JP2014231217A - Conductive member, injection molded article, film, fiber, tube, hollow molded product, and production method of conductive member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive member which includes: a layer including a conductive material having high adhesiveness to a base material of a conductive pattern formed by using a conductive ink, in particular an ink or a paste including metal nanoparticles and bringing about excellent conductivity; and a polyoxamide substrate, as well as production methods of them.SOLUTION: A conductive member includes a layer including a conductive material and a polyamide resin substrate.

Description

  The present invention relates to a conductive member having a layer containing a conductive material directly laminated on a polyamide resin substrate, a method for manufacturing the conductive member, and the like.

  In recent years, printable electronics using ink or paste containing metal nanoparticles has attracted attention.

  Regarding the production of a conductive pattern by printing, conventionally, a high-viscosity conductive resin paste containing silver powder, a resin binder, and an organic solvent has been patterned using a printing method suitable for the high-viscosity paste. However, in recent years, attempts to pattern inks or pastes containing metal nanoparticles have been actively conducted because of the difficulty in printing fine lines due to the large size of silver powder and the decrease in conductivity due to resin binder components. ing. In addition, since the metal nanoparticles are coated with a dispersant, the pattern formed by simply applying and drying does not have electrical conductivity. In order to fuse them, sintering at about 150 ° C. is required. Further, the ink or paste containing these metal nanoparticles has the feature that the higher the temperature, the more the metal nanoparticles are fused and the higher the electrical conductivity.

  Conventionally, not only glass and ceramics but also various flexible and foldable films such as polyethylene terephthalate film, polyethylene naphthalate film, polyimide film, polycarbonate film, etc. have been used as substrates for forming conductive patterns used in printing. Is done. However, as described above, in order to sufficiently exhibit the conductivity of the ink or paste containing metal nanoparticles, the film is required to have heat resistance under baking conditions at a high temperature. Furthermore, since the ink or paste containing metal nanoparticles becomes almost a metal component in the dried state after sintering, there is a problem that it is difficult to ensure sufficient adhesion with these organic films.

  Therefore, in order to solve such a problem, a base material is disclosed in which an adhesive layer for ensuring close contact with the layer obtained by sintering ink or paste containing metal nanoparticles on the base material is disclosed ( Patent Documents 1 to 3). For example, Patent Document 1 discloses a method of applying a primer treatment by applying a coating containing an Ag metal oxide to a base material. Patent Document 2 discloses a method of forming a compound (silane coupling agent having a thiol group, amino group, carboxyl group or ureido group) layer having a group capable of binding to a metal on the substrate surface. Furthermore, Patent Document 3 discloses a method for forming an adhesive layer made of a thermoplastic resin.

JP2012-231171 JP 2006-54214 A JP 2006-93297 A

  However, separately providing these adhesive layers on the base material increases the production process and leads to an increase in cost of the final product. Furthermore, in high-temperature firing in which an ink or paste containing metal nanoparticles becomes highly conductive, depending on the components used for the adhesive layer, this layer may deteriorate, leading to a decrease in adhesion.

  The present invention has been made in view of the problems as described above, and has an adhesive property to a base material of a conductive pattern formed using a conductive ink, particularly an ink or paste containing metal nanoparticles. It is an object of the present invention to provide a conductive member characterized by having a layer containing a conductive material directly laminated on a polyamide resin substrate that is high and has excellent conductivity, and a method for producing the conductive member. Furthermore, it is possible to provide an injection-molded product having excellent conductivity and an extrusion-molded product such as a film, a fiber, a tube, and a hollow molded product.

  In order to achieve the above object, the present inventors have conducted intensive research, and as a result, a conductive member having a layer containing a conductive material directly laminated on a polyamide resin substrate is a conductive ink, In particular, the inventors have found that a conductive pattern formed using an ink or paste containing metal nanoparticles has high adhesion to a base material, and that excellent conductivity can be obtained, leading to the present invention. Furthermore, the inventors have found that excellent conductivity can be obtained for an injection-molded product or an extrusion-molded product such as a film, a fiber, a tube, or a hollow molded product using the present invention.

  That is, the present invention relates to a conductive member having a layer containing a conductive material directly laminated on a polyamide resin substrate.

  The present invention also relates to a conductive member, wherein the conductive material includes metal nanoparticles, and the metal of the metal nanoparticles is silver or copper.

  Furthermore, in the present invention, in the polyamide resin, the dicarboxylic acid component is oxalic acid, and the diamine component is 1,6-hexamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, isophoronediamine, and The present invention relates to a conductive member comprising two or more diamine components selected from the group consisting of 1,3-bisaminomethylcyclohexane.

  The present invention also relates to a conductive member in which a conductive pattern is formed by printing or applying the conductive material on the layer containing the conductive material.

  The present invention also relates to an injection molded product having a layer containing a conductive material directly laminated on a polyamide resin substrate.

  Furthermore, the present invention relates to a film, a fiber, a tube, and a hollow molded article having a layer containing a conductive material directly laminated on a polyamide resin substrate.

  The present invention also provides a method for producing a conductive member comprising a layer containing a conductive material directly laminated on a polyamide resin substrate, wherein the conductive material is printed or applied to a polyoxamide substrate, and the conductive material is formed. It is related with the manufacturing method of the electrically-conductive member characterized by heat-processing a conductive material above 180 degreeC, and shape | molding the layer containing an electroconductive material.

  As described above, according to the present invention, the conductive ink, in particular, the conductive pattern formed by using the ink or paste containing metal nanoparticles is highly adhesive to the base material, and has excellent conductivity. It is possible to provide a conductive member having a layer containing a conductive material directly laminated on the obtained polyamide resin substrate, and a method for manufacturing the conductive member. Furthermore, by utilizing the moldability of the polyamide resin, not only the base material but also an injection molded product having excellent conductivity and an extruded product such as a fiber, a tube, and a hollow molded product are provided. Can do.

  Hereinafter, the present invention will be described in detail.

(1) Component of polyamide resin
The polyamide resin used in the present invention includes a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b), the dicarboxylic acid (a) includes an oxalic acid compound, and the diamine (b) is 1,6. -Two or more diamines selected from the group consisting of hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, isophoronediamine and 1,3-bisaminomethylcyclohexane are included.

(1-1) Dicarboxylic acid (a)
The dicarboxylic acid (a) used in the present invention is a dicarboxylic acid compound having reactivity with an amino group and providing a unit derived from a dicarboxylic acid as a constituent unit of the polyamide resin of the present invention. A oxalic acid compound that provides a unit derived from oxalic acid, which is one type, is included. Examples of the dicarboxylic acid compound include compounds derived from dicarboxylic acid, and examples of the compound derived from dicarboxylic acid include esters derived from dicarboxylic acid.

  The oxalic acid compound used in the present invention is a compound that provides a unit derived from oxalic acid, and is a compound derived from oxalic acid such as oxalic acid and / or oxalic acid ester. The oxalic acid compound only needs to have reactivity with an amino group. When producing polyamide at a high polymerization temperature, if oxalic acid itself is used as a raw material, oxalic acid may be thermally decomposed. Therefore, the oxalic acid compound in the production at a high polymerization temperature is derived from oxalic acid. The compounds obtained are preferred.

  Examples of oxalic acid diesters of alicyclic alcohols include dicyclohexyl oxalate.

  Examples of oxalic acid diesters of aromatic alcohols include diphenyl oxalate.

  The oxalic acid diester is preferably at least one selected from the group consisting of an oxalic acid diester of an aliphatic monohydric alcohol having more than 3 carbon atoms, an oxalic acid diester of an alicyclic alcohol, and an oxalic acid diester of an aromatic alcohol. n-Butyl, di-i-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.

  These oxalic acid compounds can be added alone or in combination of two or more at the time of producing the polyamide resin.

  Examples of dicarboxylic acid compounds other than oxalic acid compounds include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and compounds derived therefrom.

  Aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid. Examples include acids, azelaic acid, sebacic acid, and suberic acid.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid.

  Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3 -Phenylenedioxydiacetic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid Can be mentioned.

  These dicarboxylic acid compounds other than these oxalic acid compounds can be added alone or in combination of two or more when the polyamide resin is produced.

  Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible regardless of the presence or absence of dicarboxylic acids other than oxalic acid compounds.

  The content of units derived from dicarboxylic acids and / or polycarboxylic acids other than oxalic acid compounds contained in the polyamide resin is 50 mol in the total amount of units derived from all dicarboxylic acids and all polycarboxylic acids contained in the polyamide resin. %, More preferably 20 mol% or less, further preferably 10 mol% or less, further preferably 5 mol% or less, and further preferably 1 mol% or less.

(1-2) Diamine (b)
The diamine (b) used in the present invention is selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, isophoronediamine and 1,3-bisaminomethylcyclohexane. Containing two or more diamines.

  From the viewpoint of increasing the molecular weight of the polyamide resin, the diamine (b) contains 1,9-nonanediamine and 2-methyl-1,8-octanediamine (also referred to as C9 diamine), which are diamines having 9 carbon atoms. Is preferred. The content of units derived from 1,9-nonanediamine and 2-methyl-1,8-octanediamine contained in the polyamide resin, that is, the content of units derived from C9 diamine is a unit derived from all diamines contained in the polyamide resin. Is preferably 1 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, further preferably 60 mol% or more, and more preferably 80 mol%. % Or more, more preferably 90 mol% or more.

  More preferably, the diamine (b) contains 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine. The melting point and thermal decomposition temperature of the polyamide resin (polymer in nitrogen) 1% weight loss temperature) of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine contained in the polyamide resin from the viewpoint of the balance between the balance and other characteristics. The total content of units is preferably 10 mol% or more, more preferably 20 mol% or more, and more preferably 40 mol% or more in the total amount of units derived from all diamines contained in the polyamide resin. More preferably, it is 60 mol% or more, more preferably 80 mol% or more, more preferably 90 mol% or more. Theft is more preferable.

  The molar ratio of the sum of 1,9-nonanediamine and 2-methyl-1,8-octanediamine to 1,6-hexanediamine, that is, the molar ratio of diamine having 9 carbon atoms and 1,6-hexanediamine is: Maintains excellent properties of polyamide (hereinafter also referred to as PA92) obtained by polymerizing 1,9-nonanediamine, 2-methyl-1,8-octanediamine and oxalic acid compound, and in particular, melt moldability and low water absorption From the viewpoint of increasing the melting point of the polyamide resin (A) without impairing the properties, and particularly improving the mechanical properties, it is preferably 1:99 to 99: 1. The molar ratio of C9 diamine to 1,6-hexanediamine is more preferably 5.1: 94.9 to 99: 1, still more preferably 10:90 to 99: 1, and the melting point of the polyamide resin (A) is reduced. From the viewpoint of making the polymerization and molding process (melt moldability) easier, the temperature is more preferably 20:80 to 99: 1, more preferably 30:70 to 98: 2, and the polyamide resin (A From the viewpoint of making the melting point of) less than 280 ° C. and making the melt moldability easier, it is more preferably 30:70 to 90:10, and further preferably 30:70 to 70:30.

  The molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of C9 diamine, which is a diamine having 9 carbon atoms, is 1:99 to 99: 1 from the viewpoint of increasing the molecular weight of the polyamide resin. It is preferably 5:95 to 95: 5, more preferably 5:95 to 40:60 or 60:40 to 95: 5, and even more preferably 5:95 to 30:70 or More preferably, it is 70:30 to 90:10. By including the above content of units derived from 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine, it becomes possible to slow the crystallization rate, A polyamide resin excellent in extrusion molding or the like is obtained.

  From the viewpoint of increasing the glass transition temperature of the polyamide resin, the diamine (b) preferably contains isophorone diamine or 1,3-bisaminomethylcyclohexane, and includes 1,6-hexanediamine, isophorone diamine or 1,3-bisamino. More preferably, it contains methylcyclohexane. The molar ratio of 1,6-hexanediamine and isophoronediamine or 1,3-bisaminomethylcyclohexane is preferably 1:99 to 99: 1 from the viewpoint of not impairing melt moldability and low water absorption. Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90: 10.

  Other diamines can be contained as long as the effects of the present invention are not impaired. Specifically, as other diamines other than 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine, isophoronediamine and 1,3-bisaminomethylcyclohexane, ethylenediamine, Propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1 , 5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl Aliphatic diamines such as -1,9-nonanediamine, alicyclic diamines such as cyclohexanediamine, p-ph Examples include aromatic diamines such as nylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. These can be added alone or in combination of two or more.

  The content of other diamine-derived units is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50 mol% in all diamine-derived units of the polyamide resin. Preferably it is 20 mol% or less, More preferably, it is 10 mol% or less, More preferably, it is 5 mol% or less, More preferably, it is 1 mol% or less.

(2) Manufacture of polyamide resin The polyamide resin used in the present invention can be manufactured using any method known as a method of manufacturing polyamide, and is preferably used from the viewpoint of high molecular weight and productivity. Is to produce a diamine (b) and a dicarboxylic acid (a) by a polycondensation reaction in a batch or continuous manner, and more preferably a pre-polycondensation step of the diamine (b) and the dicarboxylic acid (a). And a post-polycondensation step, or a pressure polymerization method described in WO2008-072754.

  The two-stage polymerization method and the pressure polymerization method are specifically shown by the following operations.

(2-1) Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then the diamine (b) and the dicarboxylic acid (a) are mixed. When mixing, a solvent in which both the diamine (b) and the dicarboxylic acid (a) are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, toluene, xylene, trichlorobenzene, phenol, trifluoroethanol and the like can be used, and particularly, toluene can be preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this.

  The charging ratio of the diamine (b) and the dicarboxylic acid (a) is 0.8 to 1.5 (molar ratio), in terms of high molecular weight, in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). ), Preferably 0.91 to 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).

  The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature reached is 3-6 hours.

(Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature rising process, the final ultimate temperature of the pre-polycondensation step, that is, preferably 80 to 150 ° C., is finally preferably 220 ° C. or higher and 350 ° C. or lower, more preferably 230 ° C. or higher and 330 ° C. or lower, and further preferably 240 ° C. A temperature range of 300 ° C. or lower is reached.

  It is preferable to carry out the reaction while keeping the temperature rising time preferably 1 to 8 hours, more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(2-2) Pressure polymerization method First, the diamine (b) is placed in a pressure-resistant container and purged with nitrogen, and then heated to a reaction temperature under a sealing pressure. Thereafter, while maintaining the sealed pressure state at the reaction temperature, the dicarboxylic acid (a) is injected into the pressure resistant vessel to start the polycondensation reaction. The reaction temperature is not particularly limited as long as the polyamide produced by the reaction of diamine (b) and dicarboxylic acid (a) can maintain a slurry or solution state and does not thermally decompose. The charging ratio of the diamine (b) and the dicarboxylic acid (a) is 0.8 to 1.5 (molar ratio), preferably 0.91 in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). To 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).

  Next, while maintaining the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of the polyamide resin obtained in the present invention, since the melting point is 245 to 300 ° C., it rises to 250 to 350 ° C., preferably 255 to 330 ° C., more preferably 260 to 300 ° C. Warm up. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(3) Properties of polyamide resin The polyamide resin used in the present invention has a molecular weight of 1.8 to 6.0, relative viscosity ηr measured at 25 ° C. using a 1.0 g / dl 96% concentrated sulfuric acid solution. The molecular weight is preferably in the range of 2.0 to 5.5, particularly preferably 2.5 to 4.5. If the molecular weight is low, the melt viscosity tends to be low and not suitable for hollow molding. On the other hand, when the molecular weight increases, the melt viscosity increases and the melt moldability tends to deteriorate.

(4) Addition of other polymer In addition to the polyamide resin used in the present invention, the resin composition of the present invention may contain other polymers as long as the effects of the present invention are not impaired. Other polymers include other polyamides, such as polyoxamides other than polyamide resins, aromatic polyamides, aliphatic polyamides, alicyclic polyamides, etc., and heats such as polyamide and polypropylene, polyethylene ether, polyphenylene ether, polyphenylene sulfonic acid, etc. A plastic polymer is mentioned.

  The content of the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but in the resin composition of the present invention, the total is preferably less than 50% by mass, more preferably 30% by mass or less. Preferably, 10 mass% or less is more preferable.

(5) Additives The polyamide resin used in the present invention can contain other additives as long as the effects of the present invention are not impaired. Examples of the additives include pigments, dyes, colorants, and heat resistance. Agent, antioxidant, weathering agent, ultraviolet absorber, light stabilizer, compatibilizer, lubricant, crystal nucleus material, crystallization accelerator, mold release agent, antistatic agent, plasticizer, antistatic agent, flame retardant , Glass fiber, lubricant, filler, reinforcing fiber and the like. These additives can be contained alone or in combination of two or more. The content is not particularly limited as long as it does not impair the effects of the present invention, but in the resin composition of the present invention, the total content is preferably 50% by mass or less, more preferably 30% by mass or less. A mass% or less is more preferable.

  As the heat-resistant agent, a copper-containing compound is preferable, and among them, copper halides such as copper iodide and copper bromide are preferable. As content of a copper containing compound, 10-1000 ppm is preferable in the resin composition of this invention. Usually, an alkyl halogen compound is further added as a secondary antioxidant.

  Examples of the system antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant, and one or more of them can be contained in the resin composition of the present invention.

  Examples of phenolic antioxidants include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, N, N′-hexamethylenebis (3,5- Di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl) -4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2, 4,8,10-tetraoxaspiro [5,5] undecane and the like, among which pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate N, N′-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), or one or more thereof, contained in the resin composition of the present invention can do.

  Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphin 6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [ d, f] [1,3,2] dioxaphosphenine 6-yl] oxy] -ethyl] ethanamine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc. In particular, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin 6-yl ] Oxy] -ethyl] ethanamine, one or more It can be contained in the light of the resin composition.

  Sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (dodecylthio) propionate] methane 1 type, or 2 or more types can be contained in the resin composition of the present invention.

(6) Polyamide resin molding process The polyamide resin molding process obtained by the present invention includes all known molding process methods applicable to polyamide, such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure, and stretching. These can be processed into films, sheets, molded products, fibers, hollow molded products, and the like. Furthermore, an object molded into a three-dimensional shape using these resins or the like can also be used as a support.

  When a film is used as the substrate, the thickness of the substrate is not particularly limited and is appropriately selected depending on the application, but is usually about 1 to 300 μm, preferably 2 to 200 μm, and more preferably, 3 to 150 μm. If it is thinner than 1 μm, the operability tends to be poor, and if it is 300 μm or more, it becomes rigid and the operability is lowered, and the weight tends to increase and the cost is further increased.

(7) Conductive member and manufacturing method thereof The conductive material containing metal nanoparticles used for the conductive member as the electronic component according to the present invention is used for forming a known or commercially available conductive pattern. Colloids, inks or pastes containing metal nanoparticles can be widely used. For example, silver paste MDot-SLP / H made by Mitsuboshi Belting, NPS typeHP made by Harima Chemicals, CA-2503-4 made by Daiken Chemical. Among these, a silver paste MDot-SLP / H made by Mitsuboshi Belting is preferably used from the viewpoint of adhesiveness with a condensate film (sol-gel film). Silver or copper is preferably used as the metal of the metal nanoparticles.

  The film thickness after firing of the ink or paste containing metal nanoparticles is not particularly limited, but is usually 0.1 to 30 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 15 μm. If the thickness of the ink or paste containing metal nanoparticles after baking is less than 0.1 μm, sufficient performance as a wiring material may not be obtained. Moreover, when the film thickness after baking is thicker than 30 micrometers, a crack may enter.

  In the present invention, the ink or paste containing metal nanoparticles is formed with a pattern by various printing methods or coating methods. For example, arbitrary linear pattern formation using a dispenser printing method capable of performing linear application, arbitrary linear or planar shape using various types of inkjet printing methods such as thermal, piezo, micro pump, static electricity, etc. Pattern formation, letterpress printing method, flexographic printing method, planographic printing method, intaglio printing method, gravure printing method, reverse offset printing method, sheet-fed screen printing method, rotary screen printing method, etc. Can be formed. Also, using various known coating methods such as gravure roll method, slot die method, spin coating method, etc., forming a pattern as a continuous surface on the entire surface or a part of the laminated substrate, lamination using an intermittent coating die coater, etc. A pattern can be formed as an intermittent surface on the entire surface or part of the substrate, or an ink or paste containing metal nanoparticles can be attached to the entire laminated substrate by using a dip coating method (also referred to as a dip method). More preferable printing methods include an inkjet printing method, a flexographic printing method, a gravure printing method, a reverse offset printing method, a sheet-fed screen printing method, and a rotary screen printing method.

  The ink or paste containing metal nanoparticles patterned by these methods can be fired to form a conductive pattern. The firing conditions at this time are considerably limited depending on the base material used, but the higher the temperature, the better because the pattern strength increases with the progress of excellent conductivity and sintering. In particular, when a polyamide resin is used as a base material, it is preferable to fire at 150 to 250 ° C., and in view of better cohesion and conductivity and productivity, it is preferable to fire at 180 to 200 ° C. preferable.

  Here, the case where an ink or paste containing metal nanoparticles is used as the conductive layer is shown. Metal plating can be further performed on the conductive pattern formed on the substrate by a wet plating process. Thereby, the electrical conductivity of an electroconductive member can further be improved. In this case, the metal to be used is not limited as long as it is a metal that can be wet-plated. For example, a generally well-known electroless nickel plating process can be used. Furthermore, only electroless plating may be used, or a metal different from the metal formed by electroless plating may be further formed by electrolytic plating as an electrode layer for electrolytic plating.

  The conductive member according to the present invention is used as a transparent electromagnetic wave shield used by bonding to various flat display panels such as a plasma display panel, an aircraft liquid crystal panel, and a car navigation liquid crystal panel. It can also be used as various antennas used for RFID, wireless LAN, power feeding by electromagnetic induction, electromagnetic wave absorption, and the like. Furthermore, it can be used for manufacturing an electronic circuit which is produced by repeatedly printing many times using bus electrodes and address electrodes used in various flat display panels, or semiconductor ink, resistance ink, and dielectric ink in combination.

(8) Injection-molded product For the conductive material containing metal nanoparticles used for the conductive member as the electronic component according to the present invention, only the base material having conductivity can be obtained by taking advantage of the moldability of the polyamide resin. In addition, an injection molded product having conductivity is included. The resulting injection-molded product can be applied to a wide range of fields such as mobile display cases such as mobile phones, conductive barriers, antistatic materials, electromagnetic shielding materials, electrodes, connectors, sensors, and heating elements. It is.

(9) Extrusion product Further, the conductive material containing the metal nanoparticles used for the conductive member as the electronic component according to the present invention has a conductive fiber by utilizing the moldability of the polyamide resin, Extruded products such as tubes and hollow molded products are included. The obtained extrusion-molded product has a conductive member used for a charging device, a developing device, a transfer device, etc. in an electrophotographic image forming apparatus, a semiconductive belt, a conductive roll used as a charging member or a transfer member, It can be used to produce a removal material or the like.

(10) Characteristics of Conductive Member The present invention is advantageous in that both high adhesion and high conductivity characteristics can be achieved even in a conductive member obtained by firing a silver nanoparticle paste under high temperature conditions. Although described in detail below in Examples, the conductive member obtained by firing the silver nanoparticle paste produced in the present invention under high temperature conditions satisfies both the following performances in the cross-cut peel test and conductivity. In the cross peel test, the peel area has a peel strength of less than 5%, preferably 0%. Further, in the method for evaluating conductivity, the conductivity is 25 μΩ · cm or less, preferably 20 μΩ · cm or less, more preferably 15 μΩ · cm or less. Furthermore, it is preferable not to be thermally deformed. From the viewpoint of the conductivity limitation that can be realized by the firing temperature of the metal nanoparticle paste or the process temperature at the time of production, it is desired that the metal nanoparticle paste is not thermally deformed at 180 ° C. or higher and 200 ° C. depending on conditions.
Even when a polyimide base material having high heat resistance is used as a conductive member or the like, it is necessary to achieve both high adhesion and high conductivity characteristics.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example.

[Evaluation method, molding method]
<Evaluation method of adhesion strength of conductive member: cross-cut peeling>
The surface of the conductive member printed and baked with ink containing silver nanoparticles is cut into 11 cuts that intersect each other at 1 mm intervals vertically and horizontally, and adhesive tape (“Cello Tape (registered trademark)” manufactured by Nichiban Co., Ltd.) is applied. After peeling, the degree of peeling was measured. As a notation method of peeling, peeling area 0% = 10 points, less than 5% = 8 points, 5% to less than 15% = 6 points, 15% to less than 35% = 4 points, 35% to less than 65% = 2 Points, 65% or more = 0 points.

<Method for evaluating conductivity of conductive member>
Using a resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the conductivity was measured by a four-terminal method with a measurement voltage of 10V.

<Thermal deformation of conductive member>
About the electrically-conductive member which printed and baked the ink containing a silver nanoparticle with respect to the injection-molded test piece, the external appearance after heat-firing was confirmed visually and it was confirmed whether there was no deformation | transformation before and after a heating.

<Film forming 1>
Pellets were supplied to a single screw extruder equipped with a T die, and a film having a thickness of 100 μm was formed under the conditions of an extruder set temperature of 260 ° C., a screw rotation speed of 40 RPM, and a film take-up speed of 5 m / min.

<Film forming 2>
Film forming was performed using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. 500
A polyamide resin was heated and melted at 300 ° C. for 5 minutes in a reduced pressure atmosphere of ˜700 Pa, then pressed at 5 MPa for 1 minute to form a film, and then the reduced pressure atmosphere was returned to normal pressure and then cooled at room temperature at 5 MPa for 2 minutes. To obtain a film.

<Injection molding>
Using an FAS-T100D injection molding machine manufactured by FANUC, a test piece of 150 mm × 150 mm × 3 mmt was prepared at a cylinder temperature of 260 ° C. and a mold temperature of 95 ° C.

[Production of polyamide resin (A-1)]
(Production Example 1)
Into a pressure vessel with an internal volume of about 150 L equipped with a raw material inlet, a nitrogen gas inlet, a pressure outlet, a stirrer, a thermometer, a torque meter, a pressure gauge, a pressure regulator, and a polymer outlet directly connected to a pump, b) 1,9-nonanediamine 20.1 kg (127 mol) and 2-methyl-1,8-octanediamine 3.5 kg (22 mol) were charged, and the pressure vessel was pressurized to 0.5 MPaG with nitrogen gas. Then, after repeating the operation of releasing nitrogen gas to normal pressure and replacing with nitrogen, the system was heated while stirring under a sealing pressure. After the internal temperature was raised to 150 ° C. over about 1 hour, 30.2 kg (149 mol) of dibutyl oxalate dicarboxylic acid (a) was supplied into the reaction vessel at a flow rate of 1.49 L / min by a pump and the temperature was raised at the same time. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPaG by butanol produced by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. Meanwhile, the internal pressure was adjusted to 0.5 MPaG while the generated butanol was extracted from the pressure release port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure relief port, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was adjusted to 260 ° C., and the reaction was continued at 260 ° C. until the torque value reached a constant value. Thereafter, the stirring was stopped and the system was pressurized to 1 MPaG with nitrogen and allowed to stand. Then, the pressure was released to an internal pressure of 0.5 MPaG, and the polyamide resin (A-1) (hereinafter sometimes referred to as PA92) was used as a pressure vessel. A string was extracted from the lower outlet. The string-like PA92 was immediately cooled with water and pelletized by a pelletizer.

[Production of polyamide resin (A-2)]
(Production Example 2)
Into a pressure vessel with an internal volume of about 150 L equipped with a raw material inlet, a nitrogen gas inlet, a pressure outlet, a stirrer, a thermometer, a torque meter, a pressure gauge, a pressure regulator, and a polymer outlet directly connected to a pump, a diamine ( b) 1,6-hexamethylenediamine 8.2 kg (71 mol) 1,9-nonanediamine 10.5 kg (66 mol) and 2-methyl-1,8-octanediamine 1.9 kg (12 mol) were charged, After pressurizing the pressure vessel with nitrogen gas to 0.5 MPaG, the operation of releasing the nitrogen gas to atmospheric pressure was repeated, and after replacing with nitrogen, the system was heated while stirring under a sealing pressure. After the internal temperature was raised to 170 ° C. over about 1.5 hours, 30.2 kg (149 mol) of dibutyl oxalate of dicarboxylic acid (a) was fed into the reaction vessel at a flow rate of 1.49 L / min with a pump and the temperature was raised at the same time. did. The internal pressure in the pressure vessel immediately after the supply increased to 0.45 MPaG by butanol produced by the polycondensation reaction, and the temperature of the polycondensate increased to about 200 ° C. Thereafter, the temperature was raised to 250 ° C. Meanwhile, the internal pressure was adjusted to 0.5 MPaG while the generated butanol was extracted from the pressure release port. Immediately after the temperature of the polycondensate reached 250 ° C., butanol was extracted from the pressure relief port, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was changed to 270 ° C., and the reaction was continued at 270 ° C. until the torque value became a constant value. Thereafter, the stirring was stopped and the system was pressurized to 1 MPaG with nitrogen and allowed to stand. Then, the pressure was released to an internal pressure of 0.5 MPaG, and the polyamide resin (A-2) (hereinafter also referred to as PA92 / 62) was obtained. A string was extracted from the lower outlet of the pressure vessel. The string-like PA92 / 62 was immediately cooled with water and pelletized by a pelletizer.

[Production of polyamide resin (A-3)]
(Production Example 3)
The above-mentioned PA92 is supplied to a twin screw extruder at a ratio of 95% by weight and PA6T / 6I EMS-CHEMIE AG Grivory G21 at a ratio of 5% by weight, and melt kneaded under the condition of a cylinder temperature of 260 ° C. After being extruded and cooled and solidified, it was cut with a pelletizer to obtain a pellet-like polyamide resin composition.

[Production of polyamide resin (A-4)]
(Production Example 4)
70% by weight of PA92 and 30% by weight of glass fiber T-251H manufactured by Nippon Electric Glass Co., Ltd. are supplied to a twin screw extruder, melt-kneaded at a cylinder temperature of 260 ° C., and extruded as a strand. After cooling and solidifying, it was cut with a pelletizer to obtain a polyamide resin composition in the form of a pellet.

[Production of polyamide resin (A-5)]
(Production Example 5)
(I) Pre-polycondensation step: The inside of a separable flask having a stirrer, an air cooling tube, a nitrogen inlet tube, and a raw material inlet and having an internal volume of 5 liters is replaced with nitrogen gas having a purity of 99.9999%. , 1211 g (5.9876 mol) of dibutyl oxalate was charged. The container was kept at 80 ° C., and 407.9 g (2.3950 mol) of isophoronediamine and 417.5 g (3.5926 mol) of 1,6-hexanediamine were added with stirring to carry out a polycondensation reaction. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 200 ml / min.

(Ii) Post-polycondensation step: The prepolymer obtained by the above operation was charged into a 5 L pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet and polymer outlet. The operation of keeping the inside of the pressure vessel under a pressure of 3.0 MPa or more and then releasing the nitrogen gas to normal pressure was repeated 5 times, and then the system was heated up under a nitrogen stream and normal pressure. The internal temperature was raised to 120 ° C. over 1.5 hours. At this time, butanol was confirmed to be distilled. While distilling butanol, the temperature was raised to 290 ° C. over 5 hours and allowed to react for 2 hours. Thereafter, the temperature in the system was lowered to 285 ° C., stirring was stopped, and the mixture was allowed to stand for 25 minutes. Then, the system was pressurized to 3.5 MPa with nitrogen, and the polymer was extracted from the lower part of the pressure vessel in a string shape. The string-like polymer was immediately cooled with water, and the water-cooled string-like polymer was pelletized with a pelletizer. The obtained polymer was a white tough polymer.

[Production of polyamide resin (A-6)]
(Production Example 6)
(I) Pre-polycondensation step: The inside of a separable flask having a stirrer, an air cooling tube, a nitrogen inlet tube, and a raw material inlet and having an internal volume of 5 liters is replaced with nitrogen gas having a purity of 99.9999%. , 1211 g (5.9876 mol) of dibutyl oxalate was charged. While maintaining this container at 80 ° C., 511.0 g (3.5926 mol) of 1,3-bisaminomethylcyclohexane and 278.3 g (2.3950 mol) of 1,6-hexanediamine were added with stirring, and polycondensation was performed. Reaction was performed. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 200 ml / min.

(Ii) Post-polycondensation step: The prepolymer obtained by the above operation was charged into a 5 L pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet and polymer outlet. The operation of keeping the inside of the pressure vessel under a pressure of 3.0 MPa or more and then releasing the nitrogen gas to normal pressure was repeated 5 times, and then the system was heated up under a nitrogen stream and normal pressure. The internal temperature was raised to 120 ° C. over 1.5 hours. At this time, butanol was confirmed to be distilled. While distilling butanol, the temperature was raised to 285 ° C. over 5 hours and reacted for 2 hours. Thereafter, the temperature in the system was lowered to 280 ° C., stirring was stopped, and the system was allowed to stand for 25 minutes, and then the system was pressurized to 3.5 MPa with nitrogen, and the polymer was extracted from the lower part of the pressure vessel in a string shape. The string-like polymer was immediately cooled with water, and the water-cooled string-like polymer was pelletized with a pelletizer. The obtained polymer was a white tough polymer.

<Silver paste printing method and evaluation of adhesion and conductivity>
Example 1
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-1) obtained by the method of Production Example 1. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 200 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Example 2)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-2) obtained by the method of Production Example 2. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 200 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

Example 3
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-3) obtained by the method of Production Example 3. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 200 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

Example 4
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-1) obtained by the method of Production Example 1. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 180 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Example 5)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-2) obtained by the method of Production Example 2. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 180 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Example 6)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-3) obtained by the method of Production Example 3. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 180 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Example 7)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 2” from the polyamide resin (A-5) obtained by the method of Production Example 5. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 200 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Example 8)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 2” from the polyamide resin (A-5) obtained by the method of Production Example 5. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 180 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

Example 9
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 2” from the polyamide resin (A-6) obtained by the method of Production Example 6. Then, the electrically conductive member by which the silver nanoparticle paste was printed was produced by baking at 200 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Comparative Example 1)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-1) obtained by the method of Production Example 1. Then, the electrically-conductive member in which the silver nanoparticle paste was printed was produced by baking at 150 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Comparative Example 2)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-2) obtained by the method of Production Example 2. Then, the electrically-conductive member in which the silver nanoparticle paste was printed was produced by baking at 150 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Comparative Example 3)
A silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. is printed on one side of a film formed by the method of “Film Molding 1” from the polyamide resin (A-3) obtained by the method of Production Example 3. Then, the electrically-conductive member in which the silver nanoparticle paste was printed was produced by baking at 150 degreeC for 30 minute (s) with ventilation oven. At this time, the paste thickness after firing was 10 μm. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

  From the results of Examples 1 to 9 and Comparative Examples 1 to 3, it can be confirmed that both high adhesion and high conductivity characteristics can be achieved by baking the silver nanoparticle paste at a high temperature of 180 ° C. or higher.

(Reference Example 1)
Using a polyimide film (Upilex SGA, Ube Industries, Ltd., Upilex SGA, thickness 25 μm) as a base material, a silver nanoparticle paste was printed in the same manner as in Example 4 to produce a conductive member on which the silver nanoparticle paste paste was printed. . At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

(Reference Example 2)
Using a polyimide film (Kapton 100EN manufactured by Toray DuPont Co., Ltd., thickness 25 μm) as a base material, a silver nanoparticle paste was printed in the same manner as in Example 4 to produce a conductive member on which the silver nanoparticle paste was printed. . At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1. Table 1 shows the evaluation results of the adhesion by "Method for evaluating the adhesion strength of the conductive member: grid peel" and the evaluation results of the conductivity by "Method for evaluating the conductivity of the conductive member".

  As is clear from the results of Reference Examples 1 and 2, it is difficult to achieve both high adhesion and high conductivity characteristics in a polyimide substrate having high heat resistance. The polyamide resin obtained in the present invention is advantageous in that it can achieve both high adhesion and high conductivity even in a conductive member obtained by baking a silver nanoparticle paste under a high temperature condition without any special treatment.

(Example 10)
Silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection-molding the polyamide resin (A-1) obtained by the method of Production Example 1 into a plate shape by the method described above. After printing, the conductive member on which the silver nanoparticle paste was printed was produced by baking at 200 ° C. for 30 minutes in a blowing oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

(Example 11)
Silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection-molding the polyamide resin (A-1) obtained by the method of Production Example 1 into a plate shape by the method described above. After printing, the conductive member on which the silver nanoparticle paste was printed was produced by baking at 180 ° C. for 30 minutes in a blowing oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

(Comparative Example 4)
Silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection-molding the polyamide resin (A-1) obtained by the method of Production Example 1 into a plate shape by the method described above. After printing, the conductive member on which the silver nanoparticle paste was printed was produced by baking at 150 ° C. for 30 minutes in a blowing oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

(Example 12)
Silver nanoparticle paste MDot manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection-molding the glass fiber composite polyamide resin (A-4) obtained by the method of Production Example 4 into a plate shape by the method described above. -After printing SLP / H, the electroconductive member in which the silver nanoparticle paste was printed was produced by baking at 200 degreeC for 30 minute (s) with a ventilation oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

(Example 13)
Silver nanoparticle paste MDot manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection-molding the glass fiber composite polyamide resin (A-4) obtained by the method of Production Example 4 into a plate shape by the method described above. -After printing SLP / H, the electroconductive member in which the silver nanoparticle paste was printed was produced by baking at 180 degreeC for 30 minute (s) with a ventilation oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

(Comparative Example 5)
Silver nanoparticle paste MDot manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection-molding the glass fiber composite polyamide resin (A-4) obtained by the method of Production Example 4 into a plate shape by the method described above. -After printing SLP / H, the electroconductive member on which the silver nanoparticle paste was printed was produced by baking at 150 degreeC for 30 minute (s) with a ventilation oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

  According to the results of Examples 10 to 13 and Comparative Examples 4 and 5, not only the film but also the injection molded product has high adhesion and high conductivity characteristics by firing the silver nanoparticle paste at a high temperature condition of 180 ° C. or higher. It can be confirmed that both are compatible.

(Comparative Example 6)
After printing the silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection molding ABS resin (EX190 manufactured by UMG-ABS Co., Ltd.) into a plate shape by the method described above, air blowing The conductive member on which the silver nanoparticle paste was printed was produced by baking for 30 minutes at 200 ° C. in an oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2. It was confirmed that the base material was greatly deformed by heating, and the conductivity was deteriorated by cracking of the conductive pattern.

(Comparative Example 7)
After printing the silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection molding ABS resin (EX190 manufactured by UMG-ABS Co., Ltd.) into a plate shape by the method described above, air blowing The conductive member on which the silver nanoparticle paste was printed was produced by baking for 30 minutes at 180 ° C. in an oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2. It was confirmed that the base material was greatly deformed by heating, and the conductivity was deteriorated by cracking of the conductive pattern.

(Comparative Example 8)
After printing the silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. by screen printing on one side of a test piece obtained by injection molding ABS resin (EX190 manufactured by UMG-ABS Co., Ltd.) into a plate shape by the method described above, air blowing The conductive member on which the silver nanoparticle paste was printed was produced by baking for 30 minutes at 150 ° C. in an oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2. It was confirmed that the base material was greatly deformed by heating, and the conductivity was deteriorated by cracking of the conductive pattern.

(Comparative Example 9)
After printing the silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. on one side of a test piece obtained by injection-molding a polycarbonate resin (Taflon A2200 manufactured by Idemitsu Kosan Co., Ltd.) into a plate shape by the method described above, air blowing The conductive member on which the silver nanoparticle paste was printed was produced by baking for 30 minutes at 200 ° C. in an oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2. It was confirmed that the substrate was deformed by heating.

(Comparative Example 10)
After printing the silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. on one side of a test piece obtained by injection-molding a polycarbonate resin (Taflon A2200 manufactured by Idemitsu Kosan Co., Ltd.) into a plate shape by the method described above, air blowing The conductive member on which the silver nanoparticle paste was printed was produced by baking for 30 minutes at 180 ° C. in an oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2. It was confirmed that the substrate was deformed by heating.

(Comparative Example 11)
After printing the silver nanoparticle paste MDot-SLP / H manufactured by Mitsuboshi Belting Co., Ltd. on one side of a test piece obtained by injection-molding a polycarbonate resin (Taflon A2200 manufactured by Idemitsu Kosan Co., Ltd.) into a plate shape by the method described above, air blowing The conductive member on which the silver nanoparticle paste was printed was produced by baking for 30 minutes at 150 ° C. in an oven. At this time, the paste thickness after firing was 10 μm. "Evaluation method of adhesion strength of conductive member: cross-cut peel" results of adhesion evaluation, conductivity evaluation result of "conductive member conductivity evaluation method", "presence of thermal deformation" of the substrate visually The confirmed results are shown in Table 2.

  According to the results of Comparative Examples 6 to 11, the polyamide resin (A-1) injection-molded body obtained by the method of Production Example 1 is compared with the ABS resin and polycarbonate resin which are generally suitably used as the injection-molded body. When used as a substrate of a conductive member on which a silver nanoparticle paste is printed, it can be confirmed that various properties such as high adhesion, high conductivity, and no thermal deformation of the substrate during heating can be achieved.

  A conductive member comprising a layer containing a conductive material of the present invention and a polyoxamide substrate includes a conductive pattern base formed using a conductive ink, in particular, an ink or paste containing metal nanoparticles. It is possible to provide a conductive member having high adhesion to a material and having excellent conductivity, and a method for producing them.

Claims (7)

  A conductive member comprising a layer containing a conductive material directly laminated on a polyamide resin substrate.   The conductive member according to claim 1, wherein the conductive material includes metal nanoparticles, and the metal of the metal nanoparticles is silver or copper.   In the polyamide resin, the dicarboxylic acid component is oxalic acid, and the diamine component is 1,6-hexamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, isophoronediamine and 1,3-bisamino. The conductive member according to claim 1, comprising two or more diamines selected from the group consisting of methylcyclohexane.   The conductive member according to claim 1, wherein a conductive pattern is formed on the layer containing the conductive material by printing or applying a conductive material.   An injection molded product comprising a layer containing a conductive material directly laminated on a polyamide resin substrate.   A film, fiber, tube, or hollow molded article having a layer containing a conductive material directly laminated on a polyamide resin substrate. In a method for manufacturing a conductive member including a layer including a conductive material and a polyamide resin substrate,
Print or apply a conductive material to the polyamide substrate,
A method for producing a conductive member, wherein the conductive material is heat-treated at 180 ° C. or higher to form a layer containing the conductive material.