JP2010106245A - Low temperature thermosetting electroconductive coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for preparing electroconductive coated base materials excellent in appearance of a coating film, transparency, electroconductivity, scratch resistance, solvent resistance, adhesiveness to a base material, and the like, and also to provide the electroconductive coated base materials using the composition. <P>SOLUTION: The thermosetting electroconductive coating composition comprises: an electroconductive polymer; a heat-reactive crosslinking agent comprising a melamine resin derivative; an acid generator; and a solvent or dispersion medium. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a conductive coating composition having thermosetting properties at low temperatures and maintaining a pot life for a long time, and a conductive coated substrate using the same. Such coated substrates include liquid crystal displays, electroluminescent displays, plasma displays, electrochromic displays, solar cells, touch panels, and electronic component packaging materials such as soft trays, hard trays, carrier tapes, cover tapes, spacer tapes, etc. It can be used for imparting an antistatic function and / or a transparent electrode function to various films and sheets.

In order to impart conductivity to the resin base material, a coating solution containing a conductive polymer is used. As the conductive polymer, polythiophene, polypyrrole, polyaniline, and derivatives thereof are known. Among them, a dispersion of a composite composed of polyethylenedioxythiophene and a dopant has chemical stability and a conductive coating film to be obtained. It is widely used because of its excellent conductivity and transparency. By blending a binder resin or a surfactant with this polythiophene-based conductive polymer, it is possible to form a conductive coating film having excellent film formability and adhesion to a substrate. The coating composition for heat-resistant coating does not have thermosetting property at low temperature, and in particular, polyethylene, polypropylene, polystyrene, polyvinyl chloride, triacetyl cellulose, cycloolefin-based polymer, polyethylene terephthalate, polybutylene, which are not heat resistant. When using a substrate such as terephthalate, polyethylene naphthalate, polycarbonate, or polyacrylic polymer, heat cannot be applied sufficiently, resulting in insufficient thermosetting, and high scratch resistance, water resistance, and organic solvent resistance. A conductive coating film cannot be obtained. In particular, when a roll coating having high productivity is applied in the coating, since heat cannot be applied for a long time in the process, it is thermally cured at a relatively low temperature and in a short time, and scratch resistance and There is a need for a conductive coating composition that can form a solvent-resistant coating film.

Melamine resin is used in industrial coatings as a cross-linking agent that imparts thermosetting properties at low temperature to the coating solution, and the strength of the resin coating is improved by cross-linking of melamine, resulting in scratch resistance, water resistance, and solvent resistance. It is known that the property is imparted to the coating film. For example, Patent Document 1 shows that in a solvent-based paint, a melamine resin having a smaller imino group content and oligomer amount has better crosslinkability and promotes curing of the hydroxyl group-containing resin at a low temperature. It is described that a coating film having sufficient solvent resistance can be formed even at a low curing temperature (70 ° C. × 30 minutes) by using in combination with an acid catalyst as an agent. In Patent Document 2, a solvent-soluble conductive polymer fine particle having a surfactant structure is dissolved in a solvent together with a binder resin, and melamine is added as a crosslinking agent and cured to form a conductive layer having high conductivity. A possible conductive composition is provided.

Patent Document 3 discloses a method for forming an antistatic layer using a conductive polymer composition containing a water-soluble melamine resin. After applying an aqueous dispersion of a polythiophene-based conductive polymer containing a binder resin and a melamine resin to a substrate, a coating film excellent in adhesion and water resistance can be formed by drying and curing at 100 ° C. for 3 minutes. . Moreover, in patent document 3, since the storage stability of a compound is not good, the process of apply | coating a melamine resin containing coating liquid and a conductive polymer aqueous solution separately is proposed. In Patent Document 4, by adding a condensate of melamine resin and at least one carbonyl compound to a polythiophene-based conductive polymer dispersion, water resistance and solvent resistance of a conductive coating film containing a polyurethane resin are improved. The storage stability of the liquid is also shown to be good. In this document, by adding a dispersion solvent, it is possible to add a hydrophobic melamine resin to an aqueous solution, and an antistatic coating film excellent in solvent resistance can be prepared under curing conditions of 130 ° C. × 5 minutes.

Patent Document 5 shows the use of a radiation-sensitive acid generator as a curing accelerator for a photosensitive resin in resist applications. By adding a small amount of a urea-based resin and a melamine-based resin as a crosslinking agent, the photosensitive resin is used. Curing of is promoted. After the blended composition is applied to a substrate by a spin coating method, a resist pattern is formed through curing and development steps after acid generation by radiation irradiation.

Thus, Patent Document 1 shows that by adding a sulfonic acid catalyst as a melamine resin and a curing accelerator to the composition, low temperature curability and solvent resistance of the obtained coating film are improved. Patent Documents 2 to 4 describe use in conductive coating applications.

Special table 2003-523424 gazette JP 2006-146249 A JP 2006-119349 A JP 2007-131849 A JP 2008-106777 A

However, although patent document 1 is an organic solvent type coating composition, the conductive polymer is not mix | blended and cannot be used as a conductive coating material.

Patent Document 2 shows an example of a solvent-type conductive coating composition, but does not mention curability at low temperatures. It is difficult to say that no acid catalyst is added and the resin has sufficient low-temperature curability. Patent Document 3 mentions that the storage stability of a composition comprising an aqueous thiophene conductive polymer, a binder resin, and a melamine resin is not good. Since the crosslinking of the melamine resin crosslinking agent proceeds even in a solution, the polymerization tends to proceed under acidic conditions, and depending on the composition, gelation or precipitation occurs. In conductive polymers, anionic compounds such as sulfonic acid are often used as dopants, and the solution is often acidic. Therefore, when a melamine resin is blended, the stability of the solution is not maintained. is there. In Patent Document 4, gelation is suppressed by adding alkanolamine to a polythiophene-based conductive polymer to neutralize it, and a coating film having excellent solvent resistance can be formed while maintaining the stability of the solution. However, under such neutral conditions, the crosslinking reaction of melamine during film formation is difficult to be accelerated, and a curing condition of 130 ° C. × 5 minutes is required. At 130 ° C., it is difficult to use a base material having low heat resistance, and a curing time of 5 minutes is not desirable from the viewpoint of productivity. Thus, it is possible to form a coating film excellent in scratch resistance and solvent resistance by the addition of melamine resin, but the curability at low temperature without adding a curing accelerator such as an acid catalyst is not sufficient. On the other hand, when the acid catalyst is added, the stability of the solution is lowered, so that it is difficult to achieve both low-temperature curability and solution stability.

In Patent Document 5, it is shown that the crosslinking of the melamine resin proceeds at a low temperature of about 100 ° C. by using an acid generator that generates an acid upon exposure as a curing accelerator. However, since the use of this composition is a resist, a conductive polymer is not compounded and cannot be used for a conductive coating application. Melamine resin is used as a crosslinking agent for photosensitive resins, and a coating film formed from this type of photosensitive resin composition does not have sufficient scratch resistance or solvent resistance. Furthermore, since many photosensitive resins, acid generators, and melamine resin derivatives are hydrophobic, this composition cannot be blended with an aqueous conductive polymer.

As described above, it is possible to form a coating film with excellent appearance, conductivity, transparency, scratch resistance, solvent resistance, adhesion to the substrate, etc., under milder curing temperature and time conditions. In addition, a conductive coating composition that can sufficiently maintain the stability (pot life) of the solution has not been developed yet.
The present invention has been made to solve the above conventional problems, and the object thereof is excellent in coating film appearance, conductivity, transparency, scratch resistance, solvent resistance, and adhesion to a substrate. An object of the present invention is to provide a composition for conductive coating that has a thermosetting property capable of forming a conductive coating film at a low temperature and that can sufficiently maintain a pot life.

As a result of intensive studies to solve the above problems, the present inventors have found that a conductive polymer (a), a thermal crosslinking agent (b) composed of a melamine resin derivative, and an acid generator (c) By mixing with the dispersion medium (d), it is possible to form a coating film excellent in appearance, conductivity, transparency, scratch resistance, solvent resistance, and adhesion to a substrate in thermosetting at a low temperature. And it discovered that the composition for thermosetting electroconductive coatings in which the pot life of a coating liquid was maintained in the practical range was obtained, and came to complete this invention.

That is, the present invention
(A) a conductive polymer;
(B) a thermal crosslinking agent comprising a melamine resin derivative,
(C) an acid generator, and
(D) It relates to a thermosetting conductive coating composition characterized by containing a solvent or a dispersion medium.

The conductive polymer (a) has the following formula (I):

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group, or a C _1-4 alkylene group which may be substituted together) It is preferable that it is a composite of poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) having a repeating structure of and a dopant.

It is preferable that the thermal crosslinking agent (b) made of a melamine resin derivative is a full ether melamine resin.

The acid generator (c) is preferably a sulfonyl compound or a derivative thereof.

The acid generator (c) is preferably contained in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the thermal crosslinking agent (b).

The conductive polymer (a) is a water-based conductive polymer, the solvent or dispersion medium (d) is a mixture of water and an organic solvent, and the organic solvent contains at least one organic solvent that is miscible with water. Is preferred.

The thermosetting conductive coating composition preferably further contains a surfactant.

The thermosetting conductive coating composition preferably further contains a binder resin.

Moreover, this invention apply | coats the said composition for thermosetting electroconductive coatings to a base material, after generating an acid from an acid generator (c), a conductive layer is formed by thermosetting a composition. The present invention relates to a method for producing a conductive coated substrate.

The acid generator (c) contained in the thermosetting conductive coating composition is a thermosensitive acid generator, and it is preferable to generate an acid from the acid generator by heating.

The acid generator (c) contained in the thermosetting conductive coating composition is a radiation-sensitive or electromagnetic-sensitive acid generator, and it is preferable to generate an acid by radiation irradiation or electromagnetic wave irradiation.

Furthermore, this invention relates to the electroconductive coating substrate which has the electroconductive layer formed by the said manufacturing method.

According to the present invention, a conductive coating film excellent in coating film appearance, conductivity, transparency, solvent resistance, scratch resistance, and adhesion to a substrate can be formed on a substrate at a low curing temperature and in a short time. Thus, a thermosetting conductive coating composition is provided which can be formed and can maintain the pot life of the composition for a long time. The base material having a conductive coating film obtained by using the composition of the present invention has conductivity and can be suitably used in a wide range of fields such as optical films and electronic component packaging materials.

FIG. 1 is a graph showing the relationship between curing temperature (y) and time (x) at which sufficient performance can be imparted to a conductive coated substrate in Examples 30 and 31 and Comparative Examples 10 and 11. The approximate curve was created using the power approximation method.

Hereinafter, components included in the thermosetting conductive coating composition of the present invention and a method for forming a conductive coating substrate using the composition will be sequentially described.

The thermosetting conductive coating composition of the present invention (hereinafter sometimes referred to as “conductive coating composition” or “composition”) includes a conductive polymer, a thermal crosslinking agent comprising a melamine resin derivative, and an acid generator. And a solvent or a dispersion medium.

1. Conductive polymer (a)
The conductive polymer (a) contained in the conductive coating composition of the present invention is a material for imparting conductivity to the substrate surface. Examples of such a conductive polymer include polythiophene, polypyrrole, polyaniline, There are polyacetylene, polyphenylene vinylene, polynaphthalene, derivatives thereof, and a complex of a dopant. Among them, a polythiophene conductive polymer composed of a complex of polythiophene and a dopant is preferably used. More specifically, the polythiophene-based conductive polymer is a composite composed of poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) and a dopant.

The poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) constituting the polythiophene-based conductive polymer has the following formula (I):

A polythiophene in a cationic form consisting of repeating structural units represented by the formula: wherein R ¹ and R ² independently of each other represent a hydrogen atom or a C _1-4 alkyl group, or are substituted together; _Or a C _1-4 alkylene group. Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Representative examples of the optionally substituted C _1-4 alkylene group formed by combining R ¹ and R ² include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1 , 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. It is. Preferred are a methylene group, 1,2-ethylene group, and 1,3-propylene group, and a 1,2-ethylene group is particularly preferred. Poly (3,4-ethylenedioxythiophene) is particularly preferable as the polythiophene having the above alkylene group.

The dopant constituting the polythiophene-based conductive polymer is an anionic polymer capable of forming a complex by forming an ion pair with the above-described polythiophene and stably dispersing polythiophene in water. Examples of such dopants include carboxylic acid polymers (eg, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (eg, polystyrene sulfonic acid, polyvinyl sulfonic acid, etc.), and the like. These carboxylic acid polymers and sulfonic acid polymers may also be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as acrylates, styrene and the like. Among these, polystyrene sulfonic acid is particularly preferable.

The polystyrene sulfonic acid preferably has a weight average molecular weight of more than 20000 and 500,000 or less. More preferably, it is 40000-200000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene conductive polymer in water may be lowered. The weight average molecular weight of the polymer is a value measured by gel permeation chromatography (GPC).

It is preferable that content of said conductive polymer is 0.01 to 1.2 weight% as solid content with respect to the whole composition. More preferably, it is 0.03 to 0.5 weight%. If the amount is less than 0.01% by weight, the conductivity is difficult to develop. If the amount is more than 1.2% by weight, precipitation may occur due to mixing with other components.

2. Thermal crosslinking agent (b)
The melamine resin derivative, which is a thermal crosslinking agent contained in the composition of the present invention, imparts thermosetting properties at low temperature to the composition, and the coating film appearance and transparency (for example, total light transmittance Tt and haze value Haze). ), Conductivity (for example, surface resistivity SR), scratch resistance, solvent resistance, and a conductive coating film having excellent adhesion to a substrate can be formed.

The melamine resin derivative is, for example, the following formula (II):

^(Wherein, R 3 to R ⁸ are represented by H or _CH 2 OR ^{9, R 9} represents an alkyl group of H or _{C 1-4)} represented by. The melamine resin in which all the substituents R ^{3 to} R ⁸ are hydrogen atoms is an imino melamine resin, the melamine resin in which all the substituents R ^{3 to} R ⁸ are CH ₂ OH is a methylol melamine resin, and the substituent R A melamine resin having a structure in which ^{3 to} R ⁸ are all CH ₂ OR ⁹ and R ⁹ is substituted with a C _1-4 alkyl group is a full ether type melamine resin. In addition, melamine resins having a structure in which two of the above three substituents are mixed in one molecule are classified into iminomethylol type, methylol ether type and imino ether type, and melamine resins in which all are mixed are iminomethylol ether type. is there. The C _1-4 alkyl group of the full ether melamine resin includes a methyl group, an ethyl group, a propyl group, a butyl group, and the like, but considering the low-temperature curability, a methyl group is preferable. The melamine resin derivative may be an oligomer self-condensed with formula (II) as a basic skeleton.

The melamine resin derivative contained in the composition of the present invention imparts curability at low temperature to the composition and can form a coating film excellent in scratch resistance and solvent resistance, and has the above structure. Resin derivatives are preferred, and among them, full ether type melamine resins are preferred from the viewpoint of solution stability and low temperature curability. Moreover, although there is no restriction | limiting in particular in the polymerization degree of a melamine resin, when the pot life is considered, the lower one is preferable and it is especially preferable that it is 1.0-1.8. Said melamine resin may be used independently or may be used in combination of 2 or more types. In this specification, the pot life of the composition means the appearance of the composition (coating liquid) (presence or absence of precipitation), the appearance of the conductive coating film, transparency, conductivity, scratch resistance, solvent resistance, It shows that various performances such as adhesion to the substrate can be sufficiently maintained even after the composition (coating liquid) is prepared and time passes.

Although there is no restriction | limiting in particular in content of the said thermal crosslinking agent (b) for the conductive coating film hardened | cured at low temperature to have abrasion resistance and solvent resistance, 100 weight of solid content of a conductive polymer (a) It is preferable that it is 30-5400 weight part with respect to a part. More preferably, it is 270 to 1650 parts by weight. When content exceeds 5400 weight part, an electroconductive coating film may whiten and transparency and electroconductivity may fall. On the contrary, when it is less than 30 parts by weight, it becomes difficult to impart sufficient scratch resistance and solvent resistance to the conductive coating film.

3. Acid generator (c)
The acid generator (c), which is a curing accelerator contained in the composition of the present invention, does not function as an acid as it is, but generates an acid by some stimulus, and is a melamine resin that is a thermal crosslinking agent (b). It promotes crosslinking of the derivative. Examples of such an acid generator include a radiation-sensitive acid generator or an electromagnetic-sensitive acid generator capable of generating an acid by radiation or electromagnetic wave irradiation, and a heat-sensitive acid generator capable of generating an acid by heat. Since it does not function as an acid in a solution unless it is irradiated with radiation, electromagnetic waves or heated, the pot life of the composition can be maintained.

Radiation here includes particle beam (high-speed particle beam) and electromagnetic radiation. As particle beam, alpha beam (α beam), beta beam (β beam) proton beam, electron beam (accelerator regardless of nuclear decay) ), Charged particle beams such as deuteron beams, neutron beams that are uncharged particle beams, cosmic rays, etc., and electromagnetic radiation includes gamma rays (γ rays), X-rays (X rays) , Soft X-rays). Examples of electromagnetic waves include radio waves, infrared rays, visible rays, ultraviolet rays (near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays), X-rays, and gamma rays. The line type is not particularly limited. For example, an electromagnetic wave having a wavelength near the maximum absorption wavelength of the acid generator to be used may be selected.

The radiation-sensitive or electromagnetic-sensitive acid generator is not particularly limited as long as it is a compound capable of generating an acid by irradiation with radiation or electromagnetic wave, and is an ionic type such as iodonium salt or sulfonium salt, a sulfonyl compound and a derivative thereof, triazine Nonionic types such as derivatives are used.

Among the ion-type radiation-sensitive or electromagnetic-sensitive acid generators, the iodonium salt-type radiation-sensitive or electromagnetic-sensitive acid generator is represented by the following formula (III).

In formula (III), R ¹⁰ and R ¹¹ each independently represents an alkyl group, a cyclic hydrocarbon group or an aryl group. X ^- represents an alkyl group, a sulfonate ion or halide ion having a cyclic hydrocarbon group or an aryl group.
Alkyl group of R ¹⁰ and R ^11, not particularly limited to cyclic hydrocarbon groups include straight-chain, branched, cyclic hydrocarbon group having 1 to 20 carbon atoms. Examples of such substituents include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, camphor group, cyclohexyl group, decyl group, dodecyl group, norbornane, Examples include norbornene. The aryl group of R ¹⁰ and ^{R 11,} not particularly limited, those having 6 to 20 carbon atoms. Examples of such an aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. These alkyl groups and cyclic hydrocarbon groups may contain functional groups such as alkoxyl groups, carbonyl groups, hydroxyl groups, sulfides, thiols, amines, oximes, cyano groups, nitrile groups, and halogens. Similarly, the aryl group may include an alkyl group, an alkoxyalkyl group, and the above-described functional group.
X ^- alkyl sulfonic acid ion, examples of the cyclic hydrocarbon group and an aryl group is not particularly limited, an alkyl group similar to R ¹⁰ and R ^11, and cyclic hydrocarbon groups and aryl groups.

Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (III) include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium heptafluorobutanesulfonate, diphenyliodonium- p-toluenesulfonate, diphenyliodonium-9,10-dimethoxyanthracenesulfonate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4- t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium-n-nona Luobutanesulfonate, bis (4-t-butylphenyl) iodonium-n-heptafluorobutanesulfonate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium- p-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium-10-camphorsulfonate, and the like. Among these, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate is particularly preferable from the viewpoint of solution stability and curability at low temperatures.

Among the ion-type radiation-sensitive or electromagnetic-sensitive acid generators, the sulfonium salt-type radiation-sensitive acid generator or electromagnetic-sensitive acid generator is represented by the following formula (IV).

In formula (IV), R ¹² , R ¹³ and R ¹⁴ each independently represents an alkyl group, a cyclic hydrocarbon group or an aryl group. X ^- represents an alkyl group, a sulfonate ion or halide ion having a cyclic hydrocarbon group or an aryl group. Examples of the alkyl group, cyclic hydrocarbon group, and aryl group of R ¹² , R ^13, and R ¹⁴ are the same as those of R ¹⁰ and R ¹¹ .

Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (IV) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium-n-nona. Fluorobutanesulfonate, bis (4-t-butylphenyl) iodonium-2,4-difluorobenzenesulfonate triphenylsulfonium-p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, tris (p-toluenyl) sulfonium nonafluorobutanesulfonate, tris (P-toluenyl) -p-toluenesulfonate, diphenyl (p-toluenyl) trifluoromethanesulfonate, diphenyl (2,4 6-trimethylphenyl) nonafluorobutanesulfonate, diphenyl (2,4,6-trimethylphenyl) -p-toluenesulfonate, diphenyl (2,4,6-trimethylphenyl) -10-camphorsulfonate, diphenyl (4- t-butylphenyl) -p-toluenesulfonate, diphenyl (4-acetoxyphenyl) -n-nonafluorobutanesulfonate, diphenyl (4-acetoxyphenyl) -p-toluenesulfonate, diphenyl (4-acetoxynaphthyl) -n-nona Fluorobutanesulfonate, diphenyl (4-acetoxynaphthyl) -p-toluenesulfonate, diphenyl (4-methoxyphenyl) -n-nonafluorobutanesulfonate, diphenyl (4-methoxyphenyl) -p-toluenes Honato, diphenyl (4-phenylthiophenyl) trifluoromethanesulfonate, diphenyl (4-phenoxyphenyl)-p-toluenesulfonate, and the like diphenyl (p- bromophenyl)-n-perfluorobutane sulfonate. Among these, diphenyl (2,4,6-trimethylphenyl) -p-toluenesulfonate is particularly preferable from the viewpoint of solution stability and curability at low temperatures.

Among nonionic radiation-sensitive or electromagnetic-sensitive acid generators, monosulfonyl compounds (formula (V)); disulfonyldiazo compounds include radiation-sensitive or electromagnetic-sensitive acid generators of sulfonyl compounds and derivatives thereof. (Formula (VI)); sulfonic acid ester compound (formula (VII)); sulfonic acid imide compound (formula (VIII)); sulfonic acid anhydride (formula (IX)) and the like. It has a structure that decomposes by absorbing water.

In formulas (V) to (IX), R ^{15 to} R ²⁰ , R ^{22 to} R ²⁴ each independently represents an alkyl group, a cyclic hydrocarbon group or an aryl group, and the alkyl group, aryl group, alkoxyl group, carbonyl group , Hydroxyl groups, thiol groups, sulfides, amines, oximes and other substituents and functional groups. Alkyl groups included in ^{R 15 ~R 20, R 22 ~R} 24, the cyclic hydrocarbon group and an aryl group is not particularly ^limited, include the same ^{R 10} and ^{R 11.}
In the formula (VIII), R ²¹ represents an alkylene group, a cyclic hydrocarbon group or an aryl group constituting a ring, and is an alkyl group, aryl group, alkoxyl group, carbonyl group, hydroxyl group, thiol group, sulfide, amine, oxime. It may contain a substituent and a functional group. Examples of such an alkylene group include an ethylene group, a propylene group, an isopropylene group, and an isobutylene group. Examples of the cyclic hydrocarbon group include a cyclohexyl group, norbornane, norbornene. The aryl group includes those having up to 20 carbon atoms, such as a phenylene group, a naphthylene group, and an anthracenylene group.

Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (V) include 2-tribromomethylsulfonylpyridine, tribromomethylsulfonylbenzene, tribromomethylsulfonyltoluene, trichloromethylsulfonyltoluene, 2-tribromo. Methylsulfonylanthraquinone, 1- (4-tribromomethanesulfonylbenzenesulfonyl) pyrrolidine, 1- (4-tribromomethanesulfonylbenzenesulfonyl) piperidine, 4- (4-tribromomethanesulfonylbenzenesulfonyl) morpholine, 4-tribromo Ethanesulfonylbenzenesulfonamide, N, N-diethyl-4-tribromomethanesulfonylbenzenesulfonamide, 1- (phenylsulfonyl) -4-[(tribromomethyl) sulfonyl] benzene, Ro-4-[(tribromomethyl) sulfonyl] benzene, 1-bromo-4-[(tribromomethyl) sulfonyl] benzene, 4-[(tribromomethyl) sulfonyl] benzophenone, (4-methylsulfidephenyl)- 2-oxo-1,1-dimethyl-sulfonyltoluene and the like.
Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (VI) include bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (cyclohexanesulfonyl) diazomethane.
Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (VII) include 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone, 1- (p-toluenesulfonyloxy) -3,3- Examples include dimethylbicyclo [2,2,1] heptan-2-one and camphorsulfonic acid nonafluorobutane.
Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (VIII) include N- (trifluoromethanesulfonyloxy) -naphthalimide, N- (n-nonafluorobutanesulfonyloxy) -naphthalimide, N- (N-Nonafluorobutanesulfonyloxy) -5-norbornene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) phthalimide and the like.
Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (IX) include p-toluenesulfonic acid anhydride, trifluoromethanesulfonic acid anhydride, and naphthalenesulfonic acid anhydride.
Among these, tribromomethylsulfonylbenzene is particularly preferable from the viewpoint of solution stability and curability at low temperatures.

Of the nonionic radiation-sensitive or electromagnetic-sensitive acid generators, the radiation-sensitive or electromagnetic-sensitive acid generator of the triazine derivative is represented by the following formula (X).

In the formula (X), R ²⁵ each independently represents an alkyl group, a cyclic hydrocarbon group or an aryl group, and an alkyl group, aryl group, alkoxyl group, carbonyl group, hydroxyl group, thiol group, sulfide, amine, oxime, etc. These substituents and functional groups may be included. Alkyl groups included in R ^25, examples of the cyclic hydrocarbon group and an aryl group is not particularly limited, include the same R ¹⁰ and R ^11.

Examples of the radiation-sensitive or electromagnetic-sensitive acid generator represented by the formula (X) include 2,4-ditriiodomethyl-6- (p-methoxybenzene) triazine, 2,4-ditriiodomethyl-6- ( m, p-dimethoxystyryl) triazine, 2,4-ditriiodomethyl-6- (2-furanethenyl) triazine, 2,4-ditriiodomethyl-6- (4-methyl-2-furanenyl) triazine and the like. Among these, 2,4-ditriiodomethyl-6- (m, p-dimethoxystyryl) triazine is particularly preferable from the viewpoint of solution stability and curability at low temperatures.

Radiation-sensitive or electromagnetic-sensitive acid generators can generate acid upon irradiation with radiation or electromagnetic waves, but they generate acid by thermal decomposition due to differences in structure stability or the influence of other components in the composition. Sometimes. When the composition is cured by generating an acid by thermally decomposing a radiation-sensitive or electromagnetic-sensitive acid generator, the conditions for imparting sufficient scratch resistance and solvent resistance to the coating film are iodonium. For salt compounds and disulfonyldiazo compounds, the time is about 3 to 10 minutes at 100 ° C, about 1 to 5 minutes at 120 ° C, and about 1 minute at 170 ° C. However, the decomposition temperature of the radiation-sensitive or electromagnetic-sensitive acid generator is often high, and heat decomposition at a high temperature in the curing process is disadvantageous in terms of thermosetting at a low temperature.

The heat-sensitive acid generator is not particularly limited as long as it is a compound that can generate an acid by a thermal reaction such as heating, and has an ionic type such as an onium salt and a non-ionic type structure such as a sulfonyl compound and its derivative. There is. The heating temperature necessary for generating an acid from the heat-sensitive acid generator varies depending on the compound, but is preferably 60 ° C to 200 ° C, more preferably 60 ° C to 120 ° C for the purpose of thermosetting at a low temperature. is there.

The onium salt type heat-sensitive acid generator is represented by the following formula (XI).

Wherein ^{(XI), R} 26 ~R ²⁸ each independently represent an alkyl group, a cyclic hydrocarbon group or an aryl group, an alkyl group, an aryl group, an alkoxyl group, a carbonyl group, a hydroxyl group, a thiol group, sulfide, amine And may contain a substituent and a functional group such as oxime. Alkyl groups included in R ²⁶ to R ^28, examples of the cyclic hydrocarbon group and an aryl group is not particularly ^limited, include the same ^{R 10} and ^{R 11.}

Examples of the heat-sensitive acid generator represented by the formula (XI) include triarylsulfonium hexafluorophosphonate, triarylsulfonium hexafluoroantimonate, triarylsulfonium trifluoromethanesulfonate, triarylsulfonium-p-toluenesulfonate, and the like. is there. Among these, triarylsulfonium hexafluoroantimonate is particularly preferable from the viewpoint of solution stability and curability at low temperatures.

The sulfonyl compound and its derivative are represented by the following formula (XII).

In formula (XII), R ²⁹ and R ³⁰ each independently represents an alkyl group, a cyclic hydrocarbon group or an aryl group, and an alkyl group, an aryl group, an alkoxyl group, a carbonyl group, a hydroxyl group, a thiol group, a sulfide, an amine And may contain a substituent and a functional group such as oxime. Alkyl groups included in R ²⁹ and ^{R 30,} examples of the cyclic hydrocarbon group and an aryl group is not particularly ^limited, include the same ^{R 10} and ^{R 11.}

As the heat-sensitive acid generator represented by the formula (XII), p-toluenesulfonylcyclohexane, p-toluenesulfonylpyrrole, p-toluenesulfonylimidazole, p-toluenesulfonylmenthol, nonafluorobutanesulfonylcyclohexane, nonafluorobutanesulfonyl Examples include pyrrole and 3-methyl- (3-p-toluenesulfonylmethyl) acetoacetate isopropyl acetate. Among these, p-toluenesulfonylcyclohexane is preferable from the viewpoint of solution stability and curability at low temperatures.

The acid generated from the acid generator contained in the present invention is not limited as long as it can accelerate the curing of the melamine resin, but considering the stability of the solution and the curability at low temperature, an inorganic acid or an organic sulfone can be used. An acid is preferred. Examples of such acids include halogenated metal anions such as hexafluoroantimonic acid and hexafluorophosphoric acid; fluorinated alkyl sulfonic acids such as trifluoromethanesulfonic acid, hexafluoropropanesulfonic acid, and nonafluorobutanesulfonic acid; camphorsulfonic acid Aliphatic cyclic sulfonic acids such as benzene sulfonic acid, p-toluene sulfonic acid, cumene sulfonic acid, pyridine sulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acid, butyl naphthalene sulfonic acid, etc. An organic sulfonic acid having a molecular weight of 120 to 327 is particularly preferable. In order to generate said acid, it is preferable to use a sulfonyl compound and a sulfonium salt compound for any of the radiation-sensitive acid generator, electromagnetic wave-sensitive acid generator, and heat-sensitive acid generator.

The acid generator contained in the present invention may be a radiation-sensitive acid generator, an electromagnetic wave-sensitive acid generator and a heat-sensitive acid generator, respectively, or may be used in combination of two or more. When a radiation-sensitive acid generator or an electromagnetic-sensitive acid generator is used in combination with a heat-sensitive acid generator, heat sensitivity is generated by the generation of acid from the radiation-sensitive acid generator or electromagnetic-sensitive acid generator by radiation or electromagnetic wave irradiation. The thermal decomposition of the acid generator is promoted to increase the curing rate, and the curability of the melamine resin at a low temperature is also improved. In this case, the content of the radiation-sensitive acid generator or electromagnetic wave-sensitive acid generator may be 10% by weight or less, preferably 1 to 5% by weight, based on the total acid generator.

Although there is no restriction | limiting in content of the said acid generator for the electrically conductive coating film hardened | cured at low temperature to have abrasion resistance and solvent resistance, when considering the curability of a melamine resin derivative, a thermal crosslinking agent (b 1) to 100 parts by weight of solid content is preferably 1 to 60 parts by weight. More preferably, it is 3 to 25 parts by weight. The higher the content, the better the thermosetting at a low temperature. However, even if it exceeds 60 parts by weight, the improvement in curability is not observed. If it is less than 1 part by weight, the coating film may not be cured. In addition, depending on the structure of the acid generator, scratch resistance and solvent resistance may be reduced due to the influence of by-products generated by decomposition, so that the molecular weight of the by-products is preferably small. For the above reasons, trihalomethanesulfonyl acid generators are preferred.

4). Solvent or dispersion medium (d)
The solvent or dispersion medium contained in the present invention is not particularly limited as long as it dissolves or disperses each component contained in the composition, and water, an organic solvent, or a mixture thereof is used. In addition, what melt | dissolves each component contained in a composition is called a solvent, and when one component of a composition is disperse | distributing uniformly, it is called a dispersion medium. In the case of an aqueous conductive polymer composition, a mixture of water and an organic solvent can be used because the melamine resin derivative and the acid generator may not dissolve in water. In this case, the organic solvent preferably contains at least one organic solvent that is miscible with water, and further preferably contains an organic solvent that is immiscible with water (hydrophobic). When using a solvent-based conductive polymer, only an organic solvent may be used, or a mixture of water and an organic solvent may be used.

4-1. An organic solvent used as an organic solvent solvent or a dispersion medium can uniformly dissolve or disperse components such as a melamine resin and an acid generator that are difficult to dissolve in water. For example, organic solvents miscible with water include the following: alcohols such as methanol, ethanol, 2-propanol and 1-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol , Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; propylene glycol , Dipropylene glycol, tri Propylene glycols such as propylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl Propylene glycol ethers such as ether; propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydride Furan, acetone, acetonitrile and the like thereof admixture. Examples of hydrophobic organic solvents include the following solvents: esters such as ethyl acetate, butyl acetate, and ethyl lactate; ethers such as diisopropyl ether and diisobutyl ether; ketones such as methyl ethyl ketone and methyl diisobutyl ketone; hexane, octane Aliphatic hydrocarbons such as petroleum ether; aromatic hydrocarbons such as toluene and xylene, and mixtures thereof. These solvents may be used alone or in combination of two or more.

When the aqueous conductive polymer is used, the content of the solvent is preferably 20 parts by weight or more with respect to 100 parts by weight of water described later. More preferably, it is 100-500 weight part. If it is less than 20 parts by weight, the film formability deteriorates and the performance may not be exhibited. If it exceeds 500 parts by weight, the stability of the conductive polymer may be reduced and gelation may occur. In addition, when using a solvent-type conductive polymer, there is no restriction | limiting in content of the said solvent.

When the organic solvent in the case of using a water-based conductive polymer is a mixture of an organic solvent miscible with water and an organic solvent immiscible with water, the content of the organic solvent immiscible with water is determined by the acid generator 100. It is preferably 500 parts by weight or more with respect to parts by weight and 100 parts by weight or less with respect to 100 parts by weight of the organic solvent miscible with water. The amount is preferably 1000 parts by weight or more with respect to 100 parts by weight of the acid generator, and 50 parts by weight or less with respect to 100 parts by weight of the organic solvent miscible with water. If the amount is less than 500 parts by weight with respect to 100 parts by weight of the acid generator, the acid generator may not be uniformly dissolved. Moreover, when it exceeds 100 weight part with respect to the organic solvent mixed with water, a solution may become cloudy or may isolate | separate.

4-2. Water contained when the conductive polymer used in the conductive coating composition of the present invention is aqueous (water-soluble and water-dispersed) includes distilled water, ion-exchanged water, ion-exchanged distilled water, and the like. And water contained in aqueous dispersions of conductive polymers and other drugs. The water content is preferably 1% by weight or more based on the entire composition.

When the composition of the present invention is an aqueous conductive coating composition, the pH of the aqueous solution is preferably in the range of 1 to 14, more preferably 1 to 7 in view of curability at low temperatures. 1.5 to 3 is particularly preferable. The pH can be adjusted with a pH adjusting agent such as a base as necessary, but the base forms an acid salt with the acid generated from the acid generator, and may reduce the effect of accelerating the curing of the acid. Better. The higher the pH, the lower the curability at low temperatures. However, since the self-crosslinking of the melamine resin in the solution is suppressed, the solution stability and pot life may be improved. Such pH adjusters include alkanolamines such as ammonia, ethanolamine, and isopropanolamine.

5). Surfactant The composition for conductive coating of the present invention may contain a surfactant. The surfactant is not particularly limited as long as the leveling property is improved and a uniform coating film can be obtained. Examples of such surfactants include the following compounds: polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic. Group-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, polyfluorinated alkylsiloxane, and other siloxane compounds; perfluoroalkylcarboxylic acid, perfluoroalkylpolyoxyethylene Fluorine-containing organic compounds such as ethanol; polyoxyethylene alkyl phenyl ether, propylene oxide polymer, ethylene Polyether compounds such as side polymers; carboxylic acids such as coconut oil fatty acid amine salts and gum rosins; castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, phosphate esters, succinic acid Ester compounds such as acid esters; sulfonate compounds such as alkyl aryl sulfonic acid amine salts and dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanol amide; There are copolymers of the system. Among these, siloxane compounds and fluorine-containing compounds are preferable from the viewpoint of leveling properties, and polyether-modified polydimethylsiloxane is particularly preferable.

The above-mentioned surfactant can also be added to impart various functions such as scratch resistance, antifouling property and blocking resistance to the coating film. The surfactant containing silicon and / or fluorine imparts water repellency to the surface of the coating film and prevents adhesion of organic compounds such as oil and fat stains. Furthermore, the removability of attached organic matter is also improved. Moreover, by providing the surface with slipperiness, the scratch resistance may be improved as a result. Some of these surfactants can improve the blocking resistance, and the uncured coating component does not adhere to the contact surface when the roll is wound. From the viewpoint of imparting such functionality, polyether ester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyfluorinated alkylsiloxane, and the like are preferable.

Among the above-mentioned surfactants, those containing an acrylic group can form a coating film mainly composed of a siloxane skeleton by radical and / or cationic polymerization of an acrylic group when an acid generator is blended. May be advantageous in curing.

Among the above-mentioned surfactants, those containing a hydroxyl group are fixed to the surface of the coating film by chemically bonding with melamine or a binder resin, so that the formed coating film has scratch resistance and solvent resistance. It may be advantageous in terms of sex.

The amount of the surfactant contained in the composition of the present invention is not particularly limited, but it is preferably 10% by weight or less, particularly preferably 0.01 to 1% by weight based on the whole composition. . When the amount of the surfactant exceeds 10% by weight, the scratch resistance and solvent resistance of the coating film may be lowered. Conversely, when the amount is less than 0.01% by weight, the leveling property may not be improved. .

6). Binder resin The conductive coating composition of the present invention may contain a binder resin.
The heat curing with the melamine resin derivative is preferably a self-crosslinking reaction of the melamine resin in consideration of the scratch resistance and solvent resistance of the coating film and the low temperature curability.
In general, melamine resins react with functional groups such as carbonyl groups and hydroxyl groups contained in binder resins, and are therefore often used as cross-linking agents for such coatings. The property is not so high as compared with the self-crosslinked coating film of melamine resin, and in addition, high temperature and long time curing conditions are often required. As a factor that the melamine self-crosslinked coating film is superior in scratch resistance and solvent resistance, the crosslink density is higher.

On the other hand, since the melamine resin immediately after film formation is not crosslinked and the coating film is oily, a blocking problem may occur due to winding of a roll or the like. In such a case, blocking can be alleviated by adding a binder resin.

The conductive coating composition of the present invention has sufficient film formability even when it does not contain a binder resin (when a melamine resin self-cross-linked coating film is formed), but the binder resin In some cases, the film-forming property may be improved.

The binder resin contained in the conductive coating composition of the present invention is not particularly limited as long as it can improve the film formability and the blocking resistance of the coating film. Examples of such a binder resin include homopolymers such as polyester, poly (meth) acrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamide, polyimide, polyvinyl alcohol, polyacryl polyol, and polyester polyol; styrene, chloride A copolymer having a copolymerization component selected from the group consisting of vinylidene, vinyl chloride, and alkyl (meth) acrylate; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( And alkoxysilane compounds such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane. These resins may contain a substituent such as hydroxyl group, sulfonyl group, carboxyl group, epoxy group and fluorine. From the viewpoint of film formability and blocking resistance, polyester, polyimide, and polyvinyl alcohol are preferable, and polyester is particularly preferable. The amount of the binder resin is not particularly limited, but usually it is preferably contained in a proportion of 100 parts by weight or less as a solid content with respect to 100 parts by weight of the melamine resin solid content, particularly preferably 5 to 20 parts by weight. When the amount exceeds 100 parts by weight, scratch resistance and solvent resistance may not be imparted to the coating film. Conversely, when the binder resin is not contained, blocking resistance may not be imparted. Considering the scratch resistance and solvent resistance of the coating film, the solid content is particularly preferably 5 to 20 parts by weight.

7). Other components 7-1. Conductivity improver A conductivity improver can be added for the purpose of improving the conductivity of the composition of the present invention. Examples of such conductivity improvers include amide compounds such as N-methylformamide, N, N-dimethylformamide, γ-butyrolactone, and N-methylpyrrolidone; ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4 -Hydroxyl group-containing compounds such as butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; isophorone , Propylene carbonate, cyclohexanone, acetylacetone, ethyl acetate, ethyl acetoacetate, methyl orthoacetate, ethyl orthoformate, etc. Alkenyl group-containing compound; sulfone compounds such as dimethyl sulfoxide and the like. Among these, N-methylpyrrolidone is particularly preferable in view of various performances such as solution stability, curability at low temperature, scratch resistance of the coating film, and solvent resistance. Although there is no restriction | limiting in particular in the usage-amount, Usually, it is preferable to contain in the quantity of 60 weight% or less in a composition.

7-2. Thickener A thickener may be added to the composition of the present invention for the purpose of improving the viscosity. Examples of such thickeners include alginic acid derivatives, xanthan gum derivatives, water-soluble polymers such as saccharide compounds such as carrageenan and cellulose. Although the amount is not particularly limited, it is usually preferable that the amount is 60% by weight or less in the composition.

8). Production Method Next, a method for producing a conductive coated substrate using the conductive coating composition will be described.
The manufacturing method of the electroconductive coating | coated base material of this invention consists of the process of heat-curing, after generating an acid from the acid generator contained in the composition for electroconductive coating. Different manufacturing processes are used depending on whether the acid generator is a heat-sensitive acid generator or a radiation-sensitive or electromagnetic-sensitive acid generator.

8-1. In the case of using a composition containing a heat-sensitive acid generator, the above-mentioned composition for conductive coating is applied to a substrate, and when the solvent is evaporated by drying, it is thermally cured simultaneously or after evaporation (curing step A). In this step, the heat-sensitive acid generator functions as a curing accelerator by decomposing in a drying and thermosetting step and generating an acid. As a condition for generating the acid, it is desirable to heat the substrate coated with the conductive coating composition at a temperature higher than the temperature at which the heat-sensitive acid generator generates an acid, specifically 60 ° C to 200 ° C. The time is preferably 10 seconds to 1 minute at the temperature.

8-2. When using a composition containing a radiation-sensitive or electromagnetic-sensitive acid generator After applying the above-mentioned conductive coating composition to a substrate and completely evaporating the solvent or dispersion medium by drying, the radiation or electromagnetic wave Radiation is generated after irradiation with an acid from a radiation-sensitive or electromagnetic-sensitive acid generator (curing step B), or after the composition is applied to a substrate and before the solvent or dispersion medium is completely volatilized. Alternatively, an acid is generated from a radiation-sensitive or electromagnetic-sensitive acid generator by irradiating an electromagnetic wave, and then the solvent or dispersion medium is evaporated by drying and simultaneously heat-cured (curing step C).

As described above, the composition of the present invention comprises a conductive polymer, a thermal crosslinking agent, an acid generator, a solvent or a dispersion medium, and optionally a surfactant, a conductivity improver, a binder resin, a thickening agent. Contains agents. These compositions are usually supplied in a state where the melamine resin derivative and the acidic component are separated in order to prevent self-crosslinking in the solution of the thermal crosslinking agent of the melamine resin derivative. Examples of the acidic component include conductive polymers and surfactants. The above liquids are mixed at a predetermined ratio before use, and used in a state where all the components are mixed. In addition, when the acidic component is neutralized with a base or the like, the storage stability can be maintained even if all components are supplied in a mixed state.

The method for preparing the conductive coating composition is not particularly limited, but the liquids are mixed with stirring with a stirrer such as a mechanical stirrer or a magnetic stirrer, and stirred for about 1 to 60 minutes. It is preferable to dilute with about 1 to 10 minutes until it becomes uniform. In consideration of the pot life of the composition, it is preferable to prepare the solution at a temperature lower than 30 ° C. Especially when the composition contains a radiation-sensitive acid generator or an electromagnetic-sensitive acid generator, radiation and electromagnetic waves are preferably prepared. It is better to prepare it in a state of blocking.

In the case of using a radiation-sensitive or electromagnetic-sensitive acid generator, the conductive coating composition is preferably applied in a state where radiation or electromagnetic waves are shielded. Moreover, although the composition is stable at room temperature around 25 ° C., when it contains an acid component, self-crosslinking in the liquid of the melamine resin derivative proceeds, so that the temperature of −20 ° C. to 20 ° C. is maintained. By applying, the pot life can be improved. It is particularly preferable to apply to the substrate while maintaining a temperature of −5 ° C. to 10 ° C. The pot life is improved as the temperature is kept low. However, when the composition is aqueous, the composition may freeze at a temperature lower than −20 ° C. The composition is preferably maintained at a temperature of -20 ° C to 20 ° C, preferably -5 ° C to 10 ° C from the time of preparation.

In order to form a conductive coating film on a substrate surface by the method of the present invention, first, a substrate having a desired shape is prepared. As the substrate, for example, a substrate made of resin or glass can be used.

Examples of the resin substrate include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionomer copolymer, polyolefin resin such as cycloolefin resin; polyethylene terephthalate, polybutylene terephthalate, polycarbonate, Polyester resins such as polyoxyethylene, modified polyphenylene, polyphenylene sulfide; polyamide resins such as nylon 6, nylon 6,6, nylon 9, semi-aromatic polyamide 6T6, semi-aromatic polyamide 6T66, semi-aromatic polyamide 9T; acrylic resin, List other resins such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride resin, triacetyl cellulose, etc. It can be. Among these, polyethylene terephthalate and triacetyl cellulose are preferably used from the viewpoints of processability and functionality.
Examples of the glass substrate include alkali-free glass, soda glass, quartz glass, and borosilicate glass. Among these, alkali-free glass is preferable from the viewpoint of functionality.

The shape of the substrate is not particularly limited, and a film-like substrate, a plate-like substrate, a film having a desired shape, a sheet, a plate, a molded product, or the like can be used. Further, as a preliminary treatment for improving the coating property, physical treatment such as corona treatment, flame treatment, plasma treatment, etc. may be applied to the substrate surface.

The conductive coating composition (coating solution) is applied to the surface of the substrate to form a coating film. The coating method of the coating liquid on the substrate surface is not particularly limited, and can be appropriately selected from methods generally used in the field. Examples include spin coating, gravure coating, bar coating, dip coating, curtain coating, die coating, and spray coating. Furthermore, printing methods such as screen printing, spray printing, ink jet printing, letterpress printing, intaglio printing, and planographic printing can also be employed.

The thickness of the coating film formed on the substrate is not particularly limited and can be appropriately selected according to the purpose. Usually, the thickness after heat drying is preferably 0.01 to 300 μm, more preferably 0.03 to 100 μm. If the thickness is less than 0.01 μm, it becomes difficult to develop the conductivity, and if it exceeds 300 μm, the conductivity, scratch resistance, and solvent resistance in proportion thereto cannot be obtained.

For drying and heat curing for evaporating the solvent of the coating film, a normal air dryer, hot air dryer, infrared dryer or the like is used. In order to perform drying and heating simultaneously, it is necessary to use a dryer having a heating means (hot air dryer, infrared dryer, etc.). Moreover, as a heating means, a heating / pressurizing roll having a heating function, a press machine, etc. can be used in addition to the dryer. The drying conditions necessary for the evaporation of the solvent are about 10 to 30 seconds at a temperature of 60 to 100 ° C.

When the composition for conductive coating contains a radiation-sensitive or electromagnetic-sensitive acid generator, a radiation or electromagnetic wave irradiation device is used to generate an acid. The wavelength of the radiation or electromagnetic wave to be irradiated is not particularly limited, and a radiation or electromagnetic wave in the vicinity of the maximum absorption wavelength of the acid generator to be used may be selected. Examples of devices that can radiate radiation or electromagnetic waves include mercury lamps such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, deep UV lamps, and low-pressure UV lamps, halide lamps, xenon flash lamps, metal halide lamps, ArF excimer lamps, KrF excimer lamps, etc. There are exposure apparatuses using an excimer lamp, an extreme ultraviolet lamp, an electron beam, and an X-ray lamp as a light source.

When the conductive coating composition contains a heat-sensitive acid generator, the coating film covering the resin substrate surface is formed from the heat-sensitive acid generator at the same time as or after the evaporation of the solvent by drying. By generating acid and thermosetting, a conductive coating film excellent in scratch resistance, solvent resistance, transparency, and adhesion to a substrate can be formed. As curing conditions for imparting sufficient scratch resistance and solvent resistance to the conductive coating film, a temperature of 25 ° C. to 200 ° C. and a time of about 30 seconds to 24 hours are necessary. Specific examples include the following conditions. 200 ° C. × 2 minutes, 170 ° C. × 3 minutes, 150 ° C. × 5 minutes, 120 ° C. × 15 minutes, 100 ° C. × 20 minutes, 80 ° C. × 2 hours, 60 ° C. × 24 hours, 100 ° C. × After 1 minute, it is about 25 ° C. × 24 hours. At higher temperatures, it can be cured in a shorter time. When using a roll coater with high productivity, although depending on the line speed and the length of the dryer, the drying and curing conditions are usually 60 to 130 ° C. for several seconds to several minutes. When the curing is insufficient, the film can be post-cured for 1 hour to several weeks in a roll film after roll coating in a dryer or storage at 25 ° C to 70 ° C.

When the conductive coating composition contains a radiation-sensitive or electromagnetic-sensitive acid generator, the solvent or dispersion medium is completely volatilized by drying, and then radiation-sensitive or electromagnetic-sensitive acid is generated by radiation or electromagnetic irradiation. The acid is generated from the agent and then thermally cured, or the composition is applied to a substrate and irradiated with radiation or electromagnetic waves before the solvent or dispersion medium is completely volatilized. Generates acid from the generator, then volatilizes the solvent or dispersion medium by drying, and at the same time heat cures, coating appearance, transparency, conductivity, adhesion to the substrate, scratch resistance, solvent resistance It is possible to form a conductive coating film having excellent properties. As curing conditions for imparting sufficient scratch resistance and solvent resistance to the conductive coating film, for example, about 3 seconds to 170 ° C. and about 5 seconds to 24 hours are necessary, and specifically, the following conditions may be mentioned: It is done. 120 ° C. × 10 seconds, 100 ° C. × 20 seconds, 80 ° C. × 30 seconds, 60 ° C. × 1 minute, 40 ° C. × 10 minutes, 25 ° C. × 30 minutes, 5 ° C. × 13 hours. When the curing is insufficient under the processing conditions of the roll coater, the film can be post-cured for 1 hour to several weeks with a dryer at 25 ° C. to 70 ° C. in the state of the roll film after roll coating.

In addition, the conductive coating composition described above can be used to generate an acid by radiation or electromagnetic wave irradiation or heating before being applied to the substrate, and then applied to the substrate, followed by drying and thermosetting, thereby providing scratch resistance. However, it is preferable to generate an acid after coating in consideration of the pot life of the coating liquid.

In the conductive coated base material obtained by using the conductive coating composition, a conductive layer containing a conductive polymer is formed on the surface of the base material. This conductive layer preferably has a surface resistivity of 10 ² to 10 ¹¹ Ω / □, and since the transmittance of the substrate is maintained, a liquid crystal display, an electroluminescence display, a plasma display, an electrochromic display It can be used as an antistatic layer and / or an electrode for various films and sheets such as solar cells, touch panels, and electronic component packaging materials such as soft trays, hard trays, carrier tapes, cover tapes, and spacer tapes.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

I. Raw materials used 1 Conductive Polymer As an aqueous dispersion containing a conductive material, an aqueous dispersion of a conductive polymer composed of a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is used. C. Clevios P (trade name) (poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (weight average molecular weight = 150,000) dispersed aqueous solution of Starck Co .; solid content 1.3% by weight, water 98. 7% by weight), and AquaPass ^(R) -01X (trade name) manufactured by Mitsubishi Rayon Co., Ltd., which is an aqueous dispersion of polyaniline (polyaniline sulfonic acid (weight average molecular weight = 10000); solid content 1.0% by weight) Using. As an organic solvent dispersion containing a conductive material, SSPY (ethyl 3-methyl-4-pyrrolecarboxylate / 3-methyl-4-pyrrolecarboxylate copolymer) manufactured by Nippon Soda Co., Ltd .: 10.0 wt. %, Weight average molecular weight = 200000) and TCNA (2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene; solid content 10.0% by weight) Using. For measurement of the weight average molecular weight, an ultrahydrogel 500 column manufactured by Waters was used.

I. 2 Melamine Resin Derivatives As melamine resin derivatives, Nicarac MW-390 (full ether type, R ⁹ : methyl group, degree of polymerization: 1.0), Nicarac MX-500 (full ether type, R ⁹ ) manufactured by Nippon Carbide Industries Co., Ltd. n-butyl group, polymerization degree: 2.4), Nicarax MX-730 (imino type, 80% by weight, polymerization degree: 2.4), and Cymel 300 (full ether type, R ⁹ ) manufactured by Nihon Cytec Industries, Ltd .: Methyl group, polymerization degree: 1.4), Cymel 303 (full ether type, R ⁹ : methyl group, polymerization degree: 1.7), Cymel 370 (methylol type, 88% by weight, R ⁹ : methyl group, polymerization degree) : 2.3) was used (all the above names are trade names).

I. 3 As an acid catalyst acid catalyst, manufactured by Wako Pure Chemical Industries, Ltd., methanesulfonic acid (molecular weight 111.3; hereinafter, MS), p-toluenesulfonic acid (molecular weight 187.2; hereinafter, p-TsOH), Dodecylbenzenesulfonic acid (molecular weight 326.8; hereinafter DBS), primary sulfuric acid, NACURE-1051 (trade name) manufactured by Enomoto Kasei Co., Ltd. (dinonylnaphthalenesulfonic acid; solid content 50.0 wt%, molecular weight 458.0 Hereinafter referred to as DNNS).
I. 4 Acid generator As a radiation-sensitive or electromagnetic-sensitive acid generator, bis (p-toluenesulfonyl) diazomethane (molecular weight 350.5; hereinafter, PAG-2), Tokyo Chemical Industry, manufactured by Wako Pure Chemical Industries, Ltd. 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone (molecular weight 366.3; hereinafter, PAG-1) manufactured by Kogyo Co., Ltd., BMPS (trade name) manufactured by Sumitomo Seika Co., Ltd. ( Tribromomethylphenylsulfone; molecular weight 392.9; hereinafter, PAG-3), BSP (trade name) (2-tribromomethylsulfonylpyridine; molecular weight 393.9; hereinafter, PAG-4), as a thermosensitive acid generator P-tosylimidazole (molecular weight 222.3; hereinafter TAG-2) manufactured by Wako Pure Chemical Industries, Ltd., Sun Aid SI80L (trade name) (Tria) manufactured by Sanshin Chemical Co., Ltd. Reelsulfonium hexafluoroantimonate; hereinafter, TAG-1) was used.

I. 5 Organic solvent Wako Pure Chemical Industries, Ltd. primary ethanol, primary toluene, and methyl ethyl ketone (hereinafter, MEK) were used.

I. 6 Most of the water was water contained in the aqueous dispersion of conductive polymer, Clevios P and aquaPass ^(R) -01X, but the newly added water was used after ion exchange treatment. The water described in Table 1 of the examples is newly added water.

I. 7 Surfactant As a surfactant, Plus Coat RY-2 (trade name) (α-perfluorononenyloxy-ω-methylpolyethylene oxide; solid content 10.0% by weight) manufactured by Kyoyo Chemical Industry Co., Ltd., Dainippon Megafac R-08 (trade name) manufactured by Ink (perfluoroalkyl oligomer; solid content: 5.0% by weight), BYK-348 manufactured by BYK-Chemie (trade name) (polyether-modified polydimethylsiloxane; solid 100% by weight), BYK-375 (trade name) (polyether siloxane-modified hydroxyl group-containing polydimethylsiloxane; solid content 100% by weight), BYK-UV3500 (trade name) (polyether-modified acrylic group-containing polydimethylsiloxane; solid Min. 100% by weight).

I. 8 Conductivity improver N-methylpyrrolidone (hereinafter referred to as NMP) manufactured by Wako Pure Chemical Industries, Ltd. was used as the conductivity improver.

I. 9 As binder component binder, POVAL KL-506 (trade name) manufactured by Kuraray Co., Ltd. (polyvinyl alcohol, hereinafter referred to as KL-506; solid content 100% by weight), plus coat Z-687 (trade name) manufactured by Kyoyo Chemical Co., Ltd. ( Polyethylene naphthalate; solid content 25.0% by weight, hereinafter, Z-687), plus coat RZ-105 (trade name) (polyester; solid content 25.0% by weight, hereinafter, RZ-105), and Toyobo Co., Ltd. Vitalnal MD-1245 (trade name) manufactured by Polyester (polyester; solid content 30.0% by weight, hereinafter, MD-1245) was used.

I. 10 Lumirror T-60 (trade name) (polyethylene terephthalate film, hereinafter referred to as PET), Corning # 1737 (trade name) (glass plate, hereinafter referred to as glass) manufactured by Toray Industries, Inc. was used as the base material.

II. As an exposure apparatus for electromagnetic wave irradiation, a Unicure manufactured by USHIO INC. Whose light source is a metal halide lamp was used.

III. Evaluation method The liquid appearance of the obtained composition, the coating appearance of the conductive coated substrate obtained using the composition, the adhesion, the scratch resistance, and the solvent resistance are evaluated in three stages, and the blocking resistance is in two stages. It was evaluated with. Moreover, SR, Tt, and Haze evaluated the measured value. The pot life was evaluated for the coating solution and the coating film when “8h”, “12h”, and “24h” had elapsed since the preparation of the solution. The appearance of the coating liquid, the appearance of the coating film, adhesion, scratch resistance, and solvent resistance were evaluated in the same manner as the initial values. On the other hand, SR, Tt, and Haze of the coating film evaluated the fluctuation | variation from the initial value of a measured value in three steps. In addition, regarding the item of initial evaluation “x”, pot life is not evaluated (“−” is entered).

III. 1 External appearance of conductive coating composition The liquid appearance after preparation of the composition was visually evaluated in three stages. Pot life was similarly evaluated.
◎: No precipitate is generated ○: A small amount of precipitate is generated ×: Gelation

III. 2 Appearance (uniformity) of the conductive coating after coating appearance was visually evaluated in the following three stages. Pot life was similarly evaluated.
A: The coating film is uniformly applied B: The coating film is partially non-uniform X: The coating film is not formed

III. 3 Surface resistivity (SR: Ω / □)
The surface resistivity was measured using Hiresta UP (MCP-HT450 type, trade name) manufactured by Mitsubishi Chemical Corporation in accordance with JIS K7194. The pot life was evaluated for the rate of increase relative to the initial value in the following three stages.
◎: 10 times or less ○: Over 10 times and less than 100 times ×: 100 times or more

III. 4 Total light transmittance (Tt:%)
The total light transmittance was measured according to JIS K7150, using a haze computer HGM-2B (trade name) manufactured by Suga Test Instruments Co., Ltd. The pot life was evaluated based on the following three levels of change with respect to the initial value.
A: greater than −0.5 and less than +0.5 ○: −1.0 to −0.5 and +0.5 to +1.0
X: Less than −1.0 and greater than +1.0

III. 5 Haze (%)
Haze was measured according to JIS K7150 using a haze computer HGM-2B (trade name) manufactured by Suga Test Instruments Co., Ltd. The pot life was evaluated based on the following three levels of change with respect to the initial value.
A: greater than −0.5 and less than +0.5 ○: −1.0 to −0.5 and +0.5 to +1.0
X: Less than −1.0 and greater than +1.0

III. 6 Adhesiveness The adhesiveness of the coating film to the substrate was evaluated according to a cross-cut peel test of JIS K5400. Evaluation was performed in the following three stages. The pot life was similarly evaluated.
◎: 10 points ○: 8 points ×: 6 points or less

III. 7 Scratch resistance and solvent resistance test The conductive coating film formed on the substrate was subjected to a dry wiping test, an ethanol wiping test, a toluene wiping test, and an acetone wiping test. In the dry wiping test, a dry cotton swab was prepared, and using this, the surface of the coating film was rubbed 5 strokes 3 cm long for 5 strokes by applying a force to write high writing pressure. Ethanol wiping, toluene wiping, and acetone wiping tests were performed in the same manner as the dry wiping test using a cotton swab soaked with acetone.

The substrate surface was visually observed, and the following three stages of evaluation were performed. The pot life was similarly evaluated.
◎: No part peeled off ○: Less than 10% peeled part ×: 10% or more peeled part

III. 8 The anti-blocking test of the electroconductive coating film formed on the anti-blocking substrate was performed using a compression molding machine AYS-5 (trade name) manufactured by Shindo Metal Industry. When the substrate (PET) coated with the composition for conductive coating is dried at 100 ° C. for 1 minute, irradiated with electromagnetic waves, then two sheets are stacked with the coated surface facing up, and pressed at a pressure of 0.5 MPa for 1 hour The blocking property was evaluated in the following two stages. The pot life was similarly evaluated.
A: Not adhered to the back surface of the superimposed PET ×: Adhered to the back surface of the superimposed PET

The components of the coating liquids prepared in the following examples and comparative examples and the appearance of the coating liquids are shown together in Table 1, and the evaluation results of the coating liquids and conductive coating substrates obtained in the respective examples and comparative examples are shown in Table 1. These are also shown in Tables 2, 3-1, 3-2, 4, 5, 6, and FIG.
The evaluation results shown in Table 2 are those of a conductive coated substrate prepared by coating immediately after preparation of the coating solution. In Tables 3-1, 3-2 and 4, “8h” means the appearance of the coating liquid 8 hours after the liquid preparation and the coating film applied 8 hours after the liquid preparation was dried and cured under the above conditions. “12h” and “24h” are the evaluation results of the coating liquid applied after 12 hours and 24 hours, respectively, and the coating film applied at each elapsed time. Table 5 shows the results of the anti-blocking test. Table 6 summarizes the temperature and time conditions necessary for the conductive coating obtained by applying the composition immediately after compounding to have sufficient scratch resistance.

(Examples 1-4, 6-29)
Each component shown in Table 1 was mixed to prepare a conductive coating composition (coating solution) in a dispersion state. Immediately after the preparation of this coating solution, No. 1 was deposited on the polyethylene terephthalate film of the base material. 4 wire bar (wet film thickness 9μm), (B) dried at 100 ° C. for 1 minute in a hot air dryer, irradiated with electromagnetic wave (95mJ / cm ² ) with uni-cure and then heat-cured, (C) with uni-cure A conductive coated substrate was obtained in each step of drying and thermosetting with a hot air dryer after irradiation with electromagnetic waves (95 mJ / cm ² ). Thermosetting was performed under the conditions of 100 ° C. × 1 minute or 100 ° C. × 1 minute and 25 ° C. × 24 hours. In addition, as a pot life evaluation, a coated substrate was similarly prepared even when 8 hours, 12 hours, and 24 hours had elapsed since the preparation of the coating solution. The evaluation results of the initial performance of the obtained conductive coated substrate are shown in Table 2, and the pot life evaluation results are shown in Tables 3-1, 3-2 and 4. In addition, the anti-blocking test of Table 5 was implemented after heat-curing after film-forming by the procedure of a process (B).

(Comparative Examples 1-9, Example 5)
Each component shown in Table 1 is mixed to prepare a coating solution, which is used to apply to the substrate in the same manner as in Examples 1 to 4 and 6 to 29, and then dried and cured in a hot air dryer. A conductive coated substrate was obtained. Curing was performed under the conditions of 100 ° C. × 1 minute or 100 ° C. × 1 minute and 25 ° C. × 24 hours. The pot life was evaluated in the same manner. The evaluation results of the initial performance of the obtained conductive coated substrate are shown in Table 2, and the pot life evaluation results are shown in Tables 3-1, 3-2 and 4.

From Comparative Examples 1 to 9, in thermosetting at low temperature, in order to impart scratch resistance and solvent resistance to the coating film, by adding a melamine resin derivative and an acid catalyst, curing conditions of 100 ° C. × 1 minute However, it can be seen that a coating film excellent in scratch resistance and solvent resistance can be formed. The curability at low temperature depends on the structure of the catalyst, and the curability of p-TsOH and DBS tends to be good. Sufficient scratch resistance and solvent resistance cannot be obtained with sulfuric acid, MS, or DNNS. Melamine resin alone does not exhibit performance. On the other hand, the higher the hydrophobicity of the pot life, the better, and the conductive polymer precipitates in sulfuric acid, p-TsOH and MS having high hydrophilicity. Among them, DBS is good in all performances, but the pot life is 8 hours even considering the structure of melamine resin and the degree of polymerization. From the above results, it can be seen that the composition of the acid catalyst, melamine resin and conductive polymer cannot achieve both low temperature curability and pot life of 8 hours or more. Referring to Examples 1 to 6, by adding an acid generator as a curing accelerator, a conductive coating film excellent in scratch resistance and solvent resistance was obtained under the same conditions as in the comparative example (100 ° C. × 1 min. Alternatively, it can be formed at 25 ° C. for 24 hours and the pot life is maintained for 12 hours or more. From Examples 7 to 25, it can be seen that almost the same performance is exhibited regardless of the type of the conductive polymer, the melamine resin derivative, and the surfactant. A binder resin may be added. When the addition amount of the acid generator exceeds 60 parts by weight with respect to 100 parts by weight of the melamine resin, the appearance of the coating film tends to deteriorate, so it is better not to add too much. Regarding the process, curing at a lower temperature after applying the composition to the substrate and then exposing it to 100 ° C. x 1 minute before volatilizing the solvent or dispersion medium compared to exposing it after completely evaporating. There is a tendency that good results are obtained and good results can be obtained even with a coating film appearance and Haze. In particular, when a crystalline compound such as MW-390 is used, when it is cured by irradiation with electromagnetic waves after drying at 100 ° C. for 1 minute, the coating film may be slightly whitened and the haze may be increased. is there. In the heat-sensitive acid generator of Example 5, the curability at 100 ° C. for 1 minute is lower than that of the electromagnetic wave-sensitive acid generator, but curing is promoted by leaving it at 25 ° C. for 24 hours thereafter. Since the coating film resistance is obtained and the pot life is also good, it can be said that it has practical performance. Further, in Example 16, the curability at 100 ° C. × 1 minute is lower than in the other examples, but curing is promoted by leaving it at 25 ° C. for 24 hours, and sufficient coating film resistance is obtained. And since the pot life is also good, it can be said that it has practical performance. As in Example 6, the performance is also exhibited by using an electromagnetic wave sensitive acid generator and a heat sensitive acid generator in combination. When Examples 26-29 are compared, it turns out that blocking resistance is improved by adding binder resin. Although the addition of the binder resin is often disadvantageous for curing at low temperature, it can be seen that sufficient low-temperature curability is maintained and blocking resistance is improved in the composition of the present invention.

(Example 30)
Each component used in Example 3 was mixed to prepare a coating solution, and this was used to apply to the substrate in the same step (C) as in Examples 1 to 4 and 6 to 29, thereby forming a conductive coated substrate. Got. Curing is performed at 5 ° C., 25 ° C., 40 ° C., 60 ° C., 80 ° C., 100 ° C., 120 ° C., 150 ° C., 170 ° C., and 200 ° C., and has sufficient scratch resistance “◎” at each temperature. The time when the conductive coated substrate was obtained is summarized in Table 6 and plotted in FIG.

(Example 31)
Each component used in Example 5 was mixed to prepare a coating solution, and this was used to apply to a substrate in the same manner as in Example 5 to obtain a conductive coated substrate. Curing was performed at 60 ° C., 80 ° C., 100 ° C., 120 ° C., 150 ° C., 170 ° C., and 200 ° C., and a conductive coated substrate having sufficient scratch resistance “◎” was obtained at each temperature. Times are summarized in Table 6 and plotted in FIG.

(Comparative Examples 10 and 11)
As Comparative Example 10, each component used in Comparative Example 2 and each component used in Comparative Example 5 as Comparative Example 11 were mixed to prepare a coating solution, and this was used as in Comparative Examples 1-9. It apply | coated to the base material and the electroconductive coating base material was obtained. After drying at 100 ° C. for 1 minute, curing is performed at 25 ° C., 40 ° C., 60 ° C., 80 ° C., 100 ° C., 120 ° C., 150 ° C., 170 ° C., and 200 ° C., and sufficient scratch resistance The time when the conductive coated substrate having “◎” was obtained was summarized in Table 6 and plotted in FIG.

Referring to FIG. 1, Comparative Example 11 containing dodecylbenzenesulfonic acid is given sufficient scratch resistance and solvent resistance under milder curing conditions than Comparative Example 10 containing no acid catalyst. However, in Example 30 using an acid generator, it can be seen that the desired conductive coated substrate can be obtained in a shorter time. Example 31 is lower than Comparative Example 11 in terms of curability and requires a long time, but is advantageous in terms of pot life. Since the curability of the coating film can be improved by a process such as post-cure, it can be said that it has sufficient practicality.

According to the present invention, a composition for producing a conductive coated substrate excellent in coating film appearance, transparency, conductivity, scratch resistance, solvent resistance, adhesion to the substrate, and the like, and the composition Provided are a method for producing a conductive coated substrate using an object and a conductive coated substrate. Conventionally, it has been difficult to form a conductive coating on the surface, and it becomes possible to form a conductive coating even on a resin base material that is not highly heat resistant. Curing is promoted even during storage, and the pot life is maintained for a long time, so that productivity in roll coating or the like is not lowered. The base material having such a conductive coating film can be used in a wide range of fields, and can be used for imparting an antistatic function and / or a transparent electrode function to various films and sheets.

Claims (12)

(A) a conductive polymer;
(B) a thermal crosslinking agent comprising a melamine resin derivative,
(C) an acid generator, and
(D) A thermosetting conductive coating composition comprising a solvent or a dispersion medium. The conductive polymer (a) has the following formula (I):

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group, or a C _1-4 alkylene group which may be substituted together) 2. The thermosetting conductive material according to claim 1, which is a composite of poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) having a repeating structure of and a dopant. Coating composition. The thermosetting conductive coating composition according to claim 1 or 2, wherein the thermal crosslinking agent (b) comprising a melamine resin derivative is a full ether type melamine resin. The composition for thermosetting conductive coating according to any one of claims 1 to 3, wherein the acid generator (c) is a sulfonyl compound or a derivative thereof. The thermosetting conductive according to any one of claims 1 to 4, wherein the acid generator (c) is contained in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the thermal crosslinking agent (b). Coating composition. The conductive polymer (a) is a water-based conductive polymer, the solvent or dispersion medium (d) is a mixture of water and an organic solvent, and the organic solvent includes an organic solvent that is miscible with at least one kind of water. The thermosetting conductive coating composition according to claim 1, wherein the composition is a thermosetting conductive coating. Furthermore, surfactant is contained, The composition for thermosetting conductive coatings of any one of Claims 1-6 characterized by the above-mentioned. Furthermore, binder resin is contained, The composition for thermosetting conductive coatings of any one of Claims 1-7 characterized by the above-mentioned. Applying the thermosetting conductive coating composition according to any one of claims 1 to 8 to a substrate, generating an acid from the acid generator (c), and then thermosetting the composition. A method for producing a conductive coated substrate, comprising forming a conductive layer by the method. The conductive coating substrate according to claim 9, wherein the acid generator (c) contained in the thermosetting conductive coating composition is a thermosensitive acid generator, and generates an acid by heating. Manufacturing method. The acid generator (c) contained in the thermosetting conductive coating composition is a radiation-sensitive or electromagnetic-sensitive acid generator, and generates an acid by radiation irradiation or electromagnetic wave irradiation. The method for producing a conductive coated substrate according to 9. The electroconductive coating | coated base material manufactured by the manufacturing method of any one of Claims 9-11.

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