JP6241677B2 - Undercoat agent for substrate with copper thin film, substrate with copper thin film and method for producing the same, and conductive film and electrode 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 And an electrode film obtained from the conductive film.

  A base material with a copper thin film refers to an article in which a copper thin film is formed on the surface of various base materials. In the field of electronic materials, a plastic film with a copper thin film has been studied as an alternative to an ITO conductive film.

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

  As an electrode film having good workability, for example, a film having a π-conjugated conductive polymer such as polythiophene, polyaniline, and polypyrrole as a conductive layer is known. However, since the conductive layer is colored, the electrode film The film has a problem in terms of color tone.

  On the other hand, as a conductive film excellent in workability, a plastic film with a copper thin film is also known. This has good conductivity because copper having a lower resistivity than ITO is used as the conductive layer, and is cheaper than anything. When a copper vapor-deposited plastic film is used as an electrode film of a display device such as a touch panel, for example, it is assumed that a large screen and a curved surface are easy.

  A conventional copper vapor-deposited plastic film is generally obtained by vapor-depositing nickel on a plastic film as a substrate and then vapor-depositing copper. This nickel vapor deposition layer functions as an anchor layer for adhering the film and the copper vapor deposition layer. And after apply | coating a resist to an electrode pattern shape to a copper vapor deposition plastic film and processing with an etching liquid (an alkaline solution, an acidic solution), the target electrode film is obtained by removing this resist.

  However, such a copper vapor-deposited plastic film has a problem that the copper vapor-deposited layer peels off or drops off from the base film after the etching process because nickel is poor in alkali resistance and acid resistance. Moreover, although this copper vapor deposition plastic film is cheap compared with an ITO electroconductive film, since nickel was more expensive than copper, it was also expensive. Therefore, a method using an undercoat agent mainly containing an organic polymer instead of nickel as an anchor layer has been proposed (see Patent Document 1).

JP-A-5-28835

  An object of the present invention is an organic polymer-based undercoat agent used for the production of a substrate with a copper thin film, and not only the initial adhesion between the plastic substrate and the copper thin film, but also the adhesion after alkali treatment (hereinafter referred to as “the adhesive”) It is an object of the present invention to provide an undercoat layer that is excellent in adhesion resistance after alkali treatment and adhesion after acid treatment (hereinafter referred to as acid resistance adhesion).

  As a result of extensive studies, the present inventor can solve the above problems with an undercoat agent containing a predetermined acrylic copolymer as a main agent, polyisocyanate as a curing agent, and a hydroxyl group or an alkoxysilyl compound that reacts with an isocyanate group as an additive. I found out.

  That is, the present invention provides an acrylic copolymer (A) obtained by reacting a hydroxyl group-containing (meth) acrylate (a1) and an alkyl (meth) acrylate (a2), and a polyisocyanate curing agent (B) having at least three isocyanate groups. And an undercoat agent for a copper thin film-attached substrate containing a silane coupling agent (C).

  The present invention also relates to a substrate with a copper thin film having a substrate film, an undercoat layer formed by curing the undercoat agent, and a copper thin film layer.

  Moreover, this invention applies the said undercoat agent to the surface of a base material, then forms a cured undercoat layer (1) by applying heat to the base material, and then the cured undercoat layer (1 And a method for producing a substrate with a copper thin film, characterized in that a copper thin film layer is formed thereon.

  Moreover, this invention relates also to the electroconductive film which uses the said base material with a copper thin film, and the electrode film obtained from the said electroconductive film.

  The undercoat agent of the present invention forms a smooth coating film on the surface of a substrate. Moreover, this coating film is hardened | cured with a heat | fever and gives the undercoat layer which is excellent not only in the initial adhesiveness of a base material and a copper thin film but in both alkali-proof adhesiveness and acid-resistant adhesiveness. In the present specification, these adhesions are sometimes simply referred to as “adhesion”.

  Since the base material with a copper thin film of the present invention has good initial adhesion between the base material and the copper vapor-deposited film, alkali resistance and acid resistance, the copper thin film base material is treated with an etching solution or an acidic solution. However, it is difficult for the copper vapor-deposited film to fall off the base material. Among the copper thin film substrates, those having a plastic film as the substrate are particularly useful as a conductive film replacing the ITO conductive film.

  The conductive film of the present invention can be used as various electrode films for applications such as touch panels, IC card substrates, IC tag substrates, electronic paper substrates, flexible display substrates, and the like. In particular, it is suitable as an electrode film for touch panels such as smartphones and tablet PCs.

  The undercoat agent for a copper vapor deposition film of the present invention (hereinafter sometimes simply referred to as an undercoat agent) is a hydroxyl group-containing (meth) acrylate (a1) (hereinafter also referred to as a component (a1)) and an alkyl (meth). A polyisocyanate curing agent having an acrylic copolymer (A) (hereinafter also referred to as (A) component) obtained by reacting acrylate (a2) (hereinafter also referred to as (a2) component) and at least three isocyanate groups. It is a composition containing (B) (hereinafter also referred to as component (B)) and a silane coupling agent (C) (hereinafter also referred to as component (C)).

  As the component (a1) constituting the component (A), various known compounds can be used without particular limitation as long as the compound has a (meth) acryloyl group and at least one hydroxyl group in the molecule. Specifically, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-methacrylic acid 3- Hydroxybutyl, 4-hydroxybutyl (meth) acrylate, hydroxycyclohexyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate, 4- (hydroxymethyl) cyclohexylmethyl 2-hydroxypropionate, ( Examples include hydroxy (meth) acrylates such as hydroxyphenyl methacrylate, N- (2-hydroxyethyl) acrylamide, N- (1-methyl-2-hydroxyethyl) acrylamide, and the like. be able to.

  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 in the molecule. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, (meth) acrylic Tert-butyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate, ( Examples include docosyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and the like, which can be used in combination of two or more. .

  The reaction component of component (A) is at least one monomer (a3) selected from the group consisting of aromatic vinyl monomers, (meth) acrylonitrile and (meth) acrylamide (hereinafter also referred to as component (a3)). .) Can be included.

  As the component (a3), various known compounds can be used without particular limitation as long as they have a vinyl group and an aromatic ring in the molecule. Specifically, for example, styrenes such as styrene, α-methylstyrene, t-butylstyrene, aryl such as phenyl (meth) acrylate, benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate (Meth) acrylates and the like can be mentioned, and two or more of these can be combined.

  Specific examples of the component (a4) include acrylonitrile and / or methacrylonitrile.

  Specific examples of the component (a5) include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and the like. Moreover, these can combine 2 or more types.

  As the component (a3), the (meth) acrylonitrile and / or the (meth) acrylamide is particularly preferable from the viewpoint of improving the adhesion between the copper thin film and the undercoat layer.

  In the present invention, as vinyl monomers other than the components (a1) to (a3), for example, 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1 Α-olefins such as pentene, 1-hexene, vinylcyclohexane, 2-methylvinylcyclohexane, (meth) allyl alcohol, 4-penten-1-ol, 1-methyl-3-buten-1-ol, and 5 -Unsaturated alcohols such as hexen-1-ol, unsaturated carboxylic acids such as (meth) acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, fumaric acid, (anhydrous) maleic acid, and itaconic acid Acids can be used in combination. Moreover, these can combine 2 or more types.

  The amount (mol%) of each component is not particularly limited, but is usually as follows from the viewpoint of the balance of initial adhesion, alkali resistance and acid resistance.

<Aspect not using (a3) component>
(A1) component: about 2 to 25 mol%, preferably about 5 to 20 mol% (a2) component: about 75 to 98 mol%, preferably about 80 to 95 mol%

<Aspect using (a3) component>
(A1) component: about 3-25 mol%, preferably about 5-20 mol% (a2) component: about 30-90 mol%, preferably about 35-80 mol% (a3) component: 7-60 mol% Degree, preferably about 15 to 45 mol%

  The component (A) can be produced by various known methods. Specifically, for example, by subjecting each of the above components to a copolymerization reaction in the absence of a solvent or in an appropriate organic solvent, usually in the presence of a radical polymerization initiator at about 80 to 180 ° C. for about 1 to 10 hours. Can be obtained. Examples of the radical polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, t-butyl peroxybenzoate, dicumyl peroxide, lauryl peroxide, 2,2′-azobisisobutyronitrile, dimethyl-2 , 2′-azobisisobutyrate and the like. In addition, although the usage-amount is not specifically limited, Usually, it is the range used as about 0.1 to 2 weight% with respect to the total weight of the monomer which comprises (A) component. Examples of the organic solvent include those described below.

   Although the physical properties of the component (A) are not particularly limited, from the viewpoint of initial adhesion and alkali resistance, the hydroxyl value is usually about 10 to 150 mgKOH / g, preferably about 20 to 100 mgKOH / g, and more preferably 30 to 80 mgKOH. / G. The hydroxyl value is a value measured according to JIS-0070. Similarly, the glass transition temperature is about 0 to 100 ° C., preferably 10 to 40 ° C. from the viewpoint of initial adhesion and alkali resistance.

  As the component (B), various known ones can be used without particular limitation as long as they are polyisocyanates having at least three isocyanate groups in the molecule. (B) A component gives a crosslinked structure to the undercoat layer of this invention by making a urethanation reaction with (A) component.

  Specific examples of the component (B) include one derivative (b1) (hereinafter referred to as the component (b1)) selected from the group consisting of a biuret body, an isocyanurate body and an adduct body of a diisocyanate compound, the component (b1). (B2) (hereinafter referred to as component (b2)), triisocyanate compound (b3) (excluding those corresponding to components (b1) and (b2)) (hereinafter referred to as (b3) Component)) and at least one selected from the group consisting of other polyisocyanate compounds (hereinafter referred to as component (b4)). Among these, the component (b1) is particularly preferable from the viewpoint of the balance of initial adhesion, alkali resistance, and acid resistance.

  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 isocyanurate 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.)

  (B2) A diol compound constituting the component, although not particularly limited, the aliphatic diols are preferable, particularly ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, neopentyl. One kind selected from the group consisting of glycol, 1,6-hexanediol, octanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol and the like is preferable.

  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), and two or more of them may be combined. .

  Examples of the component (b4) include hexafunctional polyisocyanate (product name “Duranate MHG-80B”, manufactured by Asahi Kasei Chemicals Corporation).

  Further, the ratio of the component (B) to the component (A) is not particularly limited, but from the viewpoint of the balance of initial adhesion, alkali resistance and acid resistance, the hydroxyl group of the component (A) and the isocyanate of the component (B) The equivalent ratio [NCO / OH] with the group is usually about 0.5 to 5, preferably about 1 to 2.

  The component (C) reacts with the component (A) and / or the component (B), and is organically integrated into the undercoat layer made of the undercoat agent of the present invention. It is considered that the alkali resistance is improved.

(C) As a component, various well-known silane coupling agents are mentioned. Specifically, the general formula _{^{(1): X 1 -Si (}} R 1) a in ^(OR _{2) 3-a} ^(formula (1), ^{X 1,} and one selected from the group consisting of hydroxyl and isocyanate groups (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 reactive alkoxysilyl compound represented by these can be used.

Examples of X ^{1 in the} general formula (1) include a functional group containing one kind selected from the group consisting of an isocyanate group, an epoxy group, a thiol group, an amino group, and an acid anhydride group.

Examples of the reactive functional group in X ¹ that is an isocyanate group include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, and 3-isocyanatepropylmethyldiethoxysilane. Silane etc. are mentioned, You may combine 2 or more types.

Examples of the reactive functional group in X ¹ that is an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxy. Silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like may be mentioned, and two or more may be combined.

Examples of the reactive functional group in X ¹ having a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Silane etc. are mentioned, You may combine 2 or more types.

Examples of the reactive functional group in X ¹ that is an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane and the like, and two or more of them may be combined.

Examples of the reactive functional group for X ¹ that is an acid anhydride group include 3-trimethoxysilylpropyl succinic anhydride.

As the component (C), from the viewpoint of a balance between initial adhesion, alkali adhesion and acid adhesion, a functional alkoxysilyl compound having an isocyanate group as a functional group in X ¹ and / or a reactive alkoxysilyl compound having an epoxy group Is preferred.

  In addition, although content of (C) component is not specifically limited, Usually, it is about 0-20 weight part with respect to 100 weight part (solid content conversion) of (A) component, Preferably it is about 5-15 weight part.

  The undercoat agent of the present invention may further contain a urethanization catalyst (D) (hereinafter referred to as component (D)) as necessary. The component (D) accelerates the curing reaction of the components (A) and (B) and improves the initial adhesion, alkali resistance, and acid resistance of the undercoat agent of the present invention.

  Specific examples of the component (D) include monobutyltin tris (2-ethylhexanoate), monobutyltin oxide, bismastrioctate / 2-ethylhexanoic acid, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyl. Tin urethanation catalysts such as tin distearate, dioctyl tin oxide, dioctyl tin diacetate and dioctyl tin versatate, bismuth urethanation catalysts such as bis (2-ethylhexanoic acid) tin and bismuth octylate, and diazabicyclooctane , Dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, organic amine-based urethanization catalysts such as triethylamine and triethylenediamine, and the like may be used in combination.

  Although the usage-amount of (D) component is not specifically limited, About 0.1-2 weight part normally with respect to a total of 100 weight part (solid content conversion) of (A) component, (B) component, and (C) component, Preferably it is 0.5-1.5 weight part.

  The undercoat agent of the present invention can be obtained by mixing the component (A), the component (B) and the component (C), and, if necessary, the component (D) by various known means. Moreover, at the time of mixing, various organic solvents (henceforth (E) component) can be used as a dilution solvent as needed. Specific examples of the component (E) include methyl ethyl ketone and lower ketones of methyl isobutyl ketone, aromatic hydrocarbons such as toluene, alcohols such as ethyl alcohol and propyl alcohol, propylene glycol monomethyl ether acetate, and ethyl cellosolve acetate. Ether esters, ethyl acetate, chloroform, dimethylformamide and the like may be mentioned, and two or more may be combined. Moreover, although the usage-amount of (E) component is not specifically limited, Usually, the solid content density | concentration of the undercoat agent of this invention is the range used as about 1 to 60 weight% normally.

  In addition, the undercoat agent of the present invention can contain other leveling agents, antioxidants, ultraviolet absorbers, inorganic particles, and the like. Examples of the inorganic particles include silica, titania, alumina, zinc oxide, tin oxide, zirconia, ITO (indium tin oxide), ATO (antimony tin oxide), aluminum hydroxide, calcium hydroxide, and magnesium hydroxide. Is mentioned.

  The base material with a copper thin film of the present invention is a laminate having various base materials, an undercoat layer formed by curing the undercoat agent of the present invention, and a copper thin film layer.

  The substrate is not particularly limited, and various known materials can be used as long as a copper thin film can be formed on the surface. Specific examples include plastics, metals, cellulose materials, and glass. Examples of the plastic include polyester, polyvinyl chloride, polyamide, polyimide, polycarbonate, polyethylene, and polypropylene. Examples of the cellulose material include paper, nanocellulose paper, and wood.

  The shape of the substrate is not particularly limited. For example, a spherical shape, a cylindrical shape, a rectangular parallelepiped shape, a plate shape, or a film shape may be used. In addition, the substrate may be partially or entirely uneven or curved. 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. Moreover, although the thickness of this base film is not specifically limited, Usually, it is about 50-200 micrometers. Moreover, although the thickness of an undercoat layer is not specifically limited, Usually, it is about 0.1-5 micrometers.

  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 vapor deposition film or a copper sputtered film is not specifically limited, Usually, it is about 0.1-2 micrometers.

  Although the manufacturing method of the base material with a copper thin film of the present invention is not particularly limited, generally, by applying the undercoat agent according to the present invention to the surface of the base material, and then applying heat to the base material. There is a method of forming a cured undercoat layer (1) and then forming a copper thin film layer on the cured undercoat layer (1).

Coating conditions are not particularly limited, and examples of coating means include spray, roll coater, reverse roll coater, gravure coater, knife coater, bar coater, dot coater, and the coating amount is not particularly limited. The dry solid content is about 0.01 to 10 g / m ² .

  The heating conditions are not particularly limited, and the temperature is usually about 80 to 150 ° C. and the time is about 10 seconds to 2 minutes. By this treatment, it is considered that the component (A), the component (B) and the component (C) react together in an organic manner to give an undercoat layer (1) excellent in initial adhesion, alkali adhesion resistance and acid resistance adhesion. .

  The electrode film of the present invention is an electronic component obtained from the conductive film of the present invention. In particular, an electrode film obtained from a copper-deposited plastic film or a copper sputtered film among the conductive films of the present invention is useful as an alternative to an electrode film using an ITO conductive film.

  The electrode film of the present invention is obtained by coating the resist of the conductive film of the present invention in an electrode pattern, treating the resist with an etching solution (alkali solution, acidic solution), and then removing the resist. The shape of the electrode pattern is not particularly limited, and examples thereof include 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. Further, “parts” in the examples represent weight standards. Moreover, a hydroxyl value and an acid value are the values measured based on JIS-0070. The glass transition temperature is a value measured using a commercially available measuring instrument (product name “DSC8230B”, manufactured by Rigaku Corporation).

Production Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 94.5 parts (about 0.81 mol) of hydroxyethyl acrylate (HEA), 742.5 of methyl methacrylate (MMA) Parts (about 7.4 mol), 378 parts (about 2.9 mol) of butyl acrylate (BA) and 135 parts (about 1.3 mol) of styrene (St) and 1452.1 parts of methyl ethyl ketone (MEK) The system was set to 80 ° C. Next, 6.75 parts of 2,2′-azobis (2-methylbutyronitrile) (ABN-E) was added, and the mixture was kept warm at around 80 ° C. for 6 hours. Then, 18.9 parts of ABN-E was 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-1) having a glass transition temperature of 30 ° C. and a hydroxyl value of 35 mgKOH / g.

Production Example 2
In a reaction vessel similar to Production Example 1, 60 parts (about 1.13 mol) of acrylonitrile (AN), 51 parts (about 0.44 mol) of HEA, 121.5 parts (about 1.21 mol) of MMA, and BA 67.5 parts (about 0.53 mol) and about 310 parts of ethyl acetate were charged, and the reaction system was set to 70 ° C. Next, about 3.0 parts of ABN-V was charged and kept warm at around 70 ° C. for 6 hours. Next, about 3.0 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature and mixed with 390.0 parts of methyl ethyl ketone to obtain a solution of an acrylic copolymer (A-2) having a glass transition temperature of about 30 ° C. and a hydroxyl value of about 80 mgKOH / g.

Production Example 3
In the same reaction vessel as in Production Example 1, AN 60 parts (about 1.13 mol), acrylamide (AAM) 15 parts (about 0.21 mol), HEA 51 parts (about 0.44 mol), MMA 72 parts ( About 0.72 mol), and 102 parts (about 0.80 mol) of BA, and about 450 parts of ethyl acetate, and the reaction system was set to 70 ° C. Next, about 3.0 parts of ABN-V was charged and kept warm at around 70 ° C. for 6 hours. Next, about 3.0 parts of ABN-V was charged, and the reaction system was further kept at the same temperature for 4 hours. Thereafter, the reaction system was cooled to room temperature, and 250 parts of methyl ethyl ketone was mixed to obtain a solution of an acrylic copolymer (A-3) having a glass transition temperature of about 13 ° C. and a hydroxyl value of about 80 mgKOH / g.

Production Example 4
In a reaction vessel similar to Production Example 1, HEA 94.5 parts (about 0.81 mol), MMA 877.5 parts (about 8.8 mol) and BA 378 parts (about 2.9 mol) and methyl ethyl ketone 1452. 1 part was charged and the reaction system was set to 80 ° C. Next, 6.75 parts of ABN-E was charged and kept warm at around 80 ° C. for 6 hours. Subsequently, 18.9 parts of ABN-E was 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-4) having a glass transition temperature of 30 ° C. and a hydroxyl value of 35 mgKOH / g.

<Preparation of undercoat agent>
Example 1
100 parts of (A-1) component of Production Example 1 and hexamethylene diisocyanate adduct (trade name “Takenate D110N”, manufactured by Mitsui Chemicals, Inc.) as component (B) were adjusted to a solid content of 30% with methyl ethyl ketone. 17 parts of a solution and 10 parts of a solution prepared by adjusting an isocyanate group-containing silane coupling agent (trade name “KBE-9007”, manufactured by Shin-Etsu Silicone Co., Ltd.) to 30% solid content with methyl ethyl ketone as component (C) were mixed well. An undercoat agent was prepared.

Example 2
100 parts of the component (A-1) in Production Example 1, 17 parts of a solution prepared by adding 30% solids of Takenate D110N with methyl ethyl ketone as the component (B), and solid KBE-9007 with methyl ethyl ketone as the component (C) An undercoat agent was prepared by thoroughly mixing 20 parts of a solution adjusted to 30%.

Example 3
100 parts of the component (A-1) of Production Example 1, 17 parts of a solution prepared by adjusting the solid content of Takenate D110N to 30% with methyl ethyl ketone as the component (B), and a commercially available epoxy silane coupling agent as the component (C) An undercoat agent was prepared by thoroughly mixing 10 parts of a solution (trade name “Syra Ace 510”, manufactured by Nimi Shoji Co., Ltd.) adjusted to 30% solid content with methyl ethyl ketone.

Example 4
100 parts of the component (A-1) of Production Example 1, 17 parts of a solution prepared by adjusting the solid content of Takenate D110N to 30% with methyl ethyl ketone as the component (B), and Silaace 510 as the solid content with methyl ethyl ketone as the component (C) An undercoat agent was prepared by thoroughly mixing 20 parts of a solution adjusted to 30%.

Example 5
100 parts of component (A-2) of Production Example 2 and biuret of hexamethylene diisocyanate (trade name “Duranate 24A-100”, manufactured by Asahi Kasei Chemicals Co., Ltd.) as component (B) to a solid content of 30% with methyl ethyl ketone 26 parts of the adjusted solution and 10 parts of a solution prepared by adjusting KBE-9007 to 30% solid content with methyl ethyl ketone were mixed well to prepare an undercoat agent.

Example 6
100 parts of component (A-3) of Production Example 3 and a solution obtained by adjusting a hexamethylene diisocyanate nurate (trade name “Coronate HX”, manufactured by Tosoh Corporation) as component (B) to a solid content of 30% with methyl ethyl ketone 28 parts and 10 parts of a solution prepared by adjusting KBE-9007 to 30% solid content with methyl ethyl ketone were mixed well to prepare an undercoat agent.

Example 7
100 parts of the component (A-4) of Production Example 4 , 17 parts of a solution in which Takenate D110N was adjusted to 30% solid content with methyl ethyl ketone as the component (B), and an isocyanate group-containing silane coupling agent (trade name) as the component (C) An undercoat agent was prepared by thoroughly mixing 10 parts of a solution prepared by adjusting “KBE-9007” (manufactured by Shin-Etsu Silicone Co., Ltd.) to a solid content of 30% with methyl ethyl ketone.

Example 8
100 parts of the component (A-4) of Production Example 4 , 17 parts of a solution prepared by adjusting the solid content of Takenate D110N to 30% with methyl ethyl ketone as the component (B), and solid KBE-9007 with methyl ethyl ketone as the component (C) Even though it was adjusted to 30%, 20 parts of the solution was mixed well to prepare an undercoat agent.

Example 9
100 parts of the component (A-4) of Production Example 4 , 17 parts of a solution prepared by adjusting the content of Takenate D110N to 30% with methyl ethyl ketone as the component (B), and a commercially available epoxy silane coupling agent as the component (C) An undercoat agent was prepared by thoroughly mixing 10 parts of a solution (trade name “Syra Ace 510”, manufactured by Nimi Shoji Co., Ltd.) adjusted to 30% solid content with methyl ethyl ketone.

Example 10
100 parts of the component (A-4) of Production Example 4 , 17 parts of a solution prepared by adding Takenate D110N to 30% solid content with methyl ethyl ketone as the component (B), and Silaace 510 as the solid content with methyl ethyl ketone as the component (C) An undercoat agent was prepared by thoroughly mixing 20 parts of a solution adjusted to 30%.

Comparative Example 1
100 parts of the component (A-1) of Production Example 1 and 17 parts of a solution in which Takenate D110N was adjusted to 30% solid content with methyl ethyl ketone as the component (B) were mixed well to prepare an undercoat agent.

Comparative Example 2
Underpart agent was prepared by thoroughly mixing 100 parts of component (A-4) of Production Example 4 and 17 parts of a solution in which Takenate D110N was adjusted to 30% solid content with methyl ethyl ketone as component (B).

<Preparation of copper vapor deposition film>
The undercoat agent of Example 1 was applied to a commercially available polyester film (trade name “Lumirror U48”, manufactured by Toray Industries, Inc., 150 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, 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 film was obtained. The copper vapor deposition film was obtained similarly about the undercoat agent of another Example and a comparative example.

(Initial adhesion)
100 square grids are put on the copper vapor deposition surface of the copper vapor deposition film according to Example 1 with a cutter knife, and an adhesive tape (product name “Sero Tape (registered trademark)”, manufactured by Nichiban Co., Ltd.) is pasted on the copper vapor deposition surface. After being attached, the appearance of the copper vapor surface was evaluated when it was peeled once in the vertical direction. Next, the adhesive tape was again applied to the copper vapor deposition surface and peeled off in the vertical direction, and then the appearance of the copper vapor deposition surface when it was applied again and peeled off in the vertical direction was evaluated. Similarly, the copper vapor deposition films of other examples and comparative examples were evaluated for the appearance of the copper vapor deposition surface (initial adhesion of the copper vapor deposition layer) at the first peeling and the third peeling. did.

(Acid resistance adhesion)
After the copper vapor deposition film according to Example 1 was immersed in a 4% hydrogen chloride aqueous solution heated to 40 ° C. for 5 minutes, the adhesion of the copper vapor deposition layer was evaluated by a cross cut test as described above. The adhesion was evaluated in the same manner for the copper deposited films of other examples and comparative examples.

(Alkali resistance)
After the copper vapor deposition film according to Example 1 was immersed in a 4% aqueous sodium hydroxide solution heated to 40 ° C. for 5 minutes, the adhesion of the copper vapor deposition layer was evaluated by a cross-cut test as described above. The adhesion was evaluated in the same manner for the copper deposited films of other examples and comparative examples.

Claims (16)

Acrylic copolymer having a hydroxyl value of 10 to 150 mgKOH / g and a glass transition temperature of 30 to 100 ° C. obtained by reacting a hydroxyl group-containing (meth) acrylate (a1) and an alkyl (meth) acrylate (a2) ( A) and
A polyisocyanate curing agent (B) having at least three isocyanate groups;
Containing a silane coupling agent (C),
Undercoat agent for copper thin film base material. The component (A) further comprises at least one monomer (a3) selected from the group consisting of an aromatic vinyl monomer, (meth) acrylonitrile and (meth) acrylamide as a reaction component. Undercoat agent. The undercoat agent according to any one of claims 1 and 2 , wherein the component (B) is one derivative (b1) selected from the group consisting of an adduct, an isocyanurate, and a biuret of a diisocyanate compound. The undercoat agent according to any one of claims 1 to 3 , 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. One of ^{_{X 1 -Si (R 1) a}} (OR 2) 3-a ( formula (1), ^{X 1,} selected from the group consisting of hydroxyl group and an isocyanate ^group: (C) component, the general formula ⁽¹⁾ 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 undercoat agent in any one of Claims 1-4 which is a reactive alkoxysilyl compound represented by this. Furthermore, the undercoat agent in any one of Claims 1-5 containing a urethanization catalyst (D). (D) The undercoat agent of Claim 6 whose usage-amount of a component is 0.1-2 weight part with respect to 100 weight part (solid content conversion) of (A) component. The base film, according to claim 1 to 7 or of the undercoat layer undercoating agent obtained by curing and the copper thin film with a substrate having a copper thin film layer. The base material with a copper thin film according to claim 8 , wherein the base material is plastic. The substrate with a copper thin film according to claim 9 , wherein the plastic is a plastic film. The substrate with a copper thin film according to claim 10 , wherein the plastic film is a polyester film. Copper thin film layer is a copper deposition film or a copper sputtered film, or a copper thin-film substrate with claims 8-11. On the surface of the substrate
Apply the undercoat agent according to any one of claims 1 to 7 ,
Next, a cured undercoat layer (1) is formed by applying heat to the substrate,
Next, a copper thin film layer is formed on the cured undercoat layer (1),
The manufacturing method of a base material with a copper thin film. The manufacturing method of Claim 13 whose method of forming a copper thin film layer on the said hardening undercoat layer (1) is a vacuum evaporation method or a sputtering method. Conductive film made using either of the copper thin film substrate with claims 8-12. An electrode film obtained from the conductive film of claim 15 .