KR102061585B1 - Conductive adhesive sheet, method for manufacturing same and electronic terminal obtained by using same - Google Patents

Abstract

The conductive adhesive sheet of the present invention is a conductive adhesive sheet having a conductive adhesive layer on at least one side of the conductive substrate, and the conductive substrate is subjected to plating treatment including an electroless plating treatment on a wet polyester-based nonwoven substrate. It is an electroconductive base material obtained by making it contain, The said electroconductive adhesive layer relates to the electroconductive adhesive sheet characterized by containing electroconductive particle in 3 mass%-50 mass% with respect to the whole of the said electroconductive adhesive layer.

Description

CONDUCTIVE ADHESIVE SHEET, METHOD FOR MANUFACTURING SAME AND ELECTRONIC TERMINAL OBTAINED BY USING SAME

This invention relates to the electroconductive adhesive sheet which can be used for manufacture of electronic devices, such as a portable electronic terminal, for example.

Background Art In recent years, high integration has been progressed along with miniaturization, thinning, and high performance of electronic devices such as communication devices. In the production of the electronic device, a conductive adhesive sheet is often used for the purpose of shielding electromagnetic waves that may be generated from the electronic device, or imparting antistatic properties to arbitrary portions.

As said electroconductive adhesive sheet, the adhesive sheet which has an electroconductive adhesive layer containing an electroconductive filler on the electroconductive base material which consists of metal foils, for example is known (for example, refer patent document 1 and 2).

Since the electrically conductive adhesive sheet using the above-mentioned metal foil is not enough from a soft point of view, if there exists a micro step | step in the surface of a to-be-adhered body, it cannot follow the said step part, and an adherend, an adhesive layer, and In some cases, voids were formed at the interface of the film.

On the other hand, when the said electroconductive adhesive sheet is affixed on the wrong position of a to-be-adhered body, industrially, the rework property of the level which can be easily peeled off immediately after the sticking is calculated | required.

However, the conductive adhesive sheet as described above is often not sufficient in view of the reworkability, and may not be reused and reattached.

As mentioned above, the electroconductive adhesive sheet which combined the electroconductivity of the level which can fully shield an electromagnetic wave, etc., the level of flexibility which can follow the step part which a to-be-adhered body has, etc., and rework property is not known yet.

Japanese Patent Application Laid-Open No. 2004-263030 JP 2009-79127 A

An object of the present invention is to provide an electroconductive adhesive sheet having both a level of conductivity capable of shielding electromagnetic waves and the like, a level of flexibility that can be traced to a step portion of the adherend, and reworkability.

In this invention, the said electroconductive base material is obtained by performing the plating process containing an electroless-plating process to a wet polyester type nonwoven fabric base material among the electroconductive adhesive sheets which have an electroconductive adhesive layer on at least one side of an electroconductive base material. ,

The said subject was solved by using the electroconductive adhesive sheet which the said electroconductive adhesive layer contains 3 mass%-50 mass% of electroconductive particle with respect to the said whole electroconductive adhesive layer.

The electroconductive adhesive sheet of this invention is compatible with the electroconductivity of the level which can fully shield an electromagnetic wave, etc., and the level of flexibility and rework property which can be traced to the step part derived from the fine unevenness which an adherend etc. have, etc. Since it has the outstanding adhesive force, it can be used suitably for the electromagnetic wave shield sheet which can be used for manufacture of electronic devices, etc., the adhesive sheet for earth | ground fixing for preventing the electrostatic charge, etc., for example.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows the structural example of the conductive adhesive sheet of this invention.
2 is a schematic view showing a configuration example of a conductive adhesive sheet of the present invention.
3 is a view showing the results of evaluation of followability of the conductive adhesive sheet of Example 1. FIG.
4 is a view showing the evaluation results of the traceability of the conductive adhesive sheet of Reference Example 1. FIG.

In the electroconductive adhesive sheet of this invention, in the electroconductive adhesive sheet which has an electroconductive adhesive layer on at least one side of an electroconductive base material, when the said electroconductive base material performs a plating process containing an electroless-plating process to a wet polyester type nonwoven fabric base material, It is obtained by this and the said conductive adhesive layer contains 3 mass%-50 mass% of electroconductive particle with respect to the said whole conductive adhesive layer, It is characterized by the above-mentioned.

The "sheet" as used in this invention means the form which has at least one electroconductive adhesive layer on the at least single side | surface of an electroconductive base material. In addition, the said sheet contains all the product forms, such as a sheet | leaf, a roll shape, a thin plate shape, and a strip shape (tape form), for example.

As a structure of the electroconductive adhesive sheet of this invention, the structure which has the said single layer or multiple layers of the said conductive adhesive layer on the single side | surface of an electroconductive base material, for example, the structure which has the said single layer or multiple layers of the said conductive adhesive layer on both surfaces of the said electroconductive base material is mentioned, for example. have.

As an electroconductive adhesive sheet of this invention, you may have other layers other than the said electroconductive base material and electroconductive adhesive layer as needed.

As said electroconductive adhesive sheet, it is preferable to use what has a total thickness of 100 micrometers or less, It is more preferable to use what has a total thickness of 60 micrometers or less, It is more preferable to use what has a total thickness of 40 micrometers or less, It is more preferable because it can maintain excellent flexibility, conductivity and adhesion, and contribute to thinning of electronic devices and the like.

Moreover, as a minimum of the total thickness of the said electroconductive adhesive sheet, it is preferable that it is 5 micrometers or more. In addition, the said total thickness points out the thickness of the electroconductive adhesive sheet itself which does not contain a peeling film.

As a conductive base material which comprises the electroconductive adhesive sheet of this invention, what was obtained by giving the wet polyester type nonwoven fabric base material the plating process containing an electroless-plating process can be used.

As said electroconductive base material, it is preferable to use what has a thickness of 6 micrometers-50 micrometers, for example, and it is more preferable to use what has a thickness of 10 micrometers-30 micrometers.

As said electroconductive base material, it is preferable to use the thing whose tensile strength of the MD (flow) direction is 3N / 20mm-35N / 20mm, It is more preferable to use what is 5N / 20mm-30N / 20mm, It is more preferable to use 10N / 20mm-27N / 20mm.

Moreover, as said electroconductive base material, it is preferable to use the thing whose tensile strength of the TD (width) direction is 0.5N / 20mm-35N / 20mm, and it is more preferable to use what is 3N / 20mm-30N / 20mm. It is preferable to use what is 10N / 20mm-27N / 20mm.

By using the electroconductive base material which has the tensile strength of MD (flow) direction and TD (width) direction of the said range, it is hard to produce tearing of an electroconductive adhesive sheet at the time of rework, and can maintain outstanding rework property, Moreover, the electroconductive adhesive sheet provided with favorable adhesiveness of an electroconductive base material and an electroconductive adhesive layer can be obtained.

As said electroconductive base material, it is hard to produce tearing of an electroconductive adhesive sheet when reworking (peeling) to use that [the tensile strength of MD direction / the tensile strength of TD direction] is 0.7-1.3, and excellent rework property It is preferable because it can maintain. In addition, the said tensile strength points out the value measured by pulling at the speed | rate of 300 mm / min according to JISZ0237-2010.

Moreover, as said electroconductive base material, it is preferable to use what has surface resistance value (X-axis direction, y-axis direction) of 0.5 ohm / 25mm * 25mm or less, and it is 0.1 ohm / 25mm * 25mm or less It is more preferable to use what has a value (X-axis direction, y-axis direction), and it is more preferable to use what has surface resistance value (X-axis direction, y-axis direction) of 0.05 ohms / 25 mm x 25 mm or less. In addition, it is particularly preferable to use one having a surface resistance value (x, y) of 0.01 Ω / 25 mm × 25 mm or less to provide even more excellent conductivity.

Moreover, as said electroconductive base material, it is preferable to use the thing which has a vertical surface resistance value (z-axis direction) of 0.1 ohms / 25mmx25mm or less, and the vertical surface resistance value of 0.05 ohms / 25mmx25mm or less ( It is more preferable to use what has a z-axis direction), It is preferable to use what has a vertical surface resistance value (z-axis direction) of 0.03 ohms / 25mmx25mm or less, It is 0.01 ohms / 25mmx25mm It is especially preferable to use what has the following vertical surface resistance value (z-axis direction) in order to provide more excellent electroconductivity. In addition, the measuring method of the said surface resistance value (X-axis direction, y-axis direction) and the vertical surface resistance value (z-axis direction) points out the value measured by the method as described in an Example.

When manufacturing the said electroconductive base material, a wet polyester type nonwoven fabric base material is used. By using the said specific nonwoven fabric base material, peeling of the plating layer formed by the plating process can be prevented, and the electroconductive adhesive sheet provided with the further rework property can be obtained.

As said wet polyester type nonwoven fabric base material, what was obtained by papermaking polyester fiber disperse | distributed to water etc. can be used.

As said polyester fiber, it is preferable to use the fiber which has a diameter of 2 micrometers-10 micrometers, for example, and it is more preferable to use the fiber which has a diameter of 3 micrometers-8 micrometers.

Although it does not specifically limit as said papermaking method, For example, the method of using a round paper machine, a short paper machine, a long paper machine, and a diagonal short paper machine is mentioned.

As said wet polyester type nonwoven fabric base material, it is preferable to use what was heated etc. for the purpose of binding between polyester fibers after papermaking by the said method.

As said wet polyester base nonwoven fabric base material, it is more compatible with more excellent flexibility and strength, and it is preferable to use what has a basis weight of the range of 2g / m <2> -20g / m <2>, and it is 4g / m <2> -16g / m <2> It is more preferable to use what has a basis weight, and it is more preferable to use the thing which has a basis weight of the range of 6g / m <2> -15g / m <2>, and it is thin and excellent in obtaining the electrically conductive adhesive sheet excellent in reworkability.

As said wet polyester nonwoven fabric base material, it is preferable to use what has a thickness of 5 micrometers-50 micrometers, It is more preferable to use what has a thickness of 10 micrometers-30 micrometers, What has a thickness of 14 micrometers-20 micrometers Particular preference is given to using.

As said wet polyester type nonwoven fabric base material, it is preferable to use the thing of 2N / 20mm-30N / 20mm of tensile strength in the MD (flow) direction, and to use what is 5N / 20mm-28N / 20mm. It is more preferable to use what is 10N / 20mm-25N / 20mm.

Moreover, it is preferable to use the thing of 0.3N / 20mm-30N / 20mm in tensile strength of the said TD (width) direction as said wet polyester type nonwoven fabric base material, and it is 2N / 20mm-27N / 20mm It is more preferable to use, and it is more preferable to use what is 9N / 20mm-25N / 20mm. In addition, the said tensile strength points out the value measured by pulling at the speed | rate of 300 mm / min according to JISZ0237-2010.

The said electroconductive base material can be manufactured by performing the plating process containing an electroless plating process to the said wet polyester type nonwoven fabric base material. Here, the "plating treatment including an electroless plating treatment" means a treatment for carrying out an electroless plating treatment once or plural times, a treatment for carrying out an electrolytic plating treatment once or plural times after the electroless plating treatment, and electrolysis It refers to the process which performs an electroless plating process 1 time or several times after performing a plating process 1 time or several times. In this invention, after performing an electroless plating process, it is preferable to perform an electroless plating process or an electrolytic plating process further, and after performing an electroless plating process, it is more preferable to perform an electrolytic plating process further.

As the electroless plating method, for example, the surface of the nonwoven fabric substrate is immersed by immersing the wet unsaturated polyester nonwoven substrate in a liquid containing a catalyst such as palladium or an electroless plating solution containing metal ions and a reducing agent. The method of forming a metal film in the above is mentioned.

In addition, when performing the electroless plating treatment, in addition to the above-described steps, a step of washing the wet polyester nonwoven base material, a step of activating the catalyst, a wet polyester nonwoven base material, and a water-washed or dried plated material You may go through a process.

As a preferable method of the electroless plating treatment, the wet polyester nonwoven substrate is washed with water, washed with water, a catalyst is applied to the wet polyester nonwoven substrate, washed with water, the catalyst is activated, washed with water, The wet polyester type nonwoven fabric base material is immersed in an electroless plating solution, and the method of washing with water and drying is mentioned.

Examples of the metal ions included in the electroless plating solution include ions such as copper, nickel, silver, platinum, aluminum, and the like. The use of at least one ion of copper or nickel provides further superior conductivity and It is preferable to make low cost compatible, and it is more preferable to use copper ion, in order to provide more excellent adhesiveness.

It is preferable that the said metal ion contains 0.001 mol / l-0.2 mol / l with respect to the said electroless plating liquid.

The metal ion is preferably derived from copper sulfate, nickel sulfate, nickel chloride, palladium chloride, silver chloride, silver nitrate, and mixtures thereof, and using copper sulfate, nickel sulfate, and nickel chloride is more excellent in both conductivity and low cost. Preferred are the presence of copper or nickel ions suitable below.

Examples of the reducing agent that may be contained in the electroless plating solution include sodium hypophosphite, sodium borohydride, potassium borohydride, Rochelle salt, dimethylamine borane, diethylamine borane, formalin, and hydrazine compounds. Hydrazine, hydrazine hydrochloride, hydrazine sulfate, methyl hydrazine, 1,2-dimethyl hydrazine, acethydrazine, phenyl hydrazine and the like can be used hydroquinone, it is preferable to use sodium hypophosphite or formalin.

It is preferable that the said reducing agent is contained 0.001 mol / l-0.4 mol / l with respect to the said electroless plating liquid.

As said electroless plating liquid, in addition to the said component, what contains a complexing agent, a pH adjuster, a buffer, a plating promoter, a stabilizer etc. can be used as an auxiliary component.

Examples of the complexing agent include organic acid salts such as sodium citrate, potassium citrate and rochelle salt, thioglycolic acid, ammonia, triethanolamine, glycine, ethylenediamine, ethylenediamine diacetate, o-aminophenol, pyridine and the like. It is preferable to use sodium citrate.

It is preferable that the said complexing agent is contained 0.001 mol / l-4.0 mol / l with respect to the said electroless plating liquid.

As said pH adjuster, it is preferable to use sodium hydroxide, ammonium hydroxide, an inorganic acid, an organic acid, etc., for example.

As the buffer, it is preferable to use, for example, alkali metal salts of organic acids, inorganic acids, sodium citrate, sodium acetate, ammonium chloride, ammonium sulfate, oxycarboxylic acid, dihydrogen phosphate, boric acid, carbonic acid and the like.

As the plating accelerator, sulfides, fluorides and the like can be used.

As the stabilizer, lead chlorides, sulfides, nitrides, 2,2-bipyridine, 2-mercaptobenzothiazole, nicotinic acid and the like can be suitably used.

The metal, such as copper, laminated | stacked on the surface of the said wet-polyester type nonwoven fabric base material by the said electroless-plating method, has more outstanding adhesiveness and electroconductivity, and it is 1 g in order to reduce the cost of the said process, It is preferable that it is the range of / m <2> -20g / m <2>, It is more preferable that it is the range of 3g / m <2> -10g / m <2>, It is more preferable that it is the range of 5g / m <2> -8g / m <2>.

As the conductive substrate used in the present invention, as described above, after the electrolytic metal plating treatment of the wet polyester nonwoven fabric substrate, it is preferable to further use an electroless plating treatment or an electroplating treatment, and in particular electrolytic plating. It is more preferable to use the treated one because the plating layer can be stably formed in a relatively short time, since the production cost can be reduced and the strength can be increased.

Examples of the electrolytic plating solution that can be used for the electrolytic plating treatment include a nickel plating solution containing a copper plating solution containing copper pyrophosphate, a copper cyanide bath, a copper sulfate bath, and the like, a watt bath, a chloride bath, a sulfamic acid bath, and the like. Or a chromium plating solution containing a surge bath or the like, or a plating solution containing gold, silver, tin, zinc, or the like can be used.

As the said electroconductive base material, using the thing whose outermost layer is the plating layer containing nickel is preferable because it is excellent in storage stability, excellent in adhesiveness with a wet polyester type nonwoven fabric base material, and a plating layer, and excellent in electroconductivity.

The outermost layer preferably contains 1 g / m 2 to 10 g / m 2 of nickel, more preferably 2 g / m 2 to 8 g / m 2, more preferably 2.5 g / m 2 to 6 g / m 2 as described above. It is more preferable to make both adhesiveness and electroconductivity compatible.

As a preferable aspect of the said electroconductive base material, For example, in the wet polyester type nonwoven fabric base material, the electroconductive base material in which the electroless copper plating process and electrolytic nickel plating process were performed in order, and the wet polyester type nonwoven fabric base material, The electroconductive base material in which the electroless copper plating process, the electrolytic copper plating process, and the electrolytic nickel plating process was performed in order is mentioned.

Next, the conductive adhesive layer which comprises the conductive adhesive sheet of this invention is demonstrated.

The said electroconductive adhesive layer contains 3 mass%-50 mass% of electroconductive particle with respect to the said electroconductive adhesive layer whole. The electroconductive adhesive sheet which has such a conductive adhesive layer has outstanding electroconductivity.

As said conductive adhesive layer, it is preferable to use what contains 5 mass%-50 mass% of electroconductive particle with respect to the said whole conductive adhesive layer, It is more preferable to use what contains 10 mass%-50 mass%, 15 It is preferable to use the thing containing mass%-45 mass% since it can express the more excellent electroconductivity, the level | flexibility of the level which can follow a step part which an adherend etc. have, and rework property.

As said conductive adhesive layer, it is preferable to use the thing of thickness of 3 micrometers-25 micrometers, It is more preferable to use the thing of thickness of 5 micrometers-20 micrometers, It is more preferable to use what is thickness of 7 micrometers-18 micrometers, The electroconductive adhesive sheet which was more excellent in adhesiveness and thickness reduction can be obtained.

As said electroconductive adhesive layer, it can form by using the adhesive composition containing electroconductive particle and an adhesive component.

As electroconductive particle contained in the said electroconductive adhesive layer, metal particles, such as gold, silver, copper, nickel, and aluminum, electroconductive resin particles, such as carbon and graphite, the said resin, solid glass beads, and hollow glass, for example The particle | grains with which the surface of the beads was metal-coated, etc. can be used. Especially, it is preferable to use nickel particle, copper particle, or silver particle as said electroconductive particle in order to have more excellent electroconductivity and adhesive strength, and to further improve the productivity of an electroconductive adhesive sheet further.

Moreover, as said electroconductive particle, the surface acicular nickel particle which has many acicular shapes on the particle | grain surface manufactured by the carbonyl method, the thing which smoothed the surface acicular particle | grains, and made it into spherical particle | grains, or ultra-high pressure swirling after Copper particle | grains and silver particle | grains manufactured by the maize method are mentioned.

It is preferable to use a spherical or surface acicular shape as said electroconductive particle. As said electroconductive particle, it is preferable to use what has an aspect ratio of 1-2, It is more preferable to use what has an aspect ratio of 1-1.5, It is more preferable to use what has an aspect ratio of 1-2 More preferred. The said aspect ratio can be measured by observing the surface of the said electroconductive particle using a scanning electron microscope.

As the conductive particles, those having a tap density of 2 g / cm 3 to 7 g / cm 3 are preferable because sedimentation and aggregation are difficult when forming the conductive pressure-sensitive adhesive layer, and have a tap density of 3 g / cm 3 to 6 g / cm 3. It is more preferable to use what is used, and it is more preferable to use what has a tap density of 4 g / cm <3> -5g / cm <3>.

As said electroconductive particle, it is preferable to use that whose particle diameter d50 is 3 micrometers-20 micrometers, and whose particle diameter d85 is 6 micrometers-40 micrometers.

The said particle diameter d50 of the said electroconductive particle becomes like this. More preferably, it is 4 micrometers-15 micrometers, More preferably, it is 5 micrometers-12 micrometers, Especially preferably, it is 6 micrometers-10 micrometers.

Moreover, the said particle diameter d85 of the said electroconductive particle becomes like this. More preferably, it is 8 micrometers-30 micrometers, More preferably, it is 9 micrometers-25 micrometers, Especially preferably, it is 10 micrometers-20 micrometers. Moreover, when using combining 2 or more types of electroconductive particle, it is preferable to use what the average particle diameters d50 and d85 of these mixtures are the said ranges.

The particle size d50 represents a 50% cumulative value (median diameter) in the particle size distribution, and the particle diameter d85 represents an 85% cumulative value. Specifically, the particle diameter is a value measured by laser analysis and scattering method. As a measuring apparatus, the value measured with the laser diffraction type particle size distribution analyzer SALD-3000 made by Shimadzu Corporation.

As said electroconductive particle, it is preferable to select and use what the said particle diameter d50 becomes 50%-150% of the thickness of the said electroconductive adhesive layer, It is more preferable to select and use what becomes 60%-120%, 70 It is more preferable to select and use what becomes% to 100%.

Moreover, as said electroconductive particle, it is more preferable to select and use what the said particle diameter d85 becomes 80%-200% of the thickness of the said electroconductive adhesive layer, and it is more preferable to select and use what becomes 100%-150%. And it is more preferable to select and use what becomes 110%-140%.

By using the electroconductive particle of the said particle diameters d50 and d85, it is further more excellent in electroconductivity and adhesive strength, and can further improve the production efficiency of an electroconductive adhesive sheet.

It is preferable to use the said electroconductive particle in the range of 5 mass parts-100 mass parts with respect to 100 mass parts of adhesive components (solid content) contained in the said electroconductive adhesive layer, and it is more preferable to use it in the range of 10 mass parts-100 mass parts. It is especially preferable to use in the range of 20 mass parts-80 mass parts, since it is more excellent in electroconductivity and adhesive strength, and can further improve the production efficiency of an electroconductive adhesive sheet. Specifically, it is preferable to use the said electroconductive particle in the range of 5 mass parts-100 mass parts with respect to 100 mass parts of acrylic polymers (solid content) contained in the said conductive adhesive layer, and in the range of 10 mass parts-100 mass parts It is more preferable to use, and it is especially preferable to use in the range of 20 mass parts-80 mass parts, since it is more excellent in electroconductivity and adhesive strength, and can further improve the production efficiency of an electroconductive adhesive sheet.

As a method of mixing the said electroconductive particle and the said adhesive component, the method of mixing an adhesive substance, such as an electrically conductive substance, an acrylic polymer which is an adhesive component, and the said additive etc. is mentioned, for example. The pressure-sensitive adhesive components such as the acrylic polymer, the solvent, and the additive may be mixed in advance if necessary. Dispersing mixers, such as a dissolver, a butterfly mixer, a BDM biaxial mixer, and a planetary mixer, can be used for the said mixing. Especially, it is preferable to use the dissolver and butterfly mixer which can add moderate share which can suppress the raise of the viscosity at the time of the said mixing.

Moreover, as an adhesive component which comprises the said conductive adhesive layer, an acrylic adhesive composition, a silicone type adhesive composition, a rubber type adhesive composition etc. can be used, for example. Especially, it is preferable to use an acrylic adhesive composition as said adhesive component, in order to reduce reduction of an electroconductive adhesive sheet production cost, and to further improve adhesiveness.

As said acrylic adhesive composition, what contains an acrylic polymer can be used, for example.

As said acrylic polymer, what is obtained by superposing | polymerizing a monomer component can be used.

As said monomer component, the monomer component containing the (meth) acrylate which has a C1-C14 alkyl group can be used, for example.

As (meth) acrylate which has the said C1-C14 alkyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, etc. can be used individually or in combination of 2 or more types.

Especially, as (meth) acrylate which has the said C1-C14 alkyl group, it is preferable to use the (meth) acrylate which has a C12-C12 alkyl group, and it is C4-C9 It is more preferable to use (meth) acrylate which has a linear or branched alkyl group, and it is more preferable to use n-butylacrylate and 2-ethylhexyl acrylate individually or in combination of 2 types.

It is preferable to use the (meth) acrylate which has the said C1-C14 alkyl group in 80 mass%-98.5 mass% with respect to whole quantity of the said monomer component, and it is 90 mass%-98.5 mass% It is more preferable to use at.

Moreover, when manufacturing the acrylic polymer used for this invention, a polar vinyl monomer can be used as said monomer component. As said polar vinyl monomer, the vinyl monomer which has a hydroxyl group, the vinyl monomer which has a carboxyl group, the vinyl monomer which has an amide group, etc. can use 1 type (s) or 2 or more types.

As a vinyl monomer which has a carboxyl group, acrylic acid, methacrylic acid, itaconic acid, maleic acid, (meth) acrylic acid dimer, crotonic acid, ethylene oxide modified succinic acid acrylate, etc. can be used, Among these, acrylic acid or methacrylic acid is used. It is preferable to use, and it is more preferable to use acrylic acid.

As a vinyl monomer which has the said carboxyl group, it is preferable to use in the range of 1 mass%-10 mass% with respect to whole quantity of the said monomer component, It is more preferable that it is 1.5 mass%-6 mass%, It is 2 mass%-4 mass mass It is more preferable that it is% because it is excellent in the initial stage adhesive strength with respect to the metal surface which comprises a to-be-adhered body, and since the outstanding adhesive strength with respect to a to-be-adhered body can be expressed even if the conductive adhesive tape is preserve | saved under high temperature, high humidity. Moreover, since acrylic acid which is preferable as a vinyl monomer which has the said carboxyl group is used in the range of 1 mass%-6 mass% with respect to the whole quantity of the said monomer component can achieve more excellent wettability with respect to a to-be-adhered body, and adhesive strength. desirable.

As a vinyl monomer which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylate which has hydroxyl groups, such as (meth) acrylate, can be used.

As a vinyl monomer which has the said amide group, N-vinylpyrrolidone, N-vinyl caprolactam, acryloyl morpholine, acrylamide, N, N- dimethyl acrylamide, etc. can be used, for example.

Examples of other vinyl monomers include sulfonic acid group-containing monomers such as vinyl acetate, ethylene oxide-modified succinate acrylate and 2-acrylamide-2-methylpropanesulfonic acid, 2-methoxyethyl (meth) acrylate, and 2- Terminal alkoxy modified (meth) acrylates, such as phenoxyethyl (meth) acrylate, etc. can be used.

It is preferable to use the said polar vinyl monomer in 0.2 mass%-15 mass% with respect to whole quantity of the said monomer component, It is more preferable to use in 0.4 mass%-10 mass%, More preferably, it is 0.5 mass%- It is more preferable to use in the range of 6 mass% because it is easy to adjust adhesive strength to the suitable range.

The said acrylic polymer can be manufactured by superposing | polymerizing the above-mentioned monomer component by well-known methods, such as solution polymerization method, block polymerization method, suspension polymerization method, and emulsion polymerization method, Among these, production cost reduction and production efficiency of In order to improve, it is preferable to use a solution polymerization method.

As an acrylic polymer obtained by the said method, it is preferable to use what has a weight average molecular weight of 300,000-1,500,000, and it is more preferable to use what has a weight average molecular weight of 500,000-1,200,000.

Since the said electroconductive adhesive layer improves cohesion force further, and shows the effect which was further excellent in adhesiveness, it is preferable to form the three-dimensional crosslinked structure.

The grade of the said crosslinking can be recognized by using the gel fraction represented by the insoluble content after immersing in toluene which is a good solvent of the said acrylic polymer for 24 hours as the index. As said conductive adhesive layer, it is preferable to use that whose gel fraction is 25 mass%-65 mass%, It is more preferable to use what is 35 mass%-60 mass%, It is 40 mass%-55 mass% It is more preferable to use because it can make cohesion force and peeling resistance of a shear direction better.

In addition, the said gel fraction can be computed with the following formula | equation.

Gel fraction (mass%) = {(pressure sensitive adhesive layer mass after immersion in toluene) / (pressure sensitive adhesive layer mass before immersion in toluene)} × 100

Adhesive layer mass = (mass of electroconductive adhesive sheet)-(mass of base material)-(mass of electroconductive particle)

When forming the conductive adhesive layer provided with the said crosslinked structure, it is preferable to use what contains a crosslinking agent with the said acrylic polymer etc. as an adhesive, for example.

As said crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a chelate type crosslinking agent, an aziridine type crosslinking agent, etc. can be used, for example. It is preferable to use the thing corresponding to the functional group which the said acrylic polymer has for the kind of the said crosslinking agent. For example, when using what has a carboxy group as said acrylic polymer, it is suitable to use an isocyanate type crosslinking agent.

It is preferable to select and use the said crosslinking agent in the said gel fraction of the said electroconductive adhesive layer becoming the said range.

The said electroconductive adhesive layer may contain tackifying resin for the purpose of further improving the adhesive force.

Examples of the tackifying resins include rosin-based resins, terpene-based resins, petroleum resins such as aliphatic (C5) and aromatic (C9), styrene-based resins, phenol-based resins, xylene-based resins, and methacryl-based resins. Can be used. Especially, as said tackifying resin, it is preferable to use rosin-type resin, and it is more preferable to use superposition | polymerization rosin-type resin. It is preferable that the usage-amount of the said tackifying resin is 10 mass parts-50 mass parts with respect to 100 mass parts of (meth) acrylic-type polymers.

The said conductive adhesive layer may contain various additives as needed.

As said additive, a plasticizer, a softener, a metal deactivator, antioxidant, a pigment, dye, etc. can be used, for example.

As an adhesive which can be used for formation of the said conductive adhesive layer, what contains the said electrically conductive substance of the predetermined amount and the said adhesive component can be used.

Moreover, as said electroconductive adhesive layer, what contains a triazole type compound can be used.

Examples of the triazole compound include benzotriazole, tolyltriazole and its potassium salt, 3- (N-salicyloyl) amino-1,2,4triazole, and 2- (2'-hydroxy5methylphenyl ) Benzotriazole and the like can be used, and the use of benzotriazole is particularly preferable because it can suppress a decrease in adhesion strength which can occur when left in an excellent adhesion holding force and a high temperature, high humidity environment.

It is preferable to use the said triazole type compound in 0.05 mass part-3.0 mass parts with respect to 100 mass parts (solid content) of an acrylic adhesive composition, It is more preferable to use in the range of 0.1 mass part-1.5 mass parts, 0.3 It is more preferable to use it in the range of mass part-1.0 mass part because it can suppress the fall of the adhesive strength which may arise when it is left under the outstanding adhesive holding force and high temperature, high humidity environment.

The adhesive obtained by the said method can be used only for formation of a conductive adhesive layer. It is preferable that the solid content of the said adhesive is the range of 10 mass%-70 mass%, It is more preferable that it is the range of 30 mass%-55 mass%, It is more preferable that it is the range of 43 mass%-50 mass%.

In the conductive adhesive sheet of the present invention, the adhesive is applied to the surface of the release film, for example, using a roll coater or a die coater, and the coating layer is dried in an environment of about 50 ° C to 120 ° C to remove the solvent. By the step of forming a conductive adhesive layer, and then laminating the conductive adhesive layer on both surfaces of the conductive substrate, and performing thermal lamination as necessary, and then, as necessary, about 15 ° C to 50 ° C. It can manufacture by going through the process of curing about 48 to 168 hours at temperature.

It is preferable to perform the said thermal lamination at 40 degreeC-120 degreeC, It is more preferable to carry out at 50 degreeC-100 degreeC, It is more preferable to carry out at 60 degreeC-90 degreeC.

Moreover, as the electroconductive adhesive sheet of this invention, what laminated | stacked the film may be sufficient before it affixes on a to-be-adhered body.

As said peeling film, For example, paper, such as graft paper, glassine paper, and quality paper; Resin films such as polyethylene, polypropylene (OPP, CPP) and polyethylene terephthalate; The laminated paper which laminated | stacked the said paper and the resin film, and the thing which performed peeling process of silicone resin etc. to one or both surfaces of the paper which was filled with clay, polyvinyl alcohol, etc. can be used.

Examples of suitable configurations of the conductive adhesive sheet of the present invention are shown in FIGS. 1 and 2. FIG. 1: is a single-sided adhesive sheet which laminated | stacked the conductive adhesive layer 2 on the conductive base material 1. FIG. 2 is a double-sided adhesive sheet which laminated | stacked the conductive adhesive layer 2 on both surfaces of the electroconductive base material 1. In these structures, the structure in which the peeling film was provided in the surface of the adhesive layer 2 can be used preferably.

Since the electroconductive adhesive sheet of this invention is excellent in flexibility, and has favorable adhesiveness to an adherend, electroconductivity, and rework property, it is useful for the shielding of electromagnetic waves used for electrical and electronic devices, etc., for grounding fixation of antistatic charge. . In particular, there is an uneven part, and it can apply suitably to the use used by affixing to the built-in components of small electronic terminals, such as a portable electronic device in which sticking of a conductive adhesive sheet is difficult.

EXAMPLE

An Example is demonstrated concretely below.

Preparation Example 1 [Conductive Substrate (A)]

Wet polyester nonwoven fabric "Type A" made by Miki Tokushu Seishi Co., Ltd. (basic weight 10 g / m <2>, thickness 15 micrometers, diameter 5 micrometers (average diameter) of polyester fiber) 10 g / l of tin chloride, hydrochloric acid It was immersed in the aqueous solution containing 20 ml / l for about 5 minutes at normal temperature, and then washed with water.

Next, the washed water was immersed in an aqueous solution containing 1 g / l palladium chloride and 20 ml / l hydrochloric acid at room temperature for about 10 minutes, and then washed with water.

Next, the above-washed thing was 40 containing 10 g / l copper sulfate, 7 ml / l formaldehyde, 8 g / l sodium hydroxide, 30 g / l ethylenediamine tetraacetic acid tetrasodium acetate (EDTA-4Na) and 0.25 ml / l stabilizer. It was immersed in the electroless plating liquid adjusted to ° C for 20 minutes, and then washed with water to obtain a wet polyester nonwoven fabric subjected to electroless plating.

Next, the electroless-plated wet polyester nonwoven fabric is immersed in an electrolytic copper plating solution (manufactured by Okuno Seiyaku Kogyo Co., Ltd.), and the plating amount of copper by the electrolytic copper plating solution is 6 g / m 2. By electrolytic copper plating process, the wet polyester nonwoven fabric by which the electrolytic copper plating process was carried out was obtained.

Next, the electrolytic copper plated wet polyester nonwoven fabric includes nickel sulfate 240g / l, nickel chloride 45g / l, boric acid 30g / l, saccharine 2g / l and 1,4-butyndiol 0.2g / l. The electroconductive base material A was produced by immersing in the electrolytic nickel plating liquid, electrolytic nickel plating process, washing with water, and drying so that the plating amount of nickel by the said electrolytic nickel plating liquid might be 4 g / m <2>.

Preparation Example 2 [Conductive Substrate (B)]

Asahi Kasei Co., Ltd. wet polyester nonwoven fabric "silkyfine WS7A-05-6" instead of the wet polyester nonwoven fabric "type A" made by Miki Tokushu Seishi Co., Ltd. (basic weight 6 g / m2, thickness 18) A conductive substrate (B) was produced in the same manner as in Production Example 1, except that 4.5 µm and a diameter of the polyester fiber (average diameter) were used.

Preparation Example 3 [Conductive Substrate (C)]

Asahi Kasei Co., Ltd. wet polyester nonwoven fabric "silky phosphorus WS7A-04" instead of the wet polyester nonwoven fabric "type A" made by Miki Tokushu Seishi Co., Ltd. (basic weight 4 g / m <2>, thickness 16micrometer, Conductive base material (C) was produced in the same manner as in Production Example 1, except that 4.5 µm (average diameter) of polyester fiber was used.

Preparation Example 4 [Conductive Substrate (D)]

Nippon Seishi Papia's wet polyester nonwoven fabric "5.5 g / m2" (Basic weight 5.5 g / m2, 14 micrometers in thickness) instead of the wet polyester nonwoven fabric "type A" made by Miki Tokushushi Co., Ltd. Conductive base material (D) was produced in the same manner as in Production Example 1, except that 4.5 µm (average diameter) of polyester fiber was used.

Preparation Example 5 [Conductive Substrate (E)]

Wet polyester nonwoven fabric "type A" made by Miki Tokushushi Co., Ltd. (normal basis weight 10 g / m <2>, thickness 15 micrometers, diameter 5 micrometers (average diameter) of polyester fiber) under normal temperature 10 g / of tin chloride It was immersed in an aqueous solution containing 1 and 20 ml / l of hydrochloric acid for about 5 minutes, washed with water, and then immersed in an aqueous solution containing 1 g / l of palladium chloride and 20 ml / l hydrochloric acid for about 10 minutes, and washed with water.

Next, the washed water contained 10 g / l copper sulfate, 7 ml / l formaldehyde, 8 g / l sodium hydroxide, 30 g / l ethylenediaminetetrabasic tetrasodium acetate (EDTA-4Na), and a stabilizer (0.25 ml / l). The electroconductive base material (E) was immersed in the electroless plating liquid adjusted to 40 degreeC to 60 minutes, electroless-plated so that the plating amount of copper by the said electroless plating liquid may be 6 g / m <2>, and it washed with water and dried. )

Preparation Example 6 [Conductive Substrate (F)]

Wet polyester nonwoven fabric "type A" made by Miki Tokushushi Co., Ltd. (normal basis weight 10 g / m <2>, thickness 15 micrometers, diameter 5 micrometers (average diameter) of polyester fiber) under normal temperature 10 g / of tin chloride It was immersed in an aqueous solution containing l and 20 ml / l of hydrochloric acid for about 5 minutes, washed with water, and then immersed in an aqueous solution containing 1 g / l of palladium chloride and 20 ml / l hydrochloric acid for about 10 minutes, and washed with water.

Next, the washed water was added to a 40 ° C electroless plating solution containing 20 g / l nickel sulfate, 30 g / l sodium citrate, 15 g / l sodium hypophosphite and 30 g / l ammonium chloride, and adjusted to pH 9.5 with ammonia water. The electroconductive base material F was produced by immersion for 60 minutes, electroless-plating process so that the plating amount of nickel by the said electroless-plating liquid may be set to 6 g / m <2>, and then washing with water and drying.

Preparation Example 7 [Conductive Substrate (G)]

Wet polyester nonwoven fabric "type A" made by Miki Tokushushi Co., Ltd. (normal basis weight 10 g / m <2>, thickness 15 micrometers, diameter 5 micrometers (average diameter) of polyester fiber) under normal temperature 10 g / of tin chloride It was immersed in an aqueous solution containing l and 20 ml / l of hydrochloric acid for about 5 minutes, washed with water, and then immersed in an aqueous solution containing 1 g / l of palladium chloride and 20 ml / l hydrochloric acid for about 10 minutes, and washed with water.

Next, the washed water contained 10 g / l copper sulfate, 7 ml / l formaldehyde, 8 g / l sodium hydroxide, 30 g / l ethylenediaminetetrabasic tetrasodium acetate (EDTA-4Na), and a stabilizer (0.25 ml / l). It was immersed in the electroless copper plating liquid adjusted to 40 degreeC to 60 minutes, electroless copper plating process was carried out so that the plating amount of copper by the said electroless copper plating liquid might be 6 g / m <2>, and it washed with water, and electroless copper plating process was carried out. A wet polyester nonwoven was obtained.

Next, the electroless copper-plated wet polyester nonwoven fabric contains 20 g / l nickel sulfate, 30 g / l sodium citrate, 15 g / l sodium hypophosphite and 30 g / l ammonium chloride, and adjusted to pH 9.5 with ammonia water. The electroconductive base material G was produced by immersion for 30 minutes in the 40 degreeC electroless nickel plating liquid, electroless nickel plating process so that the plating amount of nickel by the said electroless nickel plating liquid might be 4 g / m <2>, and then washing with water. .

Preparation Example 8 [Conductive Substrate (H)]

Wet polyester nonwoven fabric "Type A" made by Miki Tokushu Seishi Co., Ltd. (basic weight 10 g / m <2>, thickness 15 micrometers, diameter 5 micrometers (average diameter) of polyester fiber) 10 g / l of tin chloride, hydrochloric acid It was immersed in the aqueous solution containing 20 ml / l for about 5 minutes at normal temperature, and then washed with water.

Next, the washed water was immersed in an aqueous solution containing 1 g / l palladium chloride and 20 ml / l hydrochloric acid at room temperature for about 10 minutes, and then washed with water.

Next, the above-washed thing was 40 containing 10 g / l copper sulfate, 7 ml / l formaldehyde, 8 g / l sodium hydroxide, 30 g / l ethylenediamine tetraacetic acid tetrasodium acetate (EDTA-4Na) and 0.25 ml / l stabilizer. It was immersed in the electroless plating liquid adjusted to ° C for 20 minutes, and then washed with water to obtain a wet polyester nonwoven fabric subjected to electroless plating.

Next, the electroless plated wet polyester nonwoven fabric includes nickel sulfate 240g / l, nickel chloride 45g / l, boric acid 30g / l, saccharin 2g / l and 1,4-butyndiol 0.2g / l. The electroconductive base material H was produced by immersing in the electrolytic nickel plating liquid, electrolytic nickel plating process, washing with water, and drying so that the plating amount of nickel by the said electrolytic nickel plating liquid might be 4 g / m <2>.

Preparation Example 9 [Conductive Substrate (I)]

Asahi Kasei Co., Ltd. make the purese (The thing which copper and nickel plated on the dry polyester nonwoven fabric) made electroconductive base material (I).

Preparation Example 10 [Conductive Substrate (J)]

Dry polyester nonwoven fabric "Miraifu TY0503FE" made by JX Nikko Corporation Seki Energy Co., Ltd. in place of the wet polyester nonwoven fabric "type A" made by Miki Tokushu Seishi Co., Ltd. (basic weight 8 g / m2, thickness 28micrometer, Conductive base material J was produced in the same manner as in Production Example 1, except that 12 µm (average diameter) of polyester fiber was used.

Preparation Example 11 [Conductive Substrate (K)]

[Plating Nonwoven K]

Dry polyester nonwoven fabric "Miraifu T10" made by JX Nikko Nesseki Energy Co., Ltd. (a basis weight 10 g / m2, thickness 28 micrometers) instead of the wet polyester nonwoven fabric "type A" made by Miki Tokushu Seishi Conductive base material K was produced in the same manner as in Production Example 1, except that 10 µm (average diameter) of polyester fiber was used.

Preparation Example 12 [Conductive Substrate (L)]

Instead of using the wet polyester nonwoven fabric "D54E" made by Nippon Seishipia Co., Ltd. (base weight 16 g / m 2, thickness 43 µm) in place of the wet polyester nonwoven fabric "Type A" manufactured by Miki Tokushu Seishi Co., Ltd. And the conductive base L were produced in the same manner as in Production Example 1.

Preparation Example 1 [Preparation of Acrylic Adhesive Composition (1)]

96.4 parts by mass of n-butyl acrylate, 0.1 parts by mass of 2-hydroxyethyl acrylate, 3.5 parts by mass of acrylic acid and a polymerization initiator in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a dropping funnel. 0.1 mass part of isobutyl nitrile was melt | dissolved in 100 mass parts of ethyl acetate, and the inside of the reaction container was nitrogen-substituted, and it superposed | polymerized at 80 degreeC for 12 hours, and obtained the acrylic copolymer solution of the weight average molecular weight 600,000.

10 mass parts of superposition | polymerization rosin pentaerythritol ester (Arakawa Chemical Co., Ltd. make, Pencel D-135, softening point 135 degreeC) with respect to 100 mass parts of solid content of the said acryl-type copolymer solution, and disproportionated rosin glycerin ester (Arakawaga 10 mass parts of Kaku Kogyo Co., Ltd. product, superester A-100, softening point 100 degreeC), and adjusts the solid content concentration of the said acryl-type copolymer to 45 mass% using ethyl acetate, The acrylic adhesive composition (1) Got.

Preparation Example 2 [Preparation of Acrylic Adhesive Composition (2)]

99.9 parts by mass of n-butyl acrylate, 0.1 parts by mass of 2-hydroxyethyl acrylate, and 0.1 mass of 2,2'-azobisisobutylnitrile as a polymerization initiator in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a dropping funnel. The part was melt | dissolved in 100 mass parts of ethyl acetate, and the inside of the reaction container was nitrogen-substituted, and it superposed | polymerized at 80 degreeC for 12 hours, and obtained the acrylic copolymer solution of the weight average molecular weight 600,000.

10 mass parts of superposition | polymerization rosin pentaerythritol ester (Arakawa Chemical Co., Ltd. product, Pencel D-135, softening point 135 degreeC) with respect to 100 mass parts of solid content of the said acryl-type copolymer solution, a disproportionated rosin glycerin ester (Arakawaga 10 mass parts of Kaku Kogyo Co., Ltd. make, superester A-100, softening point 100 degreeC), and adjusts the solid content concentration of the said acryl-type copolymer to 45 mass% using ethyl acetate, The acrylic adhesive composition (2) Got.

Preparation Example 3 [Preparation of Acrylic Adhesive Composition (3)]

92.9 parts by mass of n-butyl acrylate, 0.1 parts by mass of 2-hydroxyethyl acrylate, 7 parts by mass of acrylic acid, and 2,2'-azobis as a polymerization initiator in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a dropping funnel. 0.1 mass part of isobutyl nitrile was melt | dissolved in 100 mass parts of ethyl acetate, and the inside of the reaction container was nitrogen-substituted, and it superposed | polymerized at 80 degreeC for 12 hours, and obtained the acrylic copolymer solution of the weight average molecular weight 600,000.

10 mass parts of superposition | polymerization rosin pentaerythritol ester (Arakawa Chemical Co., Ltd. product, Pencel D-135, softening point 135 degreeC) with respect to 100 mass parts of solid content of the said acryl-type copolymer solution, a disproportionated rosin glycerin ester (Arakawaga 10 mass parts of Kaku Kogyo Co., Ltd. make, superester A-100, softening point 100 degreeC), and adjusts the solid content concentration of the said acryl-type copolymer to 45 mass% using ethyl acetate, The acrylic adhesive composition (3) Got.

Preparation Example 4 [Preparation of Acrylic Adhesive Composition (4)]

97.4 parts by mass of n-butyl acrylate, 0.1 parts by mass of 2-hydroxyethyl acrylate, 2.5 parts by mass of acrylic acid, and 2,2'-azobis as a polymerization initiator in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a dropping funnel. 0.1 mass part of isobutyl nitrile was melt | dissolved in 100 mass parts of ethyl acetate, and the inside of the reaction container was nitrogen-substituted, and it superposed | polymerized at 80 degreeC for 12 hours, and obtained the acrylic copolymer solution of the weight average molecular weight 600,000.

10 mass parts of superposition | polymerization rosin pentaerythritol ester (Arakawa Chemical Co., Ltd. product, Pencel D-135, softening point 135 degreeC) with respect to 100 mass parts of solid content of the said acryl-type copolymer solution, a disproportionated rosin glycerin ester (Arakawaga 10 mass parts of Kaku Kogyo Co., Ltd. make, superester A-100, softening point 100 degreeC), and adjusts the solid content concentration of the said acryl-type copolymer to 45 mass% using ethyl acetate, The acrylic adhesive composition (4) Got.

Preparation Example 5 [Preparation of Conductive Adhesive Composition (1A-1)]

100 mass parts (45 mass% of solid content) of the said acrylic adhesive composition (1) and nickel powder "NI123J" made from Fukuda Kinzoku Hakuhoon Kogyo Co., Ltd. (particle diameter d50: 6.3 micrometer, particle diameter d85: 10.0micrometer, tap density: 22.5 mass parts of 4.3 g / cm <3> and the smoothing process of Inc. "NI123"), 2.5 mass parts of Banokku NC40 (isocyanate crosslinking agent made from DIC, 40 mass% of solid content) as a crosslinking agent, 0.23 mass parts of benzotriazole were mixed, and the electrically conductive adhesive (1A-1) was obtained by stirring what adjusted the solid content concentration to 47 mass% using ethyl acetate for 10 minutes using the dispersion stirrer.

Preparation Example 6 [Preparation of Conductive Adhesive Composition (1A-2)]

A conductive adhesive (1A-2) was obtained in the same manner as in Preparation Example 5, except that the amount of nickel powder "NI123J" manufactured by Fukuda Kinzoku Hakuhoon Kogyo Co., Ltd. was changed from 22.5 parts by mass to 9 parts by mass.

Preparation Example 7 [Preparation of Conductive Adhesive Composition (1A-3)]

A conductive adhesive (1A-3) was obtained in the same manner as in Preparation Example 5, except that the amount of nickel powder "NI123J" manufactured by Fukuda Kinzoku Hakuhoon Kogyo Co., Ltd. was changed from 22.5 parts by mass to 36 parts by mass.

Preparation Example 8 [Preparation of Conductive Adhesive Composition (1A-4)]

A conductive adhesive (1A-4) was obtained in the same manner as in Preparation Example 5, except that the amount of nickel powder "NI123J" manufactured by Fukuda Kinzoku Hakuhoon Kogyo Co., Ltd. was changed from 22.5 parts by mass to 0 parts by mass.

Preparation Example 9 [Preparation of Conductive Adhesive Composition (1A-5)]

A conductive adhesive (1A-5) was obtained in the same manner as in Preparation Example 5, except that the amount of nickel powder "NI123J" manufactured by Fukuda Kinzoku Hakuhoon Kogyo Co., Ltd. was changed from 22.5 parts by mass to 67.5 parts by mass.

Preparation Example 10 [Preparation of Conductive Adhesive Composition (2A)]

A conductive adhesive (2A) was obtained in the same manner as in Preparation Example 5, except that the acrylic adhesive composition (2) was used instead of the acrylic adhesive composition (1).

Preparation Example 11 [Preparation of Conductive Adhesive Composition (3A)]

A conductive adhesive 3A was obtained in the same manner as in Preparation Example 5, except that the acrylic adhesive composition 3 was used instead of the acrylic adhesive composition 1.

Preparation Example 12 [Preparation of Conductive Adhesive Composition (4A)]

A conductive adhesive (4A) was obtained in the same manner as in Preparation Example 5 except that the acrylic adhesive composition (4) was used in place of the acrylic adhesive composition (1).

Preparation Example 13 [Preparation of Conductive Adhesive Composition (1B)]

Except for using 22.5 parts by mass of nickel powder "NI123" (particle diameter d50: 10.7, particle diameter d85: 25.0 µm) manufactured by Inc., Inc., in place of the nickel powder "NI123J" manufactured by Fukuda Kinzoku Hakuhoon Kogyo Co., Ltd. And the conductive adhesive (1B) were obtained by the method similar to the preparation example 5.

Example 1

The said conductive adhesive composition (1A-1) is coated on the peeling film "PET38 * 1 A3" made by Nippa Corporation using a comma coater so that the thickness of the conductive adhesive layer after drying may be 9 micrometers, and it is 80 degreeC The conductive adhesive layer was produced by drying for 2 minutes with the dryer set to.

Next, the said electroconductive adhesive layer was affixed on both surfaces of the said electroconductive base material A, they were thermally laminated at 80 degreeC, and the electrically conductive adhesive sheet was produced by curing at 40 degreeC for 48 hours.

Example 2

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate (B) was used instead of the conductive substrate (A).

Example 3

A conductive adhesive sheet was produced in the same manner as in Example 1, except that the conductive substrate (C) was used instead of the conductive substrate (A).

Example 4

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate (D) was used instead of the conductive substrate (A).

Example 5

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive adhesive composition (1A-2) was used instead of the conductive adhesive composition (1A-1).

Example 6

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive adhesive composition (1A-3) was used in place of the conductive adhesive composition (1A-1).

Example 7

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive adhesive composition 2A was used in place of the conductive adhesive composition 1A-1 and the curing time was changed from 48 hours to 120 hours. did.

Example 8

A conductive adhesive sheet was produced in the same manner as in Example 1 except for using the conductive adhesive composition 3A instead of the conductive adhesive composition 1A-1.

Example 9

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive adhesive composition 4A was used in place of the conductive adhesive composition 1A-1.

Example 10

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the thickness of the conductive adhesive layer was changed from 9 µm to 7 µm.

Example 11

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the thickness of the conductive adhesive layer was changed from 9 µm to 15 µm.

Example 12

Conductive adhesive composition in the same manner as in Example 1 except for using the conductive adhesive composition 1B instead of the conductive adhesive composition 1A-1 and changing the thickness of the conductive adhesive layer from 9 μm to 18 μm. The sheet was produced.

(Example 13)

Conductive adhesive composition in the same manner as in Example 1 except for using the conductive adhesive composition 1B instead of the conductive adhesive composition 1A-1 and changing the thickness of the conductive adhesive layer from 9 μm to 13 μm. The sheet was produced.

Example 14

The electroconductive adhesive sheet of Example 14 was created like Example 1 except having used plating nonwoven fabric E instead of plating nonwoven fabric A.

Example 15

A conductive adhesive sheet was produced in the same manner as in Example 1, except that the conductive substrate (F) was used instead of the conductive substrate (A).

Example 16

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate (G) was used instead of the conductive substrate (A).

(Example 17)

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate (H) was used instead of the conductive substrate (A).

(Comparative Example 1)

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate (I) was used instead of the conductive substrate (A).

(Comparative Example 2)

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate (J) was used instead of the conductive substrate (A).

(Comparative Example 3)

A conductive adhesive sheet was produced in the same manner as in Example 1, except that the conductive substrate (K) was used instead of the conductive substrate (A).

(Comparative Example 4)

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive substrate L was used instead of the conductive substrate A.

(Comparative Example 5)

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive adhesive composition (1A-4) was used instead of the conductive adhesive composition (1A-1).

(Comparative Example 6)

A conductive adhesive sheet was produced in the same manner as in Example 1 except that the conductive adhesive composition (1A-5) was used instead of the conductive adhesive composition (1A-1).

Reference Example 1

Electroconductive copper foil (CF-T9FZ-SV, manufactured by Fukuda Kinzoku Hakuhoon Co., Ltd.) treated with an inorganic rust preventive (chromate) having a thickness of 9 µm in place of the conductive substrate (A) was conductive in the same manner as in Example 1. An adhesive sheet was produced.

The following evaluation was performed about the said electroconductive base material, electroconductive adhesive layer, and electroconductive adhesive sheet, and the result obtained was shown in the following table | surface. In addition, the amount of acrylic acid in a table | surface shows the usage-amount (mass%) of acrylic acid with respect to the whole quantity of the monomer component used for manufacture of an acrylic copolymer. In addition, the metal amount in a table | surface shows content (mass%) of electroconductive particle with respect to the whole conductive adhesive layer. In addition, the followability evaluation results of Example 1 and Reference Example 1 are shown in Figs. 3 and 4.

[Particle size]

The particle diameter of electroconductive particle points out the value measured using the isopropanol for a dispersion medium using the laser diffraction type particle size distribution analyzer SALD-3000 made from Shimadzu Corporation.

[Conductive (Conductive Adhesive Sheet)]

One side of the 30 mm width x 30 mm width conductive adhesive sheet was affixed to a 25 mm x 25 mm brass electrode. 30 mm x 80 mm copper foil (thickness 35 micrometers) was affixed on the other surface of the electroconductive adhesive sheet.

The terminal is connected to the said brass electrode and the said copper foil in the state which applied the surface pressure of 20 N from the said brass electrode, and it is a milliohm meter (Enuefugairoskei) in the environment of 23 degreeC and 50% RH. The resistance value at the time of flowing a 10 mA electric current using ()) was measured. The case where the said resistance value was 500 m (ohm) or less was made into the pass.

[Thickness (conductive adhesive layer)]

Using each electroconductive adhesive composition, the sample which carried out PET film 25 micrometers (S25 by Unichika company) was produced to the electroconductive adhesive layer formed on the peeling film, and the thickness made the thickness meter "TH-102" made by Tester Sangyosha. Measured using. From the said measured value, the value which reduced the thickness of the said peeling film and PET film was made into the thickness of an electroconductive adhesive layer.

[Thickness (conductive adhesive sheet)]

The thickness of the electroconductive adhesive sheet was measured using the thickness meter "TH-102" made from Tester Sankyo.

[Conductive (conductive description)]

A conductive base material having a width of 30 mm x 30 mm was inserted into two brass electrodes of 25 mm x 25 mm, and a terminal was connected to each brass electrode while applying a load of 20 N in surface pressure from the brass electrode. In the environment of 23 degreeC and 50% RH, the resistance value at the time of flowing 10 mA of electric currents was measured using the milliohmmeter (made by Enuefugaerosetkei).

[Adhesiveness]

A 20 mm wide conductive adhesive sheet was prepared, and one surface was placed by using a 25-micrometer-thick polyethylene terephthalate film (S25, manufactured by Unichika Co., Ltd.) as a test piece.

Next, the pressure-sensitive adhesive layer of the test piece was attached to a stainless steel plate (hereinafter, referred to as a stainless steel plate) subjected to hairline polishing using 360 water-resistant polishing paper in an environment of 23 ° C. and 50% RH, and a 2.0 kg roller was attached from the upper surface thereof. They squeezed by reciprocating.

Next, after leaving the crimped one at room temperature for 1 hour, using a tensile tester (Tenshiron RTA-100, manufactured by Eian Dodisha), 180 degree peel adhesion was tested by testing at a normal temperature of 300 mm / min. Measured. The said adhesive force test was done about each adhesive layer (double-sided adhesive layer) of an electroconductive adhesive sheet, and the lower value was described in the table.

[Followability]

A conductive adhesive sheet was affixed by hand to the metal plate which has a substantially semi-circular step of 5 mm in depth and 10 mm in width, and the followability to the step was evaluated.

○: could follow the step

X: It cannot follow a level | step difference, and steaming or tearing arise

[Rework Castle 1]

When the adhesive force was measured by the said method, the presence or absence of the extraction | attachment to the stainless steel plate was evaluated.

◎: No remaining

(Circle): There exists a solution in less than 10% of range with respect to the area of stainless steel plate.

X: Solvent exists in the range of 10% or more with respect to the area of a stainless steel plate.

[Rework Castle 2]

When the adhesive force was measured by the said method, it evaluated whether the electrically conductive adhesive sheet was torn. The test was implemented using five electroconductive adhesive sheets, and the following reference | standard evaluated.

◎: All 5 pieces do not tear

○: 4 no tearing

X: Two or more tears generate | occur | produce

TABLE 1

TABLE 2

TABLE 3

As it turned out from the said table, the adhesive sheets of Examples 1-18 of this invention were excellent in followability, and also adhesiveness, electroconductivity, and reworkability were also favorable. On the other hand, although the adhesive sheets of Comparative Examples 1-4 were excellent in followability, electroconductivity, and adhesiveness, they were remarkably inferior to rework property. The adhesive sheet of Comparative Example 5 was inferior in conductivity. The adhesive sheet of Comparative Example 6 was inferior in adhesiveness and rework property. Moreover, the adhesive sheet of a reference example is inferior in traceability, and the steaming and tearing generate | occur | produced in the step part.

One… Conductive base
2… Conductive Adhesive Layer

Claims (14)

As an electroconductive adhesive sheet which has an electroconductive adhesive layer on at least one side of an electroconductive base material,
The said electroconductive base material is obtained by performing the plating process containing an electroless plating process to a wet polyester type nonwoven fabric base material, The thickness of the said wet polyester type nonwoven fabric base material is 14 micrometers-20 micrometers, and basis weight is 6 g / M 2 to 15 g / m 2,
The said conductive adhesive layer is a layer formed using the acrylic adhesive containing electroconductive particle and an acrylic polymer, The said acrylic polymer is obtained by superposing | polymerizing the monomer component containing 1 mass%-6 mass% acrylic acid,
The said conductive adhesive layer contains 3 mass%-50 mass% of electroconductive particle with respect to the said whole conductive adhesive layer, The thickness of the said conductive adhesive layer is 3 micrometers-25 micrometers, The conductive adhesive sheet characterized by the above-mentioned. The method of claim 1,
The electroconductive adhesive sheet whose said electroconductive particle contains copper or nickel. The method of claim 1,
The electroconductive adhesive sheet whose said electroless-plating process is a process performed using at least 1 sort (s) of copper or nickel. The method of claim 1,
The said electroconductive base material is obtained by giving an electroless plating process to a wet polyester type nonwoven fabric base material, and then performs an electroless plating process or an electrolytic plating process further. The method of claim 4, wherein
The conductive adhesive sheet obtained by performing electroless nickel plating process after the said electroconductive base material performs an electroless copper plating process to a wet polyester type nonwoven fabric base material. The method of claim 4, wherein
The said electroconductive base material is obtained by performing an electroless copper plating process, an electrolytic copper plating process, and an electrolytic nickel plating process in order to a wet polyester type nonwoven fabric base material. delete delete The method of claim 1,
Electroconductive adhesion whose tensile strength (MD direction) of the said wet polyester type nonwoven fabric base material is 2N / 20mm-30N / 20mm, and whose tensile strength (TD direction) is 0.3N / 20mm-30N / 20mm Sheet. The method of claim 1,
The conductive adhesive sheet whose average particle diameter d50 of the said electroconductive particle is 3 micrometers-20 micrometers. The method of claim 1,
The conductive adhesive sheet, wherein the conductive adhesive layer and the conductive substrate are laminated by thermal lamination at a temperature of 40 ° C to 120 ° C. The thing which mounted the said conductive adhesive layer on the at least single side | surface of the said conductive base material is laminated at the temperature of 40 degreeC-120 degreeC, The Claims 1-6 and 9-11 characterized by the above-mentioned. The manufacturing method of the electroconductive adhesive sheet of any one of Claims. The electronic terminal which has a structure in which the electroconductive adhesive sheet in any one of Claims 1-6 and 9-11 is affixed on the component. delete

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