Material and method for making an electroconductive pattern

Materials and methods for making conductive patterns

Field of invention

The invention relates to a material and a method for manufacturing conductive patterns.

Background of the invention

Electroluminescent devices and transparent ITO (indium tin oxide) electrodes for photovoltaic energy cells are used to make flexible LC displays. These electrodes are manufactured by vacuum-spraying ITO onto ITO. This method involves high temperatures (up to 250 ° C), so glass substrates are usually used. Because of high manufacturing cost, low flexibility (flexibility) and extensibility (this is due to the brittleness of the ITO layer and the glass substrate), the range of possible applications is limited. Therefore, the importance of all-organic devices is increasing, which includes a plastic resin as a substrate and an organic conductive polymer layer as an electrode. Such plastic electronic parts can realize low cost devices with novel characteristics (Physics World, March 1999, pages 25-39). The flexible plastic substrate can be provided with a conductive polymer layer by a continuous roll coating method (compared with a batch blowing method such as a spray coating method), and the formed organic electrode can be manufactured with higher flexibility and Electronic device with lower weight characteristics.

The manufacture and use of conductive polymers (such as polypyrrole, polyaniline, polyacetylene, polyparaphenylene, polythiophene, polystyrene, polythiophene ethylene, and polyphenylene sulfide) are well known in the art. By.

EP-A 440 957 discloses a dispersion of polythiophene, which is composed of a structural unit of formula (I) in the presence of a polyanion:

<chemistry general="n"><img file="TW554249B_D0001.tif" /></chemistry>

Where R ¹ And R ² Independently represent hydrogen or C _1-4 -Alkyl or together form an optionally substituted C _1-4 Alkenyl residues. In addition, EP-A-686662 discloses a neutral polythiophene consisting of A) a repeating structural unit of formula (I),

<chemistry general="n"><img file="TW554249B_D0002.tif" /></chemistry>

Where R ¹ And R ² Independently represent hydrogen or C _1-4 -Alkyl or together form an optionally substituted C _1-4 Alkenyl residues, preferably a methylene group optionally substituted with alkyl, _1- C _12- Alkyl or phenyl substituted 1,2-ethylene residues, or 1,2-cyclohexene residues, and B) a type comprising a di- or polyhydroxy- and / or carboxyl or amido or lactam group A mixture of organic compounds; and the conductive coating formed by them is tempered at high temperature (preferably between 100 and 250 ° C) for 1 to 90 seconds to improve their resistance to &lt; 300 ohms / square.

PA 614 123 discloses a water-soluble conductive substance composition comprising a polyacid and a polymer (which includes at least one conjugated region composed of a repeating unit containing a basic atom of its conjugate). However, although the water-soluble conductive substance polymer includes at least one conjugated region composed of a repeating unit containing a conjugated basic atom thereof, only polyaniline and substituted polyaniline are exemplified.

EP-A 382 046 discloses a conductive resistance material, in particular comprising at least one ion radiation-sensitive polymer and a soluble conductive oligomer or a soluble conductive polymer. The substituted thiophene polymers are exemplified, but there are no special ion-radiation-sensitive polymers. EP-A3 38 786 discloses a negative-sense light-coated color adhesive film, which comprises: (i) a transparent substrate; (ii) a photosensitive layer on the substrate, the photosensitive layer comprising a photosensitive, negative 2. Polymerizable azo salt compounds (which are polymers of 3-methoxy-4-azodiphenylamine sulfate and 4,4'-bis-methoxymethyldiphenyl ether precipitated as chloride salts) Condensation product), the azo salt compound is present in an amount sufficient to make the layer photosensitive; and a water-insoluble, water-swellable adhesive resin in an amount sufficient to adhere the layer components to a homogeneous adhesive film; and at least A coloring agent in an amount sufficient to make the layer uniform in color; wherein when the photosensitive layer is imagewise exposed to sufficient actinic radiation, the adhesive film can be developed using only water.

The coating of the organic conductive polymer can be patterned using known micro-etching techniques. A method is disclosed in WO-A-97 18944 in which a positive or negative photoresist is applied over a coating of an organic conductive polymer, and after the step of selectively exposing the photoresist to UV light, Photoresist development, etching the conductive polymer layer, and finally stripping the undeveloped photoresist with an organic solvent to obtain a patterned layer. A similar technique was disclosed in Synthetic Metals in 1988, Vol. 22, pp. 265-27l, for the design of fully organic thin film transistors. This method is cumbersome because they involve many steps and require the use of harmful chemicals.

The purpose of the invention

One aspect of the present invention is to provide a material having an outermost layer that can be processed into a conductive pattern by a simple and convenient method involving a small number of steps and without using harmful chemicals.

Summary of invention

The conductive pattern can be realized by using the material of the present invention (which is enhanced by conductivity if necessary), by exposing the pattern, with or without subsequent single-sided wet processing steps, and enhanced conductivity as needed. No etching liquid or organic solvent is required.

The aspect of the present invention can be realized by manufacturing a conductive pattern material. The material includes a support and an exposure distinguishable element, which is characterized in that the exposure distinguishable element includes an outermost layer (which contains a polyanion and a substituted Or an unsubstituted thiophene polymer or copolymer), and optionally a second layer adjacent to the outermost layer; and wherein the outermost layer and / or the optional second layer contains a photosensitive component, which is exposed when exposed The removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer can be changed.

These objects can also be achieved by a method of making conductive patterns on a support, which includes the following steps:-providing a material as described above;-exposing the material by patterning, thereby obtaining exposure and unexposure of the outermost layer The difference in the removability of the area, using a developer as appropriate;-processing the material, using a developer as appropriate to remove the outermost area; and-treating the material as appropriate to increase the conductivity of the outermost unremoved area Sex. -These objects can also be achieved without a removal step by a method of manufacturing a conductive pattern on a support, which includes the following steps:-providing a material for manufacturing a conductive pattern, the material comprising a support and

An exposure distinguishable element, characterized in that the exposure distinguishable element includes an outermost layer (which contains a polyanion and a ⁶ Ω / square (surface-resistance polymer or copolymer of substituted or unsubstituted thiophene), and optionally a second layer adjacent to the outermost layer; and wherein the outermost layer and / or the optional The second layer contains a bis (arylazosulfonate) compound according to formula (I): MO ₃ SN = N-Ar-L-Ar-N = N-SO ₃ M (I) where Ar is a substituted or unsubstituted aryl group, L is a divalent linking group, and M is a cation; when exposed, the exposed portion of the outermost layer can be changed relative to the outermost layer. Removability of the unexposed portion; and-exposing the material in a patterned manner, thereby obtaining a reduction in conductivity of the exposed area relative to the unexposed area, using a developer as appropriate.

Other advantages and specific examples of the present invention will become apparent from the following description.

Detailed description of the invention

The term "support" means a "self-supporting material" that distinguishes it from a "layer" that is coated on a support but is not itself self-supporting. It also includes any processing required to adhere to the exposed distinguishable element, or any layer that is coated to aid adhesion.

The term conductivity is intended to have less than 10 ⁶ Ω / squared surface resistivity. Antistatic material has 10 ⁶ Up to 10 ¹¹ The surface resistivity in the Ω / square range cannot be used as an electrode.

The term "conductive pattern" means a pattern formed by the outermost unremoved region according to the present invention, which is conductive or can be made conductive by post-treatment.

Conductivity enhancement refers to a process that enhances conductivity, for example, by contact with a high-boiling point liquid (such as an organic compound containing a di- or polyhydroxy- and / or carboxyl or amido or endoamine group), as appropriate Heating is preferably performed at a high temperature (preferably between 100 and 250 ° C.) for a period of preferably 1 to 90 seconds, resulting in an increase in conductivity. In addition, <img file="TW554249B_D0003.tif" /> In the case of aprotic compounds of 15 (such as N-methyl-pyrrolidone), temperatures below 100 ° C can be used. Such conductivity enhancement can be observed with polythiophene and occurs during or after the preparation of the outermost layer. Particularly preferred liquids for this treatment are N-methyl-pyrrolidone and diethylene glycol, as disclosed in EP-A 686 662 and EP-A1003 179.

The term "removability" as used in the description of the present invention and the scope of the patent application is intended to be mechanically removable in the absence of liquid, or can be borrowed with or without simultaneous or subsequent use of wiping or other mechanical removal devices. Removed with liquid. The use of a liquid can dissolve, swell or disperse the outermost layer according to the invention, making removal possible or feasible.

The term "exposure distinguishable element" means an element, and when exposed, the characteristics or composition of the exposed portion of the element will change relative to the characteristics or composition of the unexposed portion of the element.

The term "polyazo salt" includes all compounds having at least two groups bearing two nitrogen atoms bonded together by a double or triple bond, such groups including -NN ⁺ And -N = NR group (such as -N = N-SO ₃ M group).

The term "resin containing an azo salt" means a resin having a group with two nitrogen atoms bonded together by a double or triple bond, such groups including -NN ⁺ And -N = NR group (such as -N = N-SO ₃ M group).

After the trace pattern is exposed, in the case of the outermost layer removed portion (area), the term "surface resistivity" means that the portion (area) of the outermost portion (area) of the distinguishable element that is exposed according to the present invention has been removed The ratio of the surface resistance to the surface resistance of the unremoved portion (area) of the outermost portion (area) of the distinguishable element exposed according to the present invention If it is, it is subject to the treatment to enhance the conductivity of the unremoved part (region) of the outermost layer).

After exposure of the trace pattern, in the case of the outermost unremoved portion (area), the term "surface resistivity" means the surface resistance of the exposed portion (area) of the outermost layer relative to the surface of the unexposed portion (area) of the outermost layer. Resistance ratio.

Material for making conductive patterns

According to the present invention, the material for making conductive patterns need not be conductive by itself, as long as the patterns produced by such materials can be made conductive by a post-processing procedure. In addition, in order to produce a conductive pattern, it is not necessary to remove the material from the outermost layer of the polymer or copolymer containing a substituted or unsubstituted thiophene according to the present invention, after processing as appropriate to remove residual photosensitive components, as long as Only different removability can be produced after exposure. In this case, the presence of the photosensitive component can produce this effect upon exposure, and change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer. If necessary, the second layer must be between the outermost layer and the support, because it cannot be the outermost layer.

Conductivity

The term "conductive" refers to the electrical conductivity of a material. Surface resistivity R _S (Unit Ω; often expressed as Ω / square). In addition, the conductivity can be used as the volume resistivity R _v = R _s .d (where d is the thickness of the layer), bulk conductivity k _v = 1 / R _v [Unit: S (Siemens) / cm] or surface conductivity k _s = 1 / R _s [Unit: S (Siemens). Square].

All values of resistivity appearing herein are determined according to one of the following methods. In the first method, the conductive outermost-coated support was cut to obtain a strip having a length of 27.5 cm and a width of 35 mm, and was pasted with a strip electrode so as to be 10 cm perpendicular to the edge of the strip The distance covers its width. The electrode system is made from the conductive polymer ECCOCOAT CC-2 (available from Emerson &amp; Cumming Specialty Polymers). A constant potential was applied to the electrodes and the current flowing through the circuit was measured on a pico-ammeter KEITHLEY 485. Calculate the surface resistivity (Ω / square) from the potential and current, considering the geometry of the area between the electrodes.

In the second method, the surface resistivity is measured by contacting the outermost layers with parallel copper electrodes that are 35 mm in length and 35 mm apart to form wire contacts. The electrodes are separated by an iron furon insulator. This allows direct measurement of surface resistivity.

Support

Supports for use in accordance with the present invention include polymer films, silicone plastics, oxides, glass, polymer film reinforced glass, glass / plastic laminates, metal / plastic laminates, paper, and laminate paper, as appropriate, Provide an undercoat or other adhesion-promoting device to help adhere to the exposed distinguishable component. Suitable polymer films are poly (ethylene terephthalate), poly (ethylene terephthalate), polystyrene, polyetherether, polycarbonate, polyacrylate, polyamide, polyimide Ammonium amine, cellulose triacetate, polyene, and polyvinyl chloride are optionally treated by corona discharge or glow discharge or provided with an undercoat.

In the case where conductive patterns are manufactured by removing exposed or unexposed areas, such treatment or undercoating should not prevent complete removal, however, if conductive patterns can be achieved without removing exposed or unexposed areas, then This treatment will make removal of unexposed or unexposed areas more difficult.

In a first specific example of the material according to the invention, the support system is treated with a corona discharge or a glow discharge. However, corona discharge and glow discharge can make the polymer film used as a support without a primer coating. This material can be developed and gently wiped at the same time as appropriate, while still producing superior conductivity between the exposed and unexposed areas.

Exposure distinguishable element

According to the present invention, the exposure distinguishable element is an element, and when exposed, the characteristics or composition of the exposed portion of the element are changed relative to the characteristics or composition of the unexposed portion of the element. Examples of such changes are the degree of crosslinking induced by exposure; the increase or decrease in exposure induced by solubility; and the increase or decrease in exposure induced by adhesion to the support.

According to the present invention, changes in the characteristics or composition of these exposed distinguishable elements are due to the presence of the photosensitive elements in the outermost layer and / or the second layer, which may allow the exposed or unexposed portions of the outermost layer to be removed ( With the aid of a developer as appropriate), that is, when exposed, the removability can be made more removable (positive) or irremovable (negative) by a developer.

In the second specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a polyazo salt or a resin containing an azo salt. , Which reduces the removability of the exposed part of the outermost layer. Compositions containing azo salt resins can also be used. If the photosensitive component is a polyazo salt or a resin containing an azo salt, then increasing the pH of the coating dispersion and solution used in the preparation of the exposed distinguishable element has been found to improve the storage life, which is based on Retention of the properties of the materials of the invention upon storage. A pH between 2.5 and 9 is preferred, and a pH between 3 and 6 is particularly preferred. These pH values can be achieved, for example, by adding neodymium hydroxide. In the third specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a quinone azo compound that increases the exposed portion of the outermost layer. Removability.

In a fourth specific example of the material according to the present invention, the outermost layer has less than 10 ⁶ Ω / squared surface resistivity.

In a fifth specific example of the material according to the present invention, the outermost layer has less than 10 ⁴ Ω / squared surface resistivity.

In the sixth specific example of the material according to the present invention, after the outermost layer is treated with a so-called conductivity enhancement method, ⁶ Ω / squared surface resistivity.

Polymer or copolymer of substituted or unsubstituted thiophene In the seventh specific example of the material according to the present invention, the polymer of substituted or unsubstituted thiophene corresponds to the following formula (II):

<chemistry general="n"><img file="TW554249B_D0004.tif" /></chemistry>

Where n is greater than 1 and R ¹ And R ² Each independently represent hydrogen or an optionally substituted C _1-4 Alkyl or together represents an optionally substituted C _1-4 Alkenyl or a optionally substituted cycloalkenyl (preferably vinyl), an optionally alkyl-substituted methylene, an optionally substituted C _1-12 Alkyl- or phenyl-substituted alkenyl, 1,3-propenyl or 1,2-cyclohexenyl.

A method for preparing such a polythiophene group and an aqueous dispersion containing the polythiophene and a polyanion is described in EP-A-440957 and the corresponding case US-P-5300575. Basically, the preparation of polythiophene is carried out in the presence of a polymerizable polyanionic compound, and is obtained by the oxidative polymerization reaction of 3,4-dialkoxythiophene or 3-4-alkenyldioxythiophene according to the following formula: to make:

<chemistry general="n"><img file="TW554249B_D0005.tif" /></chemistry>

Where R ¹ And R ² Is as defined above.

The stable polythiophene aqueous dispersion having a solid content of 0.05 to 55% by weight and preferably 0.1 to 10% by weight can be dissolved in an organic solvent or preferably in water by dissolving the thiophene, polybasic acid and an oxidizing agent corresponding to the above formula ( It optionally contains some amount of organic solvent), and then the solution or emulsion formed is stirred at 0 ° C to 100 ° C until the polymerization reaction is completed. The polythiophene formed by the oxidative polymerization reaction is positively charged. The position and number of such positive charges cannot be reliably determined. Therefore, it is not described in the general formula of the repeating unit of the polythiophene polymer.

Oxidants are those typically used in the oxidative polymerization of pyrrole, as described, for example, in J. Am. Soc. <img file="TW554249B_D0006.tif" /> , 454 (1963). A preferred cheap and easy to handle oxidant is an iron (III) salt, such as FeCl ₃ , Fe (ClO ₄ ) ₃ And iron (III) salts of organic acids and inorganic acids containing organic residues. Other suitable oxidants are H ₂ O ₂ K ₂ Cr ₂ O ₇ , Alkaline persulfate or ammonium persulfate, alkaline perborate, potassium permanganate and copper salts (such as copper tetrafluoroborate). Air or oxygen can also be used as an oxidant. Theoretically, 2.25 equivalents of oxidant per mole of thiophene are necessary for its oxidative polymerization (J. Polym. Sci. Part A, Polymer Chemistry, Vol. 26, p. 1287, 1988). However, in practice, oxidants are used in excess, for example more than 0.1 to 2 equivalents per mole of thiophene.

Polyanion

The polyacid forms a polyanion or, in addition, the polyanion can be added as a salt, such as a basic salt, of the corresponding polyacid. Preferred polybasic acids or their salts are polymerizable carboxylic acids such as poly (acrylic acid), poly ((meth) acrylic acid) and poly (maleic acid), or polymerizable sulfonic acids such as poly (styrenesulfonic acid) Acid) or poly (ethylene sulfonic acid). In addition, such copolymers of carboxylic acid and / or sulfonic acid-and other polymerizable monomers (such as styrene or acrylate) can also be used.

In an eighth specific example of the material according to the present invention, the polyanion is poly (styrene sulfonate).

The molecular weight of these polyanion-forming polyanions is preferably between 1000 and 2x10 ⁶ , Especially between 2000 and 5x10 ⁵ between. These polyacids or their basic salts are available from shopping malls and can be prepared according to known methods, as described in Houben-Weyl, Methoden der Organische Chemie, Bd. E20 Markro-molekulare Stoffe, Teil 2, (1987) , pp. 1141.

Dispersions of polyanions and polymers or copolymers of substituted or unsubstituted thiophenes

Coating dispersions or solutions of polyanionic and substituted or unsubstituted thiophene polymers or copolymers may also contain other ingredients, such as one or more adhesives, one or more surfactants, spacer particles, UV-sharpness compounds, or IR-absorbent.

Anionic and nonionic surfactants are preferred. Suitable surfactants include ZONYL ^TM FSN100 and ZONYL ^TM FSO100, an ethoxylated nonionic fluorine-surfactant, has the structure F (CF ₂ CF ₂ ) _y CH ₂ CH ₂ O (CH ₂ CH ₂ O) _x H, where x = 0 to about 15 and y = 1 to about 7, both from DuPont.

Coating dispersions or solutions of polyanionic and substituted or unsubstituted thiophene polymers or copolymers preferably also contain an organic compound, that is, a linear, branched, or cyclic aliphatic C _2-20 Hydrocarbon or a optionally substituted aromatic C _6-14 A hydrocarbon or piperan or furan; an organic compound containing at least two hydroxyl groups or at least one -COX or -CONYZ group, wherein X represents -OH and Y and Z independently of each other represent H or alkyl; or one contains at least one intrinsic group Amino heterocyclic compounds. Examples of such organic compounds are e.g. N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, N, N, N ', N'-tetrakidone Methylurea, formamide, dimethylformamide and N, N-dimethylacetamide. Preferred examples are sugars or sugar derivatives such as arabinose, sucrose, glucose, fructose and lactose; or di- or polyhydric alcohols such as sorbitol, xylitol, mannitol, mannose, galactose, sorbose, Gluconic acid, ethylene glycol, di- or tris (ethylene glycol), 1,1,1-trimethylol-propane, 1,3-propanediol, 1,5-pentanediol, 1,2,3- Glycerol, 1,2,4-butanetriol, 1,2,6-hexanetriol or an aromatic di- or polyhydric alcohol, such as resorcinol.

Polyazo salt

A polyazo salt is a salt having at least two groups with two nitrogen atoms bonded together by a double or triple bond. Such groups include -N N ⁺ And -N = NR group (such as -N = N-SO ₃ M group), such as bisazo, trisazo, tetrasazo, bis (arylazosulfonic acid), tris (arylazosulfonic acid), and tetras (arylazosulfonic acid) Acid) salt.

When exposed, exposure distinguishable elements containing polyazo salts are changed from water-removable to water-unremovable (due to the destruction of azo salt groups). In addition, the photolysis products of azo may increase the content of polyazo The degree of cross-linking of the polymerizable adhesive or resin (if any) of the salt, thereby selectively changing the surface from removable to irremovable, and becoming an image pattern. Unexposed areas remain unchanged and can be removed. Polyazo salt compositions can also be used.

The bisazo salts used in the present invention include: amine benzidine tetrazolium chloride, 3,3'-dimethylamine benzidine tetrazolium chloride, 3,3'-dimethoxyamine benzidine Tetrazolium chloride, 4,4'-diaminodiphenylamine tetrazolium chloride, 3,3'-diethylamine benzidine tetrazolium chloride, 4-aminodiphenylamine couple Azosulfate, 4-aminodiphenylamine azo chloride, 4-N-hexahydropyridylaniline azosulfate, 4-diethylaminoaniline azosulfate and azophenylamine and Oligomer condensation products of formaldehyde.

In the ninth specific example of the material according to the present invention, the photosensitive components that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed are bis (arylazosulfonic acid) salt, tris (aryl Azosulfonic acid) salt or tetrakis (aryl azosulfonic acid) salt, which reduces the removability of the exposed portion of the outermost layer.

In a tenth specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a bis (arylazosulfonate) according to formula (I) Acid) salt, which reduces the removability of the exposed part of the outermost layer: MO ₃ SN = N-Ar-L-Ar-N = N-SO ₃ M (I) wherein Ar is a substituted or unsubstituted aryl group, L is a divalent linking group, and M is a cation. L represents a substituted or unsubstituted divalent aryl group or a substituted or unsubstituted saturated or unsaturated alkenyl group, and the chain is optionally substituted with at least one oxygen atom, sulfur atom, or nitrogen atom. Ar preferably represents unsubstituted phenyl or phenyl substituted with one or more alkyl, aryl, alkoxy, aryloxy or amine groups. M preferably represents a cation, such as NH ₄⁺ Or a metal ion, such as Al, Cu, Zn, alkaline earth metal or alkali metal cation.

Particularly suitable bis (arylazosulfonic acid) salts according to the present invention are:

<tables><img file="TW554249B_D0007.tif" /></tables>

In the eleventh specific example of the material according to the present invention, when exposed, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer is a bis (arylazosulfonic acid) salt, which reduces The removability of the exposed part of the outermost layer is selected from the group consisting of BADS01, BADS02, and BADS03.

According to the present invention, in a first specific example of a method for manufacturing a conductive pattern on a support without a removing step, the aryl azosulfonate according to formula (I) is selected from the group consisting of BADS01, BADS02, and BADS03. Group.

Resin containing azo salt

The term "resin containing an azo salt" means a resin having a group with two nitrogen atoms bonded together by a double or triple bond, such groups including -N N ⁺ And -N = NR group (such as -N = N-SO ₃ M group). Suitable azo salt-containing resins according to the present invention include polymers or copolymers of aryl azo sulfonates and condensation products of aromatic azo salts. Such condensation products are described in DE-P-1 214086.

When exposed, exposure distinguishable elements containing azo salt-containing resins are changed from water-removable to water-removable (due to the destruction of azo salt groups). In addition, the photolysis products of azo may increase The degree of cross-linking of the polymerizable adhesive or resin of the azo salt (if present), thereby selectively changing the surface from removable to irremovable, and becoming an image pattern. Unexposed areas remain unchanged and can be removed.

In a twelfth specific example of the material according to the present invention, when exposed, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer is a polymer or copolymer of aryl azosulfonate , Which reduces the removability of the exposed part of the outermost layer.

In a thirteenth specific example of the material according to the present invention, when exposed, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer is a polymer or copolymer of aryl azosulfonate , Which reduces the removability of the exposed part of the outermost layer, which is represented by the following formula III:

<chemistry general="n"><img file="TW554249B_D0008.tif" /></chemistry>

Where R ⁰ , R ¹ And R ² Each independently represents hydrogen, an alkyl group, a nitrile group, or a halogen (such as C1), L represents a divalent linking group, n represents 0 or 1, A represents an aryl group, and M represents a cation. L preferably represents a divalent linking group and is selected from the group:-(X) _t -CONR ³ -,-(X) _t -COO-, -X- and-(X) _t -CO-, where t represents 0 or 1; R ³ Represents hydrogen, alkyl, or aryl; X represents alkylene, alkylene, alkyleneoxy, alkyleneoxy, alkylenethio, alkylenethio, alkyleneamine, alkyleneamine, oxygen , Sulfur or amine. A preferably represents unsubstituted aryl (such as unsubstituted phenyl) or aryl (such as phenyl), and may be substituted with one or more alkyl, aryl, alkoxy, aryloxy, or amine groups. M preferably represents a cation, such as NH ₄⁺ Or a metal ion, such as Al, Cu, Zn, alkaline earth metal or alkali metal cation.

Polymers or copolymers of aryl azo sulfonates can be obtained by using aryl azo sulfonate monomers with other aryl azo sulfonate monomers and / or with ethylene monomers such as (meth) acrylic acid or Its ester, (meth) acrylamide, acrylonitrile, ethylene acetate, vinyl chloride, vinylidene chloride, styrene, a-methylstyrene, etc.) are prepared by homopolymerization or copolymerization reaction. A particularly preferred comonomer is hydroxyethyl (meth) acrylate. When used in the present invention, the aryl azo sulfonate monomers suitable for preparing such aryl azo sulfonate polymers and copolymers are:

<tables><img file="TW554249B_D0009.tif" /></tables>

<tables><img file="TW554249B_D0010.tif" /></tables>

Specific examples of suitable arylazosulfonate polymers are described in EP-A-771645.

According to the present invention, suitable azo salt-containing resins are provided as follows. In the case of polymers and copolymers of aryl azosulfonates, the proportions of the individual monomers are expressed as weight percentages.

<tables><img file="TW554249B_D0011.tif" /></tables>

<tables><img file="TW554249B_D0012.tif" /></tables>

In a fourteenth specific example of the material according to the present invention, in the exposure distinguishable element, the weight ratio of the polymer or copolymer of aryl azosulfonate to the polymer or copolymer of substituted or unsubstituted thiophene is Between 10: 200 and 400: 200.

Composition of polyazo salt and resin containing azo salt

In a fifteenth specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is aryl azosulfonate (which reduces the outermost layer Removability of the exposed portion) and bis (aryl azosulfonate) (which reduces the removal of the outermost exposed portion) resin.

In a sixteenth specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a type containing a weight percentage ranging from 60% / 40% to 10 % / 90% of aryl azosulfonate (which reduces the removability of the outermost exposed portion) and bis (aryl azosulfonate) (which reduces the removability of the outermost exposed portion) combination.

In a seventeenth specific example of the material according to the present invention, a photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a type containing a weight percentage ranging from 50% / 50% to 20%. % / 80% of aryl azosulfonate (which reduces the removability of the outermost exposed portion) and bis (aryl azosulfonate) (which reduces the removability of the outermost exposed portion) combination.

In an eighteenth specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a hydroxyethyl methacrylate and 4-methyl Copolymers of acrylamido-aminophenyl-azo-sulfonate (which reduces the removability of the outermost exposed portion) and bis (arylazosulfonate) (which reduces the removability of the outermost exposed portion) Removal).

Quinone azo compound

In a nineteenth specific example of the material according to the present invention, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer when exposed is a quinone azo compound that increases the exposed portion of the outermost layer. Removability.

In a twentieth specific example of the material according to the present invention, when exposed, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer is an o-quinone-azo compound (NQD), which Increase the removability of the outermost exposed part.

Particularly preferred o-quinone-azo compounds are o-naphthoquinone azosulfonates or o-naphthoquinone azocarboxylates of various hydroxy compounds and o-naphthoquinone azosulfonamides of various aromatic amine compounds. Or o-naphthoquinone azocarboxyamide.

Two variations of the NQD system can be used: one-component system and two-component system. In the former case, the sulfonic acid or carboxylic acid group is directly connected to a phenolic hydroxyl group of a water-insoluble, alkali-soluble or swellable resin having a phenolic hydroxyl group. It is preferred that certain phenolic hydroxyl groups remain unsubstituted. Examples of such compounds include phenol, cresol, resorcinol and pyrogallol. Examples of preferred water-insoluble, alkali-soluble or swellable resins having a phenolic hydroxyl group include phenol-formaldehyde resin, cresol-formaldehyde resin, pyrogallol-acetone resin, and resorcinol-benzaldehyde resin. Typical examples include esters of naphthoquinone- (1,2) -azosulfonic acid and phenol-formaldehyde resin or cresol-formaldehyde resin, and naphthoquinone- (1,2) -azo- (2) -5- Esters of sulfonic acid and pyrogallol-acetone resin (as disclosed in US 3,635,709) and naphthoquinone- (1,2) -azo- (2) -5-sulfonic acid and resorcinol-benzene Ester of triphenol-acetone copolymerization condensate (as disclosed in Japanese Patent Application Laid-Open No. 55-76346).

Examples of other useful compounds are polyesters which have hydroxyl groups esterified with ortho-naphthoquinone-azosulfonyl chloride at their end groups (as described in Japanese Patent Application Laid-Open No. Sho 50-117503); p-hydroxyl groups Homopolymer of styrene or its copolymer with other copolymerizable monomers esterified with o-naphthoquinone-azosulfonyl chloride (as described in Japanese Patent Application Laid-Open No. Sho 50-113305); alkyl acrylates -A condensate of acryloxyalkyl carbonate-hydroxyalkyl acrylate copolymer with o-naphthoquinone-azosulfonyl chloride (as described in US 3,859,099); p-hydroxystyrene and may Monomers copolymerized therewith and copolymers of ortho-naphthoquinone-azo-sulfonic acid or ortho-naphthoquinone-azo-carboxylic acid (as described in US 3,759,711); and polyhydroxybenzophenone with ortho -Naphthoquinone-azosulfonyl chloride esters.

In a twenty-first specific example of the material according to the present invention, when exposed, the photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer is an o-quinone-azo compound (PQD), which The removability of the exposed portion of the outermost layer is increased, and the exposure distinguishable element further comprises an alkali-soluble resin.

Particularly suitable quinone azo compounds according to the present invention are:

<tables><img file="TW554249B_D0013.tif" /></tables>

Adhesive

In the material for making conductive patterns according to the present invention, the exposed distinguishable element includes an adhesive.

In the twenty-second specific example of the material according to the present invention, if a photosensitive component that can change the removability of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer exists in the outermost layer when exposed, the outermost layer may include An adhesive such as polyvinyl alcohol and vinylidene chloride, methyl methacrylate, and itaconic acid (88/10/2) terpolymer.

In the twenty-third specific example of the material according to the present invention, if a photosensitive component that can change the removability of the exposed portion of the outermost layer with respect to the unexposed portion of the outermost layer exists in the second layer when exposed, select as appropriate The second layer may contain an adhesive such as a copolymer of polyvinyl alcohol and hydroxyethyl methacrylate.

Suitable adhesives for use in the present invention are described in EP-A-564911 and include water-soluble polymers such as poly (vinyl alcohol), water-soluble homo- and co-polymers of acrylic acid and water of methacrylic acid Soluble homo- and co-polymers and polymer latex. Preferred adhesives include both homo- and co-polymers of poly (vinyl alcohol) and hydroxyethyl methacrylate and 2-methyl-2-acrylic acid 2-phosphino) ethyl ester. Such adhesives may be hardened (such as epoxy silane, such as 3-glycidoxypropyltrimethoxysilane described in EP-A564911), which is particularly suitable when coated on a glass substrate of.

In the application of NQD as a two-component system, various low molecular weight NQD sulfonic acid or carboxylic acid derivatives are mainly dissolved in certain water-insoluble, alkali-soluble or swellable resins; the latter is used as a polymerizable adhesive for NQD . Preferably, the 1,2 naphthoquinone azo substituted by 4- or 5-sulfo or carboxyl group is 1,2 naphthoquinone azo-4- or-5-sulfonic acid or carboxylic acid and one having at least two Esters of phenolic phenolic compounds (especially a phenolic compound having at least three phenolic hydroxyl groups). Other suitable 1,2 naphthoquinone-2-azo compounds are disclosed in GB-A739645 and US 4,266,001. Preferred water-insoluble, alkali-soluble or swellable resins are resins, which contain phenolic hydroxyl groups, or sulfonamide groups. Particularly preferred are resins having phenolic hydroxyl groups, and phenolic hydroxyl functionalized derivatives of poly (meth) propane, which can be synthesized from, for example, hydroxyethyl (meth) acrylate. The best is a synthetic novolac resin, and typical examples thereof are phenol-formaldehyde resin, cresol-formaldehyde resin, and phenol-cresol-formaldehyde copolymerization condensation resin, as described in Japanese Patent Application Laid-Open No. 55-57841.

Exposure process

The material according to the present invention can be image-wise exposed to ultraviolet light combined with blue light or infrared light having a wavelength range of 250 to 500 nanometers as needed. When a traced image is exposed, a developer is used to produce a difference in removability between exposed and unexposed areas. Useful exposure sources are high-to-moderate pressurized halogen mercury vapor lamps (such as 1000 watts) or lasers with an emission wavelength range of about 700 to about 1500 nanometers, such as semiconductor laser diodes, an Nd: YAG laser Or Nd: YLF laser.

Development process

After exposure of the tracing image, the material is developed in a developer, which may be deionized water or preferably an aqueous substrate. During development, the exposed (positive) or unexposed (negative) areas are removed together with the conductive polymer, thereby obtaining a conductive pattern. Suitable aqueous developers are deionized water, AZ303 (Clariant) or EN232 (AGFA-GEVAERT NV). When an undercoat layer (also referred to as a matrix layer) is present on the support, it is preferable to rub thoroughly with toilet paper during development to avoid residual conductivity. Wiping can be done in the processing fluid or in a different water bath after the development stage. Obtained by applying a high-pressure water column after the development stage, thereby avoiding contact with the conductive area. In addition, if conductivity enhancement is required, the developer may include a conductivity enhancer, thereby combining a developing step and a step of contacting the conductivity enhancer.

Although the present invention will be described in the following specific preferred examples, it should be understood that this is not intended to limit the present invention to these specific examples. All percentages given in the examples refer to weight percentages unless otherwise indicated.

Examples

Not mentioned above for exposing components in distinguishable elements: PEDOT = poly (3,4-ethylenedioxythiophene) PSS = poly (styrenesulfonic acid) LATEX01 = dichloroethylene, methyl Terpolymer of methyl acrylate and itaconic acid (88/10/2), obtained as a 30% aqueous dispersion.

Z6040 = Glycidoxypropyltrimethoxysilane from ZONYL ^TM FSO100 = an ethoxylated nonionic gas surfactant with structure F (CF ₂ CF ₂ ) _y CH ₂ CH ₂ O (CH ₂ CH ₂ O) _x H, where X = 0 to about 15 and y = 1 to about 7, from DuPont ingredients used in the undercoat: LATEX02 = 26.5 mole% terephthalic acid, 20 mole% isophthalic acid, 3.5 moles Copolymer of ear% 5-sulfoisophthalic acid and 50 mole% of ethylene glycol, obtained as a 20% aqueous dispersion; LATEX03 = copolymer of 80% ethyl acrylate and 20% methacrylic acid, at 27% Obtained from water dispersion; LATEX04 = copolymer of 49% methyl methacrylate, 49% butadiene and 2% itaconic acid; KIESELSOL 100F = colloidal silicone from Bayer, obtained from 30% water dispersion; KIESELSOL 300F = Colloidal silicone from Bayer, obtained as a 30% aqueous dispersion; ARKOPON ^TM T = N-methyl-N-2-sulfoethyl-oleylamine sodium salt of HOECHST, a surfactant obtained from HOECHST, supplied at a concentration of 40%; MERSOLAT ^TM H76 = Bayer's sodium pentadecyl sulfonate, supplied at a concentration of 76%; ULTRAVON ^TM W = CIBA-GEIGY sodium aryl sulfonate, supplied at 75-85% concentration; ARKOPAL ^TM N060 = nonylphenyl polyethylene glycol from HOECHST; HORDAMER ^TM PEO2 = polyethylene from HOECHST; obtained as a 40% aqueous dispersion; PAREZRESIN ^TM = Melamine-formaldehyde resin, from American cyanamide company, obtained with 80% solid solution;

The following supports with a 100 micron polyethylene terephthalate film as the base were used in the examples:

<tables><img file="TW554249B_D0014.tif" /></tables>

An AHLBRANDT consisting of two quartz electrodes, a round-bottom processor roller and a 15kHz generator ^TM Corona processor (model 53-02) is used for corona discharge treatment of polyethylene terephthalate film in air. The air gap between the electrode and the film is 1.2 mm. The film is imparted at a speed of 10 m / min by a corona processor with a watt density of 400 Wmin / m². Moderate adhesion.

The glow discharge treatment of the polyethylene terephthalate film is performed in a vacuum system consisting of a reactor vessel, a vacuum pump, a gas inlet, a DC power source, and a titanium glow cathode. The operating conditions used were a conveying speed of 40 m / min, an air pressure of 10-2 mbar, and a power density of 40 Wmin / m2, and the distance between the cathode and the film was 100 mm.

The poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonate) [PEDOT / PSS] dispersion was used in the examples in an aqueous dispersion of PEDOT / PSS at a weight ratio of 1: 2.4. Prepared by the method described in EP-A-1 079 397. The particle size of the PEDOT / PSS latex was determined by the CPS disc centrifugal measurement method to have a maximum narrowness of 25 nm and an average particle size of 30-50 nm.

Example 1

In Example 1, a negative photosensitive compound was used to form a pattern on the outermost layer of polythiophene. 40 ml / m 2 (40 micron wet thickness) of the coating dispersion described in Table 1 was applied to the bottom side of support number 1. The composition of the outermost layer after drying is also shown in Table 1.

<tables><img file="TW554249B_D0015.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 30-75 seconds (at 2 mW / cm²) (= 0.06-0.15 J / cm² exposure) and treated with deionized water. The results are shown in Table 2.

<tables><img file="TW554249B_D0016.tif" /></tables>

The results in Table 2 show that, for samples II to VII according to the present invention, a structured outermost layer containing conductive PEDOT / PSS was obtained, and the grain formation method of exposure and development did not substantially affect the outermost layer. Conductivity. After treatment, the surface resistivity of the unexposed area is 10 ⁴ Ω / square or more. When the material is thoroughly wiped with toilet paper during processing, 10 ¹⁰ Surface resistivity above Ω / square.

Example 2

In Example 2, a negative photosensitive compound was used to form the pattern of the outermost layer of polythiophene. The coating dispersion liquid described in Table 3 was applied to the bottom side of the support body No. 1 with 40 ml / m 2 (40 micron wet thickness) and the composition is shown in Table 3 after drying.

<tables><img file="TW554249B_D0017.tif" /></tables>

Exposing the sample to a PRIMJTON through a mask ^TM The CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 250 seconds (at 2 mW / cm²) (= 0.5 Joule / cm² exposure) was treated in water while wiped with toilet paper in water and the result Presented in Table 4.

<tables><img file="TW554249B_D0018.tif" /></tables>

The results in Table 4 show that in samples XX to XIV according to the present invention, a structured outermost layer containing conductive PEDOT / PSS was obtained. After treatment, the surface resistivity of the unexposed area is 10 ⁵ Ω / square or more. When the material is thoroughly wiped with toilet paper during processing, 10 ¹⁰ Surface resistivity above Ω / square.

Example 3

In Example 3, NDP04 (a homopolymer of ADS-MONOMER 01) was mixed in the outermost layer containing PEDOT / PSS to form the pattern of the outermost layer of polythiophene. Samples XV to XXXIV were prepared by coating the dispersion liquid described in Table 5 at 40 ml / m 2 on the support body Nos. 1 to 8 to 40 cm thick. After drying, samples XV to XXIV have a composition also shown in Table 5.

<tables><img file="TW554249B_D0019.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM The CDL1502i UV exposure unit (from AGFA-GEVAERT NV) for 200 seconds (at 2 mW / cm²) (= 0.5 Joule / cm² exposure) and was treated in water (gentle wipe with water and toilet paper). The results are shown in Table 6.

<tables><img file="TW554249B_D0020.tif" /></tables>

The results in Table 6 show that the concentration of NDP04 in the outermost layer containing PEDOT / PSS has an effect on the observed resistance ratio (unexposed / exposed areas) (that is, for the difference between processing between exposed and unexposed areas). Significant impact, in case of support reserve number 1, changes from 4 to 26.3.

The results shown in Table 6 also show that the special support resistivity ratio used in the unexposed / exposed areas (that is, the difference between the exposed and unexposed areas) has a significant impact, ranging from 2 to 5 × 10 ⁸ 。&gt;10 ⁸ Extremely high resistance ratios are observed in support numbers 2, 3, and 5 (that is, supports with a corona discharge or glow discharge treatment or supports using a special undercoat layer of support number 5). In the case of samples XV, XVI, and XVII coated on the support body number 1,&gt; 10 can be obtained by thoroughly wiping with toilet paper during the treatment ⁷ Ω / square surface resistivity (results are not shown in Table 6).

The mask for exposing the above samples is composed of high and low density alternating lines with lines as low as 6 microns in width. These lines can be clearly reproduced in the patterned material, showing conductive lines with similar widths and non-conductive spaces.

Example 4

In Example 4, various copolymers mixed with ADS-MONOMER01 were mixed in the outermost layer containing PEDOT / PSS to form the pattern of the outermost layer of polythiophene. Samples XXV to XXX were applied to a support No. 3 (a glow-discharge-treated polyethylene terephthalate film) to a thickness of 50 microns by coating the dispersion described in Table 7 at 50 ml / m 2. be made of.

<tables><img file="TW554249B_D0021.tif" /></tables>

<tables><img file="TW554249B_D0022.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL 1502i UV exposure and contact exposure unit (from AGFA-GEVAERT NV) for 200 seconds (at 4 mW / cm²) (= 0.8 Joules / cm² exposure) and treated in water (gentle wipe with toilet paper in water ). The results are shown in Table 8.

The results in Table 8 show that samples XXV to XXX have surface resistivities of unexposed to exposed areas greater than 2200 after treatment.

<tables><img file="TW554249B_D0023.tif" /></tables>

Example 5

In Example 5, samples XXXI to XXXIV were prepared by adding a solution mixed with a copolymer of ADS-MONOMER01 and N-methylpyrrolidone to a PEDOT / PSS aqueous dispersion, first preparing the compounds given in Table 9 Dispersion. Then, 50 ml / m 2 of these dispersions were coated on a support No. 3 (a glow discharge-treated polyethylene terephthalate film) to a wet thickness of 50 μm, and dried to the surface. The composition shown in 9.

<tables><img file="TW554249B_D0024.tif" /></tables>

Because the conductivity enhancement liquid N-methylpyrrolidone is present in the coating dispersion, the conductivity enhancement occurs during coating, resulting in the PEDOT / PSS-outermost layer being prepared in the absence of N-methylpyrrolidone (According to the teachings of EP-A 686662 and EP-A 1 003 179) the same outermost layer has a lower surface resistivity.

Exposing the sample to a PRINTON through a mask ^TM The CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 200 seconds (at 4 mW / cm²) (= 0.8 Joule / cm² exposure) is treated in water (gentle wipe with water and toilet paper) and The results are shown in Table 10.

The results in Table 10 show that samples XXXI to XXXIV had surface resistivities of unexposed to exposed areas greater than 9000 after treatment.

<tables><img file="TW554249B_D0025.tif" /></tables>

Example 6

In Example 6, samples XXV to XL were prepared by adding a solution mixed with the copolymer of ADS-MONOMER 01 to a PEDOT / PSS aqueous dispersion, and first preparing the dispersion given in Table 11. These dispersions of 40 ml / m 2 were then applied to support No. 3 (a glow discharge treated polyethylene terephthalate film) to a wet thickness of 40 microns and dried. Because no conductivity-enhancing liquid is present in the coating dispersion, no conductivity enhancement occurs during coating, resulting in a higher surface resistivity of the PEDOT / PSS-outermost layer than another existing one.

<tables><img file="TW554249B_D0026.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 100 seconds (at 4 mW / cm²) (= 0.4 Joule / cm² exposure) and immersed in water (treatment liquid A) or 2.5 A wt% aqueous ammonia solution (treatment liquid B) in 25 ° C water was gently moved and dried at 50 ° C for 4 minutes. The results are shown in Table 12.

The sample was then treated in a 10% diethylene glycol aqueous solution for 1 hour to enhance the conductivity of the sample, and then the conductivity enhancement solution at 25 ° C was dried at 110 ° C for 20 minutes. Then, the surface resistivity of the exposed and unexposed areas was measured. The enhanced surface resistivity values are shown in Table 12.

<tables><img file="TW554249B_D0027.tif" /></tables>

Example 6 shows that those with the outermost layer of PEDOT / PSS with no conductivity enhancement as raw materials and those with the outermost layer of PEDOT / PSS with conductivity enhancement as raw materials (see Example 5) can achieve similar unexposed / exposed Area resistance ratio. The premise is that the structured outermost layer is post-treated with a conductive enhancement solution, and then dried / tempered at an appropriate temperature. However, it should be noted that post-treatment with a conductivity enhancing solution also enhances the conductivity of any PEDOT / PSS remaining in the unexposed area due to incomplete removal.

Example 7

The sample VII, X, X, and XII of Example 2 were traced in a hot mold with a NdYAG laser (1064 nm) with a 22-micron bright spot size, an 11-micron dot pitch, and a scanning speed of 2 m / s Ground exposure. The image plane power is set at 100 mW. The exposed samples were treated in water (gently wiped with toilet paper in water).

For samples IX, X, XI and XII, a structured outermost layer containing PEDOT / PSS was obtained, which had a similar surface resistivity as in Example 2. For Sample VIII (Comparative Example), the outermost layer containing PEDOT / PSS containing structured conductivity was not obtained because the outermost layer containing PEDOT / PSS was removed in the unexposed and exposed areas. Surface resistivity of unexposed area is 10 ⁴ Ω / square or more. When the material is thoroughly wiped with toilet paper during processing, the surface resistivity of the unexposed area can be above 1010Ω / square.

Example 8

The samples VIII, X, X, X, and XII of Example 2 were applied in a hot mold with a diode laser (830 nm) having a bright spot size of 11 microns, a pitch of 6 microns, and a scanning speed of 2 m / s. Trace pattern exposure. The image plane power is set at 81 mW. The exposed samples were treated in water (gently wiped with toilet paper in water). The results were similar to those obtained in Example 7.

Example 9

Example 9, a positive photosensitive compound was used as a pattern for forming the outermost layer of polythiophene. Support No. 1 was first coated with a solution (15 micron wet thickness) of PQD01 in methyl ethyl ketone (1: 2 volume: volume). Samples XLI to XLII were prepared by coating the PEDOT / PSS-containing dispersion liquid shown in Table 13 with a wet thickness of PQD01 to 67 microns and drying. The outermost layers containing PEDOT / PSS of samples XLI and XLII contained 100 and 400 PEDOT / PSS, respectively.

<tables><img file="TW554249B_D0028.tif" /></tables>

The sample XLI consists of the PEDOT / PSS layer side of the support, and the sample XLII consists of the uncoated side of the support, each through a mask with a PRINTON ^TM The CDL1502i UV exposure unit was exposed for 80 seconds (at 4 mW / cm²) (= 0.32 Joules / cm²) and treated with AZ303 (CLARIANT) for 80 seconds. The outermost layer containing PEDOT / PSS of the structured conductivity of the trace pattern was obtained. The exposure method and the development method do not affect the outermost layer's conductivity. The surface resistivity of the unexposed area is 1.6x10 in the example of the sample XLI ⁴ Ω / square, 10 in the case of sample XLII ¹⁰ Ω / square. When the material is thoroughly wiped with toilet paper during processing, the surface resistivity of the exposed area can be 10 ¹⁰ Ω / square or more. Samples XLI and XLII obtained resolutions of 20 microns and 50 microns, respectively.

Example 10

In Example 10, the positive photosensitive compound and the conductive polymer were present in the same layer. Support No. 1 was coated with the following coating dispersion (Table 14) at 50 ml / m 2 (50 micron wet thickness).

<tables><img file="TW554249B_D0029.tif" /></tables>

Pass the mask sample on a PRINTON ^TM The CDL 1502i UV exposure unit was exposed for 60 seconds (at 4 mW / cm²) (= 0.24 Joule / cm² exposure) and treated with AZ351B (CLARIANT). The outermost layer containing PEDOT / PSS with the structured conductivity of the copy image. Surface resistivity of unexposed areas after development is 10 ⁴ Ω / square or more. When the material is thoroughly wiped with toilet paper or through a high-pressure air jet, the surface resistivity of the exposed area can be obtained at 10 ¹⁰ Ω / square or more. A resolution of 6 microns was obtained.

Example 11

In Example 11, BADS01 and BADS02 (negative photosensitive bis (aryl azosulfonic acid) salt) were used to form the pattern of the exposed distinguishable element. Sample XLIV was prepared by coating the support No. 3 with the coating dispersion shown in Table 15 at 40 ml / m 2 (40 μm wet thickness), which does not contain a conductive enhancement solution.

<tables><img file="TW554249B_D0030.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL1502i UV exposure unit (from AGFA-GEVAERT NV) for 400 seconds (at 4 mW / cm²) (= 1.6 Joules / cm² exposure), rinse with deionized water and dry at 50 ° C for 4 minutes . The surface resistivities of the unexposed and exposed areas of the exposed distinguishable elements before or after being rinsed and dried with water are shown in Table 16.

<tables><img file="TW554249B_D0031.tif" /></tables>

It was noted that all samples containing BADS01 reached low surface resistivity without the use of conductivity enhancement treatment. No need to wipe to remove unexposed areas.

The results in Table 16 show that samples XLIV to XLIX were exposed and unexposed on the surface of a light-differentiable element containing BADS01 before the conductivity of the surface resistance ratio (which varies with BADS01 concentration) increased with exposure to unexposed areas. There are differences in surface resistivity between regions. The highest surface conductivity ratio before conductivity enhancement is 3.4x10 ⁹ This is observed with 100% by weight of BADS01 (200 mg / m² BADS01) relative to PEDOT / PSS100.

Conductivity enhancement reduces the surface resistivity of the exposed area by up to 700 times, and the amount of enhancement decreases with increasing BADS01 concentration, showing the characteristics of enhanced conductivity of BADS01.

Sample L has a different surface conductivity. The light distinguishable element containing BADS01 is equivalent to that achieved by samples XLV to XLIX, but the conductivity enhancement of sample L is significantly lower than those of samples XLV to XLIX.

Example 12:

Example 12 differs from Example 11 in that ammonia is mixed to improve the stability of the outermost layer containing PEDOT / PSS. Support No. 3 was coated with the coating dispersion shown in Table 17 at 40 ml / m 2 (40 micron wet thickness).

<tables><img file="TW554249B_D0032.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL1502i UV exposure unit (from AGFA-GEVAERT NV) for 250 seconds (at 4 mW / cm²) (= 1.0 Joule / cm² exposure), rinse with deionized water and dry at 50 ° C for 4 minutes . The surface resistivities of the unexposed and exposed areas of the exposed distinguishable elements before or after washing and drying with water are shown in Table 18.

The results in Table 18 show that samples LII and LIII, before and after the conductivity of the surface resistance ratio (which varies with the BADS01 concentration) of the exposed to unexposed areas, is enhanced, the exposed and unexposed surfaces of the light-differentiable element containing BADS01 There are differences in surface resistivity between regions. Maximum surface conductivity ratio before conductivity enhancement 4.4x10 ⁸ It was observed on 100-mg / m² BADS01.

<tables><img file="TW554249B_D0033.tif" /></tables>

Example 13:

In Example 13, NDP33 (a negative photosensitive copolymer) mixed with BADS01 or BADS03 (negative photosensitive bis (aryl azosulfonic acid) salt) and BADS03 alone were used to form an exposure distinguishable element The pattern. Samples LIV to LVII were prepared by coating the support No. 3 with the coating dispersion shown in Table 19 at 50 ml / m 2 (50 micron wet thickness), which did not contain a conductive enhancement liquid.

<tables><img file="TW554249B_D0034.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 150 seconds (at 4 mW / cm²) (= 0.6 Joule / cm² exposure) and is immersed in a 2.5% by weight ammonia solution ( 25 ° C water), move gently, rinse with deionized water, dry at 50 ° C for 4 minutes, treat with 10% diethylene glycol aqueous solution for 1 minute, thereby improving conductivity, and finally dry at 110 ° C for 10 minutes. The results are shown in Table 20.

The results in Table 20 show that in the samples LIV to LVII according to the present invention, a structured conductive outermost layer containing PEDOT / PSS was obtained. Surface resistivity of unexposed areas below 10 ⁵ Ω / square, and the surface resistivity of the unexposed area is greater than 10 ¹³ Ω / square. The highest RS ratio of the unexposed / exposed areas after the conductivity improvement was observed in sample LVI combined with BADS03 and NDP33 and sample LVII with BADSO3 alone.

Unlike Examples 11 and 12, in which superior RS ratios of unexposed / exposed areas were also observed after increasing conductivity with BADS01, bubbles were observed in the exposed areas, using ADS-MONOMER01-copolymer NDP33 and BADS01. The composition does not generate bubbles in the exposed area. This can be attributed to the use of the BADS01 and ADS-MONOMER01 compositions.

<tables><img file="TW554249B_D0035.tif" /></tables>

Example 14

In Example 14, NDPl5 (a negative photosensitive copolymer) mixed with BADS01 (a negative bis (aryl azosulfonate) compound) was used to form a pattern of an exposed distinguishable element. Samples LVIII to LXII were prepared by coating the support No. 3 with the coating dispersion shown in Table 21 at 40 ml / m 2 (40 μm wet thickness), which does not contain a conductive enhancement liquid.

<tables><img file="TW554249B_D0036.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL 1502i UV exposure exposure unit (from AGFA-GEVAERT NV) for 400 seconds (at 4 mW / cm²) (= 1.6 Joules / cm² exposure) and is immersed in a 2.5% by weight ammonia solution ( 25 ° C water), move gently, rinse with deionized water, dry at 50 ° C for 4 minutes, treat with 10% diethylene glycol aqueous solution for 1 minute, thereby improving conductivity, and finally dry at 110 ° C for 10 minutes. The results are shown in Table 22.

<tables><img file="TW554249B_D0037.tif" /></tables>

The results in Table 20 show that in the samples LVIII to LXII according to the present invention, a structured conductive outermost layer containing PEDOT / PSS was obtained. Surface resistivity of unexposed areas below 10 ⁴ Ω / square, and the surface resistivity of the unexposed area is&gt; 10 ¹⁵ Ω / square. Maximum RS ratio of unexposed / exposed areas after improved conductivity is 2.9x10 ¹² It was observed in sample LVIII.

As in Example 13 (in which a superior RS ratio of unexposed / exposed areas was also observed after the conductivity was improved with the composition of ADS-MONOMER01-copolymer and BADS01), some samples: samples LVIII, LIX and LX, in No bubbles were observed in the large exposure area.

Example 15

In Example 15, NDP15 (a negative photosensitive copolymer) mixed with BADS01 (a negative bis (aryl azosulfonate) compound) was used to form a pattern of an exposed distinguishable element. Samples LXIII to LXVII were prepared by coating the support No. 3 with the coating dispersion shown in Table 23 at 50 ml / m 2 (50 micron wet thickness), which did not contain a conductive enhancement liquid.

<tables><img file="TW554249B_D0038.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM In the CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) (at 4 mW / cm²), the exposure time is set in Table 24, and it is immersed in 2.5% by weight aqueous ammonia solution (25 ° C water). Move at moderate temperature, rinse with deionized water, dry at 50 ° C for 4 minutes, treat with 10% diethylene glycol aqueous solution for 1 minute, thereby improving conductivity, and finally dry at 110 ° C for 10 minutes. The results are shown in Table 24.

<tables><img file="TW554249B_D0039.tif" /></tables>

The results in Table 24 show that in the samples LXIII to LXVII according to the present invention, a structured conductive outermost layer containing PEDOT / PSS was obtained. Surface resistivity of unexposed areas is less than 2x10 ⁴ Ω / square, and the surface resistivity of the unexposed area significantly changed from the sample LXIII to 10 of LXV ⁵ Up to 10 ⁷ Ω / square changes to&gt; 10 of samples LXVI and LXVII ¹⁴ Ω / square. The highest Rs ratio of 7.4x10 in the unexposed / exposed areas after the conductivity improvement was observed in sample LXVI.

Only sample LXVII was observed with bubbles in the large exposure area.

Embodiment 16:

Example 16 reveals the negative striation performance of different layer structures on the branch support number 1 and the branch support number 3. The composition of the layers is shown in Table 25.

<tables><img file="TW554249B_D0040.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM In the CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) (at 4 mW / cm²), the exposure time is given in Table 26, and rinsed with deionized water. The surface resistivities of the unexposed and exposed areas of the exposed distinguishable elements before or after rinsing with water deionized water are shown in Table 26. Only the sample LXXI need not be wiped with soft toilet paper in water.

<tables><img file="TW554249B_D0041.tif" /></tables>

Although the samples LXVIII, LXIX, LXX, LXXII, and LXXIII only have the ADS-MONOMER 01 homopolymer on the bottom layer, and the conductivity enhancement of the outer layer containing PEDOT / PSS is the result of the presence of N-methyl-pyrrolidone, so the sample LXIX, LXX and LXXIII have moderately different surface resistivities, and samples LXVIII and LXXII have quite different surface resistivities. This shows that the structure of the outermost layer containing PEDOT / PSS may have a UV-exposing resin containing an aryl sulfamate group in an adjacent layer.

Samples with ADS-MONOMER 01 homopolymer on the bottom layer and its adjacent layer containing PEDOT / PSS outermost layer LXXI and LXXIV have quite different surface conductivity, regardless of whether the outer layer containing PEDOT / PSS is coated with conductivity enhancer N -Methyl-pyrrolidone.

Example 17:

Example 17 discloses the negative striation performance of different layer structures on the support strut number 1 and the support strut number 3. The composition of the support and layer used is shown in Table 27. Both layers 1 and 2 were coated to a thickness of 50 microns.

<tables><img file="TW554249B_D0042.tif" /></tables>

<tables><img file="TW554249B_D0043.tif" /></tables>

Exposing the sample to a PRINTON through a mask ^TM CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 100 seconds (at 4 mW / cm²) (= 0.4 Joule / cm² exposure), and rinsed with deionized water. Samples LXXVI and LXXIX were not wiped, and samples LXXVII and LXXX required gentle wiping. The surface resistivities of the unexposed and exposed areas of the exposed distinguishable elements before or after rinsing with water deionized water are shown in Table 28.

Conductivity enhancement was then performed on the samples LXXVI and LXXIX by immersing the developed material in a 10% N-methyl-pyrrolidone aqueous solution for 1 minute, and then drying at 50 ° C for 10 minutes. The surface resistivity of the unexposed and exposed areas after the conductivity enhancement is shown in Table 28.

<tables><img file="TW554249B_D0044.tif" /></tables>

The results in Table 28 clearly show that for a material having an outermost layer coated with N-methyl-pyrrolidone containing PEDOT / PSS-dispersion, and a conductivity enhancer, the support No. 3 (glow discharge Treated polyethylene terephthalate film) has a higher Rs ratio of exposed to unexposed areas after treatment than the material coated on support number 1. For the sample LXXVI with NDP14 (an ADS-MONOMER01 hydroxyethyl methacrylate copolymer) in the bottom layer and the outermost layer containing PEDOT / PSS, and having a coating with a PEDOT / PSS-dispersion containing no conductivity enhancer For the LXXIX sample containing the outermost layer of PEDOT / PSS, this effect is negligible after the conductivity is enhanced with N-methyl-pyrrolidone.

For the material having the outermost layer coated with the N-methyl-pyrrolidone-containing PEDOT / PSS-dispersion, the material coated on the support No. 3 all showed extremely high exposure versus unexposed Regional Rs ratio, at least 4x10 ⁸ , Regardless of whether NDP14 (an ADS-MONOMER 01 hydroxyethyl methacrylate copolymer) is present in the bottom layer and the outermost layer containing PEDOT / PSS or only in the bottom layer. Furthermore, the sample LXXVI with NDP14 on the bottom layer and the outermost layer containing PEDOT / PSS, and the outermost layer containing PEDOT / PSS coated with a PEDOT / PSS-dispersion solution containing a non-conductive enhancer N-methyl-pyrrolidone Sample LXXIX, after increasing conductivity with the conductivity enhancer N-methyl-pyrrolidone, showed approximately 3x10 ⁸ Very high Rs ratio of exposure to unexposed areas.

This example shows that the ADS-MONOMER copolymer is as effective as a photosensitive component when mixed in an adjacent layer containing the outermost layer of PEDOT / PSS. When exposed, the exposed portion of the outermost layer containing PEDOT / PSS can be changed relative to The outermost unexposed portion can be removed.

Example 18

In Example 18, BADS02 (a negative photosensitive bis (aryl azosulfonate)) with different concentrations was used in the outer layer containing PEDOT / PSS for the pattern of forming the outer layer of polythiophene. Support No. 1 was coated with the coating dispersion shown in Table 29 at 40 ml / m 2 (40 micron wet thickness).

<tables><img file="TW554249B_D0045.tif" /></tables>

<tables><img file="TW554249B_D0046.tif" /></tables>

Exposing the sample through a mask to a PR on a glass filter] [NTON ^TM CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 400 seconds (at 4 mW / cm²) (= 1.6 Joules / cm² exposure), and rinsed with deionized water. However, as long as a subsequent water rinse is performed, no difference in surface resistivity is observed regardless of whether an exposure time of 100 seconds or 400 seconds is used. If the material comes into contact with water, the decomposition process appears to continue.

The surface resistivities of the unexposed and exposed areas of the exposed distinguishable elements before or after rinsing with water deionized water are shown in Table 30.

<tables><img file="TW554249B_D0047.tif" /></tables>

<tables><img file="TW554249B_D0048.tif" /></tables>

The results in Table 30 show the surface resistivity ratio of exposure to unexposed areas (which varies with the BADS02 concentration). Without removing the unexposed areas, the difference between the exposed and unexposed areas of the surface of the element with light that contains BADS02 is removed Have different surface resistivities. Maximum surface conductivity ratio 10 ⁴ At 87 mg / m² (2.0x10- ⁴ Moore / square meter) observed on BADS02.

When the exposed distinguishable elements of samples LXXXII to LXXXVIII were subsequently wiped with soft water-wet toilet paper, the unexposed areas were removed, thereby increasing the surface resistivity of the unexposed areas to about 10 ⁶ Ω / square. A stronger wipe increases the surface resistivity of the unexposed area to about 10 ¹⁰ Ω / square.

Example 19

In Example 19, BADS01, BADS02, and BADS03 (negative photosensitive bis (aryl azosulfonate)) were used to form the pattern of the outermost layer of polythiophene. Samples LXXXIX to LCIII were prepared by coating the support No. 1 with the coating dispersion shown in Table 31 at 40 ml / m 2 (40 μm wet thickness), followed by drying at 50 ° C. for 5 minutes. However, in the case of a dispersion containing diethylene glycol, it is dried at 110 ° C for 5 minutes.

<tables><img file="TW554249B_D0049.tif" /></tables>

Expose the sample through a mask to a PRINTON on a glass filter ^TM CDL 1502i UV exposure unit (from AGFA-GEVAERT NV) for 400 seconds (at 4 mW / cm²) (= 1.6 Joule / cm² exposure), and treated in 2.5% NH4OH aqueous solution and deionized Rinse with water. The surface resistivities of the unexposed and exposed areas of the exposed distinguishable elements before or after rinsing with water deionized water and drying at 50 ° C. for 4 minutes are shown in Table 32.

The results in Table 32 show that in terms of the surface resistivity ratio of the exposure to the unexposed areas, there are different surface resistivities between the exposed and unexposed areas of the surface of the light distinguishable element containing BADS01, BADS02, and BADS03. The highest surface conductivity ratio of 16,666 was observed on BADS02.

When the exposed distinguishable elements of samples LXXXIX to LCIII were subsequently wiped with soft water-wet toilet paper, the unexposed areas were removed, thereby increasing the surface resistivity of the unexposed areas to about 10 ⁶ Ω / square. A stronger wipe increases the surface resistivity of the unexposed area to about 10 ^1o Ω / square.

<tables><img file="TW554249B_D0050.tif" /></tables>

The invention may include any feature or combination of features disclosed herein, either implicitly or explicitly, or any general discussion thereof, whether or not it relates to an invention that is within the scope of this application. In view of the foregoing description, it will be apparent that those skilled in the art can make various modifications within the scope of the present invention.