CN104488040A - Conductive paste for laser etching, conductive thin film, and conductive laminate - Google Patents

Abstract

To provide a conductive paste for laser etching, which is suitable for laser etching that is capable of producing a high-density electrode circuit wiring line having an L/S of 50/50 mum or less at low cost with a little burden on the environment, said high-density electrode circuit wiring line having been considered difficult to be produced by conventional screen printing methods. A conductive paste for laser etching, which contains (A) a binder resin that is formed of a thermoplastic resin, (B) a metal powder and (C) an organic solvent; a conductive thin film that is formed using the conductive paste; a conductive laminate; an electrical circuit; and a touch panel.

Description

Laser ablation processing conductive paste, conductive membrane and electroconductive laminate

Technical field

The present invention relates to the manufacture method of the conductive pattern manufacturing the high conductive pattern of the configuration density of in-plane, and be applicable to the conductive paste of this manufacture method.Typically, conductive pattern of the present invention can be used for the electrode loop distribution of transparent touch panel.

Background technology

In recent years, carry and develop sharp with the high performance that is the electronic equipments of the transparent touch panel of representative such as mobile phone, notebook computer, e-book and miniaturization.In order to the high performance reaching these electronic equipments is with miniaturized, except requiring the raising of the miniaturization of carried electronic component, high performance, integrated level, also require that these are by the densification of interconnective for electronic component electrode loop distribution.As the mode of transparent touch panel, except the resistive film mode that the quantity of electrode loop distribution is few, the universal of capacitance-type of the increasing number of electrode loop distribution is also advancing hastily in recent years, with regard to this viewpoint, requires the densification of electrode loop distribution consumingly.In addition, in order to display frame being become larger, and due to the requirement in commodity design, having and wanting the frame portion by being used for configuring electrode loop distribution to become narrower requirement, with regard to this viewpoint, also requiring the densification of electrode loop distribution.In order to meet above requirement, seeking the technology of the arranged in high density can implementing the electrode loop distribution exceeded in the past.

The configuration density of the electrode loop distribution of the frame portion of the transparent touch panel of resistive film mode is as follows: the line of in-plane and the width of spacing are respectively 200 μm (below, referred to as L/S=200/200 μm) more than left and right, in the past, such configuration density was formed by the silk screen printing of conductive paste.If the touch panel of capacitance-type, then the requirement of L/S is less than about 100/100 μm, also exist further and require that L/S is the situation of less than 50/50 μm, if adopt the electrode loop distribution of silk screen printing to form technology, be difficult to tackle above-mentioned requirements.

Instead the electrode loop distribution of silk screen printing forms an example of the candidate of technology, can be enumerated as photoetching process.If use photoetching process, then formation L/S is the fine rule of less than 50/50 μm is also likely.But, in photoetching process, also there is technical problem.Photolithographic most typical example is the gimmick of use sense photosensitiveness photoresistance; generally speaking; the Copper Foil position of the surface substrate after forming copper foil layer is coated with photonasty photoresistance; by the method for directly to draw etc. of photomask or laser by desired pattern exposure; to carry out the development of photonasty photoresistance; afterwards by using chemicals the Copper Foil position beyond desired pattern is dissolved and removed, to form the thread pattern of Copper Foil.Therefore, because liquid waste processing and carrying capacity of environment are large, and operation is miscellaneous, also there is many problems from the viewpoint of the viewpoint of production efficiency, cost.

Prior art document

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 2010-237573 publication

Patent documentation 2: Japanese Patent Laid-Open 2011-181338 publication

Summary of the invention

The problem that invention will solve

The object of the present invention is to provide, can low cost and low environmental load ground manufactures the L/S being difficult to tackle by silk screen print method is the high-density electrode loop distribution of less than 50/50 μm.In addition, be also to provide the conductive paste being applicable to such manufacture method.

The means of dealing with problems

The present inventor conducts in-depth research for the manufacture method configuring electrode loop distribution in the in-plane direction to high-density, found that: on insulating properties base material, form the layer be made up of adhesive resin and conductive powder body, irradiate by utilizing laser and its part is removed from insulating properties base material, thus the high-density electrode loop distribution that the L/S being difficult to realize by silk screen print method is less than 50/50 μm can be manufactured.In addition, the conductive paste of the layer that the formation of fitting mutually with this manufacture method is made up of adhesive resin and conductive powder body has also been found to be suitable for be formed.That is, the technical scheme that is made up of following component of the present application.

(1) a laser ablation processing conductive paste, it contains the adhesive resin (A), metal powder (B) and the organic solvent (C) that are made up of thermoplastic resin.

(2) the laser ablation processing conductive paste Gen Ju (1), it is characterized in that, described adhesive resin (A) is number-average molecular weight is 5,000 ~ 60,000 and glass transition temperature is the thermoplastic resin of 60 ~ 100 DEG C.

(3) according to (1) or the laser ablation processing conductive paste described in (2), it is characterized in that, described adhesive resin (A) is selected from the one kind or two or more mixture in the group that is made up of mylar, polyurethane resin, epoxy resin, vinyl chloride resin, cellulose-derived resin.

(4) according to (1) or the laser ablation processing conductive paste described in (2), it is characterized in that, described adhesive resin (A) is selected from by acid number 50 ~ 300 equivalent/10 ⁶the mylar of g and acid number 50 ~ 300 equivalent/10 ⁶one kind or two or more mixture in the group of the polyurethane resin composition of g.

(5) according to the conductivity laser ablation processing conductive paste according to any one of (1) ~ (4), it is characterized in that, further containing laser absorbent (D).

(6) conductive membrane, it is that laser ablation processing conductive paste according to any one of (1) ~ (5) formed.

(7) electroconductive laminate, it is that conductive membrane described in lamination (6) and base material form.

(8) electroconductive laminate Gen Ju (7), is characterized in that, described base material has transparent conductivity layer.

(9) circuit, it uses the conductive membrane described in (6) or (7) or the electroconductive laminate described in (8) to form.

(10) a kind of circuit, it has distribution position, described distribution position is by irradiating the laser being selected from carbon dioxide laser, YAG laser, optical-fiber laser and semiconductor laser in a part for the conductive membrane described in (6), thus the part removing described conductive membrane is formed.

(11) circuit Gen Ju (9), is characterized in that, described conductive membrane is formed on transparent conductivity layer.

(12) touch panel, it comprises (9) ~ (11) according to any one of circuit as member of formation.

Invention effect

Conductive paste of the present invention is the conductive paste containing adhesive resin (A), metal powder (B) and the organic solvent (C) be made up of thermoplastic resin, by adopting this formation, laser ablation processing suitability can be formed excellent, even and if to the conductive membrane of the excellent adhesion after the initial of base material and hygrothermal environment load after laser ablation processing.In addition, the suitability of laser ablation processing herein excellence refers to, utilizes laser ablation to process and makes peeling off from base material at least partially of conductive membrane, and when making it the fine rule forming about L/S=30/30 μm, meet: 1) guarantee the conducting between fine rule two ends; 2) insulation between adjacent fine rule is guaranteed; 3) narrow line shape is good; Such 3 conditions.In addition, compared to the conductive paste not containing laser absorbent (D), the conductive paste containing laser absorbent (D) of embodiments of the present invention uprises for sharp light-struck sensitivity, improves the more excellent effect such as laser scanning speed, reduction Laser output so can play.

Accompanying drawing explanation

[Fig. 1] represents that the laser ablation used in embodiments of the invention, comparative example processes the schematic diagram of the pattern of irradiating laser on suitability evaluation test film.Irradiating laser on white position, to remove the conductive membrane that base material is formed.Not irradiating laser on position, site.The unit of the size Expressing in figure is mm.

The explanation of symbol

1a, 2a, 3a, 4a: terminal 1a, 2a, 3a, 4a

1b, 2b, 3b, 4b: fine rule 1b, 2b, 3b, 4b

1c, 2c, 3c, 4c: terminal 1c, 2c, 3c, 4c

5: the pattern that laser ablation flexibility (adaptability) of operation evaluation test sheet is formed

Embodiment

" forming the composition of conductive paste of the present invention "

Laser ablation processing conductive paste in the present invention is as neccessary composition containing the adhesive resin (A), metal powder (B) and the organic solvent (C) that are made up of thermoplastic resin.

< adhesive resin (A) >

The kind of adhesive resin (A) is thermoplastic resin, there is no particular limitation, can be enumerated as: mylar, epoxy resin, phenoxy resin, polyamide, polyamide-imide resin, polycarbonate resin, polyurethane resin, phenolic resins, acrylic resin, polystyrene, styrene-acrylic resins, Styrene-Butadiene, phenolic resins, polyethylene-based resin, polycarbonate-based resin, phenolic resins, alkyd resins, styrene-acrylic resins, styrene butadiene copolymers resin, polysulfone resin, polyethersulfone resin, vinyl chloride-vinyl acetate copolymer resin, ethene-vinyl acetate copolymerization, polystyrene, silicones, fluorine resin etc., these resins can use individually or as mixture of more than two kinds.Preferably, mixture one kind or two or more in the group be made up of mylar, polyurethane resin, epoxy resin, vinyl chloride resin, cellulose-derived resin is selected from.In addition, in the middle of these resins, preferably containing mylar and/or polyester component as the polyurethane resin (following, to be sometimes referred to as polyester polyurethane resin) of copolymer composition as adhesive resin (A).

Mylar is used to be that the degree of freedom of MOLECULE DESIGN is high as one of advantage of the adhesive resin (A) in the present invention.Selected dicarboxylic acids and the glycol component forming mylar, can freely make copolymer composition change, in addition, also easy in strand or molecular end connection functional group.Therefore, the resin properties such as the glass transition temperature that can adjust the mylar of gained aptly, the compatibility of other composition that mixes with in base material and conductive paste.

As the example of dicarboxylic acids of copolymer composition that may be used for the mylar used in adhesive resin of the present invention (A), can list: the aromatic binary carboxylic acids such as terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids; The aliphatic dicarboxylic acids such as butanedioic acid, glutaric acid, adipic acid, decanedioic acid, dodecanedicarboxylic acid, azelaic acid; The binary acid, 1 of the carbon numbers such as dimeric dibasic acid 12 ~ 28,4-cyclohexane dicarboxylic acid, 1, the Cycloaliphatic dicarboxylic acids such as 3-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxyl hydrogenated bisphenol A, dicarboxyl A Hydrogenated Bisphenol A S, dimeric dibasic acid, hydrogenated dimer acids, hydrogenated naphthalene dicarboxylic acids, tricyclodecane-dicarboxylic acid; The hydroxycarboxylic acid such as hydroxybenzoic acid, lactic acid.In addition, in the scope of effect not damaging invention, also can also with the carboxylic acid more than ternary such as trimellitic anhydride, PMA, the unsaturated dicarboxylic acids such as fumaric acid and/or 5-sulfoisophthalic acid sodium etc. contain the dicarboxylic acids of Sulfonic acid metal salt groups as copolymer composition.

As the example of polyalcohol of copolymer composition that may be used for the mylar used in adhesive resin of the present invention (A), can list: ethylene glycol, propylene glycol, 1, ammediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, 5-pentanediol, 2-methyl isophthalic acid, ammediol, 2, 2-diethyl-1, ammediol, 2-butyl-2-ethyl-1, ammediol, 1, 9-nonanediol, 1, the aliphatic dihydroxy alcohols such as 10-decanediol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, the cycloaliphatic diols such as dimer diol.In addition, in the scope of effect not damaging invention, also can be used together the polyalcohol of more than the ternarys such as trimethylolethane, trimethylolpropane, glycerol, pentaerythrite, polyglycerol as copolymer composition.

Can be used as the mylar that the adhesive resin (A) in the present invention uses, with regard to the viewpoint of the durability such as intensity or thermal endurance, moisture-proof and resistance to sudden heating etc., among all acid composition forming described mylar, the copolymerization ratio of aromatic binary carboxylic acid preferably more than 60 % by mole, be more preferably more than 80 % by mole, be preferably more than 90 % by mole further, be preferably more than 98 % by mole especially.It is preferred embodiment that all acid composition is all made up of aromatic binary carboxylic acid.If the copolymerization ratio of aromatic binary carboxylic acid composition is too low, then the glass transition temperature of the mylar of gained will become lower than 60 DEG C, and the humidity resistance of the conductive membrane of gained, durability are tended to reduce.

Can be used as the mylar that adhesive resin in the present invention (A) uses, with regard to the viewpoint of the durability such as intensity or thermal endurance, moisture-proof and resistance to sudden heating etc., among the whole polyalcohols forming described mylar, the carbon number of main chain be less than 4 dihydroxylic alcohols be preferably more than 60 % by mole, be more preferably more than 80 % by mole, be preferably more than 95 % by mole further.Among whole polyol component, if the carbon number of main chain is that the copolymerization ratio of the dihydroxylic alcohols of less than 4 is too low, then the glass transition temperature of the polyurethane resin of gained will become lower than 60 DEG C, and the humidity resistance of the conductive membrane of gained, durability are tended to reduce.

Polyurethane resin is used also to be preferred embodiment as the adhesive resin (A) in the present invention.Identical with the situation of mylar, as for polyurethane resin, also by the copolymer composition of selected suitable composition as formation polyurethane resin, and in strand or molecular end connect functional group, thus can suitably adjust glass transition temperature, with the resin properties such as the compatibility of other composition mixed in base material and conductive paste.

Although the copolymer composition as polyurethane resin also there is no and limits especially, with regard to the viewpoint of the maintenance of the degree of freedom of design or humidity resistance, durability, be preferably and PEPA is used as the polyester polyurethane resin of copolymer composition.As the suitable example of described PEPA, among the above-mentioned mylar that can be used as adhesive resin of the present invention (A), polyalcohol can be enumerated.

Can be used as the polyurethane resin that the adhesive resin (A) in the present invention uses, such as, by polyalcohol and PIC reaction and obtain.As the PIC that the copolymer composition that can be used as above-mentioned polyurethane resin uses, can be exemplified by: 2, 4-toluene di-isocyanate(TDI), 2, 6-toluene di-isocyanate(TDI), PPDI, 4, 4 '-methyl diphenylene diisocyanate, m-benzene diisocyanate, 3, 3 '-dimethoxy-4 ', 4 '-biphenyl diisocyanate, 2, 6-naphthalene diisocyanate, 3, 3 '-dimethyl-4, 4 '-biphenyl diisocyanate, 4, 4 '-diphenyl diisocyanate, 4, 4 '-vulcabond diphenyl ether, 1, 5-naphthalene diisocyanate, m xylene diisocyanate, IPDI, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI) etc., also can be aromatic diisocyanate, any one in aliphatic diisocyanate and alicyclic diisocyanate.In addition, in the scope not damaging effect of the present invention, can be used together the isocyanate compound of more than trivalent as copolymer composition.

In the polyurethane resin used as the adhesive resin (A) in the present invention, optionally can copolymerization have can with the compound of the functional group of isocyanate reaction.As can with the functional group of isocyanate reaction, preferred hydroxyl and amido, both can have wherein any one, also can have two kinds.As its object lesson, can be enumerated as: dimethylolpropionic acid, dihydromethyl propionic acid, 1, 2-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2, 3-butanediol, 2, 2-dimethyl-1, ammediol, 3-methyl isophthalic acid, 5-pentanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexylene glycol, 2, 2-dimethyl-3-hydroxypropyl-2 ', 2 '-dimethyl-3 '-hydroxy propionate, 2-normal-butyl-2-ethyl-1, ammediol, 3-ethyl-1, 5-pentanediol, 3-propyl group-1, 5-pentanediol, 2, 2-diethyl-1, ammediol, 3-octyl group-1, 5-pentanediol, 3-phenyl-1, 5-pentanediol, 2, 5-dimethyl-3-sodium sulfo group-2, 5-hexylene glycol, dimer diol (such as, Unichema International (ユ ニ ケ マ イ ン タ ー Na シ ョ Na Le) Inc. PRIPOOL-2033) etc. there is in every 1 molecule the compound of 2 hydroxyls, there is in every 1 molecules such as trimethylolethane, trimethylolpropane, glycerol, pentaerythrite, polyglycerol the alcohol of the hydroxyl of more than 3, in every 1 molecules such as monoethanolamine, diethanol amine, triethanolamine, there is the hydroxyl of more than 1 and the amino alcohol of amido, aliphatic diamine or the m-xylene diamine such as ethylenediamine, 1,6-hexamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1,11-hendecane diamines, 1,12-dodecamethylene diamine, 4,4 '-diaminodiphenyl-methane, 3,4 '-diamino-diphenyl ether, 4, has the compound of 2 amidos in every 1 molecules such as aromatic diamine such as 4 '-diamino-diphenyl ether.Above-mentioned number-average molecular weight is less than 1, have in every 1 molecule of 000 more than 2 can with the compound of the functional group of isocyanate reaction, both can be used alone, even if multiple and with also without any problem.

There is no particular limitation for the number-average molecular weight of the adhesive resin (A) in the present invention, but preferred number average molecular weight is 5,000 ~ 60,000.If number-average molecular weight is too low, then durability, the humidity resistance aspect of formed conductive membrane are unsatisfactory.On the other hand, if number-average molecular weight is too high, although then the cohesiveness (cohesive force) of resin increases, as the raising such as durability of conductive membrane, laser ablation processing suitability significantly worsens.

The glass transition temperature of the adhesive resin (A) in the present invention is preferably more than 60 DEG C, is more preferably more than 65 DEG C.If glass transition temperature is low, although then there is the situation that laser ablation processing suitability improves, but the worry existed as the hygrothermal environment reliability decrease of conductive membrane, in addition, cause case hardness to reduce, and produce containing paste composition to the transfer of contact object side in manufacturing process and/or when using because of adherence (タ ッ Network), and the worry that conductive film reliability reduces.On the other hand, if consider printing, adaptation, dissolubility, paste viscosity and laser ablation processing suitability etc., the glass transition temperature of the adhesive resin (A) that then the present invention is used is preferably less than 150 DEG C, be more preferably less than 120 DEG C, be preferably less than 100 DEG C further.

Adhesive resin (A) in the present invention though acid number there is no particular limitation, by having the acid number of particular range, and there is the situation that the adaptation of base material is significantly improved of can making.Man-hour is added at the laser ablation of conductive membrane, although the temperature that sometimes there is laser irradiating part position periphery rises and situation that the adaptation of conductive membrane and base material declines, but as adhesive resin (A), by using the adhesive resin with the acid number of particular range, thus sometimes also there is the situation that adaptation can be suppressed to decline.The acid number of adhesive resin (A) is preferably 50 ~ 350eq/ton, is more preferably 100 ~ 250eq/ton.If acid number is too low, then there is the tendency of the adaptation step-down between the conductive membrane formed and base material.On the other hand, if acid number is too high, the water absorption of then not only formed conductive membrane uprises, and there is the possibility of the hydrolysis promoting adhesive resin because of the catalytic action produced by carboxyl, and has the tendency that the reliability causing conductive membrane reduces.

< metal powder (B) >

As the metal powder (B) that the present invention is used, can be enumerated as: the precious metal powders such as silver powder, bronze, platinum powder, palladium powder; The base metal powder such as copper powder, nickel powder, aluminium powder, brass powder; With the base metal powder etc. after the precious metal platings such as silver or alloying.These metal powders can be used alone, in addition also can and use.Wherein, if consider conductivity, stability, cost etc., be then preferably silver powder separately or based on silver powder.

The metal powder (B) that the present invention is used shape though there is no particular limitation.As the example of the shape of in the past known metal powder, there is flake (flakey), spherical, described in dendroid (branch is crystalline), Japanese Patent Laid-Open 9-306240 publication 1 time spherical particles aggregate becomes the shape (aggegation shape) etc. after 3D shape, wherein, spherical, aggegation shape and laminar metal powder is preferably used.

The center-diameter (D50) of the metal powder (B) that the present invention is used is preferably less than 4 μm.By the metal powder (B) that use center-diameter is less than 4 μm, thus the narrow line shape of laser ablation working position tendency becomes good.When in use heart footpath is greater than the metal powder of 4 μm, the narrow line shape after laser ablation processing is deteriorated, and result causes fine rule to contact each other, has the possibility causing short circuit.Further, use laser ablation processing, have and once peel off the possibility that the conductive membrane after removing is attached to working position again.Metal powder (B) though the lower limit of center-diameter there is no particular limitation, from the viewpoint of cost and particle diameter as the then easily aggegation that attenuates, result causes dispersion to become difficulty, so center-diameter is preferably more than 80nm.If center-diameter becomes be less than 80nm, then except the cohesiveness of metal powder increase, laser ablation processing suitability worsen except, also undesirable from the viewpoint of cost.

In addition, center-diameter (D50) refers to, in the integral distribution curve (volume) obtained by any assay method, its accumulated value becomes the particle diameter (μm) of 50%.In the present invention, by using laser diffraction and scattering formula particle size distribution analyzer (Nikkiso Company Limited's system, MICROTRAC HRA) and measuring integral distribution curve with total reflection pattern.

The content of metal powder (B), it is with regard to the good viewpoint of the conductivity of formed conductive membrane, with thermoplastic resin (A) 100 mass parts for benchmark, is preferably more than 400 mass parts, is more preferably more than 560 mass parts.In addition, the content of (B) composition, it is with regard to viewpoint good in the adaptation between base material, with thermoplastic resin (A) 100 mass parts for benchmark, is preferably below 1,900 mass parts, is more preferably 1, below 230 mass parts.

< organic solvent (C) >

Organic solvent used in the present invention (C) is though there is no particular limitation, but with regard to the viewpoint evaporation rate of organic solvent being remained on suitable scope, preferred boiling point is more than 100 DEG C, is less than 300 DEG C, and more preferably boiling point is more than 150 DEG C, is less than 280 DEG C.Typically, conductive paste of the present invention uses three-roll grinder etc. the dispersion of thermoplastic resin (A), metal powder (B), organic solvent (C) and other composition optionally to be made, if now the boiling point of organic solvent is too low, then solvent evaporates in dispersion, and have the composition forming conductive paste than the worry changed.On the other hand, if the boiling point of organic solvent is too high, then there is solvent a large amount of residual possibility in film according to drying condition, thus have the worry that the reliability causing film reduces.

In addition, as organic solvent used in the present invention (C), preferred thermoplastic resin (A) is solvable and can make the organic solvent that metal powder (B) disperses well.Object lesson, can be enumerated as: TC acetate (EDGAC), ethylene glycol butyl ether acetate (BMGAC), diethylene glycol monobutyl ether acetate (BDGAC), cyclohexanone, toluene, isophorone, gamma-butyrolacton, phenmethylol, the Solvesso 100 of Exxon chemical company, 150, 200, propylene glycol monomethyl ether acetate, adipic acid, the mixture of the dimethyl ester of butanedioic acid and glutaric acid (such as, DuPont joint-stock company DBE), terpinol etc., wherein, dissolubility with regard to the formulated component of thermoplastic resin (A) is excellent, solvent volatility appropriateness during continuous printing, and for using the viewpoint that the suitability of the printings such as silk screen print method is good, preferred EDGAC, BMGAC, BDGAC and their mixed solvent.

As the content of organic solvent (C), with paste total weight 100 weight portion for benchmark, be preferably more than 5 weight portions, below 40 weight portions, be preferably more than 10 weight portions further, below 35 weight portions.If the too high levels of organic solvent (C), then paste viscosity will become too low, and during fine rule printing, tendency becomes and easily drips.On the other hand, if the content of organic solvent (C) is too low, then except becoming high as the viscosity of paste, outside when making it to form conductive membrane, such as screen printability significantly declines, the thickness of the conductive membrane also formed to some extent is thickening, the situation that laser ablation processability reduces.

< laser absorbent (D) >

In conductive paste of the present invention, also can hybrid laser absorbent (D).Herein, laser absorbent (D) refers to, have the strong additive absorbed to the wavelength of laser, namely laser absorbent (D) itself can be conductivity also can be non-conductive.Such as, when using YAG laser that the wavelength of basic wave is 1064nm as light source, the strong dyestuff that absorbs and/or pigment can be had as laser absorbent (D) using being used in wavelength 1064nm place.By hybrid laser absorbent (D), thus conductive membrane of the present invention absorbing laser efficiently, and promoting volatilization or the thermal decomposition of the adhesive resin (A) caused by generating heat, its result improves laser ablation processing suitability.

In the middle of laser absorbent used in the present invention (D), as the example of laser absorbent with conductivity, can be enumerated as: the carbon such as carbon black, graphite powder system filler.The mixing of carbon system filler is also improved the effect of conductive membrane conductivity of the present invention, following effect can be expected: such as, because carbon black has absorbing wavelength near 1060nm, if so irradiate the laser of the wavelength of the 1064nm such as YAG laser, optical-fiber laser, then because of conductive membrane efficiently absorbing laser and to swash light-struck highly sensitive, even when improving that to swash the situation of light-struck sweep speed and/or lasing light emitter be low-power (low exert oneself), good laser ablation processing suitability also can be obtained.As the content of described carbon system filler, with metal powder (B) 100 weight portion for benchmark, be preferably 0.1 ~ 5 weight portion, be more preferably 0.3 ~ 2 weight portion.When the blending ratio of carbon system filler is too low, improves the effect of conductivity and improve the effect of sharp light-struck sensitivity little.On the other hand, when the blending ratio of carbon system filler is too high, the conductivity of conductive membrane is tended to reduce, and further, also has resin to adsorb to the position, space of carbon, sometimes also produces the problem reduced with the adaptation of base material.

In the middle of laser absorbent used in the present invention (D), as the example of dielectric laser absorbent, can be enumerated as: known dyestuff, pigment and infrared absorbent.More particularly, can be enumerated as: the dyestuffs such as azo dyes, metallic complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine dye, carbonium dye, quinoneimine dye, methine dyes, cyanine dye, side sour cyanines pigment, pyralium salt, metal thiolate complex; As pigment, black pigment, yellow uitramarine, orange pigment, brown pigments, red pigment, violet pigment, blue pigment, viridine green, fluorescent pigment, metal powder pigment and polymer are in conjunction with pigment.Specifically, can use: insoluble azo colour, azo lake pigment, condensed azo pigment, chelate azo pigments, phthualocyanine pigment, anthraquione pigmentss, perylene and purple cyclic ketones series pigments, thioindigo series pigments, quinacridone pigment, dioxazine pigment, isoindoline series pigments, quinoline dai ketone series pigments, dye mordant pigment (dye pays け レ ー キ face material), azine pigments, nitroso pigments, nitropigments, natural pigment, fluorescent pigment, inorganic pigment.As the example of infrared absorbent, can be enumerated as: the NIR-IM1 of the infrared absorbent of diimmonium salt form, the NIR-AM1 (Jun Shi NagaseChemtex Inc.) of ammonium salt type.Preferably, containing these dielectric laser absorbent (D) 0.01 ~ 5 weight portions, preferably 0.1 ~ 2 weight portion.When the blending ratio of dielectric laser absorbent (D) is too low, the effect improved swashing light-struck sensitivity is little.When the blending ratio of dielectric laser absorbent (D) is too high, the worry of the conductivity reduction of conductive film, the tone of laser absorbent becomes remarkable in addition, sometimes there is the situation undesirable for purposes.

In conductive paste of the present invention, following inorganic matter can be added.As inorganic matter, can use: the various carbide such as carborundum, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, ramet, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, diamond carbon lactams; The various borides such as the various nitride such as boron nitride, titanium nitride, zirconium nitride, zirconium boride; The various oxides such as titanium oxide (titanium dioxide), calcium oxide, magnesium oxide, zinc oxide, cupric oxide, aluminium oxide, silica, cabosil; The various titanium oxygen compounds such as calcium titanate, magnesium titanate, strontium titanates; Molybdenum bisuphide sulfides; The various fluoride such as magnesium fluoride, fluorocarbons; The various metallic soaps such as aluminum stearate, calcium stearate, zinc stearate, dolomol; And talcum, bentonite, talcum (タ Le Network), calcium carbonate, bentonite, kaolin, glass fibre, mica etc.By adding these inorganic matters, printing or thermal endurance sometimes can be made to improve, make mechanical property or long durability improve further.Wherein, in conductive paste of the present invention, with regard to giving the viewpoint of durability, printing suitability, particularly silk screen printing suitability, preferential oxidation silicon.

In addition, in conductive paste of the present invention, can mix: thixotropy conferring agents, defoamer, fire retardant, tackifier, hydrolysis preventing agent, levelling agent, plasticizer, antioxidant, ultra-violet absorber, fire retardant, pigment, dyestuff.Further, as resin decomposition inhibitor, can suitably mix carbon imidodicarbonic diamide, epoxides etc.They both can be used alone and also can be used together.

< curing agent (E) >

In conductive paste of the present invention, also can mixing energy and adhesive resin (A) react in the degree not damaging effect of the present invention curing agent.By mixed curing agent, although there is curing temperature to uprise, the possibility that the load of production process increases, due to during dried coating film or laser ablation time the heat that produces and produce crosslinked, can expect that the humidity resistance of film improves.

The curing agent that can react with adhesive resin of the present invention (A), though its kind also indefinite, with regard to adaptation, resistance to bend(ing), curability etc., preferred isocyanate compound especially.Further, if use isocyanate-terminated compound as these isocyanate compounds, then storage stability improves, so preferably.As the curing agent beyond isocyanate compound, can be enumerated as: the known compounds such as the amino resins such as methylated melamine, butylated melamines, benzoguanamine, carbamide resin, acid anhydrides, imidazoles, epoxy resin, phenolic resins.In these curing agent, also can be used together the known catalyst or promoter selected depending on its kind.As the combined amount of curing agent, mix under the degree not damaging effect of the present invention, though there is no particular limitation, but with adhesive resin (A) 100 mass parts for benchmark, be preferably 0.5 ~ 50 mass parts, be more preferably 1 ~ 30 mass parts, be preferably 2 ~ 20 mass parts further.

As the example of the isocyanate compound that can mix in conductive paste of the present invention, have the PIC etc. of more than aromatic series or aliphatic vulcabond, 3 valencys, also can be low molecular compound, macromolecular compound any one.Such as, can be enumerated as: the aliphatic diisocyanate such as tetramethylene diisocyanate, hexamethylene diisocyanate; The aromatic diisocyanates such as toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, XDI; The alicyclic diisocyanates such as hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, dimer acid diisocyanate, IPDI; Or the compound containing terminal isocyanate group that low molecule active dydrogen compounds or various polyester polyols alcohols, polyether polyols alcohols, the polyamide-based high molecular reactive hydrogen compound etc. such as the excess quantity of the trimer of these isocyanate compounds and these isocyanate compounds and such as ethylene glycol, propylene glycol, trimethylolpropane, glycerol, D-sorbite, ethylenediamine, monoethanolamine, diethanol amine, triethanolamine react and obtain.In addition, as the end-capping reagent of NCO, can be enumerated as: such as, the phenol such as phenol, benzenethiol, methylbenzene phenyl-sulfhydrate, ethyl thiophenol, cresols, xylenols, resorcinol, nitrophenol, chlorophenol; The oximes such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime; The alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols; The halogen substiuted alcohols such as chlorethanol, 1,3-bis-chloro-2-propyl alcohol; The tertiary alcohols such as the tert-butyl alcohol, tert-pentyl alcohol; The lactams such as epsilon-caprolactams, δ-valerolactam, butyrolactam, azetidinone, in addition, also can be enumerated as: aromatic amine, acid imide, acetylacetone,2,4-pentanedione, acetoacetic ester, malonic ester isoreactivity methylene compound; Thio-alcohol, imines class, imidazoles, ureas, biaryl compound class, sodium hydrogensulfite etc.Wherein, from curability, be preferably oximes, imidazoles, amine especially.

" physical property required by conductive paste of the present invention "

Conductive paste of the present invention, its F value is preferably 60 ~ 95%, is more preferably 75 ~ 95%.F value refers to, with all solids composition 100 mass parts contained in paste for benchmark, represents the numerical value of packing quality part, represents with F value=(packing quality part/solid constituent mass parts) × 100.So-called packing quality part refers to the mass parts of electroconductive powder herein; Solid constituent mass parts refers to the mass parts of the composition beyond solvent, comprises all electroconductive powders, adhesive resin, other curing agent or additive.If F value is too low, then cannot obtain the conductive membrane representing satisfactory electrical conductivity, if F value is too high, then the adaptation between conductive membrane and base material and/or the case hardness of conductive membrane are tended to reduce, and also cannot avoid the reduction of printing.In addition, electroconductive powder herein refers to, by the both sides of metal powder (B) and nonmetal formed electroconductive powder.

" manufacture method of conductive paste of the present invention "

Conductive paste of the present invention, as mentioned above, can use three-roll grinder etc. that thermoplastic resin (A), metal powder (B), organic solvent (C) and other composition are optionally carried out disperseing and made.Herein, making step is more specifically shown.First, thermoplastic resin (A) is dissolved in organic solvent (C).Then, add metal powder (B), and optionally add additive, and use double planetary mixer (ダ Block Le プ ラ ネ タ リ ー) or dissolvers, planetary blender etc. to implement pre-dispersed.Subsequently, use three-roll grinder to disperse, thus obtain conductive paste.The conductive paste of acquisition like this can optionally filter.Even if use other disperser, such as: pearl mill, kneader, extruder etc. carry out disperseing also without any problem.

" conductive membrane of the present invention, electroconductive laminate and their manufacture method "

Conductive paste of the present invention be coated with or be printed in form film on base material, then making dried coating film by making the organic solvent (C) contained in film volatilize, thus conductive membrane of the present invention can be formed.Conductive paste coating or the method be printed on base material limit especially though be there is no, but preferably use silk screen print method to print, because silk screen print method operation is easy, and be universal technology using conductive paste to form silk screen print method in the industry of circuit.In addition, using conductive paste coating or be printed in than final as on wide a little position, circuit necessary conductive membrane position, with regard to the load that more effectively reduces laser ablation operation and form circuit of the present invention viewpoint with regard to preferably.

As the base material of coating conductive paste of the present invention, preferably use the material of excellent in dimensional stability.Such as, can be enumerated as: the film be made up of the material of the pliability excellences such as polyethylene terephthalate, Polyethylene Naphthalate, butylene terephthalate or Merlon.In addition, the inorganic material such as glass also can use as base material.Though the thickness of base material is without limiting especially, being preferably 50 ~ 350 μm, from forming the viewpoints such as the mechanical property of pattern material, shape stability or operability, being more preferably 100 ~ 250 μm.

In addition, carry out physical treatment and/or chemical treatment by the surface of the base material to coating conductive paste of the present invention, the adaptation of conductive membrane and base material can be improved.As the example of the method for physical treatment, can be enumerated as: sand-blast, the wet shotcrete technology method of injection containing atomic liquid, Corona discharge Treatment method, plasma processing method, ultraviolet or vacuum ultraviolet treatment with irradiation method etc.In addition, as the example of chemical treatment method, can be enumerated as: strong acid treatment method, highly basic facture, oxidizer treatment method, coupling agent treatment etc.

In addition, described base material also can be the base material with transparent conductivity layer.Can by conductive membrane lamination of the present invention on transparent conductivity layer.The material of described transparent conductivity layer there is no and limits especially, such as, can be enumerated as: take tin indium oxide as the ito film that principal component is formed.In addition, transparent conductivity layer not only can be formed on whole of base material, also can use and be waited with the part removing transparent conductivity layer by etching.

The operation of volatile organic solvent (C) is preferably carried out at normal temperatures and/or under heating.When heating, because the conductivity of dried conductive membrane or adaptation, case hardness become well, so heating-up temperature is preferably more than 80 DEG C, be more preferably more than 100 DEG C, preferably more than 110 DEG C further.In addition, with regard to the energy-conservation viewpoint in the thermal endurance of the transparent conductivity layer of ground and production process, heating-up temperature is preferably less than 150 DEG C, is more preferably less than 135 DEG C, is preferably less than 130 DEG C further.When being mixed with curing agent in conductive paste of the present invention, if carry out the operation making organic solvent (C) volatilize under heating, then reaction will be cured.

The thickness of conductive membrane of the present invention is set to suitable thickness according to the purposes used.But the viewpoint that just conductivity of dried conductive membrane is good, process the good viewpoint of suitability with laser ablation, the thickness of conductive membrane is preferably more than 3 μm, less than 30 μm, is more preferably more than 5 μm, less than 20 μm.If the thickness of conductive membrane is excessively thin, then there is the possibility that can not obtain as the conductivity desired by circuit.If thickness is blocked up, then the exposure that laser ablation machining needs will become excessive, sometimes exist the hurtful situation of base material.In addition, if the deviation of thickness is large, then can produce deviation on conductive membrane is etched easness, tend to easily produce and to cause the short circuit between circuit because etching deficiency or because etching the excessively broken string caused.Therefore, the words that the deviation of thickness is little as well.

" circuit of the present invention and its manufacture method "

At the position being irradiated with a laser absorption, the energy of laser is converted into heat, produces thermal decomposition and/or volatilization because temperature rises, thus peels off removal irradiated site.In order to remove from base material the position be irradiated with a laser conductive membrane of the present invention efficiently, preferably, the wavelength of conductive membrane of the present invention to irradiating laser has strong absorption.Therefore, as laser species, preferably at any one composition forming conductive membrane of the present invention, there is the laser species in the strong wave-length coverage absorbed with energy.

As general laser species, can be enumerated as: excimer laser (wavelength of basic wave is 193 ~ 308nm), YAG laser (wavelength of basic wave is 1064nm), optical-fiber laser (wavelength of basic wave is 1060nm), CO ₂laser (wavelength of basic wave is 10600nm), semiconductor laser etc., essentially no opinion uses the laser of which kind of mode, which kind of wavelength all without any problem.By selecting to irradiate the laser species that and base material consistent with the absorbing wavelength scope of arbitrary constituent of conductive membrane does not have by force the strong wavelength absorbed, thus effectively can carry out the removal of the conductive membrane of laser irradiating part position, and avoid the infringement of base material.With regard to this type of viewpoint, as the laser species irradiated, the wavelength of its basic wave is preferably in the scope of 532 ~ 10700nm.Such as, when using polyester film, polyester film is formed the transparent conductivity laminate of ITO layer or, polyester film forms ITO layer and by etching using the laminate after removing its part as base material, use YAG laser or optical-fiber laser, be just difficult to the hurtful viewpoint of base material preferred especially because base material does not have absorption to the wavelength of basic wave.

Laser power (レ ー ザ ー exerts oneself), there is no particular limitation for Q modulating frequency, be adjusted to: the conductive membrane of laser irradiating part position can be removed and the base material of ground does not damage.Generally speaking, preferably, laser power suitably regulates in the scope of 0.5 ~ 100W, Q modulating frequency 10 ~ 400kHz.If laser power is too low, then the removal of conductive membrane is tended to become insufficient, but by reduce laser sweep speed or increase scanning times can avoid such tendency to a certain degree.If laser power is too high, then the position causing conductive membrane to be stripped because of the thermal diffusion from illuminated portion becomes more much larger than laser light beam diameter, the possibility having live width to become meticulous or break.

The sweep speed of laser, just because man-hour (タ Network ト タ イ system) reduce and production efficiency improve viewpoint and Yan Yuegao is better, specifically, be preferably more than 1000mm/s, be more preferably more than 1500mm/s, be preferably more than 2000mm/s further.If sweep speed is excessively slow, then not only production efficiency can reduce, and conductive membrane and base material have the worry of the sustain damage because of thermal history.Though the upper limit of process velocity there is no and limits especially, if sweep speed is too high, then the removal of the conductive membrane of laser irradiating part position becomes incomplete and has the possibility of short circuit.In addition, if sweep speed is too fast, then compare at rotation angle position and the straight line position of the pattern formed, sweep speed cannot be avoided to slow down, so the thermal history of rotation angle position uprises compared with straight line position, there is the significantly reduced worry of physical property of the conductive membrane of the laser ablation working position periphery of rotation angle position.

Laser scanning can move the emitter of laser, the irradiated body of mobile illuminated laser or both combinations any one all can, such as, by using XY platform to realize.In addition, also by using galvanometer mirror (ガ Le バ ノ ミ ラ ー) etc. to carry out laser scanning to change the direction of illumination of laser.

When laser irradiates, by using collector lens (achromatic lens etc.), the energy density of per unit area can be improved.The benefit of the method can be enumerated as: compared to the situation using mask, because the energy density of per unit area being become large, even so low power laser oscillator also can carry out laser ablation processing with high sweep speed.When being irradiated to conductive membrane by the laser after optically focused, there is necessity of adjusting focal length.Necessity that the coating film thickness that the with good grounds especially base material of adjustment of focal length is coated with and carrying out adjusts, but be preferably adjusted to: damage can not be brought to base material, and the conductive membrane pattern removed and specify can be peeled off.

The same pattern repeatedly laser scanning carried out repeatedly is one of preferred embodiment.Even when there is the incomplete conductive membrane position of removal in first time scanning, or form the composition of conductive membrane removed when being again attached on base material, the conductive membrane of laser irradiating part position still can be removed completely by scanning repeatedly.Though the upper limit of scanning times there is no and limits especially, because working position periphery stands repeatedly thermal history, and have impaired, variable color, possibility that Physical properties of coating film declines, so be necessary to note.In addition, with regard to the viewpoint of production efficiency, yes, and scanning times is more few better.

It is also one of preferred embodiment that same pattern does not carry out repeatedly laser scanning repeatedly.As long as can not bring harmful effect to the characteristic of the conductive membrane of gained, electroconductive laminate and circuit, yes, and the fewer production efficiency of scanning times is more excellent.

" touch panel of the present invention "

Conductive membrane of the present invention, electroconductive laminate and/or circuit can be used as the member of formation of touch panel.Described touch panel both can be resistive film mode also can be capacitance-type.This paste can be suitable for arbitrary touch panel, but is formed, so be specially adapted to the electrode wiring of the touch panel of capacitance-type because being more suitable for fine rule.In addition, as the base material forming described touch panel, preferably use the base material with the transparent conductivity layer of ito film etc. or pass through the base material that etching removes a part of conductive layer.

Embodiment

List following examples, comparative example for describing the present invention further in detail, but the present invention is not implemented example restriction.In addition, each measured value described in embodiment, comparative example measures by the following method.

1. number-average molecular weight

Make resin concentration become about 0.5 % by weight in oxolane sample resin dissolves, and use the polytetrafluoroethylene made membrane metre filter in 0.5 μm, aperture, thus make GPC mensuration sample.Using oxolane as mobile phase, use gel permeation chromatograph (GPC) Prominence (trade name) of Shimadzu Seisakusho Ltd., differential refraction rate is detected meter (RI meter) as detector, divide the GPC carrying out resin samples to measure with column temperature 30 DEG C, flow 1mL/.In addition, number-average molecular weight is using polystyrene standard as scaled value, and omission is equivalent to molecular weight and is less than the part of 1000 and calculates.GPC post uses shodex KF-802,804L, 806L of Showa Denko K. K.

2. glass transition temperature (Tg)

Sample resin 5mg is loaded aluminum sample dish and seals, use differential scanning calorimeter (DSC) DSC-220 that Seiko instrument and equipment Co., Ltd. (セ イ コ ー イ Application ス Star Le メ Application Star (strain)) is made, carry out measuring until temperature rises to 200 DEG C with programming rate 20 DEG C/minute, ask for glass transition temperature by the extended line of the baseline below glass transition temperature with the intersection point temperature of wiring place representing maximum inclination in transition.

3. acid number

Accurate weighing sample resin 0.2g is also dissolved in the chloroform of 20mL.Then, use the phenolphthalein solution in indicator, carry out titration with the potassium hydroxide of 0.01N (ethanolic solution).The unit of acid number is set as eq/ton, i.e. the equivalent of every 1 ton of sample.

4. resin composition

By sample resin dissolves in deuterochloroform, use VARIAN 400MHz-NMR device, pass through ¹h-NMR analyzes and tries to achieve resin composition.

5. paste viscosity

Viscosimetric analysis is at sample temperature 25 DEG C, uses BH type viscosimeter (Dong Ji industry society system), implements to measure under 20rpm.

6. the storage stability of conductive paste

Conductive paste is loaded in plastic containers, after sealing, at 40 DEG C, store 1 month.The evaluation of viscosimetric analysis and the test piece by above-mentioned 5. electroconductive laminate test films making is carried out after storage.

Zero: there is no significant viscosity B coefficent, and maintain initial ratio resistance, pencil hardness and adaptation.

×: regard as significant viscosity and to rise (more than 2 times of initial viscosity) or significant viscosity declines (less than 1/2 of initial viscosity), and/or, any one during ratio resistance, pencil hardness and/or adaptation decline.

7. the making of electroconductive laminate test film

Respectively in the PET film (Dong Li society Lumirror S) of carrying out annealing in process of thickness 100 μm and ito film (tail vat Industrial Co., Ltd system, KH300), use the polyester half tone of 200 meshes and by silk screen print method to print conductive paste, thus form the pattern comprehensively smeared of wide 25mm, long 450mm, then heat 30 minutes at 120 DEG C in heated air circulation type drying oven, it can be used as electroconductive laminate test film.In addition, coating thickness to dry film thickness during adjustment printing is 6 ~ 10 μm.

8. adaptation

Use described electroconductive laminate test film and according to JIS K-5400-5-6:1990, use Cellotape (registered trade mark) (Nichiban joint-stock company), evaluated by disbonded test.But the cutting number of all directions of grid pattern is set to 11, cutting interval is set to 1mm.100/100 indicates without stripping and adaptation is good, and 0/100 represents and peels off completely.

9. ratio resistance

Measure sheet resistor and the thickness of described electroconductive laminate test film, and calculate ratio resistance.Thickness uses GaugeStand ST-022 (little Ye Ce device society system), with the thickness of the thickness of PET film for Measurement Zero Point 5 cured coating films, and uses its mean value.Sheet resistor uses MILLIOHMMETER4338B (HEWLETT PACKARD Inc.) to measure for 4 test films, and use its mean value.In addition, the scope using this milliohm table to detect is 1 × 10 ^-2below (Ω cm), and 1 × 10 ^-2ratio resistance more than (Ω cm) is outside measurement range.

10. pencil hardness

Electroconductive laminate test film is placed on the SUS304 plate of thickness 2mm, measures pencil hardness according to JIS K 5600-5-4:1999.

11. humidity resistance tests:

By electroconductive laminate test film in 80 DEG C of heating 300 hours, then in 85 DEG C, 85%RH (relative humidity) heats 300 hours, place after 24 hours at normal temperatures afterwards, then carry out various evaluation.

The evaluation of 12. laser ablation processing suitabilities

By silk screen print method, on polyester base material (Dong Li society Lumirror S (thickness 100 μm)), conductive paste printing is coated into the rectangle of 2.5 × 10cm.T400 stainless (steel) wire (thick 10 μm of emulsion, wire diameter 23 μm (Tokyo Process Service society system)) is used as half tone, to print with scraper speed 150mm/s.After printing coating, in heated air circulation type drying oven, carry out the drying of 30 minutes with 120 DEG C and obtain conductive membrane.In addition, paste dilution is adjusted to thickness and becomes 5 ~ 12 μm.Then, the conductive membrane be made carries out laser ablation processing, make the pattern with the straight line portion of 4 long 50mm as shown in Figure 1, it can be used as laser ablation to process suitability evaluation test film with said method.Laser ablation between the line of above-mentioned straight line portion is processed by and the laser of beam diameter 30 μm is respectively scanned 2 times to carry out with 60 μm of spacing.Lasing light emitter uses optical-fiber laser, and is set as: Q modulating frequency 200kHz, power 10W, sweep speed 2700mm/s.

Assessment item, condition determination are as described below.

(evaluation of laser ablation working width)

In described laser ablation processing suitability evaluation test film, measure the live width having removed the position of conductive membrane.Measure and use laser microscope (Keyence VHX-1000) to carry out, following commentary valency judgment standard judges.

Zero; The live width having removed the position of conductive membrane is 28 ~ 32 μm

△; The live width having removed the position of conductive membrane is 24 ~ 27 μm or 33 ~ 36 μm

×; The live width having removed the position of conductive membrane is less than 23 μm or more than 37 μm

(between laser ablation processing suitability evaluation (1) fine rule two ends conduction)

In described laser ablation processing suitability evaluation test film, evaluated by the conducting between the two ends of whether guaranteeing fine rule 1b, 2b, 3b, 4b.Specifically, respectively between terminal 1a-terminal 1c, connect tester between terminal 2a-terminal 2c, between terminal 3a-terminal 3c, between terminal 4a-terminal 4c and confirm conducting, below state metewand and judge.

Zero; Article 4, fine rule all has conducting between the two ends of fine rule

△; Article 4, in the middle of fine rule, without conducting between the two ends of 1 ~ 3 fine rule

×; Article 4, fine rule all between the two ends of fine rule without conducting

(between laser ablation processing suitability evaluation (2) adjacent fine rule insulating properties)

In described laser ablation processing suitability evaluation test film, by whether guaranteeing that insulation between adjacent fine rule is to evaluate.Specifically, respectively for connecting tester between terminal 1a-terminal 2a, between terminal 2a-terminal 3a, between terminal 3a-terminal 4a to confirm with or without conducting, and judge with following metewand.

Zero; Insulation is between all adjacent fine rules

△; It is insulation between the adjacent fine rule of a part

×; All do not insulate between all adjacent fine rules

(having removed the evaluation of the residue at the position of conductive membrane)

In described laser ablation processing suitability evaluation test film, use laser capture microdissection sem observation to remove the position of conductive membrane, and determine whether the attachment of residue with following metewand.

Zero: removing the position of conductive membrane without residue.

△: have a little residue at the position of removing conductive membrane.

×: many residues can be observed at the position of removing conductive membrane.

(evaluation of the conductive membrane after laser ablation and the adaptation of base material)

By using the belt stripping test of Cellotape (registered trade mark) (Nichiban (share) Inc.), the adaptation removing the conductive membrane that the position of conductive membrane is mingled with in described laser ablation processing suitability evaluation test film and remain position and base material is evaluated.This evaluation be after 24 hours that are made at test film immediately (initially), thereafter further 85 DEG C, leave standstill 120 hours and leave standstill 24 hours at normal temperatures under the hygrothermal environment of 85%RH (relative humidity) after (after hot resistance test) carry out.

Zero: unstripped.△ a: part is peeled off.×: all peel off.

The Production Example of resin

The Production Example of mylar P-1

Terephthalic acid (TPA) 700 parts, M-phthalic acid 700 parts, trimellitic anhydride 16.9 parts, ethylene glycol 983 parts and 2-methyl isophthalic acid is put in the reaction vessel possessing blender, condenser and thermometer, ammediol 154 parts, and add pressure at nitrogen atmosphere 2 atmospheric pressure, expend 3 hours and be warming up to 230 DEG C from 160 DEG C, to carry out esterification.After release pressure, put into butyl titanate 0.92 part, then slowly reduce pressure in reaction system, expend 20 minutes and be decompressed to 5mmHg, further under the vacuum of below 0.3mmHg, at 260 DEG C, carry out the polycondensation reaction of 40 minutes.Then, under nitrogen flowing, be cooled to 220 DEG C, and throw in trimellitic anhydride 50.6 parts, carry out the reaction of 30 minutes to obtain mylar.The composition of the copolymer polyester resin P-1 of gained is as shown in table 1 with transitivity.

The Production Example of mylar P-2 ~ P-11

In the Production Example of mylar P-1, change kind and the blending ratio of monomer, manufacture mylar P-2 ~ P-11.The composition of the copolymer polyester resin of gained and resin characteristics are as shown in table 1 ~ 2.

[table 2]

BPE-20F: the ethylene oxide adduct (Sanyo changes into industrial society system) of bisphenol-A

BPX-11: the propylene oxide adduct (rising sun electrification society system) of bisphenol-A

The Production Example of polyurethane resin U-1

In the reaction vessel possessing blender, condenser, thermometer, after adding 1000 parts of mylar P-7, neopentyl glycol (NPG) 80 parts and dimethylolpropionic acid (DMBA) 90 parts, put into TC acetate (EDGAC) 1087 parts, dissolve at 85 DEG C.Afterwards, add 4,4 '-methyl diphenylene diisocyanate (MDI) 460 parts, 85 DEG C carry out 2 hours reaction after, add the dibutyl tin laurate 0.5 part as catalyst, and at 85 DEG C, make it reaction 4 hours further.Then, use EDGAC 1940 parts of dilute solutions, obtain the solution of polyurethane resin U-1.The solid component concentration of the polyurethane resin solution of gained is 35 quality %.By as mentioned above and the resin solution obtained drips on polypropylene film, and use the spreader of stainless steel to extend, obtain the film of resin solution.It is left standstill 3 hours to make solvent evaporates in the hot-air drier of adjusted to 120 DEG C, then, peels off resin film from polypropylene film, thus obtain the dry resin film of film-form.The thickness of dry resin film is about 30 μm.Using the sample resin of this dry resin film as polyurethane resin U-1, and the evaluation result of various resin characteristics is shown in table 3.

The Production Example of polyurethane resin U-2 ~ U-8

Except by PEPA, have and replace with except the compound shown in table 3 with the compound of the group of isocyanate reaction and PIC, all the other manufacture polyurethane resin U-2 ~ U-8 with the method identical with the Production Example of polyurethane resin U-1.The evaluation result of the resin characteristics of polyurethane resin U-2 ~ U-8 is shown in table 3.

DMBA: dimethylolpropionic acid

NPG: neopentyl glycol

DMH:2-butyl-2-ethyl-1,3-PD

MDI:4,4 '-methyl diphenylene diisocyanate

IPDI: IPDI

Embodiment 1

Mylar P-1 being dissolved in EDGAC makes solid component concentration be the solution 2860 parts (being converted into solid constituent is 1000 parts), 7 of 35 quality %, the laminar silver powder 1 of 888 parts, the MK Conc as Kyoeisha Chemical Co., Ltd. of 71 parts of levelling agent, the Disperbyk130 of (share) Inc. of BYK chemistry Japan of as dispersant 30 parts and the EDGAC mixing of 300 parts as solvent, and carry out 3 dispersions at freezing type three roller mixing roll.Afterwards, the conductive paste of gained is printed in after on specified pattern, dry in 120 DEG C × 30 minutes, obtain conductive membrane.Use this conductive membrane to measure basic physical properties, then, carry out the discussion of laser ablation processing.The evaluation result of paste and paste film, laser ablation processability is shown in table 4.

Embodiment 2 ~ 13

Change resin and the formula of conductive paste, implement embodiment 2 ~ 17.The formula of conductive paste and evaluation result are shown in table 4 ~ table 6.In embodiment, by the baking oven comparison low temperature of 120 DEG C × 30 minutes and the heating of short time thus good Physical properties of coating film can be obtained.In addition, the adaptation after testing with the adaptation of ito film, hygrothermal environment is also good.

In addition, in table 4 ~ table 7, adhesive resin, conductive powder, additive and solvent use following material.

Adhesive resin PH-1:In Chem PKKH (phenoxy resin, number-average molecular weight 14000, Tg=71 DEG C)

Silver powder 1: laminar silver powder (D50:2 μm)

Silver powder 2: spherical silver powder (D50:1 μm)

Carbon black: Tokai Carbon Co., Ltd. #4400

Ketjen black (ケ ッ チ ェ Application Block ラ ッ Network): Lion Corporation ketjen ECP600JD

Graphite powder: the graphite BF that in (share), more blacklead industry is made

Curing agent: Asahi Chemical Corp MF-K60X

Curing catalysts: Common medicine Co., Ltd KS1260

Levelling agent: Kyoeisha Chemical Co., Ltd. MK Conc

The Disperbyk130 of (share) Inc. of dispersant 1:BYK chemistry Japan

Dispersant 2:BYK chemistry Japan (share) Inc. Disperbyk2155

The Disperbyk180 of (share) Inc. of dispersant 3:BYK chemistry Japan

Additive 1: Japanese Aerosil (share) Inc. silica R972

Additive 2:Nagase Chemtex (share) Inc. NIR-AM1

Additive 3: the light acrylate PE-3A (pentaerythritol triacrylate) of Kyoeisha Chemical Co., Ltd.'s system

EDGAC:Daicel (share) Inc. TC acetate

BMGAC:Daicel (share) Inc. ethylene glycol butyl ether acetate

BDGAC:Daicel (share) Inc. diethylene glycol monobutyl ether acetate

TPOL: Japanese Terpene chemistry (share) Inc. terpinol

[table 4]

[table 5]

[table 6]

Comparative example 1

Lauryl silver carboxylate (1000g) and butylamine (480g) are dissolved in toluene (10L).Then, drip formic acid (150g), directly at room temperature stir 1.5 hours.Add a large amount of methyl alcohol, the agglutinator precipitation of Nano silver grain, thus by its decant.Repeatedly after decant 3 times, under reduced pressure make drying precipitate.Then, the sediment 1000g of gained (wherein, 920g silver, silver carboxylate amine complex 80g) is scattered in terpinol 1860g again, and obtains the conductive paste comprising Nano silver grain (silver powder 3).The silver powder 3 of gained is by transmission electron microscope photo, and its particle diameter is about 10nm.The solid component concentration of conductive paste is 35 quality %.The conductive paste of use gained is made into electroconductive laminate test film identically with embodiment and laser ablation processes suitability evaluation test film, evaluates identically with embodiment.Evaluation result is shown in table 7.Its initial Physical properties of coating film of this conductive silver paste constituent is significantly severe, and particularly adaptation is not enough, impracticable.

Comparative example 2

Lauryl amine is dissolved in terpinol, is made into the solution of solid component concentration 12 % by weight.In this solution 1000 parts (solid constituent 120 weight portion), add 8083 parts silver powder 4 (spherical silver powder (D50=1 μm), then add 250 parts to be broken to the glass dust ((bismuth oxide (Bi that average grain diameter is 1.5 μm by pearl abrasive dust ₂o ₃) as principal component glass powder (bismuth oxide content 80.0 ~ 99.9%) and continue mixing, after mixing, use three-roll grinder to disperse this solution, thus be made into the conductive paste containing glass powder.The conductive paste of use gained is made into electroconductive laminate test film identically with embodiment and laser ablation processes suitability evaluation test film, and evaluates identically with embodiment.Evaluation result is shown in table 7.The initial Physical properties of coating film of this conductive silver paste constituent is significantly severe, and particularly adaptation is not enough, impracticable.In addition, laser ablation processability is significantly severe, and in the scope wider than irradiated site, the film according to the larger width range of the width penetrating laser beam is peeled off, and can not process the live width of regulation.In addition, adaptation and the humidity resistance of the fine rule part after laser ablation processing are also not enough.

[table 7]

Industrial utilizability

Laser ablation processing conductive paste of the present invention can provide a kind of keep laser ablation to process suitability, simultaneously hygrothermal environment are excellent in reliability, the conductive membrane of the film durability that can be maintained as conductive membrane, can be used as being applied to and be mounted in such as, the conductive paste of the touch panel in mobile phone, notebook computer, e-book etc.

Claims (12)

1. a laser ablation processing conductive paste, it contains the adhesive resin (A), metal powder (B) and the organic solvent (C) that are made up of thermoplastic resin.

2. laser ablation processing conductive paste according to claim 1, is characterized in that, described adhesive resin (A) is number-average molecular weight is 5,000 ~ 60,000 and glass transition temperature is the thermoplastic resin of 60 ~ 100 DEG C.

3. laser ablation processing conductive paste according to claim 1 and 2, it is characterized in that, described adhesive resin (A) is selected from the one kind or two or more mixture in the group that is made up of mylar, polyurethane resin, epoxy resin, vinyl chloride resin, cellulose-derived resin.

4. laser ablation processing conductive paste according to claim 1 and 2, is characterized in that, described adhesive resin (A) is selected from by acid number 50 ~ 300 equivalent/10 ⁶the mylar of g and acid number 50 ~ 300 equivalent/10 ⁶one kind or two or more mixture in the group of the polyurethane resin composition of g.

5. the conductivity laser ablation processing conductive paste according to any one of Claims 1 to 4, is characterized in that, further containing laser absorbent (D).

6. a conductive membrane, it is that laser ablation processing conductive paste according to any one of Claims 1 to 5 formed.

7. an electroconductive laminate, its conductive membrane according to claim 6 that has been lamination and base material and obtain.

8. electroconductive laminate according to claim 7, is characterized in that, described base material has transparent conductivity layer.

9. a circuit, it uses the conductive membrane described in claim 6 or the electroconductive laminate described in claim 7 or 8 to form.

10. a circuit, it has distribution position, described distribution position is by irradiating the laser being selected from carbon dioxide laser, YAG laser, optical-fiber laser and semiconductor laser in a part for conductive membrane according to claim 6, thus the part removing described conductive membrane is formed.

11. circuit according to claim 9, is characterized in that, described conductive membrane is formed on transparent conductivity layer.

12. 1 kinds of touch panels, it comprises circuit according to any one of claim 9 ~ 11 as member of formation.