JP2005165043A - Toner, conductive functional member, antistatic sheet and print circuit member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner having a low content of metal powder and reducing the environmental load, and to provide an antistatic sheet and a printed circuit board using the toner. <P>SOLUTION: The toner 1 comprises at least a core part 11 made of a conductive polymer gel 2 essentially comprising water and containing a conductive conjugated polymer, a surfactant and/or an alcohol, and a resin part 12 applied on the surface of the core part 11. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner and a conductive functional member, an antistatic sheet, and a printed circuit member using the toner.

Using electrophotographic technology, a toner containing a conductive material can be printed on the base material to impart conductivity to the base material. For example, RF-ID (Radio Frequency-Identification) It is used as means for forming printed circuit boards such as antenna coils, printed circuit board circuits, liquid crystal display electrodes, and keyboard membrane circuits.
In addition to the printed circuit board, it is also used for forming an antistatic sheet.

Conventionally, as a toner for forming a circuit board, toner composed of a core part such as metal particles and an insulating resin part covering the surface of the core part is used (Patent Documents 1 and 2). reference.).
When discarding printed circuit boards and electronic components manufactured using toner containing such metal particles, it is difficult to separate the metal powder constituting the toner from organic components such as resin parts. They are disposed of by landfill or incineration with little recycling of resources.
In particular, conventional toner for circuit board formation uses metal particles as a core part, and even if a printed circuit board or electronic component manufactured using this toner is incinerated, the metal component remains, which is an environmental burden. Will be enormous.
JP 2002-151828 A JP 2003-255594 A

  The object of the present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a toner having a low metal content and reduced environmental load, and a conductive functional member, an antistatic sheet, and a printed circuit member using the toner.

That is, the toner according to the present invention has a core portion composed of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol, and a surface of the core portion. It is characterized by comprising at least a resin part provided.
In conventional wiring forming toners, metal particles are used as a substantially spherical core. On the other hand, in the present invention, the conductive polymer gel is used instead of the conventional metal particles as the substantially spherical core portion, so that the content of the metal component in the toner can be reduced as compared with the conventional one.

In the toner structure, the conductive conjugated polymer is doped with a dopant.
Thereby, the density | concentration of the carrier of a conductive polymer gel can be raised, and electroconductivity can be improved.

  The conductive functional member according to the present invention includes at least a base material and a conductive portion made of toner provided on at least one surface of the base material, and the toner includes water as a main component, a conductive conjugated polymer, It is characterized by comprising a core part made of a conductive polymer gel containing a surfactant and / or alcohol, and a resin part provided on the surface of the core part.

  The antistatic sheet according to the present invention includes at least a base material and a conductive portion made of toner provided on at least one surface of the base material, and the conductive portion has a planar shape, and the toner includes A core part composed of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol, and a resin part provided on the surface of the core part It is characterized by that.

  The printed circuit member according to the present invention includes at least a base material and a conductive portion made of toner provided on at least one surface of the base material, and the conductive portion has a linear shape, and the toner includes A core part composed of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol, and a resin part provided on the surface of the core part It is characterized by that.

  The toner has a metal component content reduced as compared with conventional wiring forming toners. For this reason, in the conductive functional member, the antistatic sheet, and the printed circuit member described above, the content of the metal component can be reduced compared to the conventional case because the conductive portion is made of the toner.

According to the toner of the present invention, the metal component can be reduced as compared with the conventional case. Therefore, when a printed circuit board or an electronic component formed using the toner is discarded, an environmental load can be reduced.
In addition, according to the conductive functional member, the antistatic sheet, and the printed circuit member according to the present invention, the conductive portion provided on at least one surface of the base material is composed of the toner of the present invention described above. Compared to the metal component content, the environmental burden when discarded is reduced.

FIG. 1 is a schematic cross-sectional view showing an example of the toner 1 of the present invention. The toner 1 includes at least a substantially spherical core portion 11 made of a conductive polymer gel 2 and a resin portion 12 provided on the surface of the core portion 11.
The particle diameter of the toner 1 is preferably 15 μm or less, and more preferably 8 μm or less. Thereby, an excellent resolution can be realized. For example, when the toner 1 is transferred and fixed on a substrate or the like, a pattern wiring having a fine line width can be formed.

The conductive polymer gel 2 contains water 21 as a main component and includes a conductive conjugated polymer 22, a surfactant 23 and / or alcohol.
The conductive polymer gel 2 is formed by gelling the conductive conjugated polymer 22 itself with the surfactant 23 and / or alcohol, such as that proposed in Japanese Patent Application No. 2003-19120. Is applicable.

  FIG. 2 is a schematic diagram showing an example of the molecular structure of the conductive conjugated polymer 22. The conductive conjugated polymer 22 is poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (hereinafter also referred to as PEDOT / PSS), and is poly (3,4-ethylenedioxy). Thiophene (hereinafter also referred to as PEDOT) is doped with polystyrene sulfonic acid (hereinafter also referred to as PSS) as a dopant.

FIG. 3 (A) is an explanatory view schematically showing a colloidal aqueous dispersion of PEDOT / PSS, and FIG. 3 (B) shows an example of the colloidal aqueous dispersion of PEDOT / PSS shown in FIG. It is explanatory drawing which shows typically an example of the conductive polymer gel 2 of this invention obtained by adding surfactant 23 and gelatinizing.
As shown in FIG. 3A, the PEDOT / PSS colloidal aqueous dispersion has PEDOT / PSS molecules dispersed in water 21. By adding the surfactant 23 to the PEDOT / PSS colloidal aqueous dispersion and placing it under gelation conditions, a three-dimensional network is formed via the surfactant 23 as shown in FIG. It is formed and gels easily by including water 21 therein, whereby the conductive polymer gel 2 of the present invention is obtained.

  The gelation by adding the surfactant 23 (and / or alcohol) to the colloidal aqueous dispersion of PEDOT / PSS and placing it under gelation conditions is physically or chemically three-dimensional. It is thought that this is due to the formation of a network, and that the resulting gel exhibits conductivity is believed to be due to electronic conductivity and / or ionic conductivity. Of course, it is not limited to these ideas.

  Examples of the conductive conjugated polymer 22 include polyacetylene, polyphenylene, polypyrrole, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyphenylene vinylene, polythiophene vinylene, polyperiphthalene, polyanthracene, poly Examples include at least one selected from naphthalene, polypyrene, polyazulene, and derivatives thereof. Among them, polypyrrole or polythiophene shown in FIG. 2 is preferable because it is highly stable and reliable and easily available. Used.

The conductive conjugated polymer 22 is preferably doped with a dopant, whereby the carrier concentration of the conductive polymer gel 2 is increased, and the conductivity can be improved.
Examples of the dopant include at least one selected from iodine, arsenic fluoride, iron chloride, perchloric acid, sulfonic acid, perfluorosulfonic acid, polystyrene sulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, and derivatives thereof. However, among them, polystyrene sulfonic acid is preferable because high conductivity can be easily adjusted.

  Specifically, the colloidal dispersion of the conductive conjugated polymer 22 is obtained, for example, by polymerizing 3,4-ethylenedioxythiophene in the presence of a catalyst such as iron (III) toluenesulfonate. Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) colloidal aqueous dispersion (hereinafter referred to as PEDOT / PSS) (trade name: BaytronP, conductive polymer (PEDOT / PSS) concentration of about 1. 3% by mass, manufactured by Bayer).

The surfactant 23 is not particularly limited, and may be a known cationic surfactant, anionic surfactant, amphoteric surfactant, nonionic surfactant, or a mixture of two or more thereof. At least one selected surfactant can be used.
Examples of the cationic surfactant include quaternary alkyl ammonium salts and alkyl pyridinium halides.
Examples of the anionic surfactant include alkyl sulfuric acid or its ester salt, polyoxyethylene alkyl ether sulfuric acid or its salt, alkyl benzene sulfonic acid or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl sulfosuccinic acid or its salt, alkyl Examples thereof include diphenyl ether disulfonic acid or a salt thereof, fatty acid or a salt thereof, naphthalenesulfonic acid or a formalin condensate thereof.
Examples of amphoteric surfactants include alkyl betaines, amine oxides, hydrolyzed collagens, and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene rubitol fatty acid ester, polyoxyethylene fatty acid ester , Polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, or derivatives thereof.

Among these surfactants 23, long-chain alkylbenzene sulfonic acids are particularly preferred because gelation efficiency is improved.
The addition amount of the surfactant 23 used in the present invention in the conductive polymer gel is not particularly limited, but is usually preferably 0.1 to 30 parts by mass with respect to 1 part by mass of the conductive polymer. More preferably, it is 0.5 to 10 parts by mass.
If it is less than 0.1 parts by mass, it may not be gelled, and if it exceeds 30 parts by mass, it may not gelate.

The alcohol is not particularly limited, and at least one alcohol selected from known monohydric alcohols and polyhydric alcohols or a mixture of two or more thereof can be used.
Examples of monohydric alcohols include branched or linear alcohols such as ethanol, isopropyl alcohol, and butanol, cyclic alcohols, polymeric alcohols, and mixtures of two or more thereof.
Examples of the polyhydric alcohol include glycols such as ethylene glycol and propylene glycol, chain polyhydric alcohols such as glycerin, erythritol, xylitol, and sorbitol, cyclic polyhydric alcohols such as glucose and scroll, polyethylene glycol, and polyvinyl alcohol. Examples thereof include polymeric polyhydric alcohols such as or a mixture of two or more thereof.
Among these alcohols, isopropyl alcohol, ethylene glycol, and polyethylene glycol can be preferably used. Among them, polyhydric alcohols such as ethylene glycol and polyethylene glycol are preferable for the following reasons. Ethylene glycol has an effect of gelation even at a low concentration and can be particularly preferably used because it is not volatile. Further, the molecular weight of polyethylene glycol is not particularly limited, but a molecular weight of 1000 is more preferable than a molecular weight of 400 because gelation occurs even if the addition amount is small.

The concentration of the alcohol used in the present invention in the conductive polymer gel 2 is not particularly limited, but is usually preferably 1 to 70 parts by weight, more preferably 10 parts per 1 part by weight of the conductive polymer. -50 mass parts. If it is less than 1 part by mass, it may not be gelled, and if it exceeds 70 parts by mass, it may become too thin to be gelled.
In the present invention, the surfactant 23 and the alcohol can be used alone, but they can also be used in combination at any ratio.
In the present invention, the ratio of the surfactant 23 and the alcohol when used in combination is not particularly limited.

As a method of gelling the conductive conjugated polymer 22 with the surfactant 23 and / or alcohol, the following methods can be applied.
First, the surfactant 23 and / or alcohol as an additive is added to a colloidal dispersion liquid and / or a conductive conjugated polymer solution in which the conductive conjugated polymer 22 is colloidally dispersed in water 21. Pour in and add to avoid bubbles.
Next, it is left in an open space or sealed space in a normal atmospheric pressure without being subjected to vibration for a predetermined time (hereinafter referred to as stationary).
As described above, a three-dimensional network is formed and easily gelled, and the conductive polymer gel 2 that is a constituent component of the toner 1 can be stably obtained.
Here, the conductive conjugated polymer solution is obtained by dissolving the conductive conjugated polymer 22 in, for example, water or an organic solvent. In the present invention, the conductive conjugated polymer colloid dispersion liquid and the conductive conjugated polymer solution can be used alone, but they can also be used in combination at any ratio.

The core 11 constituting the toner 1 is composed of the conductive polymer gel 2 and the shape thereof is not particularly limited, but is in the form of particles.
The conductive polymer gel 2 constituting the core part 11 is preferably 40 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the toner 1, so that when the toner 1 is transferred to a substrate or the like , Sufficient conductivity can be imparted to the substrate.

The surface of the core part 11 is covered with a resin part 12. The resin portion 12 is made of an insulating resin that serves as a binder, and a resin that is used as a known binder for toner can be applied. For example, a resin capable of fixing the toner by heat, such as styrene-acrylic copolymer resin, polyester resin, epoxy resin, or a resin mixture in which a conductive polymer is added to these.
The resin constituting the resin part 12 is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the toner 1, whereby sufficient chargeability can be imparted to the surface of the toner 1.
An insulating portion made of various insulating components such as a resin is provided on the surface of the core portion 11, that is, the interface between the core portion 11 and the resin portion 12 to improve the chargeability of the toner 1 surface. The developability may be improved.

Further, a charge control agent 13 is provided on the surface of the toner 1 so that the polarity (charging polarity) to be charged on the surface of the toner 1 when the toner 1 is charged can be adjusted.
As the charge control agent 13, known ones can be applied, and examples thereof include quaternary ammonium salts, azo metal-containing complexes, salicylic acid metal complexes, calixarenes, amino group-containing fluorides, and the like. Depending on the charging polarity, it is appropriately selected and used.
The charge control agent 13 is preferably 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the toner 1, whereby the surface of the toner 1 can have a desired charge polarity.

Further, a release agent 14 is attached to the surface of the toner 1. As the release agent 14, known ones can be applied, and examples thereof include olefin wax and carnauba wax.
The release agent 14 is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner 1, whereby sufficient release properties can be obtained.

The toner 1 of the present invention described above can be produced by a known method such as a pulverization method, a polymerization method, or a particle precipitation method.
For example, the conductive polymer gel 2 is finely pulverized into particles to be the core portion 11, and the finely pulverized particles of the conductive polymer gel 2 and the resin to be the resin portion 12 are mixed and granulated. Thus, the toner 1 in which the surface of the core portion 11 is coated with the resin portion 12 can be manufactured.
The conductive polymer gel 2 constituting the core portion 11 of the toner 1 is the same polymer compound (organic compound) as the insulating resin (binder) constituting the resin portion 12, and is easily compatible and compatible. It is excellent and can easily be in a state where the entire surface of the core portion 11 is uniformly coated with the resin portion 12.
In conventional toner for circuit board formation, the metal particles that make up the core part and the resin that makes up the resin part that covers the surface of the toner are difficult to mix, and it is difficult to coat the entire surface of the core part with the resin part was there. As a result, the core portion is exposed on the surface of the toner, the chargeability of the toner is lowered, and there is a problem in that defective development occurs.
On the other hand, in the present invention, as described above, the entire surface of the core portion 11 can be uniformly covered with the resin portion 12, and the toner 1 that is excellent in chargeability and can suppress development defects and the like can be realized. .

The toner 1 of the present invention can be transferred and fixed to a substrate by a known development method.
Examples of the transfer method include toner image transfer methods such as electrostatic latent image transfer, electrostatic corona transfer, electrostatic belt transfer, electrostatic roller transfer, adhesive transfer, pressure transfer, and magnetic transfer. When multiple colors or a plurality of toners are used in combination, a multiple transfer system such as a multiple development system, a transfer drum system, an intermediate transfer system, or a tandem system can be applied.
In the conventional circuit forming toner, the core portion is composed of metal particles, has a high true density, and requires a large charge amount for development.
On the other hand, in the present invention, the core portion 11 is made of resin in the same manner as a toner for a normal plain paper copier (PPC). Can be transferred and fixed on a substrate.

Next, the conductive functional member, the antistatic sheet 3 and the printed circuit member of the present invention will be described.
The conductive functional member of the present invention includes at least a sheet-like base material made of a resin film such as PET (polyethylene terephthalate) or paper, and a conductive portion made of toner provided on at least one surface of the base material. It is.
The conductive portion is formed by transferring and fixing the toner 1 of the present invention described above onto a substrate. Since the toner 1 is as described above, detailed description thereof is omitted.
The base material is not limited to a sheet-like material, and any member that can transfer and fix the toner 1 on the surface can be used without particular limitation.

As described above, the toner 1 can be transferred and fixed to a substrate by a known development method, and even a fine conductive portion can be formed with high accuracy.
For this reason, the conductive portion is not limited to a shape or the like, and may be one in which the toner 1 is transferred and fixed on at least one surface of the substrate in a linear shape or a planar shape.
Here, the line shape is a pattern shape such as a wavy line, a straight line, a curve, a coil shape, a polygonal shape such as a triangle or a quadrangle, a circular shape, an elliptical shape, or a combination thereof, a character, a symbol, or the like. The shape consists of one or more straight lines or curves.
By forming a plurality of linear conductive portions without a pitch (interval), a planar conductive portion can be obtained.
Examples of the planar conductive portion include a conductive portion whose one surface has a polygonal shape such as a triangle or a quadrangle, a circular shape, an elliptical shape or the like, a combination thereof, or a shape such as a symbol.

In addition, the conductive portion is not limited to the one formed on the surface of the base material. For example, the conductive portion is formed by transferring and fixing the toner 1 on the inner surface of a hole, a depression, a groove, or the like provided on the base material. It doesn't matter.
For this reason, it can be set as the one-dimensional, two-dimensional, and three-dimensional conductive part by combining one or more linear conductive parts. For example, a one-dimensional conductive part can be used as a wiring or the like, and a two-dimensional conductive part can be used as a pattern wiring, an electrode, an electromagnetic coil, an antenna, or the like. Further, the three-dimensional conductive portion can be used as a through electrode or the like.

Such a conductive part can be adjusted in its impedance characteristics, conductivity, etc. by appropriately determining its thickness, width, length, shape, etc., and the conductive function member utilizes the conductivity of the conductive part. It can be applied to various uses.
For this reason, the conductive functional member can be used as, for example, a wiring board, and can be applied to various electronic devices by mounting various electronic components such as a light emitting element and an IC chip on a base material. It can also be used as an IC tag, an IC label, or the like.

FIG. 4 is a schematic cross-sectional view showing an example of the antistatic sheet 3 of the present invention. The antistatic sheet 3 is an example of the conductive functional member, and the conductive portion 32 provided on the sheet-like base material 31 has a planar shape.
In the antistatic sheet 3 shown as an example in FIG. 4, the conductive portion 32 is provided on the entire upper surface of the base material 31.
In the antistatic sheet 3, the conductive portion 32 imparts conductivity to the surface of the antistatic sheet 3 (the surface of the base material 31) so that the base material 31 is not charged.
Note that the conductive portion 32 may have a configuration provided on a part of at least one surface of the base material 31.

Moreover, the printed circuit member of this invention is an example of the said electroconductive functional member, and the electroconductive part provided in the sheet-like base material has comprised the linear form.
The linear conductive portion can be used as, for example, a pattern wiring, an electrode, a through electrode, an electromagnetic coil, an antenna, or the like. For this reason, the printed circuit member can be used as a wiring board, an IC tag, an IC label, or the like.
As described above, a plurality of linear conductive portions are formed without a pitch (interval) to form a planar conductive portion. Therefore, the conductive portion may be a planar conductive portion.

According to the toner 1 of the present invention, since the core portion 11 is composed of the conductive polymer gel 2, the toner 1 is compared with the toner using metal particles as the core portion as in the conventional wiring forming toner. The content of the metal component therein can be reduced. As a result, when the printed circuit board or electronic component formed using the toner 1 is discarded, the environmental load can be reduced.
In the conductive functional member, the antistatic sheet 3 and the printed circuit member of the present invention, the conductive portion 32 provided on at least one surface of the base material 31 is composed of the toner 1 of the present invention, so that the conventional core Compared to the toner using wiring forming toner whose part is composed of metal particles, the metal component metal component can be reduced, and the environmental load when discarded can be reduced.

The technical scope of the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
For example, an external additive or the like may be attached to the surface of the toner 1 in order to improve fluidity. As this external additive, known ones can be applied, and examples thereof include inorganic fine particles such as silica, alumina, titania (titanium oxide), and resin fine particles.
Further, a coating agent such as a silicone-based polymer or a fluorine-based polymer, carbon black, or the like may be attached to the surface of the toner 1.

Further, the toner 1 may be provided with a magnetic material according to the transfer and fixing method (development method) of the toner 1.
For example, magnetic particles such as iron particles and ferrite particles, and magnetic materials such as particles having a resin portion coated on the surface of the magnetic particles, toner contained in the core portion 11 and the resin portion 12, and the magnetic material The toner may be attached to the surface of the toner 1.
Further, depending on the developing method of the toner 1, there is a case where a carrier is mixed with the toner 1, and the carrier powder is mixed with the toner 1 powder according to the transfer and fixing method (developing method) of the toner 1. It doesn't matter.
A known carrier can be used as the carrier, and examples thereof include resin fine particles and magnetic powder. The particle diameter of the carrier is preferably 200 μm or less, more preferably 100 μm or less, whereby a sufficient resolution can be obtained.

  The toner of the present invention can impart conductivity to a base material by transferring and fixing to the base material. For example, an antistatic sheet, an antenna coil for RF-ID, a circuit of a printed circuit board, a liquid crystal display It can be used to form printed circuit boards such as electrode electrodes and keyboard membrane circuits. In addition to the printed circuit board, it can also be used for adhesion of terminals and lead wires of electronic components, formation of internal conductor films (interlayer connection conductive layers) of multilayer ceramic capacitors, and the like.

FIG. 3 is a schematic cross-sectional view illustrating an example of the toner of the present invention. It is a schematic diagram which shows an example of the molecular structure of a conductive conjugated polymer. (A) is explanatory drawing which shows typically the colloid aqueous dispersion of PEDOT / PSS, (B) is explanatory drawing which shows typically an example of the conductive polymer gel of this invention. It is a cross-sectional schematic diagram which shows an example of an antistatic sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Toner, 2 ... Conductive polymer gel, 3 ... Antistatic sheet, 11 ... Core part, 12 ... Resin part, 21 ... Water, 22 ... Conductive conjugated polymer, 23 ... ··· Surfactant, 31 ··· Base material, 32 · · · Conductive part

Claims (5)

  Consists of at least a core part composed of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or alcohol, and a resin part provided on the surface of the core part Toner.   The toner according to claim 1, wherein the conductive conjugated polymer is doped with a dopant. A substrate and at least a conductive portion made of toner provided on at least one surface of the substrate;
The toner includes a core portion made of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol, and a resin portion provided on the surface of the core portion. A conductive functional member characterized by comprising: A substrate and at least a conductive portion made of toner provided on at least one surface of the substrate;
The conductive portion has a planar shape,
The toner includes a core portion made of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol, and a resin portion provided on the surface of the core portion. An antistatic sheet characterized by comprising: A substrate and at least a conductive portion made of toner provided on at least one surface of the substrate;
The conductive part has a linear form,
The toner includes a core portion made of a conductive polymer gel containing water as a main component and containing a conductive conjugated polymer, a surfactant and / or an alcohol, and a resin portion provided on the surface of the core portion. A printed circuit member comprising:

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