[go: up one dir, main page]

WO2009125740A1 - Pâte conductrice pour un élément chauffant plan, et circuit imprimé et élément chauffant plan utilisant celle-ci - Google Patents

Pâte conductrice pour un élément chauffant plan, et circuit imprimé et élément chauffant plan utilisant celle-ci Download PDF

Info

Publication number
WO2009125740A1
WO2009125740A1 PCT/JP2009/057054 JP2009057054W WO2009125740A1 WO 2009125740 A1 WO2009125740 A1 WO 2009125740A1 JP 2009057054 W JP2009057054 W JP 2009057054W WO 2009125740 A1 WO2009125740 A1 WO 2009125740A1
Authority
WO
WIPO (PCT)
Prior art keywords
heating element
parts
conductive paste
planar heating
polyurethane resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/057054
Other languages
English (en)
Japanese (ja)
Inventor
亮 浜崎
和洋 阿部
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Priority to JP2010507232A priority Critical patent/JP5370357B2/ja
Publication of WO2009125740A1 publication Critical patent/WO2009125740A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater

Definitions

  • the present invention relates to a conductive paste, and more particularly to forming a circuit or forming a planar heating element by applying, printing, or curing a conductive paste on a film or substrate. It is. More specifically, the present invention relates to a planar heating element having PTC (Positive Temperature Coefficient) characteristics.
  • PTC Pressure Temperature Coefficient
  • the planar heating element is used for floor heating, anti-fogging of mirrors in automobiles and bathrooms, and heat insulation for pets and foliage plants.
  • a planar heating element with a self-temperature control function that is, a PTC characteristic
  • a planar heating element is composed of a resin and a conductive material, and as the temperature of the planar heating element rises, the resin undergoes volume expansion, and the conduction between the conductive substances is blocked. It is said that the characteristics are expressed.
  • a planar heating element having such PTC characteristics is obtained by kneading a conductive material made of carbon black, graphite, metal powder, or the like into an olefin resin, and dispersing or dissolving the resin and the conductive material in a solvent.
  • coated and dried what is formed are proposed (for example, patent document 1).
  • the former has been a method by extrusion molding or press molding, and the latter has been a method of applying to a substrate by means such as screen printing. The latter method is often used from the viewpoint that the shape can be freely designed, and the paste type is widely used to enable screen printing.
  • Patent Document 3 a conductive paste having improved PTC characteristics by using a resin having a glass transition temperature of 50 ° C. or lower has been proposed (for example, Patent Document 3).
  • Patent Document 3 a conductive paste having improved PTC characteristics by using a resin having a glass transition temperature of 50 ° C. or lower has been proposed.
  • the PTC characteristics tend to deteriorate. This is because, when the base resin is exposed to a temperature around 40 ° C. to 70 ° C., which is the use temperature of the planar heating element, for a long time, a minute fluidized portion is generated in the resin and the dispersion structure of the conductive fine particles changes. This is considered to be a cause.
  • Patent Document 4 a conductive paste combining a crystalline resin has been proposed (for example, Patent Document 4).
  • the PTC characteristics can be improved by blending a crystalline resin having a large volume change before and after melting.
  • an ink-like or paste-like PTC composition is prepared using such a crystalline resin as a base polymer.
  • the biggest challenge in manufacturing is the compatibility between the solvent solubility of the base polymer and the PTC characteristics. That is, in order to obtain an ink-like or paste-like composition, it is indispensable to dissolve the base polymer in an appropriate solvent.
  • the degree of crystallinity of the polymer is high, the PTC characteristics are excellent, but it is difficult to dissolve in the solvent.
  • the resistance value may drop rapidly after reaching the peak temperature beyond the melting point. It is considered that this is because when the temperature is raised above the melting point and the crystalline polymer is melted, the conductive fillers dispersed therein come into contact with each other again and become conductive.
  • the PTC composition having such properties is heated to a peak temperature or higher for some reason, the self-temperature control function is lost and a large current flows. As a result, the temperature rises and eventually burns down. It can be connected.
  • JP-A-1-304704 Japanese Patent Laid-Open No. 10-183039 JP 2000-88672 A JP 2001-76850 A
  • the object of the present invention is to improve the problems of these conventional conductive resin compositions and conductive pastes. That is, while using a polymer having a crystalline melting point as the resin, the solvent solubility is good, and even if repeated heating is performed, the specific resistance and PTC characteristics are good, and even if the temperature is raised above the melting point, It is an object of the present invention to provide a conductive paste for a planar heating element that does not cause a rapid decrease in resistance value.
  • the present invention has been reached. That is, the present invention has very good PTC characteristics while maintaining solvent solubility, good return characteristics in which the specific resistance returns to its original value even when repeatedly raised and lowered, and the temperature is raised above the melting point.
  • the present invention relates to the following conductive paste, a printed circuit using the same, and a planar heating element.
  • a conductive paste for a planar heating element comprising a polyurethane resin (I) having a crystalline melting point and conductive particles (II).
  • the conductive paste for planar heating element according to (1) wherein the crystalline melting point of the polyurethane resin (I) is 20 to 100 ° C.
  • the polyurethane resin (I) is obtained by reacting at least an amorphous polyester polyol, a crystalline polyester polyol having a melting point of 5 to 120 ° C., and a polyisocyanate as main components (1) or ( The conductive paste for planar heating elements as described in 2).
  • the conductive paste of the present invention has basic physical properties such as good conductivity, PTC characteristics, return characteristics, adhesion, and bending resistance, and is suitable for use as a planar heating element.
  • the conductive paste of the present invention has good storage stability and provides good PTC characteristics.
  • the PTC characteristic means a characteristic that the circuit resistance increases as the temperature rises. In the present invention, as shown in the examples, for example, the ratio of the resistance change at 80 ° C. and 30 ° C. (sheet resistance (80 ° C.)). If the sheet resistance (30 ° C.) is 3 or more, it is defined as “having PTC characteristics”.
  • the magnification is preferably 5 or more, more preferably 10 or more, and still more preferably 100 or more. Although an upper limit is not specifically limited, Generally it is 50000 or less.
  • the dry film thickness is generally limited to 20 ⁇ m or less, and therefore a specific resistance much lower than that of an extrusion molding type conductive resin composition is required.
  • the specific resistance of the conductive paste of the present invention is preferably 600 ⁇ ⁇ cm or less, more preferably 450 ⁇ ⁇ cm or less, and still more preferably 400 ⁇ ⁇ cm or less.
  • the lower limit is not particularly limited, but is generally 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm or more.
  • the polyurethane resin (I) used in the present invention preferably has a crystalline melting point.
  • the term “having a crystalline melting point” in the present invention indicates that a peak of heat of fusion exists when a differential scanning calorimetry (DSC) measurement is performed by a method described later.
  • DSC differential scanning calorimetry
  • the polyurethane resin has a crystalline melting point, the PTC characteristics are remarkably improved as the polymer volume changes in the vicinity of the crystalline melting point.
  • the range of the melting point is not particularly limited, but is preferably 10 to 100 ° C, more preferably 20 to 80 ° C. When the temperature is 100 ° C.
  • the solubility in a solvent is remarkably inferior, so that an operation such as heating and melting is required immediately before the workability during production tends to deteriorate.
  • the melting point is lower than 20 ° C., the resin expands near room temperature, and the resistance value may become unstable.
  • other resins other than polyurethane having a crystalline melting point include other urethane resins, polyester resins, epoxy resins, phenol resins, acrylic resins, styrene-acrylic resins, styrene-butadiene copolymers, Polystyrene, polyamide resin, polycarbonate resin, and ethylene-vinyl acetate copolymer resin may be used in combination.
  • the type is not limited, but polyester resins and polyurethane resins are preferable from the viewpoints of adhesion to a substrate, flex resistance, and solvent solubility.
  • the above combination resin may or may not have a crystalline melting point.
  • the number average molecular weight of the polyurethane resin (I) having a crystalline melting point used in the present invention is preferably 3000 or more, more preferably 8000 or more from the viewpoint of bending resistance. When the number average molecular weight is less than 3000, good flex resistance is difficult to obtain, and the paste viscosity is lowered and printability may be lowered.
  • the upper limit is not particularly limited, but is preferably 100,000 or less from the viewpoint of paste viscosity and solubility.
  • the polyurethane resin (I) having a crystalline melting point used in the present invention is preferably one obtained by reacting at least an amorphous component, a crystalline component, and a chain extension component.
  • amorphous component as used herein means that only the component, and when a differential scanning calorimeter (DSC) is measured by the method described later, there is no peak of heat of fusion. Shows a peak of heat of fusion when measured in the same manner.
  • the amorphous component is preferably an amorphous polyol
  • the crystalline component is a crystalline polyol
  • the chain extender is preferably a polyisocyanate.
  • amorphous polyol examples include polyether polyol and polyester polyol, and polyester polyol is preferable from the viewpoint of freedom of molecular design.
  • Amorphous polyester polyol is obtained by condensation of dicarboxylic acid and polyol.
  • dicarboxylic acid examples include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and the like, C12-28 dibasic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride Acid, 2-methylhexahydrophthalic anhydride, dicarboxy hydrogenated bisphenol A, dicarboxy hydrogenated bisphenol S, dimer acid, hydrogenated dimer acid, hydrogenated naphthalene dicarboxylic acid, tricyclodecane dicarboxylic acid, and other alicyclic dicarboxylic acids Acid, hydroxy
  • aromatic dicarboxylic acid is copolymerized in an amount of 40 mol% or more of all acid components. It is preferable that More preferably, it is 50 mol% or more. Further, within the range that does not impair the effects of the invention, polyvalent carboxylic acids such as trimellitic anhydride and pyromellitic anhydride, unsaturated dicarboxylic acids such as fumaric acid, and sulfonic acids such as sodium 5-sulfoisophthalic acid A metal base-containing dicarboxylic acid may be used in combination.
  • polyol used examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, dimer diol and the like.
  • polyhydric polyols such as a trimethylol ethane, a trimethylol propane, glycerol, a pentaerythritol, a polyglycerol, in the range which does not impair the effect of invention.
  • Examples of the crystalline polyol constituting the polyurethane resin (I) having a crystalline melting point used in the present invention include polyether polyols and polyester polyols. Polyester polyols are preferred from the viewpoint of freedom of molecular design. Crystalline polyester polyol is obtained by condensation of dicarboxylic acid and polyol.
  • dicarboxylic acid examples include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and the like, C12-28 dibasic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride Acid, 2-methylhexahydrophthalic anhydride, dicarboxy hydrogenated bisphenol A, dicarboxy hydrogenated bisphenol S, dimer acid, hydrogenated dimer acid, hydrogenated naphthalene dicarboxylic acid, tricyclodecane dicarboxylic acid, and other alicyclic dicarboxylic acids Acid, hydroxy
  • aromatic dicarboxylic acid is copolymerized in an amount of 40 mol% or more of all acid components. It is preferable that More preferably, it is 50 mol% or more. Furthermore, the aromatic dicarboxylic acid is preferably terephthalic acid. Further, within the range that does not impair the effects of the invention, polyvalent carboxylic acids such as trimellitic anhydride and pyromellitic anhydride, unsaturated dicarboxylic acids such as fumaric acid, and sulfonic acids such as sodium 5-sulfoisophthalic acid A metal base-containing dicarboxylic acid may be used in combination.
  • polyol used examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, dimer diol and the like.
  • polyhydric polyols such as a trimethylol ethane, a trimethylol propane, glycerol, a pentaerythritol, a polyglycerol, in the range which does not impair the effect of invention.
  • Plaxel 230, Plaxel 240, Plaxel CD220, Plaxel H1P which are crystalline polycaprolactone diols
  • DYNACOLL7330, DYNACOLL7340, DYNACOLL7390 which are crystalline copolyesters) commercial products such as Degussa
  • crystalline copolyesters HT-310, HT-400, HS2H-350S, HS2H-500S, HS2H-1000S manufactured by Toyokuni Oil Co., Ltd.
  • These may be used alone or in combination of two or more in order to adjust the melting point, there is no problem.
  • the crystalline diol constituting the polyurethane resin having a crystalline melting point used in the present invention preferably has a melting point in the range of 5 to 120 ° C., more preferably in the range of 20 to 100 ° C.
  • the melting point is less than 5 ° C.
  • the melting point as polyurethane is lowered, and the resistance value at room temperature may become unstable when used as a planar heating element.
  • the melting point exceeds 120 ° C., the handling property is not good, the melting point as polyurethane is increased, and the solubility in a solvent may be deteriorated.
  • two or more crystalline diols within the above melting point range may be used in combination, or a crystalline diol within the above melting point range and a crystalline diol outside the above range are used in combination. You can also
  • the crystalline diol constituting the polyurethane resin having a crystalline melting point used in the present invention is preferably in the range of 1,000 to 20,000 in terms of number average molecular weight, more preferably in the range of 4000 to 10,000. If the number average molecular weight is less than 1000, crystallinity may not be exhibited. On the other hand, when it is 20000 or more, it may remain without being copolymerized, and the crystallinity may be increased and the solubility in a solvent may be deteriorated.
  • two or more kinds of crystalline diols within the range of the number average molecular weight may be used in combination, or crystalline diols within the range of the number average molecular weight and crystallinity outside the range. A diol can also be used in combination.
  • the conductive paste of the present invention can be used by blending the crystalline diol in addition to the polyurethane resin (I) having a crystalline melting point.
  • the crystalline diol may be contained in a range of 50% by weight or less, more preferably 20% by weight or less with respect to 100% by weight of the polyurethane resin having a crystalline melting point.
  • the stability of the solvent is remarkably lowered, and when used as a planar heating element, the resistance value may be remarkably lowered at a temperature exceeding the melting point of the crystalline diol. .
  • the crystalline diol itself in an amount of 50% by weight or less can be appropriately blended with the polyurethane resin.
  • the crystalline polyester polyol constituting the polyurethane resin (I) having a crystalline melting point used in the present invention is preferably 85 to 300 parts by weight with respect to 100 parts by weight of the amorphous polyester polyol which is another constituent. More preferably, it is 120 to 200 parts by weight with respect to 100 parts by weight of the amorphous polyester polyol. If the crystalline polyester polyol is less than 85 parts by weight with respect to 100 parts by weight of the amorphous polyester polyol, the crystallinity may not be exhibited.
  • the amount of the crystalline diol is more than 300 parts by weight with respect to 100 parts by weight of the amorphous polyester diol, the crystallinity becomes strong and the solubility in a solvent may be extremely deteriorated.
  • Polyisocyanates constituting the polyurethane resin (I) having a crystalline melting point used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 2,6-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-diphenylene diisocyanate 4,4'-diisocyanate diphenyl ether, 1,5-naphthalene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate , And toluene diisocyan
  • a urea bond be introduced into the polyurethane resin having a crystalline melting point used in the present invention.
  • a urea bond is formed, for example, by reacting an isocyanate compound and a diamine compound. Introducing urea bonds increases the number of hydrogen-bonding sites between molecules, resulting in toughness of the coating film, and when used as a planar heating element, when it reaches the peak temperature beyond the melting point, it rapidly resists. It can suppress that a value falls. That is, resistance value stability at high temperatures can be ensured. This is because the hydrogen bonds in the molecule can maintain intermolecular cohesion even after the temperature is raised above the melting point, so that the conductive fillers dispersed in the system come into contact with each other again. It is expected to be no longer conducting.
  • a method for introducing a urea bond, in polyurethane polymerization a method of reacting polyisocyanate and diamine in a lump, a method of adding a polyisocyanate group equivalent to diamine and diamine at the end of the reaction of polyurethane polymerization, Examples include a method in which an isocyanate group is excessively reacted with a diol to prepare a prepolymer, and then an equivalent amount of diamine is introduced with respect to the excess isocyanate group. Any method may be used for producing the polyurethane resin used in the present invention.
  • Diamines used for introducing the urea bond include ethylenediamine, metaxylenediamine, 4,4′-diaminodiphenylmethane, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine.
  • the amount of urea bonds in the polyurethane resin (I) having a crystalline melting point used in the present invention is preferably in the following range.
  • the urea bond amount in the present invention means a urea group equivalent (eq / ton) per ton of resin, and is a value calculated from the monomer composition ratio of the polyurethane resin.
  • the preferable urea bond amount is preferably 10 to 1000 (eq / ton), more preferably 50 to 500 (eq / ton). If it is less than 10 (eq / ton), it does not contribute to the toughness of the coating film, and the PTC characteristics cannot maintain the intermolecular cohesive force after being heated above the melting point. There is a concern that the filler comes into contact again and becomes conductive. On the other hand, when it exceeds 1000 (eq / ton), the varnish stability tends to be remarkably deteriorated.
  • the polyurethane resin (I) used in the present invention may be copolymerized, if necessary, with a chain extension component having a molecular weight of less than 5000 and having two or more functional groups that react with isocyanate groups in one molecule.
  • Compounds having a molecular weight of less than 1000 and having two or more functional groups that react with isocyanate groups include hexanediol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1, 3-butylene glycol, 2,3-butylene glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3-hydroxypropanoate, 2-normalbutyl-2-ethyl-1,3- Propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2,2-diethyl 1,3-propanedio
  • the conductive paste of the present invention preferably has an F value of 25 to 80%. Preferably it is 35 to 70%, more preferably 40 to 65%.
  • the solid mass part referred to here includes all carbon particles other than the solvent, other fillers, resins including polyester resins, and other curing agents and additives.
  • the F value is less than 25%, the specific resistance tends to increase. Moreover, it exists in the tendency for adhesiveness and / or pencil hardness to fall. If it exceeds 80%, the PTC characteristics tend to deteriorate.
  • the conductive fine particles (II) are not particularly limited, but are preferably carbon particles from the viewpoint of specific resistance and PTC characteristics.
  • the carbon particles used in the present invention are preferably spherical, and the shape is particularly preferably spherical in terms of specific resistance, PTC characteristics, and return characteristics.
  • the term “spherical” as used herein means that when the carbon particles are enlarged and observed with an electron microscope, which will be described later, the cross section thereof is almost circular and the ratio of the minor axis to the major axis is 80% or more. More preferably, it is 90% or more.
  • the average particle size of the carbon particles used in the present invention is preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and most preferably 7 ⁇ m or less.
  • the lower limit is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more.
  • the average particle diameter exceeds 30 ⁇ m, when screen printing is performed, the screen may be clogged, or the storage stability of the paste may be reduced due to sedimentation of the spherical carbon particles. If the average particle size is less than 0.1 ⁇ m, the conductivity may decrease, or the oil absorption may increase and the viscosity of the paste may increase, making it impossible to sufficiently fill the spherical carbon particles.
  • spherical carbon particles commercially available ones such as MC0520, MC1020 (manufactured by Nippon Carbon Co., Ltd.), GCP10 (manufactured by Unitika Ltd.) can be used.
  • the conductive particles (II) are preferably contained in a ratio of 40 to 400 parts by weight with respect to 100 parts by weight of the polyurethane resin (I).
  • the crystalline melting point It is preferably contained in an amount of 40 to 200 parts by mass, more preferably 60 to 180 parts by mass from the viewpoint of dispersibility, and 80 to 170 parts in terms of coating film hardness and adhesion. Most preferably, parts by weight are included.
  • the amount is less than 40 parts by mass, desired conductivity is difficult to obtain, and the return characteristics tend to deteriorate.
  • the amount is more than 200 parts by mass, there is a tendency that the PTC characteristic tends to be lowered or dispersion becomes difficult.
  • conductive fine particles other than carbon particles may be further used.
  • the known flaky silver powder, spherical silver powder, three-dimensional higher order silver powder, dendritic silver powder, graphite powder, carbon powder, nickel powder, copper powder, gold powder, palladium powder, aluminum powder, indium powder as long as the characteristics are not deteriorated
  • the spherical carbon particles are contained at least 20% by mass, more preferably 30% by mass or more of the total amount of conductive fine particles.
  • the upper limit is preferably 60% by mass or less, more preferably 40% by mass or less from the viewpoint of cost.
  • particularly preferable other conductive fine particles include graphite powder and conductive carbon black.
  • non-conductive filler such as silica powder, fumed silica, colloidal silica, talc, and barium sulfate may be blended for the purpose of adjusting paste viscosity.
  • known inorganic substances may be added to the conductive paste of the present invention, for example, silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, Various carbides such as chromium carbide, molybdenum carbide, calcium carbide, diamond carbon lactam, various nitrides such as boron nitride, titanium nitride, zirconium nitride, various borides such as zirconium boride, titanium oxide (titania), calcium oxide, oxidation Various oxides such as magnesium, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica, various titanate compounds such as calcium titanate, magnesium titanate, strontium titanate, sulfides such as molybdenum disulfide, magnesium fluoride , Fluorocarbon Various metal soaps such as various fluoride,
  • an antifoamer a flame retardant, a tackifier, a hydrolysis inhibitor, a leveling agent, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a pigment, and a dye
  • carbodiimide, epoxy and the like can be used as appropriate as a resin degradation inhibitor. These can be used alone or in combination.
  • the conductive paste of the present invention may contain a curing agent that can react with an organic resin.
  • a curing agent that can react with an organic resin.
  • the curing agent capable of reacting with these resins is not particularly limited, but an isocyanate compound is particularly preferable from the viewpoint of adhesion, flex resistance, curability, and the like. Further, these isocyanate compounds are preferably used after being blocked from the viewpoint of storage stability.
  • curing agents other than isocyanate compounds include known compounds such as amino resins such as methylated melamine, butylated melamine, benzoguanamine, and urea resin, acid anhydrides, imidazoles, epoxy resins, and phenol resins.
  • the isocyanate compound there are aromatic and aliphatic diisocyanates, and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
  • aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
  • isocyanate group blocking agent examples include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; -Lactams such as caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propylolactam, and other aromatic amines, imides, acetylamine Tons, acetoacetic ester, active methylene compounds,
  • cross-linking agents can be used in combination with known catalysts or accelerators selected according to the type.
  • solvent used in the conductive paste of the present invention there are no limitations on the type of solvent used in the conductive paste of the present invention.
  • Aliphatic hydrocarbons such as octane and decane, esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate
  • alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol, acetone, methyl ethyl ketone and methyl Ketones such as isobutyl ketone and cyclohexanone
  • the conductive paste of the present invention has PTC characteristics as long as it is at least 3 times the ratio of change in resistance at 80 ° C. and 30 ° C. (sheet resistance (80 ° C.) / Sheet resistance (30 ° C.)). Then, there is another important index for performance. It is called “return characteristics”.
  • the difference (rate of change) between the resistance value at room temperature before the temperature rise and the resistance value at room temperature after the temperature rise and after cooling is within ⁇ 1 to 100%. . That is, even if the temperature rise and fall is repeated, it becomes an index that exhibits stable PTC characteristics.
  • the stability of the resistance value at high temperatures is also important.
  • the stability of the resistance value at a high temperature means that there is no significant decrease in the resistance value when the temperature is raised to 80 ° C. and further raised to a higher temperature.
  • the stability of the resistance value at high temperature is good because the resistance value after heating up to 120 ° C. is equal to or higher than the resistance value at 80 ° C. Also means a reduction of less than 20%.
  • a significant decrease in resistance value in a high temperature range is not preferable from a safety standpoint because it conducts at a high temperature.
  • the conductive paste of the present invention is printed on a plastic film such as a PET film (sheet) by a known method such as screen printing, rotary screen printing, gravure printing, transfer printing, roll coating, comma coating, flow coating or spray coating. It can be used for circuits and sheet heating elements.
  • Glass transition temperature (Tg) and melting point (Tm) 5 mg of sample was put in an aluminum sample pan and sealed, and measured with a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc. up to 200 ° C. at a temperature rising rate of 20 ° C./min.
  • the maximum peak temperature of heat of fusion was determined as the crystalline melting point.
  • the glass transition temperature was determined by the temperature at the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope at the transition.
  • Acid value 0.2 g of a sample was precisely weighed and dissolved in 20 ml of chloroform. Subsequently, it titrated with 0.01N potassium hydroxide (ethanol solution). A phenolphthalein solution was used as an indicator.
  • Adhesion A conductive paste was screen printed on a PET film that had been annealed to a thickness of 100 ⁇ m, a 25 ⁇ 200 mm pattern was printed, dried and cured at 150 ° C. for 30 minutes, and used as a test piece. The dry film thickness was adjusted to 20-30 ⁇ m. The test piece was used for evaluation according to JIS K5600 5-6. Cellophane tape CT-12 (manufactured by Nichiban Co., Ltd.) was used as the adhesive tape.
  • Pencil hardness The surface hardness was evaluated in accordance with JIS K5400 using the high-quality pencil specified in JIS S6006 using the test piece prepared in (1).
  • Resistance value stability at high temperature In this method, the temperature was raised to 80 ° C. and then further compared to the resistance value at 80 ° C. after the temperature was raised to 120 ° C.
  • polyester polyols (B) to (D) The polyester polyols (A) were synthesized in the same manner. Polyester polyols (B) to (C) had no crystalline melting point and were amorphous, while polyester polyols (D) to (E) had a crystalline melting point. The results are shown in Table 1.
  • Synthesis of polyurethane resin having crystalline melting point Synthesis of polyurethane resin (a) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 1000 parts of the polyester polyol (A) of the synthesis example was added to 630 parts of ethyl carbitol acetate and 210 parts of butyl cellosolve acetate. Dissolved at 80 ° C. Subsequently, after adding 250 parts of diphenylmethane diisocyanate, the reaction was carried out for 2 hours.
  • polyester polyol (B) of the synthesis example 1000 parts of polyester polyol (B) of the synthesis example, HS2H-500S (manufactured by Toyokuni Oil Co., Ltd., melting point 70 ° C., number average molecular weight 5000) 500 parts was dissolved in 1100 parts of cyclohexanone at 80 ° C. Subsequently, 148 parts of diphenylmethane diisocyanate was added and reacted for 2 hours. Thereafter, 0.3 part of dibutyltin dilaurate was added as a catalyst and reacted at 80 ° C. for 4 hours.
  • HS2H-500S manufactured by Toyokuni Oil Co., Ltd., melting point 70 ° C., number average molecular weight 5000
  • the solution was diluted with 630 parts, Solvesso 150: 970 parts, ethyl carbitol acetate 1683 parts, and butyl cellosolve acetate 561 parts to obtain a polyurethane resin (c).
  • the solid content concentration of the obtained polyurethane resin solution was 25.0 (% by weight).
  • the number average molecular weight of the polyurethane resin (c) was 41000, the acid value was 11 eq / ton, and Tm was 55 ° C.
  • the solution was diluted with 833 parts of cyclohexanone and 150: 4235 parts of Solvesso to obtain a polyurethane resin (d).
  • the solid content concentration of the obtained polyurethane resin solution was 25.0 (% by weight).
  • the number average molecular weight of the polyurethane resin (d) was 44000, the acid value was 21 eq / ton, and Tm was 72 ° C.
  • polyurethane resin (e) In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 1000 parts of polyester polyol (B) and 1000 parts of polyester polyol (E) in the synthesis example were added to 1085 parts of ethyl carbitol acetate and 363 parts of butyl cellosolve acetate. Dissolved at 80 ° C. Next, after adding 172 parts of diphenylmethane diisocyanate, the reaction was carried out for 2 hours. Thereafter, 0.3 part of dibutyltin dilaurate was added as a catalyst and reacted at 80 ° C. for 4 hours.
  • the solution was diluted with 2281 parts of cyclohexanone, 2090 parts of ethyl carbitol acetate and 697 parts of butyl cellosolve acetate to obtain a polyurethane resin (e).
  • the solid content concentration of the obtained polyurethane resin solution was 25.0 (% by weight).
  • the number average molecular weight of the polyurethane resin (e) was 45000, the acid value was 19 eq / ton, and Tm was 25 ° C.
  • the resulting polyurethane resin solution had a solid content concentration of 25.1 (% by weight).
  • the number average molecular weight of the polyurethane resin (f) was 45000, the acid value was 12 eq / ton, the Tm was 46 ° C., and the urea bond amount was 70 eq / ton.
  • polyester polyol (B) of synthesis example ODX688 which is an amorphous copolymerized polyester diol (manufactured by Dainippon Ink, Inc.) 1500 parts, 50 parts of 1,6-hexanediol as a chain extender, 150 parts of neopentyl glycol, 2750 parts of ethyl carbitol acetate and 920 parts of butyl cellosolve acetate as solvents were charged and dissolved at 80 ° C.
  • B polyester polyol
  • ODX688 which is an amorphous copolymerized polyester diol (manufactured by Dainippon Ink, Inc.) 1500 parts, 50 parts of 1,6-hexanediol as a chain extender, 150 parts of neopentyl glycol, 2750 parts of ethyl carbitol acetate and 920 parts of butyl cellosolve acetate as solvents were charged and dissolved
  • polyurethane resin (h) 20 parts of polyester polyol (A) 1000 parts of synthesis example and Plaxel 220 (manufactured by Daicel Chemical Industries, melting point 55 ° C., number average molecular weight 2000) in a reaction vessel equipped with a stirrer, a condenser and a thermometer Then, 570 parts of ethyl carbitol acetate and 190 parts of butyl cellosolve acetate were added and dissolved at 80 ° C. Next, 120 parts of diphenylmethane diisocyanate (MDI) was added and the reaction was continued for 1 hour.
  • MDI diphenylmethane diisocyanate
  • polyurethane resin (i) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 1000 parts of polyester polyol (B) of the synthesis example and 900 parts of Plaxel 210 (manufactured by Daicel Chemical Industries, melting point 47 ° C., number average molecular weight 1000) Then, 1680 parts of ethyl carbitol acetate and 560 parts of butyl cellosolve acetate were added and dissolved at 80 ° C.
  • polyester polyol (B) of the synthesis example 1000 parts of polyester polyol (B) of the synthesis example and 900 parts of Plaxel 210 (manufactured by Daicel Chemical Industries, melting point 47 ° C., number average molecular weight 1000) Then, 1680 parts of ethyl carbitol acetate and 560 parts of butyl cellosolve acetate were added and dissolved at 80 ° C.
  • Table 2 summarizes the physical properties of the polyurethane resins (a) to (i).
  • the obtained conductive paste was slightly black and had a good viscosity.
  • the specific resistance was 4.8 ⁇ ⁇ cm.
  • the PTC characteristic was as bad as 2.7 times.
  • the conductive paste of the present invention has extremely good PTC characteristics, and further provides a planar heating element having good conductivity, return characteristics, resistance stability at high temperatures, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Surface Heating Bodies (AREA)
  • Resistance Heating (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention porte sur une pâte conductrice pour des éléments chauffants plans qui présente une excellente solubilité dans un solvant même si un polymère avec un point de fusion cristallin est utilisé en tant que résine dans celle-ci, qui présente également une excellente résistance spécifique et d'excellentes propriétés PTC même avec un chauffage répété, et qui ne perd pas de manière abrupte une résistance, même lorsqu'elle est chauffée au-dessus de son point de fusion. La pâte conductrice pour des éléments chauffants plans comporte une résine de polyuréthane (I) avec un point de fusion cristallin et des particules conductrices (II). Dans cette pâte conductrice pour des éléments chauffants plans, le point de fusion cristallin de la résine de polyuréthane (I) est de préférence 20 à 100°C, et la résine de polyuréthane (I) est de préférence une résine dans laquelle au moins un constituant amorphe et un constituant cristallin ont été amenés à réagir.
PCT/JP2009/057054 2008-04-07 2009-04-06 Pâte conductrice pour un élément chauffant plan, et circuit imprimé et élément chauffant plan utilisant celle-ci Ceased WO2009125740A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010507232A JP5370357B2 (ja) 2008-04-07 2009-04-06 面状発熱体用導電性ペースト及びこれを用いた印刷回路、面状発熱体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-099472 2008-04-07
JP2008099472 2008-04-07

Publications (1)

Publication Number Publication Date
WO2009125740A1 true WO2009125740A1 (fr) 2009-10-15

Family

ID=41161873

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/057054 Ceased WO2009125740A1 (fr) 2008-04-07 2009-04-06 Pâte conductrice pour un élément chauffant plan, et circuit imprimé et élément chauffant plan utilisant celle-ci

Country Status (3)

Country Link
JP (1) JP5370357B2 (fr)
KR (1) KR101601996B1 (fr)
WO (1) WO2009125740A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5321931B1 (ja) * 2011-10-24 2013-10-23 Ｄｉｃ株式会社 湿気硬化型ポリウレタンホットメルト樹脂組成物、接着剤及び物品
WO2015076390A1 (fr) * 2013-11-22 2015-05-28 東洋ドライルーブ株式会社 Composition chauffante au carbone et élément chauffant au carbone
JP2016523296A (ja) * 2013-06-14 2016-08-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 電導性熱可塑性ポリウレタンから製造される加熱可能な成形品
WO2022215486A1 (fr) * 2021-04-09 2022-10-13 東洋紡株式会社 Composition électroconductrice
WO2023067910A1 (fr) * 2021-10-22 2023-04-27 東洋紡株式会社 Composition conductrice
WO2023067909A1 (fr) * 2021-10-22 2023-04-27 東洋紡株式会社 Composition conductrice

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120121041A (ko) * 2011-04-26 2012-11-05 (주)피엔유에코에너지 비표면적이 특정한 저항성분을 포함하는 면상발열체 조성물 및 이를 이용한 면상발열체
KR20120121037A (ko) * 2011-04-26 2012-11-05 (주)피엔유에코에너지 특정한 저항온도계수를 갖는 면상발열체 조성물 및 이를 이용한 면상발열체
KR101437825B1 (ko) * 2012-08-13 2014-09-05 주식회사 부일하우징 열가소성 폴리우레탄이 코팅된 면상발열체 제조방법.
JP7255971B2 (ja) * 2018-03-15 2023-04-11 株式会社イノアックコーポレーション 車両内装部材

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01107488A (ja) * 1987-10-21 1989-04-25 Asuku Hiiteingu:Kk 導電性発熱体及びその製造方法
JP2004014286A (ja) * 2002-06-06 2004-01-15 Matsushita Electric Ind Co Ltd 発熱体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01107488A (ja) * 1987-10-21 1989-04-25 Asuku Hiiteingu:Kk 導電性発熱体及びその製造方法
JP2004014286A (ja) * 2002-06-06 2004-01-15 Matsushita Electric Ind Co Ltd 発熱体

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5321931B1 (ja) * 2011-10-24 2013-10-23 Ｄｉｃ株式会社 湿気硬化型ポリウレタンホットメルト樹脂組成物、接着剤及び物品
JP2016523296A (ja) * 2013-06-14 2016-08-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 電導性熱可塑性ポリウレタンから製造される加熱可能な成形品
JP2019167546A (ja) * 2013-06-14 2019-10-03 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 電導性熱可塑性ポリウレタンから製造される加熱可能な成形品
WO2015076390A1 (fr) * 2013-11-22 2015-05-28 東洋ドライルーブ株式会社 Composition chauffante au carbone et élément chauffant au carbone
JP5866073B2 (ja) * 2013-11-22 2016-02-17 東洋ドライルーブ株式会社 炭素発熱組成物及び炭素発熱体
CN105637977A (zh) * 2013-11-22 2016-06-01 东洋德来路博株式会社 碳放热组合物及碳放热体
WO2022215486A1 (fr) * 2021-04-09 2022-10-13 東洋紡株式会社 Composition électroconductrice
WO2023067910A1 (fr) * 2021-10-22 2023-04-27 東洋紡株式会社 Composition conductrice
WO2023067909A1 (fr) * 2021-10-22 2023-04-27 東洋紡株式会社 Composition conductrice

Also Published As

Publication number Publication date
JP5370357B2 (ja) 2013-12-18
JPWO2009125740A1 (ja) 2011-08-04
KR101601996B1 (ko) 2016-03-17
KR20100133407A (ko) 2010-12-21

Similar Documents

Publication Publication Date Title
JP5370357B2 (ja) 面状発熱体用導電性ペースト及びこれを用いた印刷回路、面状発熱体
JP4968410B2 (ja) 導電性ペースト、導電性膜、タッチパネル、及び導電性薄膜の製造方法
JPWO2008133073A1 (ja) 導電性ペースト及びこれを用いた印刷回路、面状発熱体
JP5773292B2 (ja) レーザーエッチング加工用導電性ペースト、導電性薄膜および導電性積層体
JP6303367B2 (ja) 導電性ペースト、導電性膜及びタッチパネル
KR20240027882A (ko) 기계적 특성의 우수한 조합을 갖는 열 전도성 폴리우레탄 접착제
CN107849210B (zh) 氨基甲酸酯改性聚酰亚胺系树脂溶液
WO2021205917A1 (fr) Composition adhésive et feuille adhésive, stratifié et carte de circuit imprimé
CN115298027A (zh) 白色易粘接性聚酯膜
JP2005078967A (ja) 導電性ペースト
JP2008202019A (ja) 絶縁性樹脂組成物
JP2008269876A (ja) 導電性ペースト及びこれを用いた印刷回路、面状発熱体
JP2005259546A (ja) ロータリースクリーン印刷機用導電性ペースト及びそれを用いた導体回路
JP4547623B2 (ja) 導電性ペースト
JP3312600B2 (ja) Ｐｔｃ特性を有する樹脂組成物
JP7515644B1 (ja) カルボキシ基含有ポリウレタン樹脂及び樹脂組成物
JP2007242397A (ja) 導電性ペースト及びこれを用いた印刷回路、面状発熱体
JP3790869B2 (ja) 金属めっき下地用導電性ペースト
KR101874301B1 (ko) 핫멜트 접착제용 폴리우레탄 수지 및 이를 포함하는 2액형 폴리우레탄 핫멜트 접착제 및 핫멜트 접착제용 폴리우레탄 수지의 제조방법.
JP2006085978A (ja) 導電性樹脂組成物及びこれを用いた面状発熱体
JP7545133B2 (ja) Ｐｔｃ抵抗体、および面状発熱体
JP5061608B2 (ja) コーティング組成物、積層体及びフレキシブルフラットケーブル
JP2002094201A (ja) 導電性ペースト
JP2002008441A (ja) 導電性ペースト
JP6103986B2 (ja) ポリエステル樹脂組成物、およびそれから得られる塗膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09730479

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010507232

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20107022290

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09730479

Country of ref document: EP

Kind code of ref document: A1