JP2008093914A - Copper-clad plastic substrate and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper-clad plastic substrate in which a thin metal film layer to be a seed layer is simply formed by coating or a printing method on a plastic substrate and which is superior in adhesion between a copper layer and the seed layer, heat resistance, electric characteristics, and productivity and can be used appropriately as a two-layer CCL. <P>SOLUTION: In the copper-clad plastic substrate, an anchor layer (2) containing an anion exchangeable substance is laminated on at least one side of the plastic film substrate (1), the seed layer (4) obtained by applying or printing a dispersing element (3) of conductive substance particles coated with a protective substance and drying it is laminated on the anchor layer (2), and a conductor layer (5) of copper is formed on the seed layer (4) by electroless plating and/or electroplating of copper. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a copper-coated plastic substrate in which a copper conductor layer is formed on a plastic film substrate. Specifically, the present invention relates to a copper-coated plastic substrate suitably used as a substrate for flexible printed circuit boards (FPC), automatic tape bonding tapes (TAB), printed wiring boards (PWB), and the like, and a method for manufacturing the same.

  In recent years, there has been a demand for higher wiring density and higher functionality in printed wiring boards due to downsizing of electronic devices and higher speed of operation. For this reason, a copper-coated plastic substrate in which copper is laminated on a plastic substrate such as a polyimide film having good heat resistance and insulation is used as a printed wiring board substrate material. These are called copper clad laminates (CCL), and are classified into “3-layer CCL” and “2-layer CCL” depending on the configuration, and the present invention particularly relates to a 2-layer CCL application.

As a method of laminating copper on a plastic substrate, there is a method of bonding a plastic substrate and a copper foil with an adhesive, and what is obtained in this way is called a three-layer CCL. The adhesive is insufficient in electrical insulation and heat resistance, so the price is low, but there are problems in electrical insulation, dimensional stability and heat resistance.
Therefore, recently, the casting type that coats polyimide varnish on copper foil, the laminate type two-layer CCL that bonds polyimide film and copper foil with polyimide adhesive, or sputtering on plastic film substrate such as polyimide. A two-layer CCL obtained by a method of directly forming a copper layer by dry plating such as a method, an ion plating method, a vapor deposition method or an electroless plating method has been developed.
Until now, most of these plastic substrates have been polyimide resin films, but polyethylene terephthalate films, polyethylene naphthalate films, aramid films, liquid crystal polymers, and the like have been studied.
The two-layer CCL generally has better heat resistance and electrical characteristics than the three-layer CCL and does not require an adhesive, so it is thinner and softer and has good dimensional stability.

As a manufacturing method of the two-layer CCL, conventionally, the following methods have been studied.
1) A method of forming a barrier layer made of a different metal by electroless plating on a polyimide film to prevent diffusion of copper into polyimide, and forming a copper layer thereon by plating (Japanese Patent Laid-Open No. 63-286580) Publication).
2) A method of producing a copper polyimide substrate by hydrophilizing the surface of the polyimide resin film, applying a catalyst, performing electroless plating, and thereafter performing electroless plating or electrolytic copper plating (JP-A-5-90737). Issue gazette).
3) A method of forming a copper layer by electroless copper plating after providing an electroless plating layer of Co, Ni, or Ni—Co alloy on the surface of the polyimide film (Japanese Patent Laid-Open No. 6-21157).
4) After forming a metal layer on one side or both sides of the insulating film by dry plating (sputtering method) using at least one of Ni, Cr, and chromium oxide without using an adhesive, and hydrophilizing There is a method of forming an electroless plating layer and further forming an electrolytic copper plating layer (Japanese Patent Laid-Open No. 10-200273).
All of these methods form a thin film metal layer called a seed layer, which serves as a core of plating on the film substrate, and provides adhesion between the copper layer and the plastic film by electroless plating or dry plating. On top of this, there is a method of forming a copper layer by electroless plating or electrolytic plating, and there are problems that the operation is complicated, the productivity is inferior, the adhesion between the copper layer and the seed layer is poor, and the cost is high.
JP 63-286580 A JP-A-5-90737 JP-A-6-21157 JP-A-10-200273

  The object of the present invention is to provide an adhesive force between a copper layer and a seed layer, in which a metal thin film layer to be a seed layer is simply formed on a plastic substrate by a coating or printing method in view of the above-described problems of the prior art. An object of the present invention is to provide a copper-coated plastic substrate that is excellent in heat resistance, electrical characteristics, and productivity, and that is suitably used as a two-layer CCL.

In order to achieve the above object, the inventors have found a novel method capable of easily forming a metal thin film layer having good adhesion to a copper layer on a plastic film without damaging the plastic film due to high temperature processing. The present invention has been reached.
That is, in the present invention, an anchor layer (2) containing a substance having anion exchange ability is laminated on at least one surface of a plastic film substrate (1), and a protective substance is formed on the anchor layer (2). A seed layer (4) formed by applying or printing the coated dispersion (3) of conductive material particles and drying is laminated, and electroless copper plating and / or electrolysis is further formed on the seed layer (4). The present invention relates to a copper-coated plastic substrate in which a copper conductor layer (5) is formed by copper plating.

  The present invention also relates to the copper-coated plastic substrate according to the invention, wherein the conductive material particles have an average particle diameter of 0.001 to 10 μm.

  In the present invention, the conductive material particles are one kind of particles selected from the group consisting of gold, silver, copper, nickel, platinum, palladium, and iron, or a mixture of two or more kinds of particles. It is related to the copper-coated plastic substrate of the invention, characterized in that it is a particle of an alloy composed of two or more kinds or a mixture of these particles.

  Further, the present invention provides the copper-coated plastic substrate of the above invention, wherein the protective substance comprises at least one selected from the group consisting of a pigment dispersant, a surfactant, a saturated fatty acid, and an unsaturated fatty acid. About.

  Further, the present invention includes the anchor layer (2) containing particles having an anion exchange ability and / or particles having no anion exchange ability with an average particle diameter of 0.001 to 20 μm. The present invention relates to a copper-coated plastic substrate of the invention.

  Further, in the present invention, the anchor layer (2) reacts with a diol compound (a) having a carboxyl group, a polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and an organic diisocyanate (c). And a polyurethane polyurea resin (C) obtained by reacting a urethane prepolymer (d) having an isocyanate group at the terminal with a polyamino compound (e), and an epoxy resin having two or more epoxy groups (D And a copper-coated plastic substrate according to the present invention.

  Furthermore, the present invention forms an anchor layer (2) containing a substance having anion exchange capacity on at least one surface of the plastic film substrate (1), and a protective substance on the anchor layer (2). A dispersion (3) of conductive material particles coated with is coated or printed, dried to provide a seed layer (4), and electroless copper plating and / or electrolytic copper on the seed layer (4). The present invention relates to a method for producing a copper-coated plastic substrate, wherein a copper conductor layer (5) is formed by plating.

  According to the present invention, a metal thin film layer to be a seed layer can be easily formed on a plastic film by a coating or printing method, and as a two-layer CCL excellent in adhesive strength, heat resistance, electrical characteristics, and productivity with a copper layer A copper-coated plastic substrate that can be suitably used can be provided.

Hereinafter, the present invention will be described in more detail based on embodiments, but the present invention is not limited to these embodiments unless departing from the technical idea of the present invention.
<Plastic film substrate (1)>
The plastic film substrate (1) used in the present invention is not particularly limited. For example, polyethylene terephthalate, polyethylene naphthalate, polyether ketone, polyether imide, polyphenylene sulfide, polyarylate, polyamide, polyimide, A heat-resistant film made of aramid or the like is preferably used. Among these, a heat-resistant film is particularly excellent, and a polyimide film is desirable in terms of mechanical, electrical and chemical properties. In the present invention, as the polyimide film, a commercially available polyimide film having a trade name such as “Kapton” (manufactured by DuPont), “Apical” (manufactured by Kaneka), or “Upilex” (manufactured by Ube Industries) may be used. The thickness is preferably 5 to 75 μm.
After forming an anchor layer (2) containing a substance having anion exchange capacity on both sides or one side of a plastic film substrate (1), a conductive substance coated with a protective substance on the anchor layer (2) A seed layer (4) is formed by applying or printing a dispersion (3) of particles and drying, and a copper conductor layer is formed on the seed layer (4) by electroless copper plating and / or electrolytic copper plating. By forming the copper-coated plastic substrate of the present invention can be obtained.

<Dispersion of conductive material particles coated with protective material (3)>
The dispersion (3) of conductive material particles coated with a protective material used in the present invention serves as a core of electroless plating or electrolytic plating of copper, and serves as a conductor layer during electrolytic plating. A layer (seed layer) for preventing diffusion to the substrate is formed. In addition, the conductive material particles of the present invention are covered with a protective material.
Further, the dispersion (3) of conductive material particles coated with a protective material used in the present invention may contain other additives, liquid medium, resin and / or a precursor thereof, if necessary. For example, it can be used as an aspect of a conductive coating agent or a conductive ink.
Further, the seed layer (4) is formed by applying or printing the conductive coating agent or conductive ink on the anchor layer (2).
In the present invention, in forming the seed layer, it is not always necessary to cover the entire surface of the anchor layer (2), and the seed layer may be partially covered or may be a pattern such as a circuit.

  Examples of the conductive material particles used in the present invention include gold, silver, copper, nickel, platinum, palladium, iron, cobalt, tungsten, titanium, indium, iridium, rhodium, silver-plated copper, silver-copper composite, Particles made of a metal such as an alloy such as a silver-copper alloy or amorphous copper can be used. Among these, gold, silver, copper, nickel, platinum, palladium, and iron are preferable, and gold, silver, copper, and nickel are more preferable, and silver is more preferable in terms of conductivity and cost. In addition, the conductive material particles include inorganic powders coated with the above metals, metal oxides such as silver oxide, indium oxide, antimony oxide, zinc oxide, tin oxide, antimony-doped tin oxide, indium-tin composite oxide, carbon Black, graphite particles, and the like can also be used. These conductive substance particles can be used alone or in combination of two or more.

As the conductive material particles coated with the protective material used in the present invention, for example, the above metal particles coated with the protective material can be used, and the average particle diameter is in the range of 0.001 to 10 μm. Can be used.
Examples of the conductive material particles in the above range include particles (A) obtained by a normal production method such as a wet method, an atomizing method, or an electrolytic method. As the shape of these particles (A), for example, any shape such as flakes, scales, plates, spheres, substantially spheres, agglomerated spheres, dendrites, and foils can be used. A thing with a diameter of 1-10 micrometers can be used conveniently.

Furthermore, in the present invention, the conductive material particles coated with the protective material are, for example, an average particle diameter of 0.001 to 0.00 obtained by a normal production method such as a liquid phase method, a gas phase method, a melting method, and an electrolytic method. 1 μm particles (B) can be more preferably used. Among these, in consideration of production costs and man-hours, particles obtained by a liquid phase method in which a metal compound is reduced using ultrasonic waves, ultraviolet rays, or a reducing agent in a liquid phase are preferable.
By using the conductive material particles in the above range, a conductive film can be formed at a low temperature and in a short time.
When particles having an average particle diameter exceeding 10 μm are used, not only the conductivity of the formed conductive film, that is, the seed layer, is lowered, but also the fusion property at low temperature is inferior, which is not preferable.
Although it depends on the conductive film forming method, it is more preferable to use particles having an average particle diameter of 0.001 to 0.05 μm.
The average particle size of the particles (A) and particles (B) is a particle size distribution measuring device using a dynamic light scattering method (for example, “Microtrack” or “Nanotrack” manufactured by Nikkiso Co., Ltd.). Is a value measured by
Only one of the particles (A) and the particles (B) may be used, or both may be used in combination. Moreover, only 1 type may be used for particle | grains (A) and it may use it in combination of 2 or more type. The same applies to the particles (B).

The surface of the conductive material particles used in the present invention is protected by a protective material. The protective material prevents aggregation of the conductive material particles, for example, when a conductive coating agent or a conductive ink is used. It is necessary to improve the dispersion stability of the conductive material particles, and it is preferable to use a compound having one or more affinity groups in the molecule for the conductive material particles. More preferably, it contains at least one selected from the group consisting of an activator, a saturated fatty acid, and an unsaturated fatty acid.
The affinity group for the conductive material particles varies depending on the type of the conductive material particles, but in general, for example, an amino group, a quaternary ammonium group, a hydroxyl group, a cyano group, a carboxyl group, a thiol group, a sulfone group, and the like. Although polar groups, such as an acid group, are mentioned, it is not limited to these. These affinity groups may be contained only in either the main chain or the side chain of the compound, or may be contained in both the main chain and the side chain.

  Although it does not specifically limit as a pigment dispersant used by this invention, As a commercial item, for example, Solsperse 3000, Solsperse 9000, Solsperse 17000, Solsperse 24000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse 36000, Solsperse 41000 ( LFKA4009, EFKA4046, EFKA4047, EFKA4080, EFKA4010, EFKA4015, EFKA4050, EFKA4055, EFKA4060, EFKA4330, EFKA4300, EFPAR7, EFPAR 7462 Addisper PB822, Addisper PN41 , Azisper PA111 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.), TEXAPHOR-UV20, TEXAPHOR-UV21, TEXAPHOR-UV61 (above, manufactured by Cognis Japan Co., Ltd.), Disperbyk-101, Disperbyk-103, Disperbyk-106, Disperbyk-110 , Disperbyk-111, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-167, Disperbyk-168, Disperbyk-170, DisperDik-170, DisperDik-7 -182 (above BYK Japan Co., Ltd.), and the like. These pigment dispersants may be used alone or in combination of two or more, or may be used in combination with a pigment dispersant and a compound other than the pigment dispersant.

In general, anionic, nonionic, zwitterionic, and cationic surfactants are known as the surfactant used in the present invention, but any of them can be used.
Examples of the anionic surfactant include alpha sulfo fatty acid methyl ester salts, alkylbenzene sulfonates, alkyl sulfate esters, alkyl ether sulfate esters, monoalkyl phosphate esters, alpha olein sulfonates, alkane sulfonates. Etc.
Nonionic surfactants include, for example, glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, fatty acid alkanolamide, polyoxyethylene alkyl ether, alkyl glucoside, polyoxy Examples include ethylene alkyl phenyl ether.

Examples of zwitterionic surfactants include alkylamino fatty acid salts, alkylbetaines, and alkylamine oxides.
Examples of the cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, N-methylbishydroxyethylamine fatty acid ester hydrochloride, and the like.
In addition, reactive surfactants such as fluorine-based surfactants and allyl-based reactive surfactants, and polymer surfactants such as cationic cellulose derivatives, polycarboxylic acids, and polystyrene sulfonic acids can also be used. These are also commercially available as wetting and dispersing agents. 101, Disperbyk-108, Disperbyk-130 (above, manufactured by Big Chemie Japan Co., Ltd.) and the like.
One of these surfactants may be used alone, or two or more thereof may be used in combination, or a surfactant and a compound other than the surfactant may be used in combination.

The saturated fatty acid and / or unsaturated fatty acid used in the present invention is not particularly limited, and conventionally known fatty acids can be used.
Examples of linear saturated fatty acids include propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, Examples include heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, mellicic acid, and laxelic acid.
Examples of linear unsaturated fatty acids include acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid. Examples include acids and stearol acids. Of these, caproic acid, enanthic acid, caprylic acid, myristic acid, oleic acid, stearic acid and the like are preferable in consideration of the stability and low-temperature decomposability of the dispersion.
Examples of branched fatty acids include isobutyric acid, isovaleric acid, 2-ethylhexanoic acid, 2-ethylisohexanoic acid, 2-propylheptanoic acid, 2-butyloctanoic acid, 2-isobutylisooctanoic acid, 2-pentylnonanoic acid, 2-isopentylnonanoic acid, 2-hexyldecanoic acid, 2-hexylisodecanoic acid, 2-butyldodecanoic acid, 2-isobutyldodecanoic acid, 2-heptylundecanoic acid, 2-isoheptylundecanoic acid, 2-isopeptyliso Undecanoic acid, 2-dodecylhexanoic acid, 2-isododecylhexanoic acid, 2-octyldodecanoic acid, 2-isooctyldodecanoic acid, 2-octylisododecanoic acid, 2-nonyltridecanoic acid, 2-isononylisotridecane Acid, 2-decyldodecanoic acid, 2-isodecyldodecanoic acid, 2-decylisododecane 2-decyltetradecanoic acid, 2-octylhexadecanoic acid, 2-isooctylhexadecanoic acid, 2-undecylpentadecanoic acid, 2-isoundecylpentadecanoic acid, 2-dodecylheptadecanoic acid, 2-isododecylisoheptadecanoic acid 2-decyloctadecanoic acid, 2-decylisooctadecanoic acid, 2-tridecylheptadecanoic acid, 2-isotridecylisoheptadecanoic acid, 2-tetradecyloctadecanoic acid, 2-isotetradecyloctadecanoic acid, 2-hexa Decyl hexadecanoic acid, 2-hexadecyl tetradecanoic acid, 2-hexadecyl isohexadecanoic acid, 2-isohexadecyl isohexadecanoic acid, 2-pentadecyl nonadecanoic acid, 2-isopentadecyl isononadecanoic acid, 2-tetradecyl Behenic acid, 2-isotetradecylbe Phosphate, 2-tetradecyl Isobe hen acid, and 2-iso-tetradecyl Isobe strange acid.
Examples of the tertiary fatty acid include pivalic acid, neononanoic acid, neodecanoic acid, equacid 9 (produced by Idemitsu Petrochemical Co., Ltd.), equacid 13 (produced by Idemitsu Petrochemical Co., Ltd.), and the like.
These saturated fatty acids and / or unsaturated fatty acids are preferably those having 3 to 22 carbon atoms. Moreover, you may use individually by 1 type or in combination of 2 or more types. Moreover, you may use combining a saturated fatty acid and / or unsaturated fatty acid, and another compound.

The protective material is preferably used in the range of 1 to 2000 parts by weight, more preferably in the range of 10 to 100 parts by weight, based on 100 parts by weight of the conductive material particles. When the amount is less than 1 part by weight, the effect of the protective substance cannot be obtained and the conductive substance particles are aggregated. On the other hand, when the amount exceeds 2000 parts by weight, the presence of an excessive protective substance that does not contribute to stabilization adversely affects the conductivity and physical properties of the obtained conductive film, that is, the seed layer.
In the present invention, it is particularly preferable that the protective material for the conductive material particles contains at least one of a saturated fatty acid and an unsaturated fatty acid. This is because by using conductive material particles coated with a protective material containing saturated fatty acid and / or unsaturated fatty acid, a conductive film can be produced in a short time without requiring high temperature.

  In addition, since the conductive material particles coated with the protective material used in the present invention have good dispersion stability in the liquid medium, the solubility of the protective material covering the particles is not impaired. Various liquid media can be used as a dispersion mode.

Examples of the liquid medium used in the present invention include ester solvents, ketone solvents, glycol ether solvents, aliphatic solvents, aromatic solvents, alcohol solvents, ether solvents, water, and the like. Two or more types can be mixed and used.
Examples of the ester solvent include ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, (Iso) amyl acetate, cyclohexyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, propionic acid Examples include isoamyl and γ-butyrolactone.
Examples of ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, acetonyl acetone, isophorone, cyclohexanone, methylcyclohexanone, and the like. Is mentioned.

  Examples of glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono n-butyl ether, triethylene glycol monomethyl ether , Triethylene glycol Of ethyl ether, triethylene glycol mono n-propyl ether, triethylene glycol mono n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono n-propyl ether, tripropylene glycol mono n-butyl ether, and these monoethers Examples thereof include acetic acid esters and dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

Examples of the aliphatic solvent include normal paraffinic solvents such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, No. 0 solvent L, M, and H (Shin Nihon). Petroleum Co., Ltd.), normal paraffin SL, L, M (manufactured by Nippon Oil Corporation), isoparaffinic solvents such as isohexane, 2,2,3-trimethylpentane, isooctane, 2,2,5-trimethylhexane, and isosol 200, 300, 400 (manufactured by Nippon Oil Corporation), Supersol FP2, 25, 30, 38 (manufactured by Idemitsu Kosan Co., Ltd.) and cycloparaffinic solvents include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethyl Cyclohexane, Naphthezol 160, 200, 220 (Nippon Oil Co., Ltd. Made by the company), AF Solvent No. 4, No. 5, No. 6, No. 7 (Nippon Oil Co., Ltd.), and the like.
Examples of the aromatic solvent include toluene, xylene, ethylbenzene, naphthalene, tetralin, solvent naphtha and the like.
Examples of the alcohol solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, 1- Ethyl-1-propanol, 2-methyl-1-butanol, isoamyl alcohol, t-amyl alcohol, sec-isoamyl alcohol, neoamyl alcohol, hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pen Tanol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, benzyl alcohol, α-terpineol Cyclohexanol, 3-methoxybutanol, diacetone alcohol and the like.
Examples of the cyclic ether solvent include tetrahydrofuran and 1,3-dioxolane. Other liquid media include dimethyl carbonate, ethyl methyl carbonate, and di-n-butyl carbonate.
The liquid medium may be used alone or in combination of two or more.

<Anchor layer (2) containing a substance having anion exchange capacity>
Next, the anchor layer (2) comprising a substance having anion exchange ability constituting the present invention will be described.
In addition to supporting the seed layer (4) and the copper conductor layer (5) on the plastic film substrate (1), the anchor layer (2) develops the conductivity of the seed layer (4). It has a function to make it.
The substance having anion exchange capacity contained in the anchor layer (2) promotes the fusion of the conductive substance particles coated with the protective substance, and develops the film formability of the conductive substance film even at low temperatures. Is.

The substance having anion exchange ability contained in the anchor layer of the present invention refers to a substance exhibiting anion exchange reaction. The ion exchange reaction is generally a phenomenon in which ions in a compound are exchanged with ions having the same sign in a medium in contact with the ion.
Examples of the substance having anion exchange ability used in the present invention include those having an ionic group involved in ion exchange and an anion exchange group. For example, examples of the anion exchange group include an ammonium group, a phosphonium group, a sulfonium group, an amino group, a primary amine, a secondary amine, and a tertiary amine.
When the conductive material particles coated with the protective material come into contact with the material having anion exchange ability, the bulky anions in the protective material coated with the conductive material particles by the material having the anion exchange ability, etc. Are, for example, F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , ClO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , CrO ₄ ⁻ , CO ₃ ²⁻ , PO ₄ ³⁻ , HPO ₄ ^{2. _{-, H 2 PO 4 -,}} OH - by being rapidly replaced ions such, is exposed surfaces of the conductive material particles, even film formation temperature at low temperatures, conductive for expressing the conductivity The material particles can be fused and formed into a film.

Examples of the substance having anion exchange ability used in the present invention include an anion exchange resin, a cationic compound such as a cation activator, and an inorganic anion exchanger.
In general, an anion exchange resin can be prepared by aminating a crosslinked polymer matrix composed of a styrene / divinylbenzene copolymer after chloromethylation. The chloromethyl group is easily introduced by reacting chloromethyl ether in the presence of an anhydrous aluminum chloride catalyst. Amination is a reaction in which a chloromethyl group is treated with an amine, and various anion exchange resins can be obtained depending on the type of amine.
A compound in which a quaternary ammonium group is introduced using trimethylamine is called a strongly basic type I, and a quaternized compound using dimethylethanolamine is called a strongly basic type II. Any of them can be used. In addition, when a primary to tertiary amine is introduced, a weakly basic resin is obtained, which can also be used.
The above-mentioned styrene / divinylbenzene copolymer is obtained by suspension polymerization, and transparent and homogeneous crosslinked spherical particles are generally called gel-type, while other high-boiling organics such as water-insoluble aromatic hydrocarbons. A porous material obtained by adding a solvent is called a macroporous type, and a porous material obtained by adding an organic solvent such as 2-butanol that hardly swells the produced polymer is called an MR type resin. Can be used.

As the cationic compound, for example, a quaternary ammonium salt or a compound having a quaternary ammonium salt can also be used. Quaternary ammonium salts can generally be made by reacting tertiary amines with alkyl halides. Examples of the quaternary ammonium salt include cyclic quaternary ammonium salts such as N-methylpiperidine methiodide having a nitrogen atom in the ring and quinoline methiodide, and benzalkonium chloride, benzethonium chloride, Cationic activators such as halogenated alkyltrimethylammonium halides, alkylpyridinium halides, and halogenated salts of higher amines can be used, and these can also be used.
Similarly, resin compounds into which these quaternary ammonium bases are introduced, and resin compounds into which ammonium groups, phosphonium groups, sulfonium groups, amino groups, primary amines, secondary amines, and tertiary amines are introduced. Can be used. For example, acrylic resins, urethane resins, polyamine resins, acrylamide resins, allylamine polymerization resins, diallylamine polymerization resins, and the like. In addition, polymerized resins of dicyandiamidine and dicyandiamide, cation-modified resins obtained by directly cation-modifying resins, and the like can also be used.
Examples of the acid group that forms the quaternary ammonium salt include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , ClO ₃ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , CrO ₄ ⁻ , and CO 2. Any of ₃ ²⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , OH ^{− and the} like can be used.

Inorganic anion exchangers, that is, so-called solid bases include, for example, activated carbon, tin oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, aluminum oxide, zirconium oxide, titanium dioxide and other metal oxides, magnesium carbonate , Metal carbonates such as calcium carbonate, ZnO / ZrO ₂ , MgO / TiO ₂ , CaO / P ₂ O ₅ , SiO ₂ / CaO / MgO, SiO ₂ / Al ₂ O ₃ , SiO ₂ / SrO, SiO ₂ / BaO ZnO / SiO ₂ , TiO ₂ / ZrO ₂ , Al ₂ O ₃ / TiO ₂ , SiO ₂ / ZrO ₂ , Al ₂ O ₃ + ZrO ₂ , SiO ₂ / TiO ₂ , MoO ₃ / SiO ₂ , MoO ₃ / Al _{2 O 3, Al} 2 O ₃ / composite oxide such as MgO, zeolite, Na / MgO, / MgO, metal vapor deposited metal oxide such as _{Na / Al 2 O 3, KNH} 2 / Al 2 O 3, EuNH / K-Y imine supported metal oxides such _{as, KF / Al 2 O 3,} LiCO 3 / SiO 2 And metal oxides carrying an alkali metal salt.
Further, as the inorganic anion exchanger, for example, silica, colloidal silica, titania coated with, for example, aluminum oxide or the like and the surface charge cationized can be used.
The substances having anion exchange ability may be used alone or in combination of two or more.

Furthermore, the anchor layer (2) containing a substance having anion exchange ability used in the present invention contains particles having anion exchange ability and / or particles having no anion exchange ability, if necessary. Can be made. These particles may be organic particles or inorganic particles.
The inclusion of the particles in the anchor layer (2) makes it easy for the substance having anion exchange ability to be uniformly present in the anchor layer, and the substance is coated with a substance having anion exchange ability and a protective substance. This is because the anion exchange reaction is more efficiently performed when the conductive substance particles come into contact with each other.
Moreover, it is preferable that the average particle diameter of the particle | grains which have the said anion exchange ability used and the particle | grains which do not have anion exchange ability is 0.001-20 micrometers. Use of fine particles having an average particle diameter of more than 20 μm is not preferable because not only film formability is deteriorated but also stability, physical properties and the like are lowered.

Examples of the inorganic particles having or not having the anion exchange ability include clay, diatomaceous earth, aluminum silicate, calcium silicate, magnesium silicate, hydrotalcite, talc, kaolin, calcined kaolin, saponite, mordenite, barium sulfate, Magnesium sulfate, iron (II) sulfate, calcium sulfate, magnesium hydroxide, zinc oxide, zinc hydroxide, zinc sulfide, lead oxide, magnesium phosphate, aluminum chloride, synthetic amorphous silica, colloidal silica, aluminum hydroxide, lithopone , Zeolite, montmorillonite and the like. Among these inorganic particles, amorphous silica and colloidal silica are preferable.
Examples of organic particles having or not having anion exchange ability include natural products such as starch, acrylics such as polymethyl methacrylate, polystyrenes, styrene / acrylics, nylon 6, nylon 12, and nylon 6-12. Examples thereof include resin particles made of olefins such as nylon, high density polyethylene, low density polyethylene, polypropylene, and tetrafluoroethylene, polyesters, phenols, and benzoguanamines.
These particles can be used singly or in combination of two or more.

Next, the manufacturing method of the coating agent for forming an anchor layer (2) is demonstrated.
The coating agent for forming the anchor layer (2) is prepared by mixing the substance having anion exchange ability with a liquid medium, and further, if necessary, an antifoaming agent, a leveling agent, a lubricant, a dispersing agent, a resin and / or The precursors are mixed and dispersed by a conventionally known method, for example, using a ball mill, attritor, sand mill, jet mill, three roll mill, paint shaker or the like, or by a conventionally known method, for example, a mixer. It can be produced by stirring and mixing using a dissolver.

  As the coating agent used in the present invention, a liquid medium can be appropriately selected and used according to the type of the plastic film substrate (1) forming the conductive film and the coating method. As the liquid medium, for example, ester solvents, ketone solvents, glycol ether solvents, aliphatic solvents, aromatic solvents, alcohol solvents, ether solvents, water, and the like can be used. Can also be used in combination.

  Examples of the ester solvent include ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, (Iso) amyl acetate, cyclohexyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, propionic acid Examples of ketone solvents include acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, dipropyl ketone, diisobutyl ketone, and methyl. Amyl, acetonyl acetone, isophorone, cyclohexanone, and methyl cyclohexanone.

Examples of glycol ether solvents include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono n-propyl ether, dipropylene glycol mono n-butyl ether, triethylene glycol monomethyl ether , Triethylene glycol Of ethyl ether, triethylene glycol mono n-propyl ether, triethylene glycol mono n-butyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono n-propyl ether, tripropylene glycol mono n-butyl ether, and these monoethers Acetates,
And dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

Examples of the aliphatic solvent include normal paraffinic solvents such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, No. 0 solvent L, M, and H (Shin Nihon). Petroleum Co., Ltd.), normal paraffin SL, L, M (manufactured by Nippon Oil Corporation), isoparaffinic solvents such as isohexane, 2,2,3-trimethylpentane, isooctane, 2,2,5-trimethylhexane, and isosol 200, 300, 400 (manufactured by Nippon Oil Corporation), Supersol FP2, 25, 30, 38 (manufactured by Idemitsu Kosan Co., Ltd.) and cycloparaffinic solvents include, for example, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane , Ethylcyclohexane, naphthesol 160, 200, 220 (New Japan Co. oil Ltd.), AF Solvent No. 4, No. 5, No. 6, No. 7 (Nippon Oil Co., Ltd.).
Examples of the aromatic solvent include toluene, xylene, ethylbenzene, naphthalene, tetralin, solvent naphtha and the like.
Examples of alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, 1-ethyl- 1-propanol, 2-methyl-1-butanol, isoamyl alcohol, t-amyl alcohol, sec-isoamyl alcohol, neoamyl alcohol, hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, Heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, benzyl alcohol, α-terpineol, cyclo Hexanol, 3-methoxybutanol, diacetone alcohol and the like.
Examples of the cyclic ether solvent include tetrahydrofuran and 1,3-dioxolane. Other liquid media include dimethyl carbonate, ethyl methyl carbonate, and di-n-butyl carbonate.
The liquid medium may be used alone or in combination of two or more.

  The anchor layer (2) is further provided with a film-forming property of the seed layer (4) in order to improve the adhesion to the plastic film substrate (1) to be used and the adhesion to the seed layer (4). For the purpose of improving, an appropriately selected resin can be included. Examples of the resin include polyurethane resin, polyurethane polyurea resin, (unsaturated) polyester resin, alkyd resin, butyral resin, acetal resin, polyamide resin, acrylic resin, styrene / acrylic resin, polystyrene resin, nitrocellulose, benzylcellulose, Cellulose (tri) acetate, casein, shellac, gelatin, gilsonite, rosin, rosin ester, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, Carboxymethyl ethyl cellulose, carboxymethyl cellulose Borocellulose, ethylene / vinyl alcohol resin, styrene / maleic anhydride resin, polybutadiene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinylidene fluoride resin, polyvinyl acetate resin, ethylene / vinyl acetate resin, vinyl chloride / vinyl acetate Resin, vinyl chloride / vinyl acetate / maleic acid resin, fluorine resin, silicone resin, epoxy resin, phenoxy resin, phenol resin, maleic acid resin, urea resin, melamine resin, benzoguanamine resin, ketone resin, petroleum resin, chlorinated polyolefin resin One type or two or more types selected from modified chlorinated polyolefin resins, chlorinated polyurethane resins and the like can be used.

  In the present invention, particularly preferred as the resin to be contained in the anchor layer (2) are polyurethane polyurea resin (C) and an epoxy resin having two or more epoxy groups (from the viewpoint of adhesion to the substrate and heat resistance). D).

Preferably, the polyurethane polyurea resin (C) is obtained by reacting a diol compound (a) having a carboxyl group with a polyol (b) other than (a) and an organic diisocyanate (c) having a number average molecular weight of 500 to 8000. It is obtained by reacting the urethane prepolymer (d) having an isocyanate group at the terminal with the polyamino compound (e).
Examples of the diol compound (a) having a carboxyl group include dimethylol alkanoic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, and dimethylolpentanoic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. In particular, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of reactivity and solubility.

  The polyol (b) other than (a) having a number average molecular weight of 500 to 8000 is a polyol other than the diol compound (a) having a carboxyl group, which is generally known as a polyol component constituting the polyurethane resin. The number average molecular weight (Mn) of the polyol (b) is appropriately determined in consideration of the heat resistance, adhesive strength, solubility and the like of the obtained polyurethane polyurea resin (C), and is preferably 1000 to 5000. If Mn is less than 500, the number of urethane bonds in the resulting polyurethane polyurea resin (C) increases, the flexibility of the polymer skeleton tends to decrease and the adhesiveness tends to decrease, and Mn exceeds 8000. And the number of carboxyl groups derived from the diol compound (a) in the polyurethane polyurea resin (C) decreases. As a result, the reaction point with the epoxy resin is reduced, so that the heat resistance of the anchor layer tends to be lowered.

Examples of the polyol (b) other than (a) having a number average molecular weight of 500 to 8000 include, for example, various polyether polyols other than carboxyl group-containing diol compounds, polyester polyols, polycarbonate polyols, polybutadiene glycols, or These mixtures can be used.
Examples of polyether polyols include polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran.

  Examples of polyester polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl- Saturated or unsaturated low molecular weight diols such as 1,5-pentanediol, hexanediol, octanediol, 1,4-butylenediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimer diol, adipic acid, and phthalic acid , Diphthalic acid such as isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, or their anhydrides Let me get Polyester polyols, alkyl glycidyl ethers such as n-butyl glycidyl ether or 2-ethylhexyl glycidyl ether, monocarboxylic acid glycidyl esters such as versatic acid glycidyl ester, and anhydrides of the above dicarboxylic acids And polyester polyols obtained by reacting in the presence of a hydroxyl group-containing compound such as a polyester, or polyester polyols obtained by ring-opening polymerization of a cyclic ester compound.

Examples of polycarbonate polyols include:
1) A reaction product of glycol or bisphenol and a carbonate ester, or 2) a reaction product obtained by reacting glycol or bisphenol with phosgene in the presence of alkali can be used.
Examples of the glycol used in the case of 1) or 2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl-1. , 8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol and the like.

Examples of the bisphenol used in the case 1) or 2) include, for example, bisphenols such as bisphenol A and bisphenol F, and compounds obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to these bisphenols. Etc.
Examples of the carbonic acid ester used in the case 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.
Further, examples of the alkali used in the case 2) include sodium hydroxide and potassium hydroxide.

The various polyols exemplified as the polyol (b) other than (a) having a number average molecular weight of 500 to 8000 may be used alone or in combination of two or more.
Furthermore, a diol compound (a) having a carboxyl group, a polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and an organic material within the range in which the adhesive performance of the obtained polyurethane polyurea resin (C) is not lost. When the diisocyanate (c) is reacted, low molecular diols other than the diol compound (a) having a carboxyl group may be used in combination. Examples of the low molecular diols that can be used in combination include various low molecular diols used for the production of the polyol (b).

  When synthesizing the urethane prepolymer (d), the diol compound (a) having a carboxyl group and the polyol (b) other than (a) having a number average molecular weight of 500 to 8000 are 1 mol of polyol (b). The diol compound (a) having a carboxyl group is preferably used at a ratio of 0.1 mol to 4.0 mol, more preferably at a ratio of 0.2 mol to 3.0 mol. (B) When the amount of (a) used per 1 mol is less than 0.1 mol, the epoxy resin (D) and the crosslinkable carboxyl group decrease, and the heat resistance of the anchor layer (2) tends to decrease. . On the other hand, if it exceeds 4.0 mol, the adhesion of the anchor layer (2) tends to be lowered.

As the organic diisocyanate (c), aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate, or a mixture thereof can be used, and isophorone diisocyanate is particularly preferable.
Examples of aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-benzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate. 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and the like.

Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, and the like.

The urethane prepolymer (d) having an isocyanate group at the terminal comprises a diol compound (a) having a carboxyl group, a polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and an organic diisocyanate (c). It is obtained by reacting.
The conditions for synthesizing the urethane prepolymer (d) having an isocyanate group at the terminal are not particularly limited except that the isocyanate group becomes excessive with respect to the hydroxyl group, but the ratio of isocyanate group / hydroxyl group is mol. The ratio is preferably in the range of 1.2 / 1 to 3/1.

The reaction temperature is usually from room temperature to 120 ° C., but preferably from 60 to 100 ° C. from the viewpoint of production time and side reaction control.
The polyurethane polyurea resin (C) is obtained by reacting the urethane prepolymer (d) having an isocyanate group at the terminal with the polyamino compound (e).
The polyamino compound (e) functions as a chain extender, and includes, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, and 2- Amines having a hydroxyl group such as (2-aminoethylamino) ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, and di-2-hydroxypropylethylenediamine can also be used. . Of these, isophoronediamine is preferably used.

When the polyurethane preurea resin (C) is synthesized by reacting the urethane prepolymer (d) having an isocyanate group at the terminal with the polyamino compound (e), the reaction is performed to adjust the molecular weight of the obtained polyurethane polyurea resin (C). A terminator can be used in combination.
As the reaction terminator, dialkylamines such as di-n-butylamine, dialkanolamines such as diethanolamine, and alcohols such as ethanol and isopropyl alcohol can be used.

  The conditions for reacting the urethane prepolymer (d) having an isocyanate group at the terminal, the polyamino compound (e) and, if necessary, the reaction terminator are not particularly limited, but the urethane prepolymer (d) has a free condition. When based on the amount of isocyanate groups, the total molar ratio of the polyamino compound (e) and the amino groups in the reaction terminator is preferably in the range of 0.5 to 1.3. When the molar ratio is less than 0.5, the heat resistance of the anchor layer (2) tends to be insufficient, and when it exceeds 1.3, the polyamino compound (e) and the reaction terminator remain unreacted. It remains and the odor tends to remain.

Solvents used for synthesizing the polyurethane polyurea resin (C) include aromatic solvents such as benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, isopropanol and n-butanol, acetone, methyl ethyl ketone and methyl isobutyl. Examples include ketone solvents such as ketones and ester solvents such as ethyl acetate and butyl acetate. These solvent can be used individually by 1 type or in mixture of 2 or more types.
It is preferable that the weight average molecular weight of the obtained polyurethane polyurea resin (C) exists in the range of 5000-100000. When the weight average molecular weight is less than 5,000, the heat resistance of the anchor layer (2) tends to be inferior, and when it exceeds 100,000, the adhesion of the anchor layer (2) tends to be lowered.

The epoxy resin (D) contained in the anchor layer (2) is a resin having two or more epoxy groups and may be liquid or solid.
The epoxy resin (D) includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, spiro ring type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, terpene type epoxy resin, tris (glycidyl). Glycidyl ether type epoxy resins such as oxyphenyl) methane and tetrakis (glycidyloxyphenyl) ethane, Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane, Tetrabromobisphenol A type epoxy resin, Cresol novolac type epoxy resin, Phenol novolak type epoxy resin Examples thereof include resins, α-naphthol novolac type epoxy resins, brominated phenol novolac type epoxy resins and the like.
These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Of these, bisphenol A type epoxy resin, cresol novolac type epoxy resin, or tetrakis (glycidyloxyphenyl) ethane is preferably used from the viewpoint of high adhesion and heat resistance.

  The blending ratio of the epoxy resin (D) and the polyurethane polyurea resin (C) is preferably 3 to 200 parts by weight of the epoxy resin (D) with respect to 100 parts by weight of the polyurethane polyurea resin (C). More preferably, it is 100 parts by weight. (C) When (D) is less than 3 parts by weight with respect to 100 parts by weight, the heat resistance of the anchor layer (2) tends to be low. On the other hand, when (D) is more than 200 parts by weight, the adhesion of the anchor layer (2) tends to be lowered.

  The coating agent for forming the anchor layer (2) includes phenolic resins, silicone resins, urea resins, acrylic resins, polyester resins, as long as the performance such as heat resistance and bending resistance is not impaired. Polyamide resins, polyimide resins and the like can be included.

The coating agent contains a curing accelerator and / or a curing agent for the purpose of promoting the reaction between the polyurethane polyurea resin (C) and the epoxy resin (D) and the reaction between the epoxy resins (D). be able to. As the curing accelerator, tertiary amine compounds, phosphine compounds, imidazole compounds and the like can be used, and as the curing agent, dicyandiamide, carboxylic acid hydrazide, acid anhydrides and the like can be used.
Among the curing accelerators, the tertiary amine compounds include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, 1,5-diazabicyclo (4.3.0) nonene-5. Etc. Examples of the phosphine compound include triphenylphosphine and tributylphosphine. Examples of imidazole compounds include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenylimidazole. Includes a latent curing accelerator having improved storage stability, such as a type in which an imidazole compound and an epoxy resin are reacted to insolubilize in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule.

Examples of the carboxylic acid hydrazide as the curing agent include succinic acid hydrazide and adipic acid hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride and trimellitic anhydride.
As these curing accelerators or curing agents, the above-mentioned compounds may be used alone or in combination of two or more, and the amount used is a total (only one of the curing accelerator or the curing agent is used. The case where it is used is also included) and is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin (D).
In addition, the coating agent is a silane coupling agent, antioxidant, pigment, dye, tackifying resin, plasticizer, ultraviolet absorber, antifoaming agent, leveling as long as the insulation, adhesion and heat resistance are not deteriorated. Conditioners, fillers, flame retardants, etc. may be added.

<Formation of anchor layer (2) containing a substance having anion exchange ability>
First, a coating agent containing a substance having an anion exchange ability is applied or printed on the plastic film substrate (1) by a conventionally known method. The coating or printing method may be appropriately selected according to the type of substrate and the application, for example, gravure printing, flexographic printing, ink jet printing, spray coating, spin coating, die coating, lip coating, knife coating, dip coating, It is applied or printed by methods such as curtain coating, roll coating, and bar coating. Then, according to the kind of base material to be used, the anchor layer (2) whose coating film thickness is about 1-20 micrometers is obtained by drying for about several seconds to about 5 minutes at the temperature of about 50-100 degreeC.
The surface of the plastic film substrate (1) can be subjected to corona discharge treatment or plasma treatment as necessary for the purpose of improving the adhesion with the anchor layer (2).

<Formation of seed layer (4)>
Since the dispersion (3) of conductive material particles coated with a protective material used in the present invention is excellent in dispersion stability, a film forming method may be appropriately selected depending on the application. That is, conventionally known methods such as gravure printing, flexographic printing, ink jet printing, dispenser printing, spray coating, spin coating, die coating, lip coating, knife coating, dip coating, curtain coating, roll coating, bar coating, etc. The seed layer (4) can be formed by applying or printing on the anchor layer (2) and then drying. As a drying condition, for example, a seed layer can be obtained by simply leaving it at room temperature (about 25 ° C.) for several minutes, but by drying at a drying temperature of 50 to 150 ° C. for several seconds to several tens of minutes, a denser seed layer Can be obtained.
If the plastic film substrate (1) cannot be exposed to high temperatures due to the type of plastic film substrate (1), after forming a film on the anchor layer, for example, heating in an oven overnight at 40 ° C. is sufficient. Film properties can be obtained.

  The seed layer (4) constituting the present invention is subjected to heat treatment or heat pressure treatment after film formation, whereby the surface roughness is reduced and the film formability can be further improved. Heating and pressing treatment is more preferable, but any method may be selected according to the type of the plastic film substrate to be used.

<Formation of copper conductor layer (5)>
By forming the copper conductor layer (5) on the seed layer (4) by the following method, the copper-coated plastic substrate of the present invention can be obtained.
As a method for forming the copper conductor layer (5), for example, on the seed layer, by a dry plating process such as sputtering, vacuum deposition, or ion plating, and / or electrolytic copper plating or electroless The copper conductor layer (5) can be formed by a wet plating process such as a copper plating method.
Among the above methods, the copper conductor layer is preferably formed by electrolytic copper plating and / or electroless copper plating. However, the copper conductor layer (5) is formed by combining the dry process and the wet process. May be.
For example, after forming a copper conductor layer having a thickness of 200 to 5000 mm by a dry plating process, a copper conductor layer may be further formed thereon by a wet plating process until a predetermined thickness is reached, A copper conductor layer may be formed by combining an electroless plating process and an electrolytic plating process.
The film thickness of the copper conductor layer (5) is not particularly limited as long as the optimum film thickness is selected according to the application, but is preferably 800 to 35 μm. If the thickness is less than 800 mm, the conductivity and mechanical strength are lowered, and if it exceeds 35 μm, the wiring pitch is hindered and the productivity is lowered.
After forming the copper conductor layer (5), a resist layer having a desired wiring pattern is formed on the copper conductor layer according to a conventional method, and the exposed portion of the copper conductor layer and the seed layer are removed by etching. Thereafter, the resist layer is peeled and removed to obtain a flexible wiring board free from defects such as chipping or disconnection.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”.

<Synthesis of conductive particles coated with protective material>
[Conductive fine particle synthesis example 1]
Attach 200 parts of toluene and 18.1 parts of silver propionate while stirring at room temperature in a nitrogen atmosphere with a separable four-necked flask equipped with a condenser, thermometer, nitrogen gas inlet tube, and stirring device. Then, 2.3 parts of diethylaminoethanol (0.2 moles per mole of metal) and 2.8 parts of oleic acid (0.1 moles per mole of metal) were added and dissolved as a dispersant. Then, when 73.1 parts of 20% SUDH (succinic acid dihydrazide) aqueous solution (2 mol of hydrazide groups with respect to 1 mol of metal) was added as a reducing agent, the liquid color changed from pale yellow to dark brown. In order to further promote the reaction, the temperature was raised to 40 ° C. to advance the reaction.
After leaving and separating, the aqueous layer is taken out to remove excess reducing agent and impurities, distilled water is added to the toluene layer several times, washing and separation are repeated, and silver fine particles whose surface is coated with propionic acid Of toluene dispersion was obtained. The obtained silver fine particle dispersion had an average particle diameter of 5 ± 2 nm, a silver concentration of 75%, and was stable with no change in particle diameter even after being stored at 40 ° C. for one month.
In addition, the said silver density | concentration showed the density | concentration of silver in solid content of a dispersion, and the measurement was based on the thermal analysis measuring device (Hitachi Ltd. make "TG-DTA").

[Conductive fine particle synthesis example 2]
A dispersion of silver fine particles whose surface was coated with pentanoic acid was obtained in the same manner as in Synthesis Example 1 except that 18.1 parts of silver propionate was changed to 20.9 parts of silver pentanoate. The obtained silver fine particle dispersion had an average particle diameter of 5 ± 1 nm, a silver concentration of 82%, and was stable with no change in particle diameter even after being stored at 40 ° C. for one month.

[Conductive fine particle synthesis example 3]
A dispersion of silver fine particles whose surface was coated with hexanoic acid was obtained in the same manner as in Synthesis Example 1 except that 18.1 parts of silver propionate was changed to 22.3 parts of silver hexanoate. The obtained silver fine particle dispersion had an average particle size of 5 ± 2 nm, a silver concentration of 80%, and was stable with no change in particle size even after storage at 40 ° C. for one month.

In addition, the number average molecular weight and weight average molecular weight which were described in the Example are the number average molecular weight and weight average molecular weight of polystyrene conversion calculated | required by GPC measurement, and the conditions of GPC measurement are as follows.
Equipment: Shodex GPC System-21 (manufactured by Showa Denko)
Column: Shodex KF-802, KF-803L, KF-805L
A total of 3 (made by Showa Denko) are connected and used.
Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Temperature: 40 ° C
Sample concentration: 0.3% by weight
Sample injection volume: 100 μl
<Synthesis of polyurethane polyurea resin (C)>

[Resin synthesis example 1]
A number average molecular weight (hereinafter referred to as “Mn”) obtained from adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube. Diol = 414, dimethylol butanoic acid 8 parts, isophorone diisocyanate 145 parts and toluene 40 parts were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 816 parts of the obtained urethane prepolymer solution was added to a mixture of 27 parts of isophoronediamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and the mixture was heated at 70 ° C. for 3 hours. The reaction was performed to obtain a polyurethane polyurea resin solution having a weight average molecular weight (hereinafter referred to as “Mw”) = 54,000. To this, 144 parts of toluene and 72 parts of 2-propanol were added for dilution to obtain a polyurethane polyurea resin (A-1) solution having a solid content of 30%.

[Resin synthesis example 2]
Mn = 981 obtained from adipic acid, 3-methyl-1,5-pentanediol and 1,6-hexane carbonate diol in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping device, and nitrogen introduction tube Diol 390, dimethylolbutanoic acid 16 parts, isophorone diisocyanate 158 parts, and toluene 40 parts were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 814 parts of the obtained urethane prepolymer solution was added to a mixture of 29 parts of isophoronediamine, 3 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, and the mixture was heated at 70 ° C. for 3 hours. Reaction was performed to obtain a polyurethane polyurea resin solution having Mw = 43,000. To this, 144 parts of toluene and 72 parts of 2-propanol were added for dilution to obtain a polyurethane polyurea resin (A-2) solution having a solid content of 30%.

[Resin synthesis example 3]
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, 352 parts of diol having Mn = 1002 obtained from adipic acid and 3-methyl-1,5-pentanediol, dimethylol 32 parts of butanoic acid, 176 parts of isophorone diisocyanate and 40 parts of toluene were charged and reacted at 90 ° C. for 3 hours in a nitrogen atmosphere. To this, 300 parts of toluene was added to obtain a urethane prepolymer solution having an isocyanate group at the terminal. Next, 810 parts of a solution of the obtained urethane prepolymer was added to a mixture of 32 parts of isophoronediamine, 4 parts of di-n-butylamine, 342 parts of 2-propanol, and 576 parts of toluene, By reacting for a period of time, a polyurethane polyurea resin solution having Mw = 35,000 was obtained. To this, 144 parts of toluene and 72 parts of 2-propanol were added for dilution to obtain a polyurethane polyurea resin (A-3) solution having a solid content of 30%.

<Preparation of adhesive 1>
100 parts of epoxy resin (“JER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts of carboxylated NBR (“Nipol 1072” manufactured by Nippon Zeon Co., Ltd.) as the elastomer, 30 parts of 4,4′-diaminodiphenylsulfone as the curing agent, and agitation 0.05 parts of acid was dissolved in methyl ethyl ketone (MEK) to obtain an adhesive 1 having a solid content of 20%.

<Preparation of adhesive 2>
In a solid content ratio, 17 parts of nickel powder, 1.55 parts of a dispersant “DISPER BYK-116” manufactured by Big Chemie, and 9.8 parts of the polyurethane polyurea resin obtained in Synthesis Example 1 were mixed, and toluene and isopropyl alcohol were mixed. The mixture was diluted with a mixed solvent (weight ratio of 1/1) to adjust the solid content to 30%, and passed 3 times with a sand mill to obtain adhesive 2 as a nickel dispersion. The adhesive 2 was stored in a nitrogen atmosphere at 25 ° C. in a desiccator.

[Example 1]
As a coating agent containing a substance having anion exchange capacity, polyurethane polyurea resin A-1: 100 parts in solid content ratio, 30 parts of cationic resin ("Saftomer ST-2000H" manufactured by Mitsubishi Chemical Corporation), and bisphenol A type Mix 10 parts of epoxy resin (“JER1001” manufactured by Japan Epoxy Resin Co., Ltd.) and dilute with toluene / isopropyl alcohol mixed solvent (weight ratio of both 1/1) to adjust the solid content to 20%. The mixture was stirred for 20 minutes using a dissolver to obtain a coating agent.
Next, this coating agent was coated on a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm) using a bar coater, and dried at 75 ° C. for 5 minutes, whereby the coating thickness after drying. An anchor layer having a thickness of about 0.5 μm was obtained.

Next, the silver fine particle dispersion obtained in the conductive fine particle synthesis example 1 was applied on the anchor layer so as to have a wet film thickness of 1 μm with a bar coater, and dried at 100 ° C. for 1 minute. A seed layer was formed.
Subsequently, a copper conductor layer having a thickness of 8 μm was formed on the seed layer by electrolytic copper plating with a plating solution composition shown in Table 1.
The plating conditions were as follows: the temperature of the plating solution was 25 ° C., the stirring was air stirring, the current density during energization was 3 A / dm ² , and the time was about 10 minutes.

[Example 2]
As a coating agent containing a substance having anion exchange capacity, 100 parts of polyurethane polyurea resin A-3 in a solid content ratio, 30 parts of a cationic resin (“Saftomer ST-2100” manufactured by Mitsubishi Chemical Corporation), and a phenol novolac type 10 parts of epoxy resin “JER152” (manufactured by Japan Epoxy Resin Co., Ltd.) is mixed, and 10 parts of colloidal silica (“Snowtex AK” manufactured by Nissan Chemical Industries, Ltd.) is added as fine particles having anion exchange capacity, and water and Add a liquid medium that is a mixture with isopropyl alcohol (weight ratio of both is 1/1), dilute, adjust the solid content to 20%, and stir for 20 minutes using a dissolver to apply the coating agent. Obtained.
Next, this coating agent was coated on a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm) using a bar coater, and dried at 120 ° C. for 5 minutes, whereby the coating thickness after drying. An anchor layer having a thickness of 1.5 μm was obtained.
Next, the silver fine particle dispersion obtained in the conductive fine particle synthesis example 1 is coated on the anchor layer so as to have a wet film thickness of 2 μm with a bar coater, and dried at 75 ° C. for 5 minutes to form a seed layer. Formed.
Subsequently, electrolytic copper plating was performed on the seed layer by the same method as in Example 1 to form a copper conductor layer having a thickness of 8 μm.

[Example 3]
As a coating agent containing a substance having an anion exchange capacity, polyurethane polyurea resin A-1 in a solid content ratio: 100 parts, tetrafunctional epoxy resin “JER1031S” (manufactured by Japan Epoxy Resin Co., Ltd.) 10 parts, and cationic resin ( "Saftomer ST-2100NSA" manufactured by Mitsubishi Chemical Co., Ltd.) is mixed with 10 parts, and further diluted with 25 parts of a liquid medium (weight ratio of 1/1) of water and isopropyl alcohol. The content was adjusted to 20% and stirred for 20 minutes using a dissolver to obtain a coating agent.
Next, this coating agent was coated on a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm) using a bar coater, and dried at 75 ° C. for 5 minutes, whereby the coating thickness after drying. An anchor layer having a thickness of 2 μm was obtained.
Next, the silver fine particle dispersion obtained in the conductive fine particle synthesis example 3 is coated on the anchor layer so as to have a wet film thickness of 3 μm with a bar coater, and dried at 75 ° C. for 5 minutes to form a seed layer. Formed.
Subsequently, electrolytic copper plating was performed on the seed layer by the same method as in Example 1 to form a copper conductor layer having a thickness of 8 μm.

[Example 4]
As a coating agent containing a substance having an anion exchange capacity, 100 parts of polyurethane polyurea resin A-2 in a solid content ratio: 10 parts of a tetrafunctional epoxy resin “JER1031S”, a cationic resin (“Papiogen P-105 manufactured by SENKA CORPORATION) ”) 10 parts is mixed, and further 10 parts of colloidal silica (“ Snowtex O ”manufactured by Nissan Chemical Industries, Ltd.) is added as fine particles having no anion exchange capacity, and the liquid medium is a mixture of water and isopropyl alcohol. (The weight ratio of the two was 1/1), the solid content was adjusted to 20%, and the mixture was stirred for 20 minutes using a dissolver to obtain a coating agent.
Next, this coating agent is applied onto a polyethylene naphthalate film (“Teonex Film Q83” manufactured by Teijin DuPont Films Co., Ltd., thickness 25 μm) using a bar coater and dried at 75 ° C. for 5 minutes. As a result, an anchor layer having a thickness of 1.5 μm after drying was obtained.
Next, the silver fine particle dispersion obtained in the conductive fine particle synthesis example 3 is coated on the anchor layer so as to have a wet film thickness of 1 μm with a bar coater, and dried at 75 ° C. for 5 minutes to form a seed layer. Formed.
Subsequently, electrolytic copper plating was performed on the seed layer by the same method as in Example 1 to form a copper conductor layer having a thickness of 8 μm.

[Example 5]
15 parts of polyacetal resin ("Surek KW-1" manufactured by Sekisui Chemical Co., Ltd.), 60 parts of colloidal silica ("Snowtex AK" manufactured by Nissan Chemical Industries, Ltd.) as fine particles having anion exchange capacity, water and diethylene glycol monoethyl 25 parts of a liquid medium which is a mixture with ether acetate (weight ratio of water / diethylene glycol monoethyl ether acetate = 4/6) was mixed and stirred for 20 minutes using a dissolver to obtain a coating agent.
Next, this coating agent is printed on an aramid film (“Mikutron” manufactured by Toray Industries, Inc., thickness: 12.5 μm) by an ink jet method, and dried in a hot air drying oven at 100 ° C. for 10 minutes. An anchor layer having a thickness of 5 μm was obtained.
Next, the silver fine particle dispersion obtained in the conductive fine particle synthesis example 1 is printed on the anchor layer by an ink jet method, dried in a hot air drying oven at 150 ° C. for 10 minutes, and an average film thickness of 0.5 μm. The seed layer was formed.
Next, a copper conductor layer having a thickness of 8 μm was formed on the seed layer by electroless copper plating with a plating solution composition shown in Table 2.

In Table 2, “EDTA” and “PEG1000” represent the following, respectively.
EDTA: ethylenediaminetetraacetic acid PEG1000: polyoxyethylene glycol having a number average molecular weight of 1000

[Comparative Example 1]
A copper conductor layer was formed on a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm) in the same manner as in Example 5.

[Comparative Example 2]
On a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm), the adhesive 1 obtained by preparing the adhesive 1 was applied with a blade coater so that the dry film thickness was 20 μm, and 75 ° C. Was dried for 5 minutes to form an adhesive layer.
The obtained adhesive layer surface was overlaid with a non-glossy surface of 1 / 2oz electrolytic copper foil (manufactured by Nikko Gouldfoil Co., Ltd., JTC foil), passed through a laminating machine at 80 ° C, and then vacuum heat at 150 ° C The press was pressed for 2 minutes, and further post-cured in an oven at 150 ° C. for 3 hours to obtain a three-layer CCL in which the plastic film substrate and the copper foil were bonded together via an adhesive layer.

[Comparative Example 3]
A nickel layer having a thickness of 100 mm was formed as a seed layer on a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm) by a vacuum deposition method.
Next, after being immersed in a weak alkaline degreasing agent for 1 minute, it was washed with water for 2 minutes. Next, after immersing in a 2 mol / l aqueous potassium hydroxide solution to make the exposed film hydrophilic, in the same manner as in Example 1, copper having a thickness of 8 μm was formed on the seed layer by electrolytic copper plating. The conductor layer was formed.

[Comparative Example 4]
On the polyimide film ("Kapton 100H" manufactured by DuPont, thickness 25 μm), a chromium layer having a thickness of 8 mm is provided by sputtering, and further, the nickel content is 7% by weight by sputtering. A seed layer was formed by providing a 20 mm nickel-chrome alloy layer.
Next, after forming a copper layer having a thickness of 1.5 mm on the seed layer by electroless plating, a copper conductor layer having a thickness of 8 μm was formed by electrolytic copper plating in the same manner as in Example 1. .

[Comparative Example 5]
The adhesive 2 obtained in the preparation of the adhesive 2 is taken out from the desiccator in a nitrogen atmosphere, and coated on a polyimide film (“Kapton 100H” manufactured by DuPont, thickness 25 μm) using a bar coater. By drying for a minute, an adhesive layer having a coating thickness of 2 μm after drying was obtained.
Next, the silver fine particle dispersion 1 obtained in the conductive fine particle synthesis example 1 is coated on the adhesive layer so as to have a wet film thickness of 1 μm with a bar coater, and dried at 75 ° C. for 5 minutes to seed. A layer was formed.
Subsequently, electrolytic copper plating was performed on the seed layer by the same method as in Example 1 to form a copper conductor layer having a thickness of 8 μm.

The adhesion strength, solder heat resistance, and insulation properties of the copper-coated plastic substrates obtained in Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Table 3.

<Adhesion strength test (peel strength)>
The copper-coated plastic substrate was subjected to JIS-C6481.
A copper pattern having a width of 2 mm was formed on the copper conductor layer by etching, and the strength was measured when the copper pattern having a width of 2 mm was peeled off in a 90-degree direction using Tensilon.
The measured values were converted to 10 mm width and displayed.

<Solder heat resistance>
The test was conducted according to JIS-C6481.
Cut the above copper-coated plastic substrate to a size of 20 mm x 20 mm, leave it in an atmosphere of 40 ° C / 90% RH for 24 hours, float on a solder bath at a predetermined temperature for 30 seconds, The maximum temperature of the solder bath at which no blistering or peeling occurred was measured.

<Insulation characteristics>
In accordance with JIS-C6471, 9.3, pattern of land / space = 2.5mm / 1mm is formed on the copper conductor layer of the coated plastic substrate, and the line insulation resistance value (Ω) when DC voltage 500V is applied is measured. did.

In Examples 1 to 5, according to the present invention, a copper-coated plastic substrate having excellent adhesion between copper and a plastic film substrate, excellent solder heat resistance after being left under high temperature and high humidity, and excellent insulating properties Could be provided.
Example 5 is an example in which a plastic film other than a polyimide resin film is used as a plastic film substrate. However, since a high temperature is not required for seed layer formation, a film having inferior heat resistance compared to polyimide can be applied. It is.
Comparative Example 1 is an example in which the anchor layer and the seed layer are not provided, but the adhesiveness between the copper layer and the plastic film substrate is completely obtained although the appearance change does not occur in the solder heat resistance test. It is not practical.
Comparative Example 2 was a three-layer CCL and was inferior in insulation.
Although the comparative examples 3 and 4 are based on the conventional two-layer CCL, it is inferior to the adhesiveness of copper and a plastic film base material.
The adhesive 2 that is a nickel dispersion used in Comparative Example 5 was oxidized and blackened, and the nickel powder settled down. Thus, the handling property was poor, and the adhesive 2 could not be used.

Claims (7)

  An electroconductive substance in which an anchor layer (2) containing a substance having anion exchange ability is laminated on at least one surface of a plastic film substrate (1) and coated with a protective substance on the anchor layer (2) A seed layer (4) formed by applying or printing a particle dispersion (3) and drying is laminated, and a copper conductor is further formed on the seed layer (4) by electroless copper plating and / or electrolytic copper plating. A copper-coated plastic substrate, wherein a layer (5) is formed.   The copper-coated plastic substrate according to claim 1, wherein the conductive material particles have an average particle diameter of 0.001 to 10 μm.   The conductive material particles are one kind of particles selected from the group consisting of gold, silver, copper, nickel, platinum, palladium, and iron, or a mixture of two or more kinds of particles, or two or more kinds The copper-coated plastic substrate according to claim 1, wherein the copper-coated plastic substrate is a particle of an alloy made of or a mixture of these particles.   The copper-coated plastic according to any one of claims 1 to 3, wherein the protective substance comprises at least one selected from the group consisting of a pigment dispersant, a surfactant, a saturated fatty acid, and an unsaturated fatty acid. substrate.   The anchor layer (2) contains particles having an anion exchange ability and / or particles having no anion exchange ability with an average particle diameter of 0.001 to 20 µm. A copper-coated plastic substrate as described in 1.   The anchor layer (2) is obtained by reacting a diol compound (a) having a carboxyl group, a polyol (b) other than (a) having a number average molecular weight of 500 to 8000, and an organic diisocyanate (c). Coating agent containing polyurethane polyurea resin (C) obtained by reacting urethane prepolymer (d) having isocyanate group with polyamino compound (e) and epoxy resin (D) having two or more epoxy groups The copper-coated plastic substrate according to claim 1, wherein the copper-coated plastic substrate is formed from the following.   An electroconductive substance formed by forming an anchor layer (2) containing a substance having anion exchange capacity on at least one surface of a plastic film substrate (1), and covering the anchor layer (2) with a protective substance A dispersion (3) of particles is applied or printed, and dried to provide a seed layer (4). Further, a copper conductor layer (electroless copper plating and / or electrolytic copper plating is applied on the seed layer (4). 5) forming a copper-coated plastic substrate.