WO2016121316A1 - Substrate equipped with electroconductive film - Google Patents

Abstract

The objective of the present invention is to provide a substrate equipped with an electroconductive film, there being good adhesion between the substrate and the electroconductive film and no imperfections on the surface of the electroconductive film. A substrate equipped with an electroconductive film, having an underlayer film and an electroconductive film in the stated order on the surface of the substrate, the underlayer film being obtained from a coating composition that contains the following components (A), (B), and (C): (A) A hydrolysis condensation product of an epoxy-group-containing a trialkoxysilane (B) A polyamine (C) At least one substance selected from the group comprising organic acids with a pKa at 25°C of 2.0-6.0, and C2-5 alcohols having a perfluoroalkyl group and/or a perfluoroalkylene group

Description

Substrate with conductive film

The present invention relates to a substrate with a conductive film in which a conductive film is formed on the substrate surface with good adhesion. This application claims priority to Japanese Patent Application No. 2015-012375 filed on Jan. 26, 2015, the contents of which are incorporated herein by reference.

Conventionally, conductive films formed using conductive inks or pastes containing metal particles and conductive polymers have been widely used to form electrodes and circuits for electronic components, electromagnetic wave shields, and the like. Further, due to recent demands for miniaturization of devices and circuits, for example, attempts have been made to form conductive film wiring on a flexible substrate such as polyimide so that the substrate can be stored in a folded state.

However, such a substrate has low heat resistance, and it is necessary to sinter the conductive ink at a low temperature when forming the conductive film. In particular, when a conductive film is formed by applying and sintering a conductive ink or paste containing fine metal particles on a substrate, there is a problem that the conductive film is easily peeled off from the substrate because the adhesion between the conductive film and the substrate is low. is there.

Therefore, a method for improving the adhesion between the substrate and the conductive film laminated thereon is known by forming a base film on the substrate surface. For example, in Patent Document 1, an overcoat agent containing vinyl chloride / acrylic / polycarbonate as a primer composition is applied on a plastic substrate, and then dried at 80 ° C. for 30 minutes to form a base film, and It describes a method for obtaining a substrate with a conductive film by applying a conductive composition comprising silver oxide and a fatty acid silver salt on a base film, followed by heating at 180 ° C. for 3 minutes. In Patent Document 2, a base film containing an organic salt or an inorganic salt and a binder resin such as polyvinyl alcohol is formed on a glass substrate whose surface has been subjected to oxygen plasma treatment, and further, a quencher is formed on the base film. A method for forming a conductive film having no unevenness and good adhesion to a substrate by forming a circular dot pattern of silver nanoink containing sodium acid as a dispersant with an inkjet device and drying at 150 ° C. for 30 minutes is described. Yes.

On the other hand, as a method for surface modification by applying a coating material on the surface of a substrate, a composition containing the following (A), (B), and (C-1) or (C-2) is used. A method is known in which a thin film having excellent adhesion and hardness to a substrate is formed on the surface by heating after coating on a material. (See Patent Document 3)
(A) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
(B) polyamines, and (C-1) n-pentanol or (C-2) an organic acid or perfluoroalkyl group and / or perfluoroalkylene having a pKa in the range of 2.0 to 6.0 at 25 ° C C2-C5 alcohols having a group

JP 2009-252494 A JP 2010-272402 A International Publication No. 2014/119282 Pamphlet

In the base film described in Patent Document 1, the conductive composition is limited to a composition containing silver oxide and a fatty acid silver salt, and is not a general-purpose one that can be used for conductive ink in general. In addition, the method described in Patent Document 2 is a method for forming a conductive pattern by an ink jet method, in which the conductive film has a uniform film thickness in the case of combining a metal particle-containing ink having specific physical properties and a primer layer having specific properties. And the effect of adhesion to the substrate can be obtained.

The present invention has been made in view of the above circumstances, and has good adhesion between a base material and a conductive film regardless of the type of the base material or conductive ink, and has a conductive film with no unevenness on the surface. It aims at providing the base material with a film | membrane.

As a result of diligent studies to solve the above problems, the present inventor found that when a conductive film was laminated on a base material provided with a base film formed from a specific coating composition on the surface, the base material and the conductive film The present invention was completed by finding that a substrate with a conductive film having good adhesion to the surface and having no unevenness on the surface of the conductive film was obtained.

That is, the present invention
(1) A base material with a conductive film having a base film and a conductive film in this order on the surface of the base material, wherein the base film contains the following components (A), (B), and (C): A substrate with a conductive film, which is a film obtained from the coating composition;
(A) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
(B) polyamines,
(C) at least selected from the group consisting of organic acids having a pKa in the range of 2.0 to 6.0 at 25 ° C., and alcohols having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group 1 type (2) The substrate with a conductive film according to (1), wherein the substrate is a resin substrate,
(3) The base material with a conductive film according to (1), wherein the conductive film contains a sintered body of metal fine particles,
(4) The substrate with a conductive film according to (3), wherein the sintered body of metal fine particles is a sintered body of silver fine particles, and (5) metal fine particles in which the conductive film is dispersed in a solvent or a resin. It is related with the base material with a conductive film as described in (1) which is a sintered compact of the conductive ink or conductive paste to contain.

According to the present invention, by providing in advance a base film obtained by applying a specific coating composition on a base material, the adhesion to the base material regardless of the type of the base material or the conductive composition. Can be obtained, and a substrate with a conductive film having a conductive film with no unevenness on the surface can be obtained.

The present invention is a substrate with a conductive film having a base film and a conductive film in this order on the surface of the base material, wherein the base film comprises the following components (A), (B), and (C): It is a base material with an electrically conductive film which is a film | membrane obtained by apply | coating the coating composition containing on a base material, and drying.
(A) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
(B) polyamines,
(C) at least selected from the group consisting of organic acids having a pKa in the range of 2.0 to 6.0 at 25 ° C., and alcohols having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group 1 type Hereinafter, the base material with an electrically conductive film which concerns on this invention is demonstrated in detail.

(1) Substrate Examples of the substrate used in the present invention include resin substrates such as polyimide and polyester, glass-epoxy substrates, silicone substrates, ceramic substrates, and glass substrates.

The material of the resin substrate used in the present invention is not particularly limited. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, Polyarylate, polyimide (PI), polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), cycloolefin polymer (COP), polyamide, fluororesin, nylon, polymethyl methacrylate, polyacrylate, Examples include polyarylate. The base material which laminated | stacked the different material which has these materials as a main component may be sufficient. Especially, the base material formed from a polyethylene terephthalate, a polyethylene naphthalate, or a polyimide is preferable from the point which is excellent in a softness | flexibility.

The shape may be any shape such as a film shape, a sheet shape, or a plate shape, but a film shape is particularly preferable. The film-like substrate may be made of an unstretched film or may be made of a stretched film. Moreover, even if it is a single layer film, the laminated film which laminated | stacked two or more layers by means, such as a lamination and a coating, may be sufficient.

The thickness of the film-like substrate is not particularly limited, but is usually 1 to 1000 μm, preferably 3 to 500 μm. It is preferable to have flexibility enough to handle a roll-to-roll process.

(2) Undercoat film The undercoat film of the present invention is formed on the surface of the base material, and the adhesiveness between the conductive film and the base material and the film formability of the conductive film are improved by modifying the base material surface like glass. It is a film formed for the purpose of improvement.

Below, the coating composition (henceforth the coating composition of this invention) containing the following component (A), (B), and (C) for forming a base film is explained in full detail.
(A) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
(B) polyamines,
(C) at least selected from the group consisting of organic acids having a pKa in the range of 2.0 to 6.0 at 25 ° C., and alcohols having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group 1 type

(A) Hydrolyzed condensate of epoxy group-containing trialkoxysilane Epoxy group-containing trialkoxysilane and / or raw material used in the production of the epoxy group-containing trialkoxysilane hydrolyzed condensate used in the coating composition of the present invention The structure of the hydrolysis condensate is not particularly limited as long as it is a compound having an epoxy group in addition to the functional group portion lost due to hydrolysis or the like. For example, the structure is not limited to the following formula (I-1) or (I -2) can be exemplified.

In the formula, R represents a hydrocarbon group having an epoxy group or a glycidoxy group, and R ₁ represents an alkyl group having 1 to 10 carbon atoms which may have a substituent. In R, one or more epoxy groups or glycidoxy groups may be contained, and preferably 1 to 3 are included, and both epoxy groups and glycidoxy groups may be contained.
In addition to the epoxy group and glycidoxy group, R may have other substituents, and may have —O—, —CO—, —COO— or the like as a linking group.
As the “hydrocarbon group” of the “hydrocarbon group having an epoxy group or glycidoxy group” of R, specifically, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, An aryl group, an arylalkyl group, an arylalkenyl group and the like can be exemplified, and the carbon number is preferably in the range of 1 to 30, more preferably in the range of 1 to 10.
Specific examples of the “alkyl group” include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, and isopentyl group. , Neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group , Heptadecyl group, stearyl group and the like.

Specific examples of the “cycloalkyl group” include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

The “cycloalkylalkyl group” is a group in which a cycloalkyl group and an alkyl group are bonded. Specifically, a cyclopropylmethyl group, a cyclopropylethyl group, a cyclopropylpropyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, Examples thereof include a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, and the like. Preferably, a cycloalkyl group having 3 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded to each other.

Specific examples of the “alkenyl group” include a vinyl group, a prop-1-en-1-yl group, an allyl group, a but-1-en-1-yl group, a but-2-en-1-yl group, But-3-en-1-yl group, but-1-en-2-yl group, but-3-en-2-yl group, penta-1-en-1-yl group, penta-4-ene- 1-yl group, penta-1-en-2-yl group, penta-4-en-2-yl group, 3-methyl-but-1-en-1-yl group, hexa-1-en-1- Yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7 Examples include -en-1-yl group, buta-1,3-dien-1-yl group, and the like.

Specific examples of the “cycloalkenyl group” include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, and 3-cyclohexene. Examples thereof include a 1-yl group and the like.

Specific examples of the “alkynyl group” include ethynyl group, prop-1-in-1-yl group, prop-2-yn-1-yl group, but-1-in-1-yl group, but-3- In-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa-1-in-1-yl group, hexa-5-in-1-yl group And hept-1-in-1-yl group, octa-1-in-1-yl group, octa-7-in-1-yl group and the like.

“Aryl group” means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, in addition to fully unsaturated, partially saturated groups are also included. Specifically, a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group and the like can be exemplified.

The “arylalkyl group” is a group in which an aryl group and an alkyl group are bonded. Specifically, a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl group, Examples thereof include a phenyl-n-pentyl group and an 8-phenyl-n-octyl group, and a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded is preferable.
The “arylalkenyl group” is a group in which an aryl group and an alkenyl group are bonded, and specifically includes a styryl group, a 3-phenyl-prop-1-en-1-yl group, a 3-phenyl-prop-2-yl group. En-1-yl group, 4-phenyl-but-1-en-1-yl group, 4-phenyl-but-3-en-1-yl group, 5-phenyl-pent-1-en-1-yl Group, 5-phenyl-pent-4-en-1-yl group, 8-phenyl-oct-1-en-1-yl group, 8-phenyl-oct-7-en-1-yl group, naphthylethenyl group, etc. And a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are bonded is preferable.

The above-mentioned “hydrocarbon group” may have a substituent other than an epoxy group and a glycidoxy group. Specific examples of such a substituent include a halogen atom, an alkyl group, an alkenyl group, and an alkoxy group. And (meth) acryloxy groups.
Here, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
As an alkyl group and an alkenyl group, the same specific example as the alkyl group and alkenyl group in said R can be illustrated.

As "an alkyl group having 1 to 10 carbon atoms" of "the alkyl group which has ~ carbon atoms 1 be 10 substituted" in R _1, the number of carbon atoms in the R is the same as the alkyl group having 1 to 10 Things can be illustrated.
Specific examples of the substituent “which may have a substituent” include a halogen atom, an alkoxy group, a (meth) acryloxy group, and the like. Specific examples of the halogen atom and alkoxy group include the same specific examples as the halogen atom and alkoxy group exemplified as substituents other than the epoxy group and glycidoxy group in R above.

Specific examples of the epoxy group-containing trialkoxysilane or hydrolysis condensate thereof include the following compounds, but are not limited thereto. Moreover, these can be used individually by 1 type or in mixture of 2 or more types.

Among these, glycidoxyalkyltrialkoxysilane or glycidoxyalkenylalkoxysilane is preferable, and specific examples thereof include compounds represented by the following formulae.

These can be used singly or in combination of two or more.

Specifically, the method for producing a hydrolysis-condensation product of an epoxy group-containing trialkoxysilane includes an epoxy group-containing trialkoxysilane as a raw material, water, and an amino group or imino group in which one or more hydrogen atoms are bonded. Examples of the method of mixing and stirring polyamines or imidazoles having two or more in one molecule, if necessary, acid and organic solvent can be exemplified, but the mixing order and the stirring speed are not particularly limited, and are arbitrary. Or any speed can be set. The temperature at the time of mixing and stirring is not particularly limited, and it is preferably in the range of room temperature to the boiling point of the solvent used, more preferably at room temperature. In this case, the room temperature is the outside air temperature at the place where mixing and stirring is performed, but a temperature in the range of 15 to 35 ° C. is preferable.
At room temperature, the epoxy group-containing trialkoxysilane, water, and polyamines having two or more amino groups or imino groups bonded to one or more hydrogen atoms in one molecule, or all imidazoles coexist. It is preferable to stir for 2 to 3 hours. After hydrolysis, if necessary, dilute with an organic solvent or water.
In addition to the above, water and optionally a silanol condensation catalyst are added to the epoxy group-containing trialkoxysilane, and at 5 to 100 ° C., preferably 20 to 60 ° C., 1 minute to 10 days, preferably 30 minutes to 24 hours. The method of making it react can be illustrated.
The amount of water is not particularly limited as long as the epoxy group-containing trialkoxysilane used is more than the amount that can be hydrolyzed and condensed to some extent, and specifically, 0.5 mol relative to 1 mol of trialkoxysilane used. The above is preferable, and 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 mol or more is more preferable.
The amount of the silanol condensation catalyst used is not particularly limited, but is 0. The molar ratio of the trialkoxysilyl group in the starting epoxy group-containing trialkoxysilane (silanol condensation catalyst / the silyl group) is 0.00. The range of 001 to 1.0 is preferable, and the range of 0.01 to 1.0, or 0.1 to 0.5 is more preferable.

The silanol condensation catalyst is not particularly limited as long as it hydrolyzes the alkoxy group of the epoxy group-containing trialkoxysilane and condenses the silanol to form a siloxane bond. Specifically,
Dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin ditride Dialkyltin dicarboxylates such as silmaleate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate;
Dialkyltin alkoxides such as dibutyltin dimethoxide and dibutyltin diphenoxide;
Dialkyltin chelates such as dibutyltin diacetylacetonate and dibutyltin diethylacetoacetate;
A reaction product of a dialkyltin oxide such as dibutyltin oxide or dioctyltin oxide and an ester compound such as dioctylphthalate, diisodecylphthalate or methylmaleate;
A tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid and an alcohol compound;
Tetravalent tin compounds such as a reaction product of a dialkyltin oxide and a silicate compound such as dibutyltin bistriethoxysilicate and dioctyltin bistriethoxysilicate, and an oxy derivative (stannoxane compound) of these dialkyltin compounds;
Divalent tin compounds such as tin octylate, tin naphthenate, tin stearate and tin felzatic acid, or a reaction product and a mixture of these with an amine compound such as laurylamine described later;
Monoalkyltins such as monobutyltin compounds and monooctyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide;
Titanates such as tetrabutyl titanate, tetrapropyl titanate, tetra (2-ethylhexyl) titanate, isopropoxy titanium bis (ethyl acetoacetate);
Organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, di-isopropoxyaluminum ethylacetoacetate;
Bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, calcium carboxylate, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, carboxylic acid Metal salts of carboxylic acids (2-ethylhexanoic acid, neodecanoic acid, versatic acid, oleic acid, naphthenic acid, etc.) such as cobalt, zinc carboxylate and aluminum carboxylate, or these and amine compounds such as laurylamine described later Reactants and mixtures;
Chelating compounds such as zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium acetylacetonate bis (ethylacetoacetate), titanium tetraacetylacetonate;
Aliphatic primary such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine Amines;
Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearyl Aliphatic secondary amines such as amines;
Aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine;
Aliphatic unsaturated amines such as triallylamine and oleylamine;
Aromatic amines such as lauryl aniline, stearyl aniline, triphenylamine; and
Other amines include monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenyl Guanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene (DBU), etc. Amine compounds, or salts of these amine compounds with carboxylic acids, etc .;
Reactants and mixtures of amine-based compounds and organotin compounds such as laurylamine and tin octylate reactants or mixtures;
Low molecular weight polyamide resin obtained from excess polyamine and polybasic acid;
Reaction product of excess polyamine and epoxy compound;
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) Aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N- (β-aminoethyl) aminopropylmethyldiethoxysilane, N -(Β-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl -Γ- Aminopropyltriethoxysilane and the like can be exemplified.
Moreover, silane coupling agents having amino groups such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and the like, which are modified derivatives of these, and ferrastic Examples include known silanol condensation catalysts such as acidic catalysts such as fatty acids such as acids and organic acidic phosphate compounds, and basic catalysts.

Specifically, as the organic acidic phosphate compound of the acidic catalyst, (CH ₃ O) ₂ P (═O) (OH), (CH ₃ O) P (═O) (OH) ₂ , (C ₂ H ₅ O) ₂ P (═O) (OH), (C ₂ H ₅ O) P (═O) (OH) ₂ , (C ₃ H ₇ O) ₂ P (═O) (OH), (C ₃ H ₇ O) P (═O) (OH) ₂ , (C ₄ H ₉ O) ₂ P (═O) (OH), (C ₄ H ₉ O) P (═O) (OH) ₂ , (C ₈ H ₁₇ O) ₂ P (═O) (OH), (C ₈ H ₁₇ O) P (═O) (OH) ₂ , (C ₁₀ H ₂₁ O) ₂ P (═O) (OH), ( _{C 10 H 21 O) P (} = O) (OH) 2, (C 13 H 27 O) 2 P (= O) (OH), (C 13 H 27 O) P (= O) (OH) 2, _{(C 16 H 33 O) 2} P (= O) _{OH), (C 16 H 33} O) P (= O) (OH) 2, (HOC 6 H 12 O) 2 P (= O) (OH), (HOC 6 H 12 O) P (= O) ( OH) ₂ , (HOC ₈ H ₁₆ O) P (═O) (OH), (HOC ₈ H ₁₆ O) P (═O) (OH) ₂ , [(HOCH ₂ CH (OH) O] ₂ P ( _{= O) (OH), [} (HOCH 2 CH (OH) O] P (= O) (OH) 2, [(HOCH 2 CH (OH) C 2 H 4 O] 2 P (= O) (OH) , [(HOCH ₂ CH (OH) C ₂ H ₄ O] P (═O) (OH) _{2 and the} like.

A photoacid generator can also be used as a silanol condensation catalyst. Specific examples of photoacid generators include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), fluoroalkyl phosphate (PF _m (RF) _6-m ⁻ (RF represents a fluorinated alkyl group). M represents an integer of 0 to 5)), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ), tetraphenylborate, tetrakis (Trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO ₄ ⁻ ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), Toluene sulfonate ion, trinitrobe Zensurufon anion, a sulfonium salt or iodonium salt having an anion such as trinitrotoluene sulfonate anion can be used.

Silanol condensation catalysts can be used singly or in combination of two or more. In the coating composition of the present invention, polyamines or imidazoles are used as the curing agent or curing accelerator for the epoxy group-containing trialkoxysilane, and therefore polyamines and imidazoles are preferably used as the silanol condensation catalyst. .

The z-average particle diameter measured by the dynamic light scattering method of the hydrolysis-condensation product of the epoxy group-containing trialkoxysilane used in the coating composition of the present invention is a viewpoint of film hardness, coating unevenness during coating, etc. From 5 to 50 nm is preferable, and 5 to 30 nm is more preferable. When it is larger than 50 nm, the pot life is short, there is a problem in storage stability, and smear may occur after coating. When it is smaller than 5 nm, the hardness of the coating film obtained from this composition May become insufficient.

(B) Polyamines The polyamines used in the coating composition of the present invention are not particularly limited as long as they are compounds having two or more amino groups or imino groups bonded to one or more hydrogen atoms in one molecule. Specifically, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, methylaminopropylamine, ethylaminopropylamine, N, N'- Dimethylhexamethylenediamine, bis (2-methylaminoethyl) ether, menthanediamine, isophoronediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane Adduct, screw (4-ami (Cyclohexyl) methane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylenediamine, and the like. These may be used alone or in combination of two or more. Can be mixed and used. Among these, polyalkylene polyamines are preferable, and specific examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dipropylenetriamine.
The amount of polyamines used is not particularly limited, but is 1 / (total of all nitrogen atoms in one molecule of polyamines per 1 mol of epoxy groups in epoxy group-containing trialkoxysilane and / or its hydrolysis condensate. (Number of hydrogen atoms) It is preferable to use at least mol, and the range is 1.2 times to 10 times mol, 1.5 times to 5 times mol of 1 / (number of all hydrogen atoms on all nitrogen atoms in one molecule of polyamine). Or a range of 1.8 to 2.5 moles. When less than 1 / (total number of hydrogen atoms on all nitrogen atoms in one molecule of polyamine) is less than 1 mol, curing may be insufficient and a film with high hardness may not be obtained. 1 / (polyamines 1 When it is larger than 10 times the mole of all hydrogen atoms on all nitrogen atoms in the molecule, polyamines may remain and a film having sufficient hardness may not be obtained.

(C) an organic acid having a pKa in the range of 2.0 to 6.0 at 25 ° C., and an alcohol having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group. As the organic acid used, it is preferable to use an organic acid having a pKa at 25 ° C. in the range of 2.0 to 6.0, preferably in the range of 3.0 to 5.0. Specific examples of such organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isocaproic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, and 3-chloropropion. Acid, 2-bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethylmalonic acid, adipic acid, succinic acid , Pimelic acid, phthalic acid, glutaric acid, oxaloacetic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, o-anisic acid, m-anisic acid, p-anisic acid, benzoic acid, o- Chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p- Torobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, salicylic acid, phthalic acid, ilophthalic acid, trans-cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glucholic acid, crotonic acid, lactic acid, 2-hydroxy Examples include -2-methylpropionic acid, pyruvic acid, mandelic acid, malic acid, levulinic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid and the like.
Especially, an aliphatic monocarboxylic acid, benzoic acid, or substituted benzoic acid can be illustrated preferably.
The amount of the organic acid used is not particularly limited, but is preferably in the range of 0.3 to 1.2 mol, preferably 0.5 to 1.0 mol, or 0.6 to 0, relative to 1 mol of the polyamine used. A range of .9 mol is more preferred.
When the amount is less than 0.3 mol, the storage stability of the composition may be lowered. When the amount is more than 1.2 mol, a coating film having sufficient hardness may not be formed.

Specific examples of the alcohol having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group used in the coating composition of the present invention include 2,2,2-trifluoroethanol, 1,1 , 2,2,2-pentafluoroethanol, 3,3,3-trifluoro-1-propanol, 2,2,3,3,3-pentafluoro-1-propanol, 1,1,2,2,3 , 3,3-heptafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2-trifluoromethyl-2-propanol, 2-methyl-1,1,1 , 3,3,3-hexafluoro-2-propanol, 2,2,3,3,4,4,4-heptafluoro-1-butanol, nonafluoro-t-butanol, 2,2,3,3 , It can be exemplified 4,5,5- octafluoro-1-pentanol.
Although the usage-amount of the fluorinated alcohol in this composition is not restrict | limited in particular, 30 mass% or more of the whole composition is preferable, and 40 mass% or more is more preferable. When it is less than 30% by mass, the long-term storage stability of the composition may be lowered.

(Blend proportion of the total amount of components (A) and (B) in the composition)
The solid content concentration in the coating composition of the present invention is not particularly limited, but considering the appearance of the coating film, coating properties, curability, coating film properties, storage stability of the composition, etc., (A) epoxy group It is preferable to use such an amount that the hydrolyzed condensate of the contained trialkoxysilane and the solid content concentration of the (B) polyamine are in the range of 0.5 to 50% by mass with respect to the total mass, 1.0 to 30 More preferred are ranges of mass%, 1.0 to 20 mass%, 1.0 to 10 mass%, 1.5 to 5.0 mass%, or 1.8 to 3 mass%. If it is less than 0.5% by mass, it may be difficult to form a film uniformly. If it is more than 50% by mass, the stability of the composition, the transparency of the coating film, the appearance, or There may be a problem in coating properties.
The usage-amount of an organic solvent and water can be suitably determined in the range which can be adjusted to the said solid content concentration.

(solvent)
The coating composition of the present invention can use an organic solvent to adjust the solid content concentration in the composition, and as such a solvent, any solvent that can maintain the uniformity and stability of the solution can be used. Specific examples include, but are not limited to, methanol, ethanol, propyl alcohol, isopropyl alcohol, n-butanol, s-butanol, t-butanol, n-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Alcohols such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetrahydropyran, etc. Ethers, acetone, methyl ethyl ketone, acetylacetone, cyclohexanone and other ketones, methyl acetate, esters such as ethylene glycol monoacetate, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, pyrrolidone, N-methylpyrrolidone, etc. Examples of the amides include alcohols having 1 to 5 carbon atoms. These can be used alone or in combination of two or more.
It is preferable to use water as the other solvent. In that case, the organic solvent to be used is preferably an organic solvent that dissolves in water. In addition, the ratio of water to the organic solvent is not particularly limited as long as it is an amount ratio that makes a uniform solution as a composition after using a necessary amount. When an organic solvent that dissolves relatively well in water such as alcohol having 3 or less carbon atoms is used, the mass ratio of water to organic solvent (water / organic solvent) is preferably in the range of 30/70 to 95/5. , 50/50 to 90/10, 60/40 to 80/20, or 65/35 to 75/25 are more preferable.
In addition, when an organic solvent that is relatively difficult to dissolve in water such as alcohol having 4 or more carbon atoms is used, the amount of water used for hydrolysis of trialkoxysilane is low because the solubility of water in the organic solvent is low. It is preferable to use it in an amount in a range where the composition becomes more than the necessary amount.

(Other ingredients)
Furthermore, other curing agents or curing accelerators can be added as necessary. For example, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2 ) Octane (triethylenediamine), N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethyl Aliphatic amine compounds such as ethylenediamine, N, N-dimethylcyclohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol, piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) Alicyclic rings such as undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4-aminocyclohexyl) methane, N, N'-dimethylpiperazine, 1,8-diazabicyclo (4,5,0) undecene-7 Formulas and heterocyclic amine compounds, aromatic amine compounds such as benzylmethylamine, dimethylbenzylamine, pyridine, picoline, epoxy compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, ketone-capped polyamines, etc. Modified amine compounds, dicyandiamide, guanidine Other amine compounds such as organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, etc .;
Imidazoline compounds such as 2-methylimidazoline and 2-phenylimidazoline;
Amide compounds such as polyamide obtained by condensation of dimer acid and polyamine;
Active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids;
Phenol novolak, cresol novolak, polyol, polymercaptan, polysulfide, 2- (dimethylaminomethylphenol), 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol Phenols such as tri-2-ethylhexyl hydrochloride, alcohols, thiols, ethers or thioethers;
Urea-based, thiourea-based or Lewis acid-based compounds such as butylated urea, butylated melamine, butylated thiourea, boron trifluoride;
Alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine, dialkylphosphine such as dimethylphosphine and dipropylphosphine, second phosphine such as diphenylphosphine and methylethylphosphine, and third such as trimethylphosphine and triethylphosphine Phosphorus compounds such as phosphine;
Phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, tetramethylene maleic anhydride, trimellitic anhydride Acid anhydrides such as acid, chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), methylcyclohexene tetracarboxylic anhydride, polyazeline acid anhydride Physical compounds;
Onium such as aryldiazonium salt, diaryliodonium salt, triarylsulfonium salt, triphenylsilanol-aluminum complex, triphenylmethoxysilane-aluminum complex, silyl peroxide-aluminum complex, triphenylsilanol-tris (salicylide) aluminum complex Salt compounds;
An active silicon compound-aluminum complex compound can be exemplified.
Furthermore, if necessary, a tetraalkoxysilane, a trialkoxysilane other than an epoxy group-containing trialkoxysilane, or a dialkoxysilane can be added and used. Specific examples of such alkoxysilanes include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (isopropoxy) silane, and tetra (n-butoxy) silane;
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane , N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloro Ropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluoro Decyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane Silane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxy Lan, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- (meth) acryloyl Oxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureido Trialkoxysilanes such as propyltrimethoxysilane and 3-ureidopropyltriethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxy Silane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyl Dimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethyl Examples thereof include dialkoxysilanes such as xyloxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, and the like. Can be used for Specific examples of such a partial hydrolysis-condensation product include trade names “MKC silicate MS51”, “MKC silicate MS56”, “MKC silicate MS57”, and “MKC silicate MS60” manufactured by Mitsubishi Chemical Corporation (both are tetramethoxy). Silane condensate); trade names “Ethyl silicate 40” and “ethyl silicate 48” (both are condensates of tetraethoxysilane) manufactured by Colcoat Co., Ltd. As specific examples of the alkoxysilane condensate, trade names “MKC silicate MS56B15”, “MKC silicate MS56B30”, “MKC silicate MS58B15”, “MKC silicate MS56I30”, “MKC silicate MS56F20” manufactured by Mitsubishi Chemical Corporation; Product name of It can be exemplified MS-485 ", and the like.
In the coating composition of the present invention, other components can be added depending on the application, and specifically, various surfactants, dyes, pigments, dispersion materials, water repellent materials, thickeners, A fragrance | flavor, an antimicrobial component, etc. can be illustrated.

Although the manufacturing method in particular of the coating composition of this invention is not restrict | limited, Specifically, the following methods etc. can be illustrated.
i) Water, polyamines, and organic acid or fluorinated alcohol and, if necessary, an organic solvent are mixed and stirred at room temperature, and then an epoxy group-containing trialkoxysilane and / or a hydrolysis condensate thereof is added. Dilute with organic solvent.
ii) Mixing and stirring water, epoxy group-containing trialkoxysilane and / or hydrolysis condensate thereof, polyamines, and an organic solvent as required at room temperature, then adding an organic acid or fluorinated alcohol, Dilute with.
iii) Water, an epoxy group-containing trialkoxysilane and / or its hydrolysis condensate, polyamines, organic acid or fluorinated alcohol and, if necessary, an organic solvent are mixed and stirred at room temperature and diluted with an organic solvent.
The stirring temperature is not particularly limited, but is preferably in the range of room temperature to the boiling temperature of the solvent used, and more preferably at room temperature. In this case, the room temperature is the outside temperature of the place where the stirring is performed, but a range of 15 to 35 ° C. is preferable.

(3) Conductive Film The conductive film of the present invention is a film that is provided on a base material having a base film formed on the surface, and is obtained by applying conductive ink and heating or sintering. Preferably, a sintered body of metal fine particles is included.

Although it does not restrict | limit especially as a conductive ink to be used, It is preferable to use an organic material, for example, the ink containing conductive polymer compounds, such as a polyethylene dioxythiophene (PEDOT) / polystyrene sulfonic acid (PSS), and a metal microparticle. Examples thereof include ink and paste dispersed in a solvent or resin. Among these, it is preferable to use an ink in which metal fine particles are dispersed.

Examples of the metal fine particles contained in the conductive ink include gold, silver, platinum, palladium, rhodium, osmium, ruthenium, iridium, copper, nickel, cobalt, iron, tin, chromium, titanium, tantalum, tungsten, and indium. A metal or an alloy thereof can be used, and it is particularly preferable to use gold, silver, palladium, or copper. The shape and size of the metal fine particles are not particularly limited, but those having an average particle diameter of 1 nm to 100 nm are preferably used.

Examples of the conductive ink include water-based conductive ink and organic conductive ink, but organic conductive ink in which metal fine particles are dispersed in an organic dispersion medium is particularly preferable. The content of the metal fine particles in the conductive ink is 10 to 60% by mass, and if necessary, other components include a dispersant, a resin, a solvent, or the like.

(4) Manufacturing method of base material with conductive film The base material with a conductive film of the present invention is formed by forming a base film on the base material, further laminating the conductive film on the base film, and then heating or sintering. Obtained.

The undercoat film of the present invention is formed by applying the coating composition to the surface of a substrate by a known coating method such as brush, spray, dip, spin coating, bar coating, or gravure printing, and then drying the coating composition. be able to. Drying can be performed by room temperature drying and / or heating. Specifically, it is carried out at 20 ° C. to 250 ° C., preferably 20 ° C. to 150 ° C. for 10 seconds to 24 hours, preferably 30 seconds to 10 hours. The undercoat film to be obtained is not particularly limited, but is preferably more than 10 nm and not more than 5 μm.

Further, prior to the formation of the base film on the substrate, the substrate may be subjected to a surface treatment in advance. Examples of the surface treatment include plasma treatment, corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, and chemical treatment. However, if the surface of the base material is greatly roughened, the flatness of the surface of the conductive film pattern to be formed is impaired, so these treatments are performed so that the surface of the base material is not greatly roughened. Preferably, it is done.

The conductive film of the present invention can be obtained by laminating a coating film made of conductive ink on a base material provided with the base film on the surface, and heating or sintering the coating film. The coating film made of a conductive ink can be formed using a known coating method such as screen printing, ink jet printing, spin coating, roll coating, spray coating or the like.

The heating or sintering atmosphere may be an atmospheric oxidizing atmosphere (for example, air). The heating or sintering temperature is in the range of 100 ° C. to 300 ° C., preferably in the range of 100 ° C. to 200 ° C. The heating or sintering time is 30 seconds to 24 hours, preferably about 10 minutes to 10 hours.

The film thickness of the conductive film is preferably 2000 nm or less, more preferably 1000 nm or less, and most preferably 500 nm or less.

The base material with a conductive film of the present invention can be suitably used for, for example, production of circuits such as electronic circuits and antennas, electromagnetic wave absorbers, light reflectors, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited thereto.

[Example 1]
1. Preparation of coating composition To a solution obtained by dissolving 0.125 g (1.02 mmol) of benzoic acid in 17.15 g of 2-propanol, 0.125 g (1.21 mmol) of diethylenetriamine and 7.350 g of water were added and mixed. did. Further, 0.500 g (2.12 mmol) of 3-glycidoxypropyltrimethoxysilane (GPTMS) was added to this solution, and the mixture was stirred at room temperature for 2 hours to obtain a coating composition (A-1 having a solid content of 3.0% by mass). )

2. Formation of Undercoat Film A coating composition (A-1) was formed on a 20 mm × 20 mm polyimide (PI) film. The prepared coating composition (A-1) was applied to the PI film by a bar coating method and then dried in an oven (100 ° C., 10 minutes) to obtain a film (B-1) with an undercoat film.

3. Formation of conductive film A silver ink (product name “SR6000”, manufactured by Bando Chemical Co., Ltd., 40% by mass of silver, tetradecane dispersion) was applied onto the film (B-1) with a base film by spin coating (rotation speed 1500 rpmm, 60 seconds). After coating, the film was dried in an oven (100 ° C., 60 minutes) to obtain a film with conductive film (C-1).

4). Evaluation of adhesion The cross-cut peel test of the obtained film with conductive film (C-1) was conducted according to the cross-cut tape peel test method described in JIS K-5400 (1999). The conductive film on the PI resin film was cross-cut in a 1 mm × 1 mm grid pattern, and a peel test was performed using a transparent adhesive tape. When the conductive film of each grid was evaluated with an optical microscope, no peeling was observed (non-peeling number / test number = 100/100). Therefore, it was found that the PI film and the conductive film were in close contact.
For comparison, the same cross-cut tape peeling test was performed on the film (cC-1) in which the conductive film was formed on the PI film on which the base film was not formed. / Number of tests = 95/100).

[Example 2]
A conductive film was formed by the same method as in Example 1 except that the PI resin film was changed to a polyethylene naphthalate (PEN) film to obtain a film with conductive film (C-2).

For the obtained film with conductive film (C-2), the adhesion was evaluated by the same method as in Example 1. As a result, no peeling of the conductive film on each grid was observed (non-peeling number / test). Number = 100/100). Therefore, it was found that the PEN film and the conductive film were in close contact with each other.
For comparison, the film (cC-2) in which the conductive film was formed on the PEN film on which the base film was not formed was subjected to the same cross-cut tape peeling test, and peeling was observed (non-peeling number) / Number of tests = 74/100).

[Example 3]
A conductive film was formed by the same method as in Example 1 except that the PI resin film was changed to a polyethylene terephthalate (PET) film to obtain a film with conductive film (C-3).

For the obtained film with conductive film (C-3), adhesion was evaluated by the same method as in Example 1. As a result, no peeling of the conductive film on each grid was observed (non-peeling number / test). Number = 100/100). Therefore, it was found that the PET film and the conductive film were in close contact.

Claims (5)

1. A base material with a conductive film having a base film and a conductive film in this order on the surface of the base material, wherein the base film contains the following components (A), (B), and (C): A substrate with a conductive film, which is a film obtained from
   (A) Hydrolysis condensate of epoxy group-containing trialkoxysilane,
   (B) polyamines,
   (C) at least selected from the group consisting of organic acids having a pKa in the range of 2.0 to 6.0 at 25 ° C., and alcohols having 2 to 5 carbon atoms having a perfluoroalkyl group and / or a perfluoroalkylene group 1 type
2. The base material with a conductive film according to claim 1, wherein the base material is a resin base material.
3. The base material with a conductive film according to claim 1, wherein the conductive film contains a sintered body of metal fine particles.
4. The base material with a conductive film according to claim 3, wherein the sintered body of metal fine particles is a sintered body of silver fine particles.
5. The base material with a conductive film according to claim 1, wherein the conductive film is a sintered body of a conductive ink or a conductive paste containing metal fine particles dispersed in a solvent or a resin.