KR100995561B1 - Process for preparing electroconductive coatings - Google Patents

Abstract

An aqueous dispersion of a latex particle having a polymer consisting of a structural unit comprising a monomer unit of the formula (I) and at least one polyanionic compound, the size of which is usually 40 nm or less, wherein the aqueous dispersion is di or polyhydroxy- and / Or a carboxyl group or an amide or lactam group-containing organic compound, and an aprotic compound having a dielectric constant? Of ≧ 15, wherein the latex particles comprise the at least one polyanionic compound and the polymer in a weight ratio of at least 4 An aqueous dispersion of latex particles; And preparing an aqueous solution or an aqueous dispersion of the aforementioned polymer by polymerizing with an initiator in a reaction medium in the presence of at least one polyanionic compound under oxidizing or reducing conditions.

(I)

(I)

Wherein R ¹ and R ² independently of one another represent a hydrogen or C _1-5 -alkyl group, or together form an optionally substituted C _1-5 -alkylene moiety.

Description

Process for preparing electroconductive coatings

Technical Field

The present invention relates to a method of making an electroconductive coating.

Background

Polythiophenes are widely studied because of their interesting electrical and / or optical properties. Polythiophenes are electrically conductive upon chemical or electrochemical oxidation or reduction. The electrical conductivity of the polythiophene that can finally be reached is determined by its chemical composition, the stereoregularity of the thiophene polymerization in the polythiophene chain and its π-conjugation length. Stereoregularity problems do not occur when unsubstituted thiophenes or thiophenes substituted with the same groups in the 3- and 4-positions are polymerized.

EP-A 339 340 discloses polythiophenes comprising structural units of the formula: and a process for the oxidative polymerization of the corresponding thiophenes:

Wherein A represents an optionally substituted C 1 -C 4 -alkylene radical.

EP-A 440 957 discloses a dispersion in which a polythiophene is composed of a structural unit of formula (I) in the presence of a polyanionic compound, specifically its example contains 3,4-ethylenedioxythiophene in water. [EDOT] in the presence of poly (styrene sulfonic acid) 1: 1.29 (Example 2), 1: 2.2 (Examples 7 and 8) 1: 4 (Examples 1, 3, 4 and 10), 1: 6 Example 5 and a method of polymerization in a weight ratio of 1: 8.33 (Example 6) are disclosed.

Wherein R ¹ and R ² independently of one another represent a hydrogen or C 1 -C 4 alkyl group or together form an optionally substituted C 1 -C 4 -alkylene moiety.

In 2001, it was reduced from passive matrix OEL's to OEL3-3 (Elschner et al.), A paper presented at ASIA DISPLAY / IDW'01 held in October in Nagayo, Japan. High resistivity PEDOT / PSS for crosstalk has been disclosed and characteristic data of standard BAYTRON ^™ P and BAYTRON ^™ P types AI4083 and CH8000 are presented, which are shown below:

BAYTRON P type Resistivity (Ω-㎝) Center of particle size distribution [nm] PSS: PEDOT composition (weight ratio) Standard One 110 2.5: 1 VP AI4083 500-1000 55 6: 1 VP CH8000 70,000-200,000 20 20: 1

Elschner et al. Found that the reduced conductivity in several grade steps for the standard BAYTRON ^™ P shifts the center of the particle size distribution from about 100 nm to 20 nm, while the size of the gel particles is in its number-swelling state. It is reported that it should be noted that the size is measured at, and smaller after dehydration. Bayer's current product documentation shows the following characteristics for these three BAYTRON ^TM P grades:

BAYTRON P-type ^TM Resistivity
(Ω-cm) Particle Size Distribution (Swelled State) d ₅₀ (nm) d ₉₀ (nm) d ₅₅ (nm) VP AI4083 1000 <200 VP CH8000 100,000 <35 <60 <200

Aqueous dispersions of PEDOT / PSS are available from Bayer under the name BAYTRON ^™ P. ^The molar ratio in standard BAYTRON ^TM P by ¹³ C NMR analysis was found to be 2.7 (weight ratio of 3.50) as disclosed in Polymer, volume 43, pages 7003 to 7006, P. Adriaensens et al. It was found to be 2.1 (weight ratio of 2.72) in PEDOT / PSS standard aqueous dispersion sold by AGFA-GEVAERT NV.

Table 1:

PEDOT Type Initial Aromatic Carbon Atomic Strength of PSS Initial Aliphatic Carbon Atomic Strength of PSS Average Initial Carbon Atomic Strength of PSS Initial Ether Carbon Atomic Strength of PEDOT PSS / PEDOT BAYTRON P ^TM Sample 1 445 454 449.5 164 2.7 BAYTRON ^TM P Sample 2 246 260 253 85 3.0 AGFA-GEVAERT PSS / PEDOT Dispersion 446 493 470 226 2.1

The electrical conductivity of PEDOT / PSS (PSS: PEDOT ratio is 0.24 to 3.33) prepared from an aqueous solution of EDOT and NaPPS and acetonitrile (AN) solution increases as the PSS: PEDOT ratio decreases as one skilled in the art intuitively foresee. (M. Lefebvre et al., Chem. Materials, Vol 11, pages 262-268, 1999) because of the higher concentration of PEDOT, an inherent conductive component.

Solvent used Obtained PSS: PEDOT Ratio Initial Conductivity [S cm ^-1 ] AN / water 0.48 1.3 AN / water 0.67 1.0 AN / water 0.71 1.5 AN / water 0.91 0.3 AN / water 1.0 2.5 AN / water 3.33 6 X 10 ^-3 water 0.24 9.9 water 2.0 0.3 water 2.5 0.4

EP-A-686 662 includes A) natural polythiophenes having repeating structural units of formula (I), and B) di or polyhydroxy- and / or carboxyl or amide or lactam group containing organic compounds. Mixture; And

Wherein R ¹ and R ² independently represent hydrogen or C 1 -C 4 alkyl groups with respect to each other, or are optionally substituted with C 1 -C 4 alkylene moieties, preferably methylene, C 1 -C 12 -alkyl optionally substituted with alkyl groups Or 1,2-ethylene residue or 1,2-cyclohexane residue optionally substituted with a phenyl group;

Disclosed is a conductive coating from the mixture wherein the resistance is preferably adjusted to increase to <300 kPa / square. The example of EP-A 686 662 also discloses a process for polymerizing EDOT in water in the presence of poly (styrene sulfonic acid) at a weight ratio of 1: 3.57.

WO 03 / 001299A includes a support and a light-exposure differentiable element, the exposure differential element optionally comprising an outermost layer comprising a polymer or copolymer of a polyanion and a substituted or unsubstituted thiophene. A second layer continuous to the outermost layer, wherein the outermost layer and / or the optional second layer are capable of varying the removal rate of the exposed portion of the outermost layer relative to the unexposed portion of the outermost layer upon exposure. Disclosed is a material for forming an electrically conductive pattern, comprising a component sensitive to light. WO 03 / 001299A is contacted with high boiling liquids such as di- or polyhydroxy- and / or carboxyl groups or amides or lactam group-containing organic compounds, and optionally at high temperatures, preferably at 100 to 250 ° C. Preferably, a method for improving conductivity is disclosed which increases conductivity by heating for 1 to 90 seconds. Alternatively, in the case of aprotic compounds having a dielectric constant ≧ 15, for example N-methyl-pyrrolidinone, temperatures up to 100 ° C. may be used. Such conductivity enhancement is observed with polythiophene and may occur during or after the outermost layer production. Particularly preferred liquids for such treatments are N-methyl-pyrrolidinone and diethylene glycol (disclosed in EP-A 686 662 and EP-A-1 003 179). The PEDOT / PSS dispersions used in all examples of WO 03 / 001299A have a narrow particle size distribution as measured by a CPS disk centrifuge with a PEDOT: PSS weight ratio of 1: 2.4 and a maximum of 25 nm, with an average particle size of 30 50 nm.

EP-A-1 003 179 provides an aqueous composition comprising a polythiophene, a polyanionic compound and an aprotic compound having a dielectric constant? Applying the composition to an object forming a layer; And drying the layer to form a conductive polymer layer on the object, wherein the object and the layer maintain a temperature of 100 ° C. or less, and the conductive polymer layer has a resistivity of 2 kΩ / □ or less. A method of forming a conductive polymer layer on an object is disclosed. EP 1 003 179 also discloses a process for polymerizing EDOT in water in the presence of poly (spirene sulfonic acid) in a weight ratio of 1: 2.46.

In addition, Proceedings of SPIE, volume 4464, pages 85-92, Kim et al., 2002, also discloses a small amount of polyalcohol, using BAYTRON ^TM P having a mean particle size of 25 nm-75 nm as starting material, For example, a method of rapidly increasing the conductivity of PEDOT / PSS without losing optical transparency by adding glycerol has been reported, and references in Organic Electronics, volume 3, pages 143-148, Pettersson et al. BAYTRON ^{TM with} PEDOT: PSS weight ratio 1: 2.5 as starting material A method of increasing the conductivity of PEDOT / PSS has been reported without the loss of transparency by the addition of sorbitol using P.

A common drawback of the conductive polymers produced and studied so far is that their conductivity is still low for some applications, and their visible light transmittance is not high enough and / or they are not processable.

Purpose of the Invention

Accordingly, aspects of the present invention provide a poly (3,4-alkylenedioxy-thiophene) which, as polymerized, provides high electrical conductivity, high visible light transmittance and / or good processability upon oxidation or reduction. To provide 4-alkylenedioxy-thiophene.

Further aspects and advantages of the invention will be described below.

Summary of the Invention

Unpublished European Application No. EP01000780 discloses an optimum surface resistance observed for PEDOT / PSS dispersions produced in a reaction medium containing less than 3 ml of oxygen per 1 liter of reaction medium, while the surface resistance of the layer comprising PEDOT / PSS is reacted. It is disclosed that the oxygen concentration in the medium decreases with decreasing. Therefore, when studying the effect of the preparation of PSS / PEDOT latex on the properties of layers made of this latex, it is important to use PSS / PEDOT latex prepared in a reaction medium containing similar concentrations of oxygen. Surprisingly, reference is made to Chem. Materials, volume 11, pages 262-268, M. Lefebvre et al., 1999 and in OEL3-3, Elschne et al., Published at ASIA DISPLAY / IDW'01 in Nagayo, Japan, October 2001. Contrary to what has been reported to decrease in electrical conductivity with increasing PSS: PEDOT ratio, certain oxygen in the reaction medium is present if certain additives, such as polyhydroxy compounds such as N-methyl-pyrrolidinone and diethylene glycol, are present in the dispersion. It was found that the surface resistance of the layer prepared with the aqueous dispersion of PEDOT / PSS latex prepared in the presence of concentration decreased with increasing PSS / PEDOT ratio. In EP-A 0 686 662 and EP-A 1 003 179, it is known that heating a layer comprising PSS / PEDOT latex increases the conductivity of the layer, although it is known that the high PSS / PEDOT It is difficult to anticipate overall that the conductivity is further improved at the ratio, ie at lower concentrations of PEDOT.

An aspect of the invention is an aqueous dispersion of latex particles, wherein the latex particles comprise a polymer consisting of a structural unit comprising a monomer unit of formula (I) and at least one polyanion compound, the primary particle size being 40 nm or less The aqueous dispersion is dihydroxy group, polyhydroxy group, carboxyl group, amide group, lactam group, dihydroxy group and carboxyl group, dihydroxy group and amide group, dihydroxy group and lactam group, polyhydroxy group and carboxyl group, polyhydroxy group and amide group, or polyhydroxy group And a lactam group-containing organic compound, or an aprotic compound having a dielectric constant ε of ≧ 15, wherein the latex particles comprise the at least one polyanion compound and the polymer, at least four, the at least one polyanion to the polymer Water dispersion, characterized in that it comprises a weight ratio of the compound It is realized by:

Wherein R ¹ and R ² independently of one another represent a hydrogen or a C _1-5 -alkyl group, or together form an optionally substituted C _1-5 -alkylene moiety.

An aspect of the present invention is to prepare an aqueous solution or an aqueous dispersion of a polymer consisting of structural units comprising monomer units of the formula (I) by polymerizing with an initiator in a reaction medium in the presence of one or more polyanionic compounds under oxidizing or reducing conditions. Setting a weight ratio of the at least one polyanionic compound to the structural unit in the polymerization reaction in a range of 4: 1 to 20: 1; The polymer and dihydroxy group, polyhydroxy group, carboxyl group, amide group, lactam group, dihydroxy group and carboxyl group, dihydroxy group and amide group, dihydroxy group and lactam group, polyhydroxy group and carboxyl group, polyhydroxy group combined with the at least one polyanionic compound Preparing a first coating composition comprising an amide group or an organic compound containing a polyhydroxy group and a lactam group in an aqueous or non-aqueous medium; Coating the first coating composition on an object to form a first layer; And heating the first layer at a temperature of 100 ° C. or higher.

(I)

(I)

Another aspect of the present invention is to prepare an aqueous solution or aqueous dispersion of a polymer consisting of structural units comprising monomer units of the formula (I) by polymerizing with an initiator in a reaction medium in the presence of one or more polyanionic compounds under oxidizing or reducing conditions. As a step, the weight ratio of the at least one polyanionic compound to the structural unit in the polymerization reaction is in the range of 4: 1 to 20: 1; Preparing a second coating composition comprising in said aqueous or non-aqueous medium said polymer combined with said at least one polyanionic compound and said aprotic compound having a dielectric constant? Coating the second coating composition on an object to form a second layer; And heating the second layer at a temperature of 50 ° C. or higher.

An aspect of the present invention is to prepare an aqueous solution or an aqueous dispersion of a polymer comprising a structural unit of formula (I) by polymerizing with an initiator in a reaction medium in the presence of a polyanion under oxidizing or reducing conditions to produce a polyanion during the polymerization reaction. Molar ratio of the structural unit of formula (I) to the anionic group in the range of 4: 1 to 10: 1; The polymer and the dihydroxy group, polyhydroxy group, carboxyl group, amide group, lactam group, dihydroxy group and carboxyl group, dihydroxy group and amide group, dihydroxy group and lactam group, polyhydroxy group and carboxyl group, polyhydroxy group and amide group bonded to the poly anion Or preparing a first coating composition comprising an organic compound containing a polyhydroxy group and a lactam group in an aqueous or non-aqueous medium; Coating the first coating composition on an object to form a first layer; And heating the first layer at a temperature of 100 ° C. or higher.

(I)

(I)

An aspect of the present invention is to prepare an aqueous solution or an aqueous dispersion of a polymer comprising a structural unit of formula (I) by polymerizing with an initiator in a reaction medium in the presence of a polyanion under oxidizing or reducing conditions to produce a polyanion during the polymerization reaction. Molar ratio of the structural unit of formula (I) to the anionic group in the range of 4: 1 to 10: 1; Preparing a second coating composition comprising the polymer bonded to the poly anion and an aprotic compound having a dielectric constant? Of ≧ 15 in an aqueous or non-aqueous medium; Coating the second coating composition on an object to form a second layer; And heating the second layer at a temperature of 50 ° C. or higher.

(I)

(I)

Preferred embodiments of the invention will be disclosed in the detailed description of the invention.

Detailed description of the invention

As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. That is, for example, "one thiophene according to formula (I)" includes one or more such thiophenes, and "polymerization of one thiophene according to formula (I)" means one such thiophene. The above copolymerization is included.

The term polymer includes both homopolymers, copolymers, terpolymers, graft polymers and block copolymers as well as chain and condensed polymers.

C _{1 -5} - alkylene rep term represents a 1,2-ethylenedioxy, 1,3-propylene dioxy, 1,4-alkylenedioxy, and 1, 5-pentylene alkylenedioxy.

The term initiator means a kind capable of initiating polymerization.

The term alkyl means all possible variants for each number of carbon atoms in the alkyl group, with three carbon atoms: n-propyl and isopropyl; N-butyl, isobutyl and tert-butyl when having 4 carbon atoms; For 5 carbon atoms, n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl, 2-methyl-butyl and the like.

For the purposes of the present invention, the term aqueous medium is at least 60% by volume, preferably at least 80% by volume of water, and optionally methanol, ethanol, 2-propanol, butanol, iso-amyl alcohol, octanol, cetyl alcohol and the like. Alcohol; Glycols such as ethylene glycol; glycerin; N-methyl pyrrolidinone; Methoxypropanol; And water miscible organic solvents such as ketones such as 2-propanone and 2-butanone.

For the purposes of the present invention the term non-aqueous medium means any liquid which is not included in the term aqueous medium.

The term electrical conductivity means that the surface resistance is 10 ⁶ Ω / □ or less.

The term "improving conductivity" means dihydroxy group, polyhydroxy group, carboxyl group, amide group, lactam group, dihydroxy group and carboxyl group, dihydroxy group and amide group, dihydroxy group and lactam group, polyhydroxy group and carboxyl group, polyhydroxy group and amide group, or By a contact with a high boiling liquid such as a polyhydroxy group and a lactam group-containing organic compound, and then heating at a high temperature, preferably 100 to 250 ℃, preferably 1 to 90 seconds means a method for improving the conductivity. In contrast, in the case of an aprotic compound having a dielectric constant ≧ 15, such as N-methyl-pyrrolidinone, a temperature of 100 ° C. or less is used. Such conductivity enhancement is observed when using polythiophene and can occur during and after the outermost layer preparation. Particularly preferred liquids for such treatment are N-methyl-pyrrolidinone and diethylene glycol as disclosed in EP-A 0 686 662 and EP-A 1 003 179.

PEDOT as used herein refers to poly (3,4-ethylenedioxythiophene).

EDOT as used herein refers to 3,4-ethylenedioxythiophene.

ADOT as used herein refers to 3,4-alkylenedioxythiophene.

PSS represented herein refers to poly (styrenesulfonic acid) or poly (styrenesulfonate).

PET as used herein refers to poly (ethylene terephthalate).

Latex Water dispersion

According to the invention, in a first aspect of an aqueous dispersion of latex, the latex has a primary particle size of 30 nm or less.

According to the invention, in a second aspect of an aqueous dispersion of latex, the weight ratio of said at least one polyanionic compound to said polymer is a weight ratio of said at least one polyanionic compound to said structural unit in the preparation of the aqueous dispersion of latex. Is the same as

According to the present invention, in a third aspect of the aqueous dispersion of latex, the latex particles comprise the weight ratio of the at least one polyanion compound to the polymer, at least 4 and at most 20, of the polymer. It includes.

According to the present invention, in a fourth aspect of the aqueous dispersion of latex, immediately before adding the initiator, the latex is prepared in a reaction medium comprising up to 8500 mg of oxygen per liter of reaction medium.

According to the present invention, in the fifth aspect of the aqueous dispersion of latex, just prior to adding the initiator, the latex is prepared in a reaction medium comprising up to 2000 mg of oxygen per liter of reaction medium.

According to the present invention, in the sixth aspect of the aqueous dispersion of latex, immediately before adding the initiator, the latex is prepared in a reaction medium comprising up to 1000 mg of oxygen per L.

According to the present invention, in the seventh aspect of the aqueous dispersion of latex, immediately before adding the initiator, the latex is prepared in a reaction medium comprising up to 500 mg of oxygen per liter of reaction medium.

According to the present invention, in an eighth aspect of the aqueous dispersion of latex, just prior to adding the initiator, the latex is prepared in a reaction medium comprising up to 100 mg of oxygen per liter of reaction medium.

According to the invention, in the ninth aspect of the aqueous dispersion of latex, immediately before adding the initiator, the latex is prepared in a reaction medium comprising up to 3 mg of oxygen per liter of reaction medium.

According to the present invention, in the tenth aspect of the aqueous dispersion of latex, just prior to adding the initiator, the latex is prepared in a reaction medium comprising up to 1.5 mg of oxygen per liter of reaction medium.

According to the present invention, in an eleventh aspect of the aqueous dispersion of latex, immediately before adding the initiator, the latex is prepared in a reaction medium comprising up to 0.5 mg of oxygen per liter of reaction medium.

According to the invention, in the twelfth aspect of the aqueous dispersion of said latex, the monomer units according to formula (I) are optionally alkyl group-substituted 3,4-methylenedioxy-thiophene units, optionally alkyl or aryl Formula wherein the group-substituted 3,4-ethylenedioxythiophene units, optionally alkyl or aryl group-substituted 3,4-ethylenedioxythiophene units, R ¹ and R ² together form a 1,2-cyclohexene group Units according to (I), optionally alkyl or aryl group-substituted 3,4-propylenedioxythiophene units, optionally alkyl or aryl group-substituted 3,4-butylenedioxythiophene units and optionally alkyl or Aryl group-substituted 3,4-pentylenedioxythiophene units.

According to the invention, in a thirteenth aspect of an aqueous dispersion of latex, the polymer is at 25 ° C. and at least 25 ° C., at least one 3,4-alkylenedioxythiophene compound having a solubility in water of at most 2.2 g / L. A copolymer of one or more 3,4-alkylenedioxythiophene compounds having a solubility of at least 2.2 g / L.

According to the present invention, in a fourteenth aspect of an aqueous dispersion of latex, the polymer is at 25 ° C. and at least 25 ° C., at least one 3,4-alkylenedioxythiophene compound having a solubility in water of at most 2.2 g / L. One or more 3,4-alkylene-dioxythiophene copolymers having a solubility of at least 2.2 g / L and at least 25, at least one of the 3,4-alkylene-dioxythiophenes having a solubility in water of at least 2.2 g / L. The compound is 3,4-dihydro-2H-thieno [3,4-b] [1,4] dioxin-2-yl) methanol, 3,4-dihydro-2H-thieno [3,4- b] [1,4] dioxe-3-ol, (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl-methoxy) -acetic acid ethyl ester , (2,3-dihydro-thieno [3,4-b] [1,4] dioxin-2-yl-methoxy) -acetic acid, 2- {2- [2- (2-methoxy- Ethoxy) -ethoxy] -ethoxymethyl} -2,3-dihydro-thieno [3,4-b] [1,4] dioxine and 4- (2,3-dihydro-thieno [ 3,4-b] [1,4] dioxine-2-ylmethoxy) -butane-1-sulfonic acid sodium salt Is selected.

Method for preparing an aqueous solution or aqueous dispersion of a polymer comprising monomer units according to formula (I)

According to the invention, one step of the preparation process is an aqueous solution or aqueous dispersion of a polymer consisting of structural units comprising monomer units of the formula (I) by polymerizing with an initiator in the reaction medium in the presence of one or more poly anions under oxidizing or reducing conditions In this case, the weight ratio of the at least one polyanion compound to the structural unit in the polymerization reaction is in the range of 5: 1 to 20: 1.

According to the invention, in a first embodiment of the process, the molar ratio of the polymer or copolymer of (3,4-dialkoxythiophene) to at least one polyanionic compound in solution or dispersion is from 1: 5 to 1 :. 8.0.

According to the invention, in a second embodiment of this process, the monomer units of formula (I) are present in the reaction medium at a concentration of up to 60 mM.

The oxygen concentration in the reaction medium can be determined by any method, such as freeze-thaw technique, by prolonged bubbling of an inert gas such as argon, nitrogen or helium through the reaction medium, by oxygen in a sacrificial reaction under an inert gas blanket. It can be adjusted by the method and the like.

According to the invention, in a third embodiment of this process, the inert atmosphere is nitrogen, helium or argon atmosphere.

See, for example, the Journal of the American Chemical Society, volume 85, pages 454-458 (1963) and J. Chem. As disclosed in Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988), the oxidant used for the oxidative polymerization of pyrrole may be used for the oxidative polymerization of thiophene.

In the present invention, according to a fourth embodiment of this process, the polymerization is oxidative, and the inexpensive and readily available oxidizing agents used for initiating the polymerization include iron (III) salts such as FeCl ₃ , Fe (OTs) ₃ and Iron (III) salts of the same organic acid, H ₂ O ₂ , K ₂ (Cr ₂ ) ₇ , alkali and ammonium persulfates, alkali perborates and potassium permanganate.

In theory, oxidative polymerization of thiophene requires 2.25 equivalents of oxidizing agent per mole of thiophene of formula (I) (see, eg, J. Polymer Science Part A Polymer Chemistry, volume 26, pages 1287-1294 (1988)). ). In practice, an excess of 0.1 to 2 equivalents of oxidant per polymerized unit is used. Persulfates and iron (III) salts do not corrode and have significant technical advantages in use. In addition, the oxidative polymerization of the thiophene compound according to formula (I) proceeds very slowly in the presence of certain additives so that the thiophene and the oxidant can be applied to the substrate to be treated together as a solution or a paste. After application of such solutions or pastes, the oxidative polymerization can be promoted by heating of the coated substrate, which is disclosed in US Pat. Nos. 6,001,281 and WO 00/14139, incorporated herein by reference.

Reduction polymerization is described in Apperloo et al., Chem. Eur Journal, volume 8, pages 2384-2396, 2002 and references Tetrahedron Letters, volume 42, pages 155-157, 2001; And the Stille pathway (organic tin) or the Suzuki pathway (organic boron) as disclosed in Macromolecules, volume 31, pages 2047-2056, 1998, respectively, or in reference to Bull. Chem. Soc. Japan, volume 72, page 621, 1999; And nickel complexes as disclosed in Advanced Materials, volume 10, pages 91-116, 1998.

Polymers comprising monomer units according to formula (I) may be prepared by chemically copolymerizing monomer units according to formula (I) with other polymerizable heterocyclic compounds such as pyrrole.

Oxygen measurement

The oxygen concentration can be measured with a Mettler Toledo (Mettler Toledo) retrieving an available infrastructure 6000 O ₂ sensor (InPro 6000 Series O ₂ sensors) for using Nick process unit 73 O ₂ (Knick Process Unit 73 O ₂₎ from. Clark polarographic sensors basically consist of a working electrode (anode), a counter / control electrode (cathode), and an oxygen permeable membrane that isolates the electrode from the medium. The transmitter provides a constant polarization voltage at the anode, which is needed to reduce oxygen. Oxygen molecules traveling through the membrane are reduced at the anode. At the same time oxidation takes place at the cathode and the oxidized cathode metal (silver) is released into the electrolyte. The electrolyte closes the electrical circuit between the cathode and the anode (ion conduction). The current generated in this way is measured by a transmitter and is proportional to the partial pressure of oxygen (O ₂ ) in the sample medium.

The amount of oxygen in the 6% by weight aqueous solution of poly (styrenesulfonic acid) measured by this method is 6.5 mg / L.

The poly (styrenesulfonic acid) solution at 25 ° C., 1013 mbar, bubbled with oxygen and saturated with oxygen, has an oxygen content of 38,45 mg / L. This value can be regarded as the maximum solubility of oxygen in a poly (styrenesulfonic acid) solution at 25 ° C., 1013 mbar.

Electrochemical Polymerization of Polymers Containing Monomer Units According to Formula (I)

Polymers containing monomer units according to formula (I) may be prepared by electrochemical oxidation polymerization. The electrochemical oxidative polymerization of the thiophene compound according to formula (I) is carried out at a temperature in the range from -78 ° C to the boiling point of the solvent used, preferably in the range from -20 ° C to 60 ° C. The reaction time depends on the desired thiophene, which generally ranges from a few seconds to several hours. Electrochemical polymerization of thiophene compounds is disclosed in Dietrich et al., Journal Electroanalytical Chemistry, volume 369, pages 87-92, 1994.

Suitable inert liquids for use in the electrochemical oxidation of thiophene compounds according to formula (I) are water, alcohols such as methanol and ethanol, ketones such as acetophenone, halogenated such as methylene chloride, chloroform, tetrachloromethane and fluorohydrocarbons Hydrocarbons, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, nitriles such as acetonitrile and benzonitrile, sulfoxides such as dimethyl sulfoxide, dimethyl sulfone, phenyl Sulfones such as methylsulfone and sulfolane, methyl acetamide, dimethyl acetamide, dimethyl formamide, pyrrolidone, N-methyl-pyrrolidone, caprolactam, liquid aliphatic amides such as N-methyl-caprolactam, diethyl Aliphatic and aliphatic and aromatic mixtures such as ethers and anisoles Liquid ureas such as ether, tetramethylurea or N, N-dimethyl-imidazolidinone.

The electrolyte additives used in the electrochemical polymerization of thiophene compounds according to formula (I) are preferably free acids or usually conductive salts, which exhibit a certain solubility in the solvent used. Particularly suitable electrolytes are alkali, alkaline earth metal or optionally alkylated ammonium, phosphonium, sulfonium or oxonium cations in combination with perchloric acid, tosylate, tetrafluoroborate or hexafluorophosphonate anions.

The electrolyte additive is used in an amount such that a current of at least 0.1 mA flows during the electrochemical oxidation.

The electrochemical polymerization can be carried out continuously or discontinuously. Known electrode materials are ITO-coated glass, precious metal or steel mesh, carbon-filled polymers, deposited metal-coated insulating layers and carbon felt.

The current density in electrochemical oxidation can vary within wide ranges. According to an eighth embodiment of the invention, this current density is between 0.0001 and 100 mA / cm 2. According to a ninth embodiment of the invention, the current density is between 0.01 and 40 mA / cm 2. At this current density the voltage is set to about 0.1-50V.

Polymers comprising monomer units according to formula (I) may be prepared by electrochemically copolymerizing monomer units according to formula (I) with other polymerizable heterocyclic compounds such as pyrrole.

Poly anion compounds

The polyanionic compounds used in the dispersions according to the invention are disclosed in EP-A 440 957, which are polymerizable carboxylic acids such as polyacrylic acid, polymethacrylic acid or polymaleic acid, and poly (styrene sulfonic acid). Polysulfonic acid. These polycarboxylic acids and polysulfonic acids may be copolymers in which vinylcarboxylic acids and vinylsulfonic acids are copolymerized with other polymerizable monomers such as acrylic acid esters, methacrylic acid esters and styrene.

According to the present invention, in a sixteenth embodiment of an aqueous dispersion of latex, the at least one polyanion compound comprises polystyrene sulfonic acid.

Industrial usability

Chemically or electrochemically prepared polymers comprising monomer units of formula (I) exhibit high electrical conductivity with low absorbance for visible light and high absorbance for infrared light. Thus, this layer has high electrical conductivity, high transparency to visible light and heat shielding. Such polythiophenes can be applied to a variety of rigid or flexible substrates, for example ceramics, glass and plastics, which are particularly suitable for flexible substrates such as plastic sheeting, the substrates being substantially bent and deformed without a polythiophene layer. Loss of electrical conductivity.

Thus, such polythiophenes include photo films, thermal recording materials and photothermographic recording materials in photovoltaic devices, batteries, capacitors and organic and inorganic electroluminescent devices, in electromagnetic shielding layers, in thermal shielding layers. It can be used in a wide range of electrostatic coatings, in smart windows, in electrochrome devices, in sensors for organic and bio organic materials, in field transistors, in printed substrates, in conductive resin adhesives, and in freestanding electroconductive films. Handbook of Oligo- and Polythiophenes, Edited by D. Fichou, Wiley-VCH, Weinheim (1999).

The invention is illustrated through comparative examples and examples. In these examples the percentages and ratios are by weight unless otherwise indicated.

Serving Layer No. used in the Examples. 01 has the following composition:

Copolymer of 88% vinylene chloride, 10% methylene acrylate and 2% itaconic acid 79.1% Kieselsol® 100F, colloidal silica, from Bayer 18.6% Mersolat® H, surfactants, from Bayer 0.4% Ultravon® W, surfactants, from CIBA-GEIGY 1.9%

Method for preparing 3,4-alkylenedioxythiophene-polymer

Example  One

At 25 ° C., a suitable reaction vessel equipped with a stirrer and a nitrogen inlet is provided for a given PEDOT-type in Table 2 and the amount of the poly (styrene sulfonic acid) [PSS] (Mw = 290,000) solution shown in Table 2. Amount of deionized water was added and mixed. Nitrogen was bubbled through this mixture for 30 minutes, and then an amount of EDOT was added to this solution in the amounts indicated for PEDOT-type in Table 2. The concentration of oxygen using a 6000 series O ₂ in the infrastructure and the solution measured by nick process unit 73 O ₂ were shown in Table 2. The polymerization reaction was initiated by addition of Fe ₂ (SO ₄ ) ₃ .9H ₂ O and Na ₂ S ₂ O ₈ in amounts corresponding to concentrations of 0.13 and 41.6 mM, respectively. The EDOT concentration in the reaction mixture was 30 mM and the PSS concentration was 57 mM. The reaction mixture was then stirred at 25 ° C. for 7 hours and then an amount of Na ₂ S ₂ O _{8 added} to the concentration corresponding to the concentration of 6.95 mM for the given PEDOT-type. After further reaction for 16 hours, the reaction mixture was treated twice with an ion exchanger (300 mL Lewatit ^™ S100MB + 500 mL Lewatit ^™ M600MB). The resulting mixture was further heat treated at 95 ° C. for 2 hours and the resulting mucus mixture was treated with a high shear [microfluidizer, 60 MPa (600 Bar)].

TABLE 2

PEDOT Type
O ₂ in the reaction medium amount
[Mg / l]
EDOT
weight
[g]
PSS Fe ₂ (SO ₄ ) ₃ .9H ₂ O
Weight [g] Na ₂ S ₂ O ₈ water
Weight (g)
5.6% by weight of the solution
Weight [g] Final concentration [mM] Initial amount added [g] Addition amount after 7 hours [g] One 0.080 213 10649 * 57 3.75 428.2 71.6 39531 2 0.995 213 11218 # 57 3.75 428.2 71.6 38782 3 0.995 213 11218 # 57 3.75 428.2 71.6 38782 4 6.5 12.78 562.5 57 0.225 25.7 4.3 2437.5 5 8.36 12.78 562.5 57 0.225 25.7 4.3 2437.5 6 38.45 12.78 562.5 57 0.225 25.7 4.3 2437.5

* 4.93 wt% PSS aqueous solution

# 4.68 wt% PSS aqueous solution

Method for producing a type 1 electrically conductive layer using the dispersion based on the dispersion of Example 1

Copolymer latex (88/10/2) and N-methyl pyrrolidinone of 3-glycidoxypropyl-trimethoxysilane, ZONYL® FSO100, vinylidene chloride, methacrylate and itaconic acid were dispersed in Example 1 A coating dispersion was prepared by adding to a doctor bleed coating on a 175 μm poly (ethylene terephthalate) support and dried at 45 ° C. for 3.5 minutes to prepare a type 1 layer having the following composition:

PEDOT / PSS 100 ㎎ / ㎡

PEDOT 28.9 mg / ㎡

ZONYL FSO100 8 mg / ㎡

3-glycidoxypropyl-trimethoxysilane 100 mg / m 2

Of vinylidene chloride, methacrylate and itaconic acid

Copolymer Latex (88/10/2) 100 mg / ㎡

N-methyl pyrrolidinone 2 mL / ㎡

Properties of Electrically Conductive Layers Prepared from Dispersions Based on the Dispersions of Example 1

A visible light filter was used to measure a stack of 10 strips with a Macbeth® TD904, and then the optical density of one strip was obtained from it to determine the optical density of the layer. The values shown in Table 3 include the optical density of PET-supports.

The printed layer was contacted with a parallel copper electrode 35 mm long and 35 mm apart to form a line contact and insulated with Teflon® insulators to provide a layer contact at room temperature of 25 ° C. and 30% relative humidity. Surface resistance was measured. This made it possible to measure the surface resistance directly. The results are shown in Table 3:

TABLE 3

PEDOT Type Amount of PEDOT / PSS Dispersion [g] O ₂ amount in reaction medium [mg / L] PEDOT / PSS concentration [% by weight] Initial surface resistance
[Ω / □] Optical density of PET support One 90,000 0.080 0.82 1500 2 95,844 0.995 0.77 2010 3 91,111 0.995 0.81 1830 4 1800 6.5 1.09 2900 0.067 5 1535 8.36 0.82 4120 6 1760 38.45 1.11 21000 0.066

The results shown in Table 3 indicate that the surface resistance of the PEDOT / PSS layer with a PSS: PEDOT molar ratio of 1.90 increased strongly with increasing oxygen concentration in the reaction medium.

Example  2

At 25 ° C., the poly (styrene sulfonic acid) [PSS] (Mw = 290,000) solution in the amount indicated in Table 4 was placed in a suitable reaction vessel equipped with a stirrer and a nitrogen inlet and the amount given for the given PEDOT-type in Table 4. Mixed with deionized water. After bubbling nitrogen through this mixture for 30 minutes, the amount of EDOT indicated in Table 4 was added to the solution for the given PEDOT-type. The oxygen concentration in this solution was measured by _a Nick process unit 73 O _a using INPRO 600 series O ₂ , and the result was <1.0 mg / L. The polymerization reaction was initiated by adding Fe ₂ (SO ₄ ) ₃ .9H ₂ O and Na ₂ S ₂ O ₈ in amounts corresponding to concentrations of 0.13 and 41.6 mM, respectively. The EDOT concentration in the reaction mixture was 30 mM and the PSS concentration was 57 mM. The reaction mixture was then stirred at 25 ° C. for 7 hours and then an additional amount of Na ₂ S ₂ O ₈ corresponding to the concentration of 6.95 mM was added for the given PEDOT type. After 16 hours of further reaction, the reaction mixture was transferred twice with an ion exchanger (300 mL Lewatit ^™ S100MB + 500 mL Lewatit ^™ M600MB). The resulting mixture was further heat treated at 95 ° C. for 2 hours and the resulting viscous mixture was subjected to high shear [microfluidizer, 60 MPa (600Bar)].

Table 4

PEDOT
type EDOT
Weight [g] PSS Fe ₂ (SO ₄ ) ₃ · 9H ₂ O Weight [g] Na ₂ S ₂ O ₈ Initial addition amount [g] Na ₂ S ₂ O ₈
Later addition
[g] Water weight [g]
5.99% by weight of solution [g] Final concentration [mM] 7 12.78 438.23 57 0.225 25.7 4.3 2061.77 8 12.78 438.23 57 0.225 25.7 4.3 2061.77

Method and Properties of Preparation of Type 1 Electrically Conductive Layer of Dispersions Based on the Dispersions of Example 2

An electrically conductive layer of type 1 consisting of a dispersion based on the dispersion of Example 2 was prepared and properties were evaluated as described for the dispersion of Example 1. The results are summarized in Table 5.

Table 5

PEDOT Type Amount of PEDOT / PSS Dispersion [g] PEDOT / PSS concentration [% by weight] Initial surface resistance
[Ω / □] O.D. 7 1950 1.02 1200 0.066 8 1840 1.03 1200 0.065

Considering together the results of Tables 3 and 5, the initial surface resistance of the PEDOT / PSS layer is highly dependent on the amount of oxygen in the reaction medium during the polymerization of 3,4-ethylenedioxythiophene in the presence of poly (styrenesulfonic acid). The lower the oxygen concentration in the medium, the lower the surface resistance.

Example 3

At 25 ° C., the poly (styrene sulfonic acid) [PSS] (Mw = 290,000) solution in the amount shown in Table 6 was placed in a suitable reaction vessel equipped with a stirrer and a nitrogen inlet, and the amount shown for the given PEDOT-type in Table 6 Mix with as much deionized water. After bubbling nitrogen through this mixture for 30 minutes, an amount of EDOT as indicated for the given PEDOT-type in Table 7 was added to the solution, wherein the concentration of EDOT was 30 mM. The oxygen concentration in this solution was <1.0 mg / L as measured by the Nick process unit 73 O ₂ using INPRO 6000 series O ₂ . The polymerization was then initiated by addition of Fe ₂ (SO ₄ ) ₃ .9H ₂ O and Na ₂ S ₂ O ₈ in amounts corresponding to 0.13 and 41.6 mM, respectively. The EDOT concentration in the reaction mixture was 30 mM and the concentrations of PSS are given for certain PDOT-types in Table 6.

Table 6

PEDOT
type EDOT
Weight [g] PSS Fe ₂ (SO ₄ ) ₃ · 9H ₂ O Weight [g] Na ₂ S ₂ O ₈
Initial addition amount
[g] Addition amount of Na ₂ S ₂ O ₈ after 7 hours [g] water
weight
[g] 4.81 wt% Weight of the solution [g] Final concentration
[mM] 9 10.65 219.13 23 0.187 21.4 3.58 2280.87 10 10.65 219.13 23 0.187 21.4 3.58 2280.87 11 10.65 347.75 36 0.187 21.4 3.58 2152.25 12 10.65 347.75 36 0.187 21.4 3.58 2152.25 13 42.60 1752.25 46 0.748 85.64 14.32 8247.08 14 213 525 ** 57 3.75 428.2 71.6 39531 15 213 525 ** 57 3.75 428.2 71.6 39531 16 213 525 ** 57 3.75 428.2 71.6 39531 17 10.65 711.18 74 0.187 21.4 3.58 1788.2 18 10.65 711.18 74 0.187 21.4 3.58 1788.2 19 8.52 1137.89 149 0.149 17.1 2.86 862.11 20 8.52 1137.89 149 0.149 17.1 2.86 832.11 21 213 27907.3 # 149 3.75 428.2 71.6 22092.7 22 213 27907.3 # 149 3.75 428.2 71.6 22092.7 23 213 27907.3 # 149 3.75 428.2 71.6 22092.7

* Same conditions as PEDOT Type 17 except that the heat treatment was not performed for 2 hours at 95 ℃.

# 4.90 wt% aqueous solution of PSS

** 4.93 wt% PSS aqueous solution

The reaction mixture was then stirred at 25 ° C. for 7 hours and then an additional amount of Na ₂ S ₂ O ₈ corresponding to the concentration of 6.95 mM for the given PEDOT-type was added. After an additional 16 hours of reaction time, the reaction mixture was treated twice with an ion exchanger (300 mL Lewatit ^™ S100MB + 500 mL Lewatit ^™ M600MB). The resulting mixture was further heat treated at 95 ° C. for 2 hours and the resulting mucus mixture was treated with a high shear [microfluidizer, 60 MPa (600 Bar)].

PSS: PEDOT weight ratio and molar ratio, PEDOT / PSS- concentration, viscosity measured by Ubbelohde viscometer in a thermostated bath at 25 ° C, peak particle in bmodal size distribution Table 7 shows the number and number of particles having a particle size of 1 μm or more per mL.

TABLE 7

PEDOT Type PSS / PEDOT
Weight ratio PSS / PEDOT molar ratio PEDOT / PSS
Concentration (% by weight) Viscosity
cP Peak Particle Size After Homogenization # Parts / mL / 1㎛ 9 0.98 0.76 0.73 226 47 4.7 x 10 ⁷ 10 0.98 0.76 0.65 120 45 1.6 x 10 ⁷ 11 1.55 1.20 0.86 225 44 1.7 x 10 ⁷ 12 1.55 1.20 0.82 150 42 2 x 10 ⁷ 13 1.98 1.53 0.81 45 31 8.3 x 10 ⁶ 14 2.46 1.90 - 56 25 7.6 x 10 ⁶ 15 2.46 1.90 - 24 - - 16 2.46 1.90 - 28 - - 17 3.18 2.45 One 64 33 3.6 x 10 ⁷ 18 3.18 2.45 0.93 60 32 3.2 x 10 ⁷ 19 6.36 4.91 1.83 94 27 2.9 x 10 ⁷ 20 6.36 4.91 1.89 118 26 3.3 x 10 ⁷ 21 6.42 (50 L) 4.96 1.55 59 26 1.1 x 10 ⁷ 22 6.42 (50 L-UT) 4.96 1.66 53 23 1.2 x 10 ⁷ 23 Not heat treated 4.96 1.32 59 18 1.5 x 10 ⁷

The relative amount of PSS bound or unbound using aqueous gel permeation chromatography using UV-vis absorption detection as the area of peak (A ₂₅₄ ) at 254 nm, and the relative amount of bound PEDOT Was measured and otherwise no shift occurred and PEDOT was not measured as the area of the peak at 785 nm (A ₇₈₅ ). A ₂₅₄ / A ₇₈₅ gives the relative molar amounts of PSS to bound PEDOT. To obtain representative results, the dispersion had to be microfluidized at 60 MPa (600 bar) before running GPC. If microfluidization is not achieved, the PEDOT-peaks are very small due to agglomerated latex that cannot be transported through the column. The molecular weight of PEDOT against the sodium poly (styrene sulfonate) standard was simultaneously measured. The results are shown in Table 8.

From the GPC measurements, it can be seen that PSS is substantially bound to PEDOT since the relative ratio of PSS / PEDOT is significantly proportional to the molar ratio actually present.

Table 8

PEDOT Type PSS / PEDOT
Weight ratio PSS / PEDOT molar ratio PEDOT M _n PEDOT M _w A ₂₅₄ A ₇₈₅ Relative molar ratio of PSS / PEDOT A ₂₅₄ / A ₇₈₅ 9 0.98 0.76 1.2 x 10 ⁵ 2.9 x 10 ⁵ 0.0019 0.008 2.38 11 1.55 1.20 4.5 x 10 ⁵ 7.2 x 10 ⁵ 0.0032 0.0013 2.46 12 1.55 1.20 4.4 x 10 ⁵ 7.6 x 10 ⁵ 0.0031 0.0014 2.21 13 1.98 1.53 2.0 x 10 ⁵ 4.9 x 10 ⁵ 0.0049 0.0031 1.58 17 3.18 2.45 2.8 x 10 ⁵ 7.9 x 10 ⁵ 0.0073 0.0025 2.92 18 3.18 2.45 3.0 x 10 ⁵ 8.9 x 10 ⁵ 0.0066 0.0024 2.75 19 6.36 4.91 4.9 x 10 ⁵ 9.5 x 10 ⁵ 0.0156 0.0029 5.38 20 6.36 4.91 4.9 x 10 ⁵ 9.1 x 10 ⁵ 0.0161 0.0023 7.0

Method and Characterization of Type 1 Conductive Layer of Dispersions Based on the Dispersions of Example 3

An electrically conductive layer of type 1 was prepared from the dispersion based on the dispersion of Example 3, wherein the amounts of ZONYL® FS0100, 3-glycidoxypropyltrimethoxysilane, copolymer latex and N-methylpyrrolidinone were constant The amount of latex was retained and the amount of latex was changed to obtain a constant amount of PEDOT [28.9 mg / m 2]. These layers had the same properties as described for the dispersion of Example 1, and the results are shown in Table 9.

Surprisingly, the results in Table 9 indicate that the surface resistance decreases with increasing PSS: PEDOT ratio in the PEDOT / PSS containing layer prepared substantially without oxygen according to the present invention. This is described in the literature on PEDOT / PSS [published in 1999, M. Lefebvre et al., Chem. Mater ,. volume 11, pages 262-268], which discloses that surface resistance increases with increasing PSS: PEDOT ratio.

Table 9

PEDOT Type Coating amount of the entire layer [mg / ㎡] Weight% of PEDOT in Layer PSSA / PEDOT Weight Ratio Surface resistance [Ohm / square] OD excluding PET support OD with PET support 9 265.5 10.9 0.99 3000 - 0.061 10 265.5 10.9 0.99 3300; 3680 0.028 0.062 11 282.3 10.2 1.57 1700 - 0.065 12 282.3 10.2 1.57 1600; 1710 0.031 0.065 13 294.1 9.8 1.98 1800 - - 14 308 9.4 2.46 1500; 2010 0.027 - 15 308 9.4 2.46 2010 0.028 - 16 308 9.4 2.46 1830 0.028 - 17 329.7 8.8 3.21 870; 1000 0.028 0.063 18 329.7 8.8 3.21 770 - 0.065 19 422.4 6.8 6.42 730 - 0.064 20 422.4 6.8 6.42 720 - 0.065 21 422.4 6.8 6.42 (50 L) 640 - 0.066 22 422.4 6.8 6.42
(50L-UT) 640 - 0.065 23 422.4 6.8 6.42
No heat treatment 690 - 0.067

Method for producing a conductive layer of type 2 consisting of a dispersion based on the dispersion of Example 3

3-Glycidoxypropyltrimethoxysilane, ZONYL ^™ FSO100 and diethylene glycol were added to the aqueous PEDOT / PSS-dispersion to prepare a coating dispersion according to the following composition. Coated on and dried at 140 ° C. for 1 minute to form a coating layer:

PEDOT / PSS: Amount adjusted to maintain a constant PEDOT dose of 20.2 mg / m 2

3-glycidoxypropyltrimethoxysilane: 24 mg / m 2

^{ZONYL TM FSO 100: 11 ㎎ /} ㎡

Diethylene Glycol [DEG] (Theoretical) 1.33 mL / ㎡

Properties of Conductive Layer of Type 2 Prepared from Dispersion Based on Example 3

The optical density and surface resistance of the layer were measured as described above for the type 1 electrically conductive layer. The results are summarized in Table 10.

Table 10

PEDOT Type Coating amount of the entire layer [mg / ㎡] Weight% of PEDOT in Layer PSSA / PEDOT Weight Ratio PSSA / PEDOT molar ratio Surface resistance [Ohm / square] OD excluding PET support 10 75.2 26.9 0.99 0.76 1340 0.017 12 86.9 23.2 1.57 1.21 869 0.016 14 105 19.2 2.46 1.90 736 0.012 15 105 19.2 2.46 1.90 794 0.013 16 105 19.2 2.46 1.90 754 0.013 17 120.0 16.8 3.21 2.48 640 0.013 20 184.9 10.9 6.42 4.96 520 0.013

The results in Table 10 surprisingly show that the surface resistance decreases with increasing PSS: PEDOT ratio of the PEDOT / PSS containing layer prepared substantially without oxygen, according to the present invention. This is described in the literature on PEDOT / PSS, published in 1999, M. Lefebvre et al., Chem. Mater ,. volume 11, pages 262-268], which discloses that surface resistance increases with increasing PSS: PEDOT ratio.

How to measure the actual ratio of PSS / PEDOT

Samples of PEDOT-dispersions of types 10, 13, 17 and 19/20 are placed in a CHRIST BETA 2-16 shelf freeze-dryer until all of the water has evaporated (ie The powder was dried by lyophilization under high vacuum (0.7 mbar) until the temperature reached room temperature).

The resulting lyophilized sample was then analyzed with ¹³ C CP / MAS using a 200 MHz spectrometer at 11 different contact times in the ms range at a spin rate of 6.4 kHz, with each measurement repeated 3000 times for signal to noise ratio. Increased. References [P. The entire process as described in Adriaensens et al., Polymer, volume 43, pages 7003 to 7006, 2002 took 30 minutes for each sample. C-shift from the EDOT ring (68 ppm) was well separated from the aliphatic PSS signal (near 40 ppm). In (strength) versus contact time (CT) characteristics were analyzed according to the following equation:

In (carbon strength) = In (initial carbon strength ₀ )-t / T _{1 ρ} H

The initial carbon strength thus obtained was used to determine the quantitative molar ratio of PSS: PEDOT. The T _{1 ρ} H relaxation time is different for each signal and for each sample. Quantitative results require a long measurement sequence. The T _{1 ρ} H relaxation times of the aromatic PSS carbon atoms, aliphatic PSS carbon atoms and carbon atoms of each PEDOT-type PEDOT-ether group are shown in Table 11 below.

Table 11

PEDOT Type T _{1 ρ} H [ms] of PSS aromatic carbon atom T _{1 ρ} H [ms] of PSS aromatic carbon atom Of PEDOT ether carbon atom
T _{1 ρ} H [ms] 13 3.6 2.3 2.8 17 4.4 3.1 2.9 19/20 2.8 1.9 1.9 10 1.6 1.0 1.1

The average of the initial aromatic carbon atom strength of PSS, the initial aliphatic carbon atom strength of PSS and the initial carbon atom strength of PSS, the initial ether carbon atomic strength of PEDOT, and the average carbon initial strength of PSS and the initial ether carbon of PEDOT thus obtained The ratio of atomic intensities is shown in Table 12 along with the PSS / PEDOT theoretical molar ratios.

The agreement between the theoretical and actual molar ratios of PSS / PEDOT is very good, indicating the efficiency of the method used. Thus, the molar ratios obtained from the ¹³ C CP / MAS analysis are in full agreement with the theoretical molar ratios.

Table 12

PEDOT Type PSS / PEDOT molar ratio
(Theoretical value) Initial Aromatic Carbon Atomic Strength of PSS Initial Aliphatic Carbon Atomic Strength of PSS Average Initial Carbon Atomic Strength of PSS Initial Ether Carbon Atomic Strength of PEDOT Average Initial Carbon Atomic Strength of PSS / Initial Ether Carbon Strength of PEDOT 13 1.55 232 223 228 155 1.47 17 2.45 421 415 418 160 2.61 19/20 4.91 343 335 339 66 5.14 10 0.76 73 47 60 73 0.82

Example 4

At 25 ° C., in a suitable reaction vessel equipped with a stirrer and nitrogen inlet, add a solution of poly (styrene sulfonic acid) [PSS] (Mn = 160,000 and Mw = 600,000) as shown in Table 13 and PEDOT-type in Table 13. Mix with an amount of deionized water given for. After bubbling nitrogen gas through this mixture for 30 minutes, an amount of EDOT as indicated for the given PEDOT-type in Table 13 was added to the solution to obtain an EDOT concentration of 30 mM. The oxygen concentration in this solution was <1.0 mg / L as measured by the Nick process unit 73 O ₂ using INPRO 6000 series O ₂ . The polymerization reaction was initiated by adding Fe ₂ (SO ₄ ) ₃ .9H ₂ O and Na ₂ S ₂ O ₈ in amounts corresponding to concentrations of 0.13 and 41.6 mM, respectively. The EDOT concentration in the reaction mixture was 30 mM, PSS was 46 mM for PEDOT-type 24, 37 mM for PEDOT-type 25, 59 mM for PEDOT-type 26, 69 mM for PEDOT-type 27, PEDOT- For type 28 it was 93 mM. The reaction mixture was then stirred at 25 ° C. for 7 hours and then an additional amount of Na ₂ S ₂ O ₈ corresponding to the concentration of 6.94 mM for the given PEDOT-type was added. After an additional 16 hours of reaction time, the reaction mixture was treated twice with an ion exchanger (300 mL Lewatit ^™ S100MB + 500 mL Lewatit ^™ M600MB). The resulting mixture was further heat treated at 95 ° C. for 2 hours and the resulting mucus mixture was treated with a high shear [microfluidizer, 60 MPa (600 Bar)].

Table 13

PEDOT Type
EDOT
Weight [g]
PSS Fe ₂ (SO ₄ ) ₃ .9H ₂ O
Weight [g] Na ₂ S ₂ O ₈ water
Weight [g]
4.9 wt% Weight in solution [g] Final concentration [mM] Initial amount added [g] Addition amount after 7 hours [g] 24 8.52 424.93 46 0.149 17.13 2.86 1575.07 25 8.52 523.69 37 0.149 17.13 2.86 1476.31 26 8.52 523.69 57 0.149 17.13 2.86 1476.31 27 8.52 637.4 69 0.149 17.13 2.86 1362.6 28 8.52 849.3 93 0.149 17.13 2.86 1150.7

The resulting PSS: PEDOT weight ratio and molar ratio, PEDOT / PSS-concentration, viscosity measured by an Ubbelohde viscometer in a thermostated bath at 25 ° C., peak particle size in mL and size distribution, and mL The number of particles having a sugar particle size of 1 μm or more is shown in Table 14.

Table 14

PEDOT Type PSS / PEDOT
Weight ratio PSS / PEDOT molar ratio PEDOT / PSS
Concentration [% by weight] Viscosity
cP Peak Particle Size After Homogenization [nm] # Parts / mL / 1㎛ 24 2.00 1.54 0.93 240 67 8.2 x 10 ⁵ 25 2.46 1.90 1.21 10 101 7.9 x 10 ⁵ 26 2.46 1.90 1.22 50 98 7.2 x 10 ⁵ 27 3.00 2.32 1.35 31 87 8.0 x10 ⁵ 28 4.00 3.09 1.75 57 83 8.4 x 10 ⁵

Method and Characterization of Type 1 Conductive Layer of Dispersions Based on the Dispersions of Example 4

As disclosed in Example 3, a type 1 electrically conductive layer of the dispersion based on the dispersion of Example 4 was prepared and characterized. The results for the Type 1 electrically conductive layer are summarized in Table 15.

Table 15

PEDOT Type Coating amount of the entire layer [mg / ㎡] Weight% of PEDOT in Layer PSSA / PEDOT Weight Ratio PSSA / PEDOT molar ratio Surface resistance [Ohm / square] Support
OD included 24 294.7 9.8 2.00 1.54 3300 0.059 25 308 9.4 2.46 1.90 1900 0.063 26 308 9.4 2.46 1.90 1700 0.063 27 323.6 8.9 3.00 2.32 1500 0.062 28 352.5 8.2 4.00 3.09 1300 0.062

The results in Table 15 confirm the results in Table 9, which surprisingly shows that the surface resistance decreases with increasing PSS: PEDOT ratio in PEDOT / PSS containing layers made substantially free of oxygen, according to the present invention.

Example 5

At 25 ° C., add a solution of poly (styrene sulfonic acid) [PSS] (VERSA TL77, ALCO, Mn = 25,000 and Mw = 72,000) in the appropriate reaction vessel equipped with a stirrer and PEDOT in Table 16. It was mixed with a sufficient amount of deionized water given for the -type. The amount of EDOT set forth in Table 15 for the given PEDOT-type was added to the solution to obtain an EDOT concentration of 30 mM. Oxygen concentration in this solution was measured by a Nick process unit 73 O ₂ using INPRO 6000 series O ₂ . The polymerization reaction was initiated by addition of Fe ₂ (SO ₄ ) ₃ .9H ₂ O and Na ₂ S ₂ O ₈ in amounts corresponding to concentrations of 0.13 and 41.6 mM, respectively. The EDOT concentration in the reaction mixture was 30 mM and the PSS concentration in the reaction mixture is shown in Table 16 according to the desired PEDOT-type. The reaction mixture was then stirred at 25 ° C. for 7 hours and then an additional amount of Na ₂ S ₂ O ₈ corresponding to the concentration of 6.94 mM for the given PEDOT-type was added. After an additional 16 hours of reaction time, the reaction mixture was treated twice with an ion exchanger (300 mL Lewatit ^™ S100MB + 500 mL Lewatit ^™ M600MB). The resulting mixture was further heat treated at 95 ° C. for 2 hours and the resulting mucus mixture was treated with a high shear [microfluidizer, 60 MPa (600 Bar)].

Table 16

PEDOT Type EDOT
weight
[g] The amount of oxygen in the reaction medium [mg / L] PSS Fe ₂ (SO ₄ ) ₃ .9H ₂ O
Weight (g) Of Na ₂ S ₂ O ₈
Initial amount added [g] Na ₂ S ₂ O ₈ after 7 hours
Added amount [ g ] water
Weight (g) 4.9 wt% Weight in solution [g] final
Concentration [mM] 29 8.52 6404 213.87 28 0.149 17.3 2.86 1786.13 30 8.52 4878 340.81 45 0.149 17.3 2.86 1659.19 31 8.52 8360 428.57 57 0.149 17.3 2.86 1571.43 32 8.52 7510 695.51 93 0.149 17.3 2.86 1304.49 33 8.52 7073 1391.02 185 0.149 17.3 2.86 608.98

The molecular weight of PEDOT in PEDOT-dispersion type 26 to 30 was measured by aqueous gel permeation chromatography as described in Example 3 and the results are shown in Table 17.

Table 17

PEDOT Type PSS / PEDOT
Weight ratio (theoretical value) PSS / PEDOT molar ratio (theoretical value) Mw Viscosity
[cP] Peak Particle Size After Homogenization [nm] 29 1.23 0.95 4.8 x 10 ⁵ 14 32 30 1.96 1.51 6.7 x 10 ⁵ 17.5 30 31 2.46 1.90 7.0 x 10 ⁵ 22.5 26 32 4.0 3.09 7.2 x 10 ⁵ 55 26 33 8.0 6.17 9.2 x 10 ⁵ 125 29

Method and Characterization of Type 1 Conductive Layer of Dispersions Based on the Dispersions of Example 5

An electrical conducting layer of type 1 consisting of the dispersion based on the dispersion of Example 5 as described in Example 3 was prepared and characterized. The results for the type 1 conductive layer are summarized in Table 18.

Table 18

PEDOT Type Coating amount of the entire layer [mg / ㎡] Weight% of PEDOT in Layer PSSA / PEDOT Weight Ratio PSSA / PEDOT molar ratio Surface resistance [Ohm / square] Support
OD except 29 272.4 10.6 1.23 0.95 9710 0.029 30 293.5 9.8 1.96 1.51 4240 0.029 31 308 9.4 2.46 1.90 4120 0.028 32 352.5 8.2 4.0 3.09 3650 0.024 33 468.1 6.2 8.0 6.17 2280 0.026

The results in Table 18 surprisingly indicate that even in the case of PEDOT / PSS dispersions prepared at the desired oxygen concentration in the reaction medium, the surface with increasing PSS: PEDOT ratio in the PEDOT / PSS containing layer prepared substantially free of oxygen according to the invention. It shows that the resistance is reduced. This is described in the literature on PEDOT / PSS, published in 1999, M. Lefebvre et al., Chem. Mater ,. volume 11, pages 262-268], which discloses that surface resistance increases with increasing PSS: PEDOT ratio.

Method and Characterization of Type 2 Electrical Conductive Layer of Dispersions Based on the Dispersions of Example 5

An electrical conducting layer of type 2 consisting of a dispersion based on the dispersion of Example 5 as described in Example 3 was prepared and characterized. The results for the conductive layer of type 2 are summarized in Table 19.

Table 19

PEDOT Type Coating amount of the entire layer [mg / ㎡] Weight% of PEDOT in Layer PSSA / PEDOT Weight Ratio PSSA / PEDOT molar ratio Surface resistance [Ohm / square] Support
OD except 29 80.0 25.3 1.23 0.95 2850 0.017 30 94.8 21.3 1.96 1.51 1880 0.014 31 105 19.2 2.46 1.90 1930 0.013 32 136.0 14.9 4.0 3.09 1610 0.010 33 216.8 9.3 8.0 6.17 1070 0.013

The results in Table 19 also surprisingly, even in the case of PEDOT / PSS dispersions prepared at the desired oxygen concentration in the reaction medium, the surface with increasing PSS: PEDOT ratio in the PEDOT / PSS containing layer prepared substantially free of oxygen according to the invention. It shows that the resistance is reduced. This is described in the literature on PEDOT / PSS, published in 1999, M. Lefebvre et al., Chem. Mater ,. volume 11, pages 262-268], which discloses that surface resistance increases with increasing PSS: PEDOT ratio.

The present invention will include all features disclosed herein or any combination of these features or any generalized features that are not related to the presently claimed invention. In view of the foregoing, those skilled in the art will recognize that Obviously, you can make a variety of variations.

Claims (19)

As an aqueous dispersion of latex particles, the latex particles comprise a polymer consisting of a structural unit comprising a monomer unit of formula (I) and at least one polyanionic compound, the primary particle size is 40 nm or less, and the aqueous dispersion is Dihydroxy group, polyhydroxy group, carboxyl group, amide group, lactam group, dihydroxy group and carboxy group, dihydroxy group and amide group, dihydroxy group and lactam group, polyhydroxy group and carboxyl group, polyhydroxy group and amide group, or polyhydroxy group and lactam group-containing organic Compound, or an aprotic compound having a dielectric constant ε of ≧ 15, wherein the latex particles comprise the at least one polyanionic compound and the polymer at a weight ratio of at least 4, the at least one polyanionic compound to the polymer And the latex particles immediately before adding the initiator , The reaction medium per liter of an aqueous dispersion of latex particles of the said prepared in the reaction medium with an oxygen below 100㎎.

(I) Wherein R ¹ and R ² independently of one another represent a hydrogen or C _1-5 -alkyl group, or together form an optionally substituted C _1-5 -alkylene moiety. The latex according to claim 1, wherein the weight ratio of the at least one polyanion compound to the polymer is the same as the weight ratio of the at least one polyanion compound to the monomers constituting the polymer when preparing an aqueous dispersion of the latex. Aqueous dispersion of particles. Polymerizing with an initiator in a reaction medium in the presence of at least one polyanionic compound under oxidizing or reducing conditions to produce an aqueous solution or aqueous dispersion of a polymer comprising structural units comprising monomer units of formula (I) The weight ratio of the at least one polyanionic compound to the structural unit is in the range of 4: 1 to 20: 1, and immediately before adding the initiator, up to 100 mg of oxygen per liter of the reaction medium is present in the reaction medium. Adjusting to; The polymer and dihydroxy group, polyhydroxy group, carboxyl group, amide group, lactam group, dihydroxy group and carboxyl group, dihydroxy group and amide group, dihydroxy group and lactam group, polyhydroxy group and carboxyl group, polyhydroxy group combined with the at least one polyanionic compound Preparing a first coating composition comprising an amide group or an organic compound containing a polyhydroxy group and a lactam group in an aqueous or non-aqueous medium; Coating the first coating composition on an object to form a first layer; And heating the first layer at a temperature of 100 ° C. or higher.

(I) Polymerizing with an initiator in a reaction medium in the presence of at least one polyanionic compound under oxidizing or reducing conditions to produce an aqueous solution or aqueous dispersion of a polymer comprising structural units comprising monomer units of formula (I) The weight ratio of the at least one polyanionic compound to the structural unit is in the range of 4: 1 to 20: 1, and immediately before adding the initiator, up to 100 mg of oxygen per liter of the reaction medium is present in the reaction medium. Adjusting to; Preparing a second coating composition comprising in said aqueous or non-aqueous medium said polymer combined with said at least one polyanionic compound and said aprotic compound having a dielectric constant? Coating the second coating composition on an object to form a second layer; And heating the second layer at a temperature of 50 ° C. or higher.

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