CN108781505A

CN108781505A - Conductive film covering and laser-induced thermal etching processing conductive paste

Info

Publication number: CN108781505A
Application number: CN201780016621.0A
Authority: CN
Inventors: 江口宪; 江口宪一; 坂本康博
Original assignee: Toyobo Co Ltd
Current assignee: Dongyang Textile Mc Co ltd
Priority date: 2016-03-17
Filing date: 2017-03-02
Publication date: 2018-11-09
Anticipated expiration: 2037-03-02
Also published as: WO2017159381A1; TWI710041B; CN108781505B; KR102353074B1; JP7056552B2; TW201735219A; JPWO2017159381A1; KR20180121522A

Abstract

The conductive film covering that a kind of laser-induced thermal etching width is narrow even the present invention provides, complex pattern as laser-induced thermal etching distance also can inhibit broken string, the laser-induced thermal etching processing applicability of the generation of short circuit is excellent.By the present invention in that with containing macromolecule adhesive resin, average grain diameter be at least 0.3 μm or more, 6 μm of metal powder, organic solvent and preferred average grain diameters below are 5nm or more, the conductive paste of 200nm silica below or carbon particle, a diameter of 50nm or more, 3000nm inorganic ion scavenger particle below, the annular recess defect on overlay film surface is reduced, accordingly by laser-induced thermal etching can form L/S=50/50 μm of glass-coated microwire below.

Description

Conductive film covering and laser-induced thermal etching processing conductive paste

Technical field

The present invention relates to the manufacturing methods of the high conductive pattern of the configuration density that can manufacture in-plane and can Suitable for the conductive paste of the manufacturing method, the overlay film made from electrocondution slurry (or film).In more detail, the present invention relates to And it is available for, by the part for removing conductive film covering (or conductive membrane) by exciting light light beam, being put down accordingly The conductive film covering of the high conductive pattern of configuration density in face direction.Typically, conductive pattern of the invention can be used for The electrode loop wiring of bright touch panel.

Background technology

In recent years, it is the electronics device for carrying transparent touch panel of representative with mobile phone, laptop, e-book etc. The high performance of tool is sharp developing with miniaturization.In order to reach high performance and the miniaturization of these electronic equipments, remove Require the miniaturization of electronic unit mounted, high performance, integrated level raising outside, also require these electronic unit phases The densification of inter-engaging electrode loop wiring.As the mode of transparent touch panel, in addition to the quantity of electrode loop wiring Outside few resistive film mode, the universal of the electrostatic capacity of the increasing number of electrode loop wiring is also hastily pushing away in recent years Into from this point of view, consumingly requiring the densification of electrode loop wiring.In addition, in order to show that picture becomes Bigger, and due to the requirement in commodity design has and wants the frame portion that electrode loop wiring is configured becoming narrower to want It asks, from this point of view, also requires the densification of electrode loop wiring.In order to meet requirements above, seeking can To be performed more than the technology of the arranged in high density of previous electrode loop wiring.

The configuration density of the electrode loop wiring of the frame portion of the transparent touch panel of resistive film mode is as follows：Plane side To line and the width of spacing be respectively 200 μm of (hreinafter referred to as L/S=200/200 μm) above degree, it is previous to implement to pass through The silk-screen printing of conductive paste forms such configuration density.In the touch panel of electrostatic capacity, then the requirement of L/S For 100/100 μm or so hereinafter, being further 50/50 μm or less of situation there is also L/S is required, based on silk-screen printing Becoming the situation for being difficult to cope with step by step in electrode loop wiring formation technology.

An example that the candidate of technology is formed as the electrode loop wiring for substituting silk-screen printing, can enumerate photoetching process (photolithography method).If using photoetching process, it is 50/50 μm of filament below that can also be adequately formed L/S. However, there are also problems in photoetching process.Photolithographic most typical example is the gimmick using photonasty resist, it is general and Speech is coated with photonasty resist on the copper foil position of the surface substrate after forming copper foil layer, passes through photomask or laser direct-writing Deng method by desirable pattern exposure, carry out the development of photonasty resist, then, will be desired by using chemicals Pattern other than copper foil position dissolving remove, to form the thread pattern of copper foil.Therefore, it is born by the environment that liquid waste processing is brought Lotus is big, and in addition process is miscellaneous, and it is all to aoxidize bad order generated etc. there are the angle of production efficiency, the angle of cost, by copper foil More problems.

In photoetching process, also there is the mode without using photonasty resist, for example, disclosing following skills in patent document 1,2 Art：Dry coating is formed using conductive paste, direct write is carried out with laser to it, makes the part being irradiated with a laser fixing in base Material, development remove irradiated portion, form the technology of desirable pattern.If such method, with general photoetching process phase Than, do not use photonasty resist the case where, process is simplified, but with the previously known photoetching process using photonasty resist Similarly, the developing procedure of wet technique is necessary, thus there are problems that development waste liquid processing, additionally, there may be problems with Point：Due to using the silver powder of frit (glass frit) or nano-scale as the ingredient of conductive paste, in firing process In, the problem of needing 400 DEG C or more of high temperature, needing very big energy and workable base material be limited to can be subjected to 400 DEG C with On high temperature in firing process substance the problem of.In addition have to, process is complicated, and production efficiency is inappropriate.

According to above-mentioned condition, as the candidate an example for replacing the electrode loop wiring of silk-screen printing to form technology, patent Method, the institute that a part for conductive film covering is removed by exciting light light beam in document 3, patent document 4 disclosed in technology The laser-induced thermal etching construction method of meaning attracts attention in recent years.If using laser-induced thermal etching construction method, can also be adequately formed L/S is 50/50 μm of filament below.Laser-induced thermal etching construction method refers to (claiming the layer comprising adhesive resin and conductive powder body later For conductive membrane) it is formed in insulating properties base material, the construction for being removed its part from insulating properties base material by laser irradiation Method.

The requirement strong tendency of the further graph thinning of laser-induced thermal etching construction method in by etched width constriction be L/S =30/30 μm, 20/20 μm, 15/15 μm.Further, it due to the large screen of touch panel, is removed by laser-induced thermal etching Go the distance of film also elongated, the requirement performance required by laser-induced thermal etching processing conductive paste increasingly increases, so far, By the broken string of the circuit of non-showing, short circuit band Lai bad point become big problem, seeking to improve.In order to be lost by laser Construction method is carved to obtain the glass-coated microwire of high-quality, the quality of the conductive film covering before laser-induced thermal etching is most important, much less Conductive paste itself, even printing dry solidification process also must be adequately managed.

Existing technical literature

Patent document

Patent document 1：Japanese Patent Laid-Open 2010-237573 bulletins

Patent document 2：Japanese Patent Laid-Open 2011-181338 bulletins

Patent document 3：Japan Patent Patent 2012-161485 bulletins

Patent document 4：Japanese Patent Laid-Open 2014-2992 bulletins

Invention content

Problem to be solved by the invention

Even complex pattern as the purpose of the present invention is to provide laser-induced thermal etching width narrow, laser-induced thermal etching distance Also can inhibit by the broken string in circuit, short circuit band Lai undesirable laser-induced thermal etching processing electrocondution slurry.The purpose of the present invention is realities Now have to obtain the conductive film covering of the required characteristic of high-quality glass-coated microwire in laser-induced thermal etching construction method.

The means solved the problems, such as

After further investigation, it was found that the laser-induced thermal etching processing for being most suitable for laser-induced thermal etching construction method is used Conductive film covering.That is, the present invention includes following composition.

[1] a kind of conductive film covering, which is characterized in that by the conductive composition for including conductive filler and adhesive resin In the conductive film covering of composition, be present in 50 μm of the diameter annular recess defect below on overlay film surface is 50 there are density A/cm²Below.

[2] according to the conductive film covering described in [1], which is characterized in that in the conductive film covering, the portion of annular recess is not present The surface roughness Ra divided is 0.1 or more, 1.0 μm or less.

[3] according to the conductive film covering described in [1] or [2], which is characterized in that the average film thickness of the conductive film covering is 2 μm Above, 20 μm or less.

[4] conductive film covering according to any one of [1]~[3], which is characterized in that the conductive composition at least contains To have average grain diameter be 0.3 μm or more, 6 μm of Argent grains below and average grain diameter are 5nm or more, 200nm titanium dioxides below Silicon particle, macromolecule adhesive resin, the conductive composition are substantially free of solvent.

[5] conductive film covering according to any one of [1]~[3], which is characterized in that the conductive composition at least contains To have average grain diameter be 0.3 μm or more, 6 μm of Argent grains below and average grain diameter are 5nm or more, 200nm carbon particles below, Macromolecule adhesive resin, the conductive composition are substantially free of solvent.

[6] conductive film covering according to any one of [1]~[3], which is characterized in that the conductive composition at least contains To have average grain diameter be 0.3 μm or more, 6 μm of Argent grains below and average grain diameter are 50nm or more, 3000nm ions below Agent for capturing particle, macromolecule adhesive resin, the conductive composition are substantially free of solvent.

[7] a kind of forming method of electric wiring, which is characterized in that have and appointed to remove in [1]~[6] by exciting light light beam The process of a part for conductive film covering described in one.

[8] a kind of laser-induced thermal etching processing conductive paste, which is characterized in that at least contain macromolecule adhesive resin (A), average grain diameter is 0.3 μm or more, 6 μm of metal powders (B) below, organic solvent (C) and average grain diameter be 5nm or more, 200nm silica dioxide granules below (D).

[9] according to the laser-induced thermal etching processing conductive paste described in [8], which is characterized in that described adhesive resin (A) is choosing 1 in autopolyester resin, polyurethane resin, epoxy resin, phenoxy resin, ethylene chloride resin and cellulose derivative resin Kind or mixture of more than two kinds.

[10] according to the laser-induced thermal etching processing conductive paste described in [8] or [9], which is characterized in that described adhesive resin (A) number-average molecular weight is 5,000~60,000, and the glass transition temperature of described adhesive resin (A) is less than 120 DEG C.

[11] the laser-induced thermal etching processing conductive paste according to any one of [8]~[10], which is characterized in that described molten Agent is the mixture for 2 kinds of solvents that at least boiling point is different, and the boiling point for accounting for the 1st solvent of 45~90 mass % of whole quantity of solvent is 200 DEG C or more, 270 DEG C hereinafter, the 2nd solvent boiling point than the 1st solvent 10 DEG C of low boiling point or more, for whole quantity of solvent 55~ 10 mass %.

[12] the laser-induced thermal etching processing conductive paste according to any one of [8]~[11], which is characterized in that described viscous The acid value of mixture resin (A) is less than 200 equivalent/10⁶g。

[13] the laser-induced thermal etching processing conductive paste according to any one of [8]~[12], which is characterized in that per 1.0g 15 μm or more of coarse Argent grain is 100 or less in slurry.

[14] a kind of laser-induced thermal etching processing conductive paste, which is characterized in that at least contain average grain diameter be 0.3 μm with Upper, 6 μm of metal powders (B) below and average grain diameter are 5nm or more, 200nm carbon particle below (E), polymer binder Resin (A), solvent (C).

[15] according to the laser-induced thermal etching processing conductive paste described in [14], which is characterized in that described adhesive resin (A) is In polyester resin, polyurethane resin, epoxy resin, phenoxy resin, ethylene chloride resin and cellulose derivative resin One kind or two or more mixture.

[16] according to the laser-induced thermal etching processing conductive paste described in [14] or [15], which is characterized in that described adhesive tree The number-average molecular weight of fat (A) is 5,000~60,000, and the glass transition temperature of described adhesive resin (A) is less than 120 DEG C.

[17] the laser-induced thermal etching processing conductive paste according to any one of [14]~[16], which is characterized in that described Solvent (C) is the mixture for 2 kinds of solvents that at least boiling point is different, accounts for the 1st solvent of 45~90 mass % of whole quantity of solvent Boiling point be 200 DEG C or more, 270 DEG C hereinafter, the 2nd solvent boiling point than the 1st solvent 10 DEG C of low boiling point or more, for whole quantity of solvent 55~10 mass %.

[18] the laser-induced thermal etching processing conductive paste according to any one of [14]~[17], which is characterized in that described The acid value of adhesive resin (A) is less than 200 equivalent/10⁶g。

[19] the laser-induced thermal etching processing conductive paste according to any one of [14]~[18], which is characterized in that every 15 μm or more of coarse Argent grain is 100 or less in 1.0g slurries.

[20] a kind of laser-induced thermal etching processing conductive paste, which is characterized in that at least contain：

Average grain diameter be 0.3 μm or more, 6 μm of Argent grains (A) below and

Average grain diameter be 5nm or more, 200nm carbon below (E) or silica dioxide granule (D),

Average grain diameter is 0.1 μm or more, 3 μm of inorganic particles (H) below,

Macromolecule adhesive resin (A),

Solvent (C).

[21] according to the laser-induced thermal etching processing conductive paste described in [20], which is characterized in that described adhesive resin (A) is In polyester resin, polyurethane resin, epoxy resin, phenoxy resin, ethylene chloride resin and cellulose derivative resin One kind or two or more mixture.

[22] according to the laser-induced thermal etching processing conductive paste described in [20] or [21], which is characterized in that described adhesive tree The number-average molecular weight of fat (A) is 5,000~60,000, and the glass transition temperature of described adhesive resin (A) is less than 120 DEG C.

[23] the laser-induced thermal etching processing conductive paste according to any one of [20]~[22], which is characterized in that described Solvent is the mixture for 2 kinds of solvents that at least boiling point is different, accounts for the boiling point of the 1st solvent of 45~90 mass % of whole quantity of solvent It is 200 DEG C or more, 270 DEG C hereinafter, the boiling point of the 2nd solvent is the 55 of whole quantity of solvent than 10 DEG C of the low boiling point or more of the 1st solvent ~10 mass %.

[24] the laser-induced thermal etching processing conductive paste according to any one of [20]~[23], which is characterized in that described The acid value of adhesive resin (A) is less than 200 equivalent/10⁶g。

[25] the laser-induced thermal etching processing conductive paste according to any one of [20]~[24], which is characterized in that every 15 μm or more of coarse Argent grain is 100 or less in 1.0g slurries.

The effect of invention

The present invention relates to laser-induced thermal etching processing conductive film coverings.The inventors discovered that：It will be coated in use laser The dry so-called laser-etching process being partially removed in the silver paste overlay film of base material, when carrying out the exploitation of glass-coated microwire formation technology, Specific pattern is observed in overlay film performance, it was found that：The place that glass-coated microwire breaks after laser-induced thermal etching, passes through institute in laser When stating specific pattern part, laser generating part dispersion is penetrated, by pulp layer ablation (ablation) to the line width for intending to cut originally More than, result leads to the broken string of glass-coated microwire.The specific pattern is made of the protrusion of annular recess part and ring center.In this way Pattern (hereinafter referred to as annular recess) refer to that pulp surface layer first becomes slowing down dry from constant rate of drying in slurry dried coating film Dry state, solvent are closed in the path of volatilization inside the pulp layer, by in pulp layer pressure get higher due to slurry table Face layer is lifted and the pattern that generates.

The drying of conductive paste overlay film is, by the not changed inorganic particle of direct physical property in the drying process, with The changed adhesive resin as decentralized medium of physical property, the compound system with solvent composition in the drying process.In this way In the case of, the volatilization of the solvent in falling rate of drying region, inorganic particle while by by being spread in decentralized medium layer The influence of the drying obstacle of accumulation and generation, so solvent passes through elongated to the apparent film thickness in drying path of overlay film or more.

Therefore, it is after making to reach falling rate of drying state to reduce as the first method of the annular recess defect of the application project Drying condition relents, at low temperature through fully prolonged dry.By such method, it may be implemented as mesh of the present invention Annular recess defect is few, conductive film covering of laser-induced thermal etching excellent in workability.

On the other hand, extending drying time, this will produce problem in productivity.The inventors discovered that：By existing in advance The ingredient for being easy to form dry path during falling rate of drying is added in electrocondution slurry composition, can be done accordingly not reducing to slow down In the case of drying temperature in dry region, the conductive film covering with better quality is realized.

In the present invention, separately added except conductive particle, average grain diameter is 5nm or more, 200nm silica below Grain, average grain diameter are 5nm or more, 200nm carbon particle below, and average grain diameter is that 50nm or more, 3000nm ion below are caught Agent particle is caught, they form desmachyme in the dry coating of slurry, create the path of the solvent volatilization in pulp layer, have Promote the effect of diffusion.It is further preferred that by using the mixed solvent of specified conditions is met as solvent, the volatilization of solvent Further promoted, as a result, even if becoming if the movement of solvent after slurry film reaches falling rate of drying steady.It is logical The such method of combination is crossed, annular recess can be reduced, can obtain and be processed by L/S=50/50 μm of laser-induced thermal etching below It can inhibit the undesirable suitable conductive film covering of broken string in circuit in the pattern of formation.

In addition, in this composition, residual solvent is difficult to remain inside film, as a result, adaptation is modified.Further, since energy Prevent in advance along in laser-induced thermal etching residual solvent drastically volatilize distribute wash away (flushing), so can be further Positive effect is generated to productivity.

Description of the drawings

[Fig. 1] be the annular recess generated in conductive membrane by silver paste silk-screen printing and after being allowed to dry based on The reflected image of laser microscope, concave-convex picture, cross section profile.

[Fig. 2] is the schematic diagram of laser-induced thermal etching flexibility (adaptability) of operation evaluation test piece.

Symbol description

1a, 2a, 3a, 4a are respectively：Terminal 1a, terminal 2a, terminal 3a, terminal 4a

1b, 2b, 3b, 4b are respectively：Filament 1b, filament 2b, filament 3b, filament 4b

1c, 2c, 3c, 4c are respectively：Terminal 1c, terminal 2c, terminal 3c, terminal 4c

Specific implementation mode

The conductive film covering of the present invention, is made of the conductive composition containing conductive filler and adhesive resin, special Sign is that be present in 50 μm of the diameter annular recess defect below on overlay film surface is 50/cm there are density²Hereinafter, excellent Selection of land, in the conductive film covering, there is no annular recess part surface roughness Ra be 0.1 or more, 1.0 μm with Under, it is further preferred that the average film thickness of conductive film covering is 2 μm or more, 20 μm or less.

An example of annular recess defect in the present invention is as shown in Figure 1.About annular recess defect, film thickness is from the portion that surrounding reduces Divide and form ring-shaped, there is the section morphology of the volcano caldera (caldera) shape for the central uplift surrounded by ring.Although still Do not observe the process for the defect for generating such form in detail, but due to the unseasoned overlay film after just terminating in printing It is not observed in surface, so it is regarded as the defect generated in the drying process of conductive film covering.

Laser-induced thermal etching construction method refers to being obtained by being removed by the coating drying of conductive paste with laser ablation Conductive film covering unnecessary portion come the method that forms glass-coated microwire.There is " bubble impression " in the film before laser-induced thermal etching As " holiday " etc., when the defect that conductive film covering is not present for part, it can easily understand that the part can become etching Disconnection defect afterwards.Although annular recess defect is the bigger bumps of film coated surface, it is not necessarily required to exist and leads The part that electric overlay film is completely absent.Nevertheless, after the existing part of annular recess defect easily becomes laser-induced thermal etching processing Glass-coated microwire broken string.

Such phenomenon is considered as being caused by following situations：The central spud of annular recess defect is recessed by the ring-type of surrounding It falls into, half adiabatci condition is placed in film, so generating the savings of heat in center portion, cause abnormal ablation (ablation)。

Therefore, in order to obtain good laser-induced thermal etching, the number of annular recess defect present in conductive film covering is few Person is excellent, and there are density to be necessary for 50/cm²Hereinafter, preferably 20/cm²Hereinafter, further preferably 8/cm²With Under, it is preferably separately 3/cm²Below.

In addition, in the present invention, the surface roughness Ra of the part that annular recess is not present be preferably 0.1 or more, 1.0 μm hereinafter, Further preferably 0.1 or more 0.8 μm hereinafter, further preferably 0.1 μm or more 0.6 μm or less.

In addition, the present invention conductive film covering average film thickness be 2 μm or more, 20 μm hereinafter, preferably 3 μm or more, 14 μm with Under, further preferably 4 μm or more 11 μm or less.

The conductive film covering that the annular recess defect of the present invention is few can be realized by following methods：Will contain conductive filler with The conductive paste of adhesive resin and solvent at low temperature and by fully for a long time, such as 60 DEG C~100 DEG C or so, 60 Minute~under conditions of 300 minutes or so, it is allowed to dry solidification, however, in actual manufacturing process, in the dry of electrocondution slurry Such long-time is spent during dry, and this is virtually impossible to.

In the present invention, by any means in (1) at least as follows~(3), it can obtain as the present invention's The few conductive film covering of the annular recess defect of purpose.

(1) using at least average grain diameter be 0.3 μm or more, 6 μm of Argent grains below and average grain diameter be 5nm or more, 200nm silica dioxide granules below, the also method of the conductive paste containing solvent except macromolecule adhesive resin；

(2) using at least average grain diameter be 0.3 μm or more, 6 μm of Argent grains below and average grain diameter be 5nm or more, 200nm carbon particles below, the also method of the conductive paste containing solvent except macromolecule adhesive resin；

(3) using at least average grain diameter be 0.3 μm or more, 6 μm of Argent grains below and average grain diameter be 50nm or more, 3000nm ion capturing agent particles below, the also method of the conductive paste containing solvent except macromolecule adhesive resin.

The electrocondution slurry of the present invention at least contains：

(A) macromolecule adhesive resin,

(B) average grain diameter be 0.3 μm or more, 6 μm of metal powders below,

(C) organic solvent,

(D) average grain diameter is 5nm or more, 200nm silica dioxide granule below.In this composition, silica dioxide granule is in slurry Desmachyme is formed in dry coating, has the function of promoting the solvent volatilization in pulp layer.It is further preferred that by using Meet the mixed solvent of specified conditions as solvent, the volatilization of solvent is further promoted, as a result, even if being applied in slurry After film reaches falling rate of drying, the movement of solvent also becomes steady.As a result, annular recess is reduced, can inhibit to pass through L/S=50/ The broken string that circuit in the pattern to be formed is processed in 50 μm of laser-induced thermal etchings below is bad.In addition, in this composition, residual solvent is in film Inside is difficult to remain, as a result, adaptation is modified.

The electrocondution slurry of the present invention at least contains：

At least average grain diameter be 0.3 μm or more, 6 μm of metallic particles (B) below,

Average grain diameter be 5nm or more, 200nm carbon particle below (E),

Macromolecule adhesive resin (A),

Organic solvent (C).In this composition, carbon particle forms desmachyme in dry coating, has molten in promotion pulp layer The effect of agent volatilization.It is further preferred that by using the mixed solvents of specified conditions is met as solvent, the volatilization of solvent into One step is promoted, as a result, even if becoming if the movement of solvent after slurry film reaches falling rate of drying steady.As a result, Annular recess is reduced, and can inhibit the broken string that circuit in the pattern to be formed is processed by L/S=50/50 μm of laser-induced thermal etching below It is bad.In addition, in this composition, residual solvent is difficult to remain inside film, as a result, adaptation is modified.

The electrocondution slurry of the present invention at least contains：

(B) average grain diameter be 0.3 μm or more, 6 μm of Argent grains below, and

(G) average grain diameter be 5nm or more, 200nm carbon particle below or silica dioxide granule,

(H) average grain diameter be 0.1 μm or more, 3 μm of inorganic particles below,

(A) macromolecule adhesive resin,

(E) solvent.In this composition, in addition to (G) carbon or silica dioxide granule, (H) average grain diameter is 0.1 μm or more, 3 μm or less Inorganic particle also form desmachyme in the dry coating of slurry, have the function of promote pulp layer in solvent volatilization. It is further preferred that by using the mixed solvents of specified conditions is met as solvent, the volatilization of solvent is further promoted, As a result, even if becoming if the movement of solvent after slurry film reaches falling rate of drying steady.As a result, annular recess is reduced, The broken string for processing circuit in the pattern to be formed by L/S=50/50 μm of laser-induced thermal etching below can be inhibited bad.In addition, this In composition, residual solvent is difficult to remain inside film, as a result, adaptation is modified.Further, since preventing in advance adjoint The residual solvent in laser-induced thermal etching drastically to volatilize washing away of distributing, so positive effect can be further generated to productivity Fruit.

The type of adhesive resin (A) in the present invention, is not particularly limited as long as thermoplastic resin, can enumerate Go out polyester resin, epoxy resin, phenoxy resin, (alcohol) butyral resin (butyral resin), polyamide, polyamide Imide resin, polycarbonate resin, polyurethane resin, phenol resin (phenol resin), acrylic acid (ester) resinoid (acrylic resin), polystyrene, Styrene And Chloroalkyl Acrylates (ester) resinoid, styrene-butadiene copolymer, phenol resin, Polyethylene-based resin, polycarbonate-based resin, phenol resin, alkyd resin (alkyd resin), styrene -- acrylic acid (ester) class Resin, styrene butadiene copolymers resin, polysulfone resin, polyethersulfone resin, vinyl chloride-vinyl acetate copolymer resins, second Alkene-vinyl acetate co-polymer, polystyrene, organic siliconresin (silicone resin), fluorine resin etc., these resins can It is used alone or as mixture of more than two kinds.Wherein, be preferably selected from polyester resin, polyurethane resin, epoxy resin, One kind or two or more mixture in phenoxy resin, vinyl chloride resin, cellulose derivative resin.In addition, as adhesive Resin, more preferably in these resins, using polyester resin, contain polyester component as copolymer composition polyurethane resin (with Be sometimes referred to as polyester polyurethane resin down), epoxy resin, at least one or more in phenoxy resin.

Using polyester resin as the present invention in adhesive resin the advantages of one of be：The degree of freedom of MOLECULE DESIGN It is high.The dicarboxylic acids and diol component for constituting polyester resin can be selected, so that copolymer composition is freely changed, in addition, functional group is attached It is added in strand or molecular end is also easy.Therefore, the vitrifying that can suitably adjust obtained polyester resin turns Temperature, and with the resin properties such as the compatibility of other compositions added in base material and conductive paste.

The dicarboxylic acids used as the copolymer composition that can be used as the polyester resin as the adhesive resin in the present invention Example, aromatic dicarboxylic acids, the ambers such as terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,6- naphthalene dicarboxylic acids can be enumerated The carbon numbers 12 such as aliphatic dicarboxylic acids, the dimeric dibasic acids such as amber acid, glutaric acid, adipic acid, decanedioic acid, dodecanedicarboxylic acid, azelaic acid~ 28 binary acid (dibasic acid), Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,3- cyclohexane dicarboxylic acids, 1,2- cyclohexane dicarboxylic acids, 4- methylhexahydrophthalic anhydrides, 3- methylhexahydrophthalic anhydrides, 2- methylhexahydrophthalic anhydrides, dicarboxyl hydrogen It is alicyclic to change bisphenol-A, dicarboxyl A Hydrogenated Bisphenol A S, dimeric dibasic acid, hydrogenated dimer acids, hydrogenation naphthalene dicarboxylic acids, tricyclodecane-dicarboxylic acid etc. The hydroxycarboxylic acids such as dicarboxylic acids, hydroxybenzoic acid, lactic acid.In addition, in the range of not damaging invention effect, it can be by trimellitic acid The unsaturated dicarboxylics the such as more than ternarys such as acid anhydride, pyromellitic dianhydride carboxylic acid, fumaric acid, and/or 5- sulfo isophthalate sodium salts Dicarboxylic acids Deng the alkali containing Sulfonic acid metal is used in combination as copolymer composition.

The polyalcohol used as the copolymer composition that can be used as the polyester resin as the adhesive resin in the present invention Example, can enumerate ethylene glycol, propylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, neopentyl glycol, 1,6- oneself Glycol, 3- methyl-1s, 5- pentanediols, 2- methyl-1s, 5- pentanediols, 2- methyl-1,3-propanediols, 2,2- diethyl -1,3- third The aliphatic diols such as glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,9- nonanediols, 1,10- decanediols, 1,4- hexamethylenes two The alicyclic diols such as methanol, 1,3- cyclohexanedimethanols, 1,2- cyclohexanedimethanols, dimer diols (dimer diol).This It outside, can be by trimethylolethane, trimethylolpropane, glycerine, pentaerythrite, poly- in the range of not damaging invention effect The polyalcohols more than ternarys such as glycerine is used in combination as copolymer composition.

The polyester resin used as the adhesive resin in the present invention, from adaptation, with other resins Compatibility and thermal shock resistance etc. from the point of view of, among the whole sour components for constituting the polyester resin, aliphatic two The preferred copolymerization of carboxylic acid has 10 moles of % or more, more preferable 20 moles of % or more, further preferred 30 moles of % or more.In aromatic series When the copolymerization ratio of dicarboxylic acid component is excessively high, the glass transition temperature of obtained polyester resin becomes 60 DEG C or more, exists Occur by with resin compatibility deteriorate caused by storage stability deterioration and laser-induced thermal etching process linearity The possibility that adaptation of the conductive membrane decline, obtained after laser-induced thermal etching declines.

As the adhesive resin in the present invention, polyurethane resin and preferred embodiment are used.With polyester resin The case where it is identical, about polyurethane resin, the copolymer composition of composition polyurethane resin be used as by selecting ingredient appropriate, separately into Row functional group is attached in strand or molecular end, can suitably adjust accordingly glass transition temperature, with base material and lead The resin properties such as the compatibility of other ingredients added in electrical slurry.

It about the copolymer composition of polyurethane resin, is not particularly limited, but from the degree of freedom of design, moisture-proof heat type, durable Property maintain angularly consider, it is preferable to use polyurethane resin of the polyester polyol as copolymer composition.It is more as the polyester The suitable example of first alcohol can enumerate among the polyester resin that the adhesive resin in can be used as the present invention uses Polyalcohol.

The polyurethane resin used as the adhesive resin in the present invention, such as polyalcohol and polyisocyanic acid can be passed through The reaction of ester obtains.As the polyisocyanates that the copolymer composition that can be used as the polyurethane resin uses, 2 can be enumerated, 4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, to phenylene vulcabond, 4,4 '-diphenylmethane diisocyanates Ester, metaphenylene diisocyanate, 3,3 '-dimethoxy-4 's, 4 '-biphenylene diisocyanates, 2,6- naphthalene diisocyanates, 3,3 '-dimethyl -4,4 '-biphenylene diisocyanates, 4,4 '-diphenylene diisocyanate, 4,4 '-diisocyanate two Phenyl ether, 1,5- naphthalene diisocyanates, m xylene diisocyanate, isophorone diisocyanate, two isocyanide of tetramethylene Acid esters, hexamethylene diisocyanate, toluene di-isocyanate(TDI) etc. can be aromatic diisocyanate, aliphatic diisocyanate It is arbitrary in ester and alicyclic diisocyanate.It, can will be more than ternary different in addition, within the scope of the effect of the invention Cyanate esters are used in combination as copolymer composition.

In the polyurethane resin used as the adhesive resin in the present invention, as needed it is copolymerizable have can with it is different The compound of the functional group of polyisocyanate reactant.Can be tool as the functional group that can be reacted with isocyanates, preferably hydroxyl and amino There are the functional group of either of which, or the functional group with the two.As its concrete example, it can enumerate：Dihydroxymethyl fourth Acid, dihydromethyl propionic acid, 1,2-PD, 1,2- butanediols, 1,3-BDO, 2,3-butanediol, 2,2- dimethyl -1,3- third Glycol, 3- methyl-1s, 5- pentanediols, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyls -1,3- hexylene glycol, 2,2- dimethyl - 3- hydroxypropyls -2 ', 2 '-dimethyl -3 '-hydroxy propionate, 2- normal-butyls -2- ethyls -1,3-PD, 3- ethyls -1,5- Pentanediol, 3- propyl -1,5-PD, 2,2- diethyl -1,3-PD, 3- octyls -1,5-PD, 3- phenyl -1,5- Pentanediol, 2,5- dimethyl -3- sodium sulfo groups -2,5- hexylene glycol, dimer diols are (for example, Unichem International are public Take charge of the PRIPOOL-2033 of manufacture) etc. compound in 1 molecule with 2 hydroxyls, trimethylolethane, trimethylolpropane, Alcohol, monoethanolamine with 3 or more hydroxyls in 1 molecule such as glycerine, pentaerythrite, polyglycerol, diethanol amine, three second There is 1 or more hydroxyl and the amino alcohol of amino, ethylenediamine, 1-6- hexamethylene diamines, 1,8- octamethylenediamines, 1 in 1 molecule such as hydramine, Aliphatic diamines, the meta-xylenes two such as 9- nonamethylene diamines, 1,10- decamethylene diamines, 1,11- hendecanes diamines, 1,12- dodecamethylene diamines Aromatic diamines such as amine, 4,4 '-diaminodiphenylmethane, 3,4'- diamino-diphenyls ether, 4,4'- diamino-diphenyl ethers etc. 1 Compound with 2 amino in molecule.Above-mentioned number-average molecular weight less than 1,000 1 molecule in 2 or more can with it is different The compound of the functional group of polyisocyanate reactant, you can be used alone, can also be used together by more than one.

As the epoxy resin that the adhesive resin in the present invention uses, such as bis-phenol A glycidyl ether, double can be enumerated The glycidol ethers such as phenol S glycidol ethers, novolaks glycidol ether (novolac glycidyl ether), brominated bisphenol The glycidyl ester types such as type, hexahydro-phthalic acid ethylene oxidic ester, dimer acid glycidyl ester, isocyanuric acid three shrink sweet Grease or 3, the alicyclic or aliphatic such as 4- epoxycyclohexyl-methyls carboxylate, epoxidized polybutadiene, epoxidised soybean oil Epoxides etc., you can be used alone it is a kind of, also can and with two kinds or more.Wherein, excellent from the point of view of the durability of film Bis-phenol A glycidyl ether is selected, there is the substance of 2 or more glycidyl ethers in a more preferable molecule.

The number-average molecular weight of adhesive resin in the present invention is not particularly limited, and wherein number-average molecular weight is preferably 5, 000~60,000, more preferable 10000~40000.When number-average molecular weight is too low, in the durability, resistance to of the conductive membrane of formation It is not satisfactory in terms of humid.On the other hand, when number-average molecular weight is excessively high, the cohesiveness of resin increases, as leading The raisings such as the durability of electric thin film, but laser-induced thermal etching flexibility (adaptability) of operation significantly deteriorates.

The glass transition temperature of adhesive resin in the present invention be preferably 120 DEG C hereinafter, more preferably 100 DEG C with Under.When glass transition temperature is low, the linearity after laser-induced thermal etching becomes good, and the base material adaptation after laser-induced thermal etching is tended to Become good.

The acid value of adhesive resin in the present invention is not particularly limited, but when acid value is excessively high, the conductive membrane of formation Water imbibition get higher, there are the hydrolysis of adhesive resin by the possibility promoted by the catalyst action generated by carboxyl Property, there is a possibility that the decline for the reliability for leading to conductive membrane.Hydrolysis is more notable when glass transition temperature is low.Cause This, by the way that the acid value of adhesive resin is adjusted to low acid value, preferably smaller than 400eq/ton, more preferable 300eq/ton hereinafter, So that realizing the conductive paste for having both the high reliability of conductive membrane and the linearity of laser-induced thermal etching and adaptation.

Metal powder (B) used in the present invention, can enumerate precious metal powders, the copper such as silver powder, bronze, platinum powder, palladium powder The base metals powder such as powder, nickel powder, aluminium powder, brass powder, with the noble metals such as silver plating or alloying base metal powder etc., for example, apply silver Copper powder.These metal powders can be used alone, and can also be used in combination.Among these, it is contemplated that electric conductivity, stability, cost etc., preferably Substance based on the independent and/or silver-plated silver-plated copper powder of silver powder or plating alloy for dental amalgam.

The shape of the metal powder used in the present invention is not particularly limited.The example of shape as previously known metal powder Son has sheet (flakey), spherical, dendroid (complicated and confused shape), the ball described in Japanese Patent Laid-Open 9-306240 bulletins 1 particle coacervation of shape is the shape (cohesion shape) etc. after three-dimensional shape, from the point of view of laser-induced thermal etching, in these, preferably Use the metal powder of spherical cohesion shape and sheet, further preferred sheet, cohesion shape.

The center-diameter (D50) of the metal powder used in the present invention be preferably 6 μm hereinafter, more preferably 4 μm hereinafter, further Preferably 2 μm or less.By using center-diameter in 6 μm of metal powders below, the narrow line shape of laser-induced thermal etching working position is inclined to It is good in becoming.When being more than 6 μm of metal powder using center-diameter, the narrow line shape after laser-induced thermal etching processing is deteriorated, as a result, depositing It is in contact between filament, leads to the possibility of short circuit.Further, in laser-induced thermal etching processing, there are temporary strippings Conductive membrane from removing is again attached to the possibility of working position.The lower limit of the center-diameter of metal powder has no special limit It is fixed, but cohesion is easy from the point of view of cost and when grain size attenuates, as a result cause dispersion to become difficult, so center-diameter is excellent It is selected as 80nm or more, more preferably 0.3 μm or more.When center-diameter becomes smaller than 80nm, the cohesiveness of metal powder increases, laser erosion It carves flexibility (adaptability) of operation to deteriorate, in addition to this, from the point of view of cost, this is also not satisfactory.

In addition, center-diameter (D50) refers in the integral distribution curve (volume) obtained by certain assay method, accumulation The grain size (μm) that value is 50%.It is provided in the present invention：With (the day machine dress strain formula meeting of laser diffraction and scattering formula particle size distribution device Society manufactures, MICROTRAC HRA), under the emission mode that is all-trans, measure integral distribution curve.

The content of metal powder considers from the angle with good conductivity of the conductive membrane of formation, relative to adhesive tree 100 mass parts of fat, more than preferably 400 mass parts, more than more preferably 560 mass parts.In addition, the content of ingredient, from base From the point of view of the adaptation of material is good, relative to 100 mass parts of adhesive resin, preferably 1,900 is below mass part, more excellent It is selected as 1,230 is below mass part.Can in the present invention it is preferable to use be Argent grain (silver powder).

The organic solvent (C) that can be used in the present invention is not particularly limited, but is protected from by the evaporation rate of organic solvent Hold from the point of view of proper range, preferably boiling point 100 DEG C or more, be less than 300 DEG C, more preferable boiling point 150 DEG C or more, it is small In 280 DEG C.The conductive paste of the present invention, typically by adhesive resin, metal powder, organic solvent and as needed Other compositions disperse to make in three-roll grinder, if but organic solvent at this time boiling point it is too low, have solvent in dispersion Volatilization, constitutes the ingredient of conductive paste than changed worry.On the other hand, if the boiling point of organic solvent is excessively high, Due to drying condition, there is the possibility of solvent a large amount of remainings in film, there is the worry for causing the reliability of film to reduce.

In addition, as the organic solvent that can be used in the present invention, preferably adhesive resin is solvable and metal powder can be made good The organic solvent disperseed well.As concrete example, diethylene glycol monoethyl ether acetate (EDGAC), butyl glycol ether can be enumerated Acetate (BMGAC), butyl acetate (BDGAC), cyclohexanone, toluene, isophorone, gamma-butyrolacton, benzylalcohol, The Solvesso 100 of Exxon Chemical manufacture, 150,200, propylene glycol methyl ether acetate, adipic acid, succinic acid and glutaric acid The mixtures DBE of manufacture (for example, Dupont Kabushiki Kaisha) of dimethyl esters, terpinol etc., among these, from adhesive resin Formula components dissolubility is excellent, continuous printing when solvent volatility appropriateness, to the printing based on silk screen print method etc. From the point of view of adaptability is good, preferably EDGAC, BMGAC, BDGAC and their mixed solvent.

As the content of organic solvent, relative to 100 parts by weight of slurry total weight, more than preferably 5 parts by weight, 40 weights Part is measured hereinafter, more than more preferably 10 parts by weight, below 35 parts by weight.When the too high levels of organic solvent, slurry viscosity becomes It is too low, tend to become easy the vertical liquid of generation when filament prints.On the other hand, when the content of organic solvent is too low, as slurry The viscosity of material becomes high, it sometimes appear that following situations：Such as screen printability when forming conductive membrane significantly reduces, In addition to this, the film thickness of the conductive membrane of formation thickens, and laser-induced thermal etching processability reduces.

The type of the silica dioxide granule (D) used in the conductive paste of the present invention is not particularly limited, and can be used Silica, pyrogenic silica (fumed silica) (for example, AEROSIL of AEROSIL companies of Japan manufacture), colloidal state Silica etc..In the case of not using silica dioxide granule, the filling packing in conductive membrane is poor, solvent bumping, Become easy generation annular recess.On the other hand, by using silica dioxide granule, the filling packing in conductive membrane becomes Height can inhibit annular recess to which solvent is difficult to bumping.

The average primary particle diameter of the silica dioxide granule used in the present invention is preferably 200nm hereinafter, more preferably 50nm Hereinafter, more preferably 20 μm or less.When the grain size of silicon oxide particle is big, the Packing character of filler is poor, can not inhibit annular recess.

The content of silica dioxide granule used in the present invention is preferably added relative to 100 mass parts of metal powder 25 is below mass part, and more preferably addition 10 is below mass part.

As the carbon particle (E) that can be used in the conductive paste of the present invention, Ketjen black (Ketjen can be used Black), acetylene black, furnace black, channel black, lampblack (lamp black) etc..In the case where not using carbon particle, Filling packing in conductive membrane is poor, and solvent boosts film coated surface layer in drying, becomes easy generation annular recess. On the other hand, by adding carbon particle in right amount, the filling packing in conductive membrane is got higher, solvent line dispersion homogenization, Become to be not centered at one, so annular recess can be inhibited.

The average primary particle diameter of the carbon particle used in the present invention be preferably 200nm hereinafter, more preferably 50nm hereinafter, into One step is preferably 20 μm or less.When the grain size of silicon oxide particle is big, the Packing character of filler is poor, can not inhibit annular recess.

As the content for the carbon particle that can be used in the present invention 25 are preferably added relative to 100 mass parts of metal powder Below mass part, more preferably addition 10 is below mass part.The carbon particle of the present invention also has the function of being used as laser absorbent.

As the inorganic particle (H) in the conductive paste for making an addition to the present invention, following inorganic matters can be added.As nothing Silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, ramet, niobium carbide, tungsten carbide, carbon can be used in machine object Change the various carbide such as chromium, molybdenum carbide, calcium carbide, diamond carbon lactams (diamond carbon lactam)；Boron nitride, The various nitride such as titanium nitride, zirconium nitride；The various borides such as zirconium boride；Titanium oxide (titanium dioxide), calcium oxide, magnesia, The various oxides such as zinc oxide, copper oxide, aluminium oxide；The various titanic acid compounds such as calcium titanate, magnesium titanate, strontium titanates；Curing Molybdenum sulfides；The hydrosulphates such as barium sulfate, magnesium sulfate；The various fluorides such as magnesium fluoride, fluorocarbons；Aluminum stearate, stearic acid The various metallic soaps such as calcium, zinc stearate, magnesium stearate；It is other, talcum, bentonite, talcum (talc), calcium carbonate, bentonite (bentonite), kaolin, glass fibre, mica etc..By adding these inorganic matters, exist can make printing and heat resistance, And then the case where mechanical property and long durability raising.

As the inorganic particle that can be added in the conductive paste of the present invention, it is preferable to use inorganic ion scavenger.Nothing Machine ion capturing agent refers to the inorganic particle that primary particle size is sub-micron (submicron), is the oxide or hydrogen with metal Oxide hybridized hydrotalcite.As commercially available product, IXE, IXEPLAS etc. of Toagosei Co., Ltd's manufacture can be enumerated.

The average grain diameter of the inorganic particle used in the present invention is 0.1 μm or more, 3 μm hereinafter, preferably 1 μm or more 1.2 μ M, further preferably 0.13 μm or more 0.85 μm or less.When the grain size of inorganic particle is big, the Packing character of filler is poor, can not inhibit Annular recess.

The content of inorganic particle used in the present invention preferably adds 25 matter relative to 100 mass parts of metal powder Part is measured hereinafter, more preferably addition 10 is below mass part.

Can the present invention electrocondution slurry in hybrid laser absorbent (F).Herein, laser absorbent refers to the wave to laser Long to have the additive absorbed by force, laser absorbent itself can be electric conductivity, can also be dielectric.For example, Wavelength using basic wave be the YAG laser of 1064nm as light source when, can will be at wavelength 1064nm with the dye that absorbs by force Material and/or pigment are used as laser absorbent.By adding laser absorbent, conductive membrane of the invention efficiently absorbs Laser, the volatilization and thermal decomposition of the adhesive resin caused by generating heat are promoted, as a result, laser-induced thermal etching flexibility (adaptability) of operation It improves.

It, can as the example of conductive laser absorbent among the laser absorbent that can be used in the present invention Enumerate the carbon such as carbon black, graphite powder system filler.There is no limit can enumerate Ketjen black, acetylene black, oven process charcoal to the type of carbon black Black, channel black, lampblack etc..Among these, from the point of view of electric conductivity, laser absorption, preferred Ketjen black.Carbon system filler Mixing also have the effect of improve the present invention conductive membrane electric conductivity, such as carbon black near 1060nm have absorb wave It is long, thus when the laser of 1064nm wavelength such as irradiation YAG laser, optical-fiber laser (fiber laser), due to conductive membrane height Effect ground absorbs laser, so the sensitivity to laser irradiation improves, it can be expected that following effects：Even if improving sweeping for laser irradiation When retouching speed and/or when lasing light emitter is low output, good laser-induced thermal etching flexibility (adaptability) of operation also can get.It is filled out as the carbon system The content of material, relative to 100 parts by weight of metal powder, preferably 0.1~5 parts by weight, more preferably 0.3~2 parts by weight.Carbon system fills out When the blending ratio of material is too low, improves the effect of electric conductivity and improve small to the effect of the sensitivity of laser irradiation.Another party When the blending ratio in face, carbon system filler is excessively high, the electric conductivity of conductive membrane is tended to reduce, further, it sometimes appear that The case where generating following problems point：Resin adsorption is reduced in the gap position of carbon with the adaptation of base material.

Among the laser absorbent that can be used in the present invention, as dielectric laser absorbent example, it can enumerate Go out known dyestuff, pigment and infrared absorbent.More specifically, it is even to enumerate azo dyes, metallic complex salt Nitrogen dyestuff, pyrazolone azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine The dyestuffs such as dyestuff, cyanine dye, the sour pigment (squarylium dye) in side, pyralium salt, metal thiolate complex, as Pigment, can enumerate black pigment, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, blue pigment, Viridine green, fluorescent pigment, metal powder pigment can enumerate polymer combination pigment in addition.Specifically, insoluble idol can be used Nitrogen pigment, azo lake pigment, condensed azo pigment, chelate azo pigment, phthualocyanine pigment, anthraquione pigmentss and pyrene ketone Be pigment, thioindigo (indigo plant) be pigment, quinacridone pigment, dioxazines (dioxazine) it is pigment, isoindolinone system face Material, quinoline promise phthalein ketone (quinophthalone) are pigment, dyeing lake (dye pays けレーキ) pigment, azine pigments, nitroso Pigment, nitropigments, natural pigment, fluorescent pigment, inorganic pigment.As the example of infrared absorbent, work can be enumerated (it is long rapids chemical conversion for NIR-IM1, the ammonium salt type NIR-AM1 of Diimmonium salt (diimonium salt) type infrared absorbent (NAGASE CHEMTEX) company manufactures).Preferably, containing 0.01~5 parts by weight, preferably 0.1~2 parts by weight these non-lead Electrical laser absorbent.When the containing ratio of non-conductive laser absorbent is too low, the effect of the sensitivity to laser irradiation is improved Fruit is small.When the containing ratio of non-conductive laser absorbent is excessively high, there are the electric conductivity of conductive membrane reduce worry, this Outside, the tone of laser absorbent becomes apparent, according to purposes, it sometimes appear that unsatisfactory situation.

In addition, in the conductive paste of the present invention, thixotropy conferring agents can be added, antifoaming agent, fire retardant, tackifier, resisted Hydrolytic reagent, levelling agent, plasticizer, antioxidant, ultra-violet absorber, fire retardant, pigment, dyestuff.It further, also can be appropriate It adds carbodiimide, epoxides etc. and is used as resin decomposition inhibitor.They can be used alone or are used in combination.

It, can be anti-with adhesive resin in the degree for not damaging effect of the present invention, addition in the conductive paste of the present invention The curing agent (G) answered.By adding curing agent, although there are solidification temperatures to get higher, the increased possibility of load of production process, But by crosslinking caused by the heat by being generated when dried coating film or when laser-induced thermal etching, it can expect carrying for the humidity resistance of film It is high.

About can not be limited with the curing agent that react of adhesive resin of the present invention, type, but from adaptation, resistance to Flexibility, curability angularly consider, particularly preferred isocyanate compound and/or epoxy resin.Further, about isocyanide Ester compound, when using isocyanate group has been carried out blocked isocyanate compound, storage stability improves, and It is preferred that.As the curing agent except isocyanate compound, methylated melamine, butylated melamines, benzene can be enumerated Compound well known to the amino resins such as substituted melamine, urea resin, acid anhydrides, imidazoles, phenol resin etc..In these curing agent, Can and with the well known catalyst or accelerating agent selected according to its type.It is not damage this hair as the additive amount of curing agent The degree of obvious results fruit and the amount added, are not particularly limited, wherein relative to 100 mass parts of adhesive resin, preferably 0.5~50 mass parts, more preferable 1~30 mass parts, further preferred 2~20 mass parts.

The example of isocyanate compound as the conductive paste that can be added into the present invention, there is aromatic series or aliphatic Diisocyanate, 3 yuan or more of polyisocyanates etc., low molecular compound, high-molecular compound.Example can be enumerated Such as, the aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), two The aromatic diisocyanates such as phenylmethane diisocyanate, benzene dimethylene diisocyanate, hydrogenated methylene diphenyld diisocyanate Alicyclic two isocyanides such as ester, hydrogenation benzene dimethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate The excess quantity of the tripolymer and these isocyanate compounds of acid esters or these isocyanate compounds and such as second two Low point of alcohol, propylene glycol, trimethylolpropane, glycerine, sorbierite, ethylenediamine, monoethanolamine, diethanol amine, triethanolamine etc. Sub- active dydrogen compounds or various polyester polyols alcohols, polyether polyols alcohols, polyamide-based high molecular reactive hydrogen compound etc. Compound of the end containing isocyanate group of reaction and acquisition.In addition, the block agent as isocyanate group, can enumerate example Such as phenol, benzenethiol, methylthiophenol, ethylmercapto group phenol, cresols, xylenol, resorcinol, nitrophenol, chlorophenol phenol Class；The oximes such as acetoxime, methyl ethyl ketone oxime, cyclohexanone oxime；The alcohols such as methanol, ethyl alcohol, propyl alcohol, butanol；Chlorethanol, 1,3- bis- The halogenated alcohols such as chloro- 2- propyl alcohol；The tertiary alcohols such as the tert-butyl alcohol, tert-pentyl alcohol；Epsilon-caprolactams, δ-valerolactam, butyrolactam, In addition to this lactams such as azetidinone, pyrazoles block agent can also enumerate aromatic amine, acid imide, acetyl Acetone, acetoacetic ester, malonic ester isoreactivity methylene compound, thio-alcohol, imines, imidazoles, urea class, two virtues Based compound class, sodium hydrogensulfite etc..Wherein, from the point of view of curability, particularly preferred oximes, imidazoles, amine, pyrazoles Class.

The epoxide used as curing agent in the present invention can enumerate such as bis-phenol A glycidyl ether, bisphenol S Diglycidyl ether type, the hexahydro-phthalic acid of glycidol ether, novolaks glycidol ether, brominated bisphenol etc. shrink sweet The glycidyl ester types such as grease, dimer acid glycidyl ester, triglycidyl isocyanurate or 3,4- epoxycyclohexyl first Yl carboxylic acid ester, epoxidized polybutadiene, epoxidised soybean oil etc. be alicyclic or aliphatic epoxide etc., you can is used alone one Kind, also can and with two kinds or more.Wherein, from the point of view of curability, most preferably bis-phenol A glycidyl ether, wherein further Preferred molecular weight is less than in 5000, one molecule with 2 or more glycidyl ether persons.

The viscosity of the conductive paste of the present invention is not particularly limited, and can suitably be adjusted according to the forming method of film It is whole.For example, when conductive paste is coated on base material by silk-screen printing, about the viscosity of conductive paste, printing At a temperature of viscosity when being measured with the condition of 20rpm with BH types viscosimeter, preferably 200dPas or more is further excellent It is selected as 400dPas or more, most preferably 600dPas or more.The upper limit is not particularly limited, but when viscosity is excessively high, sometimes It will appear following situations：The film thickness of conductive membrane becomes blocked up, and laser-induced thermal etching flexibility (adaptability) of operation reduces.

The conductive paste of the present invention, F values are preferably 60~95%, and more preferably 75~95%.F values are to indicate opposite The numerical value of packing quality part of 100 mass parts of all solids ingredient contained in slurry, be expressed as F values=(packing quality part/ Solid constituent mass parts) × 100.Packing quality part described herein refers to the mass parts of electroconductive powder, the matter of solid constituent Amount part refers to the mass parts of ingredient in addition to solvent, including whole electroconductive powders, adhesive resin, other curing agent, is added Add agent.When F values are too low, can not obtain display satisfactory electrical conductivity conductive membrane, when F values are excessively high, conductive membrane and The adaptation of base material and/or the case hardness of conductive membrane are tended to reduce, and can not avoid the reduction of printing.In addition, this The electroconductive powder at place refers to, metal powder and by nonmetallic both the electroconductive powders constituted.

By being coated with or being printed on base material by the conductive paste of the present invention, then forming film makes to contain in film Organic solvent volatilization, make dried coating film, can be formed accordingly the present invention conductive membrane.Conductive paste is coated with or is printed It brushes and is not particularly limited in the method on base material, wherein formed from the simplicity of process and as using conductive paste From the point of view of the universal technology of the industry of electric loop, the method preferably printed by silk screen print method.In addition, will lead Electrical slurry coating is printed in than eventually as the wider a little position in conductive membrane position needed for electric loop, this from Reduce laser-induced thermal etching process load, be efficiently formed the present invention electric loop from the point of view of be preferred.

As the base material for being coated with conductive paste of the invention, it is preferable to use the material of excellent in dimensional stability.It can be with It enumerates for example, by polyethylene terephthalate (polyethylene terephthalate), polyethylene naphthalate (polyethylene naphthalate), polybutylene terephthalate (polybutylene terephthalate) or The film that the flexible excellent material such as makrolon is formed.In addition, the inorganic material such as glass also can be used as base material use.Base material Thickness is not particularly limited, and is preferably 12.5 μm~1mm, further preferably 25 μm~0.5mm.In view of pattern forms material Whens mechanical property, shape stability or operability of material etc., it is set as above range.

In addition, progress physical treatment and/or chemistry on the surface for passing through the base material of the conductive paste in the coating present invention Processing can be such that the adaptation of conductive membrane and base material improves.As the example of physical treatment method, sandblasting can be enumerated (sandblast) method, wet shot (wet blast) method, Corona discharge Treatment method, plasma treatment of the injection containing fine-grained liquid Method, ultraviolet light or vacuum ultraviolet treatment with irradiation method etc..In addition, the example as chemical treatment method, can enumerate strong acid Facture, highly basic facture, oxidizer treatment method, coupling agent treatment etc..

In addition, the base material can be the base material with transparent conductivity layer.The conductive membrane of the present invention can be laminated in On transparent conductivity layer.The material of the transparent conductivity layer is not particularly limited, and can enumerate and is for example with tin indium oxide The ito film of principal component, the silver nanowire film formed by the threadiness silver of nano-scale.In addition, transparent conductivity layer can not only make With the entire layer of base material is formed in, the layer after the part for removing transparent conductivity layer by etching etc. can also be used.

The process for making organic solvent volatilize, preferably carries out at normal temperatures and/or under heating.When heating, after making drying Conductive membrane electric conductivity and from the point of view of adaptation, case hardness become good, heating temperature is preferably 80 DEG C or more, More preferably 100 DEG C or more, further preferably 110 DEG C or more.In addition, from the heat resistance of the transparent conductivity layer of substrate, with And in production process it is energy saving from the point of view of, heating temperature be preferably 150 DEG C hereinafter, more preferably 135 DEG C hereinafter, further it is excellent It is selected as 130 DEG C or less.When being mixed with curing agent in the conductive paste of the present invention, if being waved under heating into enforcement organic solvent The process of hair can then carry out curing reaction.

The thickness of the conductive membrane of the present invention, can be set as thickness appropriate according to usage.Wherein, from drying The angle with good conductivity consideration of conductive membrane afterwards, and from the point of view of laser-induced thermal etching flexibility (adaptability) of operation is good, The film thickness of conductive membrane is preferably 3 μm or more, 30 μm hereinafter, more preferably 4 μm or more, 20 μm hereinafter, further preferably 4 μm or more, 10 μm or less.When the film thickness of conductive membrane is excessively thin, exist can not obtain as the desired electric conductivity in circuit can It can property.When film thickness is blocked up, the laser irradiation amount needed for laser-induced thermal etching processing must be excessive, it sometimes appear that being injured to substrate tape The case where.In addition, when the deviation of film thickness is big, deviation is generated on the etching easness of conductive membrane, becomes easy generation The short-circuit between conductors caused by undercut, the tendency to break caused by etching excessively.Therefore, the deviation of film thickness is the smaller the better.

The present invention conductive membrane surface roughness Ra be preferably 0.7 μm hereinafter, more preferably 0.5 μm hereinafter, into One step is preferably 0.4 μm or less.When surface roughness Ra is excessively high, becomes easy and generate sawtooth in the etching end of conductive membrane Line (ギザ) there is a possibility that become easy the short circuit between generating line, the broken string caused by etching excessively.Due to rough surface Strong influences of the Ra by slurry composition (especially adhesive type and silver powder type), slurry viscosity, silk-screen printing condition is spent, So it is necessary to suitably adjust them, control.

The electric loop of the present invention is the electric loop for having following wiring positions：The wiring position is by shining laser It penetrates at least part of conductive paste conductive membrane formed on the substrate through the invention, it will be described from base material A part for conductive membrane removes, and is formed accordingly.According to the forming method of such electric loop, then not with photoetching process Together, it is dry process that can make pattern formation process, does not generate the waste liquid containing metal component, so without liquid waste processing etc., It can be described as environment amenable technique.In addition, process is also simple, so can inhibit and the relevant investment of manufacturing equipment, manufacture Maintenance management after equipment operation is also easy.In addition, the method to forming conductive membrane on base material by conductive paste It is not particularly limited, can be carried out by printing or application.

The illuminating method of laser is not particularly limited, can be used carry out in recent years universal laser-induced thermal etching processing unit (plant) or Person makes its dimensional accuracy person of further increasing.Laser-induced thermal etching processing unit (plant), since the image processing applications software such as CAD can will be used Data obtained are directly used in laser processing, so the switching of manufacture pattern is extremely readily.This can be used as relative to previous One of the advantages of pattern in the silk screen print method of progress is formed is enumerated.

Irradiate and absorb in the position of laser, the energy conversion of laser is heat, by temperature rise come generate thermal decomposition and/ Or volatilization, irradiated site are stripped removing.The illuminated of conductive membrane in order to efficiently remove the present invention from base material swashs The position of light, preferably conductive membrane of the invention have strong absorb to the wavelength for irradiating laser.Therefore, as laser species, Preferably select the swashing with energy in constituting any ingredient of conductive membrane of the present invention with the wavelength region absorbed by force Light type.

As laser species, excimer laser (wavelength of basic wave is 193~308nm), YAG laser (bases can be enumerated The wavelength of this wave is 1064nm), optical-fiber laser (wavelength of basic wave is 1060nm), semiconductor laser etc..Substantially, using appoint Meaning mode, arbitrary wavelength laser species all be not present any problem.It can be irradiated by selection arbitrary with conductive membrane The absorbing wavelength region of constituent is consistent and base material does not have the laser species of the wavelength absorbed by force, can efficiently carry out The removing of the conductive membrane at laser irradiation position, and can be to avoid the injury of base material.From this point of view, as photograph Laser species are penetrated, the wavelength of laser is preferably 190nm~1100nm, further preferably 500nm~1000nm.As base material, A part using the conductive membrane with polyester in the conductive membrane or layer structure in layer structure with polyester passes through When etching the film being removed, do not absorbed at the wavelength of basic wave from due to base material, so be not easy to hinder to substrate tape From the point of view of evil, YAG laser or optical-fiber laser are particularly preferably used.

Laser output, frequency are not particularly limited, but can remove laser irradiation positions with 10~40 μm of etched width Conductive membrane and substrate the mode do not damaged of base material, be adjusted.Usually, laser output preferably 0.5~ 100W, 10~1000kHz of frequency, pulse width 1000ns or less range in be suitably regulated.When laser output is too low, The tendency that the removing of conductive film becomes inadequate, but by reducing the sweep speed of laser or increasing scanning times, Such tendency can be avoided to a certain extent.When laser output is excessively high, there is a possibility that following：Due to from irradiation part The diffusion of heat, the position that conductive membrane is stripped become bigger than lasing beam diameter too many, and line width becomes meticulous or broken string.It is based on This point, laser output preferably 0.5~20W, 10~800kHz of frequency, pulse width 800ns or less range in fitted Locality is adjusted, further preferred 0.5~12W, 10~600kHz of frequency, pulse width 600ns or less.The lower limit of pulse width is excellent Select 1fs or more, further preferred 1ps or more, most preferably 1ns or more.

The sweep speed of laser is more Gao Yue from the point of view of the production efficiency raising brought by the reduction of pitch time It is good, and specifically, it is preferable in 1000mm/s or more, more preferably in 1500mm/s or more, further preferably in 2000mm/s or more.The upper limit does not have There is special limitation, generally in 10000mm/s or less.When sweep speed is excessively slow, not only production efficiency reduces, but also there are electric conductivity The worry that film and base material come to harm by thermal history.The upper limit of process velocity does not have special provision, but in scanning speed When spending high, there is a possibility that the removing of the conductive membrane at laser irradiation position becomes incomplete, short circuit.In addition, When sweep speed is too fast, then in the corner part for forming pattern, compared with straight line position, due to that can not avoid that sweep speed is made to subtract Speed, so there is a possibility that following：The hot resume of corner part become higher, the laser erosion of corner part compared with straight line position Carving the physical property of the conductive membrane on working position periphery significantly reduces.

Laser scanning can be the emitter for moving laser, the irradiated body of mobile illuminated laser or combine the two In it is any number of, such as can be realized by using XY displacement platforms (XY stage).In addition it is also possible to by using current mirror The direction of illumination that (galvano mirror) etc. changes laser carrys out scanning laser.

When irradiating laser, by using condenser (achromatic lens etc.), the energy density of per unit area can be improved. As the advantages of this method, following advantages can be enumerated：Compared with when using mask, since the energy that per unit area can be improved is close Degree, even so the laser oscillator of small output also can carry out laser-induced thermal etching processing with high sweep speed.After optically focused When laser irradiation to conductive membrane, need to focus.The adjusting of focal length, it is especially desirable to according to the film thickness for being coated on base material come It adjusts, but is preferably adjusted in a manner of damaging and can remove not to substrate tape and remove defined conductive membrane pattern Section.

It is repeated several times in same pattern and carries out laser scanning, this is one of preferred embodiment.Even if being scanned at the 1st time The ingredient of conductive membrane when the middle incomplete conductive membrane position in the presence of removing, or in composition removing is attached to once again It, also can be by Multiple-Scan, to remove the conductive membrane at laser irradiation position completely when base material.Scanning times are preferably 4 times, Further preferably 3 times.The upper limit is not particularly limited, but is damaged due to existing because working position periphery is by multiple thermal history The possibility that wound, discoloration, Physical properties of coating film reduce, so it should be noted that.In addition, from the point of view of production efficiency, scanning times It is certainly more fewer better.

It is not repeated several times in same pattern and carries out laser scanning, this is also one of preferred embodiment.As long as will not give The characteristic of the conductive membrane of gained, conductive laminate and electric loop brings harmful effect, and certainly scanning times are fewer, Production efficiency is more excellent.

The conductive membrane of the present invention, due to containing the electric conduction powder of high price with high concentration, so if it is considered that it is made If the electric loop made manufactures required totle drilling cost, then leading contained by the conductive membrane that recycling is removed from base material Electrical powder is critically important.By the way that high performance precipitron is arranged near laser irradiation position, high efficiente callback conduction is constructed Property powder system, fully cost-effective processing method can be become.

Conductive membrane, conductive laminate and/or the electric loop of the present invention can be used as the component parts of touch panel It uses.The touch panel can also be electrostatic capacity either resistive film mode.It is applicable to arbitrary touch surface Plate, but since this slurry is suitable for forming filament, so the electricity of the touch panel for electrostatic capacity can be particularly suitable for Pole wiring is used.In addition, as the base material for constituting the touch panel, it is preferable to use having ito film, silver nanowire film etc. are transparent to lead The film or glass baseplate of electric layers or they the base material after a part is removed by etching.

Embodiment

In order to illustrate the present invention in further detail, following embodiment, comparative example are enumerated, but the present invention is not limited to completely Embodiment.In addition, each measured value described in embodiment, comparative example is the value measured according to following methods.

1. number-average molecular weight

Sample adhesive resin is dissolved in tetrahydrofuran so that resin concentration become 0.5 weight % degree, with aperture be 0.5 μm polytetrafluoroethylene (PTFE) made of membrane filter, as GPC measure sample.Using tetrahydrofuran as mobile phase, Shimadzu is used Gel permeation chromatography (GPC) Prominence for making the manufacture of commercial firm of institute, using differential refractometer (in terms of RI) as detector, in column 30 DEG C of temperature, flow carry out resin samples GPC under conditions of 1mL/ minutes is measured.In addition, number-average molecular weight is poly- as standard Styrene scaled value saves and is equivalent to molecular weight and is calculated less than 1000 part.GPC columns use Showa Denko K. K Shodex KF-802,804L, 806L of manufacture.

2. glass transition temperature (Tg)

Sample adhesive resin 5mg is put into aluminum sample disk and is sealed, Seiko instrument (Seiko Instruments) strain is used Differential scanning calorimetric analysis instrument (DSC) DSC-220 of formula commercial firm manufacture, is measured with 20 DEG C/minute of heating rate to 200 DEG C, Find out the temperature of the extended line and the intersection point of the tangent line of the maximum inclination in display migration portion of glass transition temperature baseline below Degree.

3. acid value

Accurate weighing sample adhesive resin 0.2g, is dissolved in the chloroform of 20mL.Then, indicator uses phenolphthalein solution, uses The potassium hydroxide (ethanol solution) of 0.01N is titrated.The unit of acid value is eq/ton, the i.e. equivalent as every 1 ton of sample.Separately Outside, ton (ton) is metric ton (metric ton) herein.

4. resin forms

The dissolved samples adhesive resin in chloroform-d, the 400MHz-NMR devices manufactured using VARIAN pass through 1H-NMR points Analysis finds out resin composition.

5. the making of conductive laminate test film

Respectively in the PET film (Toray manufactures, Lumirror S) and ito film (tail by annealing of 100 μm of thickness Pond Industrial Co., Ltd manufactures, KH150) on, conductive paste is printed by silk screen print method with the stainless steel mesh of 400 mesh, Then the solid pattern of formation width 25mm, length 450mm use heated air circulation type drying oven, 30 are heated under conditions of 130 DEG C Minute, it regard heating gained person as conductive laminate test film.In addition, coating thickness when adjustment printing, so that desciccator diaphragm Thickness becomes 4~10 μm.

6. adaptation

With the conductive laminate test film, according to JIS K-5400-5-6：1990, with Cellotape (registered trademark) (days Stumble (Nichiban) Co., Ltd. manufacture), evaluated by disbonded test.Wherein, the cutting of all directions of checker pattern Number is 11, and 1mm is divided between cutting.100/100 indicates good without stripping, adaptation, and 0/100 indicates all strippings.

7. specific resistance (specific electrical resistance)

The sheet resistance and film thickness of the conductive laminate test film are measured, specific resistance is calculated.Film thickness uses Gauge Stand ST-022 (manufacture of little Ye Ce devices commercial firm) measures the thickness of 5 points of cured coating film, using it using the thickness of PET film as 0 point Average value.Sheet resistance uses milliohm meter (MILLIOHMMETER4338B) (manufacture of HEWLETT PACKARD commercial firms), to 4 Piece test film is measured, using its average value.In addition, this milliohm meter detectable ranging from 1 × 10^-2(Ω below Cm), 1 × 10^-2Specific resistance more than (Ω cm) is measuring outside boundary.

8. humidity resistance is tested：

By conductive laminate test film, 300 hours are heated under conditions of 80 DEG C, then 85 DEG C, 85%RH it is (relatively wet Degree) under conditions of heat 300 hours, then room temperature carry out various evaluations after 24 hours.

9. surface roughness

On the conductive laminate test film 1, with surface roughness meter (HANDYSURF E-35B, Tokyo precision commercial firm system Make, calculated based on JIS-1994), measure surface roughness Ra.

10. the evaluation of laser-induced thermal etching flexibility (adaptability) of operation

By silk screen print method, on polyester base material (the Lumirror S (100 μm of thickness) of Toray manufacture), by electric conductivity The rectangle that slurry printing is 2.5 × 10cm.Silk-screen plate using 400 mesh, 18 μm of line footpath, calendering processing, 10 μ of emulsion thickness it is stainless Steel sieve, it is scraper plate (squeegee) speed that printing machine, which uses the SSA-TF150E that Tokai Commercial Co., Ltd. manufactures, printing condition, Spend 100mm/s, scraper (scraper) speed 75mm/s, intrusion 1.0mm/s, gap (clearance) 1.5mm, scraper plate pressure 0.4MPa, 75 degree of blade angle, 80 degree of Squeegee hardness.After printing, carried out under conditions of 130 DEG C with heated air circulation type drying oven Drying in 30 minutes, obtains conductive membrane.In addition, dilution adjustment slurry, so that film thickness becomes 5~7 μm.Then, it is using Progress laser-induced thermal etching processing on conductive membrane made of method is stated, 10 4 with length 50mm as shown in Figure 2 are made The pattern of straight line portion, as laser-induced thermal etching flexibility (adaptability) of operation evaluation test piece.By with 40 μm of spacing (L/S=20/20 μm) 3 laser are scanned, to carry out laser-induced thermal etching processing.Condition is that lasing light emitter uses optical-fiber laser (wavelength：1064nm), frequency 300kHz, sweep speed 2500mm/s, pulse width 15ns suitably adjust power, implement laser-induced thermal etching processing.

11. laser-induced thermal etching flexibility (adaptability) of operation evaluates conduction between (1) filament both ends

In the laser-induced thermal etching flexibility (adaptability) of operation evaluation test piece, commented according to whether the conducting between filament both ends is able to ensure Valence.Specifically, touched between terminal 1a- terminals 1c using tester respectively, between terminal 2a- terminals 2c, between terminal 3a- terminals 3c, It is tested between terminal 4a- terminals 4c, is confirmed whether that (electricity) is connected, is judged according to following evaluation criteria.In addition, making 10 Piece test film, every 14, so to 40 filament implementation evaluations.

○：For all 40 filaments, there is conducting between the both ends of filament

△：In 40 filaments, the filament without conducting is less than 10 between the both ends of filament.

×：In 40 filaments, the filament without conducting is 10 or more between the both ends of filament.

12. laser-induced thermal etching flexibility (adaptability) of operation evaluates insulating properties between (2) adjacent filament

In the laser-induced thermal etching flexibility (adaptability) of operation evaluation test piece, according to the insulation between adjacent filament whether be able to ensure come Evaluation.Specifically, it is touched between terminal 1a- terminals 2a, between terminal 2a- terminals 3a, between terminal 3a- terminals 4a using tester respectively It is tested, is confirmed whether that (electricity) is connected, is judged according to following evaluation criteria.In addition, 10 test films are made, every 13 Standard adds up to 30 standards, implementation evaluation.

○：It is all insulation between the adjoining filament of 30 standards

△：It is insulation between adjoining filaments more than 20 standards

×：Less than being uninsulated between the adjoining filament of 20 standards

13. the evaluation of annular recess

By silk screen print method, on polyester base material (the Lumirror S (100 μm of thickness) of Toray manufacture), by electric conductivity The rectangle that slurry printing is 0.5 × 80mm.Silk-screen plate using 400 mesh, 18 μm of line footpath, calendering processing, 10 μ of emulsion thickness it is stainless Steel sieve, printing machine use Tokai Commercial Co., Ltd. manufacture SSA-TF150E, printing condition be scraper velocity 100mm/s, Scraper speed 75mm/s, intrusion 1.0mm/s, gap 1.5mm, scraper plate pressure 0.4MPa, 75 degree of blade angle, Squeegee hardness 80 Degree.After printing, drying in 30 minutes is carried out under conditions of 130 DEG C with heated air circulation type drying oven, obtains conductive membrane.Institute In the conductive membrane of acquisition, using laser microscope (KEYENCE VHX-1000), the quantity of annular recess is measured, under Evaluation criteria is stated to be judged.

Quantity (a/cm of annular recess²)

◎：0~5

○：6~20

△：21~50

×：51 or more

< Examples 1 to 3,1 > of comparative example

According to mixing ratio shown in table 1,4 kinds of electrocondution slurries are adjusted.First, adhesive resin is dissolved in the solvent of appropriate amount In so that solid component concentration becomes 35 mass %, weigh add obtained binder resin solution, silver powder 1, curing agent, Curing catalysts, remaining quantity of solvent, other additive, after they are pre-mixed, 2 times by cooling three roller kneading machines, point It dissipates.Then, 795 mesh (stainless steel mesh filter (line is installed on slurries filtration machine (PF320A of Protech companies manufacture) 16 μm of diameter, 16 μm of mesh)) filter, carry out the filtering of above-mentioned slurry.

Then, the conductive paste obtained is printed as defined pattern, so that after dry film thickness becomes 17 μm, it is dry 120 DEG C × 30 minutes, obtain conductive membrane.It uses obtained conductive membrane to measure basic physical properties, then, carries out laser The research of etching and processing.Evaluation result is as shown in table 1.

Table 1

In addition, in table 1,

Silver powder 1：Agglomerate silver powder (D50：1.3μm)

Silver powder 2：Flake silver powder (D50：1.3μm)

Silver powder 3：Spherical silver powder (D50：1.3μm)

Adhesive resin 1：The PKHC (phenoxy resin, number-average molecular weight 21000, Tg=89 DEG C) of InChem manufactures

Adhesive resin 2：The PKHC modifiers (phenoxy resin, number-average molecular weight 21000, Tg=97 DEG C) of InChme manufactures

Adhesive resin 3：Japan spins the Vylon 103 (Tg=47 DEG C, acid value 25) made

Silica 1：300 (the primary particle sizes of AEROSIL of Japanese AEROSIL manufactures：7nm)

Carbon 1：ECP600JD (the primary particle sizes of lion king manufacture：34nm)

Inorganic filler 1：The ion capturing agent IXE-PLAS A2 (intermediate values that East Asia is synthetically produced：0.2μm)

Solvent 1：Ethylene glycol monomethyl ether acetate

Solvent 2：Diethylene glycol ether acetate alone

Solvent 3：Diethylene glycol monobutyl ether acetate

Curing agent 1：The blocked isocyanate BI7960 of Baxenden manufactures

Curing agent 1：The blocked isocyanate BI7982 of Baxenden manufactures

Curing catalysts：The KS1260 of Common medicine Co., Ltd's manufacture

Dispersant 1：The Disperbyk167 of Japanese (Byk ChemieJapan) (strain formula) commercial firm manufacture of Bi Ke chemistry

Additive 1：Carboxylic acid amine salt

Additive 2：Carboxylic acid

1 > of < application examples

Use obtained electrocondution slurry P1, printed so that dry film thickness becomes 17 μm, change drying temperature with it is dry Dry time, evaluation annular recess defect, filament both ends conduction, filament both ends insulating properties.As a result as shown in 2~table of table 4.Low When through a long time is dried under conditions of temperature, display has following tendencies：Annular recess is reduced, filament both ends conduction, filament two End insulating properties is improved.

Table 2

Table 3

Table 4

2 > of < application examples

Use obtained electrocondution slurry P2~P4, printed so that dry film thickness become 17 μm, change drying temperature With drying time, insulating properties between evaluation annular recess defect, filament both ends conduction, filament both ends.As a result it is shown in 5~table of table 7。

Table 5

Table 6

Table 7

3 > of < application examples

Obtained electrocondution slurry P1~P4 is used, each drying condition is changed, finds the condition that annular recess defect tails off, evaluation Insulating properties between conduction, filament both ends between filament both ends.As a result it is shown in table 8.

Table 8

11 > of < embodiments

According to mixing ratio shown in table 11, electrocondution slurry is modulated.First, adhesive resin is dissolved in the solvent of appropriate amount, So that solid component concentration becomes 35 mass %, weighs and add obtained binder resin solution, silver powder 1, curing agent, solidification Catalyst, remaining quantity of solvent, other additive after being pre-mixed them, pass through cooling three roller kneading machines, dispersion 2 times.So Afterwards, 795 mesh (stainless steel mesh filter (16 μ of line footpath is installed on slurries filtration machine (PF320A of Protech companies manufacture) M, 16 μm of mesh)) filter, carry out the filtering of above-mentioned slurry.Then, it is defined figure by the printing of obtained conductive paste It is 130 DEG C × 30 minutes dry after case, obtain conductive membrane.Basic physical properties are measured using this conductive membrane, then, are carried out The research of laser-induced thermal etching processing.Evaluation result is as shown in table 11.

< embodiments 12~21,11~13 > of comparative example

Change the resin and formula of conductive paste, implements embodiment 12~21, comparative example 11~13.Conductive paste is matched Side and evaluation result are as shown in table 11.In embodiment, by 130 DEG C × 30 minutes relatively low temperature of baking oven and short time plus Heat can obtain good Physical properties of coating film.In addition, the evaluation to the adaptation of ito film, after hygrothermal environment is tested is also good 's.

Table 11

In addition, in table 11,

Silver powder 1：Agglomerate silver powder (D50：1.3μm)

Silver powder 2：Flake silver powder (D50：1.3μm)

Silver powder 3：Spherical silver powder (D50：1.3μm)

Adhesive resin 3：Japan spins the Vylon 600 (Tg=45 DEG C, acid value 30) made

Adhesive resin 4：Japan spins the Vylon 103 (Tg=47 DEG C, acid value 25) made

Adhesive resin 5：Japan spins the Vylon 270 (Tg=67 DEG C, acid value 30) made

Silica 2：130 (the primary particle sizes of AEROSIL of Japanese AEROSIL manufactures：16nm)

Silica 3：AEROSIL R972 (the primary particle sizes of Japanese AEROSIL manufactures：16nm)

Solvent 1：Ethylene glycol monomethyl ether acetate

Solvent 2：Diethylene glycol ether acetate alone

Solvent 3：Diethylene glycol monobutyl ether acetate

Curing agent 1：The blocked isocyanate BI7960 of Baxenden manufactures

Curing agent 1：The blocked isocyanate BI7982 of Baxenden manufactures

Curing catalysts：The KS1260 of common drug (Co., Ltd.) manufacture

Dispersant 1：The Disperbyk167 of Japanese (strain formula) commercial firm manufacture of Bi Ke chemistry

Additive 1：Carboxylic acid amine salt

Additive 2：Carboxylic acid

31 > of < embodiments

According to mixing ratio shown in table 12, electrocondution slurry is modulated.First, adhesive resin is dissolved in the solvent of appropriate amount, So that solid component concentration becomes 35 mass %, weighs and add obtained binder resin solution, silver powder 1, curing agent, solidification Catalyst, remaining quantity of solvent, other additive after being pre-mixed them, pass through cooling three roller kneading machines, dispersion 2 times.So Afterwards, 795 mesh (stainless steel mesh filter (16 μ of line footpath is installed on slurries filtration machine (PF320A of Protech companies manufacture) M, 16 μm of mesh)) filter, carry out the filtering of above-mentioned slurry.Then, it is defined figure by the printing of obtained conductive paste It is 130 DEG C × 30 minutes dry after case, obtain conductive membrane.Basic physical properties are measured using this conductive membrane, then, are carried out The research of laser-induced thermal etching processing.Evaluation result is as shown in table 12.

< embodiments 32~39,1~3 > of comparative example

Change the resin and formula of conductive paste, implements embodiment 32~39, comparative example 31~33.Conductive paste is matched Side and evaluation result are as shown in table 12.In embodiment, by 130 DEG C × 30 minutes relatively low temperature of baking oven and short time plus Heat can obtain good Physical properties of coating film.In addition, the evaluation to the adaptation of ito film, after hygrothermal environment is tested is also good 's.

Table 12

In addition, in table 12,

Silver powder 1：Agglomerate silver powder (D50：1.3μm)

Silver powder 2：Flake silver powder (D50：1.3μm)

Silver powder 3：Spherical silver powder (D50：1.3μm)

Adhesive resin 3：Japan spins the Vylon 600 (Tg=45 DEG C, acid value 30) made

Adhesive resin 4：Japan spins the Vylon 103 (Tg=47 DEG C, acid value 25) made

Adhesive resin 5：Japan spins the Vylon 270 (Tg=67 DEG C, acid value 30) made

Carbon 2：Carbon ECP (the primary particle sizes of lion king manufacture：39.5nm)

Carbon 3：TOKABLACK#5500 (the arithmetic mean diameters of East Sea charcoal element manufacture：25nm)

Carbon 4：TOKABLACK#4400 (the arithmetic mean diameters of East Sea charcoal element manufacture：38nm)

Solvent 1：Ethylene glycol monomethyl ether acetate

Solvent 2：Diethylene glycol ether acetate alone

Solvent 3：Diethylene glycol monobutyl ether acetate

Curing agent 1：The blocked isocyanate BI7960 of Baxenden manufactures

Curing agent 1：The blocked isocyanate BI7982 of Baxenden manufactures

Curing catalysts：The KS1260 of Common medicine Co., Ltd's manufacture

Additive 1：Carboxylic acid amine salt

Additive 2：Carboxylic acid

41 > of < embodiments

According to mixing ratio shown in table 13, table 14, electrocondution slurry is modulated.First, adhesive resin is dissolved in the molten of appropriate amount In agent, so that solid component concentration becomes 35 mass %, weighs and add obtained binder resin solution, silver powder 1, solidification Agent, curing catalysts, remaining quantity of solvent, other additive, after they are pre-mixed, 2 times by cooling three roller kneading machines, Dispersion.Then, 795 mesh (stainless steel mesh filter is installed on slurries filtration machine (PF320A of Protech companies manufacture) (16 μm of line footpath, 16 μm of mesh)) filter, carry out the filtering of above-mentioned slurry.Then, it is by the printing of obtained conductive paste It is 130 DEG C × 30 minutes dry after defined pattern, obtain conductive membrane.Basic physical properties are measured using this conductive membrane, so Afterwards, the research of laser-induced thermal etching processing is carried out.Evaluation result is as shown in table 13, table 14.

< embodiments 42~57,41~43 > of comparative example

Change the resin and formula of conductive paste, implements embodiment 42~57, comparative example 41~43.The formula of conductive paste And evaluation result is as shown in table 13, table 14.In embodiment, pass through 130 DEG C × 30 minutes relatively low temperature of baking oven and short time Heating, can obtain good Physical properties of coating film.In addition, the evaluation to the adaptation of ito film, after hygrothermal environment is tested is also good 's.

Table 13

Table 14

In addition, in table 13, table 14,

Silver powder 1：Agglomerate silver powder (D50：1.3μm)

Silver powder 2：Flake silver powder (D50：1.3μm)

Silver powder 3：Spherical silver powder (D50：1.3μm)

Adhesive resin 3：Japan spins the Vylon 600 (Tg=45 DEG C, acid value 30) made

Adhesive resin 4：Japan spins the Vylon 103 (Tg=47 DEG C, acid value 25) made

Adhesive resin 5：Japan spins the Vylon 270 (Tg=67 DEG C, acid value 30) made

Inorganic filler 1：Ion capturing agent IXE-700F (the intermediate values that East Asia is synthetically produced：1.5μm)

Inorganic filler 2：Ion capturing agent IXE-100 (the intermediate values that East Asia is synthetically produced：1.0μm)

Inorganic filler 3：The ion capturing agent IXE-PLAS A1 (intermediate values that East Asia is synthetically produced：0.5μm)

Inorganic filler 4：The ion capturing agent IXE-PLAS A2 (intermediate values that East Asia is synthetically produced：0.2μm)

Inorganic filler 5：The ion capturing agent IXE-PLAS B1 (intermediate values that East Asia is synthetically produced：0.4μm)

Inorganic filler 6：Stone originates in the titanium oxide CR-57 (average grain diameters of industry manufacture：0.25μm)

Inorganic filler 7：Stone originates in the titanium oxide A-100 (average grain diameters of industry manufacture：0.15μm)

Inorganic filler 8：The barium sulfate B-1 of Sakai chemistry manufacture

Inorganic filler 9：The barium sulfate B-65 of Sakai chemistry manufacture

Solvent 1：Ethylene glycol monomethyl ether acetate

Solvent 2：Diethylene glycol ether acetate alone

Solvent 3：Diethylene glycol monobutyl ether acetate

Curing agent 1：The blocked isocyanate BI7960 of Baxenden manufactures

Curing agent 1：The blocked isocyanate BI7982 of Baxenden manufactures

Curing catalysts：The KS1260 of Common medicine Co., Ltd's manufacture

Additive 1：Carboxylic acid amine salt

Industrial utilizability

The conductive film covering of the present invention, the electric conductivity of conductive filler, adhesive resin and solvent is contained by dry solidification Slurry obtains, on surface without specific defects, so laser-induced thermal etching flexibility (adaptability) of operation is excellent, can yield form L/S well =50/50 μm of glass-coated microwire below, thus can be applied to be formed all purposes of tiny circuit using printing technology, especially It can be used in the wide range of areas such as touch panel, display, digital quantizer, antistatic.

Claims

1. a kind of conductive film covering, which is characterized in that be made of the conductive composition comprising conductive filler and adhesive resin Conductive film covering in, be present in 50 μm of the diameter annular recess defect below on overlay film surface there are density be 50/cm² Below.

2. conductive film covering according to claim 1, which is characterized in that in the conductive film covering, there is no cyclic annular recessed The surface roughness Ra of sunken part is 0.1 or more, 1.0 μm or less.

3. conductive film covering according to claim 1 or 2, which is characterized in that the average film thickness of the conductive film covering is 2 μm or more, 20 μm or less.

4. conductive film covering described in any one of claim 1 to 3, which is characterized in that the conductive composition is extremely It it is less 0.3 μm or more containing average grain diameter, 6 μm of Argent grains below and average grain diameter are 5nm or more, 200nm below two Silicon oxide particle, macromolecule adhesive resin, the conductive composition are substantially free of solvent.

5. conductive film covering described in any one of claim 1 to 3, which is characterized in that the conductive composition is extremely It it is less 0.3 μm or more containing average grain diameter, 6 μm of Argent grains below and average grain diameter are 5nm or more, 200nm carbon below Particle, macromolecule adhesive resin, the conductive composition are substantially free of solvent.

6. conductive film covering described in any one of claim 1 to 3, which is characterized in that the conductive composition is extremely It it is less 0.3 μm or more containing average grain diameter, 6 μm of Argent grains below and average grain diameter are 50nm or more, 3000nm is below Ion capturing agent particle, macromolecule adhesive resin, the conductive composition are substantially free of solvent.

7. a kind of forming method of electric wiring, which is characterized in that have and remove claim 1~6 by exciting light light beam Any one of described in conductive film covering a part process.

8. a kind of laser-induced thermal etching processing conductive paste, which is characterized in that at least contain macromolecule adhesive resin A, it is average Grain size is 0.3 μm or more, 6 μm of metal powder B below, and organic solvent C and average grain diameter are 5nm or more, 200nm below two Silicon oxide particle D.

9. laser-induced thermal etching processing conductive paste according to claim 8, which is characterized in that described adhesive Resin A It is in polyester resin, polyurethane resin, epoxy resin, phenoxy resin, vinyl chloride resin and cellulose derivative resin One kind or two or more mixture.

10. laser-induced thermal etching processing conductive paste according to claim 8 or claim 9, which is characterized in that described adhesive tree The number-average molecular weight of fat A is 5,000~60,000, and the glass transition temperature of described adhesive Resin A is less than 120 DEG C.

11. laser-induced thermal etching processing conductive paste according to any one of claims 8 to 10, which is characterized in that

The organic solvent C is the mixture for 2 kinds of solvents that at least boiling point is different,

Account for the 1st solvent of 45~90 mass % of whole quantity of solvent boiling point be 200 DEG C or more, 270 DEG C hereinafter,

The boiling point of 2nd solvent is 55~10 mass % of whole quantity of solvent than 10 DEG C of the low boiling point or more of the 1st solvent.

12. the laser-induced thermal etching processing conductive paste according to any one of claim 8~11, which is characterized in that institute The acid value for stating adhesive resin A is less than 400 equivalent/10⁶g。

13. the laser-induced thermal etching processing conductive paste according to any one of claim 8~12, which is characterized in that every 15 μm or more of coarse Argent grain is 100 or less in 1.0g slurries.

14. a kind of laser-induced thermal etching processing conductive paste, which is characterized in that it is 0.3 μm or more, 6 μ at least to contain average grain diameter M metal powder B below and average grain diameter are 5nm or more, 200nm carbon particle E below, macromolecule adhesive resin A, organic Solvent C.

15. laser-induced thermal etching processing conductive paste according to claim 14, which is characterized in that described adhesive resin A is in polyester resin, polyurethane resin, epoxy resin, phenoxy resin, vinyl chloride resin and cellulose derivative resin One kind or two or more mixture.

16. the laser-induced thermal etching processing conductive paste according to claims 14 or 15, which is characterized in that the macromolecule The number-average molecular weight of adhesive resin A is 5,000~60,000, the glass transition temperature of the macromolecule adhesive resin A Less than 120 DEG C.

17. laser-induced thermal etching processing conductive paste according to any one of claims 14-16, which is characterized in that

The solvent is the mixture for 2 kinds of solvents that at least boiling point is different,

18. the laser-induced thermal etching processing conductive paste according to any one of claim 14~17, which is characterized in that institute The acid value for stating macromolecule adhesive resin A is less than 200 equivalent/10⁶g。

19. the laser-induced thermal etching processing conductive paste according to any one of claim 14~18, which is characterized in that every 15 μm or more of coarse Argent grain is 100 or less in 1.0g slurries.

20. a kind of laser-induced thermal etching processing conductive paste, which is characterized in that at least contain：

(B) average grain diameter be 0.3 μm or more, 6 μm of metallic particles below, and

(A) macromolecule adhesive resin,

(E) solvent.

21. laser-induced thermal etching processing conductive paste according to claim 20, which is characterized in that described adhesive resin It is in polyester resin, polyurethane resin, epoxy resin, phenoxy resin, vinyl chloride resin and cellulose derivative resin One kind or two or more mixture.

22. the laser-induced thermal etching processing conductive paste according to claim 20 or 21, which is characterized in that the macromolecule The number-average molecular weight of adhesive resin is 5,000~60,000, and the glass transition temperature of the macromolecule adhesive resin is small In 120 DEG C.

23. the laser-induced thermal etching processing conductive paste according to any one of claim 20~22, which is characterized in that

24. the laser-induced thermal etching processing conductive paste according to any one of claim 20~23, which is characterized in that institute The acid value for stating macromolecule adhesive resin is less than 200 equivalent/10⁶g。

25. the laser-induced thermal etching processing conductive paste according to any one of claim 20~24, which is characterized in that every 15 μm or more of coarse Argent grain is 100 or less in 1.0g slurries.