JP6011895B2 - Undercoat agent for substrate with copper thin film, substrate with copper thin film, method for producing substrate with copper thin film, and conductive film - Google Patents

Description

  The present invention uses an undercoat agent used for forming a copper thin film on the surface of various substrates, a substrate with a copper thin film having a layer made of the undercoat agent, a method for producing the same, and the substrate with a copper thin film It is related with the conductive film formed.

  In the present specification, the “substrate with a copper thin film” refers to an article in which a copper thin film is formed on the surface of various substrates such as plastic molded articles, plastic films, metals, glass, paper, nanocellulose paper, and wood. . Hereinafter, a film having a conductive layer made of a copper vapor deposition film on the surface (hereinafter referred to as copper vapor deposition) positioned as a substitute for a film having a conductive layer made of ITO (indium tin oxide) on the surface (hereinafter also referred to as ITO film). The background art will be described by taking as an example a plastic film.

  An ITO film is used as an electrode film for touch panels such as smartphones and tablet PCs because it is excellent in transparency and conductivity. However, since indium is an expensive rare metal, there is a problem in terms of cost, and since the ITO layer is generally hard and brittle, there are problems in terms of workability such as weakness to bending and deformation.

  Therefore, in this field, an attempt has been made to use an organic conductive polymer having a film forming property (for example, polythiophene, polyaniline, polypyrrole, etc.) as a conductive material instead of ITO. However, since organic conductive polymers are generally strongly colored, conductive films or electrode films using them as conductive layers still have problems in terms of color tone. In this respect, in order to improve the color tone, the amount of the organic conductive polymer used may be reduced, but the conductivity is impaired.

  On the other hand, in this field, a copper-deposited plastic film has been studied in place of the ITO film. This is because copper has a lower resistivity than ITO, exhibits conductivity comparable to that of an ITO film, has good workability, and is cheaper than anything. Therefore, the copper-deposited plastic film is useful as an electrode film for various electronic devices, and is considered to contribute to, for example, further enlargement of the touch panel and effective use as an interactive digital signage.

  The copper-deposited plastic film is generally obtained by vacuum-depositing nickel on a film surface serving as a substrate and further vacuum-depositing copper thereon. This nickel vapor deposition layer functions as an anchor layer for making a film and a copper vapor deposition layer adhere more strongly. And a resist is apply | coated to the obtained copper vapor deposition plastic film, an electrode film is drawn, Then, it is immersed in etching liquid (an alkali solution and / or acidic solution), and an electrode film is obtained by removing a resist.

  However, since the copper vapor-deposited plastic film has poor alkali resistance and acid resistance, nickel has a problem that the copper vapor-deposited layer is peeled off from the substrate film or dropped after the etching treatment.

  Further, as described above, although the copper vapor-deposited plastic film is cheaper than the ITO film, the nickel forming the anchor layer is more expensive than copper, and is therefore relatively expensive. Therefore, in this field, a copper-deposited plastic film using an undercoat agent mainly composed of an organic polymer as an anchor layer has also been studied (see Patent Document 1).

JP-A-5-28835

  In the present invention, not only the initial adhesion between the substrate and the copper thin film, but also the adhesion between the substrate and the copper thin film after the copper thin film substrate is treated with an alkali solution and an acidic solution (alkali resistance adhesion, acid resistance). The main problem is to provide a novel undercoat agent that is excellent in adhesion.

  As a result of extensive studies, the present inventor has added a predetermined active energy ray-curable compound and a reactive alkoxysilyl compound to a composition having a predetermined hydroxyl group-containing acrylic copolymer as a main agent and a predetermined polyisocyanate as a curing agent. It has been found that the above problem can be solved by using an undercoat agent that is blended and cured with both heat and active energy rays.

That is, the present invention relates to an acrylic copolymer (A) having a hydroxyl group, an alkyl ester group and a nitrile group and optionally a primary amide group, a polyisocyanate (B) having at least three isocyanate groups, and a carbon-carbon double bond-containing group. Active energy ray polymerization type compound (C) having at least three, and general formula (1): X ¹ -Si (R ¹ ) _a (OR ² ) _3-a (in formula (1), X ¹ is a hydroxyl group R ¹ represents a group containing a functional group that reacts with at least one selected from the group consisting of an isocyanate group and a polymerizable carbon-carbon double bond-containing group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² Is a hydrocarbon group having 1 to 8 carbon atoms, and a is a reactive alkoxysilyl compound (D) represented by 0, 1 or 2. about The

  Moreover, this invention relates to the electroconductive film formed using the base material with a copper thin film which has the layer which consists of the said undercoat agent, its manufacturing method, and this base material with a copper thin film.

  As described above, the undercoat agent of the present invention is a composition of a type that is cured by both heat and active energy rays. According to this, only initial adhesion between various substrates such as plastic and a copper thin film is provided. In other words, the alkali-proof adhesiveness and the acid-resistant adhesiveness are improved (hereinafter, these may be simply referred to as adhesiveness). Moreover, since the undercoat agent contains a component that is cured by active energy rays, it is possible to impart excellent hardness to the undercoat film.

  Moreover, especially the base material with a copper thin film obtained using the undercoat agent of this invention has favorable alkali-proof adhesiveness and acid-resistant adhesiveness. Therefore, even if this base material with a copper thin film is immersed in an etching solution, the copper thin film hardly falls off. Moreover, since the base material with a copper thin film can impart excellent hardness to the undercoat layer, in the manufacturing process of the base material, the copper thin film surface has good scratch resistance, and the copper thin film surface has a mesh shape. In this case, defects are less likely to occur.

  The copper thin film plastic film of the present invention can be used for various applications. Among them, a copper vapor-deposited film and a film formed by forming a copper ultra-thin film by a sputtering method are particularly suitable as an electrode film replacing the ITO film. Moreover, this electrode film can be used for a smart phone, a tablet terminal, a notebook PC, all-in-one PC, digital signage, etc., for example.

  The undercoat agent for a copper thin film-attached substrate of the present invention (hereinafter also simply referred to as an undercoat agent) is an acrylic copolymer (A) having a hydroxyl group, an alkyl ester group, a nitrile group, and optionally a primary amide group (hereinafter referred to as ( A) component)), polyisocyanate (B) having at least three isocyanate groups (hereinafter also referred to as component (B)), and active energy ray polymerization having at least three carbon-carbon double bond-containing groups. Type compound (C) (hereinafter also referred to as (C) component) and a non-aqueous composition containing a reactive alkoxysilyl compound (D) represented by a predetermined formula (hereinafter also referred to as (D) component) It is a thing.

  Since the component (A) has a hydroxyl group and a nitrile group as polar groups in the molecule, it contributes to the adhesion, particularly the acid resistance adhesion and alkali resistance resistance. In addition, when a primary amide group is further introduced into the component (A), the acid resistance and alkali resistance are further improved.

  As the component (A), various known compounds can be used without particular limitation. For example, hydroxyalkyl (meth) acrylate (a1) (hereinafter also referred to as component (a1)), alkyl (meth) acrylate (a2) (Excluding those having a hydroxyl group) (hereinafter also referred to as component (a2)) and (meth) acrylonitrile (a3) (hereinafter also referred to as component (a3)) and (meth) acrylamide (a4) as required. What makes it a reaction component is preferable.

  The component (a1) is used for introducing a hydroxyl group into the main component (A) and reacting it exclusively with the component (B) to introduce a crosslinked structure into the undercoat layer. As a result of the introduction of the crosslinked structure, the undercoat layer exhibits the desired adhesion and hardness.

  As the component (a1), various known compounds can be used without particular limitation as long as they have a (meth) acryloyl group and a hydroxyalkyl ester group in the molecule. 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, hydroxycyclohexyl (meth) acrylate, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

  As the component (a2), various known compounds can be used without particular limitation as long as they have a (meth) acryloyl group and an alkyl ester group (excluding a hydroxyalkyl group) in the molecule. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, octyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate, docosyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclopentanyl (meth) acrylate, isobornyl (meth) acrylate and the like can be mentioned, and these can be used alone or in combination of two or more.Among these, those having about 1 to 6 carbon atoms of the alkyl ester group are preferable from the viewpoint of adhesion.

  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-methylol methacrylamide.

  Although the usage-amount of each said component is not specifically limited, Usually, it is good to set it as the following ranges from viewpoints, such as adhesiveness.

<When (a4) component is not used>
Component (a1): Usually about 5 to 35 mol%, preferably about 8 to 25 mol% (a2) Component: Usually about 10 to 95 mol%, preferably about 30 to 70 mol% (a3) Component: Usually 5 to 5 mol% About 80 mol%, preferably about 15 to 65 mol%

<When (a4) component is used>
Component (a1): Usually about 5 to 35 mol%, preferably about 8 to 25 mol% (a2) Component: Usually about 10 to 87 mol%, preferably about 30 to 70 mol% (a3) Component: Usually 5 to 5 mol% About 80 mol%, preferably about 15 to 65 mol% (a4) Component: Usually about 3 to 55 mol%, preferably about 5 to 40 mol%

  In the present invention, vinyl monomers other than the components (a1) to (a4) can be included in the reaction component of the component (A). Specifically, α-olefins such as 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, vinylcyclohexane and 2-methylvinylcyclohexane Unsaturated alcohols such as (meth) allyl alcohol, 4-penten-1-ol, 1-methyl-3-buten-1-ol and 5-hexen-1-ol; styrene, α-methylstyrene and t -Styrenes such as butylstyrene; aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate and 4-methylbenzyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, dimethylaminopropyl (meth) acrylate and diethylaminopro Dialkylaminoalkyl (meth) acrylates such as pill (meth) acrylate and salts thereof; dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide Dialkylaminoalkyl (meth) acrylamides and salts thereof; N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid and Chain transfer monomers such as 2- (meth) acrylamido-2-methylpropanecarboxylic acid and salts thereof; vinylamine, aminoethyl (meth) acrylate, allyl mercaptan and Other monofunctional monomers such as ricidyl (meth) acrylate; bis (meth) acrylamides such as methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide and hexamethylene bis (meth) acrylamide; ethylene glycol di (meth) acryl Di (meth) acrylic esters such as esters and diethylene glycol di (meth) acrylic esters; divinyl esters such as divinyl adipate and divinyl sebacate; bifunctional such as diallyldimethylammonium, diallyl phthalate, diallyl chlorendate and divinylbenzene Monomers: 1,3,5 triacryloylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, triallyl trimellitate and N, N-diallylacrylamido Trifunctional monomers such as tetramethylol methane tetraacrylate, tetraallyl pyromellitate and tetrafunctional monomers such as N, N, N ′, N′-tetraallyl-1,4diaminobutane, and the like, These can be used alone or in combination of two or more. Moreover, although the usage-amount of these is also not specifically limited, Usually, it is less than 10 mol% with respect to the said (a1) component-(a4) component.

  The component (A) can be produced by various known methods. Specifically, for example, the (a1) component, the (a2) component and the (a3) component, and if necessary, the (a4) component and other monomers may be used in the absence of a solvent or an organic solvent (G) described later. In general, it can be obtained by carrying out a copolymerization reaction at about 80 to 180 ° C. for about 1 to 10 hours in the presence of a radical polymerization initiator. Moreover, the usage-amount of the organic solvent (G) is a range from which the solid content weight of the solution containing (A) component will be about 10 to 50 weight% normally.

  Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, t-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, 2,2′-azobisisobutyronitrile, 2, 2 ′. -Azobis (2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Further, the amount used is usually in the range of about 0.1 to 2% by weight based on the total weight of the reaction components constituting the component (A).

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

  (B) A component is a component which functions as a hardening | curing agent of (A) component which is a main ingredient, and if it is polyisocyanate which has at least three intramolecular isocyanate groups, various well-known things can be especially used without a restriction | limiting. Moreover, (B) component reacts also with what has an isocyanate reactive functional group (a hydroxyl group, an amino group, etc.) among the below-mentioned (C) component and (D) component, and is a crosslinked structure in the undercoat layer which concerns on this invention. give.

  As a specific example of the component (B), one kind of derivative (b1) selected from the group consisting of a biuret body, a nurate body and an adduct body of a diisocyanate compound (hereinafter also referred to as the component (b1)), the (b1) Reaction product of component and diol compound (b2) (hereinafter also referred to as component (b2)), triisocyanate compound (b3) (excluding those corresponding to components (b1) and (b2)) (hereinafter, (B3) component)), and at least one selected from the group consisting of other polyisocyanate compounds (hereinafter also referred to as component (b4)).

  Examples of the diisocyanate compound constituting the component (b1) include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and lysine diisocyanate, and dicyclohexylmethane. Examples thereof include alicyclic diisocyanates such as diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tolylene diisocyanate.

  In addition, the biuret body of the said diisocyanate compound is represented by the following structural formula.

（式中、Ｒ^３は前記ジイソシアネート化合物の残基を表す。）

(Wherein R ³ represents a residue of the diisocyanate compound.)

  Moreover, the nurate body of the said diisocyanate compound is represented by the following structural formula.

（式中、Ｒ^４は、前記ジイソシアネート化合物の残基を表す。）

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

  Moreover, the adduct body of the said 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 the remaining diisocyanate compound). Represents a group.)

  The diol compound constituting the component (b2) is not particularly limited. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, 1,6- Examples include hexanediol, octanediol, dipropylene glycol, polyethylene glycol, and polypropylene glycol, and these can be used alone or in combination of two or more. Of these, those having about 2 to 20 carbon atoms, preferably about 4 to 8 carbon atoms are preferred.

  The component (b2) can be produced by various known methods. Specifically, for example, when the component (b1) and the diol compound are used, the equivalent ratio [NCO ′ / OH ′] of the former isocyanate group (NCO ′) to the latter hydroxyl group (OH ′) is usually 5 to 5. It can be obtained by subjecting it to a urethanization reaction within a range of about 20 and preferably about 10 to 20, usually under 40 to 80 ° C. for about 1 to 5 hours. The component (b2) obtained has an isocyanate group equivalent of usually about 1 to 10 meq / g, preferably about 3 to 6 meq / g.

  Examples of the component (b3) include toluene-2,4,6-triisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, 1,6,11-undecane triisocyanate, 1,3,6- Examples include triisocyanates such as hexamethylene triisocyanate and bicycloheptane triisocyanate, and hexafunctional polyisocyanates (product name “Duranate MHG-80B”, manufactured by Asahi Kasei Chemicals Corporation).

  As the component (B), the component (b1) is particularly preferably the component (b1) containing the aliphatic diisocyanate as a constituent from the viewpoint of the balance of the initial adhesion, acid resistance, and alkali resistance.

  The amount ratio of the component (A) to the component (B) is not particularly limited, but from the viewpoint of adhesion and coating film hardness, the molar ratio of the hydroxyl group of the component (A) and the isocyanate group of the component (B) (NCO / OH) is usually in the range of about 0.2-5, preferably 1-2.

  As the component (C), various known compounds can be used without particular limitation as long as they are active energy ray polymerization type compounds having at least three carbon-carbon double bond-containing groups in the molecule. Examples of the containing group include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

  A preferred specific species of the component (C) is an active energy ray-polymerizable compound (C1) having 3 to 6 (meth) acryloyl groups and at least one hydroxyl group in the molecule (hereinafter also referred to as the component (C1). ), Active energy ray-polymerizable compound (C2) (hereinafter also referred to as (C2) component) having 3 to 6 (meth) acryloyl groups in the molecule and no hydroxyl group, 3 in the molecule Active energy ray polymerization type compound (C3) (hereinafter also referred to as (C3) component) having -6 allyl groups and at least one hydroxyl group, and 3-6 allyl groups in the molecule; Examples thereof include at least one selected from the group consisting of an active energy ray polymerizable compound (C4) having no hydroxyl group (hereinafter also referred to as (C4) component). Among these, those having a hydroxyl group are chemically bonded to those reacting with the hydroxyl group among the component (B) and the component (D) described later to form a crosslinked structure in the undercoat layer of the present invention. This is more preferable because of its increased hardness.

  Examples of the component (C1) include trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, and pentaerythritol tri (meth). Examples include hydroxyl group-containing (meth) acrylate compounds such as acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

  Examples of the component (C2) include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. And hydroxyl-free (meth) acrylate compounds such as ditrimethylolpropane tetra (meth) acrylate and glycerol tri (meth) acrylate.

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

  Although the usage-amount of (C) component is not specifically limited, Usually, when making (A) component and (B) component into 100 weight part (solid content conversion), about 10-500 weight part normally, Preferably it is 30- The range is about 300 parts by weight (all in terms of solid content).

  In addition, together with the component (C), 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 di (meth) acrylates such as ethylene oxide modified di (meth) acrylate of bisphenol A, oligomers such as polyurethane poly (meth) acrylate and polyester poly (meth) acrylate, and 2- Ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclo Nteniru (meth) acrylate and isobornyl (meth) mono (meth) acrylates such as acrylates can be used in combination.

Component (D), the general formula _{^{(1): X 1 -Si (}} R 1) a in ^(OR _{2) 3-a} ^(formula (1), ^{X 1} represents a hydroxyl group, an isocyanate group and a polymerizable carbon - carbon double A group containing a functional group that reacts with at least one selected from the group consisting of a heavy bond-containing group, R ¹ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and R ² is a hydrocarbon group having 1 to 8 carbon atoms. Wherein a represents 0, 1 or 2.).

The functional group in X ¹ of the general formula (1) representing the component (D) is, for example, 1 selected from the group consisting of an isocyanate group, a thiol group, an amino group, an epoxy group, an acid anhydride group, and a vinyl group. Species are mentioned.

Examples of the compound in which the functional group in X ¹ is an isocyanate group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, and 3-isocyanatepropylmethyldiethoxysilane. Can be mentioned.

Examples of compounds in which the functional group in X ¹ is a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Can be mentioned.

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

Examples of the compound in which the functional group in X ¹ is an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Examples include 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.

Examples of the compound whose functional group in X ¹ is an acid anhydride group include 3-trimethoxysilylpropyl succinic anhydride.

Examples of the compound in which the functional group in X ¹ is a vinyl group include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, styryltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropyl. Examples include trimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, and 3- (meth) acryloxypropyltriethoxysilane.

  Although the usage-amount of (D) component is not specifically limited, Usually, when making (A) component and (B) component into 100 weight part (solid content conversion), about 5-50 weight part normally, Preferably it is 20- The range is about 40 parts by weight.

  The undercoat agent of the present invention may contain various known inorganic particles (E) (hereinafter also referred to as (E) component) as necessary. Specifically, for example, particles such as silica, titania, alumina, zinc oxide, tin oxide, zirconia, ITO (indium tin oxide), ATO (antimony tin oxide), aluminum hydroxide, calcium hydroxide, and magnesium hydroxide are included. These may be used alone or in combination of two or more. Among these, silica and / or alumina are particularly preferable. Further, the surface of the component (E) may be subjected to various treatments. The median diameter (d50) of the component (E) is not particularly limited, but is usually about 10 nm to 5 μm.

  Although the usage-amount of (E) component is not specifically limited, Usually, when the (A) component and (B) component are 100 weight part (solid content conversion), about 1-20 weight part normally, Preferably it is 5-5. The range is about 10 parts by weight.

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

  Specific examples of the component (F) include, for example, benzophenone, 4 ′-(methylthio) -α-morpholino-α-methylpropiophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenyl. Benzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- (1 -Methylvinyl) phenyl] propanone], benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methylthio) thiol Enyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, methylbenzoylformate, Enylglyoxylic acid methyl ester, 4,4′-bis (diethylamino) -benzophenone, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1 -Phenyl-2-morpholinopropan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one and 2-ethyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 and photopolymerization initiators described in JP 2014-1390 A, and the like can be used, and these can be used alone or in combination of two or more. it can. As the component (F), for example, commercially available products such as Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 261 and Darocur 1173 can be used. Moreover, these can be used alone or in combination of two or more.

  Although the usage-amount of (F) component is not specifically limited, Usually, when (C) component is 100 weight part (solid content conversion), about 0.1-10 weight part normally, Preferably it is 1-5 weight part It is a range which becomes a grade.

  As an auxiliary for component (F), triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoate Ethyl acetate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. can do. Moreover, these can be used alone or in combination of two or more.

  The undercoat agent of the present invention may further contain an organic solvent (G) (hereinafter also referred to as the (G) component). Specifically, for example, lower ketones of methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, alcohols such as ethyl alcohol and propyl alcohol, ether esters such as propylene glycol monomethyl ether acetate and ethyl cellosolve acetate , Ethyl acetate, chloroform and dimethylformamide, and these can be used alone or in combination of two or more.

  Although the usage-amount of (G) component is not specifically limited, Usually, it is the range from which the solid content concentration of the undercoat agent of this invention will be about 1 to 60 weight% normally.

  The undercoat agent of the present invention can further contain a urethanization catalyst. Specifically, for example, organometallic catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and bismuth octylate, diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine and triethylenediamine And the like, and these can be used singly or in combination of two or more. In addition, although the usage-amount of this urethanization catalyst is not specifically limited, When (A) component and (B) component are 100 weight part (solid content conversion) normally, 0.01-0.5 weight part normally The range is preferably about 0.05 to 0.2 parts by weight.

  The undercoat agent of the present invention can contain a polythiol compound as necessary. Specifically, for example, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,4 -Bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) and dipentaerythritol Hexakis (3-mercaptobutyrate) etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Although the usage-amount of this polythiol compound is not specifically limited, Usually, when (A) component and (B) component are 100 weight part (solid content conversion), about 1-20 weight part normally, Preferably it is 5-10. It is the range which becomes about a weight part.

  In addition, when using a polythiol compound, in order to improve the pot life of the undercoat agent of this invention, various well-known ene-thiol reaction inhibitors can be used. Specifically, for example, phosphorus compounds such as triphenylphosphine and triphenyl phosphite, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2, 6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol) Radical), radical polymerization inhibitors such as N-nitrosophenylhydroxylamine aluminum salt and diphenylnitrosamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol and diaza Tertiary amines such as bicycloundecene and 2-methylimidazole , Imidazoles such as 2-ethyl-4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole, and the like. A combination of more than one species can be used.

  In addition, the undercoat agent of the present invention may contain additives such as a leveling agent, an antioxidant, a polymerization inhibitor, and an ultraviolet absorber.

  The base material with a copper thin film of the present invention is a composite base material in which an undercoat layer formed by curing the undercoat agent of the present invention and a copper thin film layer are laminated in this order on the surfaces of various base materials.

  Examples of the substrate include not only plastic materials such as polyester, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyethylene, and polypropylene, but also non-plastic materials such as metal, glass, paper, nanocellulose paper, and wood. Further, the shape of these base materials is not particularly limited, and may be, for example, a spherical shape, a cylindrical shape, a rectangular parallelepiped shape, a plate shape, or a film shape, and unevenness or a curved surface exists on a part of their surfaces. Also good. When the substrate with a copper thin film of the present invention is used as a conductive film, the substrate is preferably a plastic film, particularly a polyester film, from the viewpoints of heat resistance and optical properties. The thickness of the substrate film is not particularly limited, but is usually about 50 to 200 μm.

  The thickness of the cured 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 deposition film, a copper sputtered film, and a copper CVD film. When using the film with a copper thin film of the present invention as an electrode film, the copper thin film is particularly preferably a copper vapor-deposited film or a copper sputtered film. Moreover, although the thickness of this copper thin film layer is not specifically limited, Usually, it is about 0.1-2 micrometers.

  The manufacturing method of the base material with a copper thin film of this invention is not specifically limited. For example, (a) the undercoat agent of the present invention is applied to the surface of the base material (one side or both sides if the base material is a film, for example), and (a) C) A mode in which a cured undercoat layer is formed by further irradiating active energy rays, and (d) a copper thin film layer is formed on the cured undercoat layer.

Regarding the step (a), the conditions for applying the undercoat agent of the present invention to the surface of the base material (one side or both sides if the base material is, for example, a film) are not particularly limited. , Spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater and dot coater. The coating amount is not particularly limited, but is usually about 0.01 to 10 g / m ² as a dry solid content.

  Although the conditions at the time of applying heat to this base material are not specifically limited regarding a process (a), Usually, it is about 80 second-about 150 degreeC, and time is about 10 second-about 2 minutes. By this treatment, when the organic solvent (G) is used from the semi-cured undercoat layer, this is volatilized, and at the same time, the component (A) and the component (B) undergo urethanation reaction in the layer, and are crosslinked. Form a structure. In addition, in the urethanization reaction, those having a hydroxyl group, an amino group, a thiol group, an isocyanate group or the like among the component (C) and the component (D) are also involved.

Regarding the step (c), the conditions for irradiating the semi-cured undercoat layer with active energy rays are not particularly limited. Examples of the active energy rays include ultraviolet rays and electron beams. Examples of the ultraviolet light source include a high-pressure mercury lamp and a metal halide lamp, and the irradiation energy is usually about 100 to 2,000 mJ / cm ² . Examples of the electron beam supply method include scanning electron beam irradiation and curtain electron beam irradiation method, and the irradiation energy is usually about 10 to 200 kGy. By this treatment, the components (C) undergo a radical polymerization reaction in the heat-cured undercoat layer to form a crosslinked structure. Among the components (D), those having an active energy ray polymerizable functional group are also involved in the polymerization reaction.

  Regarding the step (d), means for forming a copper thin film layer on the cured undercoat layer is not particularly limited, but a so-called dry coating method is preferred. Specifically, for example, a physical method such as a vacuum deposition method or a sputtering method, or a chemical method such as CVD (chemical vapor phase reaction or the like) can be used.

  The conductive film of the present invention is a film formed using the substrate with a copper thin film of the present invention. In particular, a film obtained from a copper vapor-deposited plastic film or a copper sputtered film is useful as a substitute for an ITO film.

  The method for producing the conductive film is not particularly limited. However, when the conductive film is used as an electrode film, various resists are applied to the copper vapor-deposited plastic film or the copper sputtered film, and after describing the electrode pattern, an etching solution (alkaline And a method of removing the resist. The shape of the electrode pattern may be any form such as a fine line shape, a dot shape, a mesh shape, and a planar shape.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail through an Example and a comparative example, the scope of the present invention is not limited by these. In addition, "part" in an Example represents a weight reference | standard. The hydroxyl value is a value measured according to JIS-0070. The glass transition temperature is a value measured using a commercially available measuring instrument (product name “DSC8230B”, manufactured by Rigaku Corporation).

<Manufacture of (A) component>
Production Example 1
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube, 40.8 parts (13.6 mol%) of hydroxyethyl acrylate (HEA) as component (a1), component (a2) Methyl methacrylate (MMA) 72.0 parts (about 27.7 mol%) and butyl acrylate (BA) 79.2 parts (about 23.8 mol%), and (a3) acrylonitrile (AN) 48. 0 part (about 34.9 mol%) and 445.7 parts of ethyl acetate as (G) component were charged, and the reaction system was set to 70 ° C. Next, 1.2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) (ABN-V) was charged, and the mixture was kept warm at around 70 ° C. for 6 hours. Next, 2.4 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of an acrylic copolymer (A-1) having a glass transition temperature of 13 ° C. and a hydroxyl value of 80 mgKOH / g.

Production Example 2
In a reaction vessel similar to Production Example 1, 51.0 parts (13.3 mol%) of HEA as the component (a1), 72.0 parts (about 21.8 mol%) of MMA as the component (a2) and 102. 0 part (about 24.1 mol%) and 60.0 parts (about 34.3 mol%) of AN as component (a3) and 15.0 parts of acrylamide (AM) as component (a4) (about 6.4 mol) %) As well as 557.1 parts of ethyl acetate as component (G), and the reaction system was set to 70 ° C. Next, 1.5 parts of ABN-V was charged, and kept at 70 ° C. for 6 hours. Then, 3.0 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of an acrylic copolymer (A-2) having a glass transition temperature of 13 ° C. and a hydroxyl value of 80 mgKOH / g.

Production Example 3
In a reaction vessel similar to Production Example 1, 59.2 parts (12.5 mol%) of hydroxyethyl methacrylate (HEMA) as component (a1) and 196.8 parts (about 54.2 mol%) of MMA as component (a2) ) And (a3) component as AN (64.0 parts) (about 33.3 mol%) and (G) component as ethyl acetate (564.3 parts) were charged and the reaction system was set at 70 ° C. Next, 3.2 parts of ABN-V was charged and kept warm at around 70 ° C. for 6 hours. Next, 3.2 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of an acrylic copolymer (A-3) having a glass transition temperature of 92 ° C. and a hydroxyl value of 80 mgKOH / g.

Production Example 4
In a reaction vessel similar to Production Example 1, 25.5 parts (6.8 mol%) of HEA as the component (a1), 99.0 parts (about 30.5 mol%) of MMA as the component (a2), and 115. 5 parts (about 27.8 mol%), 60.0 parts of AN (about 34.9 mol%) as component (a3), and 557.1 parts of ethyl acetate as component (G) were charged, and the reaction system was heated to 70 ° C. Set. Next, 1.5 parts of ABN-V was charged, and kept at 70 ° C. for 6 hours. Then, 3.0 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of an acrylic copolymer (A-4) having a glass transition temperature of 13 ° C. and a hydroxyl value of 40 mgKOH / g.

Production Example 5
In the same reaction vessel as in Production Example 1, 76.5 parts (18.1 mol%) of HEA as the component (a1), 37.5 parts (about 10.3 mol%) of MMA as the component (a2), and BA 81. 0 parts (about 17.3 mol%), 105.0 parts (about 54.3 mol%) of AN as component (a3), and 557.1 parts of ethyl acetate as component (G) were charged, and the reaction system was heated to 70 ° C. Set. Next, 1.5 parts of ABN-V was charged, and kept at 70 ° C. for 6 hours. Then, 3.0 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 6 hours. Thereafter, the reaction system was cooled to room temperature to obtain a solution of an acrylic copolymer (A-5) having a glass transition temperature of 13 ° C. and a hydroxyl value of 120 mgKOH / g.

Comparative production example 1
In a reaction vessel similar to Production Example 1, 40.8 parts (15.1 mol%) of HEA as the component (a1), 192.0 parts (about 82.5 mol%) of MMA as the component (a2), and BA 7. 2 parts (about 2.4 mol%) and 445.7 parts of methyl ethyl ketone as component (G) were charged, and the reaction system was set at 80 ° C. Next, 1.2 parts of 2,2′-azobisisobutyronitrile (AIBN) was charged, and kept at around 80 ° C. for 5 hours. Next, 2.4 parts of AIBN were charged, and the reaction system was further kept at the same temperature for 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.

<Preparation of undercoat agent>
Example 1
(A-1) component solution 286.0 parts, (B) component as biuret of hexamethylene diisocyanate (trade name “Duranate 24A-100” manufactured by Asahi Kasei Chemicals Corporation) 25.7 parts, component (C1) 50.0 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name “Biscoat # 300”, manufactured by Osaka Organic Chemical Co., Ltd.), and 3-isocyanatopropyltriethoxysilane (trade name) as component (D) "KBE-9007", manufactured by Shin-Etsu Silicone Co., Ltd.) 40.0 parts, (E) alumina particle dispersion (trade name "NANOBYK3610", manufactured by BYK Japan Japan Co., Ltd.) 5.0 parts, and (F ) Photopolymerization initiator (trade name “Irg907”, manufactured by Ciba Japan Co., Ltd.) Parts and mixed well to prepare a undercoat agent.

Example 2
(A-1) component solution 286.0 parts, Duranate 24A-100 25.7 parts, Biscote # 300 100.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts Were mixed well to prepare an undercoat agent.

Example 3
(A-1) 286.0 parts of component solution, 25.7 parts of Duranate 24A-100, 150.0 parts of Biscote # 300, 40 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 7.5 parts of Irg907 The mixture was mixed to prepare an undercoat agent.

Example 4
(A-1) component solution 286.0 parts, duranate 24A-100 25.7 parts, biscoat # 300 150.0 parts, (D) component 3-mercaptopropyltrimethoxysilane (trade name “KBM-803”) 40.0 parts, 5.0 parts of NANOBYK3610, and 7.5 parts of Irg907 were mixed well to prepare an undercoat agent.

Example 5
(A-1) 286.0 parts of component solution, 25.7 parts of Duranate 24A-100, 200 parts of Viscoat # 300, 40.0 parts of KBM-803, 5.0 parts of NANOBYK3610 and 10.0 parts of Irg907 are mixed well. And an undercoat agent was prepared.

Example 6
(A-2) Component solution 286.0 parts, Duranate 24A-100 25.7 parts, Biscote # 300 100.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts Were mixed well to prepare an undercoat agent.

Example 7
(A-3) Component solution 286.0 parts, Duranate 24A-100 25.7 parts, Biscote # 300 100.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts Were mixed well to prepare an undercoat agent.

Example 8
(A-4) Component solution 286.0 parts, Duranate 24A-100 25.7 parts, Biscote # 300 100.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts Were mixed well to prepare an undercoat agent.

Example 9
(A-5) component solution 286.0 parts, Duranate 24A-100 25.7 parts, Viscoat # 300 50.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 2.5 parts Were mixed well to prepare an undercoat agent.

Example 10
(A-1) component solution 286.0 parts, hexamethylene diisocyanate isocyanurate (trade name “Coronate HX”, manufactured by Nippon Polyurethane Industry Co., Ltd.) 28.4 parts, biscoat # 300 100.0 parts, KBE -9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts were mixed well, and the undercoat agent was prepared.

Example 11
(A-1) component solution 286.0 parts, duranate 24A-100 25.7 parts, dipentaerythritol polyacrylate (trade name “NK Ester A-9550W”, manufactured by Shin-Nakamura Chemical Co., Ltd.) 100.0 Part, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts were mixed well to prepare an undercoat agent.

Example 12
(A-1) Component solution 286.0 parts, Duranate 24A-100 25.7 parts, NK ester A-9550W 50.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907. 5 parts was mixed well and the undercoat agent was prepared.

Example 13
(A-1) Component solution 286.0 parts, Duranate 24A-100 25.7 parts, (C2) Trimethylolpropane triacrylate (trade name “Biscoat # 295”, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 100.0 parts, 40.0 parts of KBE-9007, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907 were mixed well to prepare an undercoat agent.

Example 14
(A-1) component solution 286.0 parts, Duranate 24A-100 25.7 parts, Viscoat # 295 50.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 2.5 parts Were mixed well to prepare an undercoat agent.

Example 15
(A-1) component solution 286.0 parts, duranate 24A-100 25.7 parts, biscoat # 300 100.0 parts, (D) component 3-acryloxypropyltrimethoxysilane (trade name “KBM-5103”) “Shin-Etsu Silicone Co., Ltd.) 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts were mixed well to prepare an undercoat agent.

Example 16
(A-1) component solution 286.0 parts, duranate 24A-100 25.7 parts, biscoat # 300 100.0 parts, (D) as component 3-methacryloxypropyltrimethoxysilane (trade name “Syllar Ace”) 40.0 parts of S710 "(manufactured by Chisso Corporation), 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907 were mixed well to prepare an undercoat agent.

Example 17
(A-1) Component solution 286.0 parts, Duranate 24A-100 25.7 parts, Biscote # 300 100.0 parts, (D) Component 3-glycidoxypropyltrimethoxysilane (trade name “Syllar Ace” S510 ”(manufactured by Chisso Corporation), 40.0 parts, 5.0 parts of NANOBYK3610, and 5.0 parts of Irg907 were mixed well to prepare an undercoat agent.

Comparative Example 1
(A ′) component solution 286.0 parts, duranate 24A-100 25.7 parts, biscoat # 300 100.0 parts, KBE-9007 40.0 parts, NANOBYK3610 5.0 parts, and Irg907 5.0 parts was mixed well to prepare an undercoat agent.

Comparative Example 2
(A-1) 286.0 parts of component solution, 25.7 parts of Duranate 24A-100, 150.0 parts of Biscote # 300, 5.0 parts of NANOBYK3610, and 7.5 parts of Irg907 are mixed well. The undercoat agent which does not contain (D) component was prepared.

Comparative Example 3
(A-1) 286.0 parts of component solution, 25.7 parts of Duranate 24A-100, 200.0 parts of Biscote # 300, 5.0 parts of NANOBYK3610, and 10.0 parts of Irg907 are mixed well. The undercoat agent which does not contain (D) component was prepared.

<Preparation of copper-deposited plastic film>
The undercoat agent of Example 1 was applied to a commercially available polyester film (trade name “Lumirror U48”, manufactured by Toray Industries, Inc., 100 μm thick) with a bar coater so that the dry film thickness was about 1.0 μm. Dry at 1 ° C. for 1 minute. Subsequently, the coating film provided with a hardening undercoat layer was obtained by making it UV-cure at 300 mj / cm < ² >. The coating film was obtained similarly about the undercoat agent of another Example and a comparative example.

  Subsequently, by using a commercially available vapor deposition apparatus (product name “NS-1875-Z”, manufactured by Nishiyama Seisakusho Co., Ltd.) on the undercoat surface of the coating film, copper is vapor-deposited (thickness: about 100 nm). A vapor-deposited plastic film was obtained. The copper-deposited plastic film was similarly obtained for the undercoat agents of other examples and comparative examples.

1. Hardness test of cured undercoat layer The pencil hardness of the cured undercoat layer of each coated film of Examples and Comparative Examples was evaluated according to JIS K 5600-5-4. The results are shown in Table 1.

2. The cross-cut test was implemented based on JISK5600-5-6 about the copper vapor deposition film of each copper vapor deposition film of an initial adhesion example and a comparative example. Specifically, 100 squares are put on the copper vapor-deposited surface with a cutter knife, and an adhesive tape (product name “Cello Tape (registered trademark)”, manufactured by Nichiban Co., Ltd.) is applied, and then pulled vertically. &#21085; was counted and the number of squares without peeling was counted. Initial adhesion was similarly evaluated about the copper vapor deposition film concerning another example and a comparative example. The results are shown in Table 1. In addition, in Table 1, since the number of squares without peeling is 100, and the squares of all squares are completely smooth visually, the adhesion is determined to be the best. A special symbol “*” was added (hereinafter the same).

3. Acid-resistant adhesion After immersing the copper vapor-deposited films of Examples and Comparative Examples in a 4% hydrogen chloride aqueous solution heated to 40 ° C. for 5 minutes, the adhesion of the copper vapor-deposited film was evaluated in the same manner as described above.

4). Alkali resistance adhesion After immersing the copper vapor-deposited films of Examples and Comparative Examples in a 4% aqueous sodium hydroxide solution heated to 40 ° C. for 5 minutes, the adhesion of the copper vapor-deposited film was evaluated in the same manner as described above.

Claims (17)

An acrylic copolymer (A) having a hydroxyl group, an alkyl ester group and a nitrile group and optionally a primary amide group;
A polyisocyanate (B) having at least three isocyanate groups;
An active energy ray-polymerizable compound (C) having at least three carbon-carbon double bond-containing groups;
Formula _{^{(1): X 1 -Si (}} R 1) a in ^(OR _{2) 3-a} ^(the formula (1), ^{X 1} represents a hydroxyl group, an isocyanate group and a polymerizable carbon - consisting of carbon double bond-containing group A group containing a functional group that reacts with at least one selected from the group, R ¹ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group having 1 to 8 carbon atoms, a is 0, A reactive alkoxysilyl compound (D) represented by 1 or 2, and
An undercoat agent for a substrate with a copper thin film, comprising: Component (A) is hydroxyalkyl (meth) acrylate (a1), alkyl (meth) acrylate (a2) (excluding those having a hydroxyl group) and (meth) acrylonitrile (a3), and (meth) acrylamide (a4 if necessary) ). The undercoat agent according to claim 1. (A) The undercoat agent of Claim 1 or 2 whose hydroxyl value of a component is 30-150 mgKOH / g, and whose glass transition temperature is 0-100 degreeC. The undercoat agent according to any one of claims 1 to 3, wherein the component (B) is one derivative (b1) selected from the group consisting of an adduct of a diisocyanate compound, an isocyanurate, and a biuret. The undercoat agent according to any one of claims 1 to 4, wherein an equivalent ratio [NCO / OH] of a hydroxyl group contained in the component (A) and an isocyanate group contained in the component (B) is 0.2 to 5. Component (C) is an active energy ray polymerizable compound (C1) having 3 to 6 (meth) acryloyl groups and at least one hydroxyl group in the molecule and / or 3 to 6 (meth) in the molecule. The undercoat agent according to any one of claims 1 to 5, which is an active energy ray polymerization type compound (C2) having an acryloyl group and no hydroxyl group. The functional group in X ¹ of the general formula (1) representing the component (D) is one selected from the group consisting of an isocyanate group, a thiol group, an amino group, an epoxy group, an acid anhydride group, and a vinyl group. The undercoat agent according to any one of claims 1 to 6. Furthermore, the undercoat agent in any one of Claims 1-7 containing an inorganic particle (E). Furthermore, the undercoat agent in any one of Claims 1-8 containing a photoinitiator (F). Furthermore, the undercoat agent in any one of Claims 1-9 containing an organic solvent (G). The base material with a copper thin film by which the undercoat layer and copper thin film layer which the undercoat agent in any one of Claims 1-10 hardens | cures on the surface of a base material are laminated | stacked in this order. The base material with a copper thin film according to claim 11, wherein the base material is plastic. The substrate with a copper thin film according to claim 12, wherein the plastic is a plastic film. The substrate with a copper thin film according to claim 13, wherein the plastic film is a polyester film. On the surface of the substrate
Apply the undercoat agent according to any one of claims 1 to 10,
After applying heat to the substrate, a cured undercoat layer is formed by further irradiating active energy rays,
A copper thin film layer is formed on the cured undercoat layer,
The manufacturing method of a base material with a copper thin film. The manufacturing method of Claim 15 whose method of forming a copper thin film layer on the said hardening undercoat layer is a vacuum evaporation method or a sputtering method. The electroconductive film which uses the base material with a copper thin film in any one of Claims 11-14, or the base material with a copper thin film obtained with the manufacturing method in any one of Claims 15-16.