JP2009164041A - Conductive pattern member, forming method thereof, and organic el display device equipped with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive pattern member which is composed by means that a conductive base material such as an ITO and a fine wiring formed on its surface are electrically contacted at an arbitrary place easily and simply, and a forming method of the conductive pattern wherein a fine conductive pattern which is superior in adhesiveness with the conductive base material can be formed and conductive pattern and the conductive base material can be brought into electric contact easily and simply. <P>SOLUTION: This is the conductive pattern member which, on the conductive base material 14, has: a resin layer 16 containing conductive particles 28; a conducive pattern bonded to the resin layer and composed by covering a surface and a side surface of a pattern-shaped polymer layer 18 containing a polymer including a functional group interacting with an electroless plating catalyst or its precursor; and a conductive part 26 where a conductive layer 20 of the side surface of the polymer layer 18 of the conductive pattern and the conductive base material 14 are electrically connected through the conductive particles 28 contained in the resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive pattern member, a method for forming the conductive pattern member, and an organic EL display device having the conductive pattern as a wiring. In particular, the present invention relates to a conductive pattern useful for printed wiring boards, glass substrate wirings, organic EL wirings and the like, a method for forming the same, and an organic EL display device having wirings obtained by the method.

As a method of forming a conductive pattern such as a metal wiring on a conductive substrate such as an ITO substrate, a method of patterning a conductive ink such as metal ink directly on the substrate by a droplet discharge method (inkjet method) is available. It is known (for example, refer to Patent Document 1). However, the inkjet method has a problem that the fine wiring formability is insufficient. This is because the minimum resolution of fine lines in the ink jet method is about 30 μm, which is not a satisfactory level for the high resolution requirements of elements such as organic EL, and since the ink is ejected, the dot pattern is fine. This is due to the characteristic that the wiring layer remains uneven on the side surface or surface of the wiring, and the wiring layer becomes uneven, and the wiring resistance varies accordingly.
The variation in wiring resistance causes a variation in starting power (voltage applied to the element) when the wiring is applied to an element such as an organic EL, resulting in a problem that the luminance of the display element varies. In addition to these problems, the ink jet method also has a problem that the adhesion between the substrate and the ink is poor.

In response to this, the applicant of the present invention forms an epoxy resin layer made of an epoxy resin composition having a specific structure on an insulating substrate as a method for forming a conductive film having excellent adhesion to a substrate, and electroless plating catalyst. Alternatively, a conductive film is formed by bonding a polymer having a functional group that interacts with its precursor to form a graft polymer, and then applying an electroless plating catalyst to the graft polymer to perform electroless plating. A forming method was proposed (see Patent Document 2).
According to this method, a conductive film having excellent adhesion to the substrate can be formed in an arbitrary region, for example, on the entire surface or in a fine pattern by a simple method. However, in order to form a multilayer wiring board by laminating this conductive film, a conventional method of forming a via hole in an insulating resin layer and making electrical contact is used, and fine wiring formed in an upper layer is used. There is still room for improvement from the viewpoint that the electrical contact with the conductor substrate can be easily formed.
JP 2003-317610 A JP 2007-146103 A

The object of the present invention, which has been made in consideration of the above-mentioned problems of the prior art, is that an electrically conductive substrate such as ITO and a fine wiring formed on the surface thereof are easily electrically contacted at an arbitrary position. It is possible to form a conductive pattern member and a fine conductive pattern excellent in adhesion with the conductive base material, and easily connect the conductive pattern and the conductive base material at an arbitrary location. An object of the present invention is to provide a method for forming a conductive pattern that can be brought into electrical contact.
It is a further object of the present invention to provide an organic EL display device having a high resolution and a small variation in luminance, comprising as a wiring a fine conductive pattern formed by the conductive pattern forming method of the present invention. .

As a result of intensive studies, the present inventors have formed a resin layer containing conductive particles on a conductive substrate and formed a polymer pattern capable of receiving a plating catalyst directly bonded to the resin layer. As a result, it was found that the above problems could be solved, and the present invention was completed.
The configuration of the present invention is as follows.
<1> A patterned polymer containing a resin layer containing conductive particles on a conductive substrate, and a polymer having a functional group that binds to the resin layer and interacts with an electroless plating catalyst or a precursor thereof. A conductive pattern in which the surface and side surfaces of the layer are coated with a conductive layer, and the conductive layer on the side surface of the polymer layer of the conductive pattern and the conductive base material contain conductive particles contained in the resin layer. A conductive pattern member comprising a conductive portion in electrical contact with the conductive pattern member.
<2> The conductive particle according to <1>, wherein the conductive particle is a conductive particle having a multilayer structure in which a resin particle is a core and a conductive metal thin film layer is provided on a surface layer portion of the resin particle. Sex pattern member.
<3> The conductive particles according to <2>, wherein the conductive particles having a multilayer structure are conductive particles having a three-layer structure in which an insulating layer is further provided on the surface of the conductive metal thin film layer. Pattern member.
<4> The conductive pattern member according to any one of <1> to <3>, wherein the resin layer is a thermosetting resin layer containing an epoxy resin composition.
<5> The conductive pattern member according to <4>, wherein the epoxy resin composition contains a photoradical generator.
<6> The conductive pattern member according to <5>, wherein the photoradical generator is a polymer-type photoradical generator.
<7> The conductive pattern member according to any one of <1> to <6>, wherein the conductive substrate is a conductive substrate including a transparent conductive film.
<8> The conductive pattern member according to <7>, wherein the transparent conductive film contains tin oxide, indium oxide, zinc oxide, and a conductive polymer.

<9> (a) A step of forming a resin layer made of a thermosetting resin or a thermoplastic resin containing conductive particles on a conductive substrate, (b) a polymerizable double bond on the resin layer A compound having a functional group that interacts with the electroless plating catalyst or its precursor, or a polymerizable double bond and a functional group that interacts with the electroless plating catalyst or its precursor in the molecule. A step of forming a photoreactive layer containing a compound having (c) the photoreactive layer is exposed in a pattern, and a polymer formed by bonding with the resin layer is formed in the exposed region, thereby forming a resin layer A step of forming a patterned polymer layer thereon, (d) a step of applying an electroless plating catalyst or a precursor thereof to a region where a polymer combined with the resin layer is generated, and (e) performing electroless plating. The surface of the patterned polymer layer and A step of forming a conductive layer by forming a metal layer on the side surface; and (f) pressurizing the conductive pattern portion in the direction of the conductive substrate while heating, thereby conducting the conductive layer and the conductive layer on the side surface of the conductive pattern. Forming a conductive portion that is in electrical contact with the surface of the conductive base material via conductive fine particles contained in the resin layer.
<10> The step of forming the resin layer (a) is a step of forming a semi-cured thermosetting resin layer containing conductive particles on the conductive substrate. <9> The method for forming a conductive pattern according to the above.
<11> The method for forming a conductive pattern according to <9> or <10>, further comprising a step of activating the surface of the conductive substrate before the step of forming the resin layer (a). .
<12> The conductive material according to any one of <9> to <11>, which includes a step of removing a resin layer other than the conductive pattern formation region by etching before the step (f). Pattern formation method.
<13> An organic EL display device comprising a conductive wire formed by the conductive pattern forming method according to any one of <9> to <12>.
<14> An insulating substrate, a pixel electrode wiring provided on the insulating substrate, and an organic layer and a cathode layer sequentially stacked on the pixel electrode wiring, and connected to the pixel electrode wiring. An organic EL display device, wherein the auxiliary wiring is an auxiliary wiring formed by the method for forming a conductive pattern according to any one of <9> to <12>.

Since the present invention forms a conductive pattern using a polymer layer that is electroless plating catalyst receptive by pattern exposure and is chemically bonded to a resin layer formed on the surface of a conductive substrate. It is excellent in adhesion, and fine wiring according to exposure accuracy can be easily formed.
Furthermore, since the conductive pattern member of the present invention uses a thermosetting resin layer or a thermoplastic resin layer containing conductive particles for bonding with the polymer pattern, the conductive pattern member is heated after forming the conductive pattern by plating. By crimping the conductive pattern, only a region to which heat and pressure are applied in the conductive pattern can form a conductive portion that is easily electrically contacted with the conductive substrate. That is, in the thermocompression bonded portion, the conductive particles contained in the resin layer are interposed between the conductive layer formed by plating and the conductive base material while excluding the thermosetting resin or thermoplastic resin constituting the resin layer. The conductive particles contribute to the electrical bonding between the conductive film, in particular, the plated conductive film formed on the side surface of the polymer pattern and the conductive base material. Since the resin layer and the thermoplastic resin are uniformly dispersed, the resin layer itself functions as an insulating layer and the two layers are not electrically joined.

  Since the conductive pattern member of the present invention formed in this way has a conductive pattern excellent in fine wiring formability and adhesion to a substrate, a book having such a conductive pattern as a wiring is provided. The organic EL display device of the invention has an excellent effect of high resolution and small variation in luminance.

According to the present invention, a conductive pattern member having a conductive portion in which a conductive substrate such as ITO and a fine wiring formed on the surface thereof are in electrical contact with each other easily, and A conductive pattern that can form a fine conductive pattern with excellent adhesion to a conductive substrate, and is simply electrically contacted at any location with the conductive pattern and the conductive substrate. It is possible to provide a method for forming a conductive pattern capable of forming a portion.
In addition, by applying the conductive pattern forming method of the present invention, it is possible to provide an organic EL display device that has a fine conductive pattern as a wiring and has high brightness and small variation in luminance.

Hereinafter, each process in the conductive pattern formation method of this invention is demonstrated sequentially.
<(A) Step of forming a resin layer made of a thermosetting resin or a thermoplastic resin containing conductive particles on the conductive substrate [(a) step >>
Step (a) is a step of forming a thermosetting resin layer or a thermoplastic resin layer containing conductive particles on a conductive substrate.

[A-1. Conductive substrate
(A) As a conductive base material which can be used for the process, it can be arbitrarily selected from known conductive base materials which can be used for a wiring board, and preferably includes a base material including a transparent conductive film. Can do.
Examples of the transparent conductive film that can be used in the present invention include a transparent conductive film containing tin oxide, indium oxide, zinc oxide, and a conductive polymer. Specifically, for example, tin oxide, indium tin oxide (ITO), indium zinc oxide (IZO), PEDOT-PSS, or the like can be used. Of these, ITO is preferable from the viewpoints of electrical conductivity, transparency, and workability (etching suitability).
These conductive substrates may be used alone as a substrate, or may be used as a transparent conductive film formed on the surface of another base substrate, for example, a generally used insulating substrate.
As a method for forming the transparent conductive film on the base substrate, a known vacuum film forming method such as a sputtering method or a laser ablation method can be used.

Base substrates include epoxy resin substrates, polyimide substrates, glass substrates, PET substrates, PEN substrates, or cellulose triacetate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, polytetrafluoroethylene, cyclohexane Substrates formed from resins such as olefin polymer, polyphenylene ether, polyphenylene oxide, liquid crystal polymer, benzocyclobutene resin, polyethersulfone, polyetherimide, polyarylate, aramid resin, phenolic resin, bismaleimide triazine resin, cyanate resin Can be used.
As the base substrate, generally, a flat substrate (various substrates) is used, but the substrate is not necessarily limited to a flat substrate, and a substrate having an arbitrary shape such as a cylindrical shape may be used. it can.
In the present invention, the term “substrate surface” refers to the surface of the conductive substrate itself as well as other components (for example, electrodes) formed on the conductive substrate, such as a resin layer on the surface. It also includes a region on the substrate which is a target when forming the film. That is, to form a resin layer on the surface of the base material is an aspect in which the resin layer is directly formed on the conductive base material, and a base material in the case where other constituent elements such as electrodes are formed on the surface of the conductive base material Any of the embodiments formed so as to cover the region to be included is included.

  As the conductive substrate in the present invention, among the above-described substrates, an embodiment having a transparent conductive layer on the surface of the insulating substrate, more specifically, tin oxide, indium tin oxide (ITO), indium. Selected from epoxy resin base material, polyimide base material, glass base material, PET base material, PEN base material, etc. formed on the surface of transparent conductive film selected from zinc oxide (IZO), conductive polymer, etc. An insulating base material can be suitably used.

  In the present invention, before the step of forming a thermosetting resin layer or a thermoplastic resin layer containing conductive particles on the conductive substrate, the adhesion between the resin layer and the substrate surface described later is improved. For the purpose, a treatment step (substrate activation treatment) for activating a known substrate surface can be carried out if desired. Examples of the activation treatment of the substrate surface include UV ozone treatment and treatment of dipping in a piranha solution (sulfuric acid / 30% hydrogen peroxide = 1/1 vol mixed solution).

The resin layer formed on the surface of the conductive substrate is formed by dispersing conductive particles in a resin matrix. The resin that forms the matrix in the resin layer is either a thermosetting resin or a thermoplastic resin. However, it can be arbitrarily selected according to the purpose of use of the conductive pattern member. First, the resin component which comprises a resin layer is demonstrated.
[A-2. Thermosetting resin layer)
The thermosetting resin layer contains a thermosetting resin as a constituent component of the resin layer. Specific examples of the thermosetting resin used here include, for example, epoxy resins, phenol resins, bismaleimide resins, cyanate resins, diallyl phthalate resins, unsaturated polyester resins, polyimide resins, melamine resins, urea resins, epoxy acrylates, and the like. Although a radical polymerizable resin having an unsaturated double bond can be used, an epoxy resin is preferable from the viewpoint of thermocompression bonding, versatility, cost, etc., and the resin constituting the resin layer is an epoxy resin. You may use independently and may use an epoxy resin and other resin together.
Hereinafter, a thermosetting epoxy resin composition containing an epoxy resin suitable for forming a thermosetting resin layer in the present invention will be described.

(Thermosetting epoxy resin composition)
The thermosetting epoxy resin composition used for the thermosetting resin layer formation of this invention points out the aspect whose content of an epoxy resin is 20 mass% or more in the total solid content contained in a composition. The thermosetting epoxy resin composition preferably contains a photoradical generator useful for bonding a polymer to the surface of the resin layer by surface graft polymerization, and may further contain other resin components.

When adding other resin components, from the viewpoint that the properties of each of the plurality of resins such as the addition effect of the resin component and the strength of the epoxy resin are exhibited, and the progress of the polymer formation reaction is good, The other resin is added in the range of 30 to 300% by mass, preferably 50 to 200% by mass with respect to the epoxy resin.
Examples of resins that can be used as other resin components include phenol resins, polyimide resins, bismaleimide triazine resins, fluorine resins, and polyphenylene oxide resins.

  The thermosetting epoxy resin composition includes (A) an epoxy compound having two or more epoxy groups in one molecule, and (B) a compound having a functional group that reacts with two or more epoxy groups in one molecule. (Hereinafter, referred to as “curing agent” as appropriate) is an essential component, and (C) a photo radical generator is further preferably contained.

  (A) As an epoxy compound (including what is called an epoxy resin) having two or more epoxy groups in one molecule, two or more epoxy groups, preferably 2 to 50, more preferably 2 to 20 It is an epoxy compound (including what is called an epoxy resin) having a single molecule in one molecule. The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Such polyvalent epoxy compounds are widely disclosed in, for example, published by Masaki Shinbo “Epoxy Resin Handbook” published by Nikkan Kogyo Shimbun (1987), and these can be used.

  Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin. These may be used alone or in combination of two or more. Use of a polyfunctional epoxy, an epoxy with a low epoxy equivalent, a naphthalene type epoxy, a dicyclopentadiene type epoxy or the like provides an epoxy resin excellent in heat resistance.

(B) As a functional group in a hardening | curing agent, the functional group chosen from functional groups, such as a carboxyl group, a hydroxyl group, an amino group, a thiol group, is preferable, and what is necessary is just to select the compound which has these functional groups.
(B) Curing agents include polyfunctional carboxylic acid compounds such as terephthalic acid, bifunctional phenol compounds such as bisphenol A, bisphenol F, bisphenol S, resorcinol derivatives and catechol derivatives, phenol resins such as phenol novolac resins and cresol novolac resins. And polyfunctional amino compounds such as amino resins, 1,3,5-triaminotriazine, and 4,4′-diaminodiphenylsulfone. Among these, the (B) curing agent includes a compound having a hydroxyl group or an amino group as a functional group that reacts with an epoxy group, more specifically, a phenol resin such as a phenol novolac resin or a cresol novolac resin, an amino resin, 1 Polyfunctional amino compounds such as 1,3,5-triaminotriazine and 4,4′-diaminodiphenylsulfone are preferably used.

  As the addition amount of the (B) curing agent in the thermosetting epoxy resin composition, the ratio of the functional group of the (B) curing agent to the epoxy group in the epoxy compound contained as the component (A) is 0. It is preferably 1 to 5.0, and more preferably 0.3 to 2.0.

(C) Photoradical generator The thermosetting epoxy resin composition in the present invention preferably contains a photoradical generator in order to promote surface graft polymerization in the step (c) described later.
In addition, since the epoxy resin layer can function as an adhesive layer (stress relaxation layer) without adding a photo radical generator to the thermosetting epoxy resin composition, image formation is possible, but adhesion It is preferable to add a photo radical generator in order to increase the resistance.

In the present invention, the (C) photo radical generator used in the thermosetting epoxy resin composition may be a low molecule or a high molecule.
Specific examples of the low-molecular photopolymerization initiator include acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, α-acyloxime ester, tetramethylthiuram monosulfide, trichloromethyltriazine, and thioxanthone. A known radical generator can be used. In addition, since sulfonium salts and iodonium salts that are usually used as photoacid generators also act as radical generators upon irradiation with light, they may be used in the present invention.

Examples of the polymer photo radical generator include JP-A-9-77891, JP-A-10-45927, Japanese Patent Application No. 2006-053430, Japanese Patent Application No. 2006-264706, Photochemistry & Photobiology, Vol. 5, high molecular compounds having an active carbonyl group, trichloromethyltriazine, or thioxanthone in the side chain, as described in JP-A-5, p46 (1999).
Moreover, as a polymeric photoradical generator, the high molecular compound comprised including the structural unit shown by following compound (1)-(14) can also be mentioned, for example. In addition, the weight average molecular weight of the high molecular compound containing the structural unit shown by following (1)-(14) is 10,000 or more and 100,000 or less.

  In addition, as a photoradical generator, from a viewpoint of performing the coupling | bonding and production | generation to the resin layer of the polymer chain in the (c) process mentioned later, a polymer-type photoradical generator, for example, said (1)- It is preferable to use a polymer compound containing the structural unit represented by (14). The weight average molecular weight of the polymer-type photoradical generator is preferably 10,000 or more, and more preferably 30,000 or more. The upper limit of the weight average molecular weight is preferably 100,000 from the viewpoint of solubility.

  The epoxy compound (epoxy resin) also serves as a polymer-type photoradical generator, that is, a compound having a partial structure capable of generating radicals in the epoxy resin may be used. Examples of the epoxy compound (epoxy resin) used as the generator include compounds represented by the following (15) to (30). Here, in (15) to (30), x and y represent mole fractions, and x + y = 100 (x ≠ 0, y ≠ 0).

(C) The content of the photo radical generator is such that the production efficiency of the polymer in the step (c), the point of suppressing the decrease in the adhesion strength resulting therefrom, the point of suppressing the Tg decrease of the cured product, and the dielectric constant of the cured product are From the point of preventing problems on thermal characteristics and electrical characteristics such as increasing, it is preferably about 0.1 to 50% by mass with respect to the total solid content of the thermosetting resin composition, 1.0 to More preferably, it is about 30.0 mass%.
In addition, when using an epoxy resin having such radical generating ability, it is not necessary to add another (C) photo radical generator, but the content of the partial structure having radical generating ability is considered in consideration of the addition amount. Is preferably determined. Even when such a resin is used, (C) a photoradical generator can be used in combination according to the purpose.

(Other additives)
In the thermosetting epoxy resin composition, in addition to the components (A) to (C), various additives can be used depending on the purpose.
(Curing accelerator)
A curing accelerator for promoting thermal curing may be added to the composition. As the curing accelerator, imidazole compounds such as 2-ethyl-4-methylimidazole, pyridine compounds such as 4-dimethylaminopyridine, and organic phosphine compounds such as triphenylphosphine can be used.
When using a hardening accelerator, it is preferable to use the compounding amount in the range of 0.5 to 2% by mass when the compounding amount of the phenolic curing agent is 100% by mass.

(Sensitizer)
The thermosetting resin composition in the present invention may use a sensitizer in addition to the photoradical generator for the purpose of enhancing the polymer productivity and bonding properties. Specific examples of the sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, and thioxanthone derivatives.

(solvent)
The thermosetting resin composition in the present invention may optionally contain a solvent.
Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, acetate esters such as propylene glycol monomethyl ether acetate, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, methyl Examples include glycol derivatives such as cellosolve acetate and ethyl cellosolve acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, and the like. .
These organic solvents may be used alone or as a mixed solvent of two or more.

[A-3. Thermoplastic resin layer)
The resin layer in the present invention may be a thermoplastic resin layer using a thermoplastic resin as a matrix resin.
As the thermoplastic resin, general general-purpose resins, general-purpose engineering resins, and super-engineering resins can be used.
More specifically, for example, polyacetal, polyimide, liquid crystal polymer, polyether ether ketone, polyether sulfone, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyphenylene ether, polyphenylene sulfide, polypropylene, phenoxy resin, polyetherimide, poly Tetrafluoroethylene (PTFE) or the like can be used, but general-purpose engineering resins are preferable from the viewpoint of thermocompression bonding (the thermal deformation temperature is in a practical temperature range), and polyethylene terephthalate is particularly preferable from the viewpoint of versatility and cost. Polyester resin such as polybutylene terephthalate is preferable.
These thermoplastic resins may be used alone or in combination of two or more.

Even when a thermoplastic resin is used as the matrix resin, it contains (C) a photoradical generator mentioned as a preferred combination component in the thermosetting resin layer from the viewpoint of improving the adhesion with an adjacent layer. Is preferred.
It is preferable that the addition amount of the preferable (C) photoradical generator in a thermoplastic resin layer is about 0.1-50 mass% with respect to the total solid of a thermoplastic resin composition, and is 1-30 mass%. More preferably, it is about.

[A-4. Conductive particles]
The resin layer contains conductive particles. The conductive particles are conductive enough to realize electrical contact between the conductive layer of the conductive pattern and the underlying conductive substrate when the conductive pattern formed on the resin layer surface is heated and pressurized. The particles may have any property.
As the conductive particles, (a-4-1) metal particles, (a-4-2) particles having a conductive metal thin film layer on the surface layer with resin particles as nuclei, (a-4- 3) Conductive metal thin film layer on the surface layer of the resin particle as a core, and particles (insulating layer of resin layer / metal thin film layer / insulating layer) provided with an insulating layer sequentially In order to prevent electroless plating from being formed in the region where the patterned polymer layer is not formed in the electroless plating step (e), the resin (a-4-3) can be mentioned. Three-layered particles having an insulating thin film on the surface comprising particles / metal thin film layer / insulating layer are preferred.
This is because, when resin particles having conductive metal particles or conductive films on the surface are used, or when some particles are exposed on the surface of the layer after the formation of the resin layer, a plating film ( This is because the phenomenon that the metal film is formed in the non-formation region of the polymer pattern that is not desired to be plated is originally suppressed.

(A-4-1) Examples of the conductive metal constituting the metal particles include Au, Pt, Cu, Ni, Ag, Ir, Pd, Rh, In, Co, Zn, Cd, Al, Sn, and Ru. It is done.
(A-4-2) The resin particle having a conductive film has a thick metal layer made of the conductive metal on the surface of resin particles such as acrylic resin, epoxy resin, acrylic-styrene copolymer resin, and silicone rubber. What is formed by about 0.01-0.5 micrometer is preferable.
(A-4-1) Metal particles or (a-4-2) Resin particles having a conductive film are also available as commercial products, for example, Ni / Au plated acrylic resin particles manufactured by Sony Chemical Corporation Etc.

(A-4-3) Specific examples of the three-layer structured particles are described in JP-A Nos. 2001-11503, 2003-268346, 2004-131780, and 2005-209491. The conductive particles can be used. Examples of the material constituting the insulating layer include an acrylic resin, an epoxy resin, an acrylic-styrene copolymer resin, and insulating fine particles such as silica may be embedded in the insulating layer. The thickness of the insulating layer is preferably about 0.01 to 0.5 μm. It is also possible to control the size of the conductive particles depending on the size of the resin particles serving as the nucleus.
The insulating layer present on the outermost surface of the three-layer structure particle is not peeled off unless heat and pressure are applied. However, the insulating layer is peeled off during thermocompression bonding, and the conductive function is exhibited. Electrical contact with the conductive substrate can be obtained.

The particle size of these conductive particles can be appropriately selected depending on the thickness of the insulating layer and the desired conductivity when an electrical contact is realized, but is generally 0.01 to 10 μm, preferably 0.05 to 5 μm. Is more preferable.
The content of the conductive particles in the composition constituting the resin layer is in the range of 1 to 50% by mass in the total solid content, regardless of whether a thermosetting resin or a thermoplastic resin is used as the resin matrix. Is preferable, and the range of 3 to 20% by mass is more preferable.

[A-5. Formation of thermosetting resin layer or thermoplastic resin layer]
In this step, a thermosetting resin layer or a thermoplastic resin layer is formed on the substrate using the above-described thermosetting resin composition or thermoplastic resin composition.
The total resin content in the composition is preferably in the range of 10 to 80% by mass, and more preferably in the range of 40 to 70% by mass.
Preparation of the resin layer composition coating solution can be carried out by adding each of the components described above to a varnish dissolved in a solvent, and stirring and mixing uniformly.
As a method for forming the resin composition layer, the coating liquid for forming the resin composition is applied to the surface of the insulating base as described above by knife coating, roll coating, curtain coating, spin coating, bar coating, dip coating, etc. And uniformly applying and drying and curing.
As heating temperature at the time of drying, 20-200 degreeC is preferable, More preferably, it is 80-180 degreeC. The heating time is 1 second to 50 hours, more preferably 10 seconds to 10 hours.
When a thermoplastic resin is used, the resin layer is cured by lowering the temperature to room temperature after removing the solvent.
When a thermosetting resin is used, a semi-cured thermosetting resin layer containing conductive particles is formed on a conductive substrate, and then dried to obtain a so-called B-stage semi-cured state. preferable. The drying temperature is 20 ° C. to 150 ° C., preferably 50 ° C. to 120 ° C., and the drying time is 1 second to 1 hour, preferably 30 seconds to 10 minutes.
In order to cure the thermosetting resin, it is necessary to impart sufficient energy to form a crosslinked structure. Energy can be applied by means of ultraviolet irradiation, heating, laser, EB, or the like.

  The thickness of the resin layer in the present invention is preferably in the range of 0.01 to 10 (μm unit), preferably in the range of 0.05 to 5 (μm unit), from the viewpoint of contact property control between the substrate and the wiring. More preferably.

<(B) On the resin layer, a compound having a polymerizable double bond and a compound having a functional group that interacts with the electroless plating catalyst or its precursor, or a polymerizable double bond and no compound in the molecule. Step of Forming Photoreactive Layer Containing Compound Having Functional Group that Interacts with Electroplating Catalyst or Precursor thereof (Step (b)]>
In the step (b), a functional group that interacts with a compound having a polymerizable double bond (polymerizable compound) and an electroless plating catalyst or a precursor thereof on the resin layer formed in the step (a). A photoreactive layer containing a compound having a compound having a polymerizable double bond and a functional group that interacts with an electroless plating catalyst or a precursor thereof in the molecule is formed. From the viewpoint of the effect, it is preferable to use a compound having a polymerizable double bond and a functional group that interacts with the electroless plating catalyst or its precursor in the molecule for forming the photoreactive layer.
Hereinafter, this (b) process is demonstrated.

  When a photoreactive layer is formed from a compound having a polymerizable double bond (polymerizable compound) and a compound having a functional group that interacts with the electroless plating catalyst or its precursor, the compound used in the photoreactive layer is: Selected from compounds having a polymerizable double bond used for purification of “a compound having a polymerizable double bond in the molecule and a functional group that interacts with an electroless plating catalyst or its precursor” described in detail below One or more compounds selected from the above and one or more compounds selected from compounds having a functional group that interacts with the electroless plating catalyst or its precursor can be used in appropriate combination.

(B-1. Compound having a functional group that interacts with a polymerizable double bond and an electroless plating catalyst or a precursor thereof in the molecule)
In the present invention, as the compound having a polymerizable double bond (polymerizable compound), any of a monomer, a macromer, and a polymer compound having a polymerizable double bond can be used. As these compounds, known compounds can be arbitrarily used. Among these, compounds particularly useful in the present invention have a polymerizable double bond and have a functional group (hereinafter referred to as an interactive group) that interacts with the electroless plating catalyst or its precursor. A compound.
By this interactive group, it is possible to impart an interactive property with the electroless plating catalyst or its precursor to the formed polymer chain bonded to the resin layer. Examples of the interactive group include hydrophilic groups such as carboxyl group, hydroxyl group, amino group, sulfonic acid group, phosphonic acid group and amide group or salts thereof, nitrogen-containing heterocyclic groups such as cyano group, imidazole group and pyridine group. , And a functional group such as an ether group, and is not particularly limited in terms of production characteristics.

(monomer)
Specific examples of the monomer used in this step include (meth) acrylic acid or an alkali metal salt and amine salt thereof, itaconic acid or an alkali metal salt and amine salt thereof, styrenesulfonic acid or an alkali metal salt thereof, and the like. Amine salt, 2-sulfoethyl (meth) acrylate or alkali metal salt and amine salt thereof, 2-acrylamido-2-methylpropanesulfonic acid or alkali metal salt and amine salt thereof, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate Or alkali metal salts and amine salts thereof, polyoxyethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-di Carbon such as tyrol (meth) acrylamide, allylamine or its hydrohalide, N-vinylpyrrolidone, vinylimidazole, vinylpyridine, vinylthiophene, styrene, ethyl (meth) acrylate, n-butyl (meth) acrylate Mention may be made of (meth) acrylic acid esters having an alkyl group of from 1 to 24.

  Furthermore, as a monomer having a cyano group, acrylonitrile, cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 1-cyanoethyl (meth) acrylate 4-cyanobutyl (meth) acrylate, 5-cyanopentyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 2-cyanoethyl- (3- (bromomethyl) acrylate), 2-cyanoethyl- (3- (hydroxy Methyl) acrylate), p-cyanophenyl (meth) acrylate, o-cyanophenyl (meth) acrylate, m-cyanophenyl (meth) acrylate, 5- (meth) acryloyl-2-carbonitryl-norbornene, 6 (Meth) acryloyl-2-carbonitryl-norbornene, 1-cyano-1- (meth) acryloyl-cyclohexane, 1,1-dimethyl-1-cyano- (meth) acrylate, 1-dimethyl-1-ethyl-1- Cyano- (meth) acrylate, o-cyanobenzyl (meth) acrylate, m-cyanobenzyl (meth) acrylate, p-cyanobenzyl (meth) acrylate, 1-cyanocycloheptyl acrylate, 2-cyanophenyl acrylate, 3-cyano Phenyl acrylate, vinyl cyanoacetate, vinyl 1-cyano-1-cyclopropanecarboxylate, allyl cyanoacetate, allyl 1-cyano-1-cyclopropanecarboxylate, N, N-dicyanomethyl (meth) acrylamide, N-cyanophenyl (Meth) acrylamide, Lil cyanomethyl ether, allyl -o- cyanoethyl ether, allyl -m- cyanobenzyl ether, and allyl -p- cyanobenzyl ether.

In the present invention, as described above, not only a monomer but also a macromer or a polymer (a polymer compound having a polymerizable double bond) can be preferably used as the polymerizable compound.
The macromer that can be used in the present invention can be prepared by a known method using the monomer. The method for producing the macromonomer used in this embodiment is described in, for example, Chapter 2 of “Macromonomer Chemistry and Industry” (Editor, Yuya Yamashita) published on September 20, 1999, published by the IP Publishing Department. Various production methods have been proposed in “Synthesis”.
Among these macromonomers, a useful weight average molecular weight is in the range of 250 to 100,000, and a particularly preferable range is 400 to 30,000.

(Polymer compounds, polymers)
In the present invention, the polymer compound (polymer) having a polymerizable double bond is an ethylene addition polymerizable unsaturated group (such as a vinyl group, an allyl group, or a (meth) acryl group) as a polymerizable double bond ( The polymer which introduce | transduced the polymeric group) is pointed out, This polymer has a polymeric group in the terminal or a side chain at least, and what has a polymeric group in a side chain is more preferable.
In addition to the polymerizable group, the polymer compound having a polymerizable double bond may be a polar group such as a carboxyl group as described above, or a functional material to be introduced on the surface (for example, the above-described electroless plating). It preferably has a functional group capable of interacting with a catalyst or a precursor thereof.
The useful weight average molecular weight of the polymer compound having a polymerizable group is in the range of 1000 to 700,000, and a particularly preferred range is in the range of 2000 to 300,000.

As a method for synthesizing such a polymer compound having a polymerizable group and an interactive group, i) a method of copolymerizing a monomer having an interactive group and a monomer having a polymerizable group, ii) interaction A method of copolymerizing a monomer having a reactive group and a monomer having a double bond precursor and then introducing a double bond by treatment with a base or the like; iii) having a polymer having an interactive group and a polymerizable group There is a method of reacting with a monomer and introducing a double bond (introducing a polymerizable group).
A preferred synthesis method is, from the viewpoint of synthesis suitability, ii) a method in which a monomer having an interactive group and a monomer having a double bond precursor are copolymerized, and then a double bond is introduced by treatment with a base, iii) A method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.

  In the present invention, examples of the monomer having an interactive group that can be used to produce the surface graft polymer of ii) include (meth) acrylic acid or an alkali metal salt and amine salt thereof, itaconic acid or an alkali metal salt thereof, and the like. Amine salts, more specifically, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, N-monomethylol (meth) acrylamide, N-dimethylol (meth) acrylamide, allylamine or a hydrohalide thereof, 3 -Vinyl propionic acid or its alkali metal salt and amine salt, vinyl sulfonic acid or its alkali metal salt and amine salt, 2-sulfoethyl (meth) acrylate, polyoxyethylene glycol mono (meth) acrylate, 2-acrylamido-2-methyl Examples include lopansulfonic acid, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, N-vinyl pyrrolidone (the following structure), sodium styrene sulfonate, vinyl benzoic acid, and the like. Generally, carboxyl group, hydroxyl group, amino group And monomers having hydrophilic groups such as sulfonic acid groups, phosphonic acid groups, amide groups or salts thereof, nitrogen-containing heterocyclic groups such as cyano groups, imidazole groups and pyridine groups, and functional groups such as ether groups. it can. For some, the monomers described above can be used.

Examples of the monomer having a polymerizable group that is copolymerized with the monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate, and compounds (i-1 to i-60) described in JP-A No. 2003-335814. Among these, the following compound (i-1) is particularly preferable.

Furthermore, polymerization used to introduce unsaturated groups by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in a polymer having an interactive group Examples of the monomer having a functional group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.
ii) Regarding a method of introducing a double bond by treatment with a base after copolymerizing a monomer having an interactive group and a monomer having a double bond precursor, for example, JP-A-2003-335814 The technique described in the publication can be used.

In the present invention, the polymer having a polymerizable group and an interactive group is preferably a polymer having a cyano group as an interactive group (hereinafter referred to as “cyano group-containing polymerizable polymer”).
The cyano group-containing polymerizable polymer in the present invention is preferably a copolymer including, for example, a unit represented by the following formula (1) and a unit represented by the following formula (2).

In the above formulas (1) and (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z are each independently A single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group; L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group; To express.

When R ^{1 to} R ⁵ are substituted or unsubstituted alkyl groups, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include methoxy And a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.
R ¹ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

When X, Y and Z are a substituted or unsubstituted divalent organic group, the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. Is mentioned.
As the substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or these groups are substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like. Those are preferred.
The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.
Among _{them, - (CH 2) n -} (n is an integer of 1 to 3) are preferred, more preferably -CH ₂ -.

L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, more preferably a divalent organic group having a urethane bond, and among them, one having a total carbon number of 1 to 9 is preferable. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1) or formula (1-2).

In the above formula (1-1) and formula (1-2), R ^a and R ^b each independently represent two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. A divalent organic group formed by using, preferably a substituted or unsubstituted methylene group, ethylene group, propylene group, or butylene group, ethylene oxide group, diethylene oxide group, triethylene oxide group, tetraethylene oxide group, Examples include a dipropylene oxide group, a tripropylene oxide group, and a tetrapropylene oxide group.

L ² is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L ² preferably has 1 to 15 total carbon atoms, and particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^2.
Specifically, methylene group, ethylene group, propylene group, butylene group, phenylene group, and those groups substituted with methoxy group, hydroxy group, chlorine atom, bromine atom, fluorine atom, etc., The group which combined these is mentioned.

  As the cyano group-containing polymerizable polymer in the present invention, the unit represented by the formula (1) is preferably a unit represented by the following formula (3).

In the above formula (3), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and Z is a single bond, a substituted or unsubstituted divalent organic group. Represents an ester group, an amide group, or an ether group, W represents an oxygen atom, or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted C 1-5 substituent. And L ¹ represents a substituted or unsubstituted divalent organic group.

^{R 1} and ^{R 2} in the formula (3), the formula (1) have the same meanings as ^{R 1} and ^{R 2} in, and so are the preferable examples.

Z in formula (3) has the same meaning as Z in formula (1), and the preferred examples are also the same.
Further, ^{L 1} in the formula (3) also has the same meaning as ^{L 1} in Formula (1), and preferred examples are also the same.

  As the cyano group-containing polymerizable polymer in the present invention, the unit represented by the formula (3) is preferably a unit represented by the following formula (4).

In Formula (4), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent an oxygen atom or NR (R Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms), and L ¹ represents a substituted or unsubstituted divalent organic group. Represents.

^{R 1} and ^{R 2} in the formula (4), the formula (1) have the same meanings as ^{R 1} and ^{R 2} in, and so are the preferable examples.

L ¹ in Formula (4) has the same meaning as L ¹ in Formula (1), and the preferred examples are also the same.

In the formulas (3) and (4), W is preferably an oxygen atom.
In Formulas (3) and (4), L ¹ is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and a divalent organic group having a urethane bond. Of these, those having 1 to 9 carbon atoms in total are particularly preferred.

  Moreover, as a cyano group containing polymeric polymer in this invention, it is preferable that the unit represented by said Formula (2) is a unit represented by following formula (5).

In the above formula (5), R ⁵ represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents an oxygen atom, or NR ′ (R ′ represents a hydrogen atom or an alkyl group, preferably Represents a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms.), And L ² represents a substituted or unsubstituted divalent organic group.

R ⁵ in Formula (5) has the same meaning as R ¹ and R ² in Formula (1), and is preferably a hydrogen atom.

L ² in Formula (5) has the same meaning as L ² in Formula (2), and is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group that combines these. .
In particular, in the formula (5), the linking site with the cyano group in L ² is preferably a divalent organic group having a linear, branched, or cyclic alkylene group. The organic group preferably has 1 to 10 carbon atoms.
As another preferred embodiment, it is preferable that the linkage site to the cyano group in L ² in Formula (5) is a divalent organic group having an aromatic group, and among them, the divalent organic group However, it is preferable that it is C6-C15.

In the present invention, by using a macromer or polymer having a plurality of polymerizable groups in the side chain as well as the terminal as the polymerizable compound, the generation density of the polymer chain formed by bonding to the resin layer is improved and uniform. And a high-density polymer layer is preferable.
For this reason, even when an electroless plating catalyst or a precursor thereof is attached to such a surface graft material, the adhesion density is improved and an excellent plating receptive region can be obtained. When a macromer or a polymer is used as the polymerizable compound, since a polymerizable group exists at a high density, if a polymerization initiator is allowed to coexist or is grafted using a known method using a high energy electron beam, Since the homopolymer described above is remarkably produced and the removability of the formed homopolymer is further reduced, it can be seen that the effect of the present invention is remarkable when such a polymerizable compound is used.

  From the viewpoint of the production method, when a polymerizable compound is brought into contact with the substrate surface by a coating method using a polymer, a polymer coating film having a uniform thickness is easily formed, which is necessary for monomer coating. Since there is no need for a coating solution protection cover to be applied, and the polymerizable compound can be uniformly contacted at an arbitrary thickness, the uniformity of the formed polymer is improved, and there is also an advantage of excellent manufacturing suitability. It is. For these reasons, in the production of a large area or a large amount, it is particularly useful in terms of production suitability to use a polymer (polymer compound) having a polymerizable double bond.

  Examples of the polymer (polymer compound) having a polymerizable double bond include a compound containing a carboxylic acid (carboxylate) described in JP-A No. 2003-118043, a compound containing a cyano group described in Japanese Patent Application No. 2007-146199, and the like. Can be used.

(B-2. Formation of photoreactive layer)
As a method of forming a photoreactive layer on a thermosetting resin layer or a thermoplastic resin layer, the substrate on which the resin layer is formed is immersed in a liquid composition containing a polymerizable compound or the like. However, in the case of the step (b), if the influence on the formed conductive pattern (circuit) is taken into consideration, the polymerizable compound is applied to the surface of the resin layer. Preferably, it is applied as it is or by applying a liquid composition containing it as a main component.

  The photoreactive layer is preferably formed in the absence of a compound having a polymerization initiating ability from the viewpoint of suppressing undesired formation of a homopolymer. That is, when the photoreactive layer is formed by a single polymerizable compound, naturally other compounds do not coexist, but the polymerizable compound is dissolved in a solvent or dispersed in a dispersion medium. In the case of using such a composition, it is necessary that the composition does not contain other compounds that can participate in a polymerization reaction such as a polymerization initiator.

  Therefore, in any of the dipping method and the coating method, the composition containing a polymerizable compound is preferably a composition comprising only the polymerizable compound and a solvent or dispersion medium as a main component. Even if it contains a compound, it is preferably limited to a surfactant or the like for the purpose of improving the physical properties of the liquid composition such as coating properties and surface properties, if desired.

The solvent used in the composition containing the polymerizable compound is not particularly limited as long as it can dissolve or disperse the main component polymerizable compound, but an aqueous solvent such as water or a water-soluble solvent is preferable. Further, a surfactant may be further added to the mixture or the solvent.
Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone and cyclohexanone, N, N-dimethylformamide, Examples thereof include amide solvents such as N, N-dimethylacetamide, acetonitrile and the like.

  The surfactant that can be added to the solvent as needed may be any that dissolves in the solvent. Examples of such surfactants include an anionic interface such as sodium n-dodecylbenzenesulfonate. Activators, cationic surfactants such as n-dodecyltrimethylammonium chloride, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate ( Examples of commercially available products include non-ionic surfactants such as trade name “Tween 20” and polyoxyethylene lauryl ether.

In addition, when forming a photoreactive layer with the apply | coating method, the application amount is preferably 0.1 to 10 g / m ^{2 in} terms of solid content, and particularly preferably 0.5 to 5 g / m ² .
Moreover, the film thickness of the formed photoreactive layer is 0.1 to 10 from the viewpoint of plating coverage.
The range is preferably (μm units), more preferably 0.5 to 5 μm.

<(C) A step of exposing the photoreactive layer in a pattern, generating a polymer formed by bonding with the resin layer in the exposed region, and forming a patterned polymer layer on the resin layer [(c ) Process] >>
In the step (c), the photoreactive layer formed in the step (b) is exposed in a pattern, and a polymer bonded to the resin layer is generated in the exposed region by a reaction such as surface graft polymerization. A polymer layer is formed.

(Surface graft polymerization)
The polymer (patterned polymer layer) formed by bonding to the resin layer in the present invention is produced using a means generally called surface graft polymerization.
Graft polymerization is a method of synthesizing a graft (graft) polymer by giving an active species on a polymer compound chain and further polymerizing another monomer for initiating the polymerization, and particularly giving an active species. When a polymer compound forms a solid surface, it is called surface graft polymerization.
In the present invention, radicals are generated from a region to which energy is imparted by exposure of the resin layer, and this radical reacts with the polymerizable compound to cause surface graft polymerization, so that at least one end is bonded to the resin layer. A polymer chain is formed.

(Pattern exposure)
In this step, pattern exposure is performed to produce a polymer formed on the resin layer and bonded to the outer resin layer.
Here, exposure for generating a polymer will be described.
As the active energy ray used for exposure, a commonly used mercury lamp, metal halide lamp, xenon lamp, chemical lamp, carbon arc lamp, etc. may be used, and a light emitting diode (LED), a semiconductor laser, a fluorescent lamp, etc. A light source may be used. Further, a light source such as a hot cathode tube, a cold cathode tube, an electron beam or an X-ray, an electromagnetic wave, or the like can be used.

  In the present invention, it is preferable to use a mercury lamp, LED, or semiconductor laser as the light source. The LED or semiconductor laser is characterized by its small size. In particular, LEDs have the advantages of long life, low calorific value, low power consumption, no generation of ozone, and immediate use when turned on. In addition, a light source of 365 nm ± 20 nm is advantageous in terms of cost, and has an advantage that an existing photopolymerization initiation system can be used.

When using a metal halide lamp, the lamp should be designed 10~1000W / cm ^2, it is preferable that the illuminance of ^1mW / cm ^{2 ~100W} / cm 2 at the media surface. The exposure energy ^is preferably ^{0.1mJ / cm 2 ~100J / cm 2} .

(developing)
After exposure as described above, washing with a developing solution is performed, unreacted polymerizable compounds are removed, and only the generated patterned polymer remains on the substrate.
By this development processing, unexposed regions and impurities are easily removed, and a high-definition graft polymer pattern corresponding to the exposure conditions is formed.

As the developer used to remove the unreacted photoreactive layer (the area where no polymer is formed), use alkaline water, a mixed solution of alkaline water and a water-soluble high-boiling organic solvent. Can do.
As the alkali, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate and the like can be used. As the water-soluble high-boiling solvent, alcohols such as 2-butoxyethanol, 2,2′-butoxymethoxyethanol, and 2,2′-butoxyethoxyethanol can be preferably used.
When used as a mixed solution, it is selected from water-soluble organic solvents having a boiling point of 100 ° C. or higher, 100 to 500 ml / l, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, sodium bicarbonate, etc. A mixed aqueous solution of 1 to 20 g / l of an alkaline component is preferred. By adding a water-soluble organic solvent having a boiling point higher than that of water to the developer, it is possible to prepare a developer that is nonflammable and exhibits higher developability than an alkali developer.

  The thickness of the patterned polymer layer is preferably in the range of 0.1 μm to 10 μm, and more preferably in the range of 0.5 μm to 5 μm. In addition, the film thickness of the resin composition layer relative to the film thickness of the polymer layer is preferably 1/3, more preferably 1/5 or less, from the viewpoint of thermocompression bonding and fine wiring formability.

In this way, it is possible to produce a graft polymer that is firmly bonded to the surface of the base material in a desired pattern on the surface of an arbitrary base material and that has excellent mobility. Such a graft polymer can be attached to various functional materials due to the polar functional groups and the like, and is useful for producing a material having a functional pattern.
In addition, the formation region of such a graft polymer has a polar group, or an interaction group with an electroless plating catalyst or a precursor thereof, so that it has excellent plating acceptability when performing electroless plating described later. It becomes an area | region which has.

In the conductive pattern forming method of the present invention, after the step (a), the step (b) and the step (c) are performed to form a plating catalyst-accepting pattern polymer layer, and then conductivity is imparted. (D) process, (e) process, and (f) process required for this are performed.
In the conductive pattern forming method of the present invention, after the polymer having a functional group with which the electroless plating catalyst or its precursor interacts is generated in the step (c), the polymer is formed in the patterned region. , (D) a step of applying an electroless plating catalyst or a precursor thereof, and (e) a step of forming a conductive pattern by performing an electroless plating step, (f) thermocompression bonding of the conductive pattern portion, The step of forming a conducting portion by electrically contacting the conductor portion and the substrate surface is sequentially performed.

  Hereinafter, the (d) process, the (e) process, and the (f) process in the conductive pattern forming method of the present invention will be described.

<(D) Step of Applying Electroless Plating Catalyst or its Precursor to Region Generated with Polymer Combined with Resin Layer [(d) Step >>
In step (d) in the conductive pattern forming method of the present invention, an electroless plating catalyst or a precursor thereof is applied to the region where the polymer pattern is formed.
When the graft polymer is generated on the substrate surface, the region where the polymer pattern is formed becomes the plating receptive region. For this reason, in the step (d), an electroless plating catalyst is selectively applied to the region where the polymer is formed in a pattern, and electroless plating is performed to form a conductive pattern. A pattern member is obtained.

  (D) As for the provision of the plating catalyst carried out in the step, the type of metal such as copper plating and nickel plating is not particularly limited, and a plating catalyst or precursor thereof that can be applied to generally known electroless plating, or A metal compound that can function as an electrode for electroplating may be added.

-Electroless plating catalyst-
The electroless plating catalyst used in the step (d) is mainly a zero-valent metal, and examples thereof include Pd, Ag, Cu, Ni, Al, Fe, and Co. In the present invention, Pd and Ag are particularly preferable because of their good handleability and high catalytic ability. As a method for fixing the zero-valent metal on the graft pattern (interactive region), for example, a functional group (interactive group) that interacts with the electroless plating catalyst (precursor) on the graft pattern, A technique is used in which a metal colloid whose charge is adjusted so as to interact is applied to the interactive region. In general, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent. The charge of the metal colloid can be adjusted by the surfactant or the protective agent used here. By interacting the metal colloid thus adjusted in charge with the interactive group of the graft pattern, Metal colloid (electroless plating catalyst) can be selectively adsorbed on the graft pattern.

-Electroless plating catalyst precursor-
The electroless plating catalyst precursor used in the step (d) can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. Mainly, metal ions of zero-valent metal used in the electroless plating catalyst are used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is the electroless plating catalyst is applied to the base material, and before being immersed in the electroless plating bath, it may be changed to a zero-valent metal by a separate reduction reaction and used as an electroless plating catalyst. The precursor may be immersed in an electroless plating bath and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath.

In fact, the metal ions that are electroless plating precursors are imparted to the graft pattern in the state of a metal salt and allowed to interact. The metal salt used is not particularly limited as long as it is dissolved in an appropriate solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / N} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions, and Ag ions and Pd ions are preferable in terms of catalytic ability.

  As a method for applying a metal colloid as an electroless plating catalyst or a metal salt as an electroless plating precursor onto a graft pattern, the metal colloid is dispersed in an appropriate dispersion medium, or the metal salt is added with an appropriate solvent. A solution containing dissolved and dissociated metal ions is prepared, and the solution is applied to the surface of the substrate on which the graft pattern exists, or the substrate having the graft pattern is immersed in the solution. Contacting a solution containing a metal ion to adsorb the metal ion to the interacting group of the graft pattern formation region using an ion-ion interaction or a bipolar-ion interaction; or The interaction region can be impregnated with metal ions. From the viewpoint of sufficient adsorption or impregnation, the metal ion concentration or metal salt concentration of the solution to be contacted is preferably in the range of 1 to 50% by mass, and in the range of 10 to 30% by mass. Is more preferable. Further, the contact time is preferably about 1 minute to 24 hours, more preferably about 5 minutes to 1 hour.

<(E) Step of performing electroless plating and forming a conductive layer by forming a metal layer on the surface and side surface of the patterned polymer layer [(e) step]>
In step (e), electroless plating is performed to form a conductive pattern.
As a method for performing electroless plating treatment, specifically, an electroless plating catalyst or an electrolysis plating catalyst is formed in a region where a patterned polymer is formed (a region where a polymer chain formed by at least a part of the polymer is bonded to a resin layer). By applying a precursor and performing electroless plating, a high-density metal film according to the pattern is formed, and a conductive pattern is obtained. The formed metal pattern exhibits excellent conductivity and adhesion.

-Electroless plating-
Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
The electroless plating in the step (e) is performed, for example, by rinsing the substrate on which the electroless plating catalyst is applied in a pattern to remove excess electroless plating catalyst (metal) and then immersing it in the electroless plating bath. To do. As the electroless plating bath to be used, a generally known electroless plating bath can be used.

  In addition, when the substrate provided with the electroless plating catalyst in a pattern is immersed in the electroless plating bath with the electroless plating catalyst precursor adsorbed or impregnated in the graft pattern, the substrate is washed with water. Excess electroless plating catalyst precursor (metal salt, etc.) is removed, and then immersed in an electroless plating bath. In this case, reduction of the precursor and subsequent electroless plating are performed in the electroless plating bath. As the electroless plating bath used in this embodiment, a generally known electroless plating bath can be used as described above.

The composition of a general electroless plating bath is as follows: 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included. In addition to these, the plating bath may contain known additives such as a plating bath stabilizer.
Copper, tin, lead, nickel, gold, palladium, and rhodium are known as the types of metals used in the electroless plating bath, and copper and gold are particularly preferable from the viewpoint of conductivity.

In addition, there are optimum reducing agents and additives according to the above metals. For example, a copper electroless plating bath contains Cu (SO ₄ ) ₂ as a copper salt, HCOH as a reducing agent, and a chelating agent such as EDTA or Rochelle salt as a copper ion stabilizer as an additive. The plating bath used for electroless plating of CoNiP includes cobalt sulfate and nickel sulfate as metal salts, sodium hypophosphite as a reducing agent, sodium malonate, sodium malate, and sodium succinate as complexing agents. It is included. Further, the electroless plating bath of palladium contains (Pd (NH ₃ ) ₄ ) Cl ₂ as metal ions, NH ₃ and H ₂ NNH ₂ as reducing agents, and EDTA as a stabilizer. These plating baths may contain components other than the above components.

The film thickness of the metal film formed in this way can be controlled by the concentration of the metal salt or metal ion in the plating bath, the immersion time in the plating bath, the temperature of the plating bath, etc. Is preferably 0.1 μm or more, and more preferably 1 μm or more.
Further, the immersion time in the plating bath is preferably about 1 minute to 3 hours, and more preferably about 1 minute to 1 hour.
By this electroless plating, a conductive film (metal film) is formed on the exposed portion of the patterned polymer layer formed in the step (d), that is, on the surface and side surfaces based on the plating catalyst, and the patterned conductive layer, That is, a conductive pattern is formed.

<(F) By heating the conductive pattern portion in the direction of the conductive substrate while heating the conductive pattern portion, the conductive layer on the side surface of the conductive pattern and the conductive substrate surface are passed through the conductive fine particles contained in the resin layer. Step of electrically contacting to form a conductive portion [step (f)]>
In the step (f), while heating the conductive pattern portion, pressure is applied in the direction of the conductive substrate (hereinafter, this operation is appropriately referred to as thermocompression bonding), and the conductor portion and the substrate surface are brought into electrical contact. , Forming a conduction part. As a thermocompression bonding method, a thermocompression bonding head can be used. The temperature is 90 ° C to 200 ° C, preferably 120 ° C to 180 ° C. The heating / pressurization time is 1 second to 500 seconds, preferably 5 seconds to 60 seconds. The pressure is 1 to 5 MPa, preferably 2 to 3 MPa.
(F) Before the step, a step of etching and removing the thermosetting resin layer or the thermoplastic resin layer other than the conductive pattern portion may be performed. In this case, as an etching method, dry etching using plasma using various gases, wet etching using an alkali solution, or the like can be used. In addition, when implementing the process of removing the resin layer containing an electroconductive particle in this way, the electroconductive particle contained in a resin layer may be a covering particle which has a metal particle and a metal layer on the outermost surface.
By this thermocompression bonding, the conductive layer side surface of the conductive pattern and the conductive base material are electrically contacted through the conductive particles to form a conductive portion. The formation of the conductive portion can be confirmed by measuring the resistance value between the wiring portion and the base material.

  FIG. 1 is a cross-sectional view schematically showing one embodiment of the conductive pattern of the present invention. As shown in FIG. 1, a conductive base material 14 typified by ITO is laminated on the surface of an insulating base material 12, and a resin layer 16 containing conductive particles 28 is bonded to the surface of the insulating base material 12. A patterned polymer layer 18 containing a polymer having a functional group that interacts with an electroplating catalyst or its precursor, and a conductive pattern in which the surface and side surfaces of the polymer layer 18 are covered with a conductive layer 20. Yes, this conductive layer 20 forms a wiring or the like in a pattern. As shown in FIG. 1, in the conductive pattern, the conductive layer 20 on the side surface of the polymer layer 18 and the conductive base material 14 are in electrical contact via the conductive particles 28 contained in the resin layer 16. The conduction part 26 is formed.

  The conductive pattern forming method of the present invention can be suitably used for forming a conductive wire in a display element. Hereinafter, an organic EL display device will be described as an example.

[Organic EL display device]
The organic EL display device of the present invention includes a conductive wire formed by the conductive pattern forming method of the present invention. Here, the conductive wires that can be formed by the conductive pattern forming method of the present invention include conductive wires such as auxiliary wiring for passive panels and TFT routing wiring for active panels.

  One aspect of the organic EL display device of the present invention includes at least an insulating substrate, a pixel electrode wiring provided on the insulating substrate, and an organic layer and a cathode layer sequentially stacked on the pixel electrode wiring. Thus, the auxiliary wiring connected to the pixel electrode wiring is formed by the conductive pattern forming method of the present invention. Hereinafter, the organic EL display device of the present invention will be described with reference to the drawings, taking the organic EL display device of this aspect as an example.

FIG. 2 is a top view showing a schematic configuration of the organic EL display device 10 of the present invention. The organic EL display device 10 is configured by laminating a plurality of pixel electrode wirings 14, an organic layer 22, and a plurality of cathode layers 24 in this order on an insulating substrate 12. The auxiliary wiring 20 is a wiring formed by the conductive pattern forming method of the present invention, and is configured to be connected to the pixel electrode wiring 14.
3 is a cross-sectional view taken along line AA in FIG.

  In the present invention, as shown in FIG. 3, the resin layer 16 and the patterned polymer layer 18 can be formed only in a necessary region on the pixel electrode wiring 14. In FIG. 3, the resin layer other than the conductive pattern portion (auxiliary electrode) 20 is removed by etching or development. Through the thermocompression bonding process, the auxiliary electrode 20 and the pixel electrode wiring 14 are in electrical contact with each other at the contact portion (conduction portion) 26 via the conductive particles 28 in the resin layer 16.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to these.

[Example 1]
<Base material>
A substrate in which ITO 14 having a film thickness of about 200 nm was attached to the glass substrate 12 by CVD was washed and dried with acetone and then distilled water, and then treated with a UV ozone cleaner for 10 minutes (substrate activation treatment). .

<Step of forming a thermosetting resin layer containing conductive particles>
A thermosetting resin composition having the following composition was prepared and spin-coated on the substrate 14 under the conditions of 300 rpm for 5 seconds and then 750 rpm for 20 seconds. After application, it was dried at 80 ° C. for 5 minutes.
Thereby, a thermosetting resin layer 16 having a film thickness of 0.5 μm was formed. The conductive particles 28 were produced by a method similar to the method described in Japanese Patent Application Laid-Open No. 2003-268346 (conductive particle size 0.1 μm).

(Thermosetting resin composition)
(A) Epoxy resin (Nippon Kayaku, NC3000, epoxy equivalent 275): 3.0 parts by mass (B) Aminotriazine novolac resin (Phenolite LA7052, manufactured by Dainippon Ink and Chemicals, non-volatile content 62% by mass,
Non-volatile component phenolic hydroxyl group equivalent 120): 0.71 part by mass (C) Phenoxy resin (non-volatile component 35% by mass, Toto Kasei Co., Ltd.)
YP-50EK35): 5.0 parts by mass (D) 2-ethyl-4-methylimidazole (manufactured by Wako Pure Chemical Industries): 0.03 parts by mass (E) cyclohexanone (manufactured by Wako Pure Chemical Industries): 154.3 masses Part (F) Photoradical generator: 0.58 parts by mass (Exemplary compound 15, x = 10, y = 90, molecular weight (Mw): 46000)
(E) Conductive particles (the above particles, particle size: 0.1 μm): 2.32 parts by mass

<Step of forming photoreactive layer>
[Application of polymer compound having polymerizable group]
The surface of the thermosetting resin composition layer 16 formed as described above has an acrylic group and a carboxyl group (interactive group) as a polymerizable compound, and has a polymerizable group and an interactive group in the side chain. A coating liquid composition 1 containing a polymer having the following formula (P-1, obtained by the following synthesis example) was spin-coated at 300 rpm for 5 seconds and then at 750 rpm for 20 seconds. After application, it was dried at 80 ° C. for 5 minutes.
As a result, a photoreactive layer having a thickness of 1.5 μm was obtained.

(Coating liquid composition 1)
-Polymer (P-1) having a polymerizable group and an interactive group in the side chain 3.1 g
・ Water 24.6g
1-methoxy-2-propanol 12.3 g

(Synthesis of polymer (P-1) having a polymerizable group and an interactive group in the side chain)
18 g of polyacrylic acid (average molecular weight 25,000) is dissolved in 300 g of dimethylacetamide (DMAC), and 0.41 g of hydroquinone, 19.4 g of 2-methacryloyloxyethyl isocyanate, 0.25 g of dibutyltin dilaurate, , And reacted at 65 ° C. for 4 hours. The acid value of the obtained polymer was 7.02 meq / g. Thereafter, the carboxyl group is neutralized with a 1 mol / l (1N) sodium hydroxide aqueous solution, ethyl acetate is added to precipitate the polymer, the polymer is washed well, and has a polymerizable group and an interactive group in the side chain. 18.4 g (P-1) was obtained.

<Polymer pattern formation process>
A pattern mask (NC-1, manufactured by Toppan Printing Co., Ltd.) was adhered to the photoreactive layer thus obtained, and a 1500 W high-pressure mercury lamp (UVX-02516S1LP01, manufactured by USHIO INC., Light intensity at 254 nm: 38 mW) / Cm ² ), and the whole surface was irradiated with light for 1 minute.
Then, after being immersed in a 1% by mass aqueous sodium carbonate solution for 5 minutes, it was washed with water to obtain a material in which a polymer layer 18 composed of a polymer formed by bonding with a resin layer was formed in a pattern on an ITO / glass substrate.

<Electroless plating catalyst application process>
The obtained substrate was immersed in a 1% by mass aqueous solution of silver nitrate (manufactured by Wako Pure Chemical Industries) for 1 minute, and then washed with distilled water. By this operation, silver nitrate as a plating catalyst is adsorbed on the interactive group of the polymer layer.
<Conductive pattern formation process>
(Electroless plating)
Then, when electroless plating was performed at 40 ° C. for 20 minutes in an electroless plating bath having the following composition, the metal layer 20 was formed on the surface (upper surface and side surfaces) of the polymer layer 18.

(Composition of electroless plating bath)
・ 86mL distilled water
・ ATS Ad Copper IW-A 5ml
・ ATS Ad Copper IW-M 8ml
・ ATS Adcopper IW-C 1ml
・ NaOH 0.22g
・ 2,2'-bipyridyl 0.2mg
PH of electroless plating bath: 12.67

<Etching process>
Using a plasma surface treatment apparatus (POEM manufactured by Shinko Seiki Co., Ltd.), the thermosetting resin composition layer 16 other than the conductive pattern 20 formation region was removed by etching.
<Thermocompression process>
Using a thermocompression bonding head, the conductive pattern portion is subjected to thermocompression bonding under conditions of a temperature of 170 ° C., a pressure of 3 MPa, and a time of 15 seconds, so that the ITO 14 and the conductive pattern 20 on the substrate can be electrically contacted. The part 26 was formed, and the conductive pattern member of Example 1 was obtained.

(Example 2)
Instead of the thermosetting resin composition used in Example 1, a polyester resin having a glass transition point Tg of 45 ° C. (manufactured by Unitika, UE3210) was used, except that the conductive particles of Example 1 were contained at the same concentration. In the same manner as in Example 1, a conductive pattern member of Example 2 was obtained.

(Example 3)
In Example 1, instead of the glass substrate used as the insulating substrate, a PEN substrate (polyethylene naphthalate: Teonex Q65FA manufactured by Teijin Ltd.) having a SiON film thickness of about 200 nm was used. Thus, the conductive pattern member of Example 3 was obtained.

Example 4
In Example 2, instead of the glass substrate used as the insulating substrate, a PEN substrate (polyethylene naphthalate: Teonex Q65FA manufactured by Teijin Ltd.) having a SiON film thickness of about 200 nm was used in the same manner as in Example 2. Thus, a conductive pattern member of Example 4 was obtained.

<Evaluation>
-Peel strength-
The peel strength between the conductive pattern portion and the substrate was measured for the conductive pattern members of Examples 1 to 4 thus obtained.
The peel strength was evaluated by conducting a cross-cut tape peel test in accordance with JISK5400 (1990 edition). The number of grids remaining after tape peeling out of 100 grids is shown. As a result, none of the conductive patterns was peeled off at all.

−Resolution−
About the resolution of the wiring pattern (conductive pattern) in the conductive pattern member of Example 1- Example 4, it measured with the Hitachi Science Systems Co., Ltd. electron microscope (MiniscopeTM-1000).
Moreover, the state of the metal layer surface of the formed electroconductive pattern was confirmed on these conditions.

  As a result of the measurement, it was confirmed that all the conductive patterns produced in Examples 1 to 4 had a line and space of 10 μm / 10 μm and a uniform pattern was formed. Further, as a result of observation of the surface and side surfaces, as shown in the model diagram of FIG. 1, the surface and side surfaces of the metal layer 20 are smooth and have no irregularities, and the upper surface thereof is parallel to the resin layer surface and has a uniform thickness. Therefore, it is evaluated that there is no variation in wiring resistance due to non-uniformity of the thickness of the conductive layer.

-Contact measurement method-
The confirmation of the contact was confirmed by measuring the contact resistance of the obtained conductive pattern. FIG. 4 is a plan view of the conductive pattern shown in FIG. As shown in FIG. 4, a conductive base material 14 represented by ITO is laminated on the surface of the insulating base material 12, and a conductive layer 20 is formed on the surface thereof. The resistance value was measured by measuring the resistance between measurement point A and measurement point B and the resistance between measurement point A and measurement point C shown in FIG. The measurement point A and the measurement point B are located at both ends on the metal layer (metal wiring portion) 20, and the measurement point C is a point close to one end portion of the metal layer 20 in the conductive substrate 14.
(Formula) Contact resistance = (resistance value between A and C) − (resistance value between A and B).
The resistance between the measurement points A and C represents the plating portion (metal layer) resistance + contact resistance, and the resistance between the measurement points A and B represents the metal layer resistance. Accordingly, (AC)-(AB) in the above formula represents contact resistance.
The resistance value was measured by a four-probe method using a surface resistance meter (Loresta-EP, model number MCP-T360, manufactured by Mitsubishi Chemical Corporation) in accordance with JIS K7194 (1994 edition).
These measurement results are shown in Table 1.

  As is apparent from the results shown in Table 1, the conductive pattern forming method of Examples 1 to 4 is excellent in peeling strength and resolution, has a uniform thickness and a smooth surface, and has little variation in wiring resistance. It was confirmed that a conductive pattern can be formed. Moreover, it was confirmed from the contact resistance values of Examples 1 to 4 that conduction was established between the metal layer 20 and the conductive base material 14 such as ITO.

[Example 5]
As shown below, an organic EL display device of Example 5 was produced. In addition, the code | symbol of each component of the organic electroluminescence display in the following description respond | corresponds to each code | symbol shown by FIG. 2 or FIG. 3, respectively.

<Production of substrate with pixel electrode wiring>
A pixel electrode wiring made of ITO (150 nm) was formed and patterned on a PEN substrate (polyethylene naphthalate: Teonex Q65FA manufactured by Teijin Limited) having a SiON film thickness of about 200 nm using a known technique. Specifically, (1) Sputtered ITO film formation → (2) Resist application → (3) Mask exposure → (4) Development → (5) Wet etching → (6) Resist stripping, by performing the above six steps A substrate with pixel electrode wiring formed by forming pixel electrode wiring made of ITO at a predetermined position was produced.

<Formation of auxiliary wiring>
After performing the base material activation process on the substrate with the pixel electrode wiring, each step of the conductive pattern forming method of the present invention is performed using the thermosetting resin composition and the photoreactive composition of Example 1. As a result, an auxiliary wiring having a cross section as shown in FIG. 3 was formed. Specifically, the pixel wiring electrode 14 is formed on the insulating substrate 12, and the substrate activation process is performed on the insulating substrate 12, and then a thermosetting resin composition layer is formed on the surface of the pixel wiring electrode 14. After the formation, a photoreactive layer is laminated, and then a desired pattern exposure is performed to form a polymer layer 18 having an interactive group between the resin layer 16 and the electroless plating catalyst, and the electroless plating is formed thereon. Went. Next, the thermosetting resin layer other than the conductive pattern portion was removed by etching with oxygen plasma. Thereafter, thermocompression bonding was performed under the conditions shown in Example 1 to form auxiliary wiring 20A.
In FIG. 3, a region where the side end portion of the formed auxiliary wiring 20 </ b> A and the pixel wiring electrode 14 </ b> A are in contact with each other is a contact portion 26.

<Production of organic EL element>
As shown in FIG. 3, a hole injection layer made of 2TNATA (film thickness 140 nm) and a hole made of NPD (film thickness 10 nm) are formed in the pixel region on the substrate 12 with the pixel electrode wiring 14A on which the auxiliary wiring 20A is formed. A transport layer, a light emitting layer made of Alq (thickness 30 nm) doped with 1% by mass of t (na) py, and an electron transport layer made of Alq (thickness 20 nm) are sequentially vacuum deposited using a shadow mask to form an organic layer. 22 was formed. Further, an electron injection layer (not shown) made of LiF (film thickness 0.5 nm) and a cathode 24 made of Al (film thickness 200 nm) were formed on the organic layer 22 by vacuum deposition using a shadow mask.
In FIG. 3, a region where the organic layer 22 and the cathode 24 are laminated on the surface of the pixel wiring electrode 14A is a pixel region in the organic EL element.

<Sealing>
Finally, the organic EL element was sealed by laminating a sealing film so as to cover the entire organic layer deposition area.
Thus, an organic EL display device 10 having a configuration as shown in FIG. 2 was produced.
This organic EL display device showed good display characteristics of green light emission. The drive voltage of the organic EL display device was 14V.

It is sectional drawing which shows the one aspect | mode of the electroconductive pattern of this invention. It is a schematic block diagram which shows the one aspect | mode of the organic electroluminescence display of this invention. It is sectional drawing along the AA line of the organic electroluminescent display apparatus shown in FIG. It is the top view which specified the measurement location of contact resistance in a conductive pattern.

Explanation of symbols

10 Organic EL display device 12 Insulating substrate 14 ITO (conductive substrate)
14A Pixel electrode wiring 16 Resin layer 18 Polymer layer 20 Metal wiring part 20A Auxiliary wiring 22 Organic layer 24 Cathode 26 Contact part (conduction part)
28 Conductive particles

Claims (14)

  Surface of a patterned polymer layer containing a resin layer containing conductive particles on a conductive substrate, and a polymer having a functional group that binds to the resin layer and interacts with an electroless plating catalyst or a precursor thereof And a conductive pattern in which the side surface is coated with a conductive layer, and the conductive layer on the side surface of the polymer layer of the conductive pattern and the conductive base material are electrically connected via the conductive particles contained in the resin layer. A conductive pattern member comprising a conductive portion in contact with the conductive pattern member.   2. The conductive pattern member according to claim 1, wherein the conductive particle is a conductive particle having a multilayer structure in which a resin particle is a nucleus and a conductive metal thin film layer is provided on a surface layer portion of the resin particle. .   3. The conductive pattern member according to claim 2, wherein the conductive particles having a multilayer structure are conductive particles having a three-layer structure in which an insulating layer is further provided on the surface of the conductive metal thin film layer.   The conductive pattern member according to claim 1, wherein the resin layer is a thermosetting resin layer containing an epoxy resin composition.   The conductive pattern member according to claim 4, wherein the epoxy resin composition contains a photoradical generator.   6. The conductive pattern member according to claim 5, wherein the photo radical generator is a polymer type photo radical generator.   The conductive pattern member according to claim 1, wherein the conductive substrate is a conductive substrate including a transparent conductive film.   The conductive pattern member according to claim 7, wherein the transparent conductive film contains tin oxide, indium oxide, zinc oxide, and a conductive polymer. (A) a step of forming a resin layer made of a thermosetting resin or a thermoplastic resin containing conductive particles on the conductive substrate;
(B) On the resin layer, a compound having a polymerizable double bond and a compound having a functional group that interacts with the electroless plating catalyst or its precursor, or a polymerizable double bond and no compound in the molecule. Forming a photoreactive layer containing a compound having an electroplating catalyst or a functional group that interacts with a precursor thereof;
(C) a step of exposing the photoreactive layer in a pattern, generating a polymer formed by bonding with the resin layer in the exposed region, and forming a patterned polymer layer on the resin layer;
(D) a step of applying an electroless plating catalyst or a precursor thereof to a region where a polymer bonded to the resin layer is generated;
(E) performing electroless plating, forming a metal layer on the surface and side surfaces of the patterned polymer layer to form a conductive pattern, and
(F) By pressing the conductive pattern portion in the direction of the conductive base material while heating, the conductive layer on the side surface of the conductive pattern and the conductive base material surface are passed through the conductive fine particles contained in the resin layer. And a step of forming a conductive portion by electrical contact.   10. The step of forming the resin layer (a) is a step of forming a semi-cured thermosetting resin layer containing conductive particles on a conductive substrate. A conductive pattern forming method.   The conductive pattern forming method according to claim 9 or 10, further comprising a step of activating the surface of the conductive substrate before the step (a) of forming the resin layer.   The conductive pattern formation according to any one of claims 9 to 11, further comprising a step of removing a resin layer other than the conductive pattern formation region by etching before the step (f). Method.   An organic EL display device comprising a conductive wire formed by the conductive pattern forming method according to claim 9.   An auxiliary wiring connected to the pixel electrode wiring is provided with at least an insulating substrate, a pixel electrode wiring provided on the insulating substrate, and an organic layer and a cathode layer sequentially stacked on the pixel electrode wiring. An organic EL display device, wherein the organic EL display device is an auxiliary wiring formed by the conductive pattern forming method according to any one of claims 9 to 12.

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