JP2010222507A - Conductive copolymer, conductive pressure-sensitive adhesive using the same, and laminate for liquid crystal cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive copolymer containing a conductive polyaniline for achieving adhesivity with various materials to be bonded, heat resistance, moisture heat resistance and transparency and excellent conductivity, and to provide a pressure sensitive adhesive composition using the same and its laminate for a liquid crystal cell. <P>SOLUTION: The conductive copolymer is prepared by radically copolymerizing a conductive polyaniline (1) having an α,β-ethylenic unsaturated bond with a compound (2) having an ethylenic bond radically polymerizable with the conductive polyaniline (1). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a conductive copolymer using polyaniline having excellent conductivity, a conductive pressure-sensitive adhesive using the same, and a conductive adhesive sheet thereof.

  Conventionally, conductive materials include electromagnetic shields for plastic containers that house electronic devices such as computers, communication devices, and amplifiers, ground wires for electrical components, leakage current removers that serve as both fixing and vibration prevention, ICs, LSIs, etc. It is used as a material for transporting semiconductors and electronic parts, as a weak heating element for preventing ignition due to electrostatic discharge generated by frictional charging, and preventing condensation and freezing.

  In general, conductive materials such as charge control agents, surfactants, ionic substances, metal powders, metal oxides are used as methods for imparting electrostatic discharge to a support made of a material such as a polymer material having low electrical conductivity. Method of dispersing material powder, metal oxide whisker, carbon black, graphite, carbon fiber, metal fiber, conductive polymer powder, conductive polymer fiber, etc. in the support, or vacuuming the conductive material on the support It is well known to deposit physical materials by vapor deposition, sputtering, ion plating, etc., or by laminating conductive materials by chemical reaction, thermal decomposition, spraying, plating, coating, laminating, etc. It has been.

  In recent years, conductive polymers such as polyacetylene, polypyrrole, polythiophene, and polyaniline have been applied to fields such as capacitor solid electrolytes, battery electrodes, antistatic materials, various sensors, display elements, and display devices as new conductive materials. Has been widely considered.

  Laminates made of these conductive materials, especially in recent years due to dramatic advances in electronics, such as liquid crystal displays (LCD), plasma displays (PDP), rear projection displays (RPJ), EL displays, light emitting diode displays, etc. Various flat displays (FPDs) have been used as display devices in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays, and are also used for these protective films. Or used.

  Among these conductive polymers, polythiophene, polypyrrole, polyaniline, and the like are chemically stable in the air and have a conductivity of 100 S / cm or more, and are suitable for practical use. These conductive polymers can have a high conductivity of 1 S / cm or more by a treatment called doping that forms a complex of a dopant and a conductive polymer. Polyaniline or its derivative is a conductive polymer that exhibits high conductivity by using protonic acid as a dopant, so that it exhibits higher stability in the atmosphere than other conductive polymers such as polypyrrole. Are known.

Thus, since polyaniline and its derivatives show excellent electrical properties, they may be widely used industrially and there are many application reports.
For example, it is known that various inorganic acids (hydrochloric acid, sulfuric acid, etc.) or organic acids (carboxylic acid, sulfonic acid, organic phosphoric acid, etc.) can be used as the protonic acid. In addition, by using a sulfonic acid compound as the protonic acid, it is possible to obtain a particularly highly conductive and heat-resistant polyaniline or a derivative thereof (see Patent Document 1). However, since these materials have insoluble and infusible characteristics, it has been difficult to apply them to optical members.

  Polyaniline exhibits stable conductivity because inorganic and organic protonic acids are used as a dopant. For this reason, the method of melt | dissolving in a solvent and making it a coating material using binders, such as polyester, is disclosed (refer patent document 2). However, the conductive layer obtained from this paint has problems of low hardness and strength, and low solvent resistance and chemical resistance. In particular, polyaniline flows out when an acid as a dopant comes into contact with the solvent. Further, there is a problem that when the alkali is touched, the dopant is desorbed and the conductivity is lowered.

  Moreover, in order to improve the hardness and solvent resistance of the conductive layer, a paint that can be easily cured with ultraviolet rays or visible light is disclosed (see Patent Document 3). However, since an inorganic conductor is used, it is not easy to disperse the conductor in the binder, and a large amount of dispersant and a long time are required for dispersion. Has the disadvantage of being bad.

  There is also reported a technique called soluble polyaniline, using dodecylbenzenesulfonic acid alone, forming a salt of this with aniline, and then performing oxidative polymerization. (See Patent Document 4 and Non-Patent Document 1).

  Further, as in the above prior art, sodium dodecylbenzenesulfonate (Patent Document 5), 4-naphthoquinone-2-sulfonic acid (Patent Document 6), sulfonic acid metal salt (Patent Document 7), sulfonic acid anionic surface activity There has also been reported a technique in which an agent (Patent Document 8) and an aromatic polyvalent sulfonic acid metal salt (Patent Document 9) are used, and a salt of this and an aniline is formed, followed by oxidative polymerization.

In addition, as in the above-described conventional technology, there is a report of polymerizing anilines using a polystyrene sulfonic acid copolymer (see Patent Document 10 and Non-Patent Document 2). However, these methods cannot form a conductive film usable for an optical member.
As described above, polyaniline, which is a conductive polymer, is generally insoluble in a solvent, and does not melt, making it difficult to mold and process. Especially, it is developed for optical applications such as flat display (FPD). It was difficult to do.

  On the other hand, as an optical member such as a flat display (FPD), as described above, a conductive material is laminated on various optical films and sheets in various fields and used as a display device. For example, a polarizing film or a retardation film is laminated on a glass member for a liquid crystal cell constituting an LCD.

  These display devices use an antireflection film for preventing reflection from an external light source, a surface protection film (protection film) for preventing scratches on the surface of the display device, and the like.

  Furthermore, the FPD is not only used as a display device, but also provided with a touch panel function on the surface thereof, and may be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, and the like are also used for this touch panel.

  Various films used in the display device are used by being attached to an adherend with a pressure-sensitive adhesive. Since the pressure-sensitive adhesive is first required to be excellent in transparency because it is used for a display device, an adhesive mainly composed of a propenoic acid resin is generally used.

  By the way, among the various films described above, the polarizing film has a three-layer structure in which both surfaces of a polyvinyl alcohol-based polarizer are sandwiched between triacetyl cellulose-based protective films. Because of the characteristics of the materials that make up each layer, the polarizing film undergoes significant dimensional changes due to expansion and contraction due to heat and humidity. Therefore, the propenoic acid-based adhesive for sticking the polarizing film to the glass member for a liquid crystal cell is required to suppress the dimensional change of the polarizing film itself.

  In contrast, by making the adhesive layer itself hard or increasing the adhesive strength, it is possible to suppress a relatively small dimensional change or a relatively short-term dimensional change.

  However, with the recent increase in screen size of liquid crystal panels, the size of the polarizing film has also increased, and the amount of thermal deformation of the polarizing film has increased. When using a conventional pressure-sensitive adhesive, the stress at the time of sticking remaining in the adhesive layer is not sufficiently relaxed, so the adhesive layer cannot sufficiently follow the distortion of the polarizing film, resulting in a large liquid crystal When the panel is exposed to high temperature or high humidity, there is a problem that the polarizing film is peeled off from the glass substrate of the large liquid crystal cell, stress concentration occurs in the polarizing film, and light leakage occurs in the large liquid crystal panel.

  In addition, the polarizing film changes in dimensions while the liquid crystal panel is used over a long period of time, and the stress is accumulated in the adhesive layer. If the stress continues to accumulate in the adhesive layer, the distribution of the adhesive force between the polarizing film and the liquid crystal cell glass member becomes non-uniform. During long-term use, stress is concentrated especially on the periphery of the polarizing film, and as a result, the periphery of the liquid crystal element is brighter or darker than the center. appear.

  In addition, after laminating a polarizing film on a glass surface for a liquid crystal cell to make a laminate, in the inspection process, if there is air or dust entrainment in the laminating process, a retardation plate etc. from the glass cell surface It is peeled off and a new polarizing film or the like is pasted again.

  However, generally after lamination, the laminate is stored at a high temperature for a certain period of time to promote adhesion, and then inspected. During that time, the peel strength becomes too high and it is difficult to peel off the polarizing film, etc. After that, adhesive residue is generated, and the removability is insufficient.

  In addition, since these optical members are made of a plastic material, they have high electrical insulation, and generate static electricity during friction and peeling. Therefore, static electricity is generated even when the polarizing film is re-applied, and if voltage is applied to the liquid crystal while the static electricity generated at this time remains, the alignment of the liquid crystal molecules is lost and the panel is damaged. There is a problem that will occur. Furthermore, the presence of static electricity has the problem of attracting dust and debris and causing defects due to foreign matter. These have the same problem in color correction films and the like in plasma displays.

When transporting these optical members and electronic members or mounting them on a printed circuit board, the individual members are usually made of a transparent surface protective film (base, such as polyethylene, polyester, polypropylene) for the purpose of surface protection and functionality. Material film) is laminated.
In many cases, these surface protective films finish the role of surface protection after the incorporation of a liquid crystal display or the like is completed, and are peeled off. However, there is a problem that static electricity is generated when the surface protective film is peeled off and entraps surrounding dust. Furthermore, there may be a problem that the liquid crystal and the electronic circuit are destroyed due to peeling electrification generated when the surface protective film is peeled off.

  As described in detail, the pressure sensitive adhesive used for laminating the polarizing film on the liquid crystal cell and the color correction film on the plasma display has good optical properties (transparency), heat resistance and heat and humidity resistance, good Stress relaxation, removability, and electrostatic discharge (ESD) are required. The same performance is required for an adhesive for laminating a retardation film and various display cover films, and the same performance is also required for the surface protection film of these optical members, electronic members or printed boards. .

  In the optical member described above, the method of dissolving or dispersing the conductive material in the support requires that a certain amount or more of the conductive material is dissolved or dispersed in order to maintain the conductivity to a necessary level. There is a drawback that the mechanical strength, flexibility, and film forming property of the support are impaired. In addition, the method of physically or chemically laminating a conductive material on the support surface is limited by the type, characteristics, shape, or type of conductive material of the support, and the conductive layer is opaque. It has disadvantages such as poor adhesion and easy peeling, non-uniform conductive layer, difficulty in increasing the area, capital investment and high running cost, and is unsuitable for optical applications.

  Various configurations have been proposed for these various requirements. For example, a resin composition characterized by containing a conductive polyaniline doped with a protonic acid having a long-chain alkyl group in the molecule has been reported (Patent Document 11). Also, a protonic acid such as camphorsulfonic acid, A conductive resin composition containing a nonpolar or low polarity organic solvent and polyaniline has been reported (Patent Document 12). In addition, a protective film in which an antistatic layer is formed by dispersing an aniline polymer in a propenoic acid polymer has been reported (Patent Document 13). In addition, films in which conductive polymers such as polyaniline are laminated have been reported (Patent Documents 14, 15, 16, 17, 18). However, in these methods, when used for an optical member, there are problems such as a decrease in transparency due to poor dispersion and a loss in the balance of adhesive properties, conductivity, mechanical properties, and the like.

Japanese Patent Application No. 5-218294 JP-A-1-131288 Japanese Patent Laid-Open No. 60-60166 JP-A-7-263378 Japanese Patent Laid-Open No. Hei 6-279594 JP-A-8-337650 JP-A-5-503953 JP-A-5-504153 JP-A-6-306280 JP-A-5-262981 Japanese Patent Application Laid-Open No. 8-092542 JP-A-8-253755 JP-A-7-281420 Japanese Patent Laid-Open No. 5-331431 JP-A-11-269436 JP-A-14-193377 JP-A-16-136625 Japanese Patent Laid-Open No. 17-027945

Y. Haba et al, Synth. Met. 2000, 110, 189 L. A. Samuelson et al, Macromolecules, 1998, Vol. 31, p. 4376.

  The present invention relates to a conductive copolymer containing conductive polyaniline for realizing adhesion, heat resistance, heat and humidity resistance, transparency and excellent conductivity with various adherends, and a conductive pressure-sensitive type using the same. An object is to provide an adhesive and a laminate for a liquid crystal cell.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the first invention in the present invention is a conductive polyaniline (1) having an α, β-ethylenically unsaturated bond,
The present invention relates to a conductive copolymer obtained by radical copolymerization of the conductive polyaniline (1) and a compound (2) having an ethylenically unsaturated bond capable of radical copolymerization.

  In the second invention, the conductive polyaniline (1) is introduced by doping with a protonic acid having an α, β-ethylenically unsaturated bond, or a metal salt or ammonium salt thereof, and is doped with α, β-ethylenic unsaturation. The present invention relates to the conductive copolymer according to the invention, characterized by having a bond.

  The third invention is characterized in that the conductive polyaniline (1) is obtained by oxidative polymerization after doping a protonic acid having an α, β-ethylenically unsaturated bond or a metal salt or ammonium salt thereof into aniline. The present invention relates to the conductive copolymer of the invention.

  In the fourth invention, the conductive polyaniline (1) is obtained by doping polyaniline obtained by oxidative polymerization of aniline with a protonic acid having an α, β-ethylenically unsaturated bond, or a metal salt or ammonium salt thereof. The present invention relates to the conductive copolymer according to the first or second invention.

  The fifth invention relates to the conductive copolymer according to any one of the second to fourth inventions, wherein the protonic acid is sulfonic acid.

  Moreover, 6th invention is related with the conductive copolymer of the said invention characterized by having a carboxyl group and / or a hydroxyl group.

  In the seventh invention, the compound (2) having an ethylenically unsaturated bond comprises propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative having a hydroxyl group, and a 2-methylpropenoic acid derivative having a hydroxyl group. The conductive copolymer according to the invention is characterized by containing at least one selected from the group.

  Further, the eighth invention relates to a conductive polyaniline (1) having an α, β-ethylenically unsaturated bond and a compound (2) having an ethylenically unsaturated bond, wherein (1) / (2) = 0. Conductivity of the above invention, characterized in that it is a copolymer obtained by radical copolymerization at a ratio of 01 / 99.99 to 95/5 (weight ratio), and has a glass transition temperature of -80 to 10 ° C. It relates to a sex copolymer.

  The ninth invention also relates to a conductive pressure-sensitive adhesive comprising the conductive copolymer of the above invention and a curing agent (A) capable of reacting with a functional group in the conductive copolymer. .

  The tenth invention relates to the conductive pressure-sensitive adhesive according to the invention, characterized by containing 0.01 to 50 parts by weight of the curing agent (A) with respect to 100 parts by weight of the conductive copolymer.

  The eleventh invention relates to a conductive adhesive sheet in which a conductive pressure-sensitive adhesive layer formed from the conductive pressure-sensitive adhesive of the invention is provided on at least one surface of a sheet-like substrate.

  The twelfth invention relates to the conductive adhesive sheet according to the invention, wherein the sheet-like substrate is an optical film.

  The thirteenth invention relates to the conductive adhesive sheet according to the eleventh invention, wherein the sheet-like substrate is a protective film for an optical laminate.

  The fourteenth invention relates to the conductive adhesive sheet according to the twelfth invention, wherein the optical film is a film selected from the group consisting of a polarizing film and a color correction film.

  According to a fifteenth aspect of the present invention, there is provided a liquid crystal cell laminate comprising: a glass for a liquid crystal cell; a conductive pressure sensitive adhesive layer formed from the conductive pressure sensitive adhesive of the above invention; and an optical film. About the body.

  By using a conductive copolymer containing conductive polyaniline according to the present invention, a conductive pressure-sensitive adhesive and a conductive material having excellent adhesion, heat resistance, moist heat resistance, transparency and conductivity to various adherends. An adhesive sheet could be obtained.

Hereinafter, embodiments of the invention of this application will be described in detail.
The conductive copolymer of the present invention comprises a conductive polyaniline (1) having an α, β-ethylenically unsaturated bond (hereinafter sometimes simply referred to as conductive polyaniline (1)), the conductive polyaniline ( It is obtained by radical polymerization of a compound (2) having an ethylenically unsaturated bond that can be radically copolymerized with 1) [hereinafter referred to as a compound (2) having an ethylenically unsaturated bond].

  The polyaniline, which is the central skeleton of the conductive polyaniline (1) having an α, β-ethylenically unsaturated bond, is a polymer having an imino-p-phenylene structural unit as a main repeating unit in the reduced state as its basic skeleton. Have The polyaniline may be one having various substituents introduced therein or a copolymer structure. For example, the polyaniline is not only aniline but also a substituent having various substituents on its ring constituent atoms. Polyaniline which is a polymer of aniline may be used.

  Examples of the substituent include hydrocarbon groups such as alkyl groups and phenyl groups, halogen atoms, —OH, —SH, alkoxy groups, sulfide groups, carbonyl groups, sulfoxide groups, carboxyl groups, alkoxycarbonyl groups, amide groups, An amino group, a nitro group, a cyano group, a urea group, a carbamate group, a hydrazino group, and the like may be used. However, the side chains of these polyanilines are improved in solubility in a solvent in proportion to the amount of introduction, but if they are excessive, there is a risk that the conductivity is lowered due to steric hindrance of the molecule.

  In the present invention, the conductive polyaniline (1) needs to have an α, β-ethylenically unsaturated bond. That is, the protonic acid metal salt or ammonium salt having an α, β-ethylenically unsaturated bond, or the protonic acid metal salt or ammonium salt having an α, β-ethylenically unsaturated bond, protonates the nitrogen atom of the amino group of the conductive polyaniline ( In the present invention, the conductive polyaniline (1) having an α, β-ethylenically unsaturated bond can be synthesized. On the other hand, polyaniline obtained by removing protons from conductive polyaniline (dope type) obtained by protonating amino nitrogen atoms is called dedope type (also referred to as dedope or dedope).

  Here, the protonic acid metal salt or ammonium salt having an α, β-ethylenically unsaturated bond is not limited as long as the nitrogen atom of aniline is protonated, for example, sulfuric acid, hydrochloric acid, nitric acid, perchloric acid. Inorganic proton acids such as borohydrofluoric acid, organic acids such as organic carboxylic acids, organic phosphoric acids and organic sulfonic acids, or various metal salts and ammonium salts of these protonic acids. Of these, organic sulfonic acids, or their metal salts and ammonium salts are preferred because they are easily neutralized with the nitrogen atom of aniline and can be easily doped and have excellent stability after doping. Furthermore, these organic sulfonic acids or their metal salts and ammonium salts particularly preferably have an α, β-ethylenically unsaturated bond.

  The protonic acid having an α, β-ethylenically unsaturated bond or the protonic acid metal salt or ammonium salt having an α, β-ethylenically unsaturated bond is propenoic acid, 2-methylpropenoic acid, propenoic acid derivative, 2 -At least one compound selected from methylpropenoic acid derivatives, alkenyl group-containing compounds, or metal salts thereof are preferred.

  Examples of the propenoic acid derivatives or 2-methylpropenoic acid derivatives include, for example, sulfomethyl (2-methyl) propenoate [a combination of sulfomethyl propenoate and sulfomethyl 2-methylpropenoate, “sulfomethyl (2-methyl) propenoate” write. The same applies hereinafter. ], 2-sulfoethyl (2-methyl) propenoate, 2-sulfopropyl (2-methyl) propenoate, 3-sulfopropyl (2-methyl) propenoate, 2-sulfobutyl (2-methyl) propenoate, (2 -Methyl) propenoate 4-sulfobutyl, (2-methyl) propenoate 2-sulfobutyl, (2-methyl) propenoate 6-sulfohexyl, (2-methyl) propenoate sulfooctyl, (2-methyl) propenoate sulfodecyl Sulfonyl group-containing (2-methyl) propenoic acid alkyl esters such as (2-methyl) propenoic acid sulfolauryl, (2-methyl) propenoic acid sulfostearyl, (2-methyl) propenoic acid sulfophenoxyethyl, (2 (2-Methyl) propenoic acid containing a sulfonyl group such as -methyl) propenoic acid sulfocyclohexyl Jo esters can be mentioned.

  Examples of the metal salt or ammonium salt of the sulfonyl group-containing propenoic acid derivative or 2-methylpropenoic acid derivative include, for example, metal salts and ammonium salts of the sulfonyl group-containing (2-methyl) propenoic acid alkyl esters, (2-Methyl) propenoyloxydimethylethylammonium ethyl sulfate, (2-methyl) propenoylaminopropyltriethylammonium sulfate, and the like (2-methyl) containing a sulfonyl group such as (2-methyl) propenoylaminopropyltriethylammonium sulfate Metal salts and ammonium salts of propenoic acid alkyl esters, metal salts and ammonium salts of sulfonyl group-containing (2-methyl) propenoic acid cyclic esters, and (2-methyl) propenoic acid sulfobenzyl, (2-methyl) ) Sulfonyl such as propenoyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (2-methyl) propenoyloxyethyltrimethylammonium-p-toluenesulfonate, (2-methyl) propenoylaminopropyltrimethylammonium-p-toluenesulfonate Examples thereof include metal salts and ammonium salts of group-containing (2-methyl) propenoic acid cyclic esters.

  Examples of the alkenyl group-containing compound or a metal salt thereof include ethenylbenzene sulfonic acid, ethenyl sulfonic acid, allyl sulfonic acid, allyloxybenzene sulfonic acid, methallyl sulfonic acid, methallyloxybenzene sulfonic acid, and vinyl sulfuric acid. Alkenyl group-containing sulfonic acid compounds, ethenylbenzenesulfonate ammonium, ethenylbenzenesulfonate monomethylammonium, ethenylbenzenesulfonate dimethylammonium, ethenylbenzenesulfonate trimethylammonium, ethenylbenzenesulfonate tetramethylammonium, Ethenylammonium ethenylbenzenesulfonate, diethylammonium ethenylbenzenesulfonate, triethylammonium ethenylbenzenesulfonate, ethenylbenzenesulfone Tetraethylammonium acid, propylammonium ethenylbenzenesulfonate, dipropylammonium ethenylbenzenesulfonate, tripropylammonium ethenylbenzenesulfonate, butylammonium ethenylbenzenesulfonate, pentylammonium ethenylbenzenesulfonate or ethenylbenzenesulfone Alkenyl salts containing alkenyl groups such as hexylammonium acid, sodium ethenylbenzenesulfonate, potassium ethenylbenzenesulfonate, lithium ethenylbenzenesulfonate, magnesium ethenylbenzenesulfonate, ethenylbenzenesulfonate Metal salts of alkenyl group-containing ethenylbenzene sulfonic acid such as zinc and iron ethenylbenzene sulfonate, ethenyl Metal salts and ammonium salts of ethenyl sulfonic acid containing alkenyl groups such as ammonium sulfonate, sodium ethenyl sulfonate, potassium ethenyl sulfonate, allyl sulfone containing ammonium allylate, sodium allyl sulfonate, potassium allyl sulfonate alkenyl Metal salts and ammonium salts of acids, sodium allylalkylsulfosuccinates, ammonium salts of allyloxybenzenesulfonate, sodium allyloxybenzenesulfonate, sodium allyloxybenzenesulfonate, potassium allyloxybenzenesulfonate alkenyl groups and ammonium salts , Metal salts of alkenyl group-containing methallyl sulfonic acids such as ammonium methallyl sulfonate, sodium methallyl sulfonate, potassium methallyl sulfonate Ammonium salts, ammonium methallyloxybenzene sulfonate, sodium methallyloxybenzene sulfonate, potassium metallyloxybenzene sulfonate alkenyl group-containing methallyloxybenzene sulfonate metal salts and ammonium salts, (2-methyl) 2-propene Amidosulfonic acid [2-propenamidesulfonic acid and 2-methyl-2-propenamidesulfonic acid are collectively referred to as “(2-methyl) 2-propenamidesulfonic acid”. The same applies hereinafter. ], Tert-butyl- (2-methyl) 2-propenamidesulfonic acid, (2-methyl) 2-propenamide-2-methyl-1-propanesulfonic acid, and other alkenyl group-containing amide sulfonic acids. it can.

  In the present invention, typical methods for polymerizing the conductive polyaniline (1) having an α, β-ethylenically unsaturated bond include chemical oxidative polymerization, oxygen oxidative polymerization and electrolytic oxidative polymerization using an oxidant. There are no restrictions on its type.

  The polymerization method of the present invention can be carried out by changing the order of addition of anilines, an oxidant, and a sulfonic acid compound having an α, β-ethylenically unsaturated bond (referred to as a dopant, meaning a compound to be doped). Are roughly divided into two methods.

  For example, (I) a method in which an oxidant is added to an appropriate solvent containing a protonic acid in advance to polymerize the aniline, and after passing through a reductant, a dopant is added and then doped (post-doping type); (II) aniline is converted into a protonic acid There is a method in which a dopant is added to form a composite (doping) after being dissolved in a suitable solvent containing oxygen, followed by oxidative polymerization by adding an oxidizing agent (pre-doping type). In general, the method (I) provides a high-purity product and is industrially established, but has a low yield. The method (II) has a simple polymerization method, but the polymerization stability is poor, and the purity is low due to the presence of an undoped dopant.

  In the present invention, the polymerization method is not particularly limited, but polyaniline is previously combined with a protonic acid having an α, β-ethylenically unsaturated bond or a protonic acid metal salt or ammonium salt having an α, β-ethylenically unsaturated bond. The method (II) in which the aniline in the composite is polymerized after (doping) is more preferably used. This is because by using a dopant having an α, β-ethylenically unsaturated bond, the polymerization stability is improved, and a high-purity product is obtained by the polymerization reaction of the dopant described later.

  The oxidizing agent used in the polymerization reaction of the present invention may be any oxidizing agent that can oxidize anilines, but persulfates such as ammonium persulfate, persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide And ferric chloride. Among them, persulfates represented by ammonium persulfate are particularly preferable. The oxidizing agent is preferably used in an amount of 0.1 to 10 mol, more preferably 0.5 to 5 mol, per 1 mol of anilines. When the oxidizing agent is less than 0.1 mol, the polymerization reaction may not occur. On the other hand, if the reaction is carried out in excess of 10 moles, sulfone groups are introduced excessively and the solubility is improved, but the conductivity may be lowered.

  The polymerization solvent is not particularly limited as long as anilines, dopants and oxidizing agents are dissolved. For example, methanol, ethanol, isopropanol, acetonitrile, N-methyl-2-pyrrolidone, acetone, 2-butanone, N, N An organic polar solvent such as dimethylformamide, N-methylformamide, formamide, N, N-dimethylacetamide, dimethylsulfoxide, water, or a mixed solvent thereof is preferably used.

  The polymerization reaction temperature is preferably between -20 and 70 ° C, particularly preferably between -10 and 20 ° C. When the temperature is lower than −20 ° C., the polymerization rate is too slow, and the energy cost required for cooling is increased, which may reduce the economic efficiency. When the temperature exceeds 70 ° C. or higher, the polymerization rate is too high, and the conductive polymer settles alone, the generation rate of the conductive polymer having a side chain increases, the conductivity decreases, and the oxidation There exists a possibility that the ratio which the oxide of a monomer and a conductive polymer may increase because an effect | action is too strong may increase.

  The conductive polyaniline (1) thus obtained has a degree of polymerization of preferably 2 to 10,000, more preferably 20 to 5,000. The weight average molecular weight (Mw, hereinafter referred to as Mw) is preferably 200 to 1,000,000, more preferably 2,000 to 500,000. When the degree of polymerization is 2 or less, that is, when Mw is about 200 or less, the conductivity may be insufficient. Moreover, when Mw exceeds 1,000,000, there exists a possibility that the solubility with respect to resin or a solvent and a dispersibility may fall.

  Moreover, the range of 40-100 degreeC is preferable and, as for the glass transition point (Tg) of electroconductive polyaniline (1), the range of 50-70 degreeC is more preferable. If it is less than 50 ° C., it may be deteriorated in heat resistance when used for optical purposes. If it exceeds 100 ° C., the compatibility with the compound (2) having other ethylenically unsaturated bonds described later may be lowered.

  The conductive polyaniline (1) of the present invention is preferably in the form of powder, solution or dispersion. And it can be used for various printing inks (letterpress, offset, gravure, flexo, screen, ink jet), various paints, various coating agents, various adhesives, various pressure sensitive adhesives, various plastic masterbatches and compounds. Particularly, since it has an α, β-ethylenically unsaturated bond, it contains a polyfunctional compound described later and an oligomer of polyurethane or polyester, and is particularly suitable for a photo-curing type application that is cured by ultraviolet rays, electron beams, or radiation. preferable.

  In the present invention, the compound (2) having an ethylenically unsaturated bond is a propenoic acid, 2-methylpropenoic acid, propenoic acid derivative, 2-methylpropenoic acid derivative or alkenyl group-containing compound other than the conductive polyaniline (1). Is included. Further, it may be a compound having two or more ethylenically unsaturated bonds (hereinafter referred to as bifunctional monomer, trifunctional monomer, etc.).

Examples of the propenoic acid derivative or 2-methylpropenoic acid derivative include, for example, methyl (2-methyl) propenoate [combination of methyl propenoate and methyl 2-methylpropenoate is referred to as “methyl (2-methyl) propenoate”. To do. The same applies below. ], (2-methyl) propenoic acid ethyl, (2-methyl) propenoic acid 1-propyl, (2-methyl) propenoic acid 2-propyl, (2-methyl) propenoic acid n-butyl, (2-methyl) propene Sec-butyl acid, iso-butyl (2-methyl) propenoate, tert-butyl (2-methyl) propenoate, n-amyl (2-methyl) propenoate, iso-amyl (2-methyl) propenoate, 2-methyl) propenoic acid n-hexyl, (2-methyl) propenoic acid 2-ethylhexyl, (2-methyl) propenoic acid n-octyl, (2-methyl) propenoic acid iso-octyl, (2-methyl) propenoic acid n-nonyl, iso-nonyl (2-methyl) propenoate, decyl (2-methyl) propenoate, dodecyl (2-methyl) propenoate, (2-methyl) propyl (2-methyl) propenoic acid alkyl esters such as octadecyl penate, lauryl (2-methyl) propenoate, stearyl (2-methyl) propenoate; cyclohexyl (2-methyl) propenoate, (2-methyl) propene Benzyl acid, iso-bonyl (2-methyl) propenoate, phenyl (2-methyl) propenoate, 2-phenoxyethyl (2-methyl) propenoate, 2-oxo-1,2- (2-methyl) propenoate (2-methyl) propenoic acid cyclic esters such as phenylethyl and (2-methyl) propenoic acid 2-oxo-1,2-diphenylethyl ;, (2-methyl) propenoic acid allyl ester, (2-methyl) propenoic acid 1-methylallyl, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl) propyl 2-butenyl penate, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, 2-chloroallyl (2-methyl) propenoate, (2-methyl) 3-chloroallyl propenoate, (2-methyl) propenoate-o-allylphenyl, 2- (allyloxy) ethyl (2-methyl) propenoate, allyl lactyl (2-methyl) propenoate, citronellyl (2-methyl) propenoate (2-methyl) further containing an unsaturated group such as geranyl (2-methyl) propenoate, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, ethenyl (2-methyl) propenoate, etc. Propenoic acid esters ;, perfluoromethyl (2-methyl) propenoate, perfluoroethyl (2-methyl) propenoate, (2 -Methyl) perfluoropropyl propenoate, perfluorobutyl (2-methyl) propenoate, perfluorooctyl (2-methyl) propenoate, trifluoromethyl methyl (2-methyl) propenoate, (2-methyl) propenoic acid 2-trifluoromethylethyl, (2-methyl) propenoic acid diperfluoromethylmethyl, (2-methyl) acrylic acid 2-perfluoroethylethyl, (2-methyl) propenoic acid 2-perfluoromethyl-2-par Fluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluorobutylethyl, (2-methyl) propenoic acid 2-perfluorohexylethyl , 2-Perfluorodecylethyl (2-methyl) propenoate, (2 (2-methyl) propenoic acid perfluoroalkyl esters such as methyl) propenoic acid 2-perfluorohexadecylethyl; 2-hydroxyethyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate 3-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, 2-ethoxyethyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, ( (2-methyl) propenoate 4-hydroxybutyl and other hydroxyl group or alkoxy group-containing (2-methyl) propenoates; (2-methyl) propenoate N-methylaminoethyl, (2-methyl) propenoate N- Tributylaminoethyl, (2-methyl) propenoic acid N, N-dimethylaminoethyl, ( Amino group-containing (2-methyl) propenoates such as (methyl) propenoic acid N, N-diethylaminoethyl; glycidyl (2-methyl) propenoate, (2-methyl) propenoic acid (3,4-epoxycyclohexyl) ) (2-methyl) propenoic acid esters such as methyl, (2-methyl) propenoic acid (3-methyl-3-oxetanyl) methyl, (2-methyl) propenoic acid tetrahydrofurfuryl; 2-methylprop-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylprop-2-enoyloxypropyl) triethoxysilane, 3- (2-methylprop-2-enoyloxypropyl) triisopropoxy Silane, 3- (2-methylprop-2-enoyloxypropyl) methyldimethoxysilane, Alkoxysilyl group-containing (2-methyl) propenoates such as 3- (2-methylprop-2-enoyloxypropyl) methyldiethoxysilane and 3- (prop-2-enoyloxypropyl) trimethoxysilane; 2- (2′-hydroxy-5 ′-(2-methyl) prop-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) propa -2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(2-methyl) prop-2-enoyloxypropylphenyl) -2H-benzotriazole 2- (2′-hydroxy-5 ′-(2-methyl) prop-2-enoyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(2-methyl) prop-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-tert- Benzotriazole-based (2-methyl) propenoic acid derivatives such as butyl-5 ′-(2-methyl) prop-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole; -4- {2- (2-methyl) prop-2-enoyloxy} ethoxydiphenylmethanone,
2-hydroxy-4- {2-((2-methyl) prop-2-enoyloxy} butoxydiphenylmethanone, 2,2′-dihydroxy-4- {2- (2-methyl) prop-2-enoyloxy} ethoxy Diphenylmethanone, 2-hydroxy-4- {2- (2-methyl) prop-2-enoyloxy} ethoxy-4 ′-(2-hydroxyethoxy) diphenylmethanone and the like (2-methyl) of diphenylmethanone Propenoic acid derivatives; 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis ( 2-Methylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2- Hydroxy-4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2 -(2-Methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2- Methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) prop- 2-Enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4 -Diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4-diethylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) prop-2-enoyloxyethoxy)]-triazine-based (2-methyl) propenoic acid derivatives such as S-triazine; Alkene oxide-containing (2-methyl) propenoic acid derivatives such as an ethene oxide adduct of 2-methyl) propenoic acid;
For example, di (2-methyl) propenoic acid ethene oxide, di (2-methyl) propenoic acid triethene oxide, di (2-methyl) propenoic acid tetraethene oxide, di (2-methyl) propenoic acid Polyethene oxide, di (2-methyl) propenoic acid propene oxide, di (2-methyl) propenoic acid dipropene oxide, di (2-methyl) propenoic acid tripropene oxide, di (2-methyl) propenoic acid polypropene oxide , Di (2-methyl) propenoic acid butene oxide, di (2-methyl) propenoic acid pentene oxide, di (2-methyl) propenoic acid 2,2-dimethylpropyl, di (2-methyl) propenoic acid hydroxypivalylhydroxy Pivalate (common name: Manda), di (2-methyl) propenoic acid hydride Xipivalyl hydroxypivalate dicaprolactonate, 1,6-hexanediol di (2-methyl) propenoate, 1,2-hexanediol di (2-methyl) propenoate, di (2-methyl) propenoic acid 1 , 5-hexanediol di, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8-octane Diol, di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,9-nonanediol di, di (2-methyl) propenoic acid 1,2-decanediol, di ( 2-methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dode Diol, di (2-methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2 -Methyl) propenoic acid 1,16-hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentanediol, di (2- Methyl) propenoate 3-methyl-1,5-pentanediol, di (2-methyl) propenoate 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoate 2,4- Dimethyl-2,4-pentanediol, di (2-methyl) propenoic acid 2,2-diethyl-1,3-propanediol, di (2-methyl) propenoic acid 2, , 4-trimethyl-1,3-pentanediol, dimethyloloctane di (2-methyl) propenoate, 2-ethyl-1,3-hexanediol di (2-methyl) propenoate, di (2-methyl) propene Acid 2,5-dimethyl-2,5-hexanediol, di (2-methyl) propenoic acid 2-methyl-1,8-octanediol, di (2-methyl) propenoic acid 2-butyl-2-ethyl-1 , 3-propanediol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propenoic acid 1,5-hexanediol, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8 Octanediol, 1,2-octanediol di (2-methyl) propenoate, 1,9-nonanediol di (2-methyl) propenoate, 1,2-decanediol di (2-methyl) propenoate, di (2-methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanediol, di (2-methyl) 1,2-dodecanediol propenoic acid, 1,14-tetradecanediol di (2-methyl) propenoate, 1,2-tetradecanediol di (2-methyl) propenoate, 1,16 di (2-methyl) propenoic acid -Hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentane, di 2-methyl) propenoic acid 3-methyl-1,5-pentanediol, di (2-methyl) propenoic acid 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoic acid 2, 4-dimethyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol di (2-methyl) propenoate, 2,2,4-trimethyl-di (2-methyl) propenoate 1,3-pentanediol, di (2-methyl) propenoic acid dimethyloloctane, di (2-methyl) propenoic acid 2-ethyl-1,3-hexanediol, di (2-methyl) propenoic acid 2,5- Dimethyl-2,5-hexanediol, di (2-methyl) propenoate 2-butyl-2-ethyl-1,3-propanediol, di (2-methyl) propenoate 2,4-diethyl-1,5- Penta Diol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, di (2-methyl) propenoic acid tricyclodecane dimethylol, di (2-methyl) propenoic acid tricyclodecane dimethylol dicapro Lactonate, tetraethene oxide adduct of di (2-methyl) -2,2-bis (hydroxyphenyl) propane, tetraethene oxide addition of di (2-methyl) propenoic acid 2,2-bis (hydroxyphenyl) methane , Tetraethene oxide adduct of di (2-methyl) propenoic acid-4,4′-sulfonyldiphenol, tetraethene of di (2-methyl) propenoic acid-water added 2,2-bis (hydroxyphenyl) propane Oxide adduct, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane tetra Tenoxide adduct, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (2-Methyl) propenoic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) methane Examples include tetraethene oxide adduct-dicocaprolactonate.

Tri (2-methyl) propenoic acid glycerin, tri (2-methyl) propenoic acid trimethylolpropane, tri (2-methyl) propenoic acid trimethylolpropane tricaprolactonate, tri (2-methyl) propenoic acid as trifunctional monomers Trimethylolethane, trimethylolhexane tri (2-methyl) propenoate, trimethyloloctane tri (2-methyl) propenoate, pentaerythritol tri (2-methyl) propenoate, tri (2-methyl) propenoic acid 1,1 1,1-trishydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylpropane and the like,
Tetra (2-methyl) propenoic acid pentaerythritol, tetra (2-methyl) propenoic acid pentaerythritol tetracaprolactonate, tetra (2-methyl) propenoic acid diglycerin, tetra (2-methyl) ) Protriic acid ditrimethylolpropane, tetra (2-methyl) propenoic acid ditrimethylolpropane tetracaprolactonate, tetra (2-methyl) propenoic acid ditrimethylolethane, tetra (2-methyl) propenoic acid ditrimethylolbutane, tetra ( 2-methyl) propenoic acid ditrimethylolhexane, tetra (2-methyl) propenoic acid ditrimethyloloctane, tetra (2-methyl) propenoic acid dipentaerythritol, hexa (2-methyl) propenoic acid dipentaerythritol, Tripentaerythritol sa (2-methyl) propenoate, hepta (2-methyl) propenoate tripentaerythritol, octa (2-methyl) propenoate tripentaerythritol, hepta (2-methyl) propenoate dipentaerythritol polyalkene oxide And polyfunctional (2-methyl) propenoic acid esters.

Examples of the alkenyl group-containing compound include ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenyl. Tenylbenzene, 1? Chloro? 4? Aromatic ethenyl monomers such as isopropenylbenzene, ethenylbenzenesulfonic acid and its sodium and potassium salts; fluorine-containing ethenyls such as perfluoroethene, perfluoropropene, perfluoro (propyl vinyl ether), and ethenylidene fluoride System monomers;
For example, trialkyloxysilyl group-containing ethenyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; cis-butenedioic acid diallyl, 2-methylidene succinate diallyl, (E) -but-2-enoic acid Ethenyl ester monomers further containing an unsaturated bond such as ethenyl, (Z) -octadec-9-enoic acid ethenyl, (9Z, 12Z, 15Z) -octadeca-9,12,15-trienoic acid ethenyl; , Ethene oxide diethenyl ether, diethene oxide diethenyl ether, triethene oxide diethenyl ether, propene oxide diethenyl ether, dipropene oxide diethenyl ether, butanediol diethenyl ether, hexanediol diethenyl ether, cyclohexane dimethanol diene Tenil A Di- or triethenyl ether compounds such as ter, trimethylolpropane triethenyl ether, ethyl ethenyl ether, n-butyl ethenyl ether, isobutyl ethenyl ether, octadecyl ethenyl ether, cyclohexyl ethenyl ether, hydroxybutyl ethenyl ether, 2-ethylhexyl ethenyl ether, Monoethenyl containing unsaturated bonds such as cyclohexanedimethanol monoethenyl ether, n-propyl ethenyl ether, isopropyl ethenyl ether, isoproethenyl ether-O-propylene carbonate, dodecyl ethenyl ether, diethene oxide monoethenyl ether, octadecyl ethenyl ether, etc. Luether monomers; 2-propenenitrile, 2-methyl-2-propenenitrile, etc. Nitrile group-containing vinyl monomers; propenamide, 2-methylpropenamide, N-hydroxymethyl (2-methyl) propenamide, N-hydroxyethyl (2-methyl) propenamide, N-hydroxybutyl (2 -Methyl) propenamide, N-methoxymethyl (2-methyl) propenamide, N-ethoxymethyl (2-methyl) propenamide, N- (n-, iso-) butoxymethyl (2-methyl) propenamide, N Amide group-containing ethenyl monomers such as -methoxyethyl (2-methyl) propenamide, N-ethoxyethyl (2-methyl) propenamide, N- (n-, iso-) butoxyethyl (2-methyl) propenamide Ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate, benzene carboxylate Ethenyl esters such as nyl, ethenyl 3-phenyl-2-propenoate; 2-carboxyethyl propenoate, 2-methylidene succinic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, Unsaturated carboxylic acids such as 2-methylfumaric acid; unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione; and monoalkyl esters and dialkyl esters of the unsaturated carboxylic acids, Examples include chloroethylene, 1,1-dichloroethylene, allyl chloride, and allyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  Further, in obtaining the conductive copolymer used in the present invention, other compounds having an α, β-unsaturated double bond other than these can be used if necessary, and examples of such compounds Examples of maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; ethene, propene, 1-butene, 2- Alkenes such as butene and 2-methylpropene; dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like Is mentioned.

The conductive copolymer used in the present invention is selected by appropriately selecting an α, β-unsaturated compound to be used for polymerization, so that a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, a nitrile group are included in the structure. And various functional groups such as an oxirane group, an alkoxysilyl group, and an allyl group. In view of the crosslinking reactivity with the curing agent (B) described later, it preferably has a carboxyl group and / or a hydroxyl group.
In the conductive copolymer of the present invention, the ratio of the conductive polyaniline (1) having an α, β-ethylenically unsaturated bond to the other compound (2) having an ethylenically unsaturated bond is (1) / ( 2) = 0.01 / 99.99 to 95/5 (weight ratio) is preferable, (1) / (2) = 0.1 / 99.9 to 60/40 (weight ratio) is more preferable, (1 ) / (2) = 1/99 to 50/50 (weight ratio) is most preferable. Although the preferred range differs depending on each application, when the conductive copolymer (A) is used as a pressure-sensitive adhesive, the expected conductivity cannot be obtained when the proportion of (1) is less than 0.01. There is a fear. If it exceeds 95 or more, the stability of the conductive polyaniline (1) may be impaired.

  The conductive copolymer of the present invention can be used in various applications regardless of whether it is aqueous, solvent-based or solvent-free by appropriately selecting an α, β-unsaturated compound to be used for polymerization. It is possible to improve compatibility. For example, it can also be applied to printing inks, paints and coating agents, general adhesives, plastic master batches and compounds.

A preferred embodiment in which the conductive copolymer of the present invention is used as a conductive pressure-sensitive adhesive will be described.
In order for the conductive pressure-sensitive adhesive to exhibit well-balanced adhesive properties (particularly both tack and cohesive force), the compound (2) having an ethylenically unsaturated bond selected by polymerization of the conductive copolymer is: The glass transition point (Tg) of the conductive copolymer is preferably selected to be -80 to -10 ° C, more preferably -60 to -10 ° C. When the glass transition point is less than −80 ° C., the cohesive force of the conductive pressure-sensitive adhesive layer described later is lowered, and there is a possibility that floating and peeling occur. On the other hand, when the glass transition point exceeds 10 ° C., the adhesive force of the conductive pressure-sensitive adhesive layer may be insufficient.

  Therefore, the compound (2) having an ethylenically unsaturated bond is preferably a compound capable of forming a homopolymer having a glass transition point (Tg) of −50 ° C. or less. Specifically, for example, 2-ethylhexyl propenoate, n-butyl propenoate, n-octyl propenoate, iso-octyl propenoate, iso-octyl propenoate, n-nonyl propenoate, iso-nonyl propenoate, propenoic acid Examples include alkyl side chain propenoates or 2-methylpropenoates such as n-decyl, lauryl propenoate, stearyl propenoate, decyl 2-methylpropenoate, lauryl 2-methylpropenoate and stearyl 2-methylpropenoate. be able to. The above compound is preferably contained in an amount of 20 to 80% by weight in a total of 100% by weight of the compound (2) having an ethylenically unsaturated bond.

  Further, as other α, β-unsaturated compounds, homopolymers having a glass transition point (Tg) in the range of −20 to 200 ° C. in order to control the cohesive force of the conductive pressure-sensitive adhesive layer and improve heat resistance. It is also preferable to use an alkenyl group-containing compound or an α, β-unsaturated carboxylic acid ester capable of forming As such a compound, for example, a compound having a functional group such as hydroxyl group, carboxyl group, amino group, amide group, maleimide group, nitrile group, oxirane group, alkoxysilyl group, and allyl group is preferable.

  Furthermore, in order to form a homogeneous cross-linked structure with the curing agent (A) described later, the functional group is more preferably a carboxyl group or a hydroxyl group.

  Furthermore, when the functional group is a carboxyl group, it is preferable to use, for example, propenoic acid or 2-methylpropenoic acid.

  The weight average molecular weight (Mw) of the conductive copolymer is preferably 50,000 to 2,000,000 from the viewpoint of adhesiveness, and more preferably in the range of 200,000 to 1,500,000. . If Mw exceeds 2,000,000, the fluidity of the copolymer may be insufficient. If it is less than 50,000, the cohesive force of the conductive pressure-sensitive adhesive layer may be insufficient.

  The conductive copolymer in the present invention has a functional group capable of reacting with the curing agent (B) described later in its structure, and is obtained by polymerizing the α, β-unsaturated compound as described above. It is. The polymerization method is, for example, mass polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. using 0.001 to 5 parts by weight of a polymerization initiator with respect to 100 parts by weight of the α, β-unsaturated compound. It is synthesized by a method, preferably by solution polymerization.

  Examples of the polymerization initiator include azo compounds and peroxides. Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate), 4 , 4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] And azo compounds such as

  Examples of the peroxide include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate and di (2-ethoxyethyl) peroxydi. Carbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide and dipropionylperoxide And organic peroxides such as diacetyl peroxide.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, chain transfer agents such as α-methylethenylbenzene dimer and limonene may be used.

  The curing agent (B) used in the present invention is a compound having in the molecule a functional group capable of reacting with a functional group in the conductive copolymer. Examples of such a compound include a polyisocyanate compound, an oxirane compound, An amine compound, an aziridine compound, a carbodiimide compound, an oxazoline compound, a melamine compound, a metal chelate and the like can be mentioned. Among these, a compound having two or more functional groups in the molecule is preferably used.

  When the functional group of the conductive copolymer is a carboxyl group, examples of the functional group of the curing agent (B) include an isocyanate group, an oxirane group, an amino group, an aziridyl group, and an oxazoline group.

  When the functional group of the conductive copolymer is a hydroxyl group, examples of the functional group of the curing agent (B) include an isocyanate group and an N-methylol group.

  Among these, a polyisocyanate compound is particularly preferably used because it is excellent in the adhesion of the resin composition after the crosslinking reaction and the adhesion to the coating layer.

  Examples of the polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-triisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. can be mentioned.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, dodecamethylene diisocyanate. 2,4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl- Examples include 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane and the like.

  In addition, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, etc. can be used in combination. Furthermore, polyphenylmethane polyisocyanate (PAPI), naphthene diisocyanate, and these polyisocyanate modified products can also be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a polyisocyanate.

  These polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), xylylene diisocyanate, 4,4′-methylenebis. From the viewpoint of weather resistance, it is particularly preferable to use a non-yellowing or hardly yellowing polyisocyanate compound such as (cyclohexyl isocyanate) (hydrogenated MDI).

  When using a polyisocyanate compound as a hardening | curing agent (B), a well-known catalyst can be used as needed for reaction promotion. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use alone or in combination.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like, which can be used alone or in combination.

  Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate , Triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.

  Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Examples thereof include iron-based compounds such as iron ethylhexanoate and iron acetylacetonate, cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexate, zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. .

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Examples of oxirane compounds include 2,2-bis (hydroxyphenyl) propane / 2-chloromethyloxirane type oxirane resins, 2,2-bis (hydroxyphenyl) methane type, and 2,2-bis (4 -Hydroxyphenyl) ethane type, 2,2-bis (4-hydroxyphenyl) butane type, 4,4'-sulfonyldiphenol type, 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethene type 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene type, 2,2-bis (4-hydroxy-3-methylphenyl) propane type, 2,2-bis (4-hydroxy) -3-methylphenyl) methane type, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane type, 2,2-bis (4-hydroxy-3, -Dimethylphenyl) propane type, 2,2-bis (4-hydroxycyclohexyl) propane type, 2,2-bis (2-hydroxy-5-biphenylyl) propane type and copolymerized oxirane resins thereof, Phenol novolak type, orthocresol novolak type, para tertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethene oxide diglycidyl ether, polyethene oxide diglycidyl ether, glycerin diglycidyl Ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane and the like can be mentioned.

  Examples of the amine compound are preferably polyamines having two or more primary amino groups, and a polyamine having two or more primary amino groups not directly bonded to an aromatic ring from the viewpoint of excellent curing speed. An aromatic polyamine (which may contain an aromatic ring in its skeleton) is preferred.

Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbon at both ends of the molecule. Polypropylene glycol having an amino group bonded thereto (a propylene skeleton diamine, such as “Jeffamine D230” or “Jephamine D400” manufactured by Sun Techno Chemical Co., Ltd., or the like), a propylene skeleton triamine, such as “Jephamine T403”, or the like. , Propenediamine, butenediamine, diethenetriamine, triethenetetramine, tetraethenepentamine, pentaethenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diaminopropane, Mino bis propylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [ Sun Techno Chemical Co., Ltd. "Jeffamine EDR148" (ethylene glycol skeleton diamine)] amines such as Polyether skeleton diamine with methylene group bonded to nitrogen, 1,5-diamino-2-methylpentane (“MPMD” manufactured by DuPont Japan), metaxylylenediamine (MXDA), polyamidoamine (manufactured by Sanwa Chemical Co., Ltd.) "X2000"), isophoronediamine, 1,3-bisaminomethylcyclohexane ("1,3BAC" manufactured by Mitsubishi Gas Chemical Company), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5- Trimethyl-cyclohexylamine, dimethyleneamine with a norbornane skeleton (Mitsui Chemicals) Mention may be made of the company made "NBDA"), and the like.

Among these, particularly high curing speed, 1,3-bis aminomethyl cyclohexane, dimethylene amines norbornane skeleton, _{m-xylylenediamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH ₂ (Ethenediol skeleton diamine), propene skeleton diamine, propene skeleton triamine, and polyamidoamine (trade name: X2000) are useful.

  Ketimine, which is a reaction product of these polyamines and ketones, is also included in the amino compound, and from the viewpoints of stability, reactivity adjustment and overcoatability, acetophenone or propiophenone and 1,3-bisaminomethylcyclohexane Obtained from acetophenone or propiophenone and dimethyleneamine (NBDA) having a norbornane skeleton; obtained from acetophenone or propiophenone and metaxylylenediamine; acetophenone or propiophenone; Obtained from Jeffamine EDR148, Jeffamine D230, Jeffamine D400, etc. which are diamines of ethene oxide skeleton or propene oxide skeleton, or Jeffamine T403, which is triamine of propene skeleton It can also be used.

  Urea, melamine, benzoguanamine, cyclohexanecarboguanamine, steroguanamine, spiroguanamine, acetoguanamine, phthalogamine, 2- (4,6-diamino-1,3,5-triazin-2-yl) -benzoic acid, 3- (4,6-diamino-1,3,5-triazin-2-yl) -benzoic acid, 4- (4,6-diamino-1,3,5-triazin-2-yl) -benzoic It is also possible to use a compound in the form of a compound obtained by addition condensation of a so-called amino group-containing compound such as acid with an aldehyde compound and at the same time etherification with a monohydric alcohol.

  Examples of aziridine compounds include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisiso Phthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropane-tri-β -Aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane tris [ 3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) butyrate], Trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], pentaerythritol tetra [3- (1- Aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-etheneurea, 1,6-hexamethylenebis-N, N'-etheneurea, 2,4,6- (triethyleneimino) -Syn-triazine Bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, and the like.

  As the carbodiimide compound, a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and known polycarbodiimides can be used.

  Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide which produced | generated diisocyanate by the decarboxylation condensation reaction in presence of a carbodiimidization catalyst can also be used.

Examples of such compounds include those obtained by decarboxylation condensation reaction of the following diisocyanates.
As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  As the oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′-ethenebis (2-oxazoline), 2, 2'-ethenebis (4-methyl-2-oxazoline), 2,2'-propenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2 -Oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl- 2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4-phenyl-2-one) Sazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4 '-Dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-o -Phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4- Ethyl-2-oxazoline), 2,2′-bis (4-phenyl-2-oxazoline) and the like. Alternatively, other monomers that can be copolymerized with ethenyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and this ethenyl monomer And a copolymer thereof.

  The melamine compound is a compound having a triazine ring in the molecule, and examples thereof include melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, vinylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine and the like. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

  Examples of metal chelate compounds include compounds in which polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium are coordinated to acetylacetone and ethyl acetoacetate. Can be mentioned.

  The conductive pressure-sensitive adhesive of the present invention preferably uses 0.001 to 50 parts by weight of the curing agent (B) with respect to 100 parts by weight of the conductive copolymer, and contains 0.01 to 20 parts by weight. Is more preferable. If the amount of the curing agent (B) used exceeds 50 parts by weight, the adhesiveness of the resulting resin composition tends to decrease, and if it is less than 0.001 parts by weight, the cohesive strength decreases and the heat resistance and heat-and-moisture resistance decrease. Tend to.

  Since the three-dimensional crosslinking is caused by the reaction between the functional group in the conductive copolymer and the functional group in the curing agent (A), the coating of polyaniline (1) becomes strong and the polyaniline ( 1) The separation of the coating layer is reduced, not only ensuring adhesion with various adherends, but also suppressing the change in conductivity due to localization of the conductive polyaniline (1) contained, The heat resistance and heat-and-moisture resistance under severe conditions such as high temperature and high temperature and humidity can be improved, and it can be preferably used for optical members.

  The conductive pressure-sensitive adhesive of the present invention includes, for example, polyolefin resin, acrylic resin, alkyd resin, ethenyl resin, polyester resin, polyamide resin, polyimide resin, ABS resin, polystyrene resin, polyurethane resin, phenol resin, amino resin, and polyether. Resins, polycarbonate resins, polyacetal resins, polyarylate resins, epoxy resins, polysulfone resins, and elastomers such as polybutadiene and polyisoprene can be blended as necessary.

  The conductive pressure-sensitive adhesive of the present invention has various resins, silane coupling agents, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, tackifiers, and the like as long as the effects of the present invention are not impaired. You may mix | blend a fire, a plasticizer, a filler, an anti-aging agent, etc.

  A laminated product (hereinafter referred to as “adhesive sheet”) composed of a conductive pressure-sensitive adhesive layer and a sheet-like substrate can be obtained using the conductive pressure-sensitive adhesive of the present invention. For example, an adhesive sheet can be obtained by coating, drying and curing the conductive pressure-sensitive adhesive of the present invention on various sheet-like substrates.

  When applying the conductive pressure-sensitive adhesive, an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, methyl acetate, toluene, methyl ethyl ketone, acetone, isopropyl alcohol, other hydrocarbon solvents, or water is further added. Thus, the viscosity can be adjusted, or the conductive pressure-sensitive adhesive can be heated to lower the viscosity.

  Examples of the sheet-like base material include cellophane, various plastic sheets, rubber, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood and the like in a flat shape. Moreover, various base materials can also be used independently, and the thing in the multilayer state formed by laminating | stacking a several base material can also be used. Further, the surface can be peeled off.

Various plastic sheets, also called various plastic films, are films of polyolefin resins such as polyvinyl alcohol film, triacetyl cellulose film, polypropene, polyethene, polycycloolefin, ethylene-vinyl acetate copolymer, polyethylene terephthalate and polybutylene terephthalate. Polyester resin film, Polycarbonate resin film, Polynorbornene resin film, Polyarylate resin film, Acrylic resin film, Polyphenylene sulfide resin film, Polystyrene resin film, Ethenyl resin film Polyamide resin film, polyimide resin film, oxirane resin film, and the like.

  After applying a conductive pressure-sensitive adhesive to the sheet-like base material by an appropriate method according to a conventional method, if the conductive pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, a method such as heating If the liquid medium is removed or the conductive pressure-sensitive adhesive does not contain a liquid medium to be volatilized, the conductive pressure-sensitive adhesive layer in the molten state is cooled and solidified, A conductive pressure sensitive adhesive layer can be formed thereon.

  The thickness of the conductive pressure-sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 0.1 μm to 100 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

  The method for applying the conductive pressure-sensitive adhesive of the present invention to a sheet-like substrate is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife. Various coating methods such as a coater, reverse coater, spin coater and the like can be mentioned.

  There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the cured form of the pressure-sensitive adhesive composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

  In the conductive adhesive sheet of the present invention, a conductive pressure-sensitive adhesive layer made of the conductive pressure-sensitive adhesive of the present invention is preferably formed on the optical film. Furthermore, a sheet-like base material (also referred to as a release film) subjected to a release treatment can be laminated on the other surface of the conductive pressure-sensitive adhesive layer. In the present invention, the optical film is a so-called sheet (also referred to as a film as described above) having optical characteristics such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, and a color correction film. is there.

The conductive adhesive sheet of the present invention is preferably produced by the following method.
(A) A method of forming a sheet-like optical member on the surface of the conductive pressure-sensitive adhesive layer by coating and drying a conductive pressure-sensitive adhesive on the release-treated surface of the release film.
(A) A method in which a conductive pressure-sensitive adhesive is applied to a sheet-like substrate, dried, a conductive pressure-sensitive adhesive layer is formed, and a release treatment surface of a release film is laminated on the surface.

  The release film is peeled off from the conductive adhesive sheet thus obtained and, for example, a conductive pressure-sensitive adhesive layer is adhered to a glass member for a liquid crystal cell, thereby forming a sheet-like optical film / adhesive layer / liquid crystal cell glass. A laminate for a liquid crystal cell having a configuration of members can be obtained.

  In addition, when the conductive adhesive sheet of the present invention is used for protecting the optical member described above, a conductive material formed from the conductive pressure-sensitive adhesive of the present invention is applied to various plastic sheets that are optical laminate protective films. It is also preferred to use a conductive adhesive sheet in which a pressure sensitive adhesive layer is laminated and a release film is laminated on the other surface of the conductive pressure sensitive adhesive layer. Then, the release film is peeled off from the conductive adhesive sheet and, for example, a conductive pressure-sensitive adhesive layer is adhered to the optical member, thereby obtaining a conductive protective sheet laminate having a configuration of protective sheet / adhesive layer / optical member. it can. And when this electroconductive protection sheet is peeled from the optical member, there is an effect that the optical member is not peeled off.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Synthesis of conductive polyaniline (1)>
(Synthesis Example 1)
11.2 g (120 mmol) of aniline is added to and dissolved in an aqueous solution in which 1.96 g (20 mmol) of sulfuric acid and 103.6 g of distilled water are mixed. ) Was added and dissolved. After cooling the solution temperature to 0 ° C. or lower, an aqueous solution obtained by dissolving 32.88 g of ammonium persulfate (oxidant) (144 mmol <1.2 times the amount of aniline>) in 32.2 g of distilled water was added dropwise over 120 minutes. Then, oxidation polymerization was performed, and the mixture was further stirred at 0 ° C. or lower for 2 hours. After completion of the reaction, 500 g of distilled water was added and precipitated and precipitated, washed with distilled water and methanol, filtered and dried to obtain a conductive polyaniline having a pre-doped type α, β-ethylenically unsaturated bond.

(Synthesis Examples 2 to 6)
As the dopant used in Synthesis Example 1, tert-butyl-2-propenenitrile sulfonic acid was changed to methallyloxybenzene sulfonic acid (Synthesis Example 2), ammonium allyloxybenzene sulfonate (Synthesis Example 3), ethenylbenzene sulfonic acid. Conductive polyaniline (1) was polymerized in the same manner as in Synthesis Example 1 except that sodium (Synthesis Example 4), 2-sulfoethyl propenoate (Synthesis Example 5), and dodecylbenzenesulfonic acid (Synthesis Example 6) were changed. Got.

(Synthesis Example 7)
To an aqueous solution in which 1.96 g (20 mmol) of sulfuric acid and 103.6 g of distilled water were mixed, 11.2 g (120 mmol) of aniline was added and dissolved. After cooling the solution temperature to 0 ° C. or lower, an aqueous solution obtained by dissolving 32.88 g of ammonium persulfate (oxidant) (144 mmol <1.2 times the amount of aniline>) in 32.2 g of distilled water was added dropwise over 120 minutes. Then, oxidation polymerization was performed, and the mixture was further stirred at 0 ° C or lower for 2 hours. After the reaction, 500 g of 4N-ammonia water was added and stirred at 0 ° C. or lower for 4 hours. Thereafter, 500 g of methanol was added to cause precipitation, washed with distilled water and methanol, filtered and dried to obtain dedope-type polyaniline. Next, 10.2 g of the obtained undoped polyaniline was dissolved in 100 g of N-methyl-2-pyrrolidone, 24.88 g (120 mmol) (dopant) of tert-butyl-2-proponitrile sulfonic acid was added, and the reaction was performed. After completion, 500 g of distilled water is added to precipitate and precipitate, washed with distilled water and methanol, filtered and dried to obtain a conductive polyaniline (1) having a post-dope type α, β-ethylenically unsaturated bond. It was.

(Synthesis Example 8)
A conductive polyaniline (1) was obtained by polymerization in the same manner as in Synthesis Example 7 except that the dopant used in Synthesis Example 7 was changed except that dodecylbenzenesulfonic acid was changed.

  In the conductive polyaniline (1) obtained in Synthesis Examples 1 to 8, the yield, the average particle diameter (in toluene), the weight average molecular weight (Mw), the surface resistance value of the coating film and the stability over time are determined according to the following methods. The results are shown in Table 1.

"yield"
It was calculated from the weight of the raw material aniline, the dopant and the oxidizing agent and the weight of the conductive polyaniline (1) produced, and expressed as a percentage (%) as a yield.

<< Measurement of average particle size (in toluene) >>
2 g of the obtained conductive polyaniline was dispersed in 18 g of toluene, and the average particle diameter (nm) was measured at 25 ° C. with MICROTRAC 9349-UPA manufactured by Nikkiso Co., Ltd.

<Measurement of surface resistance of coating film>
5 g of propenoic acid ester copolymer resin solution (BPS5227-1 manufactured by Toyo Ink Co., Ltd., non-volatile content: 40%) is added to a dispersion of 2 g of the obtained conductive polyaniline in 18 g of toluene, and the resulting solution is placed on a polyethylene terephthalate film. It was applied with a # 3 bar coater and dried by heating at 100 ° C. for 2 minutes to obtain a transparent coating film having a thickness of about 1.2 μm. The surface resistance value (Ω / □) of this coating film was measured with a surface resistance meter MCT-HT450 (manufactured by Mitsubishi Chemical Corporation) at 23 ° C.-65% RH.

<< Measurement of weight average molecular weight (Mw) >>
Mw was measured using Showa Denko GPC (Gel Permeation Chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<< Stability over time >>
A dispersion of 2 g of the obtained conductive polyaniline in 18 g of toluene was placed in a 30 ml screw tube and allowed to stand at room temperature for 6 months, and the sedimentation and separation of particles were visually evaluated as follows.

○: “No abnormality”
Δ: “Slightly separated.”
×: “There is sedimentation, which is bad.”

<Synthesis of conductive copolymer>
(Synthesis Example 9)
A compound having a conductive polyaniline (1) and an ethylenically unsaturated bond (2) in a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube (2 ) Etc. were charged at the following ratios.

[Polymerization tank]
10 parts of conductive polyaniline (1) obtained in Synthesis Example 1
N-butyl propenoate 29 parts methyl propenoate 10 parts propenoic acid 0.5 parts ethyl acetate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [drip apparatus]
N-butyl propenoate 50 parts propenoic acid 0.5 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part The air in the polymerization tank was replaced with nitrogen gas, and then a nitrogen atmosphere with stirring. The reaction was started under reflux temperature. When the polymerization rate reached about 70%, the dropping of the mixture of the α, β-unsaturated compound, the polymerization initiator and the organic solvent was started from the dropping device. After completion of dropping, the mixture was further aged for 8 hours with stirring, and then 167 parts of toluene was added and cooled to room temperature to obtain a solution containing a conductive copolymer.

(Synthesis Examples 10 to 16)
The conductive polyaniline (1) used in Synthesis Example 1 was changed to the conductive polyaniline (1) obtained in Synthesis Examples 2 to 8, and the others were polymerized in the same manner as in Synthesis Example 1, A solution containing coalescence was obtained.

(Synthesis Example 17)
The conductive polyaniline (1) used in Synthesis Example 1 was not used, the composition of the compound (2) having an ethylenically unsaturated bond was slightly changed, and the polymerization tank and the dropping apparatus were respectively charged at the following ratios, Was polymerized in the same manner as in Synthesis Example 1 to obtain a solution containing the copolymer (A).

[Polymerization tank]
N-butyl propenoate 29 parts methyl propenoate 20 parts propenoic acid 0.5 parts ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
N-butyl propenoate 50 parts propenoic acid 0.5 parts ethyl acetate 36 parts 2,2′-azobisisobutyronitrile 0.05 part (Synthesis Example 18)
The composition of the compound (2) having an ethylenically unsaturated bond used in Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. Methyl ethyl ketone: 167 parts were added to obtain a solution containing the conductive copolymer (A).

[Polymerization tank]
10 parts of conductive polyaniline (1) obtained in Synthesis Example 1
2-ethylhexyl propenoate 30 parts n-butyl propenoate 10 parts 2-hydroxyethyl propenoate 0.5 parts ethyl acetate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [drip apparatus]
2-ethylhexyl propenoate 20 parts n-butyl propenoate 9 parts 2-methylpropenoic acid ethene oxide adduct
(Mole number of ethene oxide added: 9) 20 parts 2-hydroxyethyl propenoate 0.5 parts ethyl acetate 36 parts 2,2′-azobisisobutyronitrile 0.05 part

(Synthesis Example 19)
The composition of the compound (2) having an ethylenically unsaturated bond used in Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. Methyl ethyl ketone: 167 parts were added to obtain a solution containing a conductive copolymer.

[Polymerization tank]
10 parts of conductive polyaniline (1) obtained in Synthesis Example 1
N-butyl propenoate 10 parts 2-methoxyethyl propenoate 5 parts propenoic acid 1 part 2-hydroxyethyl propenoate 0.1 part methyl acetate 20 parts ethyl acetate 10 parts 2,2′-azobisisobutyronitrile 05 parts [Drip device]
N-butyl propenoate 42 parts 2-methoxyethyl propenoate 30 parts propenoic acid 1.8 parts 2-hydroxyethyl propenoate 0.1 part ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

  For the conductive copolymers obtained in Synthesis Examples 9 to 19, the solution appearance, nonvolatile content concentration (%), solution viscosity, weight average molecular weight (Mw), and glass transition point (Tg) were determined according to the following methods, and the results were obtained. Are shown in Table 2.

<< Solution appearance >>
The appearance of the conductive copolymer solution was visually evaluated.

<Measurement of non-volatile content>
About 1 g of the conductive copolymer solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated to obtain the non-volatile content concentration (%).

<< Measurement of solution viscosity >>
The conductive copolymer solution was measured at 23 ° C. with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) using a # 3 or 4 rotor at 12 rpm for 1 minute, and the solution viscosity (mPa · s).

<< Measurement of weight average molecular weight (Mw) >>
Mw was measured using Showa Denko GPC (Gel Permeation Chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

<< Measurement of glass transition point (Tg) >>
The measurement was performed by connecting a “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) to a robot DSC (differential scanning calorimeter) “RDC220” (manufactured by Seiko Instruments Inc.). About 10 mg of a sample was weighed, adjusted to an aluminum pan, and then set in a DSC apparatus (reference: the same type of aluminum pan without a sample). The sample was heated at 10 ° C./min under a nitrogen stream, and the glass transition point (Tg: ° C.) was measured from the endothermic and exothermic peaks of the DSC chart.

Example 1
TAT (tris-2,4,6- (1-aziridinyl) -1,3,5-triazine) as a curing agent (A) with respect to 100 parts by weight of the copolymer solution obtained in Synthesis Example 9 0.06 part by weight was added and stirred well to obtain a conductive pressure sensitive adhesive. This is coated on a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying is 25 μm, and dried at 100 ° C. for 2 minutes to form a conductive pressure-sensitive adhesive layer. did. One side of the antireflection film was brought into contact with the formed conductive pressure-sensitive adhesive layer to obtain a laminate having a structure of release film / conductive pressure-sensitive adhesive layer / antireflection film.

(Examples 2 to 6)
Example 1 and Example 1 were used except that the conductive copolymer solution obtained in Synthesis Example 10-13 or 15 was used instead of the conductive copolymer solution of Synthesis Example 9 used in Example 1. Similarly, an antireflection film subjected to pressure-sensitive adhesive processing was obtained.

(Comparative Examples 1 and 2)
In place of the conductive copolymer solution of Synthesis Example 9 used in Example 1, Synthesis Examples 14 and 16 were used in the same manner as in Example 1 except that the antireflection film subjected to pressure-sensitive adhesive processing was used. Obtained.

(Examples 7 and 8)
Instead of the conductive copolymer solution of Synthesis Example 9 used in Example 1, 3 parts of the polyaniline of Synthesis Example 1 or 15 was added using the conductive copolymer solution obtained in Synthesis Example 17. As a curing agent (B), TAT: 0.06 part by weight was added and stirred well to obtain a conductive pressure-sensitive adhesive, and an antireflection film was obtained in the same manner as in Example 1.

(Comparative Examples 3 and 4)
Antireflection film in the same manner as in Examples 7 and 8, except that the polyaniline obtained in Synthesis Examples 6 and 8 was used instead of the polyaniline in Synthesis Example 1 or 15 used in Examples 7 and 8, respectively. Got.

(Examples 9 and 10)
Instead of TAT of the curing agent (B) used in Example 1, TDI / TMP (trimethylopropanepropane adduct of tolylene diisocyanate), TGMXDA (N, N, N ′, N′-tetraglycidyl-m -Xylylenediamine) An antireflection film was obtained in the same manner as in Example 1 except that 0.06 part was used.

(Example 11)
Example 1 with the exception that 1.0 part by weight of HDI (hexamethylene diisocyanate) was used as the curing agent (B) with respect to 100 parts by weight of the conductive copolymer solution obtained in Synthesis Example 18. Similarly, an antireflection film was obtained.

Example 12
For 100 parts by weight of the conductive copolymer solution obtained in Synthesis Example 19, TDI / TMP (trimethylopropane propane adduct of tolylene diisocyanate) 9.0 parts by weight as the curing agent (B). An antireflection film was obtained in the same manner as in Example 1 except that was used.

  About the antireflection film which carried out the pressure-sensitive adhesion process obtained in Examples 1-12 and Comparative Examples 1-4, the heat resistance, heat-and-moisture resistance, the optical characteristic (haze), and the surface resistance value were evaluated with the following method. The results are shown in Table 3.

<Evaluation method for heat and moisture resistance>
The antireflection film was cut into a size of 150 mm × 80 mm, the release film was peeled off, and each film was attached to both surfaces of a 1.1 mm thick float glass plate using a laminator. Subsequently, the glass plate on which the antireflection adhesive sheet was adhered was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to adhere the antireflection adhesive sheet to the glass plate. Further, the laminate of the antireflection plate and the glass plate is left to stand for 1000 hours in an environment of 120 ° C. (heat resistance), and the floating after being left for 1000 hours in an environment of 80 ° C. and 90% relative humidity. The peel (wet heat resistance) was visually observed and evaluated in three stages.

○: “No floating peeling or whitening of film”
Δ: “Slightly floating peeling or film whitening is observed, but there is no practical problem”
×: “Floating peeling, film whitening, and impractical use”

<< Evaluation Method of Optical Properties (Haze) >>
The obtained conductive pressure-sensitive adhesive was applied to a release film and dried to provide a conductive pressure-sensitive adhesive layer having a thickness of 25 μm, and then the release film was further covered. The conductive pressure-sensitive adhesive layer sandwiched between the release-treated polyester films was aged at a temperature of 23 ° C. and a relative humidity of 50% for one week, and then the release-treated polyester film was removed to give the appearance of the conductive pressure-sensitive adhesive layer alone. While judging visually, haze was measured by "NDH-300A" [made by Nippon Denshoku Industries Co., Ltd.].

○: “No problem in practical use. Haze: less than 1”
Δ: “No cloudiness is observed, but haze: 1 or more and less than 3.”
X: “Slightly cloudy is recognized and there is a problem in practical use. Or, haze: 3 or more.”

<< Evaluation of surface resistance >>
The anti-reflection adhesive sheet is cut into a size of 150 mm × 80 mm, the release film is peeled off, and the exposed conductive pressure-sensitive adhesive layer surface is 23 ° C. with a surface resistance measuring device MCT-HT450 (Mitsubishi Chemical Corporation). The surface resistance value (Ω / □) was measured under 65% RH.

The contents of the abbreviations in the table are as follows.
PAEH: 2-ethylhexyl propenoate, PAB: n-butyl propenoate, PAM: methyl propenoate, PAE: ethyl propenoate, PA: propenoic acid, PAHE: 2-hydroxyethyl propenoate, PAME: 2-methoxyethyl propenoate , EAc: ethyl acetate, MeAc: methyl acetate, Tol: toluene, TAT: Tris-2,4,6- (1-azilinyl) -1,3,5-triazine, TDI / TMP: trimethylolpropane of tolylene diisocyanate Adduct body, TGMXGA: N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, HDI: hexamethylene diisocyanate.

  Since the conductive copolymer of the present invention is doped with a protonic acid having an α, β-ethylenically unsaturated bond or a protonic acid metal salt or ammonium salt having an α, β-ethylenically unsaturated bond, α , Β-ethylenically unsaturated bond. Therefore, by arbitrarily selecting the type of the compound (2) having another ethylenically unsaturated bond, it is possible to effectively cover the surface, and the solvent is soluble, finely dispersible, or moldable without impairing conductivity. And so on. Therefore, it is possible to improve transparency, weather resistance, water resistance, hydrolysis resistance, chemical resistance, heat resistance, moist heat resistance, good stress relaxation properties, optical members and printed circuit boards constituting various displays, etc. It is suitably used for such electronic members or their surface protection members.

  Therefore, it is suitable as an optical member and electronic member, as well as paints that require electrical conductivity, elastic wall materials, waterproof coating materials, floor materials, tackifiers, adhesives, adhesives for laminated structures, sealing agents, molding materials , Surface modification coating agent, binder (magnetic recording medium, ink binder, casting binder, fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), urethane foam (hard, semi-rigid, soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, fiber processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, resin for artificial marble, impact resistance for artificial marble Giving agent, ink resin, film (laminate adhesive, protective film, etc.), laminated glass resin, reactivity Shakuzai, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

Claims (15)

a conductive polyaniline (1) having an α, β-ethylenically unsaturated bond;
Conductive copolymer obtained by radical copolymerization of conductive polyaniline (1) and compound (2) having an ethylenically unsaturated bond capable of radical copolymerization   The conductive polyaniline (1) has an α, β-ethylenically unsaturated bond introduced by doping with a proton acid having an α, β-ethylenically unsaturated bond or a metal salt or ammonium salt thereof. The conductive copolymer according to claim 1.   The conductive polyaniline (1) is obtained by doping an aniline with a protonic acid having an α, β-ethylenically unsaturated bond, or a metal salt or an ammonium salt thereof, followed by oxidative polymerization. The conductive copolymer as described.   The conductive polyaniline (1) is obtained by doping polyaniline obtained by oxidative polymerization of aniline with a protonic acid having an α, β-ethylenically unsaturated bond, or a metal salt or ammonium salt thereof. The conductive copolymer according to 1 or 2.   The conductive copolymer according to any one of claims 2 to 4, wherein the protonic acid is sulfonic acid.   It has a carboxyl group and / or a hydroxyl group, The electroconductive copolymer in any one of Claims 1-5 characterized by the above-mentioned.   The compound (2) having an ethylenically unsaturated bond is at least one selected from the group consisting of propenoic acid, 2-methylpropenoic acid, a propenoic acid derivative having a hydroxyl group, and a 2-methylpropenoic acid derivative having a hydroxyl group The conductive copolymer according to claim 1, wherein the conductive copolymer is contained.   An electroconductive polyaniline (1) having an α, β-ethylenically unsaturated bond and a compound (2) having an ethylenically unsaturated bond are expressed as follows: (1) / (2) = 0.01 / 99.99-95 Conductivity according to any one of claims 1 to 7, which is a copolymer obtained by radical copolymerization at a ratio of / 5 (weight ratio), and has a glass transition temperature of -80 to 10 ° C. Copolymer.   An electroconductive pressure-sensitive adhesive comprising the electroconductive copolymer according to claim 1 and a curing agent (A) capable of reacting with a functional group in the electroconductive copolymer.   The conductive pressure-sensitive adhesive according to claim 9, comprising 0.01 to 50 parts by weight of the curing agent (A) with respect to 100 parts by weight of the conductive copolymer.   A conductive adhesive sheet comprising a conductive pressure-sensitive adhesive layer formed from the conductive pressure-sensitive adhesive according to claim 9 or 10 on at least one surface of a sheet-like substrate.   The conductive adhesive sheet according to claim 11, wherein the sheet-like substrate is an optical film.   The conductive adhesive sheet according to claim 11, wherein the sheet-like substrate is a protective film for an optical laminate. The conductive adhesive sheet according to claim 12, wherein the optical film is a film selected from the group consisting of a polarizing film and a color correction film.   A laminate for a liquid crystal cell, comprising a glass for a liquid crystal cell, a conductive pressure-sensitive adhesive layer formed from the conductive pressure-sensitive adhesive according to claim 9 or 10, and an optical film.