 1.0 μm, using a bar coating method. The cloth was applied and dried at 120 ° C for 1 minute. Then, it was UV-cured at 300 mJ / cm ² to obtain a coating film having a cured undercoat layer. The primers of other Examples and Comparative Examples were also coated in the same manner.

Then, a commercially available vapor deposition device (product name "NS-1875-Z", manufactured by Nishiyama Seisakusho Co., Ltd.) was used for the bottom coating surface of the coating film, and copper was vapor-deposited (thickness: about 100 nm). A copper-evaporated plastic film was obtained. The primers of other examples and comparative examples also obtained copper-evaporated plastic films by the same method.

1. Hardness test of hardened base coating

The pencil hardness of the cured undercoat layer of each coating film of Examples and Comparative Examples was evaluated in accordance with JIS K 5600-5-4. The results are shown in Table 1.

2. Initial adhesion

In accordance with JIS K 5600-5-6, a cross-cut test was performed on the copper-deposited films of the copper-deposited films of the examples and comparative examples. Specifically, 100 squares were drawn on the copper-deposited surface with a cutter, and an adhesive tape (product name "Cello Tape (registered trademark)", manufactured by Nichiban Co., Ltd.) was attached, and then carried out in a vertical direction. Strip and then count the number of squares that were not stripped. In other examples and comparative examples The same method was used to evaluate the initial adhesion of the copper vapor-deposited film. The results are shown in Table 1. Furthermore, when the number of unseparated squares is 100, and the four sides of any square are completely smooth visually, the adhesion is judged to be the best. Therefore, in Table 1, the "*" Symbol (the same applies hereinafter).

3.Acid resistance

The copper-deposited films of the examples and comparative examples were immersed in a 4% aqueous hydrochloric acid solution heated to 40 ° C. for 5 minutes, and then the adhesion of the copper-deposited films was evaluated in the same manner as above.

4. Alkali resistance

The copper-deposited films of the examples and comparative examples were immersed in a 4% sodium hydroxide aqueous solution heated to 40 ° C. for 5 minutes, and then the adhesion of the copper-deposited films was evaluated in the same manner as described above.

Claims (17)

A primer for a substrate with a copper film attached, comprising: an acrylic copolymer (A) having a hydroxyl group, an alkyl ester group and a nitrile group, and a primary amidine group as the case may be; and a polyisocyanate (B) Which has at least 3 isocyanate groups; the active energy ray polymerizable compound (C) which has at least 3 carbon-carbon double bond-containing groups; and the reactive alkoxysilyl compound (D), which is The general formula (1) is represented by X ¹ -Si (R ¹ ) _a (OR ² ) _3-a . In the formula (1), X ¹ represents a group containing and selected from a hydroxyl group, an isocyanate group, and a polymerizable carbon. A group of at least one functional group that reacts in a group consisting of a carbon double bond group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. The primer according to claim 1, wherein the component (A) is hydroxyalkyl (meth) acrylate (a1), alkyl (meth) acrylate (a2), and (meth) acrylic acid Nitrile (a3) and (meth) acrylamide (a4) are reacted as required; and the alkyl (meth) acrylate (a2) is excluding a hydroxyl group. The primer according to claim 1 or 2, wherein the hydroxyl value of the component (A) is 30 to 150 mgKOH / g, and the glass transition temperature is 0 to 100 ° C. The primer according to claim 1 or 2, wherein the component (B) is a derivative selected from the group consisting of an adduct of a diisocyanate compound, an isocyanurate, and a biuret. (b1). The primer according to claim 1 or 2, wherein the equivalent ratio of the hydroxyl group contained in the component (A) to the isocyanate group contained in the component (B), that is, NCO / OH is 0.2 to 5. The primer according to claim 1 or 2, wherein the component (C) is an active energy ray polymerizable compound (C1) having 3 to 6 (meth) acrylfluorenyl groups and at least one hydroxyl group in the molecule. And / or an active energy ray polymerizable compound (C2) having 3 to 6 (meth) acrylfluorenyl groups in the molecule and not having a hydroxyl group. The primer according to claim 1 or 2, wherein the functional group in X ¹ of the general formula (1) representing the component (D) is selected from the group consisting of an isocyanate group, a thiol group, an amine group, and an epoxy group. One of the group consisting of a radical, an anhydride group and a vinyl group. The primer according to claim 1 or 2, further comprising inorganic particles (E). The primer according to claim 1 or 2, further comprising a photopolymerization initiator (F). The primer according to claim 1 or 2, further comprising an organic solvent (G). A substrate with a copper film is formed by sequentially laminating an undercoat layer and a copper thin film layer on the surface of the substrate. The undercoat layer is as described in any one of claims 1 to 10. The primer is hardened. The substrate with a copper film attached thereto according to claim 11, wherein the substrate is plastic. The substrate with a copper film attached thereto as described in claim 12, wherein the plastic is a plastic film. The substrate with a copper film attached thereto as described in claim 13, wherein the plastic film is a polyester film. A method for manufacturing a substrate with a copper film, characterized in that: the surface of the substrate is coated with the primer as described in any one of claims 1 to 10, and then the substrate is heated Then, a hardened undercoat layer is further formed by irradiating active energy rays, and then a copper thin film layer is formed on the hardened undercoat layer. The manufacturing method according to claim 15, wherein the method for forming a copper thin film layer on the hardened undercoat layer is a vacuum evaporation method or a sputtering method. A conductive film is formed by using a base material with a copper thin film, and the base material with a copper thin film is the base material with a copper thin film as described in any one of claims 11 to 14, or uses A copper film-attached substrate obtained by the manufacturing method according to claim 15 or 16.