WO2010055742A1 - Pâte conductrice, film de blindage contre les ondes électromagnétiques l'utilisant, et carte de câblage imprimé flexible à blindage contre les ondes électromagnétiques - Google Patents

Pâte conductrice, film de blindage contre les ondes électromagnétiques l'utilisant, et carte de câblage imprimé flexible à blindage contre les ondes électromagnétiques Download PDF

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WO2010055742A1
WO2010055742A1 PCT/JP2009/067715 JP2009067715W WO2010055742A1 WO 2010055742 A1 WO2010055742 A1 WO 2010055742A1 JP 2009067715 W JP2009067715 W JP 2009067715W WO 2010055742 A1 WO2010055742 A1 WO 2010055742A1
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Prior art keywords
isocyanate
conductive paste
metal powder
component
urethane
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PCT/JP2009/067715
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English (en)
Japanese (ja)
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浩平 下田
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住友電気工業株式会社
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Priority to CN2009801051008A priority Critical patent/CN101952902B/zh
Publication of WO2010055742A1 publication Critical patent/WO2010055742A1/fr

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    • 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
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
    • H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
    • H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]

Definitions

  • the present invention relates to a conductive paste, an electromagnetic wave shielding film using the conductive paste, and an electromagnetic wave shielding flexible printed wiring board, and more particularly to a flexible printed wiring board that requires bending resistance.
  • the conductive paste is a paste obtained by mixing a conductive filler such as carbon black, graphite powder, noble metal powder, copper powder, nickel powder, etc., a binder resin, and a solvent. This is applied onto a film or substrate by a method such as screen printing to form a pattern, and the resin is solidified to form conductive wiring. With recent downsizing and weight reduction of electronic components, highly conductive conductive pastes are required for such applications.
  • Patent Document 1 discloses a conductive silver paste using silver as a conductive filler.
  • the shape of the silver powder used as the conductive filler is not limited, and it is granular, scale-like, plate-like, dendritic, cocoon-like, dice-like, or the like having a size of 0.1 to 100 ⁇ m.
  • the binder resin a saturated copolymerized polyester resin and a blocked isocyanate are used.
  • Patent Document 2 discloses a silver powder in which primary particles having a particle diameter of 0.1 to 5 ⁇ m are three-dimensionally connected in order to improve the bending resistance of a conductive paste, and a number average molecular weight.
  • An electrically conductive paste mainly composed of 3000 or more binders, a curing agent and a solvent is disclosed.
  • the binder include polyurethane resins and polyester resins.
  • Patent Document 3 discloses a conductive silver paste having improved conductivity and shielding characteristics by combining silver powder having a specific particle diameter, and an electromagnetic wave shielding film using the same.
  • the shield layer formed by applying and solidifying the conductive paste has heat resistance, surface smoothness, and bending resistance in addition to conductivity and electromagnetic shielding properties. Sex is required.
  • a movable part such as a hinge part of a mobile phone
  • durability at a smaller bending radius is required due to downsizing of the device, so that it is a problem to improve the bending resistance.
  • the polyester resin is a resin obtained by condensation polymerization of an acid component such as a polyvalent carboxylic acid or an acid anhydride and an alcohol component such as a polyhydric alcohol.
  • the polyester resin is appropriately selected by selecting the type of the acid component or alcohol component. Its characteristics can be controlled. For example, when many flexible components such as aliphatic dicarboxylic acid are used, the flexibility is improved. However, if a large amount of flexible components are used, the heat resistance is lowered and the required characteristics cannot be satisfied. In order to increase the heat resistance, it is necessary to increase the proportion of rigid aromatic components such as terephthalic acid, but this reduces flexibility.
  • the present invention provides a conductive paste capable of forming an electromagnetic wave shielding layer having both flexibility and heat resistance and excellent bending resistance, and an electromagnetic wave shielding film using the same.
  • the present invention is a conductive paste containing a conductive metal powder, a urethane-modified polyester resin, and a blocked isocyanate, and the urethane-modified polyester resin reacts an isocyanate component containing an acid component, an alcohol component, and an aromatic isocyanate.
  • the total of aromatic components contained in the acid component, alcohol component, and isocyanate component is 5 mol% or more and 50 mol% or less with respect to the total of the acid component, alcohol component, and isocyanate component.
  • This is a conductive paste (first invention of the present application).
  • the binder resin a urethane-modified polyester resin modified with an isocyanate component containing an aromatic isocyanate is used.
  • the sum total of the aromatic component contained in an acid component, an alcohol component, and an isocyanate component shall be 5 mol% or more and 50 mol% or less with respect to the sum total of an acid component, an alcohol component, and an isocyanate component.
  • the hydroxyl value of the urethane-modified polyester resin is preferably 5 mgKOH / g or more and 60 mgKOH / g or less (the second invention of the present application).
  • the hydroxyl value is an index indicating the molecular weight with respect to the number of crosslinking points (hydroxyl groups that react with blocked isocyanate) of the urethane-modified polyester resin. When the hydroxyl value is large, the molecular weight is small, and when the hydroxyl value is small, the molecular weight is large.
  • the hydroxyl value is less than 5 mgKOH / g, the molecular weight is large and the flexibility is excellent, but the heat resistance is lowered by reducing the number of crosslinking points for reacting with the blocked isocyanate.
  • the hydroxyl value exceeds 60 mgKOH / g, the molecular weight decreases, and the heat resistance is improved but the flexibility is lowered.
  • the blocked isocyanate has a number average molecular weight of 500 or more and 3000 or less, and is preferably a polyfunctional block polyisocyanate compound in which an adduct isocyanate of an isocyanate monomer and a polyhydroxy compound is blocked with a blocking agent (the third of the present application invention). Since such an adduct type isocyanate has a large amount of functional groups (isocyanate groups) in one molecule, the crosslinking density of the urethane-modified polyester resin after the reaction can be increased, and the heat resistance can be improved.
  • the mixing ratio of the urethane-modified polyester resin and the blocked isocyanate is 0.8 or more in terms of the molar ratio (NCO / OH) of the hydroxyl group (OH) of the urethane-modified polyester resin and the isocyanate group (NCO) of the blocked isocyanate. It is preferable that it is 3.0 or less (the fourth invention of the present application).
  • the amount of blocked isocyanate is less than this range, the crosslinking density of the urethane-modified polyester resin is lowered, and the heat resistance is lowered.
  • the heat resistance may become low because the isocyanate which does not contribute to reaction remains in binder resin.
  • a more preferable range of the molar ratio is 1.0 or more and 2.0 or less.
  • the conductive metal powder is composed of a metal powder A having an average particle diameter of 0.5 ⁇ m to 20 ⁇ m and a metal powder B having an average particle diameter of 100 nm or less, and the content ratio of the metal powder A and the metal powder B is a weight ratio. 99.5: 0.5 to 70:30, and the content ratio of the conductive metal powder is preferably 50% by weight to 85% by weight with respect to the solid content of the conductive paste. 5 invention).
  • the content ratio of the conductive metal powder is increased, the conductivity is improved. However, when the content is too high, the flexibility of the conductive paste is lowered and the bending resistance is deteriorated, so that both conductivity and bending resistance are achieved.
  • the content ratio of the conductive metal powder is preferably 50% by weight or more and 85% by weight or less.
  • the conductivity is improved and the smoothness of the surface after the conductive paste is applied can be improved. Since the smoothness of the surface affects the electromagnetic shielding characteristics as well as the electrical conductivity, the electromagnetic shielding characteristics can be further improved by improving the electrical conductivity and smoothness.
  • the present invention also provides an electromagnetic wave shielding film having a layer made of the above conductive paste on a substrate (the sixth invention of the present application). Moreover, the electromagnetic wave shield flexible printed wiring board which has a layer which consists of said electroconductive paste is provided (this invention 7th invention).
  • Such an electromagnetic wave shielding film and an electromagnetic wave shielding flexible printed wiring board are excellent in bending resistance and heat resistance, conductivity, and electromagnetic wave shielding characteristics.
  • a conductive paste capable of forming an electromagnetic wave shielding layer having both flexibility and heat resistance and excellent in bending resistance, an electromagnetic wave shielding film using the same, and an electromagnetic wave shielding flexible printed wiring board. Can do.
  • the urethane-modified polyester resin used in the present invention will be described.
  • the urethane-modified polyester resin is obtained by reacting an acid component, an alcohol component, and a urethane component.
  • a polyester resin is obtained by condensation polymerization of an acid component such as a polyvalent carboxylic acid or an anhydride thereof and an alcohol component such as a polyhydric alcohol.
  • a urethane-modified polyester resin is obtained by reacting the terminal hydroxyl group of the obtained polyester resin with an isocyanate component.
  • the isocyanate component is preferably added and reacted after the reaction between the acid component and the alcohol component, but the acid component, the alcohol component, and the isocyanate component may be reacted at the same time.
  • the acid component is not particularly limited as long as it is a polyvalent carboxylic acid or an anhydride thereof.
  • aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid and the like, succinic acid, adipic acid
  • examples thereof include aliphatic dicarboxylic acids such as glutaric acid and sebacic acid and anhydrides thereof, and unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydrides thereof. Two or more of these may be used in combination.
  • the alcohol component is not particularly limited as long as it is a polyhydric alcohol.
  • ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexane examples thereof include aliphatic glycols such as diols, aromatic glycols, alicyclic glycols, trivalent or higher alcohols such as trimethylolpropane and pentaerythritol. Two or more of these may be used in combination.
  • the isocyanate component has two or more isocyanate groups in one molecule, and an aromatic isocyanate having an aromatic ring in the molecule is essential.
  • aromatic isocyanate include xylene diisocyanate, tolylene diisocyanate, 4,4 'diphenylmethane diisocyanate, naphthalene diisocyanate, and biphenylene diisocyanate. Two or more of these may be used in combination.
  • aliphatic diisocyanate such as trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, trimethylene diisocyanate, alicyclic diisocyanate such as cyclohexane diisocyanate, etc. are used in combination as long as the spirit of the present invention is not impaired. May be.
  • the total of aromatic components in the acid component, alcohol component, and isocyanate component is 5 mol% or more and 50 mol% or less with respect to the total of all components. These materials are reacted in a conventional manner to obtain a urethane-modified polyester resin.
  • the blocked isocyanate used in the present invention is obtained by blocking the terminal isocyanate group of a polyfunctional isocyanate with a blocking agent.
  • the blocking agent is dissociated by heating, and an isocyanate group is generated. This isocyanate group reacts with the hydroxyl group of the urethane-modified polyester resin to crosslink the urethane-modified polyester resin.
  • the blocking agent examples include compounds having an active hydroxyl group such as alcohols, phenols, acid amides, oximes, and active methylene.
  • any isocyanate such as trimethylene diisocyanate, hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (MDI) can be used.
  • HDI hexamethylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • an adduct type isocyanate of an isocyanate monomer and a polyhydroxy compound represented by the general formula (I) is preferable.
  • R1 to R3 represent a group obtained by removing an isocyanate group from an aliphatic, alicyclic or aromatic diisocyanate, and R4 represents a group obtained by removing a hydroxyl group from a polyhydric alcohol compound.
  • a polyhydroxy compound is a compound having two or more hydroxyl groups in one molecule, such as glycerin, trimethylolethane, trimethylolpropane, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, etc. Is done.
  • the diisocyanate include trimethylene diisocyanate, hexamethylene diisocyanate, and diphenylmethane diisocyanate.
  • any metal such as copper, gold, silver, platinum, nickel, and alloys thereof can be used, but it is preferable to use silver powder excellent in conductivity.
  • the shape is not particularly limited, and examples thereof include a spherical shape, a scale shape, and a granular shape.
  • the content of the conductive metal powder can be arbitrarily selected according to the required characteristics. Increasing the content of the conductive metal powder can improve the conductivity, but if the content of the conductive metal powder is too large, the adhesion (cohesive force) between the resin component and the conductive metal powder will be weak, and after coating When voids enter the conductive paste, the printability and adhesiveness are affected. In addition, the conductivity also decreases. For this reason, it is preferable that content of electroconductive metal powder shall be 95% or less with respect to the whole solid content of electroconductive paste.
  • the content of the conductive metal powder is increased, the conductive paste becomes hard and the flexibility is lowered.
  • the content of the conductive metal powder is preferably 50% or more and 85% or less with respect to the total solid content of the conductive paste.
  • a metal powder A having an average particle size of 0.5 ⁇ m to 20 ⁇ m and a metal powder having an average particle size of 100 nm or less are used in combination, and the content ratio of the metal powder A and the metal powder B is expressed by weight ratio.
  • 99.5: 0.5 to 70:30 is preferable.
  • the content ratio of the metal powder A and the metal powder B exceeds 99.5: 0.5 and the metal powder A increases, the combination effect decreases and the conductivity decreases.
  • the content ratio exceeds 70:30 and the metal powder B is increased the amount of the metal powder B is increased, which is not preferable.
  • a more preferable content ratio of the metal powder A and the metal powder B is 99: 1 to 90:10.
  • the average particle size of the metal powder A is preferably 0.5 ⁇ m to 20 ⁇ m. If the thickness is 0.5 ⁇ m or less, the conductivity is lowered. On the other hand, if the average particle size exceeds 20 ⁇ m, fine printing becomes difficult. For the same reason, it is preferable to use a material having a maximum particle size that does not contain an extremely large particle size, and one having a maximum particle size in the range of 20 ⁇ m to 50 ⁇ m is preferable.
  • the particle diameter is the maximum diameter of each particle, and the average value is the average particle diameter. For the measurement, a scanning electron microscope (SEM) or the like is used.
  • the metal powder A not only one type but also a plurality of powders having different average particle sizes and shapes can be used in combination.
  • the conductivity and smoothness after coating can be further improved.
  • Metal powder B is a metal powder having an average particle size of 100 nm or less. Nano-sized powders may be agglomerated, but the average particle size refers to the particle size of primary particles. Such nano-sized powders have a large surface area and thus a large surface activity. Therefore, in order to protect the surface and suppress secondary aggregation, it is preferable to use a material whose surface is coated with an organic substance. Examples of the organic substance include polycarboxylic acid and polyacrylic acid.
  • the metal powder B having an average particle size of 100 nm or less can be produced, for example, as follows. Silver nitrate is dissolved in a mixed solvent of water and lower alcohol, and the pH is adjusted to 11 or more with aqueous ammonia. Silver particles are precipitated by adding L-ascorbic acid as a reducing agent and polyacrylic acid as a dispersing agent dissolved in the mixed solvent. The precipitated silver particles are obtained by filtration, washing and drying in a state where secondary aggregation is suppressed by the dispersant.
  • the average particle diameter of the silver particles can be changed depending on pH, temperature, concentration of each material, mixing method, and the like.
  • the silver particles produced through the above steps are obtained in a state where the surface of the generated silver particles is coated with the dispersant, particularly by using a dispersant in the reaction step. Since the dispersant is in a state of covering the surface of the silver particles at the generation stage, it is hardly affected by the outside air, and the silver particles are not easily agglomerated. Even if agglomeration occurs, the dispersing agent intervenes, so that agglomeration can be easily broken with an organic solvent or the like. Moreover, the dispersibility to resin is also favorable.
  • the above conductive metal powder, urethane-modified polyester resin, and blocked isocyanate are mixed to prepare a conductive paste.
  • the urethane-modified polyester resin and the blocked isocyanate are used after being dissolved in a solvent. Any solvent can be used as long as it can dissolve the resin, and examples thereof include ester-based, ether-based, ketone-based, ether-ester-based, alcohol-based, hydrocarbon-based, and amine-based organic solvents. .
  • a high boiling point solvent with good printability is preferable, and specifically, carbitol acetate, butyl carbitol acetate, and the like are particularly preferable.
  • additives such as thickeners and leveling agents can be added to the conductive silver paste of the present invention in order to improve printing workability.
  • inorganic fillers such as carbon and silica as long as the performance of the present invention is not impaired.
  • the electromagnetic wave shielding film of the present invention has a layer made of the above conductive paste on a substrate. After apply
  • a polyester film, a polyimide film, etc. can be used as a base material. In view of flexibility, a polyimide film is preferable.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of an electromagnetic wave shielding film.
  • a conductive paste layer 2 is provided on the substrate 1.
  • a protective film 8 may be provided on the conductive paste layer 2. The protective film 8 is peeled off during use.
  • FIG. 2 is a schematic cross-sectional view illustrating an example of an electromagnetic wave shield flexible printed wiring board.
  • a wiring made of a copper foil 5 is formed on a base material 4, and a cover lay covers the wiring.
  • the coverlay includes a coverlay film 6a made of polyimide or the like and a coverlay adhesive 6b.
  • An electromagnetic wave shielding film 3 is attached to the cover lay side of the flexible printed wiring board.
  • a conductive paste layer may be provided by directly applying a conductive paste to a flexible printed wiring board.
  • the coating thickness of the conductive paste is not particularly limited, but is preferably in the range of 10 ⁇ m to 50 ⁇ m. If the thickness is 10 ⁇ m or less, desirable electromagnetic wave shielding characteristics cannot be obtained, but if the thickness is 50 ⁇ m or more, the flexibility of the shield layer is deteriorated and the bending resistance is deteriorated.
  • Examples of the method for applying the conductive paste include screen printing, intaglio printing, lithographic printing, and dispenser. Screen printing is most preferably used from the viewpoint of the fineness, film thickness, and productivity of the wiring to be formed.
  • the conductive paste of the present invention can be directly applied to a flexible printed wiring board and solidified to form an electromagnetic wave shielding layer. Also by such a method, an electromagnetic wave shield flexible printed wiring board having a layer made of the conductive paste of the present invention can be obtained. Similarly, an electromagnetic wave shielding casing having a layer made of the conductive paste of the present invention can be obtained by applying it to the casing of an electronic device such as a personal computer or a mobile phone.
  • Examples 1 to 3, Comparative Examples 1 to 3 Preparation of conductive paste
  • a urethane-modified polyester obtained by reacting the acid component, alcohol component and isocyanate component shown in Table 1 was prepared. Specifically, the acid component and alcohol component listed in Table 1 and a mixed solvent of butyl carbitol acetate and butyl carbitol are put into a four-necked flask and heated to 60 ° C. under a nitrogen stream, and then the isocyanate compound is further added. The mixture was added and heated at 80 ° C. for 5 hours to synthesize urethane-modified polyester.
  • the produced urethane-modified polyester resin was mixed with a scaly silver powder having an average particle size of 3.0 ⁇ m, a spherical silver powder having an average particle size of 25 nm, and a blocked isocyanate as a conductive metal powder to prepare a conductive paste.
  • the compounding ratio of the urethane-modified polyester and the blocked isocyanate was an equimolar molar ratio, and the compounding ratio of the conductive metal powder was the following ratio.
  • a non-adhesive copper-clad laminate (two-layer CCL) in which a copper foil was laminated on a polyimide film was prepared, and a copper foil portion was selectively etched by a subtractive method to form a pattern having a line width of 50 ⁇ m. Further, a cover lay film was stuck thereon to produce a flexible printed wiring board for evaluation.
  • the conductive paste was applied to the cover lay film side of the flexible printed wiring board by a screen printing method and thermally cured in an oven furnace. Further, for the sliding flexibility evaluation sample, a solder resist was applied on the conductive paste and thermally cured in an oven furnace.
  • Comparative Example 1 In Comparative Example 1 in which the total of aromatic components contained in the acid component, alcohol component, and isocyanate component is less than 5 mol% with respect to the total of the acid component, alcohol component, and isocyanate component, the adhesion after reflow treatment is Low and heat resistance is poor. Similarly, Comparative Example 2 in which the aromatic component is not included in the isocyanate component also has low adhesion after reflow treatment and poor heat resistance. Further, in Comparative Example 3 in which the total of the aromatic components exceeds 50 mol%, the adhesion is good but the sliding flexibility is poor.
  • Example 4 By changing the degree of polymerization of the urethane-modified polyester resin, urethane-modified polyester resins having different hydroxyl values were produced. Using this resin, a conductive paste was prepared in the same manner as in Examples 1 to 3, and the adhesion strength, sliding flexibility and volume resistivity after reflow treatment were evaluated. The results are shown in Table 2.
  • the hydroxyl value of the urethane-modified polyester resin correlates with the adhesion after reflow treatment, and the adhesion increases as the hydroxyl value increases.
  • the adhesion is 0.8 N / cm, which is a slightly low value.
  • Example 8 in which the hydroxyl value exceeds 60 mgKOH / g has poor flexibility and results in a slightly low number of sliding and bending.
  • polyfunctional block polyisocyanate compounds having various number average molecular weights were prepared.
  • the polyfunctional block polyisocyanate compound is obtained by blocking the end of an adduct type isocyanate of an isocyanate monomer and a polyhydroxy compound with a blocking agent.
  • a conductive paste was prepared in the same manner as in Examples 1 to 3 in combination with the urethane-modified polyester resin described in Example 1, and the adhesive strength after reflow treatment, sliding flexibility, volume resistivity Evaluated.
  • Example 9 In all the samples, the adhesiveness, sliding flexibility, and specific resistance satisfy the required characteristics, but in Example 9 in which the number average molecular weight of the polyfunctional block polyisocyanate compound is less than 500, the number of sliding flexures is 8. The result is somewhat low at 10,000 times. Moreover, in Example 13 in which the number average molecular weight exceeds 3000, the volume resistance is slightly high.
  • Example 14 Using the urethane-modified polyester resin and the polyfunctional block polyisocyanate compound used in Example 1, and changing the NCO / OH ratio by changing the blending ratio of both, a conductive paste was prepared in the same manner as in Examples 1 to 3, The adhesive strength, sliding flexibility, and volume resistivity after the reflow treatment were evaluated. As a result, as shown in Table 4, in Example 14 in which the NCO / OH ratio is less than 0.8, the volume resistance value is slightly high. This is presumed to be because the crosslinking density decreases when the NCO / OH ratio is low. Moreover, in Example 18 in which the NCO / OH ratio exceeds 3.0, the adhesion after the reflow treatment is slightly low. If the NCO / OH ratio is high, it is presumed that the heat resistance is lowered due to the excess curing agent remaining.
  • Example 19 As conductive metal powder, metal powder A having an average particle diameter of 4.8 ⁇ m and metal powder B having an average particle diameter of 30 nm were prepared. By changing the content ratio of the metal powder A and the metal powder B, a conductive paste was produced in the same manner as in the methods described in Examples 1 to 3, and the adhesion strength, sliding flexibility, and volume resistivity after the reflow treatment were evaluated. . At this time, the total weight of the metal powder A and the metal powder B was obtained by multiplying the weight sum of the weight of the urethane-modified polyester resin and the blocked isocyanate by 2.333.
  • Example 19 in which the content ratio of the metal powder A and the metal powder B was less than 99.5: 0.5, the volume resistivity was slightly high. Further, in Example 23 in which the content ratio of the metal powder A and the metal powder B exceeds 70:30, the effect of improving the characteristics is not particularly seen. Since the metal powder having an average particle size of nano-size is expensive, the content ratio of the metal powder A and the metal powder B is 99.5: 0.5 to 70:30 in consideration of the characteristics and cost of the conductive paste. The range of is preferable.
  • Example 24 As conductive metal powder, metal powder A having an average particle diameter of 4.8 ⁇ m and metal powder B having an average particle diameter of 30 nm were prepared. Here, the content ratio of the metal powder A and the metal powder B is fixed at 90:10, and the content ratio of the metal powder obtained by adding the metal powder A and the metal powder B is changed to produce a conductive paste, and the reflow treatment is performed. The subsequent adhesion, sliding flexibility, and volume resistivity were evaluated. As a result, as shown in Table 6, in Example 24 in which the metal powder content ratio was less than 50% by weight, the volume resistance was slightly high. Further, in Example 28 in which the metal powder content ratio exceeds 85% by weight, the sliding bending performance is slightly low.
  • the present invention relates to a conductive paste, an electromagnetic wave shielding film using the conductive paste, and an electromagnetic wave shielding flexible printed wiring board, and can be suitably used particularly for a flexible printed wiring board requiring bending resistance.

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Abstract

L'invention porte sur une pâte conductrice contenant une poudre métallique conductrice, une résine de polyester modifiée par uréthane et un isocyanate bloc, la résine de polyester modifiée par uréthane étant obtenue par réaction d'un composant acide, d'un composant alcool et d'un composant isocyanate contenant un isocyanate aromatique, et le total des composants aromatiques contenus dans le composant acide, le composant alcool et le composant isocyanate n'étant pas inférieur à 5 % molaire mais pas supérieur à 50 % molaire du total du composant acide, du composant alcool et du composant isocyanate. La pâte conductrice possède un bon équilibre entre flexibilité et résistance à la chaleur, et est capable de former une couche de blindage ayant une excellente résistance à la flexion. L'invention porte également sur un film de blindage contre les ondes électromagnétiques utilisant la pâte conductrice et sur une carte de câblage imprimé flexible à blindage contre les ondes électromagnétiques.
PCT/JP2009/067715 2008-11-14 2009-10-13 Pâte conductrice, film de blindage contre les ondes électromagnétiques l'utilisant, et carte de câblage imprimé flexible à blindage contre les ondes électromagnétiques WO2010055742A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009801051008A CN101952902B (zh) 2008-11-14 2009-10-13 导电糊以及使用该导电糊的电磁屏蔽膜和电磁屏蔽柔性印刷布线板

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JP2008-291596 2008-11-14
JP2008291596A JP5446222B2 (ja) 2008-11-14 2008-11-14 導電性ペースト及びそれを用いた電磁波シールドフィルム、電磁波シールドフレキシブルプリント配線板

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WO2010055742A1 true WO2010055742A1 (fr) 2010-05-20

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PCT/JP2009/067715 WO2010055742A1 (fr) 2008-11-14 2009-10-13 Pâte conductrice, film de blindage contre les ondes électromagnétiques l'utilisant, et carte de câblage imprimé flexible à blindage contre les ondes électromagnétiques

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JP (1) JP5446222B2 (fr)
CN (1) CN101952902B (fr)
TW (1) TW201030766A (fr)
WO (1) WO2010055742A1 (fr)

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CN102719215A (zh) * 2012-06-28 2012-10-10 广州高金技术产业集团有限公司 导电性良好且热稳定性优良的纳米银-聚氨酯胶黏剂及其制备方法
JP2013136322A (ja) * 2011-12-28 2013-07-11 Honda Motor Co Ltd 鞍乗り型車両のブレーキ装置
WO2023188548A1 (fr) * 2022-03-31 2023-10-05 東洋紡エムシー株式会社 Film de blindage électromagnétique et stratifié

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JP2013207213A (ja) * 2012-03-29 2013-10-07 Tdk Corp 電子部品モジュール及びその製造方法
KR20150023646A (ko) * 2012-06-07 2015-03-05 다츠다 덴센 가부시키가이샤 실드 필름 및 실드 프린트 배선판
KR101302214B1 (ko) * 2013-05-15 2013-08-30 (주)드림텍 휴대단말기 전자파 차폐용 블랙 쉴드 제조 방법 및 그 제조 장치
KR20160122694A (ko) * 2014-02-12 2016-10-24 도레이 카부시키가이샤 도전 페이스트, 패턴의 제조 방법, 도전 패턴의 제조 방법 및 센서
CN110651004B (zh) 2017-07-07 2022-03-25 拓自达电线株式会社 导电性树脂组合物及使用该导电性树脂组合物的屏蔽封装体的制造方法
CN107353777A (zh) * 2017-08-16 2017-11-17 苏州城邦达力材料科技有限公司 电磁屏蔽膜涂层及电磁屏蔽膜的制备方法
WO2019073809A1 (fr) 2017-10-13 2019-04-18 タツタ電線株式会社 Boîtier de blindage
CN107942627A (zh) * 2017-11-23 2018-04-20 天津市栢力迪新材料科技有限公司 调色剂用粘接树脂组合物及其制造方法
JP6566008B2 (ja) * 2017-11-24 2019-08-28 東洋インキＳｃホールディングス株式会社 電磁波シールドシートおよびプリント配線板
KR102313686B1 (ko) 2018-02-22 2021-10-18 린텍 가부시키가이샤 필름상 소성재료, 및 지지 시트를 가지는 필름상 소성재료
WO2024117244A1 (fr) * 2022-12-02 2024-06-06 タツタ電線株式会社 Film de blindage contre les ondes électromagnétiques et procédé de fabrication de film de blindage contre les ondes électromagnétiques

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CN102719215A (zh) * 2012-06-28 2012-10-10 广州高金技术产业集团有限公司 导电性良好且热稳定性优良的纳米银-聚氨酯胶黏剂及其制备方法
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WO2023188548A1 (fr) * 2022-03-31 2023-10-05 東洋紡エムシー株式会社 Film de blindage électromagnétique et stratifié

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JP2010118280A (ja) 2010-05-27

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