TW201723003A - Conductive polymer composite and substrate - Google Patents

Abstract

The present invention provides a conductive polymer composite including: (A) a [pi]-conjugated polymer; and (B) a dopant polymer which contains a repeating unit "a" shown by the following general formula (1) and having a weight-average molecular weight in the range of 1,000 to 500,000. There can be provided a conductive polymer composite which has excellent filterability and film-formability by spin coating, and can form a conductive film having high transparency and excellent flatness. wherein R1 represents a hydrogen atom or a methyl group; R2 represents any of a single bond, an ester group, and a linear, branched, or cyclic hydrocarbon group having 1 to 12 carbon atoms, the hydrocarbon group optionally containing an ether group, an ester group, or both; "Z" represents any of a single bond, a phenylene group, a naphthylene group, an ether group, and an ester group; and "a" is a number satisfying 0 < a ≤ 1.0.

Description

Conductive polymer composite and substrate

The present invention relates to a conductive polymer composite and a substrate in which a conductive film is formed by the conductive polymer composite.

A polymer (π-conjugated polymer) having a conjugated double bond does not exhibit conductivity, but exhibits conductivity by doping with an appropriate anion molecule to become a conductive polymer material (conductive polymerization) Composition)). As the π-conjugated polymer, a (hetero) aromatic polymer such as polyacetylene, polythiophene, polyselenophene, polydecene, polypyrrole or polyaniline, or a mixture thereof is used as an anionic molecule ( For the dopant), a sulfonic acid-based anion is most often used. This is because the strong acid sulfonic acid interacts with the above π-conjugated polymer efficiently.

As the sulfonic acid-based anion dopant, a sulfonic acid polymer such as polyvinylsulfonic acid or polystyrenesulfonic acid (PSS) is widely used (Patent Document 1). Further, the sulfonic acid polymer also has a vinyl perfluoroalkyl ether sulfonic acid represented by a registered trademark Nafion film, which is used for fuel cell applications.

The polystyrene sulfonic acid (PSS) of the sulfonic acid homopolymer has high efficiency for the doping of the π-conjugated polymer due to the continuous presence of the polymer backbone sulfonic acid in monomer units, and can also be doped. The latter π-conjugated polymer has an improved dispersibility to water. This is because the hydrophilicity is maintained by the presence of an excessively present sulfonic acid group in the PSS, and the dispersibility to water is drastically improved.

Polythiophene having PSS as a dopant is expected to be a coating type conductive film material for replacing ITO (indium-stannic acid hydride) because of its high conductivity and its ability to be treated as an aqueous dispersion. However, as described above, PSS is a water-soluble resin and hardly dissolves in an organic solvent. Therefore, the polythiophene having PSS as a dopant has high hydrophilicity, but the affinity for an organic solvent or an organic substrate is low, and it is difficult to form a film on an organic substrate by dispersing it in an organic solvent.

Further, when a polythiophene having a PSS as a dopant is used for, for example, a conductive film for organic EL illumination, since the hydrophilicity of the polythiophene having PSS as a dopant as described above is very high, a large amount of moisture tends to remain in the conductive film, and The formed conductive film is easy to take in moisture from the outside atmosphere. As a result, the organic EL illuminator undergoes a chemical change, and the luminescence ability is lowered, and the moisture is condensed into defects as time passes, and the life of the entire organic EL device is shortened. Further, there is a problem that the polythiophene having PSS as a dopant has large particles in the aqueous dispersion, and the surface of the film after the film formation has large irregularities, or is suitable for organic EL illumination to produce an unilluminated portion called a dark spot. .

Further, since polythiophene having PSS as a dopant absorbs in a blue region having a wavelength of around 500 nm, when the material is applied to a transparent substrate such as a transparent electrode, it is solid-formed for functioning of the device. The concentration or film thickness complements the required conductivity, and also has an effect on the transmittance of the member.

Patent Document 2 proposes that a π-conjugated polymer formed by a repeating unit selected from the group consisting of thiophene, selenophene, porphin, pyrrole, aniline, and polycyclic aromatic compound can be wetted with an organic solvent. a conductive polymer composition comprising 50% or more of a conductive polymer of a fluorinated acid polymer neutralized with a cation, wherein a precursor of water, a π-conjugated polymer is disclosed by combining water in an arbitrary order The monomer, the fluorinated acid polymer, and the oxidizing agent form an aqueous dispersion of the conductive polymer.

However, the particles of the conventional conductive polymer are aggregated in the dispersion immediately after the synthesis, and when an organic solvent which is a high conductivity agent is further added as a coating material, aggregation is further promoted, and the filterability is deteriorated. If spin coating is carried out without filtration, there is a problem that a flat film is not obtained due to the influence of particle agglomerates, and as a result, there is a problem of poor coating.

Further, polythiophene using PSS as a dopant can also be used as a hole injection layer. At this time, a hole injection layer is provided between the transparent electrode of ITO or the like and the light-emitting layer. In order to ensure conductivity by the lower transparent electrode, high conductivity is not required in the hole injection layer. There must be no dark spots or high hole transport capability in the hole injection layer.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-146913

[Patent Document 2] Japanese Patent No. 5264723

As described above, the polythiophene-based conductive polymer using PSS as a dopant such as PEDOT-PSS having high versatility has the following problems: high conductivity but poor absorption of visible light, and poor transparency, and in an aqueous dispersion state. The high aggregability is accompanied by difficulty in filtration and purification, the film formation property at the time of spin coating, or the surface roughness of the film formation portion.

In view of the above, the present invention provides a conductive polymer composite which is excellent in filterability and excellent in film formability at the time of spin coating, and can form a conductive film having high transparency and good flatness at the time of film formation.

In order to achieve the above object, the present invention provides a conductive polymer composite comprising: (A) a π-conjugated polymer, and (B) comprising a repeating unit a represented by the following general formula (1), and a dopant polymer having a weight average molecular weight ranging from 1,000 to 500,000, (wherein R ¹ is a hydrogen atom or a methyl group, R ² is a single bond, an ester group, or a linear group having a carbon number of 1 to 12 which may have either an ether group or an ester group or both; Any of branched or cyclic hydrocarbon groups. Z is any one of a single bond, a phenylene group, a stretchy naphthyl group, an ether group, and an ester group. a is 0 < a ≦ 1.0).

In the case of such a conductive polymer composite, the filterability is good, and the spin-coating property to the inorganic or organic substrate is good, and a conductive film having high transparency and good flatness can be formed at the time of film formation.

In this case, the repeating unit a in the component (B) is preferably one or more selected from the group consisting of the repeating units a1 to a4 shown in the following general formulas (1-1) to (1-4).

(wherein R ¹ is the same as defined above. a1, a2, a3, and a4 are 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and 0<a1+a2+ A3+a4≦1.0).

As described above, the component (B) is preferably as described above, and the filterability and film formability of the material and the affinity for the organic solvent ‧ substrate are improved, and the transmittance after film formation is improved.

Further, in this case, the component (B) further preferably has a repeating unit b represented by the following general formula (2).

(where b is 0 < b < 1.0.)

By including such a repeating unit b, the conductivity can be further improved.

Further, in this case, the component (B) is preferably a block copolymer.

If the component (B) is a block copolymer, the conductivity can be further improved.

In this case, the component (A) is one or more precursor monomers selected from the group consisting of pyrrole, thiophene, selenophene, porphin, aniline, polycyclic aromatic compound, and derivatives thereof. It is preferred to polymerize.

In the case of such a monomer, since the polymerization is easy and the stability in air is good, the component (A) is easily synthesized.

Further, in this case, the conductive polymer composite is preferably one having a dispersibility in water or an organic solvent.

Moreover, the present invention provides a substrate in which a conductive film is formed by the conductive polymer composite.

As described above, the conductive polymer composite of the present invention can be formed into a conductive film by coating a film on a substrate or the like.

Moreover, the conductive film formed as described above is excellent in conductivity and transparency, and can function as a transparent electrode layer.

As described above, in the conductive polymer composite of the present invention, the dopant polymer of the (B) component containing a sulfonic acid group of the super acid is formed by complexing with the π-conjugated polymer of the component (A). Body, low viscosity Further, the filterability is good, and the film formation property at the time of spin coating is good, and when the film is formed, since the stability to light or heat is improved, durability is high, and a conductive film having good transparency, flatness, and conductivity can be formed. Moreover, in the case of such a conductive polymer composite, the affinity to the organic solvent and the organic substrate is good, and the film formation property is good regardless of the organic substrate or the inorganic substrate.

In addition, the conductive film formed of such a conductive polymer composite is excellent in conductivity, transparency, and the like, and can function as a transparent electrode layer.

As described above, the film forming property at the time of spin coating is good, and the film for forming a conductive film of a conductive film having high transparency and flatness can be formed at the time of film formation.

The inventors of the present invention have intensively studied the results of the above problems and found that by using a dopant polymer containing a repeating unit of a sulfonic acid group having a trifluoromethyl group at the β position, it is widely used as a conductive polymer material. The polystyrene sulfonic acid (PSS) of the dopant and the super acid dopant polymer interact strongly with the π-conjugated polymer, and the transparency is improved by the displacement of the visible light absorption domain of the π-conjugated polymer. The light or heat stability is enhanced by strong ionic bonding of the π-conjugated polymer to the dopant polymer. In addition, it was found that the film forming property at the time of spin coating was improved because of the good filterability, and the flatness at the time of film formation was also improved, and the present invention was completed.

That is, the present invention is a conductive polymer composite comprising (A) a π-conjugated polymer, and (B) comprising a repeating unit a represented by the following general formula (1), and having a weight average molecular weight of 1,000 Å. a dopant polymer in the range of 500,000, (wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a single bond, an ester group or a linear or branched group having a carbon number of 1 to 12 which may have either an ether group or an ester group or both. Any one of a cyclic or cyclic hydrocarbon group. Z is any one of a single bond, a phenylene group, a stilbene group, an ether group, and an ester group. a is 0 < a ≦ 1.0).

The present invention will be described in detail below, but the present invention is not limited thereto.

[(A) π conjugated polymer]

The conductive polymer composite of the present invention contains a π-conjugated polymer as the component (A). This (A) component is only required to form a π-conjugated chain. (Structure in which a single bond and a double bond are continuously connected) It is sufficient to polymerize a precursor monomer (organic monomer molecule).

As such a precursor monomer, for example, a monocyclic ring such as a pyrrole group, a thiophene group, a thiophene group, a selenophene group, a porphin group, a phenylene group, a phenylene group, a phenylene group or the like may be mentioned. Aromatic or polycyclic aromatic compounds such as acenes; acetylenes and the like, and homopolymers or copolymers of these monomers can be used as the component (A).

Among the above monomers, pyrrole, thiophene, selenophene, porphin, aniline, polycyclic aromatic compound, and derivatives thereof are preferred from the viewpoints of ease of polymerization and stability in air. Pyrrole, thiophene, aniline, and derivatives thereof are particularly preferred, but are not limited thereto.

When the conductive polymer composite of the present invention contains polythiophene as the component (A), it is considered to have high conductivity and high transparency under visible light, and is considered to be in a touch panel or an organic EL display or an organic EL. Development of the use of lighting, etc. On the other hand, when the conductive polymer composite of the present invention contains polyaniline as the component (A), it is difficult to apply to a display depending on the absorption under visible light when the polythiophene is contained and the conductivity is low. Low-viscosity spin coating is considered to be a use for preventing a charged topcoat of an electron resisting upper film in EB lithography.

Further, even if the monomer constituting the π-conjugated polymer is directly unsubstituted, the component (A) can be sufficiently electrically conductive, but in order to increase the conductivity, an alkyl group, a carboxyl group or a sulfonic acid can also be used. a monomer substituted with a group, an alkoxy group, a hydroxyl group, a cyano group, a halogen atom or the like.

Specific examples of the monomers of the azoles, thiophenes, and anilines include pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, and 3-butyl. Pyrrole, 3-octylpyrrole, 3-mercaptopyrrole, 3-dodecylpyrrole, 3,4-dimethylpyrrole, 3,4-dibutylpyrrole, 3-carboxypyrrole, 3-methyl- 4-carboxypyrrole, 3-methyl-4-carboxyethylpyrrole, 3-methyl-4-carboxybutylpyrrole, 3-hydroxypyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3- Butoxypyrrole, 3-hexyloxypyrrole, 3-methyl-4-hexoxypyrrole; thiophene, 3-methylthiophene, 3-ethylthiophene, 3-propylthiophene, 3-butylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-mercaptothiophene, 3-dodecylthiophene, 3-octadecylthiophene, 3-bromothiophene, 3-chlorothiophene, 3 -iodothiophene, 3-cyanothiophene, 3-phenylthiophene, 3,4-dimethylthiophene, 3,4-dibutylthiophene, 3-hydroxythiophene, 3-methoxythiophene, 3-ethoxy Thiophene, 3-butoxythiophene, 3-hexyloxythiophene, 3-heptyloxythiophene, 3-octyloxythiophene, 3-decyloxythiophene, 3-dodecyloxythiophene, 3- Octamethoxyoxythiophene, 3,4-dihydroxythiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutyl Oxythiophene, 3,4-dihexyloxythiophene, 3,4-diheptyloxythiophene, 3,4-dioctyloxythiophene, 3,4-dimethoxythiophene, 3,4-di‧ Dodecyloxythiophene, 3,4-extended ethyldioxythiophene, 3,4-extended ethyldithiothiophene, 3,4-propanedioxythiophene, 3,4-butylene Oxythiophene, 3-methyl-4-methoxythiophene, 3-methyl-4-ethoxythiophene, 3-carboxythiophene, 3-methyl-4-carboxythiophene, 3-methyl-4- Carboxymethylthiophene, 3-methyl-4-carboxyethylthiophene, 3-methyl-4-carboxybutylthiophene, 3,4-(2,2-dimethyl-propyldioxy)thiophene, 3,4-(2,2-diethylpropanyldioxy Thiophene, (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol; aniline, 2-methylaniline, 3-methylaniline, 2-B Aniline, 3-ethylaniline, 2-propylaniline, 3-propylaniline, 2-butylaniline, 3-butylaniline, 2-isobutylaniline, 3-isobutylaniline, 2-methyl Oxyaniline, 2-ethoxyaniline, 2-anilinesulfonic acid, 3-anilinesulfonic acid, and the like.

Wherein, it is one or two selected from the group consisting of pyrrole, thiophene, N-methylpyrrole, 3-methylthiophene, 3-methoxythiophene, and 3,4-extended ethyldioxythiophene ( The co-polymer is more suitable for use in terms of resistance and reactivity. Further, a homopolymer composed of pyrrole or 3,4-extended ethyldioxythiophene is more preferable because it has high conductivity.

Further, for practical reasons, the number of repetitions of such repeating units (precursor monomers) in the component (A) is preferably in the range of 2 to 20, more preferably in the range of 6 to 15.

Further, the molecular weight of the component (A) is preferably from about 130 to 5,000.

[(B) dopant polymer]

The conductive polymer composite of the present invention contains a dopant polymer as the component (B). The dopant polymer of the component (B) contains a super strong acid polymer comprising a repeating unit a represented by the following general formula (1) and a sulfonic acid having a trifluoromethyl group at the β position.

(wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a single bond, an ester group or a linear or branched group having a carbon number of 1 to 12 which may have either an ether group or an ester group or both. Any one of a cyclic or cyclic hydrocarbon group. Z is any one of a single bond, a phenylene group, a stretchy naphthyl group, an ether group, and an ester group. a is 0 < a ≦ 1.0.

In the general formula (1), R ¹ is a hydrogen atom or a methyl group.

R ² is a single bond, an ester group or a hydrocarbon group having a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have either an ether group or an ester group or both. For example, an alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), an alkenyl group, and the like can be given.

Z is any one of a single bond, a phenyl group, a naphthyl group, an ether group, and an ester group.

a is 0 < a ≦ 1.0, preferably 0.2 ≦ a ≦ 1.0.

Specific examples of the monomer to which the repeating unit a is given can be exemplified below.

(wherein R ¹ is the same as defined above, and X is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or an anthracene compound).

In addition, it is preferable that the repeating unit a represented by the general formula (1) includes one or more of the repeating units a1 to a4 selected from the following general formulas (1-1) to (1-4). That is, among the monomers exemplified above, it is particularly preferable to obtain a monomer of the repeating units a1 to a4.

(wherein R ¹ is the same as defined above. a1, a2, a3, and a4 are 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and 0<a1+a2+ A3+a4≦1.0.)

In the case of such a component (B), the filterability and film formability of the material and the affinity for the organic solvent ‧ substrate are improved, and the transmittance after film formation is improved.

The component (B) further preferably has a repeating unit b represented by the following general formula (2). By including such a repeating unit b, the conductivity can be further improved.

(where b is 0 < b < 1.0.)

Specific examples of the monomer to which the repeating unit b is given are exemplified below.

(wherein X ₂ is a hydrogen atom, a lithium atom, a sodium atom, a potassium atom, an amine compound, or a ruthenium compound.)

When X and X ₂ are an amine compound, (P1a-3) described in paragraph [0048] of JP-A-2013-228447 can be exemplified.

Here, as described above, a is 0 < a ≦ 1.0, preferably 0.2 ≦ a ≦ 1.0. If 0 < a ≦ 1.0 (i.e., if the repeating unit a is included), the effect of the present invention can be obtained, but if 0.2 ≦ a ≦ 1.0, a better effect can be obtained. Further, when the repeating unit a contains one or more selected from the repeating units a1 to a4, 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and 0<a1 +a2+a3+a4≦1.0 is preferably, more preferably 0≦a1≦0.9, 0≦a2≦0.9, 0≦a3≦0.9, 0≦a4≦0.9, and 0.1≦a1+a2+a3+a4≦0.9 More preferably, it is 0≦a1≦0.8, 0≦a2≦0.8, 0≦a3≦0.8, 0≦a4≦0.8, and 0.2≦a1+a2+a3+a4≦0.8.

Moreover, when the repeating unit b is included, from the viewpoint of conductivity improvement, 0.2 ≦ b < 1.0 is preferable, and 0.3 ≦ b ≦ 0.8 is more preferable.

Further, the ratio of the repeating unit a to the repeating unit b is 0.2 ≦ a ≦ 0.8 and 0.2 ≦ b ≦ 0.8 is preferable, and 0.3 ≦ a ≦ 0.6 and 0.4 ≦ b ≦ 0.7 are more preferable.

Further, the dopant polymer of the component (B) may have a repeating unit c other than the repeating unit a and the repeating unit b. Examples of the repeating unit c include, for example, a styrene type, a vinyl naphthalene type, and a vinyl decane type. , hydrazine, hydrazine, benzofuran, benzothiophene, (meth)acrylic acid, vinylcarbazole, and the like.

Specific examples of the monomer to which the repeating unit c is imparted are as follows.

As a method of synthesizing the dopant polymer of the component (B), for example, by adding a desired monomer among the monomers of the above repeating units a to c, a radical polymerization initiator is added to the organic solvent. A method of heating polymerization to obtain a dopant polymer of a (co)polymer.

As an organic solvent used in the polymerization, a Benzene, benzene, tetrahydrofuran, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone, γ-butyrolactone, and the like.

As the radical polymerization initiator, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2, 2'-azobis(2-methylpropionate), benzamyl peroxide, lauryl peroxide, and the like.

The reaction temperature is preferably from 50 to 80 ° C, and the reaction time is preferably from 2 to 100 hours, more preferably from 5 to 20 hours.

In the dopant polymer of the component (B), the monomer to which the repeating unit a is added may be one type or two or more types, but the methacrylic type and the styrene type monomer which improve the polymerizability are combined. good.

Further, when two or more types of monomers to which the repeating unit a is added are used, the respective monomers may be copolymerized randomly (randomly) or may be block copolymerized. When a block copolymerized polymer (block copolymer) is formed, a repeating portion composed of two or more types of repeating units a is aggregated to form an island structure, and a specific structure is formed around the dopant polymer. The advantage of improved conductivity.

Further, the monomers imparting the repeating units a to c may be copolymerized randomly (randomly) or may be copolymerized by blocks. At this time, as in the case of the above-described repeating unit a, it is expected to have an advantage of an increase in conductivity by being a block copolymer.

In the case of random (random) copolymerization by radical polymerization, a method of mixing a copolymerized monomer or a radical polymerization initiator and performing polymerization by heating is common. Stored in the first monomer and the radical polymerization initiator In the case where the polymerization is started next, and then the second monomer is added, the one side of the polymer molecule is a structure in which the first monomer is polymerized, and the other side is a structure in which the second monomer is polymerized. However, in this case, the intermediate portion is a mixture of the first monomer and the second monomer, and is different from the block copolymer. In the formation of the block copolymer by radical polymerization, living radical polymerization is preferably used.

A polymerization method called active radical of RAFT polymerization, because the radical at the end of the polymer is always alive, the polymerization starts with the first monomer, and the second single is added by the consumption stage. The diblock copolymer formed by forming a block of a repeating unit of the first monomer and a repeating unit of the second monomer. Further, the first monomer is started to be polymerized, and when the second monomer is added at the stage of consumption, the triblock copolymer may be formed in the case where the third monomer is added.

When RAFT polymerization is carried out, there is a characteristic that a narrowly dispersed polymer having a narrow molecular weight distribution (dispersion degree) is formed, and in particular, when a monomer is added once for RAFT polymerization, a polymer having a narrow molecular weight distribution can be formed.

Further, in the dopant polymer of the component (B), the molecular weight distribution (Mw/Mn) is preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5. If it is narrowly dispersed, the transmittance of the conductive film formed using the conductive polymer composite using this can be prevented from being lowered.

It is necessary to carry out the RAFT polymerization medium chain transfer agent, and specifically, 2-cyano-2-propylbenzothio, 4-cyano-4-phenylthiocarbonylthiovaleric acid, 2-cyano-2- Propyl lauryl trisulfonate, 4-cyano-4-[ (dodecylthiocarbonylcarbonyl)thio]pentanoic acid, 2-(dodecylthiothiocarbonylthio)-2-methylpropionic acid, cyanomethyldodecylthiocarbonate Ester, cyanomethylmethyl(phenyl)amine methyl sulfonyl thio, bis(thiobenzylidene) disulfide, bis(dodecylthiothiocarbonyl) disulfide. Among these, especially 2-cyano-2-propylbenzo sulfur is preferred.

When the dopant polymer of the component (B) contains the above repeating unit c, the ratio of the repeating units a to c is 0 < a ≦ 1.0, 0 ≦ b < 1.0, 0 < c < 1.0, more preferably 0.1 ≦. a ≦ 0.9, 0.1 ≦ b ≦ 0.9, 0 < c ≦ 0.8, more preferably 0.2 ≦ a ≦ 0.8, 0.2 ≦ b ≦ 0.8, 0 < c ≦ 0.5.

Further, a+b+c=1 is preferable.

The dopant polymer of the component (B) has a weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 200,000. When the weight average molecular weight is less than 1,000, the heat resistance is poor, and the uniformity of the complex solution with the component (A) is deteriorated. On the other hand, when the weight average molecular weight exceeds 500,000, the conductivity is deteriorated, the workability of viscosity increase is deteriorated, and the dispersibility to water or an organic solvent is lowered.

Further, the weight average molecular weight (Mw) is polyethylene oxide or polyethylene glycol of gel permeation chromatography (GPC) using water, dimethylformamide (DMF), tetrahydrofuran (THF) as a solvent. Or the measured value in terms of polystyrene.

Further, as the monomer constituting the dopant polymer of the component (B), a monomer having a sulfonic acid group may be used, but a lithium salt, a sodium salt, a potassium salt, an ammonium salt or a cerium salt of a sulfonic acid group may also be used. The salt is subjected to a polymerization reaction as a monomer, and is converted into a sulfonic acid group by using an ion exchange resin after the polymerization.

[conductive polymer composite]

The conductive polymer composite of the present invention comprises the π-conjugated polymer of the above (A) component and the dopant polymer of the component (B), and the dopant polymer of the component (B) is disposed by (A) The π-conjugated polymer of the component forms a complex.

The conductive polymer composite of the present invention preferably has dispersibility in water or an organic solvent, and is spin-coated into a film or a film for an inorganic or organic substrate (a substrate on which an inorganic film or an organic film is formed on a substrate surface). Can be good.

(Manufacturing method of conductive polymer composite)

A composite of the component (A) and the component (B), for example, a monomer which is a raw material of the component (A) is added to the aqueous solution of the component (B) or the aqueous solution of the component (B); Addition of an oxidizing agent and optionally an oxidizing catalyst to pyrrole, thiophene, aniline or a derivative monomer thereof is carried out by oxidative polymerization.

As the oxidizing agent and the oxidation catalyst, peroxodisulfate such as ammonium peroxodisulfate (ammonium persulfate), sodium peroxodisulfate (sodium persulfate) or potassium peroxydisulfate (potassium persulfate) can be used. Sulfate), a transition metal compound such as ferric chloride, iron sulfate or copper chloride, a metal oxide such as silver oxide or cerium oxide, a peroxide such as hydrogen peroxide or ozone, or a benzamidine peroxide or the like. Organic peroxides, oxygen, etc.

As a reaction solvent used in the oxidative polymerization, Use water or a mixed solvent of water and solvent. The solvent used herein is mutually miscible with water, and a solvent which can dissolve or disperse the component (A) and the component (B) is preferred. For example, N-methyl-2-pyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethylammonium, hexamethylphosphonium triazine A polar solvent such as amidoxime, an alcohol such as methanol, ethanol, propanol or butanol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, D-glucose , D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, etc. Alcohols, carbonate compounds such as ethyl carbonate and propylene carbonate; cyclic ether compounds such as dioxane and tetrahydrofuran; dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, a chain ether such as propylene glycol monoalkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether or polypropylene glycol dialkyl ether, or a heterocyclic compound such as 3-methyl-2-oxazolidinone , a nitrile compound such as acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile or benzonitrile. These solvents may be used singly or as a mixture of two or more types. The amount of the solvent which is miscible with water is preferably 50% by mass or less based on the entire amount of the reaction solvent.

Further, in addition to the dopant polymer of the component (B), an anion which can be doped to the π-conjugated polymer of the component (A) may be used in combination. As such an anion, an organic acid is preferable from the viewpoint of dedoping characteristics from the π-conjugated polymer, adjustment of dispersibility of the conductive polymer composite, heat resistance, and environmental resistance. As the organic acid, an organic carboxylic acid, a phenol, an organic sulfonic acid or the like can be exemplified.

As an organic carboxylic acid, it can be used for aliphatic, aromatic, A cyclic aliphatic or the like contains one or more carboxyl groups. For example, formic acid, acetic acid, oxalic acid, benzoic acid, citric acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, three Fluoroacetic acid, nitroacetic acid, triphenylacetic acid, and the like.

Examples of the phenols include phenols such as cresol, phenol, and anthracene.

As the organic sulfonic acid, it can be used for an aliphatic, aromatic, cyclic aliphatic or the like containing one or two sulfonic acid groups. As the one containing a sulfonic acid group, for example, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonic acid, 1-heptanesulfonic acid, 1-octane can be exemplified. Sulfonic acid, 1-decanesulfonic acid, 1-decanesulfonic acid, 1-dodecanesulfonic acid, 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 2-bromoethanesulfonic acid, 3- Chloro-2-hydroxypropanesulfonic acid, trifluoromethanesulfonic acid, colistin methanesulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid, aminomethanesulfonic acid, 1-amino-2-naphthalene Phenol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, benzenesulfonic acid, p-toluene Sulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, propylbenzenesulfonic acid, butylbenzenesulfonic acid, pentylbenzenesulfonic acid, hexylbenzenesulfonic acid, heptylbenzenesulfonic acid, octylbenzenesulfonic acid, hydrazine Benzobenzenesulfonic acid, nonylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, cetylbenzenesulfonic acid, 2,4-dimethyl Benzenesulfonic acid, dipropylbenzenesulfonic acid, 4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-amino-5-methoxy-2-methylbenzene Sulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 5-amino-2-methylbenzene-1-sulfonic acid , 4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzenesulfonic acid, p-chlorobenzenesulfonate Acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, amylnaphthalenesulfonic acid, dimethylnaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 8- A sulfonic acid group-containing sulfonic acid compound or the like which is a chloronaphthalene-1-sulfonic acid, a naphthalenesulfonic acid formaldehyde polycondensate, a melaminesulfonic acid formaldehyde polycondensate or the like.

As the one containing two sulfonic acid groups, for example, ethane disulfonic acid, butane disulfonic acid, pentane disulfonic acid, decanedisulfonic acid, m-benzenedisulfonic acid, o-benzenedisulfonic acid, P-benzenedisulfonic acid, toluene disulfonic acid, xylene disulfonic acid, chlorobenzene disulfonic acid, fluorobenzene disulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, Diethylbenzenedisulfonic acid, dibutylbenzenedisulfonic acid, naphthalene disulfonic acid, methylnaphthalene disulfonic acid, ethylnaphthalene disulfonic acid, dodecyl naphthalene disulfonic acid, pentadecyl naphthalene Sulfonic acid, butyl naphthalene disulfonic acid, 2-amino-1,4-benzenedisulfonic acid, 1-amino-3,8-naphthalene disulfonic acid, 3-amino-1,5-naphthalene disulfide Acid, 8-amino-1-naphthol-3,6-disulfonic acid, sulfonium disulfonic acid, butyl sulfonium disulfonic acid, 4-acetamide-4'-isosulfide-cyanoguanidine-2,2 '-Disulfonic acid, 4-acetamido-4'-isothiocyanate-2,2'-disulfonic acid, 4-acetamide-4'-maleimide hydrazine-2,2' -disulfonic acid, 1-ethyloxy hydrazine-3,6,8-trisulphonic acid, 7-amino-1,3,6-naphthalenetrisulfonic acid, 8-aminonaphthalene-1,3,6 Trisulphonic acid, 3-amino-1,5,7-naphthalenetrisulfonic acid and the like.

The anion other than the component (B) may be added to the solution containing the raw material monomer of the component (A), the component (B), the oxidizing agent, and/or the oxidative polymerization catalyst before the polymerization of the component (A). It may be added to a conductive polymer composite (solution) containing the components (A) and (B) after polymerization.

The composite of the component (A) and the component (B) thus obtained needs to be finely granulated by a homogenizer or a ball mill.

In the granulation, it is preferred to use a mixing dispersing machine which can impart high shear force. As the mixing and dispersing machine, for example, a homogenizer, a high pressure homogenizer, a bead mill, or the like can be exemplified, and among them, a high pressure homogenizer is preferred.

Specific examples of the high-pressure homogenizer include NanoVater manufactured by Yoshida Machinery Co., Ltd., Microfluidizer manufactured by Powrex Co., Ltd., and Ultimizer manufactured by SUGINO MACHINE Co., Ltd., and the like.

As the dispersion treatment using a high-pressure homogenizer, for example, a treatment for collimating the composite solution before the dispersion treatment with high pressure, a treatment for passing a high pressure through an orifice or a slit, and the like can be exemplified.

The impurities may be removed by filtration, ultrafiltration, dialysis or the like before or after the granulation, or may be purified by a cation exchange resin, an anion exchange resin, a chelating resin or the like.

Further, the total content of the component (A) and the component (B) in the conductive polymer composite solution is preferably 0.05 to 5.0% by mass. When the total content of the component (A) and the component (B) is 0.05% by mass or more, sufficient conductivity can be obtained, and when it is 5.0% by mass or less, a uniform conductive coating film can be easily obtained.

The content of the component (B) is preferably in the range of from 0.1 to 10 mol per mol of the sulfonic acid group in the component (B), and is in the range of from 1 to 7 mol per mol of the component (A). The amount is better. When the sulfonic acid group in the component (B) is 0.1 mol or more, the doping effect on the component (A) is high, and sufficient conductivity can be ensured. Further, when the sulfonic acid group in the component (B) is 10 mol or less, the content of the component (A) is also moderate, and sufficient conductivity can be obtained.

As an aqueous solution which can be added to the polymerization reaction, or an organic solvent which can dilute the monomer, methanol, ethyl acetate, cyclohexanone, methyl amyl ketone, butane diol monomethyl ether, propylene glycol monomethyl ether, and B can be exemplified. Glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Acid ester, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, propionic acid - butyl ester, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, and mixtures thereof.

Further, the amount of the organic solvent used is preferably from 0 to 1,000 mL, particularly preferably from 0 to 500 mL, per mol of the monomer. When the amount of the organic solvent used is 1,000 mL or less, it is economical because the reaction container does not become excessively large.

[other ingredients] (surfactant)

In the present invention, a surfactant may be added in order to improve the wettability of a workpiece such as a substrate. As such a surfactant, various surfactants of a nonionic type, a cationic type, and an anionic type are mentioned. Specific examples thereof include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylate, sorbitan ester, and polyoxyethylene sorbitan ester. a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, alkyl or alkylallyl sulfate, alkyl or alkylallylsulfonate, dialkyl Sulfosuccinate Anionic surfactant, amphoteric surfactant such as amino acid type or betaine type, acetylene alcohol surfactant, acetylene alcohol surfactant with hydroxyl group or polyethylene oxide Wait.

(high conductivity agent)

In the present invention, an organic solvent different from the main solvent may be added for the purpose of improving the conductivity of the conductive polymer composite. As such a solvent to be added, a polar solvent can be exemplified, and specific examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dimethyl hydrazine (DMSO), dimethylformamide (DMF), and N. Methyl-2-pyrrolidone (NMP), cyclobutyl hydrazine and mixtures of these. The amount of addition is preferably from 1.0 to 30.0% by mass, particularly preferably from 3.0 to 10.0% by mass.

(neutralizer)

In the present invention, the pH in the aqueous solution of the conductive polymer composite is acidic. For the purpose of neutralizing this, a nitrogen-containing aromatic cyclic compound described in paragraphs [0033] to [0045] of JP-A-2006-96975, or a paragraph [0127] of Japanese Patent No. 5264723 may be added. The cations described control the pH to neutral. By the pH of the solution being close to neutral, rust can be prevented from being applied to the printing press.

As described above, in the conductive polymer composite of the present invention, the film forming property at the time of filterability and spin coating is good, and a conductive film having high transparency and low surface roughness can be formed.

[conductive film]

The conductive polymer composite (solution) obtained as described above can be formed into a conductive film by being applied to a workpiece such as a substrate. The coating method of the conductive polymer composite (solution) can be, for example, a coating by a spin coater, a bar coater, dipping, comma coating, spray coating, roll coating, or the like. Plate printing, flexographic printing, gravure printing, inkjet printing, and the like. After the application, a conductive film can be formed by heat treatment such as a hot air circulation furnace or a hot plate, IR, UV irradiation, or the like.

As described above, the conductive polymer composite of the present invention can be formed into a conductive film by coating a film into a substrate or the like. Moreover, the conductive film formed as described above is excellent in conductivity and transparency, and can function as a transparent electrode layer and a hole injection layer.

[substrate]

Moreover, the present invention provides a substrate in which a conductive film is formed by the above-described conductive polymer composite of the present invention.

Examples of the substrate include a compound semiconductor wafer such as a glass substrate, a quartz substrate, a mask blank substrate, a resin substrate, a germanium wafer, a gallium germanium wafer, and an indium phosphide wafer, and a flexible substrate. Moreover, it can also be applied to a photoresist film as an antistatic surface coating.

As described above, in the conductive polymer composite of the present invention, the dopant polymer of the (B) component containing a sulfonic acid group of the super acid is formed by complexing with the π-conjugated polymer of the component (A). Body, low viscosity and good filterability, good film formation during spin coating, and formation when film is formed A conductive film having good transparency, flatness, durability, and electrical conductivity. Moreover, in the case of such a conductive polymer composite, the affinity to the organic solvent and the organic substrate is good, and the film formation property of both the organic substrate and the inorganic substrate is good.

In addition, the conductive film formed of such a conductive polymer composite is excellent in conductivity, transparency, and the like, and can function as a transparent electrode layer.

[Examples]

Hereinafter, the present invention will be specifically described using a synthesis example, a preparation example, a comparative preparation example, an example, and a comparative example, but the present invention is not limited thereto.

The monomers used in the synthesis examples are shown below.

Monomer 1: benzyltrimethylammonium = 3,3,3-trifluoro-2-methylpropenyloxy-2-trifluoromethylpropane-1-sulfonate

Monomer 2: benzyltrimethylammonium = 3,3,3-trifluoro-2-(3-methylpropenyloxy-1-adamantanecarbonyloxy)-2-trifluoromethylpropane-1 -sulfonate

Monomer 3: benzyltrimethylammonium = 3,3,3-trifluoro-2-trifluoromethyl-2-(4-vinylbenzylideneoxy)propane-1-sulfonate

Monomer 4: tetrabutylammonium = 3,3,3-trifluoro-2-(4-methylpropenyloxy-1-benzoyloxy)-2-trifluoromethylpropane-1-sulfonate Acid ester

[Synthesis of dopant polymer] (Synthesis Example 1)

Under a nitrogen atmosphere, 48.1 g of monomer 1 and 5.13 g of 2,2'-azobis(isobutyric acid) dimethyl ester were dissolved in methanol at 37.5 g of methanol stirred at 64 ° C for 11 hours. Solution. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 26.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and the ammonium salt was converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Weight average molecular weight (Mw) = 42,000

Molecular weight distribution (Mw/Mn)=1.61

This polymer compound was designated as (dopant polymer 1).

(Synthesis Example 2)

Under a nitrogen atmosphere, 24.0 g of monomer 1 and 9.5 g of lithium styrene sulfonate and 2,2'-azobis(isobutyrate) were added dropwise in 37.5 g of methanol stirred at 64 ° C for 4 hours. The ester 5.13 g was dissolved in a solution of 112.5 g of methanol. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 41.5 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt and a lithium salt were converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Copolymerization composition ratio (mole ratio) monomer 1: styrene sulfonic acid = 1:1

Weight average molecular weight (Mw) = 46,000

Molecular weight distribution (Mw/Mn)=1.76

This polymer compound was designated as (dopant polymer 2).

(Synthesis Example 3)

Under nitrogen atmosphere, 32.8 g of monomer 2 and 9.5 g of lithium styrene sulfonate and 2,2'-azobis(isobutyrate) dimethyl were dropped in 4 hours of methanol stirred at 64 ° C for 4 hours. 5.13 g of the ester was dissolved in a solution of 112.5 g of methanol. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 46.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and an ammonium salt and a lithium salt were converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Copolymerization composition ratio (mole ratio) monomer 2: styrenesulfonic acid = 1:1

Weight average molecular weight (Mw) = 46,000

Molecular weight distribution (Mw/Mn) = 1.52

This polymer compound was designated as (dopant polymer 3).

(Synthesis Example 4)

Under nitrogen atmosphere, 27.0 g of monomer 3 and 9.5 g of lithium styrene sulfonate and 2,2'-azobis(isobutyrate) dimethyl were dropped in 4 hours of methanol stirred at 64 ° C for 4 hours. 2.82 g of the ester was dissolved in a solution of 112.5 g of methanol. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 47.3 g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Copolymerization composition ratio (mole ratio) monomer 3: styrenesulfonic acid = 1:1

Weight average molecular weight (Mw) = 55,000

Molecular weight distribution (Mw/Mn)=1.81

This polymer compound was designated as (dopant polymer 4).

(Synthesis Example 5)

Under a nitrogen atmosphere, 34.6 g of monomer 4 and 9.5 g of lithium styrene sulfonate and 2,2'-azobis(isobutyrate) dimethyl were dropped in 4 hours under stirring at 64 ° C. 2.82 g of the ester was dissolved in a solution of 112.5 g of methanol. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 50.2 g of a white polymer.

The obtained white polymer was dissolved in 421 g of methanol, and an ammonium salt and a lithium salt were converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Copolymerization composition ratio (mole ratio) monomer 4: styrenesulfonic acid = 1:1

Weight average molecular weight (Mw) = 56,000

Molecular weight distribution (Mw / Mn) = 1.68

This polymer compound was designated as (dopant polymer 5).

(Synthesis Example 6)

Under a nitrogen atmosphere, 52.5 g of monomer 2 and 4-(1,1,1,3,3,3-hexafluoro-2-propanol) were added dropwise in 37.5 g of methanol stirred at 64 ° C for 4 hours. 7.13 g of styrene and 5.13 g of 2,2'-azobis(isobutyrate) dimethyl ester were dissolved in a solution of 112.5 g of methanol. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 43.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and the ammonium salt was converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Copolymerization composition ratio (mole ratio) monomer 2: 4-(1,1,1,3,3,3-hexafluoro-2-propanol)styrene=4:1

Weight average molecular weight (Mw) = 41,000

Molecular weight distribution (Mw/Mn)=1.64

This polymer compound was designated as (dopant polymer 6).

(Synthesis Example 7)

Under nitrogen atmosphere, 52.5 g of monomer 2 and methacrylic acid-bis 3,5-(2-hydroxy-1,1,1,3,3 were dropped in 4 hours in methanol stirred at 64 ° C for 4 hours. 3.13 g of 3-hexafluoro-2-propyl)cyclohexyl ester and 5.13 g of 2,2'-azobis(isobutyrate) dimethyl ester were dissolved in a solution of 112.5 g of methanol. Further, the mixture was stirred at 64 ° C for 4 hours. After cooling to room temperature, it was dripped into 1,000 g of ethyl acetate while stirring vigorously. The solid matter thus obtained was taken out by filtration, and dried under vacuum at 50 ° C for 15 hours to obtain 61.2 g of a white polymer.

The obtained white polymer was dissolved in 912 g of pure water, and the ammonium salt was converted into a sulfonic acid group using an ion exchange resin. The obtained polymer was subjected to ¹⁹ F-NMR, ¹ H-NMR, and GPC measurement, and was analyzed as follows.

Copolymerization composition ratio (mole ratio) monomer 2: methacrylic acid-bis 3,5-(2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl)cyclohexyl ester =4:1

Weight average molecular weight (Mw) = 23,000

Molecular weight distribution (Mw/Mn)=1.61

This polymer compound was designated as (dopant polymer 7).

[Preparation of Conductive Polymer Composite Dispersion] (Modulation example 1)

3.82 g of 3,4-extended ethyldioxythiophene was mixed with a solution of 12.5 g of the dopant polymer 1 in 1,000 mL of ultrapure water at 30 °C.

The mixed solution thus obtained was kept at 30 ° C, and while stirring, 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an iron oxide catalyst solution of ferric sulfate were slowly added, and the mixture was stirred for 4 hours to cause a reaction. .

To the resulting reaction solution, 1,000 mL of ultrapure water was added, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment liquid subjected to the above filtration treatment, and about 2,000 mL of the treatment liquid was removed by ultrafiltration, and 2,000 mL of ion exchange was added thereto. Water, using ultrafiltration to remove about 2,000 mL of liquid. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. Repeat this operation Five times, 1.3% by mass of the blue conductive polymer composite dispersion 1 was obtained.

The ultrafiltration conditions are as follows.

Cut-off molecular weight of ultrafiltration membrane: 30K

Cross flow

Supply flow rate: 3,000 mL / min

Membrane partial pressure: 0.12Pa

In addition, other modulation examples were also subjected to ultrafiltration under the same conditions.

(Modulation example 2)

In addition to changing 12.5 g of the dopant polymer 1 to 14.0 g of the dopant polymer 2, the amount of the 3,4-extended ethyldioxythiophene was changed to 2.41 g, and the amount of sodium persulfate was changed. The conductive polymer composite dispersion 2 was obtained in the same manner as in Preparation Example 1 except that the amount of the iron sulfate was changed to 1.50 g.

(Modulation Example 3)

In addition to changing 12.5 g of the dopant polymer 1 to 13.0 g of the dopant polymer 3, the amount of 3,4-extended ethyldioxythiophene was changed to 2.72 g, and the amount of sodium persulfate was changed to The conductive polymer composite dispersion 3 was obtained by the same method as in Preparation Example 1 except that the amount of the iron sulfate was changed to 1.60 g.

(Modulation Example 4)

In addition to changing 12.5 g of the dopant polymer 1 to 12.4 g of the dopant polymer 4, 8.40 g of sodium persulfate was changed to 4.50 g of ammonium persulfate, 3,4-extended ethyldioxythiophene. The conductive polymer composite dispersion 4 was obtained in the same manner as in Preparation Example 1 except that the amount of the iron oxide was changed to 2.04 g, and the amount of the iron sulfate was changed to 1.23 g.

(Modulation Example 5)

In addition to changing 12.5 g of the dopant polymer 1 to 13.1 g of the dopant polymer 5, 8.40 g of sodium persulfate was changed to 5.31 g of ammonium persulfate, 3,4-extended ethyldioxythiophene. The conductive polymer composite dispersion liquid 5 was obtained by the same method as in Preparation Example 1 except that the amount of the iron sulfate was changed to 2.41 g and the amount of the iron sulfate was changed to 1.50 g.

(Modulation Example 6)

4.65 g of 3,4-extended ethyldithiothiophene and a solution of dissolving 14.0 g of the dopant polymer 2 in 1,000 mL of ultrapure water were mixed at 30 °C.

The mixed solution thus obtained was kept at 30 ° C, and while stirring, 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an iron oxide catalyst solution of ferric sulfate were slowly added, and the mixture was stirred for 4 hours to cause a reaction. .

To the resulting reaction solution, 1,000 mL of ultrapure water was added, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment liquid subjected to the above filtration treatment, so that About 2,000 mL of the treatment liquid was removed by ultrafiltration, 2,000 mL of ion-exchanged water was added thereto, and about 2,000 mL of the liquid was removed by ultrafiltration. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 6.

(Modulation Example 7)

3.87 g of 3,4-dimethoxythiophene was mixed with a solution of 14.0 g of the dopant polymer 2 in 1,000 mL of ultrapure water at 30 °C.

The mixed solution thus obtained was kept at 30 ° C, and while stirring, 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an iron oxide catalyst solution of ferric sulfate were slowly added, and the mixture was stirred for 4 hours to cause a reaction. .

To the resulting reaction solution, 1,000 mL of ultrapure water was added, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment liquid subjected to the above filtration treatment, and about 2,000 mL of the treatment liquid was removed by ultrafiltration, and 2,000 mL of ion exchange was added thereto. Water, using ultrafiltration to remove about 2,000 mL of liquid. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.3% by mass blue conductive polymer composite dispersion. Liquid 7.

(Modulation Example 8)

4.62 g of (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol was mixed at 30 ° C, and 14.0 g of the dopant polymer 2 was dissolved in 1,000 A solution of mL of ultrapure water.

The mixed solution thus obtained was kept at 30 ° C, and while stirring, 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an iron oxide catalyst solution of ferric sulfate were slowly added, and the mixture was stirred for 4 hours to cause a reaction. .

To the resulting reaction solution, 1,000 mL of ultrapure water was added, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment liquid subjected to the above filtration treatment, and about 2,000 mL of the treatment liquid was removed by ultrafiltration, and 2,000 mL of ion exchange was added thereto. Water, using ultrafiltration to remove about 2,000 mL of liquid. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain a 1.3 mass% blue conductive polymer composite dispersion liquid 8.

(Modulation Example 9)

4.16 g of 3,4-propyldioxythiophene was mixed at 30 ° C, and 14.0 g of the dopant polymer 2 was dissolved in 1,000 mL of ultrapure water. liquid.

The mixed solution thus obtained was kept at 30 ° C, and while stirring, 8.40 g of sodium persulfate dissolved in 100 mL of ultrapure water and 2.3 g of an iron oxide catalyst solution of ferric sulfate were slowly added, and the mixture was stirred for 4 hours to cause a reaction. .

To the resulting reaction solution, 1,000 mL of ultrapure water was added, and about 1,000 mL of the solution was removed by ultrafiltration. Repeat this operation 3 times.

Then, 200 mL of sulfuric acid diluted to 10% by mass and 2,000 mL of ion-exchanged water were added to the treatment liquid subjected to the above filtration treatment, and about 2,000 mL of the treatment liquid was removed by ultrafiltration, and 2,000 mL of ion exchange was added thereto. Water, using ultrafiltration to remove about 2,000 mL of liquid. Repeat this operation 3 times.

Further, 2,000 mL of ion-exchanged water was added to the obtained treatment liquid, and about 2,000 mL of the treatment liquid was removed by ultrafiltration. This operation was repeated 5 times to obtain 1.3% by mass of a blue conductive polymer composite dispersion liquid 9.

(Modulation Example 10)

In addition to changing 12.5 g of the dopant polymer 1 to 16.0 g of the dopant polymer 6, the amount of the 3,4-extended ethyldioxythiophene was changed to 2.41 g, and the amount of sodium persulfate was changed to 5.31 g, the amount of the iron sulfate was changed to 1.50 g, and was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 10.

(Modulation Example 11)

In addition to changing 12.5 g of the dopant polymer 1 to 18.0 g of the dopant polymer 7, the amount of the 3,4-extended ethyldioxythiophene was changed to 2.41 g, and the amount of sodium persulfate was changed to 5.31 g, the amount of the iron sulfate was changed to 1.50 g, and was prepared in the same manner as in Preparation Example 1 to obtain a conductive polymer composite dispersion liquid 11.

(Modulation Example 12)

The conductive polymer composite dispersion liquid 2 and the conductive polymer composite dispersion liquid 11 are mixed at a ratio of 1:1 to obtain a conductive polymer composite dispersion liquid 12.

(Comparative modulation example 1)

5.0 g of 3,4-extended ethyldioxythiophene and a solution of 83.3 g of an aqueous solution of polystyrenesulfonic acid (18.0% by mass of Aldrich) diluted with 250 mL of ion-exchanged water were mixed at 30 °C. Otherwise, it was prepared in the same manner as in Preparation Example 1 to obtain a 1.3% by mass blue comparative conductive polymer composite dispersion 1 (PEDOT-PSS dispersion). This comparative conductive polymer composite dispersion 1 contains only polystyrenesulfonic acid as a dopant polymer.

[Examples]

20 g of the 1.3% by mass of the conductive polymer composite dispersions 1 to 12 obtained in Preparation Examples 1 to 12, 5 g of dimethyl sulfonium, 0.5 g of Surfynol 465 as a surfactant and an antifoaming agent, respectively, were mixed, and then Using aperture A 0.45 μm regenerated cellulose filter (manufactured by ADVANTEC Co., Ltd.) was subjected to filtration to prepare a conductive polymer composition, which was used as Examples 1 to 12, respectively.

[Comparative Example]

A conductive polymer composition was prepared in the same manner as in the Example except that the comparative conductive polymer composite 1 obtained in Comparative Preparation Example 1 was used, and this was designated as Comparative Example 1.

The conductive polymer compositions of the examples and comparative examples prepared as described above were evaluated as follows.

(filterability)

In the preparation of the conductive polymer composition of the above-described examples and comparative examples, when filtration was carried out using a regenerated cellulose filter having a pore size of 0.45 μm, the filter was ○, the filter was clogged, and the filter was not filtered. Table 1.

(coating property)

First, a conductive polymer composition was spin-coated (spin-coated) on a Si wafer so that the film thickness became 100±5 nm using 1H-360S SPINCOATER (manufactured by MIKASA). Then, the film was removed by baking at 120 ° C for 5 minutes in a precision thermostat to obtain a conductive film. In the conductive film, the refractive index (n, k) at a wavelength of 636 nm was determined by a spectroscopic ellipsometer VASE (manufactured by J.A. Woollam Co., Ltd.) whose incident angle was variable. It is possible to form a uniform film with ○, although the refractive index can be measured but the film is produced. The defects originating from the particles or the partial stripes are indicated by x in Table 1.

(transmission rate)

The transmittance of FT=200 nm to light having a wavelength of 550 nm was calculated by the refractive index (k) measured by a spectroscopic ellipsometer (VASE) whose incident angle was variable. The results are shown in Table 1.

(Conductivity)

First, 1.0 mL of a conductive polymer composition was dropped on a SiO ₂ wafer having a diameter of 4 Å (100 mm), and after 10 seconds, it was spin-coated to the whole using a spin coater. The spin coating conditions were adjusted so that the film thickness became 100 ± 5 nm. The conductive film was obtained by baking at 120 ° C for 5 minutes in a precision thermostat to remove the solvent.

The conductivity (S/cm) of the obtained conductive film was measured by the surface resistivity (Ω/□) and film thickness measured by using Hirista-UP MCP-HT450 and Loresta-GP MCP-T610 (all manufactured by Mitsubishi Chemical Corporation). The measured value is obtained. The results are shown in Table 1.

(Surface roughness)

A conductive film was obtained on a SiO ₂ wafer having a diameter of 4 Å (100 mm) in the same manner as the evaluation method of the conductivity. The RMS (root mean square roughness) was measured by AFM NANO-IM-8 (manufactured by Image Metrology). The results are shown in Table 1.

(viscosity)

The solid content of the conductive polymer composition was set to 1.3% by mass, and the liquid temperature was adjusted to 25 °C. A tuning-type vibrating viscometer SV-10 (manufactured by A&D Co., Ltd.) was used to measure 35 mL of a dedicated measuring element, and the viscosity immediately after the preparation was measured. The results are shown in Table 1.

As shown in Table 1, Examples 1 to 12 comprising a polythiophene as a π-conjugated polymer and comprising a dopant polymer having a repeating unit a have good filterability and, in turn, can be coated by a spin coater. The coating is applied to obtain a uniform coating film. Further, the conductivity is high, and the transmittance of visible light having λ = 550 nm is also good, and the surface roughness is also good.

On the other hand, use polystyrene without repeating unit a In Comparative Example 1 in which the enesulfonic acid was used as the dopant polymer, the filterability was poor due to high viscosity, and as a result, streaks due to particles or bubbles were generated on the film during spin coating, and a uniform coating film could not be obtained. Further, although the conductivity was high, the transmittance and surface roughness of visible light having λ = 550 nm were inferior to those of Examples 1 to 12.

As described above, it is understood that the conductive polymer composite of the present invention has low viscosity and good filterability, and is excellent in film formability at the time of spin coating, and can form transparency, flatness, durability, and A conductive film and a hole injection layer having good conductivity.

Further, the present invention is not limited to the above embodiment. The above-described embodiments are exemplified and have substantially the same configuration as the technical idea described in the patent application scope of the present invention, and all of them have the same effects, and are included in the technical scope of the present invention.

Claims (8)

A conductive polymer composite comprising: (A) a π-conjugated polymer, and (B) comprising a repeating unit a represented by the following general formula (1), and having a weight average molecular weight of 1,000 to 500,000 a range of dopant polymers, (wherein R ¹ is a hydrogen atom or a methyl group, and R ² is a single bond, an ester group or a linear or branched group having a carbon number of 1 to 12 which may have either an ether group or an ester group or both. Any one of a cyclic or cyclic hydrocarbon group; Z is any of a single bond, a phenyl group, a naphthyl group, an ether group, and an ester group; a is 0 < a ≦ 1.0). The conductive polymer composite according to claim 1, wherein the repeating unit a in the component (B) contains a repeating unit a1 to a4 selected from the following general formulas (1-1) to (1-4); One or more types, (wherein R ¹ is the same as the above; a1, a2, a3, and a4 are 0≦a1≦1.0, 0≦a2≦1.0, 0≦a3≦1.0, 0≦a4≦1.0, and 0<a1+a2+ A3+a4≦1.0). The conductive polymer composite according to claim 1 or claim 2, wherein the component (B) further comprises a repeating unit b represented by the following general formula (2), (where b is 0 < b < 1.0). The conductive polymer composite according to claim 1 or claim 2, wherein the component (B) is a block copolymer. The conductive polymer composite according to claim 1 or claim 2, wherein the component (A) is selected from the group consisting of pyrrole, thiophene, selenophene, porphin, aniline, polycyclic aromatic compound, and the like One or more precursor monomers in a group are aggregated. The conductive polymer composite according to claim 1 or claim 2, wherein the conductive polymer composite has dispersibility to water or an organic solvent. A substrate obtained by forming a conductive film by the conductive polymer composite according to any one of claims 1 to 6. The substrate according to claim 7, wherein the conductive film functions as a transparent electrode layer.