TWI660015B - Primer for base material with copper thin film, base material with copper thin film, method for producing same, conductive film and electrode film - Google Patents

Abstract

The problem to be solved by the present invention is to provide an organic polymer-based primer, which is used for manufacturing a substrate with a copper film and can form an undercoat layer. The undercoat layer is not only a plastic substrate and a copper film. The initial adhesion is excellent, and the adhesion after alkali treatment and the adhesion after acid treatment are also excellent.

The solution of the present invention is a primer for a substrate with a copper film attached, which contains: a polyester polyol (A), which uses dicarboxylic acids (a1) and diols (a2) as reaction components, And the glass transition temperature is below 80 ° C; the polyisocyanate (B) has at least 3 isocyanate groups; and the reactive alkoxysilyl compound (C) is represented by the general formula (1): X ¹ -Si (R ¹ ) _a (OR ² ) _3-a (1)

In the general formula (1), X ¹ represents a group containing a functional group capable of reacting with one selected from the group consisting of a hydroxyl group and an isocyanate group, and 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.

Description

Primer for base material with copper thin film, base material with copper thin film, method for producing same, conductive film and electrode film

The present invention relates to a primer, a substrate with a copper thin film having a layer composed of the primer, a method for manufacturing the same, a conductive film using the substrate with a copper thin film, and The electrode film obtained from the conductive film is used to form a copper thin film on the surface of various substrates.

Copper film-coated substrates refer to articles formed by forming copper films on the surface of various substrates. In the field of electronic materials, plastic films with copper films are being researched as indium tin oxide (ITO) conductivity. Membrane alternatives.

ITO conductive film has excellent transparency and conductivity, so it has been used as an electrode film for touch panels such as smart phones and tablet computers. However, indium is an expensive and rare metal, so it has a cost problem. Since the ITO layer is hard and brittle, it has problems in processability that are easily affected by bending or deformation.

As electrode films with good processability, for example, π-conjugated conductive polymers such as polythiophene, polyaniline, and polypyrrole are known as electrode layers. However, because the conductive layer is colored, the electrode film is There is a problem with hue.

On the other hand, as other conductive films having excellent processability, Know the plastic film with copper film. The copper film-attached plastic film uses copper having a lower resistivity than ITO as a conductive layer, so it has good electrical conductivity, and most importantly, it is also relatively inexpensive. It is considered that if a plastic film vapor-deposited with copper is used as an electrode film of a display device such as a touch panel, a larger screen or a curved surface is easier.

Generally, a conventional copper-deposited plastic film is obtained by vapor-depositing nickel on a plastic film as a base material, and then further depositing copper. This nickel vapor-deposited layer functions as a fixing layer for adhering a film to a copper vapor-deposited layer. In addition, a resist is coated into an electrode pattern on a plastic film on which copper is vapor-deposited, and the resist is treated with an etching solution (alkaline solution, acid solution), and then the resist is removed to obtain a target electrode film. .

However, since nickel lacks alkali resistance and acid resistance, the copper-deposited plastic film has the following problem: the copper vapor-deposited layer may peel off or fall off from the substrate film after the etching treatment. Also, although the copper-deposited plastic film is cheaper than the ITO conductive film, nickel is more expensive than copper, so the copper-deposited plastic film is still relatively expensive. Therefore, a method has also been proposed in which, instead of using nickel, a primer containing an organic polymer as a main component is used as a fixing layer (see Patent Document 1). On the other hand, when such a primer is used, blocking resistance of the primer surface is required.

[Prior technical literature] (Patent Literature)

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

The problem to be solved by the present invention is to provide an organic polymer-based primer, which is used for manufacturing a substrate with a copper film and can form an undercoat layer. The undercoat layer is not only a plastic substrate and a copper film. Excellent initial adhesion, adhesion after alkali treatment (hereinafter also referred to as alkali resistance adhesion), adhesion after acid treatment (hereinafter also referred to as acid resistance adhesion), and anti-caking Sex is also excellent.

The inventors have repeatedly and intensively studied and found that the aforementioned problems can be solved by a primer including a specific polyester polyol as a main agent, a polyisocyanate as a hardener, and an alkoxysilyl group as an additive. A compound which is capable of reacting with a hydroxyl group or an isocyanate group.

1. A primer for a substrate with a copper film attached, comprising: a polyester polyol (A) which uses dicarboxylic acids (a1) and glycols (a2) as reaction components, and has a glass transition temperature 80 ° C or lower; polyisocyanate (B) having at least 3 isocyanate groups; and a reactive alkoxysilyl compound (C), which is represented by the general formula (1): X ¹ -Si ( R ¹ ) _a (OR ² ) _3-a (1) In the general formula (1), X ¹ represents a group containing a functional group capable of reacting with one selected from the group consisting of a hydroxyl group and an isocyanate group. R ¹ represents a 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.

2. The primer according to the above 1, wherein the component (A) further comprises a polyol (a3) as a reaction component, and the polyol (a3) has at least 3 hydroxyl groups.

3. The primer according to the above 1 or 2, wherein the component (A) The glass transition temperature is 0 ~ 75 ° C.

4. The primer according to any one of 1 to 3, wherein the hydroxyl value of the component (A) is 5 to 100 mgKOH / g.

5. The primer according to any one of 1 to 4, wherein the component (B) is selected from a biuret body composed of a diisocyanate compound, an isotricyanate body composed of a diisocyanate compound, and A derivative (b1) of a diisocyanate compound in the group consisting of an adduct of an isocyanate compound.

6. The primer according to any one of 1 to 5, wherein the equivalent ratio [NCO / OH] of the hydroxyl group contained in the component (A) to the isocyanate group contained in the component (B) is 0.5. ~ 5.

7. The primer according to any one of 1 to 6, wherein the used amount of the component (C) is 1 to 20 parts by weight relative to 100 parts by weight of the component (A) (converted by solid content). .

8. The primer for a vapor-deposited copper film according to any one of 1 to 7 above, further comprising an urethane-forming catalyst (D).

9. The primer according to the above 8, wherein the used amount of the component (D) is converted to a solid content and is 0.1 to 2 parts by weight with respect to 100 parts by weight of the component (A).

10. The primer according to any one of 1 to 9 above, further comprising an active energy ray polymerizable compound (E), the active energy ray polymerizable compound (E) having at least three Carbon-carbon double bond group.

11. The primer according to the above 10, wherein the used amount of the (E) component is converted to a solid content and is 0 to 100 parts by weight relative to 100 parts by weight of the (A) component.

12. A base material with a copper film, comprising: a base material, an undercoat layer, and a copper thin film layer, wherein the undercoat layer is hardened by the undercoating agent according to any one of 1 to 11 above. to make.

13. The substrate with a copper film attached as described in 12 above, wherein the substrate is plastic.

14. The substrate with a copper film attached as described in 13 above, wherein the plastic is a plastic film.

15. The substrate with a copper film attached as described in 14 above, wherein the plastic film is a polyester film.

16. The substrate with a copper thin film according to any one of 12 to 15, wherein the copper thin film layer is a vapor-deposited copper film or a sputtered copper film.

17. A method for manufacturing a substrate with a copper film, characterized in that: the surface of the substrate is coated with the primer according to any one of 1 to 9, and then the substrate is heated, Thereby, a hardened undercoat layer (1) is formed, and then a copper thin film layer is formed on the hardened undercoat layer (1).

18. A method for manufacturing a substrate with a copper film, characterized in that: the surface of the substrate is coated with the primer as described in 10 or 11 above, and then the substrate is heated to form hardening The undercoat layer (1 ') is irradiated with active energy rays to the hardened undercoat layer, thereby forming a hardened undercoat layer (2'), and then forming a copper thin film layer on the hardened undercoat layer (2 ').

19. The manufacturing method according to 17, wherein the method for forming a copper thin film layer on the hardened undercoat layer (1) is a vacuum evaporation method or a sputtering method.

20. The manufacturing method according to 18 above, wherein the method for forming a copper thin film layer on the hardened undercoat layer (2 ') is a vacuum evaporation method or a sputtering method.

21. A conductive film obtained by using the base material with a copper thin film according to any one of the above 12 to 16.

22. A conductive film obtained by using a base material with a copper thin film obtained by the manufacturing method according to 17 or 19 above.

23. A conductive film obtained by using a base material with a copper thin film obtained by the manufacturing method according to 18 or 20 above.

24. An electrode film obtained from the conductive film according to any one of 21 to 23 above.

The primer of the present invention can form a smooth coating film on the surface of a substrate. In addition, the coating film can be hardened only by heat or only by heat and active energy rays, so that an undercoat layer can be obtained, which has not only excellent initial adhesion between the substrate and the copper film, but also alkali resistance. Both are excellent in acid resistance and acid resistance, and have good anti-caking properties.

The substrate with a copper film of the present invention has good initial adhesion, alkali-resistant adhesion, and acid-resistant adhesion to the substrate and the vapor-deposited copper film. The base material of the copper thin film is processed, and the vapor-deposited copper film does not easily fall off the base material. Therefore, among the copper film-coated substrates, especially the copper film-coated substrate is a plastic film, which is useful as a conductive film instead of an ITO conductive film.

The conductive film of the present invention can be provided as various electrode films for use in, for example, touch panels, substrates for integrated circuit cards (IC cards), substrates for integrated circuit tags (IC tags), and electronic papers. Substrates, substrates for flexible displays, and the like. Especially suitable as a smartphone Electrode film for touch panels such as tablet PCs.

The primer (hereinafter sometimes referred to simply as a primer) for a vapor-deposited copper film of the present invention is a composition containing a specific polyester polyol (A) (hereinafter also referred to as (A) component); A polyisocyanate (B) having at least 3 isocyanate groups (hereinafter also referred to as (B) component); and a specific reactive alkoxysilyl compound (C) (hereinafter also referred to as (C) component).

The component (A) is not particularly limited as long as it is a branched polyester polyol, and various known polyester polyols can be used. Specifically, for example, it is more suitable as a polyhydric alcohol, which is based on a dicarboxylic acid (a1) (hereinafter also referred to as (a1) component) and a diol (a2) (hereinafter also referred to as (a2) component) as Essential ingredients.

The component (a1) is not particularly limited, and various known dicarboxylic acids can be used. Specific examples include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, diphenylmethane-4,4'-dicarboxylic acid, and anhydrides thereof; oxalic acid and malonic acid , Succinic acid, glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and tridecanedioic acid, and more Aliphatic dicarboxylic acids such as acid anhydrides; hexahydrophthalic acid, hexahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic acid, and the like Cycloaliphatic dicarboxylic acid, etc .; and 2 or more types can be combined. The component (a1) preferably contains an aromatic dicarboxylic acid from the viewpoint of a balance between initial adhesion, alkali resistance, and acid resistance. The amount of the aromatic dicarboxylic acid used in the component (a1) is not particularly limited, but it is generally 20 to 60 mole%. about. The amount of the aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid in the component (a1) is generally about 0 to 5 mole%.

The component (a2) is not particularly limited, and various known glycols can be used. Specific examples include 1,2-propanediol, 1,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol Aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, pentanediol, and 1,6-hexanediol; 1,4- Cycloaliphatic diols such as cyclohexanedimethanol and ethylene oxide adducts of hydrogenated bisphenol A; catechol, resorcinol, hydroquinone, benzenedimethanol, and bis (hydroxyethoxylate) Group) aromatic diols such as benzene and ethylene oxide adducts of bisphenol A; etc .; and two or more of them may be combined. Moreover, it is preferable that (a2) component contains an aliphatic diol from a viewpoint of the balance of initial adhesiveness, alkali-resistant adhesiveness, and acid-resistant adhesiveness. The amount of the aliphatic diol used in the component (a2) is not particularly limited, but is generally about 20 to 60 mole%. The amount of the alicyclic diol and / or aromatic diol in the component (a2) is generally about 0 to 40 mole%.

The component (A) can further include a polyol (a3) (hereinafter also referred to as (a3) component) as an arbitrary reaction component, and the polyol (a3) has at least 3 hydroxyl groups. The component (a3) introduces a free hydroxyl group and a branched structure into the component (A), so that the layer composed of the primer of the present invention is particularly excellent in initial adhesion, alkali resistance, and acid resistance. Promotion.

The component (a3) is not particularly limited, and various known polyols can be used. Specific examples include aliphatic triols such as glycerol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, and 1,2-butanetriol; Cycloaliphatic triols such as hexanetriol; aromatics such as 1,2,3-benzenetriol and 1,3,5-benzenetriol Aromatic triols; aliphatic tetraols such as diglycerol, butaerythritol, sorbitol, pentaerythritol, and dipentaerythritol; etc .; and two or more kinds can be combined. Among the components (a3), aliphatic triols and / or aliphatics are preferred from the viewpoint of a balance between initial adhesion, alkali resistance, acid resistance, and anti-caking properties. Tetrol.

The amount of the (a1) component, the (a2) component, and the (a3) component used as necessary is not particularly limited. Generally, the starting adhesiveness, alkali-resistant adhesion, acid-resistant adhesion, and From the viewpoint of the balance of the anti-caking property, it is generally required to be within the following range.

<When the (a3) component is not used>

(a1) Ingredient: about 20 to 50 mole%, preferably about 25 to 45 mole%

(a2) Ingredients: about 50 to 80 mole%, preferably about 55 to 75 mole%

<When using (a3) component>

(a1) Ingredient: about 20 to 50 mole%, preferably about 25 to 45 mole%

(a2) Ingredient: about 47 to 77 mole%, preferably about 53 to 73 mole%

(a3) Composition: about 0.1 to 3 mole%, preferably about 0.5 to 2 mole%

Various known polycarboxylic acids (hereinafter also referred to as (a4) component) can be used together with (a1) component, (a2) component, and (a3) component. Specifically, for example, maleic acid (anhydride), phthalic acid (anhydride), 1,2,4-benzenetricarboxylic acid (anhydride), and 1,2,4,5-benzenetetracarboxylic acid (anhydride) are mentioned. , Hexahydrophthalic acid (anhydride), and succinic acid (anhydride) and other acids and / or acid anhydrides; etc .; and two or more kinds can be combined. (A4) of the The amount used is generally less than 5 mol% when the total of (a1) component, (a2) component and (a3) component is 100 mol%.

(A) The manufacturing method of a component is not specifically limited, Various well-known methods can be used. Specifically, for example, (a1) component, (a2) component, and (a3) component and / or (a4) component used as needed, and carrying out a dehydration condensation reaction by one pot method Method; a method of reacting a dehydration condensation reactant of the component (a1) with the component (a2), and reacting with the component (a3) and the component (a4) used as necessary, and the like. In any case, the reaction temperature is not particularly limited and is about 150 to 250 ° C. The reaction time is not particularly limited, and is about 5 to 10 hours. The reaction can be carried out under normal pressure or under reduced pressure.

When producing (A) component, various well-known catalysts can be used. Specific examples include germanium dioxide, tetraethoxygermanium, tetra-n-butoxygermanium, antimony trioxide, dibutyltin oxide, zinc acetate (dihydrate), monobutyltin oxide, and tetrabutoxytitanium. Etc .; and 2 or more types can be combined. Moreover, it can manufacture in the presence of the organic solvent mentioned later.

(A) The physical properties of the component are not particularly limited. From the viewpoint of the balance of initial adhesion, alkali resistance, acid resistance, and anti-caking properties, such as glass transition temperature (based on JIS-7121 The measured value obtained) is generally 80 ° C or lower, preferably 0 to 75 ° C, more preferably about 30 to 70 ° C, and even more preferably about 40 to 65 ° C. The hydroxyl value (measured value obtained in accordance with JIS-0070) ) Is generally about 5 to 100 mgKOH / g, preferably about 7 to 90 mgKOH / g, more preferably 8 to 75 mgKOH / g, and particularly preferably about 10 to 60 mgKOH / g.

The component (B) is not particularly limited as long as it is a polyisocyanate having at least three isocyanate groups in the molecule, and various known polyisocyanates can be used. ester. The component (B) can impart a crosslinked structure to the undercoat layer of the present invention by performing an amine esterification reaction with the component (A).

Specific examples of the (B) component include at least one selected from the group consisting of a biuret body composed of a diisocyanate compound, an isotricyanate body and a diisocyanate selected from a diisocyanate compound. A derivative (b1) of a diisocyanate compound (hereinafter also referred to as (b1) component) in the group consisting of an adduct of a compound; a reactant (b2) of the (b1) component and a diol compound (hereinafter (Also referred to as (b2) component); triisocyanate compound (b3) (except for components (b1) and (b2)) (hereinafter also referred to as (b3) component); and other polyisocyanate compounds (hereinafter also referred to as (Component (b4)). Among these components (B), the component (b1) is particularly preferred from the viewpoint of a balance between initial adhesion, alkali resistance, acid resistance, and blocking resistance.

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

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

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

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

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

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

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

The diol compound constituting the component (b2) is not particularly limited, and is preferably the aforementioned aliphatic diols. In particular, it is more appropriately selected from the group consisting of ethylene glycol, 1,2 -Propylene glycol, 1,3-propanediol, 1,3-butanediol, neopentyl glycol, 1,6-hexanediol, octanediol, dipropylene glycol, polyethylene glycol, and polypropylene glycol.

(b2) A component can be manufactured by various well-known methods. Specifically, it can be obtained, for example, by making the aforementioned (b1) component and the aforementioned diol compound generally the equivalent ratio of the isocyanate (NCO ') of the former to the hydroxyl group (OH') of the latter [NCO '/ OH'] is in the range of about 5 to 20, generally at 40 to 80 ° C, and the amine esterification reaction is performed for about 1 to 5 hours. The former isocyanate group (NCO ') and the latter hydroxyl group ( The equivalent ratio [NCO '/ OH'] of OH ') is preferably about 10-20. The obtained (b2) component has an isocyanate equivalent of generally about 1 to 10 meq / g, and preferably about 3 to 6 meq / g.

Examples of the component (b3) include toluene-2,4,6-triisocyanate, triphenylmethane triisocyanate, ginseng (isocyanatophenyl) phosphorothioate, and 1,6,11-11 Triisocyanates such as alkane triisocyanate, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate; and hexafunctional polyisocyanates (trade name "DURANATE MHG-80B", manufactured by Asahi Kasei Chemical Co., Ltd.) Etc .; and 2 or more types can be combined.

Examples of the component (b4) include a hexafunctional polyisocyanate (trade name "DURANATE MHG-80B", manufactured by Asahi Kasei Chemical Co., Ltd.).

The ratio of the (B) component to the (A) component is also not particularly limited, From the viewpoint of the balance of initial adhesion, alkali resistance, and acid resistance, the equivalent ratio [NCO / OH] of the hydroxyl group of (A) component to the isocyanate group of (B) component is generally It is about 0.5 ~ 5, preferably about 1 ~ 2.

It is considered that the component (C) is organically introduced into the undercoat layer composed of the undercoating agent of the present invention because it reacts with the (A) component and / or the (B) component, and therefore, it is particularly improved. Alkali resistance of the layer.

The component (C) is not particularly limited as long as it is a reactive alkoxysilyl compound represented by the general formula (1), and various known reactive alkoxysilyl compounds can be used. The general formula (1): X ¹ -Si (R ¹ ) _a (OR ² ) _3-a (In the formula (1), X ¹ represents a functional group capable of reacting with one selected from the group consisting of a hydroxyl group and an isocyanate group. R ¹ represents a 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).

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

Examples of compounds in which the reactive functional group in X ¹ is an isocyanate group include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and the like; two or more of them may be combined.

Examples of the compound in which the reactive functional group in X ¹ is an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxy Silyl, etc .; and two or more kinds can be combined.

Examples of compounds in which the reactive functional group in X ¹ is a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethyl Oxysilane, and 3-mercaptopropylmethyldiethoxysilane; etc .; and two or more of them can be combined.

Examples of compounds in which the reactive functional group in X ¹ is an amine group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl Group) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, etc. ; And 2 or more can be combined.

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

The component (C) is preferably a compound having a reactive functional group in X ¹ as an isocyanate group from the viewpoint of a balance of initial adhesion, alkali resistance, and acid resistance, and / Or a compound in which the reactive functional group in X ¹ is an epoxy group.

The amount of the component (C) used is not particularly limited, but it is generally about 1 to 20 parts by weight, and preferably about 5 to 15 parts by weight, with respect to 100 parts by weight of the component (A) (converted by solid content).

The primer of the present invention may further include an amine esterification catalyst (D) (hereinafter also referred to as (D) component) as necessary. This (D) component accelerates the hardening reaction between the (A) component and the (B) component, and thus improves the initial adhesion, alkali resistance, and acid resistance of the primer of the present invention.

Specific examples of the component (D) include ginseng (2-ethylhexanoate) monobutyltin, monobutyltin oxide, trioctanoic acid / 2-ethylhexanoate, dibutyltin dilaurate, and dilauric acid. Dioctyltin, dioctyltin distearate, oxidation Tin-based amine esterification catalysts such as dioctyltin, dioctyltin diacetate, and dioctyltin versatate; bismuth-based amines such as di (2-ethylhexanoate) and bismuth octoate Catalysts; organic amine esterification catalysts such as diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropanediamine, ethylmorpholine, dimethylethanolamine, triethylamine, and triethylenediamine Etc .; and 2 or more types can be combined.

The usage amount of the (D) component is not particularly limited, and it is generally about 0.1 to 2 parts by weight relative to 100 parts by weight (converted by solid content) of the components (A), (B), and (C). It is preferably 0.5 to 1.5 parts by weight.

In the primer of the present invention, when the primer is applied to a film substrate, it may further contain an active energy ray polymerization type compound (E) (hereinafter also referred to as (E) component), and the active energy ray polymerization type The compound (E) has at least 3 carbon-carbon double bond-containing groups in the molecule. The primer containing the (E) component can be hardened by both heat and active energy rays, thereby obtaining a primer coating having initial adhesion, alkali resistance, and acid resistance. Excellent, and also excellent in blocking resistance.

Examples of the carbon-carbon double bond-containing group of the component (E) include a vinyl group, an acryl group, an acryl group, and a methacryl group. Specific examples of the (E) component include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, and propylene oxide modified Trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol five (Meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, glycerol tri (meth) acrylate and other compounds having at least three (meth) acryl groups; pentaerythritol monohydroxy Triallyl ether, and Compounds having at least three vinyl groups, such as triallyl citrate; and two or more of them may be combined. Among these compounds, especially from the viewpoint of the hardness of the primer coating film, a compound is preferable in which the carbon-carbon double bond-containing group is a (meth) acrylfluorenyl group and the number of the group is 3 ~ 6.

The amount of the (E) component to be used is not particularly limited, and from the viewpoint of the balance of initial adhesion, alkali resistance, acid resistance, and abrasion resistance, with respect to 100 parts by weight of the component (A), Generally, it is about 1 to 100 parts by weight, preferably about 2 to 70 parts by weight (both are converted by solid content).

In addition, various known (meth) acrylates other than the (E) component can be used in combination with the (E) component. Specific examples include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (methyl) Di (methyl) such as acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and ethylene oxide modified di (meth) acrylate of bisphenol A ) Acrylates; oligomers such as polyurethane poly (meth) acrylate and polyester poly (meth) acrylate; and 2-ethylhexyl (meth) acrylate and isodecyl (meth) acrylate Ester, isooctyl (meth) acrylate, benzyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and ( Isobornyl methacrylate; vinyltrimethoxysilane, styryltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (methyl) Acrylic methoxypropyltrimethoxysilane, 3- (meth) propyleneoxypropylmethyldiethoxysilane, and 3- (meth) propyleneoxypropyltriethoxysilane, etc. ; And 2 or more can be combined.

The primer of the present invention may further include a photopolymerization initiator. (F) (hereinafter also referred to as (F) component). Specific examples include diphenyl ketone, 4 '-(methylthio) -α- (N-morpholinyl) -α-methylphenylacetone, and 2,4,6-trimethyldiphenyl. Ketone, methyl o-benzoyl benzoate, 4-phenyldiphenyl ketone, tertiary butyl anthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone}, benzyldimethyl Ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-methyl- [4- (methylthio) phenyl] 2- (N-morpholinyl) -1-acetone, 2-benzyl-2-methylamino-1- (4- (N-morpholinyl) phenyl) -butanone-1, 2 -Dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, diethyl thioxanthone ), Isopropylthioxanthone, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4- Trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl Propylpropyl) benzyl] phenyl} -2-methyl Propan-1-one, methyl benzamyl formate, methyl phenylglyoxylate, 4,4'-bis (diethylamino) -diphenyl ketone, 2-benzyl-2-di Methylamino-4- (N-morpholinyl) phenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-phenyl-2- (N- Morpholinyl) propan-1-one, 2-methyl-1- [4- (hexyl) phenyl] -2- (N-morpholinyl) propan-1-one, and 2-ethyl-2- Dimethylamino-1- (4- (N-morpholinyl) phenyl) -butanone-1-one; and a photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2014-1390; and Two or more types can be combined. As the (F) component, commercially available products such as IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 184, IRGACURE 500, IRGACURE 1000, IRGACURE 149, IRGACURE 261, and DARCUR 1173 can be used.

The amount of the (F) component to be used is not particularly limited, but it is generally about 0.1 to 3 parts by weight, and preferably about 0.5 to 2 parts by weight (both in terms of solid content) relative to 100 parts by weight of the (E) component.

Examples of the auxiliary agent of (F) include triethanolamine, triisopropanolamine, 4,4'-dimethylaminodiphenyl ketone (Michler's ketone), 4, 4'-Diethylaminodiphenyl ketone, 2-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid n-butoxyethyl Ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone and the like; and two or more kinds can be combined.

The primer of the present invention may further include inorganic particles when it is applied to, for example, a plastic film substrate. Since the inorganic particles can obtain a proper slip of the hardened layer of the primer of the present invention, the base film provided with the hardened layer is less likely to generate abnormal sounds or coating film defects during winding.

Examples of the inorganic particles include silicon dioxide, titanium dioxide, aluminum oxide, zinc oxide, tin oxide, zirconia, ITO (indium tin oxide), ATO (antimony tin oxide), aluminum hydroxide, calcium hydroxide, and Particles such as magnesium hydroxide; and two or more kinds can be combined. Among these particles, silicon dioxide and / or aluminum oxide are particularly preferred from the viewpoint of the aforementioned slippage. The surface of the particles may be subjected to various treatments. The median diameter (d50) of the particles is not particularly limited, but is generally about 10 nm to 5 μm.

The amount of the inorganic particles used is not particularly limited, but it is generally about 0 to 20 parts by weight, and preferably about 5 to 10 parts by weight (both in terms of solid content) relative to 100 parts by weight of the component (A).

The primer of the present invention may contain a thiol group-containing compound as necessary. Specifically, for example, 1,3,5-ginseng (3-mercaptobutyryloxyethyl) -1,3,5-tri-2,4,6 (1H, 3H, 5H) -trione (1 , 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), 1,4-bis (3-mercaptobutyryloxy) butyl Alkanes, trimethylolpropane (3-mercaptobutyrate), trimethylolethane (3-mercaptobutyrate), pentaerythritol (3-mercaptobutyrate), and dipentaerythritol hexa (3 -Mercaptobutyrate) and the like; and two or more kinds can be combined.

The use amount of the thiol group-containing compound is not particularly limited, and it is generally about 0 to 20 parts by weight, and preferably about 5 to 10 parts by weight, based on 100 parts by weight of the component (A) (all in terms of solid content) ).

When using the thiol group-containing compound, various known ene-thiol reaction inhibitors can be used in combination for the purpose of increasing the life of the primer of the present invention. Specific examples include phosphorus-based compounds such as triphenylphosphine and triphenyl phosphite; p-methoxyphenol, hydroquinone, 1,2,3-benzenetriol, naphthylamine, and tert-butyl Catechol, cuprous chloride, 2,6-bis (tertiarybutyl) -p-cresol, 2,2'-methylenebis (4-ethyl-6-tertiarybutylphenol) , 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, and diphenylnitrosoamine Polymerization inhibitors; benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-gins (diaminomethyl) phenol, and diazabicycloundecene Higher amines; and 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylhexylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methyl Imidazoles such as imidazole; etc .; and two or more kinds can be combined. The amount of the inhibitor used is not particularly limited, as long as it is appropriately set.

The primer of this invention can be obtained by mixing the said (A) component, (B) component, and (C) component, and other components used as needed by various well-known means.

When mixing, various known organic solvents (G) (hereinafter also referred to as (G) components) can be used as necessary. Specific examples include lower ketones such as methyl ethyl ketone or methyl isobutyl ketone; aromatic hydrocarbons such as toluene; alcohols such as ethanol and propanol; propylene glycol monomethyl ether acetate, ethyl Ether esters such as cyperidine acetate; ethyl acetate, chloroform, dimethylformamide, etc .; and two or more kinds can be combined. The amount of the organic solvent used is generally within the range of about 1 to 60% by weight of the solid content concentration of the primer of the present invention. Among these organic solvents, when the substrate is a plastic film, lower ketones are particularly preferred.

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

The copper film-attached base material of the present invention is a laminated body including various base materials, an undercoat layer hardened by the primer of the present invention, and a copper thin film layer.

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

The shape of the substrate is not particularly limited. It can be, for example, spherical, cylindrical, Cuboid, plate-like, film-like. A part or all of the surface of the substrate may be uneven or curved. When the copper film-coated substrate of the present invention is used as a conductive film, a plastic film, particularly a polyester film is preferred from the viewpoints of heat resistance and optical characteristics. The thickness of the base film is not particularly limited, but is generally about 50 to 200 μm. The thickness of the undercoat layer is not particularly limited, but is generally about 0.1 to 5 μm.

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

The manufacturing method of the copper film-attached base material of this invention is not specifically limited, Generally, the following manufacturing methods can be illustrated.

<When the (E) component is not used>

The method for producing a base material with a copper film according to the present invention is a method in which the primer (the component (E) is not contained) of the present invention is coated on the surface of the aforementioned base material, and the base material is then heated. Thereby, a hardened undercoat layer (1) is formed, and then a copper thin film layer is formed on the hardened undercoat layer (1).

<When using (E) component>

The method for producing a substrate with a copper film according to the present invention is a method in which the primer (containing the component (E)) of the present invention is applied to the surface of the substrate, and the substrate is heated, and This forms a hardened undercoat layer (1 '), irradiates the hardened undercoat layer with an active energy ray, thereby forming a hardened undercoat layer (2'), and then forms a copper thin film on the hardened undercoat layer (2 '). Floor.

The coating conditions are not particularly limited, and examples of the coating means include a sprayer, a roll coater, a reverse-roll coater, and a gravure coater. , Blade coater, bar coater, dot coater, etc .; and the coating amount is not particularly limited. Generally speaking, it is 0.01 to dry solids. About 10g / m ² .

The heating conditions are not particularly limited. Generally, the temperature is about 80 to 150 ° C, and the time is about 10 seconds to 2 minutes. We believe that by this treatment, the (A) component, the (B) component, and the (C) component can react organically and integrally to obtain an undercoat layer (1), the starting point of the undercoat layer (1). Excellent adhesion, alkali resistance, acid resistance, and blocking resistance.

The active energy ray irradiation conditions are not particularly limited, and generally, examples of the active energy ray include ultraviolet rays and electron beams. Further, as a source of supplying ultraviolet rays, for example, a high-pressure mercury lamp or a metal halide lamp can be cited, and its irradiation energy is generally about 100 to 2000 mJ / cm ² . Examples of the electron beam supply method include a scanning electron beam irradiation method and a curtain electron beam irradiation method. The irradiation energy is generally about 10 to 200 kGy. We believe that by this treatment, the (E) components in the hardened undercoat layer (1 ') will undergo radical polymerization with each other to form a crosslinked structure, and as a result, a hardened undercoat layer (2') and a hardened undercoat layer The layer (2 ') is excellent not only in initial adhesion, alkali resistance, and acid resistance, but also in blocking resistance.

The means for forming the copper thin film layer on the hardened undercoat layer (1) or the hardened undercoat layer (2 ') is not particularly limited, and a so-called dry coating method is preferred. Specific examples include physical methods such as a vacuum deposition method and a sputtering method; Chemical methods (chemical gas phase reactions, etc.). When the copper film-attached film obtained by the manufacturing method of the present invention is used for an electrode film, a vacuum evaporation method or a sputtering method is preferred.

The electrode film of the present invention is an electronic component obtained from the conductive film of the present invention. In particular, in the conductive film of the present invention, an electrode film obtained by vapor-depositing a plastic film or sputtering a copper film is useful as a substitute for an electrode film using an ITO conductive film.

The electrode film of the present invention is obtained by applying a resist to an electrode pattern on the conductive film of the present invention, and treating the resist with an etching solution (alkaline solution, acid solution).剂 REMOVING. The shape of the electrode pattern is not particularly limited, and examples thereof include a thin line shape, a dot shape, a mesh shape, and a planar shape.

[Example]

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

<Manufacturing Example 1>

(Manufacturing (A) ingredient)

In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux dehydration device, 2843.4 parts of dimethyl terephthalate (TPhDM), 1382.2 parts of ethylene glycol (EG), and 1,6-hexanediol (HG ) 449.7 parts, neopentyl glycol (NPG) 1189 parts, trimethylolpropane (TMP) 51.1 parts, and 0.79 parts of zinc acetate as a transesterification catalyst. Then, the raw material is heated, Methanol was distilled to the outside of the reaction system, and a transesterification reaction was performed at 195 ° C for 2 hours. Next, 2043.8 parts of isophthalic acid (IPhA) and 440.9 parts of azelaic acid (AzA) were added, and dehydration condensation reaction was performed at 200 ° C for 3 hours while distilling generated water out of the reaction system. The acid value of the reaction solution was 11.2 mgKOH / g. Next, the reflux device was replaced with a vacuum decompression device, 0.42 parts of tetrabutyl titanate was charged, and the pressure was reduced at 240 ° C and 0.3 kPa or less for 2 hours. Then, 2300.4 parts of methyl isobutyl ketone, 6901 parts of methyl ethyl ketone, and 219.8 parts of acetone acetone were added and mixed. In this way, a polyester polyol (A-1) was obtained. The non-volatile content of the polyester polyol (A-1) was 40%, the hydroxyl value was about 17 mgKOH / g, and the glass transition temperature was 47 ° C.

<Manufacturing Example 2>

In the same flask as in Production Example 1, 452.2 parts of terephthalic acid (TPhA), 839.9 parts of isophthalic acid (IPhA), 94.1 parts of ethylene glycol (EG), 368.3 parts of neopentyl glycol (NPG), 1745.5 parts of 2,2-bis (4-polyoxyethylene-oxyphenyl) propane (BA-P). Then, while heating and melting and removing distilled water to the outside of the reaction system, the reaction system was gradually heated up to 250 ° C. and further maintained for 3 hours. Next, a vacuum decompression device was connected to this flask, and 0.18 parts of tetrabutyl titanate was further added, and after holding for 30 minutes, the pressure-reduced polycondensation reaction was performed at 1.3 hPa for 1 hour. Then, 100 parts of the resin was transferred to a flask equipped with a thermometer, a nitrogen introduction pipe, a cooling pipe, and a stirring device, and 75 parts of methyl isobutyl ketone and 75 parts of methyl ethyl ketone were added and dissolved uniformly. In this way, a polyester polyol (A-2) was obtained. The non-volatile content of the polyester polyol (A-2) was 40%, the hydroxyl value was about 20 mgKOH / g, and the glass transition temperature was 60 ° C.

<Manufacturing Example 3>

2843.4 parts of dimethyl terephthalate (TPhDM), 1382.2 parts of ethylene glycol (EG), and 1638.7 parts of neopentyl glycol (NPG) were placed in a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux dehydration device. , 51.1 parts of trimethylolpropane (TMP), and 0.79 part of zinc acetate as a transesterification catalyst. Next, the raw material was heated, and the produced methanol was distilled to the outside of the reaction system, and a transesterification reaction was performed at 195 ° C for 2 hours. Then, 2484.7 parts of isophthalic acid (IPhA) was added, and dehydration condensation reaction was performed at 200 ° C for 3 hours while distilling generated water to the outside of the reaction system. The acid value of the reaction liquid was 11 mgKOH / g. Next, the reflux device was replaced with a vacuum decompression device, 0.42 parts of tetrabutyl titanate was charged, and the pressure was reduced at 240 ° C and 0.3 kPa or less for 2 hours. Then, 2520.2 parts of methyl isobutyl ketone and 6901 parts of methyl ethyl ketone were added and mixed. In this way, a polyester polyol (A-3) was obtained. The non-volatile content of the polyester polyol (A-3) was 40%, the hydroxyl value was 55 mgKOH / g, and the glass transition temperature was 50 ° C.

<Manufacturing Example 4>

In the same flask as in Production Example 1, 328 parts of terephthalic acid (TPhA), 328 parts of isophthalic acid (IPhA), 182 parts of ethylene glycol (EG), and 2,2-bis (4-polyoxyl) were charged. Ethylene-oxyphenyl) propane (BA-P) 762 parts. Then, while heating and melting and removing distilled water to the outside of the reaction system, the reaction system was gradually heated up to 250 ° C. and further maintained for 3 hours. Next, a vacuum decompression device was connected to this flask, and 0.18 parts of tetrabutyl titanate was further added, and after holding for 30 minutes, the pressure-reduced polycondensation reaction was performed at 1.3 hPa for 1 hour. Next, 100 parts of the resin was transferred to a flask equipped with a thermometer, a nitrogen introduction pipe, a cooling pipe, and a stirring device, and 75 parts of methyl isobutyl ketone and 75 parts of methyl ethyl ketone were added and uniformly added. Dissolve. In this way, a polyester polyol (A-4) was obtained. The polyester polyol (A-4) had a nonvolatile content of 40%, a hydroxyl value of 5 mgKOH / g, and a glass transition temperature of 70 ° C.

<Manufacturing Example 5>

In the same flask as in Production Example 1, 479 parts of terephthalic acid (TPhA), 402 parts of isophthalic acid (IPhA), 87 parts of azelaic acid (AzA), 256 parts of ethylene glycol (EG), and 1 221 parts of 6,6-hexanediol (1,6HD), 148 parts of neopentyl glycol (NPG), and 7 parts of trimethylolpropane (TMP). Then, while heating and melting and removing distilled water to the outside of the reaction system, the reaction system was gradually heated up to 250 ° C. and further maintained for 3 hours. Next, a vacuum decompression device was connected to this flask, and 0.18 parts of tetrabutyl titanate was further added, and after holding for 30 minutes, the pressure-reduced polycondensation reaction was performed at 1.3 hPa for 1 hour. Then, 100 parts of the resin was transferred to a flask equipped with a thermometer, a nitrogen introduction pipe, a cooling pipe, and a stirring device, and 75 parts of methyl isobutyl ketone and 75 parts of methyl ethyl ketone were added and dissolved uniformly. In this way, a polyester polyol (A-5) was obtained. The non-volatile content of the polyester polyol (A-5) was 40%, the hydroxyl value was 21 mgKOH / g, and the glass transition temperature was 31 ° C.

<Manufacturing Example 6>

In the same flask as in Production Example 1, 479 parts of terephthalic acid (TPhA), 402 parts of isophthalic acid (IPhA), 87 parts of azelaic acid (AzA), 256 parts of ethylene glycol (EG), and 1 354 parts of 6,6-hexanediol (1,6HD) and 23 parts of glycerol (GLY). Then, while heating and melting and removing distilled water to the outside of the reaction system, the reaction system was gradually heated up to 250 ° C. and further maintained for 3 hours. Then, a vacuum decompression device was connected to this flask, and tetrabutyl titanate 0.18 was further added. After incubation for 30 minutes, the pressure-reduced polycondensation reaction was performed at 1.3 hPa for 1 hour. Then, 100 parts of the resin was transferred to a flask equipped with a thermometer, a nitrogen introduction pipe, a cooling pipe, and a stirring device, and 75 parts of methyl isobutyl ketone and 75 parts of methyl ethyl ketone were added and dissolved uniformly. In this way, a polyester polyol (A-6) was obtained. The non-volatile content of the polyester polyol (A-6) was 40%, the hydroxyl value was 45 mgKOH / g, and the glass transition temperature was 17 ° C.

<Manufacturing Example 7>

In the same flask as in Production Example 1, 386 parts of terephthalic acid (TPhA), 292 parts of isophthalic acid (IPhA), 300 parts of azelaic acid (AzA), 251 parts of ethylene glycol (EG), and 1 348 parts of 6,6-hexanediol (1,6HD) and 23 parts of glycerol (GLY). Then, while heating and melting and removing distilled water to the outside of the reaction system, the reaction system was gradually heated up to 250 ° C. and further maintained for 3 hours. Next, a vacuum decompression device was connected to this flask, and 0.18 parts of tetrabutyl titanate was further added, and after holding for 30 minutes, the pressure-reduced polycondensation reaction was performed at 1.3 hPa for 1 hour. Then, 100 parts of the resin was transferred to a flask equipped with a thermometer, a nitrogen introduction pipe, a cooling pipe, and a stirring device, and 75 parts of methyl isobutyl ketone and 75 parts of methyl ethyl ketone were added and dissolved uniformly. In this way, a polyester polyol (A-7) was obtained. The non-volatile content of the polyester polyol (A-7) was 40%, the hydroxyl value was 30 mgKOH / g, and the glass transition temperature was 8 ° C.

Comparative Manufacturing Example 1

In the same flask as in Production Example 1, 300 parts of terephthalic acid (TPhA), 81 parts of ethylene glycol (EG), 216 parts of propylene glycol (PG), and 3 parts of trimethylolpropane (TMP) were charged. Then, while heating and melting and removing the distilled water to the outside of the reaction system, the reaction system was gradually heated up to 250 ° C, and further maintained at 3 ° C. hour. Next, a vacuum decompression device was connected to this flask, and 0.18 parts of tetrabutyl titanate was further added, and after holding for 30 minutes, the pressure-reduced polycondensation reaction was performed at 1.3 hPa for 1 hour. Then, 100 parts of the resin was transferred to a flask equipped with a thermometer, a nitrogen introduction pipe, a cooling pipe, and a stirring device, and 75 parts of methyl isobutyl ketone and 75 parts of methyl ethyl ketone were added and dissolved uniformly. In this way, a polyester polyol (α) was obtained, the non-volatile content of the polyester polyol (α) was 40%, the hydroxyl value was about 5 mgKOH / g, and the glass transition temperature was 84 ° C.

<Preparation of Primer>

[Example 1]

100 parts of the component (A-1) in Production Example 1 and an isotricyanate body of hexamethylene diisocyanate as the component (B) (trade name "CORONATE HX", manufactured by Japan Polyurethane Industry Co., Ltd.) 7.8 parts, 10 parts of an isocyanate-containing silane coupling agent (brand name "KBE-9007", manufactured by Shin-Etsu Silicone Co., Ltd.) as component (C), and commercially available tin-based amines as component (D) 1.0 part of an esterification catalyst (dioctyltin dilaurate, trade name "NEOSTANN U-810", manufactured by Nitto Kasei Co., Ltd.) was uniformly mixed to prepare a primer.

[Example 2]

100 parts of (A-1) component of Production Example 1, 7.8 parts of CORONATE HX as component (B), and 10 parts of epoxy group-containing silane coupling agent (trade name "Sila-Ace" 510 ", manufactured by JNC Co., Ltd.), and 1.0 part of NEOSTANN U-810 as the (D) component were mixed well to prepare a primer.

[Example 3]

100 parts of the component (A-1) of Production Example 1 and 7.8 parts of the component (B) CORONATE HX, 10 parts of KBE-9007 as component (C), and 1.0 part of commercially available tin-based amine esterification catalyst (dioctyltin neodecanoate, trade name "NEOSTANN U" as component (D) -830 ", manufactured by Nitto Kasei Co., Ltd.), to mix thoroughly to prepare a primer.

[Example 4]

100 parts of (A-2) component of Production Example 1, 7.8 parts of CORONATE HX as component (B), 10 parts of KBE-9007 as component (C), and 1.0 part of component (D) NEOSTANN U-830 is thoroughly mixed to formulate a primer.

[Example 5]

100 parts of (A-1) component of Production Example 1, 7.8 parts of CORONATE HX as component (B), 10 parts of KBE-9007 as component (C), and 1.0 part of component (D) A commercially available bismuth-based amine esterification catalyst (bismuth trioctoate, trade name "NEOSTANN U-600H", manufactured by Nitto Kasei Co., Ltd.) was sufficiently mixed to prepare a primer.

[Example 6]

100 parts of the component (A-2) of Production Example 2 and 10 parts of the isotricyanate body of the toluene diisocyanate as the component (B) (trade name "CORONATE 2030", manufactured by Japan Polyurethane Industry Corporation) ), 10 parts of KBE-9007 as component (C), and 1.0 part of NEOSTANN U-600H as component (D) were mixed thoroughly to prepare a primer.

[Example 7]

100 parts of the component (A-1) in Production Example 1 and 6 parts of the biuret body of hexamethylene diisocyanate as the component (B) (trade name "DURANATE" 24A-100 ", manufactured by Asahi Kasei Chemical Co., Ltd.), 10 parts of KBE-9007 as component (C), and 1.0 part of NEOSTANN U-810 as component (D) were mixed thoroughly to prepare a primer.

[Example 8]

Asahi Kasei Chemical Co., Ltd. made 100 parts of the component (A-1) of Production Example 1 and 11.3 parts of the biuret body of the hexamethylene diisocyanate as the component (B) (trade name "DURANATE P301-75E"). (Manufactured), 10 parts of KBE-9007 as component (C), and 1.0 part of NEOSTANN U-810 as component (D) were mixed thoroughly to prepare a primer.

[Example 9]

100 parts of the component (A-1) of Production Example 1, 7.8 parts of the CORONATE HX as the (B) component, and 10 parts of the mercapto-containing silane coupling agent (trade name "KBM-803" as the (C) component, (Made by Shin-Etsu Silicone Co., Ltd.) and 1.0 part of NEOSTANN U-810 as the (D) component are mixed well to prepare a primer.

[Example 10]

100 parts of (A-3) component of Production Example 1, 25 parts of CORONATE HX as (B) component, 10 parts of KBE-9007 as (C) component, and 1.0 part as (D) component NEOSTANN U-810 is thoroughly mixed to formulate a primer.

[Example 11]

100 parts of (A-4) component of Production Example 1, 2 parts of DURANATE 24A-100 as component (B), 10 parts of KBE-9007 as component (C), and 1.0 part of component (D) NEOSTANN U-810 ingredients are mixed well to adjust With primer.

[Example 12]

100 parts of (A-5) component of Production Example 1, 8 parts of CORONATE HX as (B) component, 10 parts of KBE-9007 as (C) component, and 1.0 part of (D) component NEOSTANN U-810 is thoroughly mixed to formulate a primer.

[Example 13]

100 parts of (A-6) component of Production Example 1, 20 parts of CORONATE HX as component (B), 10 parts of KBE-9007 as component (C), and 1.0 part of NEOSTANN as component (D) U-810, 12 parts of a condensate of pentaerythritol and acrylic acid (trade name "Viscoat # 300", manufactured by Osaka Organic Chemical Industry Co., Ltd.) as component (E), and 0.3 parts of a photopolymerization initiator (trade name "Irg907" (manufactured by Ciba Japan Co., Ltd.) is thoroughly mixed to prepare a primer.

[Example 14]

100 parts of (A-7) component of Production Example 7, 13.7 parts of CORONATE HX as component (B), 10 parts of KBE-9007 as component (C), and 1.0 part of component (D) NEOSTANN U-810 is thoroughly mixed to formulate a primer.

[Example 15]

100 parts of (A-7) component of Production Example 7, 13.7 parts of CORONATE HX as component (B), 10 parts of KBE-9007 as component (C), 1.0 part of NEOSTANN as component (D) U-810, 12 parts of Viscoat # 300 as the (E) ingredient, and 0.3 parts of Irg907 are thoroughly mixed to prepare a primer Agent.

[Comparative Example 1]

The KBE-9007 in Example 1 was set to 0 parts, and the procedure was the same except that the primer was prepared.

[Comparative Example 2]

100 parts of (α) component of Comparative Manufacturing Example 1, 3 parts of CORONATE HX as component (B), 10 parts of KBE-9007 as component (C), and 1.0 part of NEOSTANN as component (D) U-810 is mixed thoroughly to formulate a primer.

[Comparative Example 3]

100 parts of the component (A-1) of Production Example 2 and 10 parts of the melamine-based hardener (trade name "CYMEL 303LF") used to replace the component (B), methylated melamine resin, made by Japan Allnex Corporation ), 10 parts of KBE-9007 as the component (C), and 0.3 parts of p-toluenesulfonic acid (PTS) as a catalyst for replacing the component (D) were mixed thoroughly to prepare a primer.

[Comparative Example 4]

100 parts of the component (A-1) of Production Example 2 and 10 parts of the melamine-based hardener (trade name "CYMEL 303LF") used to replace the component (B), methylated melamine resin, manufactured by Japan Allnex Corporation ), 10 parts of Sila-Ace S510 as the component (C), and 0.3 parts of p-toluenesulfonic acid as a catalyst for replacing the component (D) are sufficiently mixed to prepare a primer.

(1) Production of a substrate with a primer layer (without (E) component)

A substrate having a hardened undercoat layer was prepared by using the bar coater with the undercoating agent of Example 1 so that the dry film thickness became about 1.0 μm. A commercially available polyester film (trade name "Lumirror U48", manufactured by Toray Co., Ltd., 150 μm thick) was applied and dried at 130 ° C for 1 minute.

(2) making vapor-deposited copper film

Next, a vapor-deposited copper film was obtained by using a commercially available vapor deposition device (trade name "NS-1875-Z", manufactured by Nishiyama Seisakusho Co., Ltd.) to vapor-deposit copper on the base coat of the substrate On the surface (about 100 nm thick). The primers of Examples 2 to 12 and 14 and Comparative Examples 1 to 4 were also performed in the same manner to obtain a vapor-deposited copper film.

(3) Production of a substrate with a primer layer (in the state where the (E) component has been used)

A substrate having a hardened undercoat layer was prepared by applying the undercoating agent of Example 13 to a dry film thickness of about 1.0 μm with a bar coater on the commercially available polyester film. And dried at 130 ° C for 1 minute. Then, the obtained coating film was irradiated with ultraviolet rays of 300 mJ / cm ² .

(4) making vapor-deposited copper film

Subsequently, a vapor-deposited copper film was obtained by vapor-depositing copper on a base coating surface (approximately 100 nm thick) of the base material using a commercially available vapor deposition device. The primer of Example 15 was also performed in the same manner to obtain a vapor-deposited copper film.

(5) Initial adhesion

The adhesion of the copper vapor-deposited layer was evaluated by cutting 100 squares with a utility knife on the copper-deposited surface of the vapor-deposited copper film of Example 1 and attaching an adhesive tape (brand name "CELLOTAPE" (Registered trademark) ", manufactured by NICHIBAN Co., Ltd.), and then peeled in the vertical direction. The vapor-deposited copper films of Examples 12 to 15 and Comparative Examples 1 to 4 were also performed in the same manner to evaluate the initial adhesion.

(6) Alkali resistance

The vapor-deposited copper film of Example 1 was immersed in a 4% sodium hydroxide aqueous solution heated to 40 ° C. for 5 minutes, and then the adhesion of the copper-deposited layer was evaluated by the same grid test as described above. The vapor-deposited copper films of Examples 12 to 15 and Comparative Examples 1 to 4 were also performed in the same manner to evaluate the alkali resistance.

(7) Acid resistance

The vapor-deposited copper film of Example 1 was immersed in a 4% hydrochloric acid aqueous solution heated to 40 ° C. for 5 minutes, and then the adhesion of the copper-deposited layer was evaluated by the same grid test as described above. The vapor-deposited copper films of Examples 12 to 15 and Comparative Examples 1 to 4 were also performed in the same manner to evaluate the acid-resistant adhesiveness.

(8) Anti-caking property

With respect to the primers of Examples 1 to 12 and 14 and Comparative Examples 1 to 4, a base material having a cured undercoat layer was prepared according to the method of the aforementioned item (1). Then, the aforementioned polyester film was laminated on the base coating surface, and left to stand for 7 days in an environment of 40 ° C. in a state where a load of 8 kg / cm ² was applied. After that, the coated film was peeled from the uncoated film, and the anti-blocking property was evaluated. Specifically, a person who can observe peeling of the coating film at the time of peeling is set to X, a person who does not observe peeling of the coating film but slightly feels resistance is set to Δ, and a person who does not peel the coating film and hardly feels resistance is set to ○ △, the case where the coating film was not peeled off and no resistance was felt was set to ○.

In addition, the primers of Examples 13 and 15 were prepared in accordance with the method of the item (3), and a base material having a primer layer was prepared. Then, according to the method of the aforementioned item (8), the anti-blocking property of the undercoat layer was evaluated.

Claims (23)

A primer for a substrate with a copper film attached, comprising: a polyester polyol (A) which uses dicarboxylic acids (a1) and glycols (a2) as reaction components, and the polyester polyol ( A) a glass transition temperature of 80 ° C. or less and a hydroxyl value of 5 to 100 mgKOH / g; a polyisocyanate (B) having at least 3 isocyanate groups; and a reactive alkoxysilyl compound (C), It is represented by the general formula (1): X ¹ -Si (R ¹ ) _a (OR ² ) _3-a (1) In the general formula (1), X ¹ represents a group containing a group selected from the group consisting of a hydroxyl group and an isocyanate group. One of the groups in the formed group is a functional group that reacts. R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. The primer according to claim 1, wherein the component (A) further comprises a polyol (a3) as a reaction component, and the polyol (a3) has at least three hydroxyl groups. The primer according to claim 1 or 2, wherein the glass transition temperature of the component (A) is 0 to 75 ° C. The primer according to claim 1 or 2, wherein the component (B) is an addition selected from a biuret body of a diisocyanate compound, an isotricyanate body of a diisocyanate compound, and an addition of a diisocyanate compound. Derivative (b1) of a diisocyanate compound in the group consisting of compounds. The primer according to claim 1 or 2, wherein the equivalent ratio [NCO / OH] of the hydroxyl group contained in the component (A) to the isocyanate group contained in the component (B) is 0.5 to 5. The primer according to claim 1 or 2, wherein the used amount of the component (C) is converted to a solid content and is 1 to 20 parts by weight relative to 100 parts by weight of the component (A). The primer according to claim 1 or 2, further comprising an amine esterification catalyst (D). The primer according to claim 7, wherein the used amount of the component (D) is converted to a solid content and is 0.1 to 2 parts by weight relative to 100 parts by weight of the component (A). The primer according to claim 1 or 2, further comprising an active energy ray polymerizable compound (E), the active energy ray polymerizable compound (E) having at least three carbon-carbon double bonds in a molecule. Of groups. The primer according to claim 9, wherein the used amount of the (E) component is converted to a solid content and is 1 to 100 parts by weight relative to 100 parts by weight of the component (A). A base material with a copper film, comprising: a base material, an undercoat layer, and a copper thin film layer. The undercoat layer is hardened by the undercoating agent according to any one of claims 1 to 10. . The substrate with a copper film attached thereto according to claim 11, wherein the substrate is plastic. The substrate with a copper film attached thereto as described in claim 12, wherein the plastic is a plastic film. The substrate with a copper thin film according to claim 13, wherein the plastic film is a polyester film. The substrate with a copper thin film according to any one of claims 11 to 14, wherein the copper thin film layer is a vapor-deposited copper film or a sputtered copper film. A method for manufacturing a substrate with a copper film, characterized in that: the surface of the substrate is first coated with the primer according to any one of claims 1 to 8, and then the substrate is heated, Thereby, a hardened undercoat layer (1) is formed, and then a copper thin film layer is formed on the hardened undercoat layer (1). A method for manufacturing a base material with a copper film, characterized in that: the surface of the base material is first coated with the primer as described in claim 9 or 10, and then the base material is heated to form hardening. The undercoat layer (1 ') is irradiated with active energy rays to the hardened undercoat layer, thereby forming a hardened undercoat layer (2'), and then forming a copper thin film layer on the hardened undercoat layer (2 '). The manufacturing method according to claim 16, wherein the method for forming a copper thin film layer on the hardened undercoat layer (1) is a vacuum evaporation method or a sputtering method. The manufacturing method according to claim 17, wherein the method for forming a copper thin film layer on the hardened undercoat layer (2 ') is a vacuum evaporation method or a sputtering method. A conductive film using the base material with a copper thin film according to any one of claims 11 to 15. A conductive film obtained by using a base material with a copper thin film obtained by the manufacturing method according to claim 16 or 18. A conductive film obtained by using a substrate with a copper thin film obtained by the manufacturing method according to claim 17 or 19. An electrode film obtained from the conductive film according to any one of claims 20 to 22.