JP6127506B2 - Catalyst paste composition for fuel cell and catalyst layer and joined body using the same - Google Patents

Description

  The present invention relates to a catalyst paste composition and a catalyst ink composition for a fuel cell, and relates to a catalyst layer, an electrode membrane assembly and a fuel cell using them.

  A fuel cell is a system that can directly convert chemical energy into electrical energy using an electrochemical system, and is expected to be a next-generation energy because of its high efficiency. In particular, solid polymer fuel cells are being actively developed for automobiles, stationary devices, and small mobile devices. Conventionally, platinum-based catalysts using platinum or platinum alloys having high oxygen reduction activity have been used as electrode catalysts for these polymer electrolyte fuel cells, but from the viewpoint of cost, resource amount, and supply stability Development of catalysts other than platinum-based catalysts (referred to as non-platinum-based catalysts) has been demanded. However, the performance of current non-platinum-based catalysts is not sufficient compared to platinum-based catalysts, so technological development of catalysts that significantly reduce the amount of platinum used or non-platinum-based catalysts that do not use platinum has been promoted. Yes.

  As such a non-platinum-based catalyst, for example, Patent Document 1 proposes a carbon material obtained by doping nitrogen into a carbonized product obtained by mixing a carbon additive with a polymer metal complex and heat-treating it. Such a carbon material doped with nitrogen can be used as a non-platinum-based catalyst having oxygen reduction activity. Patent Document 2 proposes that a carbon material obtained by introducing an ion-exchange functional group into a surface-treated carbon material by a grafting reaction can be used as a non-platinum-based catalyst.

  However, in the carbon material of Patent Document 1, since it is difficult to uniformly mix and disperse the polymer metal complex before the heat treatment and the carbon material, the introduction rate of the metal element and the nitrogen element in the carbonized material is low, so the catalyst It has the disadvantage that the activity is low and the structure of the polymer metal complex that can be used is limited. In addition, as a method for alloying nitrogen atoms in a carbon material, a method in which a carbon material is impregnated with a nitrogen-containing organic compound and firing, a method in which the surface of the carbon material is coated with a nitrogen atom-containing polymer and then fired are known. However, in the former method, the nitrogen-containing organic compound volatilizes during firing, and it is difficult to increase the nitrogen introduction rate into the carbon alloy material. In the latter method, the entire surface of the carbon material is removed. Since it is difficult to coat and control the thickness of the coating and the coating tends to be thick, there is a drawback that a highly conductive material cannot be stably produced.

  On the other hand, in the carbon catalyst of Patent Document 2, since the ion-exchangeable functional group to be introduced is introduced as a proton conduction site, it does not contribute as a catalytic active site, and is not baked after the introduction of the ion-exchangeable functional group. For this reason, the carbon structure becomes irregular, and there is a disadvantage that the oxygen reduction performance and conductivity are inferior.

  Further, the non-platinum-based catalyst described above has advantages in that it is more economical and cost superior than the platinum-based catalyst, and is excellent in durability without being poisoned. In order to improve performance, it is necessary to increase the specific surface area of the catalyst. In addition, when a non-platinum-based catalyst is dispersed to form a composition, the non-platinum-based catalyst is likely to cause aggregation, so that it is necessary to improve the dispersion stability in the composition. Also, when these compositions are applied, if the catalyst agglomerates, pinholes are formed in the coating film, or a suitable electrode film cannot be obtained, resulting in a decrease in the amount of current and a decrease in electromotive force. There is a problem. Although there is such a technical problem, no means for solving this has been found.

JP 2008-282725 A JP 2009-295441 A

  The problem to be solved by the present invention is a catalyst paste composition for a fuel cell, which has good dispersibility and low viscosity of the carbon-based catalyst material, and has excellent electrochemical characteristics, storage stability, and coatability, and It is to provide a catalyst ink composition. In addition, by using these compositions, a fuel cell catalyst layer with very little coating unevenness and pinholes when applied, and a fuel cell electrode membrane assembly having the same, and excellent battery performance A fuel cell is provided.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
The first invention is a catalyst paste composition for a fuel cell comprising a non-platinum-based carbon-based catalyst material whose catalytic active site is a carbon atom in the vicinity of a heteroatom introduced at the edge of the carbon material surface, and a dispersant. And the dispersant is selected from the group consisting of a resin having a basic functional group, a resin having an acidic functional group, a pigment derivative having a basic functional group, a pigment derivative having an acidic functional group, and a mixture thereof. The present invention relates to a fuel cell catalyst paste composition that is a dispersant .
The second invention relates to the catalyst paste composition for a fuel cell, wherein the resin having a basic functional group and / or the resin having an acidic functional group is a polyvinyl resin or a polyester resin.
The third invention is a pigment wherein the pigment derivative having a basic functional group and / or the pigment derivative having an acidic functional group is selected from the group consisting of organic dye derivatives, anthraquinone derivatives, acridone derivatives, triazine derivatives, and mixtures thereof. It is related with the said catalyst paste composition for fuel cells which is a derivative.
A fourth invention relates to a fuel cell catalyst ink composition comprising the fuel cell catalyst paste composition and at least one of a hydrogen ion conductive polymer or a water repellent material.
The fifth invention relates to a fuel cell catalyst layer formed from the fuel cell catalyst ink composition.
The sixth invention relates to a water repellent layer for a fuel cell formed from the catalyst ink composition for a fuel cell.
The seventh invention relates to a fuel cell electrode membrane assembly comprising a solid polymer electrolyte membrane, at least one of the fuel cell catalyst layer or the fuel cell water repellent layer, and a gas diffusion layer.
An eighth invention relates to a fuel cell comprising the fuel cell electrode membrane assembly.

  According to the present invention, a fuel cell catalyst paste composition and a catalyst ink composition having good dispersibility and low viscosity of the carbon-based catalyst material, and excellent electrochemical characteristics, storage stability, and coating properties. Therefore, by using these compositions, the catalyst layer for fuel cells and the electrode membrane for fuel cells having the same with little generation of coating unevenness and pinholes at the time of coating are provided. A joined body can be obtained. Therefore, it is possible to provide a fuel cell with excellent battery performance.

  Hereinafter, the present invention will be described in detail. In this specification, “catalyst paste composition for fuel cell” is referred to as “catalyst paste composition” or “paste composition”, and “catalyst ink composition for fuel cell” is referred to as “catalyst ink composition” or “ink. Sometimes referred to as “composition”. Further, the “fuel cell catalyst paste composition” and the “fuel cell catalyst ink composition” may be simply referred to as “composition”. Further, “resin” is sometimes referred to as “polymer”.

<Catalyst paste composition for fuel cell>
The proportions of the carbon-based catalyst material, the dispersant, and the solvent contained in the paste composition of the present invention are not particularly limited and can be appropriately selected within a wide range.

  Content of a dispersing agent is 0.01 to 10 weight% with respect to the carbon-type catalyst material in a catalyst paste composition, Preferably it is 0.02 to 5 weight%. By setting the content in this range, the dispersion stability of the carbon-based catalyst material can be sufficiently achieved, and at the same time, the aggregation of the carbon-based catalyst material can be effectively prevented, and the precipitation of the dispersant on the surface of the catalyst layer can be prevented. Can be prevented.

  The solvent is 60 to 99 parts by weight, preferably 65 to 97% by weight, when the catalyst paste composition is 100% by weight.

<Non-platinum-based carbon-based catalyst material>
A non-platinum-based carbon-based catalyst material (hereinafter also referred to as a carbon-based catalyst material) is a multi-component system mainly composed of aggregates of carbon (C) atoms, and is physically and chemically between these constituent units. A catalyst material having an interaction (bonding) and containing a heteroatom such as nitrogen (N), boron (B), phosphorus (P) or a transition metal such as a transition metal may be used. it can.
The inclusion of a heteroatom and a transition metal is important for having oxygen reduction activity. In general, in the case of a carbon-based catalyst material, as a catalytic active point, for example, in a structure in which four nitrogen atoms are arranged on a plane centered on the surface of the carbon material (referred to as a transition metal-N4 structure). Examples include transition metals and carbon atoms in the vicinity of heteroatoms introduced into the edge of the carbon material surface, and the presence of heteroatoms and transition metal elements is also important in the carbon-based catalyst material of the present invention.
Such a carbon-based catalyst material has an oxygen reduction catalytic ability superior in durability as compared with a conventionally known platinum-supported carbon material, and can be suitably used as a fuel cell electrode catalyst. Become. The carbon-based catalyst material can be used for both the cathode and the anode, but is often used as the cathode.

  In the carbon-based catalyst material according to the present invention, when the doping amount of nitrogen or boron (content of nitrogen or boron in the carbon-based catalyst material) is 0.1 to 40 mol%, oxygen reduction Shows good electrode activity. Further, when nitrogen and boron are simultaneously doped, a higher electrode activity is exhibited due to the interaction between the two. When both nitrogen and boron are doped, the atomic ratio (B / N) is 0.2 to 0.4, preferably 0.06 to 1.5, and the molar ratio ((B + N) / C) is preferably 0.03 to 0.4. Within these ranges, a highly active carbon-based catalyst material can be obtained.

<Carbon material>
Examples of the carbon material that is a component of the carbon-based catalyst material in the present invention include carbon black (furnace black, acetylene black, ketjen black, medium thermal carbon black), activated carbon, graphite, carbon nanotube, carbon nanofiber, carbon nanohorn, Examples include graphene nanoplatelets, nanoporous carbon, and carbon fibers. Carbon materials have various physical properties and costs such as particle diameter, shape, BET specific surface area, pore volume, pore diameter, bulk density, DBP oil absorption, surface acidity, surface hydrophilicity, and conductivity depending on the type and manufacturer. Because it is different, select the most suitable material according to the intended use and required performance.

Examples of commercially available carbon materials include:
Ketjen Black made by Akzo, such as Ketjen Black EC-300J and EC-600JD;
Furnace blacks manufactured by Tokai Carbon, such as Toka Black # 4300, # 4400, # 4500, and # 5500;
Furnace Black made by Degussa such as Printex L;
Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULT
Furnace black made by Colombian, such as RA, Conductex SC ULTRA, 975 ULTRA, PUER BLACK100, 115, and 205;
# 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B, and # 5400B furnace black manufactured by Mitsubishi Chemical Corporation;
Furnace black from Cabot, such as MONARCH 1400, 1300, 900, Vulcan XC-72R, and Black Pearls 2000;
Furnace black manufactured by TIMCAL, such as Ensaco 250G, Ensaco 260G, Ensaco 350G, and SuperP-Li;
Acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd. such as Denka Black, Denka Black HS-100 and FX-35
Carbon nanotubes manufactured by Showa Denko KK such as VGCF, VGCF-H, VGCF-X;
Carbon nanotube manufactured by Meijo Nanocarbon
graphene nanoplatelets made by XGSciences such as xGnP-C-750, xGnP-M-5;
Nano-carbon produced by Easy-N;
Carbon fiber manufactured by Gunei Chemical Industry Co., Ltd., such as Kynol carbon fiber and Kynol activated carbon fiber;
However, it is not limited to these.

<Dope raw materials for heteroatoms and transition metals>
As a carbon-based catalyst material in the present invention, as a raw material used when doping a heteroatom such as nitrogen or boron or a transition metal, any material containing a heteroatom and / or a transition metal can be used. Any organic compound (pigment, polymer, etc.) and inorganic compound (metal simple substance, metal oxide, metal salt, etc.) can be used. The transition metal preferably contains at least one selected from cobalt, iron, nickel, manganese, copper, titanium, vanadium, chromium, zinc, tin, aluminum, and magnesium.
Among these, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, tetraazaannulene compounds, etc., which are nitrogen-containing aromatic compounds and can contain transition metals in the molecule, are contained in carbon-based catalyst materials. It is preferable because it is easy to dope nitrogen and transition metal efficiently. In addition, the aromatic compound has no problem even if an electron-withdrawing functional group or an electron-donating functional group is introduced. In particular, phthalocyanine compounds are particularly preferable as raw materials because there are compounds containing various transition metals and they are inexpensive, and among them, cobalt phthalocyanine compounds, nickel phthalocyanine compounds, iron Since phthalocyanine compounds are known to have high oxygen reduction activity, carbon-based catalyst materials synthesized from them are more preferable because they are inexpensive and have high oxygen reduction activity. .

(a) Production method of carbon-based catalyst material doped with nitrogen To produce a carbon-based catalyst material doped with nitrogen, first, as a nitrogen source, phthalocyanine, acrylonitrile, EDTA (ethylenediaminetetraacetic acid), melamine, etc. And a precursor of a thermosetting resin such as a furan resin or a phenol resin are mixed and reacted by heating to obtain a nitrogen compound-containing thermosetting resin.

  For example, when phthalocyanine is used as the nitrogen-containing compound and furfuryl alcohol is used as the thermosetting resin precursor, an acid such as hydrochloric acid is added to these mixtures, and the temperature is preferably in the range of 80 to 200 ° C. The phthalocyanine-containing furan resin, which is a nitrogen compound-containing thermosetting resin, can be obtained by heating with a polymerization reaction. In order to make the nitrogen doping amount 0.1 to 40 mol%, the mixing ratio of furfuryl alcohol and melamine or phthalocyanine is C: N (molar ratio) 1: (0.07-3), preferably Is 1: (0.1 to 0.5).

  Next, the obtained phthalocyanine-containing furan resin is heat-treated at a predetermined temperature in an inert gas atmosphere such as nitrogen or helium to be carbonized. The heat treatment temperature is not particularly limited as long as it can be carbonized, but a preferable temperature is 400 to 1500 ° C, and a more preferable temperature is 500 to 1200 ° C. Subsequently, a carbon-based catalyst material having an average particle diameter of 45 μm or less, preferably 0.1 μm or less doped with nitrogen can be obtained by pulverizing preferably with a disperser such as a planetary ball mill.

  As another method for producing a carbon-based catalyst material doped with nitrogen, acetylene black, ketjen black, furnace black, graphene, carbon nanotubes, conductive carbon fibers, activated carbon, etc. are used as carbon materials, and nitrogen atoms are changed. It can obtain by mixing with the compound which has and heat-processing at predetermined | prescribed temperature similarly to the above, and carbonizing. At this time, the above carbon materials may be used alone, or some of them may be used after being mixed.

(b) Method for Producing Boron-Doped Carbon-Based Catalyst Material To produce a boron-doped carbon-based catalyst material, first, as a boron source, BF ₃ methanol complex or BF ₃ tetrahydrofuran (THF) complex, etc. The boron-containing compound and a precursor of a thermosetting resin such as a furan resin or a phenol resin are mixed and reacted by heating to obtain a boron compound-containing thermosetting resin.

For example, when BF ₃ methanol complex is used as the boron-containing compound and furfuryl alcohol is used as the precursor of the thermosetting resin, the polymerization reaction is preferably performed by heating at a temperature in the range of 80 to 200 ° C. Thus, a BF ₃ -containing furan resin can be obtained. In order to adjust the doping amount of boron atoms described above to 0.1 to 40 mol%, the mixing ratio of furfuryl alcohol and BF ₃ is 1: (0.1 to 1) in terms of C: B (molar ratio), preferably Is 1: (0.15-0.6).

Next, the obtained BF ₃ -containing furan resin is carbonized by heat treatment at the predetermined temperature described in (a) above under an inert gas atmosphere such as nitrogen or helium. Subsequently, a carbon-based catalyst material having an average particle diameter of 45 μm or less, preferably 0.1 μm or less doped with boron atoms can be obtained by pulverizing preferably with a ball mill such as a planetary ball mill.

(c) Method for producing carbon-based catalyst material doped with nitrogen and boron (thermal polymerization method)
In order to produce a carbon-based catalyst material doped with nitrogen and boron, first, a boron-containing compound and a nitrogen-containing compound are mixed with a precursor of a thermosetting resin such as a furan resin or a phenol resin, followed by a heating reaction. To obtain a boron-nitrogen compound-containing thermosetting resin.

For example, when BF ₃ methanol complex is used as the boron-containing compound, melamine is used as the nitrogen-containing compound, and furfuryl alcohol is used as the precursor of the thermosetting resin, the temperature is preferably in the range of 80 to 200 ° C. A BF ₃ -containing furan resin can be obtained by heating and causing a polymerization reaction. In order to make the doping amounts of nitrogen atom and boron atom 0.1 to 40 atom% and B / N atomic ratio 0.2 to 0.4, respectively, furfuryl alcohol, melamine and BF 3 methanol are used. The compounding ratio of the complex in terms of C: N: B (molar ratio) is 1: (0.04-2) :( 0.02-1), preferably 1: (0.3-0.7) :( 0. 4 to 1.5). Next, the obtained furan resin is carbonized at a predetermined temperature described in the above (a) under an inert gas atmosphere such as nitrogen or helium to obtain a carbon-based catalyst material doped with nitrogen and boron. Can do.

(d) Method for producing carbon-based catalyst material doped with nitrogen and boron (subcritical method)
As another method for producing a carbon-based catalyst material doped with nitrogen and boron, there is the following subcritical method. In this method, first, a nitrogen-containing compound and a boron-containing compound such as a BF ₃ methanol complex or a BF ₃ tetrahydrofuran (THF) complex as a boron source are dissolved in a solution of furfuryl alcohol or a resol type phenol resin. Perform a polymerization reaction.

For example, in the case of using a methanol solution of furfuryl alcohol, melamine as a nitrogen-containing compound, and BF ₃ methanol complex as a boron-containing compound, furfuryl is used under methanol subcritical or supercritical conditions at 200 to 350 ° C. Perform an alcohol polymerization reaction. In order to adjust the doping amounts of nitrogen and boron described above to 0.1 to 40 mol%, the mixing ratio of furfuryl alcohol, melamine, and BF ₃ methanol complex is 1 in C: N: B (molar ratio). : (0.2 to 0.8): (0.1 to 0.4), preferably 1: (0.3 to 0.7): (0.15 to 0.4). Next, by carbonizing the obtained polymer at a predetermined temperature described in the above (a) under an inert gas atmosphere such as nitrogen or helium, a carbon-based catalyst material doped with nitrogen and boron can be obtained. it can.

  The second form of the carbon-based catalyst material according to the present invention is a form in which carbon ultrafine particles having an average particle diameter of 10 to 100 nm produced by a sol-gel method are used as a precursor. Here, the ultrafine carbon particles are produced as follows. First, an aqueous solution containing a base catalyst such as phenol, formaldehyde and sodium carbonate is prepared. When this aqueous solution is kept at a predetermined temperature for a predetermined time to react phenol and formaldehyde, polymer ultrafine particles are generated in the reaction solution. The predetermined temperature is preferably 60 to 90 ° C, and more preferably 80 to 90 ° C. The predetermined time is preferably 1 to 20 hours, more preferably 8 to 18 hours. Next, the reaction solution is cooled to liquid nitrogen temperature, frozen, and dried to recover the ultrafine polymer particles. Further, the recovered polymer ultrafine particles are heated and cured at 100 to 250 ° C. for 0.5 to 10 hours, preferably at 200 to 230 ° C. for 3 to 6 hours. The cured ultrafine polymer particles are carbonized by heating under the carbonization heat treatment conditions described in the above (a) to obtain ultrafine carbon particles having an average particle size of 10 to 100 nm, preferably 10 to 30 nm. In order to obtain such ultrafine particles, the blending weight ratio of phenol, formaldehyde and sodium carbonate (phenol: formaldehyde: sodium carbonate) is 1: (1-2) :( 0.05-0.2), preferably 1: (1.4 to 1.6): (0.05 to 0.1).

<Dispersant>
In the present invention, the dispersant is selected from the group consisting of a resin having a basic functional group, a resin having an acidic functional group, a pigment derivative having a basic functional group, a pigment derivative having an acidic functional group, and a mixture thereof. It is important that it be a dispersant. By using these dispersants, a catalyst paste composition having excellent dispersion stability can be provided without impairing catalyst activity or conductivity. The catalyst paste composition of the present invention not only exhibits excellent dispersion stability, but also has excellent storage stability, and maintains its dispersed state when a hydrogen ion conductive polymer or a water repellent material is added later. Can be mixed and dispersed. Moreover, the wettability with the hydrogen ion conductive polymer can be improved. Therefore, since the adhesion between the carbon-based catalyst material and the hydrogen ion conductive polymer in the coating film and the hydrogen ion conductivity to the catalyst active site can be improved, it can be suitably used for the catalyst ink composition.

  The organic compound having a basic functional group or the acidic functional group that can be used as a dispersant in the present invention is not particularly limited as long as the functional group can act or adsorb on the surface of the carbon-based catalyst material. . However, from the viewpoint of battery performance in which electronic conductivity is important, as a suitable organic compound having a basic functional group, a pigment derivative (I-1) having a basic functional group, a resin having a basic functional group (I -2). Moreover, as an example of the organic compound which has a suitable acidic functional group, the pigment derivative (II-1) which has an acidic functional group, and resin (II-2) which has an acidic functional group are mentioned. Among the pigment derivatives having a basic functional group, preferred examples include an organic dye derivative (I-1) having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a base. And various derivatives such as a triazine derivative having a functional functional group. Further, among the pigment derivatives having a suitable acidic functional group, as preferred forms, organic dye derivatives having an acidic functional group, anthraquinone derivatives having an acidic functional group, acridone derivatives having an acidic functional group, and triazines having an acidic functional group Examples include various derivatives such as derivatives.

  Although it does not specifically limit, in preferable one Embodiment of this invention, a dispersing agent is the pigment derivative (I-1) which has the said basic functional group, or the pigment derivative (II-1) which has the said acidic functional group. Either is included as an essential component. In another preferred embodiment of the present invention, the dispersant contains, as an essential component, either the resin (I-2) having the basic functional group or the resin (II-2) having the acidic functional group. . Furthermore, in another preferred embodiment of the present invention, the dispersant is a resin (I-2) having the above basic functional group or the above acid in addition to the above various derivatives (I-1) or (II-1). Resin (II-2) which has a functional group is included. Hereinafter, each pigment derivative and resin will be described in detail.

<Pigment derivative (I-1) having basic functional group>
The pigment derivative having a basic functional group comprises an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group. One or more derivatives selected from the group may be contained.

  In particular, it is preferable to use a triazine derivative represented by the following formula (1) or an organic dye derivative represented by the following formula (6).

In the above formula (1),
X ¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ² -Y ¹ -X ³ - is and,
X ² is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
X ³ is each independently —NH— or —O—.
Y ¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following formulas (2), (3), or (4),
Q is —O—R ² , —NH—R ² , a halogen group, —X ¹ —R ¹ , or a substituent represented by any of the following formulas (2), (3), or (4). ,
R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following formula (5),
n ¹ is an integer of 1 to 4.

In the above formulas (2) to (4),
X ⁴ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or -X ⁵ -Y ² -X ⁶ - a and,
X ⁵ is —NH— or —O—.
X ⁶ is a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ² is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
v is an integer from 1 to 10,
R ³ and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or R ³ and R ⁴ together. A substituted or unsubstituted heterocyclic residue containing additional nitrogen, oxygen or sulfur atoms,
R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ⁹ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

In the above formula (5),
T is a -X ⁸ -R ^10, or W ^1,
U is, -X ⁹ -R ^11, or a W ^2,
W ¹ and W ² are each independently —O—R ²⁰ , —NH—R ²⁰ , a halogen group, or a substituent represented by any one of the above formulas (2), (3), or (4). And
R ²⁰ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
X ⁷ is —NH— or —O—.
X ^8, and X ⁹ are each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
Y ³ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
R ¹⁰ and R ¹¹ are each independently an organic dye residue, a substituted or unsubstituted heterocyclic residue, or a substituted or unsubstituted aromatic ring residue.

Specific examples of organic dye residues represented by R ^{1 in the} above formula (1) and R ¹⁰ and R ¹¹ in the above formula (5) include diketopyrrolopyrrole dyes; azo, disazo, polyazo and the like Phthalocyanine dyes; anthraquinone dyes such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone dyes; dioxazine dyes; perinone dyes; Examples include a rylene dye, a thioindigo dye, an isoindoline dye, an isoindolinone dye, a quinophthalone dye, a slen dye, and a metal complex dye. In particular, from the viewpoint of enhancing the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.

Specific examples of the heterocyclic residue and the aromatic ring residue represented by R ^{1 in the} above formula (1) and R ¹⁰ and R ¹¹ in the above formula (5) include thiophene, furan, pyridine, pyrazine, Examples include triazine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. It is done. These heterocyclic residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc.), amino groups, alkylamino groups (dimethylamino group, diethylamino group, dibutylamino group, etc.), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group) , May be substituted with an alkoxy group or halogen, etc.), and may be substituted with a phenylamino group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be substituted).

R ³ and R ⁴ in the above formulas (2) and (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Or it is the heterocyclic residue which may have the substituent containing nitrogen, oxygen, or a sulfur atom united with R < ³ > and R < ⁴ >.

Y ¹ , Y ² and Y ³ in formulas (1) to (5) each independently represent a substituted or unsubstituted alkylene group, alkenylene group or arylene group having 20 or less carbon atoms, preferably substituted Alternatively, an unsubstituted phenylene group, a biphenylene group, a naphthylene group, or an alkylene group that may have a side chain having 10 or less carbon atoms is exemplified.

In equation (6),
Z is at least one selected from the group represented by the following formulas (7), (8), and (9), n ² is an integer of 1 to 4, and R ¹² is an organic dye residue. A group, a substituted or unsubstituted heterocyclic residue, or a substituted or unsubstituted aromatic residue.

In the above formulas (7) to (9),
X ¹⁰ represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, - CH 2 -, or -X ¹¹ -Y ⁴ -X ¹² - a and,
X ¹¹ is —NH— or —O—.
X ¹² represents a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - CH 2 NHCONHCH 2 -, or -CH ₂ -,
Y ⁴ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
v ¹ is an integer from ¹ to 10,
R ¹³ and R ¹⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group, or R ³ and R ^4. Substituted or unsubstituted heterocyclic residues containing additional nitrogen, oxygen or sulfur atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ¹⁹ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

Specific examples of the organic dye residue represented by R ¹² in formula (6) include diketopyrrolopyrrole dyes; azo dyes such as azo, disazo, and polyazo; phthalocyanine dyes; diaminodianthraquinone, anthrapyrimidine, Anthraquinone dyes such as flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindolinone dyes Examples thereof include dyes; quinophthalone dyes; selenium dyes; and metal complex dyes. In particular, in order to enhance the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye.

Examples of the heterocyclic residue and aromatic ring residue represented by R ¹² in formula (6) include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone. Benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, anthraquinone, and acridone. These heterocyclic residues and aromatic ring residues are alkyl groups (such as methyl, ethyl, and butyl groups), amino groups, alkylamino groups (such as dimethylamino groups, diethylamino groups, and dibutylamino groups), Nitro group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, fluorine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group) , May be substituted with an alkoxy group, halogen, etc.), and may be substituted with a phenylamino group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) May be substituted).

R ¹³ and R ¹⁴ in formulas (7) and (8) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted phenyl group. Or a substituted or unsubstituted heterocyclic residue which together contains R ¹³ and R ¹⁴ and contains an additional nitrogen, oxygen or sulfur atom.

Specific examples of the amine component used to form the substituents represented by the above formulas (2) to (4) and the above formulas (6) to (8) include the following.
Dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N- tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, Dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutyl Aminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoe Ruamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecholine, 2,4-rupetidine, 2 , 6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N- Aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N- Butyl piperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  The method for synthesizing an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group is not particularly limited. A well-known method can be applied. For example, JP 54-62227, JP 56-118462, JP 56-166266, JP 60-88185, JP 63-305173, JP 3 A method described in JP-A No. 2676 or JP-A No. 11-199796 can be applied. The disclosure by the above publication is incorporated into a part of this specification by reference.

For example, various derivatives having a basic functional group react with an amine component after introducing a substituent represented by the following formulas (10) to (13) into an organic dye, anthraquinone, or acridone. Can be synthesized.
Formula (10):
-SO ₂ Cl
Formula (11):
-COCl
Formula (12):
-CH ₂ NHCOCH ₂ Cl
Formula (13):
—CH ₂ Cl

  Examples of the amine component include N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5. -Triazin-2-ylamino] aniline and the like can be used.

  For example, when introducing the substituent represented by the above formula (10), an organic dye, anthraquinone, or acridone is dissolved in chlorosulfonic acid and reacted with a chlorinating agent such as thionyl chloride. At that time, the number of substituents represented by the above formula (10) to be introduced into the organic dye, anthraquinone, or acridone can be controlled by adjusting conditions such as reaction temperature and reaction time.

  In addition, when introducing the substituent represented by the above formula (11), first, an organic dye having a carboxyl group, anthraquinone, or acridone is synthesized by a known method, and then thionyl chloride in an aromatic solvent such as benzene. And the like, and the like.

  During the reaction of the substituents represented by the above formulas (10) to (13) and the amine component, a part of the substituents represented by the formulas (10) to (13) are hydrolyzed, and chlorine is substituted with hydroxyl groups. There are things to do. In that case, the substituent represented by the formula (10) is a sulfonic acid group, and the substituent represented by the formula (11) is a carboxylic acid group. Each acid group may remain as a free acid. Or you may form the salt with 1-3 said metal or said amine, respectively.

  When the organic dye is an azo dye, a substituent represented by formulas (7) to (9) or the following formula (14) is previously introduced into the diazo component or coupling component, and then the coupling reaction is performed. An azo dye derivative can also be produced by carrying out the process.

In equation (14),
X ¹³ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁴ -Y ⁵ -X ¹⁵ - a and,
X ¹⁴ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Each X ¹⁵ is independently —NH— or —O—;
Y ⁵ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P ¹ is a substituent represented by any of the above formulas (2), (3), or (4),
Q ² is —O—R ²⁴ , —NH—R ²⁴ , a halogen group, —X ¹ —R ²⁵ , or a substituent represented by any one of the above formulas (2), (3), or (4). Yes,
R ²⁴ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group,
R ²⁵ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the above formula (5).

  The triazine derivative having a basic functional group, for example, uses cyanuric chloride as a starting material, and at least one chlorine of cyanuric chloride has a substituent represented by the above formulas (7) to (9) or formula (14). It is obtained by reacting the amine component to be formed (for example, N, N-dimethylaminopropylamine, N-methylpiperazine or the like) and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  As one of the effects of the various derivatives having the basic functional group, it is considered that the added derivative exerts a dispersion effect by acting (for example, adsorbing) on the surface of the carbon-based catalyst material. In the case of a carbon-based catalyst material, since the particle surface has high hydrophobicity, it is considered that the adsorption effect of various derivatives having a basic functional group is further improved, and the dispersion effect is also exhibited.

  That is, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group is completely or partially dissolved in a solvent, By adding and mixing the carbon-based catalyst material in the solution, the action (for example, adsorption) of these derivatives on the carbon-based catalyst material proceeds, and the base of the derivative that has acted (for example, adsorption) on the surface of the carbon-based catalyst material It is considered that the polarity of the functional functional group promotes the wetting of the surface of the carbon-based catalyst material with respect to the solvent and facilitates the aggregation of the carbon-based catalyst material.

  In preferable embodiment of this invention, the various derivative | guide_body which has a basic functional group is used together with resin (I-2) which has a basic functional group mentioned later. In another preferred embodiment of the present invention, various derivatives having a basic functional group are used in combination with an acidic compound. The acidic compound may be a resin (II-2) having an acidic functional group described later, or an inorganic acid described later or an organic acid having a molecular weight of 300 or less.

  As in the above-described embodiment, in addition to various derivatives having a basic functional group, the dispersion stability of the carbon-based catalyst material can be further improved by appropriately combining a resin having a basic functional group or an acidic compound. it can. In addition, since the adhesion between the carbon-based catalyst material and the hydrogen ion conductive polymer as the binder component is improved through the resin having the acidic functional group or the resin having the basic functional group, the fuel cell electrode In the case of a membrane assembly, in addition to the adhesion between the catalyst ink composition and the solid polymer electrolyte membrane, it is considered that the hydrogen ion conductivity to the catalyst active point of the carbon-based catalyst material is also improved.

  In particular, when a resin (I-2) having a basic functional group, which will be described later, is used in combination, the basic functional group acts on the surface of the carbon-based catalyst material (for example, adsorbs) like the derivative having the basic functional group. Thus, wetting of the surface of the carbon-based catalyst material to the solvent is promoted, and it is considered that the dispersion stability of the carbon-based catalyst material is further increased by repulsion due to steric hindrance of the resin.

  Moreover, when resin (II-2) which has an acidic functional group mentioned later as an acidic compound is used together, interaction (for example, acid-base interaction) of an acidic functional group and the basic functional group which the said derivative has, It is considered that the adhesion between the carbon-based catalyst material and the resin component is improved, and the dispersion stability of the carbon-based catalyst material is further increased.

  Further, when an inorganic acid or an organic acid having a molecular weight of 300 or less is used in combination as an acidic compound, the interaction between the acidic compound and the basic functional group of the derivative (for example, formation of an ion pair by neutralization (salt formation) ), And polarization or dissociation of ion pairs (salts)), the electrostatic repulsion on the surface of the carbon-based catalyst material is promoted, and it is considered that the dispersion stability of the carbon-based catalyst material is further increased. Such an embodiment is described in further detail below.

<Acid compound: inorganic acid, organic acid having a molecular weight of 300 or less>
In the catalyst paste composition of the present invention, an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group In order to obtain good dispersion and dispersion stability of the carbon-based catalyst material using one or more derivatives selected from the above, it is preferable to further add an acidic compound as a dispersion aid. The acidic compound used at this time is not particularly limited, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as carboxylic acids, phosphoric acids and sulfonic acids can be used. Among them, it is preferable to use an acidic compound that decomposes or volatilizes in the drying process during electrode preparation, and it is desirable to use an organic acid having a molecular weight of 300 or less, preferably 200 or less. Further, it is preferable to use an acid having low reactivity with the carbon-based catalyst material, and organic acids, particularly carboxylic acids are particularly preferable. Specifically, for example, formic acid, acetic acid, fluoroacetic acid, propionic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, acrylic acid, methacrylic acid, crotonic acid, malein Examples include acids, fumaric acid, itaconic acid, and citraconic acid.

  These inorganic acids and organic acids having a molecular weight of 300 or less are organic dye derivatives having basic functional groups, anthraquinone derivatives having basic functional groups, acridone derivatives having basic functional groups, or triazine derivatives having basic functional groups. For example, formation of ion pairs by neutralization (salt formation) and polarization or dissociation of ion pairs (salts). As a result, the solubility of the derivatives having these basic functional groups is improved, and an electrical interaction is induced on the surface of the carbon-based catalyst material on which the derivatives having these basic functional groups act (for example, adsorbed). It is considered that the deagglomeration of the system catalyst material is promoted. Here, the interaction is, for example, electrostatic repulsion between cations derived from a derivative having a basic functional group adsorbed on the surface of the carbon-based catalyst material, or electrostatic by an electric double layer formed by dissociated acid anions. A rebound is assumed.

  As described above, in one embodiment of the present invention, a functional group is directly formed on the surface of the carbon-based catalyst material by using the derivative having the basic functional group and preferably an inorganic acid or an organic acid having a molecular weight of 300 or less. Good dispersion can be obtained without introduction (covalent bonding) and without using a dispersion resin. As a result, good dispersion can be obtained without reducing the conductivity of the carbon-based catalyst material. Then, by using the catalyst paste composition of the present invention in which the carbon-based catalyst material is well dispersed, a cathode electrode or an anode electrode in which the carbon-based catalyst material is uniformly dispersed can be produced.

  As described above, a catalyst paste composition containing at least various derivatives having a basic functional group is prepared, and a hydrogen ion conductive polymer or a water repellent material is added to such a paste composition. The catalyst ink composition can be obtained. Furthermore, when a cathode electrode is produced using the catalyst ink composition, a derivative having a basic functional group is present on the surface of the carbon-based catalyst material. As a result, combined with the effect of uniformly dispersing the carbon-based catalyst material, the catalytic activity for oxygen in the cathode electrode can be improved.

<Resin having basic functional group (I-2)>
The catalyst paste composition of the present invention may contain a resin having a basic functional group in order to obtain good dispersion and dispersion stability of the carbon-based catalyst material. Preferred basic functional groups are primary, secondary, and tertiary amino groups or amide groups. The resin having a basic functional group is selected from the group consisting of three types of resins described below from the viewpoint of dispersion stability, that is, a polymer (G1), a polymer (G2), and a vinylamide resin. It is preferable to use more than one resin.

  The resin having the basic functional group functions as a binder for binding the carbon-based catalyst materials to each other or binding the carbon-based catalyst material to the electrode membrane assembly. The resin having such a basic functional group is selected from the group consisting of various derivatives (II-1) having an acidic functional group described later, that is, organic dye derivatives having an acidic functional group and triazine derivatives having an acidic functional group. When used in combination with one or more compounds (x ″), the dispersion stability of the carbon-based catalyst material and the adhesion of the fuel cell electrode membrane assembly can be improved.

  In the above-described embodiment, an acidic functional group of a derivative having an acidic functional group acting on (for example, adsorbing) the carbon-based catalyst material surface interacts with a basic functional group of a resin having a basic functional group (for example, an acid -Base interaction). Or the derivative | guide_body which has an acidic functional group, and resin which has a basic functional group interact (for example, acid-base interaction), On the other hand, it adsorb | sucks to the carbon-type catalyst material surface. As a result, in the above-described embodiment, the adsorption of the resin having the basic functional group to the surface of the carbon-based catalyst material is promoted, the adhesion between the carbon-based catalyst material and the resin component is improved, and the resin It is considered that the dispersion stability of the carbon-based catalyst material can be improved by the repulsion due to the obstacle. Moreover, in order to improve the adhesion between the carbon-based catalyst material and the hydrogen ion conductive polymer and the hydrogen ion conductivity to the catalytic active point of the carbon-based catalyst material, for example, the amount of the hydrogen ion conductive polymer used is reduced. We can expect reduction. Hereinafter, as specific examples of the resin having a basic functional group, three types of resins that can be suitably used in the present invention, the polymer (G1), the polymer (G2), and the vinylamide resin will be described.

<Resin having basic functional group (G1)>
Resin (G1) having a basic functional group that can be used in the present invention comprises a hydroxyl group of vinyl polymer (A1) having two hydroxyl groups in one terminal region, and an isocyanate group of diisocyanate (B1). Synthesis by reacting the isocyanate group of the urethane prepolymer (C1) having isocyanate groups at both ends obtained by reaction with the primary and / or secondary amino groups of polyamine (D1) and monoamine (E1). Is done.

  The vinyl polymer site grafted to the side chain derived from the vinyl polymer (A) has excellent affinity with a wide range of carbon-based catalyst materials and solvents, functions as a solvent affinity site, and the urea binding site of the main chain is In addition, it has an excellent ability to interact with an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group, and functions as an adsorbing group on the surface of a carbon-based catalyst material that is biased acidic via the derivative. Furthermore, an amino group can be introduced into the main chain in order to further improve the adsorptivity.

  Hereinafter, each component of the polymer (G1) having a basic functional group will be described.

<Vinyl polymer having two hydroxyl groups in one end region (A1)>
The vinyl polymer (A1) having two hydroxyl groups in one end region (hereinafter sometimes abbreviated as vinyl polymer (A1)) has two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of the ethylenically unsaturated monomer (a12) in the presence of the compound (a11). The vinyl polymer portion of the vinyl polymer (A1) is a portion having a high affinity for the carbon-based catalyst material and is represented by the following formula (15).

In the above formula (15),
R ⁵⁰¹ is a residue obtained by removing a hydroxyl group and a thiol group from the compound (a11),
R ⁵⁰² is a residue obtained by removing the double bond site and R ⁵⁰³ from the ethylenically unsaturated monomer (a12),
R ⁵⁰³ is a hydrogen atom or a methyl group,
n ⁵⁰¹ is an integer of 2 or more, preferably an integer of 3 to 200.
Here, R ⁵⁰¹ is a terminal region in the vinyl polymer (A1).

<Compound (a11) having two hydroxyl groups and one thiol group in the molecule>
As the compound (a11) having two hydroxyl groups and one thiol group in the molecule (hereinafter sometimes referred to as compound (a11)), two hydroxyl groups and one thiol group in the molecule Is not particularly limited, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propane Diol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-pro Njioru, and the like.

  A compound (a11), an ethylenically unsaturated monomer (a12), and optionally a polymerization initiator are mixed in accordance with the molecular weight of the vinyl polymer (A1) having two hydroxyl groups in one target end region. Then, the vinyl polymer (A1) can be obtained by heating. It is preferable to perform bulk polymerization or solution polymerization using 0.5 to 30 parts by weight of the compound (a11) with respect to 100 parts by weight of the ethylenically unsaturated monomer (a12). The amount of the compound (a11) used relative to 100 parts by weight of the ethylenically unsaturated monomer (a12) is more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight, particularly preferably 2 to 10 parts by weight. It is. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the amount of the compound (a11) used is less than 0.5 parts by weight, the molecular weight of the vinyl polymer site is too high, and the absolute amount thereof increases as an affinity site for the carbon-based catalyst material and the solvent. The dispersibility effect itself may be reduced. On the other hand, if the amount used exceeds 30% by weight, the molecular weight of the vinyl polymer part is too low, and the effect of steric repulsion is lost as an affinity site for the carbon-based catalyst material and the solvent. It may be difficult to suppress aggregation.

<Polymerization initiator>
In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (a12). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

<Polymerization solvent>
In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, N-methyl-2-pyrrolidone, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, diethylene glycol diethyl ether, etc. are used as a polymerization solvent. However, it is not particularly limited to these. These polymerization solvents may be used as a mixture of two or more kinds, but are preferably used for final use.

<Ethylenically unsaturated monomer (a12)>
Examples of the ethylenically unsaturated monomer (a12) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and isobornyl (meth) ) Alkyl (meth) acrylates such as acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) Aromatic (meth) acrylates such as acrylate; heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate; methoxypolypropylene glycol (meth) acrylate, and ethoxypolyethylene glycol (meta ) Alkoxy polyalkylene glycol (meth) acrylates such as acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone ( N-substituted (meth) acrylamides such as meth) acrylamide and acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) a Amino group-containing (meth) acrylates such as Relate; and include (meth) nitriles such as acrylonitrile.

  Moreover, as monomers that can be used in combination with the acrylic monomers, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate and vinyl propionate.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used in combination. As the carboxyl group-containing ethylenically unsaturated monomer, one or more kinds can be selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.

<Polymerization conditions and others>
In the present invention, among the ethylenically unsaturated monomers (a12) exemplified above, methyl methacrylate can be preferably used from the viewpoint of dispersibility and resistance. From the viewpoint of affinity with the carbon-based catalyst material and the solvent, it is more preferable to use methyl methacrylate and butyl methacrylate or t-butyl methacrylate in combination. When methyl methacrylate is used as the ethylenically unsaturated monomer (a2) and butyl methacrylate is not used, the proportion of methyl methacrylate is 30 in the total 100% by weight of the ethylenically unsaturated monomer (a12). It is preferably ˜100% by weight, and more preferably 50˜100% by weight. In addition, when methyl methacrylate and butyl methacrylate or t-butyl methacrylate are used in combination as the ethylenically unsaturated monomer (a12), the total of both is 30 to 100 weight of the ethylenically unsaturated monomer (a12). %, Preferably 50 to 100% by weight. When methyl methacrylate is used as the ethylenically unsaturated monomer (a12), further, when methyl methacrylate and butyl methacrylate or t-butyl methacrylate are used in combination, the dispersibility becomes better. While the copolymerization site of methyl methacrylate and butyl methacrylate or t-butyl methacrylate retains basic physical properties such as dispersibility, it has good affinity with a binder resin and a dispersion solvent and is highly versatile.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC of the vinyl polymer (A1) having two hydroxyl groups in one terminal region is preferably 500 to 30,000, and 1,000 to 15,000. Is more preferable, and 1,000 to 8,000 is particularly preferable. When the weight average molecular weight is less than 500, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent aggregation of the carbon-based catalyst material, and dispersion stability may be insufficient. On the other hand, if it exceeds 30,000, the absolute amount of the solvent affinity part increases, and the dispersibility effect itself may be lowered. Furthermore, the viscosity of the catalyst paste composition may increase.

  If the resin having a basic functional group has a weight average molecular weight of 500 to 30,000, it is advantageous to suppress an increase in the viscosity of the catalyst paste composition by preventing aggregation of the carbon-based catalyst material.

  The glass transition temperature (Tg) of the vinyl polymer (A1) having two hydroxyl groups in one end region is preferably 50 to 200 ° C., more preferably 50 to 120 ° C., from the viewpoint that the resistance of the coating film is improved. .

  As the Tg of the vinyl polymer (A1) having two hydroxyl groups in one terminal region, a value calculated by the following Fox formula was used. In addition, although the skeleton derived from the compound (a11) having two hydroxyl groups and one thiol group in the molecule is also present in the vinyl polymer (A1), it is excluded in the following calculation for calculating the glass transition temperature. .

      1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn

  In the above formula, W1 to Wn indicate the weight fraction of each monomer used, and Tg1 to Tgn are the glass transition temperatures of the respective homopolymers obtained from each monomer (units are absolute temperatures). "K").

The Tg of the main homopolymer used for the calculation is exemplified below.
Methyl methacrylate: 105 ° C (378K)
Butyl methacrylate: 20 ° C (293K)
t-butyl methacrylate: 107 ° C. (380 K)
Lauryl methacrylate: -65 ° C (208K)
2-ethylhexyl methacrylate: -10 ° C (263K)
Cyclohexyl methacrylate: 66 ° C (339K)
Butyl acrylate: -45 ° C (228K)
Ethyl acrylate: -20 ° C (253K)
Benzyl methacrylate: 54 ° C (327K)
Styrene: 100 ° C (373K)

<Diisocyanate (B1)>
As the diisocyanate (B1) that is a constituent element of the polymer (G1) having a basic functional group, conventionally known diisocyanate (B1) can be used. For example, aromatic diisocyanate (b11), aliphatic diisocyanate (b12). ), Araliphatic diisocyanate (b13), alicyclic diisocyanate (b14), and the like.

  Examples of the aromatic diisocyanate (b11) include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate. Examples include isocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, and 1,3-bis (isocyanatomethyl) benzene.

  Examples of the aliphatic diisocyanate (b12) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Examples include dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  As the araliphatic diisocyanate (b13), ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4- Examples include diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

  Examples of the alicyclic diisocyanate (b14) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

  As mentioned above, listed diisocyanate (B1) is not necessarily limited to these, It can also be used in combination of 2 or more types.

  As the diisocyanate (B) used in the present invention, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) is preferable because it is hardly yellow-modified.

<Polyamine (D1)>
The polyamine (D1), which is a component of the resin (G1) having a basic functional group, is a compound having at least two primary and / or secondary amino groups, and reacts with an isocyanate group to generate a urea bond. Used for. A diamine (d11) is mentioned as such an amine.

  As the diamine (d11) having two primary amino groups, known ones can be used. Specifically, ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], Trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1,4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [ Alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and tri Aliphatic diamines such as range amines; isophorone diamine and dicyclohexylmethane Alicyclic diamines such as 4,4'-diamine; and can include phenylenediamine, and an aromatic diamine such as xylylenediamine.

  Moreover, as diamine (d11) which has two secondary amino groups, a well-known thing can be used, Specifically, N, N- dimethylethylenediamine, N, N- diethylethylenediamine, and N, N Examples include '-di-tert-butylethylenediamine.

  Moreover, as diamine (d11) which has a primary and secondary amino group, a well-known thing can be used, Specifically, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias] : Ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N -Isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3- Propanediamine [alias: N-lauryl-1,3-dia It can be exemplified Nopuropan or lauryl amino propylamine], and the like.

  A polyamine is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group. This urea group is adsorbed on the carbon-based catalyst material. When the polyamine (D1) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group other than both ends. Is particularly preferable because the adsorptivity to the carbon-based catalyst material is improved.

  As such polyamine (D1), polyamines having two primary and / or secondary amino groups at both ends as shown below, and having secondary and / or tertiary amino groups at both ends (see below) d12).

  As polyamine (d12), methyliminobispropylamine [also known as N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [also known as N, N-bis (3-aminopropyl) laurylamine] , Iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, and N, N′-bisaminopropyl-1,4 -Butylene diamine etc. can be mentioned, The methyliminobispropylamine and lauryliminobispropylamine which have two primary amino groups and one tertiary amino group are preferable since reaction with diisocyanate is easy to control.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to the carbon-based catalyst material.

  As the polyamine (D1), a polymer (d13) having two or more primary and / or secondary amino groups can also be used.

  Examples of the polymer (d13) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective for preventing aggregation of the carbon-based catalyst material and suppressing an increase in the viscosity of the catalyst paste composition.

  Examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group include (meth) acrylic acid, croton Unsaturated carboxylic acids such as acid, itaconic acid, maleic acid and fumaric acid; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene and vinyltoluene; methyl (meth) (Meth) acrylic acid alkyl esters such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (Meth) acrylic acid alkyl aryl ester; glycidyl (meth) acrylate (Meth) acrylic acid substituted alkyl ester having a functional group such as 2-hydroxyethyl (meth) acrylate; tertiary amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate (meth) Acrylic acid-substituted alkyl ester; (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, tert-octyl (meth) acrylamide, etc. Alkyl (meth) acrylamides; substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; 1,3-butadiene, and isoprene Diene compounds such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol and other polymerizable oligomers (macromonomer); and vinyl cyanide.

  The polymer having a primary and / or secondary amino group has a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), preferably 300 to 75,000, 300 to 20, 000 is more preferable, and 500 to 5,000 is particularly preferable. When the weight average molecular weight is 300 to 75,000, it is effective to suppress an increase in viscosity of the catalyst paste composition by preventing aggregation of the carbon-based catalyst material.

<Monoamine (E1)>
As the amine compound that is a constituent element of the resin (G1) having a basic functional group, in addition to the polyamine (D1), a monoamine (E1) can also be used. The monoamine (E1) is a monoamine compound having one primary amino group or secondary amino group in the molecule, and the monoamine (E1) has a high molecular weight in the reaction between the diisocyanate (B1) and the polyamine (D1). It is used as a reaction terminator in order to suppress excessive conversion. The monoamine (E1) may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such polar functional groups include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

  As the monoamine (E1), conventionally known ones can be used. Specific examples include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2- Aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-me Rupropane, 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine , 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n- Propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupe Gin, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebuty Rick acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p -Benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β- Minoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4- Examples include benzylpiperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

  Among them, a monoamine compound having only a secondary amino group as an aliphatic amine having no rigidity is preferable because of its good dispersibility.

  Examples of aliphatic monoamine compounds having only secondary amino groups include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, and di-n-butylamine. , Disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, Examples include 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, and 3-pyrrolidinol.

  In addition, since the tertiary amino group does not have an active hydrogen that reacts with an isocyanate group, a diamine having a primary or secondary amino group and a tertiary amino group can be used as a monoamine (E1). In the present invention, a tertiary amino group having an effect of improving the adsorption ability to the carbon-based catalyst material can be introduced into the polymer terminal of the dispersant.

  Examples of the diamine having a primary or secondary amino group and a tertiary amino group include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, and N, N. Diamine having a primary amino group and a tertiary amino group such as 1,2,2-tetramethyl-1,3-propanediamine; and a secondary amino group such as N, N, N′-trimethylethylenediamine and a tertiary amino group And diamines having a group.

  These monoamine (E1) compounds may be used alone or in combination. In addition, the active hydrogen of the urea bond after the primary amino group and the isocyanate group react with each other has low reactivity, and under the polymerization conditions of the dispersant, it does not further react with the isocyanate group and the molecular weight does not increase.

<Urethane prepolymer (C1)>
The urethane prepolymer (C1), which is a constituent element of the polymer (G1) having a basic functional group, is composed of a hydroxyl group of a vinyl polymer (A1) having two hydroxyl groups at one end region and an isocyanate of a diisocyanate (B1). It is obtained by reacting with a group.

  For example, when the number of moles of the vinyl polymer (A1) is α and the number of moles of the diisocyanate (B1) is β, when α / β = α / (α + 1), a urethane having an isocyanate group at both ends in theory. A prepolymer is obtained. When α is a positive integer, the molecular weight increases as α increases. The actual structure control will be described later in detail.

<Synthetic catalyst (F1)>
A known catalyst (F1) can be used during the synthesis of the urethane prepolymer (C1). For example, a tertiary amine compound and an organometallic compound can be mentioned.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene (DBU).

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

  Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Mention may be made of tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate and tin 2-ethylhexanoate.

  Examples of the non-tin compound include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead oleate; lead-based compounds such as lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron systems such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt systems such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc systems such as zinc naphthenate and zinc 2-ethylhexanoate; In addition, zirconium-based compounds such as zirconium naphthenate can be mentioned.

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

  Catalysts such as the tertiary amine compounds and organometallic compounds can be used alone or in combination depending on the case.

  The organometallic compound catalyst used in the synthesis of the urethane prepolymer (E) significantly accelerates the reaction even in the further reaction with the amine described later.

<Synthetic solvent>
A known solvent is preferably used for the synthesis of the urethane prepolymer (C1). The use of a solvent serves to facilitate reaction control.

  Examples of the solvent used for this purpose include ethyl acetate, n-butyl acetate, isobutyl acetate, N-methyl-2-pyrrolidone, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol. Monoethyl ether acetate, diethylene glycol diethyl ether and the like are used, but are not particularly limited thereto.

  In particular, ethyl acetate, toluene, methyl ethyl ketone, diethylene glycol diethyl ether, or a mixed solvent thereof is preferable from the viewpoint of amine solubility such as the solubility of the urethane prepolymer (C1) and the boiling point of the solvent.

  Further, the concentration in the urethane prepolymer reaction system when using a solvent is preferably 30 to 95% by weight from the viewpoint of reaction control in terms of the solid content concentration of the urethane prepolymer, and from the viewpoint of viscosity control. More preferably, it is 40 to 90% by weight. If it is less than 30% by weight, the reaction becomes slow and unreacted substances may remain. If it exceeds 95% by weight, the reaction may partially proceed abruptly, and it is difficult to control the molecular weight or the like, which is not preferable.

<Synthesis conditions>
There are various methods for the urethanization reaction in which the urethane prepolymer (C1) is prepared by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one terminal region with the isocyanate group of the diisocyanate (B1). Can be applied. Typical methods are 1) when the reaction is carried out in the whole amount, 2) vinyl polymer (A) having two hydroxyl groups at one end region, and if necessary, a solvent is charged into the flask, and diisocyanate (B1). After dripping, it is divided roughly into the method of adding a catalyst as needed. When the reaction is precisely controlled, the method 2) is preferable. The reaction temperature for obtaining the urethane prepolymer (C1) is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed in the presence of a catalyst at 50 to 110 ° C. for 1 to 20 hours.

  The compounding ratio of the vinyl polymer (A1) having two hydroxyl groups in one end region and the diisocyanate (B1) is the integer α as the molar ratio of the vinyl polymer (A1) having two hydroxyl groups in one end region. When the molar ratio of diisocyanate (B1) is α + 1, a urethane prepolymer (C1) having isocyanate groups at both ends can be synthesized theoretically. Since the minimum α is 1, the blending molar ratio (α + 1) / α of the diisocyanate (B1) to the vinyl polymer (A1) is 2 or less. When the diisocyanate is further increased, all of the isocyanate groups in the mixture of urethane prepolymer (C1) and excess diisocyanate (B) react with primary and / or secondary amino groups of polyamine (D1) and monoamine (E1). If designed to do so, it is possible to incorporate excess diisocyanate (B1) into the dispersant molecule. When synthesizing a normal urethane prepolymer (C1), an excess polyisocyanate is often blended in anticipation of chain extension by the polyamine in the next step in order not to leave a polyol. However, there is a high possibility that impurities derived from excessive diisocyanate (B1) -derived polymer units and excess diisocyanate (B1) hydrolyzate will adversely affect the dispersibility and temporal stability of the carbon-based catalyst material. .

  Therefore, the blending molar ratio of the diisocyanate (B1) to the vinyl polymer (A1) having two hydroxyl groups in one terminal region is 1.01 to 3.00 from the viewpoint of the productivity of the urethane prepolymer (C1). Preferably, 1.30 to 2.30 is more preferable, and 1.50 to 2.00 is most preferable. When the said compounding molar ratio is too small, a dispersing agent will become high molecular weight and there exists a problem practically. Further, as described above, when the above-mentioned blending molar ratio is larger than 2.00, diisocyanate (B1) having no vinyl polymer part derived from vinyl polymer (A1) and urethane part derived therefrom increase, and the dispersibility is adversely affected. .

<Method for producing resin (G1) having basic functional group, synthesis conditions, etc.>
The polymer (G1) having a basic functional group radically polymerizes an ethylenically unsaturated monomer (a12) in the presence of a compound (a11) having two hydroxyl groups and one thiol group in the molecule. A first step of producing a vinyl polymer (A1) having two hydroxyl groups in one end region, and the hydroxyl group and diisocyanate of the vinyl polymer (A1) having two hydroxyl groups in the one end region The second step of producing a urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting with the isocyanate group of (B1), and the isocyanate group of the urethane prepolymer (C1) having an isocyanate group at both ends And a third step of reacting polyamine (D1) and monoamine (E2) with primary and / or secondary amino groups It can be produced by.

In the polymer (G1) having a basic functional group, the urethane prepolymer (C1), the polyamine (D1), and the monoamine (E1), a urethane urea resin, or a polyurethane urea having a primary or secondary amino group at the terminal The urea reaction to get
1) A method in which a urethane prepolymer (C1) solution is charged into a flask and polyamine (D1) and monoamine (E1) are dropped.
2) The method is roughly divided into a method in which a solution comprising a polyamine (D1), a monoamine (E1), and a solvent as required is charged into a flask and the urethane prepolymer (C1) solution is dropped.

  Synthesis may be carried out by appropriately selecting a method that can carry out the reaction stably, but the method of 1), which is easier to operate, is preferred if there is no problem in the reaction. The temperature of the urea reaction is preferably 100 ° C. or less. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure.

  Moreover, the compounding ratio with a urethane prepolymer (C1) and a polyamine (D1), and also monoamine (E1) as needed is not specifically limited, It selects arbitrarily by a use and required performance.

  The end point of the reaction is judged by measuring the isocyanate percentage by titration and disappearance of the isocyanate peak by IR measurement.

  The polymer (G1) having a basic functional group preferably has a weight average molecular weight (Mw) of 1,000 to 100,000, more preferably 1,500 to 50,000, particularly preferably 1,500. ~ 20,000. When the weight average molecular weight is less than 1,000, the dispersibility may be lowered. When the weight average molecular weight is more than 100,000, the interaction between the resins becomes strong and the composition may be thickened. Moreover, it is preferable that the amine value of the obtained polymer is 1-100 mgKOH / g, More preferably, it is 2-50 mgKOH / g, More preferably, it is 3-30 mgKOH / g. If the amine value is less than 1 mgKOH / g, the functional group adsorbing to the carbon-based catalyst material is insufficient, which may make it difficult to contribute to the dispersion of the carbon-based catalyst material, and if it exceeds 100 mgKOH / g, Aggregation of carbon-based catalyst materials may occur, which may cause insufficient viscosity reduction effects and defects in the coating film.

<Resin having basic functional group (G2)>
The polymer (G2) having a basic functional group that can be used in the present invention is a (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one end region; A primary and / or two polymer (C2) having an amino group obtained by reacting with a primary and / or secondary amino group of a polyamine (B2) containing one or more primary and / or secondary amino groups. It is synthesized by reacting a primary amino group with an isocyanate group of polyisocyanate (D2) containing two or more isocyanate groups.

  That is, an amino group and a urea formed by reacting a solvent affinity site derived from the polymer (A2), a primary and / or secondary amino group of the polyamine (C2), and an isocyanate group of the polyisocyanate (D2). It has a structure having an adsorptive site to a carbon-based catalyst material having a binding site. The adsorption site to the carbon-based catalyst material having the amino group and urea binding site is excellent in the ability to interact with an organic dye derivative having an acidic functional group or a triazine derivative having an acidic functional group. It is excellent in adsorptivity to the surface of the carbon-based catalyst material that is biased to acidity, and can stabilize dispersion.

  In the present specification, when expressed as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy”, unless otherwise specified, “Acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy” respectively.

<Polymer (A2) having one or two (meth) acryloyl groups in one end region>
The weight average molecular weight of the polymer (A) in the present invention is preferably from 500 to 30,000, whereby it is excellent in steric repulsion effect and high dispersibility and storage stability can be obtained. The weight average molecular weight of the polymer (A) is more preferably 2,000 to 20,000, and most preferably 5,000 to 10,000. If it is less than 500, the steric repulsion effect due to the solvent affinity block is reduced, which may be undesirable. Moreover, when exceeding 30,000, the viscosity of a dispersion becomes high and may be unpreferable.

  The polymer (A) in the present invention is preferably polyester (A21) or vinyl polymer (A22). These have good affinity for the solvent and can easily adjust the molecular weight. Moreover, the (meth) acryloyl group of one terminal area | region has a preferable acryloyl group which reaction reacts at comparatively low temperature from a viewpoint of reaction control with a primary and / or secondary amino group.

<Polyester (A21)>
The polyester (A21) can be produced by a known method. For example, the polyester (A21) can be easily obtained by ring-opening polymerization of a lactone and / or lactide using a monoalcohol having a (meth) acryloyl group as an initiator.

<Monoalcohol having (meth) acryloyl group>
The monoalcohol having a (meth) acryloyl group used as an initiator for ring-opening polymerization is not particularly limited, and 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2 One or more selected from the group consisting of 4-hydroxybutyl acrylate and 2-hydroxyethyl acrylate are used from the viewpoint of the reactivity of the hydroxyl group, including -hydroxy-3- (meth) acryloyloxypropyl methacrylate It is preferable to do this.

<Lactone and lactide>
The lactone is not particularly limited, and specific examples include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. However, from the viewpoint of ring-opening polymerizability, it is preferable to use one or more selected from the group consisting of δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone.

  Lactones can be used without being limited to the above examples, and may be used alone or in combination of two or more.

  As a lactide, what is shown by following formula (16) is preferable (a glycolide is included).

In equation (16),
R ¹ and R ² are each independently a hydrogen atom or a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms.

  Particularly preferred lactides are lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane-2,5-dione).

  The lactone and lactide may be used alone or in combination of two or more. For lactone and lactide, it is preferable to use lactone from the viewpoint of solvent affinity.

  The number of moles of lactone and / or lactide polymerized with respect to 1 mole of initiator is preferably in the range of 3 to 60 moles, more preferably 10 to 40 moles, and most preferably 15 to 30 moles. If it is less than 3 mol, the molecular weight is small, and it does not function sufficiently as a solvent affinity site. When it exceeds 60 mol, the molecular weight becomes too large, and when used as a dispersant for a carbon-based catalyst material, the viscosity of the composition becomes high and problems are likely to occur.

<Ring-opening polymerization catalyst>
As the ring-opening polymerization catalyst, known catalysts can be used without limitation. For example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium Quaternary ammonium salts such as iodo, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate and sodium benzoate; sodium alcoholate; And alkali metal alcoholates such as potassium alcoholates; Tertiary amines such as ruamine and triphenylamine; organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, and dioctyltin oxide; aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate Organic aluminum compounds such as aluminum trisacetylacetonate; organic titanate compounds such as tetra-n-butyl titanate, dimer, tetraisobutyl titanate, tetrastearyl titanate, and diisopropoxy bis (triethanolaminate) titanium; and And zinc compounds such as zinc chloride.

  The amount of the ring-opening polymerization catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm with respect to 100% by weight of the lactone and / or lactide. When the amount of the catalyst exceeds 3000 ppm, the resin may be intensely colored. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of lactone and / or lactide becomes extremely slow, which is not preferable.

<Synthesis conditions>
The lactone and / or lactide ring-opening polymerization temperature is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. If the reaction temperature is less than 100 ° C., the reaction rate may be extremely slow. On the other hand, if the polymerization temperature exceeds 220 ° C., side reactions other than the addition reaction of lactone and / or lactide, for example, depolymerization of lactone adducts to lactone monomers, formation of cyclic lactone dimers and trimers may occur. is there.

<Radical polymerization inhibitor>
When a compound having a (meth) acryloyl group is polymerized, it is preferable to add a radical polymerization inhibitor and perform the reaction under a dry air flow. As the radical polymerization inhibitor, known ones can be used without limitation, and examples thereof include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, and phenothiazine. Is preferred. These may be used alone or in combination within a range of 0.01% to 6% by weight, preferably 0.05% to 1.0% by weight, based on 100% by weight of the alcohol having a (meth) acryloyl group. .

  Polyester (A21) is a polyester having a hydroxyl group at one end obtained by ring-opening polymerization of a lactone using a monoalcohol having no (meth) acryloyl group as an initiator, a group capable of reacting with a hydroxyl group, and ( It can also be obtained by reacting a compound having a (meth) acryloyl group.

<Compound having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group>
The compound having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group is preferably a compound having an isocyanate group and a (meth) acryloyl group, and examples thereof include 2- (meth) acryloyloxyethyl isocyanate.

  In the preparation of the polyester (A21), a lactone is first subjected to ring-opening polymerization using a monoalcohol having no (meth) acryloyl group as an initiator to prepare a polyester having a hydroxyl group at one end, and then the polyester. And a compound having one dibasic acid anhydride group are reacted to prepare a polyester having a carboxyl group at one end. Subsequently, the polyester having the carboxyl group is reacted with a compound having an epoxy group and a (meth) acryloyl group, or a group capable of reacting with a hydroxyl group obtained by ring opening of the epoxy group and the (meth) acryloyl group. It can be carried out by reacting a compound having In this case, a polyester (A21) having two (meth) acryloyl groups in one end region is obtained.

<Monoalcohol without (meth) acryloyl group>
The monoalcohol having no (meth) acryloyl group may be any compound as long as it is a compound having one hydroxyl group.

  For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1- Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol , Aliphatic monoalcohols such as 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, and oleyl alcohol; benzyl alcohol, phenoxyethyl alcohol, and para Aromatic ring-containing monoalcohols such as milphenoxyethyl alcohol; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Cole monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene Glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene Glico Mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, Tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetra Propylene rubber Examples include alkylene glycol monoalkyl ethers such as coal monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether. It is done.

<Compound having one dibasic acid anhydride group>
The compound having one dibasic acid anhydride group may be any compound as long as it has one dibasic acid anhydride group.

  For example, succinic anhydride, glutaric anhydride, cyclohexane-1,2-dicarboxylic anhydride, cyclohexene 1-2-dicarboxylic anhydride, dicyclo [2,2,2] -oct-5-ene-2, 3-dicarboxylic anhydride, phthalic anhydride, naphthalene-1,2-dicarboxylic anhydride, naphthalene-2,3-dicarboxylic anhydride, anthracene-1,2-dicarboxylic anhydride, and anthracene-2, 3-dicarboxylic anhydride etc. are mentioned. Moreover, the said dibasic acid anhydride which has substituents, such as a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a heterocyclic ring, an aromatic ring, and a halogen, is also mentioned.

<Compound having epoxy group and (meth) acryloyl group>
Examples of the compound having an epoxy group and a (meth) acryloyl group include glycidyl acrylate, methyl glycidyl acrylate, 3,2-glycidoxyethyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxybutyl acrylate, and 4, Examples include 5-epoxypentyl acrylate.

  The polyester (A21) is a polyester having a carboxyl group at one end obtained by ring-opening polymerization of a lactone using a monocarboxylic acid having no (meth) acryloyl group as an initiator. A compound having a (meth) acryloyl group is reacted, and further, a group capable of reacting with a hydroxyl group which can be reacted with a hydroxyl group obtained by ring opening of an epoxy group and a compound having a (meth) acryloyl group are reacted. Can also be obtained. In this case, a polyester (A21) having two (meth) acryloyl groups in one end region is obtained.

<Monocarboxylic acid not having (meth) acryloyl group>
The monocarboxylic acid having no (meth) acryloyl group may be any compound as long as it has no (meth) acryloyl group and has a carboxyl group.

  Examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and isostearic acid.

<Vinyl polymer (A22)>
A vinyl polymer (A22) having one or two (meth) acryloyl groups in one end region is converted into a vinyl polymer (a23) having one or two hydroxyl groups in one end region and a hydroxyl group. It can be obtained by reacting a group capable of reacting with the compound (a24) having a (meth) acryloyl group.

  The vinyl polymer (a23) having one or two hydroxyl groups in one end region (hereinafter sometimes abbreviated as vinyl polymer (a23)) has one or two hydroxyl groups in the molecule. And the compound (s) having 1 thiol group can be obtained by radical polymerization of the ethylenically unsaturated monomer (a21). Since the thiol group of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, the vinyl polymer (a23) is synthesized through the S atom. The molecular weight of the vinyl polymer (a23) can be easily adjusted to the above range depending on the amount of the compound (s) used relative to the ethylenically unsaturated monomer (a21). The affinity of can also be adjusted suitably.

<Compound (s) having one or two hydroxyl groups and one thiol group in the molecule>
Examples of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule include one hydroxyl group in the molecule such as 1-mercaptoethanol and 2-mercaptoethanol. Compound (s1) having one thiol group; and 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin) ), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2 Propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1, Examples thereof include a compound (s2) having two hydroxyl groups and one thiol group in the molecule such as 3-propanediol.

  In the present invention, the compound (s2) having two hydroxyl groups and one thiol group in the molecule is preferable, and 3-mercapto-1,2-propanediol (thioglycerin) is more preferable. .

  By using the compound (s2) having two hydroxyl groups and one thiol group in the molecule, the finally obtained dispersant has an adsorption site on the carbon-based catalyst material having a plurality of amino groups, An ideal structure having a plurality of solvent affinity sites is obtained.

<Ethylenically unsaturated monomer (a21)>
Examples of the ethylenically unsaturated monomer (a21) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), Tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) Linear or branched acrylates such as acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate Kill (meth) acrylates; cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Cyclic alkyl (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate , And fluoroalkyl (meth) acrylates such as tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethylsiloxane (silicone macromer ); Tetrahydrofurfuryl (meth) acrylate and (meth) acrylates having a heterocyclic ring such as 3-methyl-3-oxetanyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene (Meth) acrylates having an aromatic ring such as glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypolyethylene glycol (meth) acrylate; 2-methoxy Ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol Monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, di (Poly) alkylene glycol monoalkyl ethers (meta) such as propylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, and polyethylene glycol monostearyl ether (meth) acrylate ) Acrylates; acrylic acid, acrylic acid dimer, methacrylic acid, a Unsaturated carboxylic acids such as conic acid, maleic acid, fumaric acid, and crotonic acid; caprolactone adducts of the above carboxylic acid (addition moles 1 to 5); 2- (meth) acryloyloxyethyl phthalate, 2- ( (Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meta) ) Acrylate, and (meth) acrylates having a carboxyl group such as ω-carboxypolycaprolactone (meth) acrylate; styrenes such as styrene and α-methylstyrene; vinyl acetate, vinyl propionate, vinyl (meth) acrylate And (meth) acryl Vinyl compounds such as allyl;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, amides having no amino group such as (meth) acrylamide, and N-vinylformamide; and no amino group Examples include acrylonitrile. These can be used alone or in admixture of two or more.

  In the present invention, among the ethylenically unsaturated monomers (a21) exemplified above, it is preferable to use an ethylenically unsaturated monomer (a22) represented by the following formula (17). The amount of the ethylenically unsaturated monomer (a22) represented by the following formula (17) is preferably 20% by weight to 100% by weight with respect to the whole ethylenically unsaturated monomer (a21), and is preferably 20 to 20%. 70% by weight is more preferred. When the monomer represented by the formula (17) is used, the solvent affinity is improved and the dispersibility is improved. If it is less than 20% by weight, the effect of improving the solvent affinity is insufficient.

In the formula (17), R ⁵ is a linear or branched alkyl group having 1 to 4 carbon atoms.

<Use amount of compound (s)>
Using the compound (s) as a chain transfer agent, the ethylenically unsaturated monomer (a21) and, optionally, a polymerization initiator are mixed and heated in accordance with the molecular weight of the target vinyl polymer (a23). Thus, the vinyl polymer (a23) can be obtained. The compound (s) is preferably subjected to bulk polymerization or solution polymerization using 0.8 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (a21), more preferably 1.5. -15 parts by weight, more preferably 2-9 parts by weight, particularly preferably 5-9 parts by weight. If it is less than 1 part by weight, the molecular weight becomes large and the viscosity of the dispersion becomes high, which is not preferable. When it exceeds 30 parts by weight, the molecular weight is decreased, and the steric repulsion effect by the solvent affinity block is decreased, which may not be preferable.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the temperature is lower than 40 ° C., the polymerization does not proceed sufficiently.

<Radical polymerization initiator>
In the radical polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (a21).

As a polymerization initiator, for example,
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2, 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis ( Azo compounds such as 4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis [2- (2-imidazolin-2-yl) propane] And organic peroxides; and benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydi -Bonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, And organic peroxides such as diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

<Compound (a24) having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group>
As the compound (a24) having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group, a compound having an isocyanate group and a (meth) acryloyl group is preferable, and examples thereof include 2- (meth) acryloyloxyethyl isocyanate. It is done.

<Polymerization solvent>
Polyester (A21) and vinyl polymer (A22) can be synthesized using no solvent or, if necessary, a solvent.

  In the case of solution polymerization, the polymerization solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, N-methylpyrrolidone and the like are used, but are not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step, or can be used as a part of a product.

<Polyamine (B2)>
The polyamine (B2) is a compound having one or more primary and / or secondary amino groups, and the primary and / or secondary amine is a polymer (A2) having a (meth) acryloyl group in one terminal region. Addition reaction with a (meth) acryloyl group produces a polymer (C2) having an amino group. Furthermore, some or all of the primary and / or secondary amines of the polymer (C2) having an amino group are reacted with the isocyanate group of the polyisocyanate (D2) to form a urea group. That is, an amino group and a urea bond existing in one end region serve as an adsorption site for the carbon-based catalyst material. A diamine (b21) is mentioned as such a polyamine (B2). In addition, when the polyamine (B2) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, This is particularly preferable because the adsorptivity to the carbon-based catalyst material is improved.

  As the diamine (b21) having two primary amino groups, known ones can be used. Specifically, ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine] can be used. ], Trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1,4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylene Diamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, And aliphatic diamines such as tolylenediamine; isophoronediamine and dicyclohexylmeta Alicyclic diamines such as 4,4'-diamine; and can include phenylenediamine, and an aromatic diamine such as xylylenediamine.

  Moreover, as diamine (b21) which has two secondary amino groups, a well-known thing can be used, Specifically, N, N- dimethylethylenediamine, N, N- diethylethylenediamine, and N, N'-di-tert-butylethylenediamine and the like can be mentioned.

  Moreover, as diamine (b21) which has a primary and secondary amino group, a well-known thing can be used, Specifically, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias] : Ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N -Isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3- Propanediamine [alias: N-lauryl-1,3-di It can be exemplified Minopuropan or lauryl amino propylamine], and the like.

  As the diamine (b21) having primary and tertiary amino groups, known diamines can be used. Specifically, N, N-dimethylethylenediamine [also known as dimethylaminoethylamine], N, N— Examples include diethylethylenediamine [alias: diethylaminoethylamine], N, N-dimethyl-1,3-propanediamine [alias: N, N-dimethyl-1,3-diaminopropane or dimethylaminopropylamine], and the like.

  As the polyamine (b22) having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, a known one may be used. Specifically, methyliminobispropylamine [also known as N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [also known as N, N-bis (3-aminopropyl) laurylamine] , Iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, and N, N′-bisaminopropyl-1, 4-butylenediamine and the like, methyliminobispropylamine having two primary amino groups and one tertiary amino group, and lauryliminobis Ropiruamin is preferably easily control of the reaction of a diisocyanate.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to the carbon-based catalyst material.

  As the polyamine (B2), a polymer (b23) having two or more primary and / or secondary amino groups can also be used.

  Examples of the polymer (b23) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective to prevent aggregation of the carbon-based catalyst material and to suppress an increase in viscosity.

  Examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group include (meth) acrylic acid, croton Unsaturated carboxylic acids such as acid, itaconic acid, maleic acid and fumaric acid; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene and vinyltoluene; methyl (meth) (Meth) acrylic acid alkyl esters such as acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (Meth) acrylic acid alkyl aryl ester; glycidyl (meth) acrylate (Meth) acrylic acid substituted alkyl ester having a functional group such as 2-hydroxyethyl (meth) acrylate; tertiary amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate (meth) Acrylic acid-substituted alkyl ester; (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, tert-octyl (meth) acrylamide, etc. Alkyl (meth) acrylamides; substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; 1,3-butadiene, and isoprene Diene compounds such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol and other polymerizable oligomers (macromonomer); and vinyl cyanide.

  The polymer having a primary and / or secondary amino group has a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), preferably 300 to 75,000, 300 to 20, 000 is more preferable, and 500 to 5,000 is particularly preferable. When the weight average molecular weight is 300 to 75,000, it is effective to suppress an increase in viscosity of the catalyst paste composition by preventing aggregation of the carbon-based catalyst material.

<Monoamine>
As the amine compound constituting the dispersant, in addition to the polyamine (B2), a monoamine can also be used. The monoamine is a monoamine compound having one primary amino group or one secondary amino group in the molecule, and the monoamine suppresses excessively high molecular weight in the reaction between the polymer (A2) and the polyamine (B). Therefore, it is used as a reaction terminator. The monoamine may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such polar functional groups include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

  As the monoamine, conventionally known monoamines can be used. Specifically, aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-amino Tridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino -2-methylpro , 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine , 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n- Propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine , , 5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebutyric acid hydrochloride Salt, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline 1-anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethyl Rubenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzyl Examples include piperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

<Polymer having amino group (C2)>
In the polymer (C2) having an amino group, as shown in the following formula (18), the primary or secondary amino group of the polyamine (B2) has one or two (meth) acryloyl groups in one end region. It can be obtained by addition reaction to the (meth) acryloyl group of the polymer (A2) having This reaction is generally called the Michael addition reaction. By adjusting the blending of the polymer (A2) and the polyamine (B2), a structure having a primary or secondary amino group capable of reacting with an isocyanate group can be obtained.

In the formula (18), X ¹ is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ¹ is a polyamine (B2) excluding the primary and secondary amino groups. R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom or an alkyl group.

  For example, as shown in the following formula (19), a molecule of a diamine (B2) having two primary amino groups for one molecule of a polymer (A2) having one (meth) acryloyl group in one end region When one is reacted, theoretically, one molecule of the polymer (C2) having one primary amino group and one secondary amino group is obtained.

In the formula (19), X ¹ is a part of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a part of the polyamine (B2) excluding the primary amino group. R ⁶ is a hydrogen atom or a methyl group.

  Further, for example, as shown in the following formula (20), one primary amino group and one secondary amino group 1 per molecule of the polymer (A2) having two (meth) acryloyl groups in one end region. When two molecules of the diamine (B2) having 1 molecule are reacted, one molecule of the polymer (C2) having 4 secondary amino groups is theoretically obtained.

In the formula (20), X ² is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a polyamine (B2) excluding the primary and secondary amino groups. R ⁶ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group.

  Furthermore, for example, as shown in the following formula (21), the diamine (B) having two primary amino groups for n molecules of the polymer (A2) having two (meth) acryloyl groups in one terminal region. In theory, one molecule of the polymer (C2) having two primary amino groups and 2n secondary amino groups is obtained. (N is a positive integer.)

In the formula (21), X ² is a part of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a part of the polyamine (B2) excluding the primary amino group. R ⁶ is a hydrogen atom or a methyl group, and n is a positive integer.

  Further, for example, as shown in the following formula (22), a diamine having two secondary amino groups (B2) with respect to n molecules of the polymer (A2) having two (meth) acryloyl groups in one terminal region. ) Molecule (n + 1) molecules are reacted, theoretically, one polymer (C2) molecule having two secondary amino groups and 2n tertiary amino groups is obtained. (N is a positive integer.)

In the formula (22), X ² is a part of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a part of the polyamine (B2) excluding the secondary amino group. R ⁶ is a hydrogen atom or a methyl group, R ⁸ is an alkyl group, and n is a positive integer.

  Theoretically, in the above four examples, the primary amino group is assumed to react preferentially because it is more reactive than the secondary amino group, but in actuality, depending on the reaction conditions, etc. In some cases, a secondary amino group may react first, even if is left. Therefore, in some cases, a polymer (C2) having a structure different from that expected may be obtained. However, since the above addition reaction proceeds almost stoichiometrically, a polymer (C2) having a target structure is obtained mostly, and there is a problem in the subsequent reaction and the function as a final dispersant. There is no.

<Synthesis conditions>
A polymer (A2) having one or two (meth) acryloyl groups in one terminal region, a polyamine (B2) having one or more primary and / or secondary amino groups, and a polymer having an amino group. The Michael reaction for obtaining the coalescence (C2) is: 1) a method in which the reaction is carried out by charging the whole amount, 2) a solution comprising polyamine (B2) and a solvent as necessary is charged into the flask, and the polymer (A2) solution is added dropwise. Broadly divided into methods. The synthesis may be carried out by appropriately selecting a method that allows the reaction to be carried out stably. However, if there is no problem in the reaction, it is preferable to apply the method 2) described above, which makes reaction control (molecular design control) easier.

  The temperature of the Michael reaction is preferably 70 ° C. or less. More preferably, it is 60 degrees C or less. Even at 60 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 70 ° C., it is difficult to control the reaction rate, and it tends to be difficult to obtain a polymer (C2) having a predetermined molecular weight and structure.

  The blending ratio of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region, the polyamine (B2) having one or more primary and / or secondary amino groups is particularly limited. It is not arbitrarily selected according to the application and required performance. The end point of the reaction is judged by measuring the amine% due to titration.

<Dispersant having amino group and urea bond>
The polymer (G2) having a basic functional group is a dispersant having an amino group and a urea bond, the primary or secondary amino group of the polymer (C2) having an amino group, and two or more isocyanate groups It is obtained by reacting the isocyanate group of the polyisocyanate (D2) having The primary or secondary amino group of the polymer (C2) having an amino group is partially or entirely formed as a urea bond by adjusting the amount of the polyisocyanate to be reacted, and the remainder is an amino group in the dispersant. Exists as.

  When the polymer (C2) having an amino group has a tertiary amino group in addition to the primary or secondary amino group, the tertiary amino group does not react with the isocyanate group, and the carbon-based catalyst is used as it is. It remains in the dispersant as a material adsorbing group.

For example, when one molecule of diisocyanate (D2) is reacted with two molecules of polymer (C2) having one primary amino group and two secondary amino groups as shown in the following formula (23) Theoretically, a primary amino group reacts with an isocyanate group to form a urea bond, and a dispersant having 4 secondary amino groups and 2 urea bonds is obtained. When W ¹ and W ² in the following formula (23) have a tertiary amino group derived from the polyamine (B2) and / or the polymer (C2), the dispersant also has a tertiary amino group.

In the formula (23), X ¹ is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and W ¹ and W ² are heavy Of the polyamine (B2) which is a precursor of the compound (C2), it is a portion excluding the primary and secondary amino groups, R ⁶ is a hydrogen atom or a methyl group, and Z ¹ is a polyisocyanate (D2 ) Is a portion excluding the isocyanate group.

Further, for example, when one molecule of diisocyanate (D2) is reacted with two molecules of polymer (C2) having one secondary amino group as in the following formula (24), The secondary amino group reacts with the isocyanate group to form a urea bond, and a dispersant having a urea bond is obtained. When W ³ in the following formula (24) has a tertiary amino group derived from the polyamine (B2) and / or the polymer (C2), the dispersant also has a tertiary amino group. The dispersant does not have an amino group having active hydrogen.

In the formula (24), X ¹ is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and W ³ is the polymer (C2). In the polyamine (B2) which is a precursor of the above, the primary amino group is excluded, R ⁶ is a hydrogen atom or a methyl group, and Z ¹ is an isocyanate group in the polyisocyanate (D2). Excluded part.

Further, for example, as shown in the following formula (25), the product of the above formula (23) is a polymer (C + 1) molecule (m + 1) molecules having two primary amino groups and 2n secondary amino groups. On the other hand, when m molecules of diisocyanate (D2) are reacted, theoretically, the primary amino group and the isocyanate group react to form a urea bond, and two primary amino groups and secondary amino groups (2 nm + 2n) And a dispersant having 2 m urea bonds is obtained. When Y ² in the following formula (25) has a tertiary amino group derived from the polyamine (B2) and / or the polymer (C2), the dispersant also has a tertiary amino group. (N and m are positive integers.)

In the formula (25), X ² is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and Y ² is the polymer (C2). In the polyamine (B2) which is a precursor of the polymer, the primary amino group is removed, W ⁴ is the portion of the polymer (C2) excluding the site having an amino group, and R ⁶ is It is a hydrogen atom or a methyl group, Z ¹ is a portion of the polyisocyanate (D2) excluding the isocyanate group, and n and m are positive integers.

  Further, for example, as shown in the following formula (26), two molecules of a polyamine (B2) having one primary amino group and one molecule of a polymer (A2) having two (meth) acryloyl groups are reacted. And (m + 1) molecules (m + 1) of the polymer (C2) having two secondary amino groups in each of the terminal regions when viewed from the portion derived from the polymer (A2). When m molecules of diisocyanate (D2) are reacted, theoretically, the secondary amino group and the isocyanate group react to form a urea bond, and a secondary amino group is formed in both terminal regions as viewed from the polyurea chain. A dispersant having two groups, one group each, is obtained. (M is a positive integer.)

In the formula (26), X ² is a portion excluding the (meth) acryloyloxy group in the polymer (A2) which is a precursor of the polymer (C2), and Y ³ is the polyamine (B2). Of these, it is a portion excluding the primary amino group, W ⁵ is a portion of the polymer (C2) excluding the site having an amino group, R ⁶ is a hydrogen atom or a methyl group, Z ¹ is a portion of the polyisocyanate (D2) excluding the isocyanate group, and m is a positive integer.

  Theoretically, in the above four examples, the primary amino group is assumed to react preferentially because it is more reactive than the secondary amino group, but in actuality, depending on the reaction conditions, etc. In some cases, a secondary amino group may react first, even if is left. Therefore, in some cases, a dispersant having a structure different from that expected may be obtained. However, since the reaction proceeds almost stoichiometrically, the polymer (C2) having a target structure is obtained mostly, and there is no problem in the function as a dispersant.

  As described above, by changing the reaction ratio between the polymer (C2) having an amino group and the polyisocyanate (D2), the molecular weight of the dispersant, the amino group (primary, secondary, and / or tertiary) and urea are changed. The amount of binding can be adjusted.

<Polyisocyanate (D2)>
As the polyisocyanate (D2), conventionally known ones can be used, but diisocyanates are preferred from the low viscosity effect of the dispersion. For example, aromatic diisocyanate (d21), aliphatic diisocyanate ( d22), aromatic-aliphatic diisocyanate (d23), alicyclic diisocyanate (d24), dimer of these diisocyanates (uretodione), reaction product of trimer of these diisocyanates (isocyanurate) and monoalcohol And reaction products of these diisocyanates and diols (urethane prepolymers of both terminal isocyanates) and the like.

  Aromatic diisocyanates (d21) include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl. Ether diisocyanate, dianisidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, naphthylene diisocyanate, and 1,3-bis (isocyanate) And methyl) benzene.

  Examples of the aliphatic diisocyanate (d22) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter sometimes abbreviated as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 2,3-butylene. Examples include diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the aromatic-aliphatic diisocyanate (d23) include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1, Examples include 4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

  Examples of the alicyclic diisocyanate (d24) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter sometimes abbreviated as IPDI), 1,3-cyclopentane diisocyanate, 1,3- Examples include cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

  As mentioned above, enumerated diisocyanate (D2) is not necessarily limited to these, It can also be used in combination of 2 or more types.

  As the diisocyanate (D2) used in the present invention, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) is preferable because it is hardly yellow-modified.

  Further, for the purpose of increasing the molecular weight of the dispersant, a polyisocyanate (d25) having 3 or more isocyanate groups in one molecule may be used. An aromatic polyisocyanate, an aliphatic polyisocyanate, Aromatic-aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be mentioned.

  As polyisocyanate (d25) having three or more isocyanate groups in one molecule, specifically, isocyanurate of the above diisocyanate and diisocyanate trimer such as biuret of the above diisocyanate, polyol adduct of the above diisocyanate, Examples thereof include copolymers of two or more of the above diisocyanates, aromatic triisocyanates, and polymeric aromatic isocyanate oligomers.

  Examples of the polyisocyanate (d25) having three or more isocyanate groups per molecule include, for example, isocyanurate of tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), isophorone diisocyanate (hereinafter abbreviated as IPDI). Isocyanurate of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), isocyanurate of hexamethylene diisocyanate (hereinafter abbreviated as HDI). , HDI biuret, HDI trimethylolpropane (hereinafter sometimes abbreviated as TMP) adduct, TDI TMP adduct, and TDI / HDI copolymer modified diisocyanate; 2,4,6- Triisocyanate Totor 1,3,5-triisocyanatobenzene, and aromatic triisocyanates such as 4,4 ′, 4 ″ -triphenylmethane triisocyanate; and polymethylene polyphenyl polyisocyanate (also known as MDI oligomer) ) And the like.

<Synthesis conditions>
The reaction between the polymer (C2) having an amino group and the polyisocyanate (D2) is 1) when the reaction is carried out by adding the whole amount, and 2) the polymer (C2) solution is charged into the flask, and the polyisocyanate (D2) is dropped. In order to make the reaction precise, 2) is preferable. The temperature of the urea reaction is preferably 70 ° C. or lower. More preferably, it is 60 degrees C or less. Even at 60 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 70 ° C., it is difficult to control the reaction rate, and it tends to be difficult to obtain a dispersant having a predetermined molecular weight and structure.

  The compounding ratio of the polyisocyanate (D2) to the polymer (C2) having an amino group is such that the equivalent of amino groups (primary and secondary amino groups) having active hydrogen of the polymer (C2) is [C2], polyisocyanate. When the isocyanate group equivalent of (D2) is [D2], [D2] / [C2] is 0.25 to 1.00, and it is preferable to react all of the isocyanate groups with amino groups having active hydrogen. From the viewpoint of the design of the dispersant that is the final product (balance between the carbon-based catalyst material adsorption site and the solvent affinity site), 0.35 to 0.9 is more preferable, and the dispersant that is the final product is used. From the viewpoint of dispersion stability of the catalyst paste composition, 0.5 to 0.8 is most preferable.

  If the blending equivalent ratio is less than 0.25, the amount of urea bonds in the dispersant, which is the final product, decreases, and the dispersibility may deteriorate. On the other hand, if the blending equivalent ratio is larger than 1.00, an isocyanate group having a high reaction activity remains, which reacts with water and the like, resulting in a high molecular weight and a high viscosity, which is not preferable. When the blending equivalent is 1.00, for example, in the reaction of polyamine (C2) having two amino groups having active hydrogen and diisocyanate (D2) having two isocyanate groups, the molecular weight is theoretically. Is not preferable from the viewpoint of molecular weight control.

  Further, when primary and / or secondary amino groups (amino groups having active hydrogen) in addition to tertiary amino groups and urea bonds are present in the dispersant skeleton, the adsorptivity to the carbon-based catalyst material is improved. The balance with the solvent-affinity part is also improved, and the dispersibility and its stability over time are also improved.

  That is, as described above, when the compounding equivalent ratio is 0.35 to 0.9, preferably 0.5 to 0.8, tertiary amino groups, urea bonds, amino groups having active hydrogen, and solvent affinity. The balance of the parts is improved and excellent dispersion stability is exhibited.

  The polymer (G2) having a basic functional group constituting the composition of the present invention is a first step for producing a polymer (A2) having one or two (meth) acryloyl groups in one terminal region. And a polyamine (B2) containing a (meth) acryloyl group and one or more primary and / or secondary amino groups of the polymer (A2) having one or two (meth) acryloyl groups in one end region. A first step of producing a polymer (C2) having an amino group, and a primary and / or second step of producing a polymer (C2) having an amino group. It can be produced by a production method comprising a third step of reacting a primary amino group with an isocyanate group of a polyisocyanate (D2) containing at least two or more isocyanate groups.

  The synthesis method and conditions for each step are as described above.

  The weight average molecular weight (Mw) of the polymer (G2) having a basic functional group constituting the composition of the present invention is preferably 1,000 to 100,000, more preferably 1,500 to 50,000. 000, particularly preferably 2,000 to 30,000. If the weight average molecular weight is less than 1,000, the stability of the catalyst paste composition may be reduced. If the weight average molecular weight exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the catalyst paste composition increases. May occur. Moreover, it is preferable that the amine value of the obtained dispersing agent is 5-100 mgKOH / g, More preferably, it is 10-70 mgKOH / g, More preferably, it is 20-50 mgKOH / g. If the amine value is less than 5 mgKOH / g, the carbon-based catalyst material and the functional group adsorbed may be insufficient, and it may be difficult to contribute to the dispersion of the carbon-based catalyst material. Aggregation of materials may occur, resulting in insufficient viscosity reduction effect and defects in the appearance of the coating film.

<Vinylamide resin>
The catalyst paste composition of the present invention may contain a vinylamide resin in order to obtain good dispersion and dispersion stability of the carbon-based catalyst material. Vinylamide resins are generally known to have an adsorption interaction with anionic species. Strictly speaking, the vinylamide resin does not correspond to a resin having a basic functional group, but its pH is slightly basic. Therefore, in this specification, it is treated as a resin having a basic functional group.
The vinyl amide resin to be used is not particularly limited, and examples thereof include polyvinyl acetamide, polyacrylamide, polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, polyvinyl pyrrolidone graft copolymer, and a copolymer of vinyl pyrrolidone and a comonomer. Can be mentioned.

  Comonomers that can be copolymerized with vinylpyrrolidone include α-olefin, vinyl acetate, ethyl acrylate, methyl acrylate, methyl methacrylate, dimethylaminomethyl methacrylate, acrylamide, methacrylamide, acrylonitrile, ethylene, styrene, maleic anhydride, Examples include acrylic acid, sodium vinyl sulfate, vinyl chloride, vinyl pyrrolidine, trimethylsiloxy vinyl silane, vinyl propionate, vinyl caprolactam, and methyl vinyl ketone.

  In addition, an acid-modified product obtained by treating the vinylamide resin with an organic acid or an inorganic acid can be used.

  Among the above-mentioned vinylamide resins, in particular, a treatment with an almost neutral vinylamide resin such as polyvinylpyrrolidone, vinylpyrrolidone-1-butene copolymer, or vinylpyrrolidone-styrene copolymer, or an organic acid or an inorganic acid. An acid-modified product of polyvinyl pyrrolidone is preferably used.

  The vinylamide resin is effective in dispersing the carbon-based catalyst material because the solvent used is excellent in wettability with respect to the solvent regardless of whether the solvent used is water or an aqueous solvent or a solvent system. It is surmised that this interaction is promoted smoothly, and the aggregation of the carbon-based catalyst materials is extremely reduced. In particular, when a highly polar solvent is used, the dispersion effect is extremely high.

<Combined effect of vinylamide resin and various derivatives having basic or acidic functional groups>
In the catalyst paste composition of the present invention, in order to further obtain good dispersion and dispersion stability of the carbon-based catalyst material, it is preferable to use various derivatives having a basic or acidic functional group in combination with the vinylamide resin. As one of the effects of the above-mentioned various derivatives having basic or acidic functional groups (hereinafter sometimes simply referred to as “derivatives”), a derivative further added to increase the wettability of the vinylamide resin with a solvent is carbon-based. By acting on the surface of the catalyst material (for example, adsorption), it is considered that dispersion proceeds due to a synergistic effect.

  Therefore, in the present invention, by using the vinylamide resin and various derivatives having a basic or acidic functional group, a functional group is not directly introduced (covalently bonded) to the surface of the carbon-based catalyst material, and a dispersion resin is further used. And good dispersion can be obtained. From these, good dispersion can be obtained without reducing the conductivity of the carbon-based catalyst material. Then, by using the catalyst paste composition of the present invention in which the carbon-based catalyst material is well dispersed, a fuel cell electrode membrane assembly in which the carbon-based catalyst material is uniformly dispersed can be produced.

  Further, in the catalyst ink composition using the catalyst paste composition of the present invention, since various derivatives having a functional group are present on the surface of the carbon-based catalyst material, the wettability of the carbon-based catalyst material to the hydrogen ion conductive polymer is increased. This improves the storage stability and coating properties of the catalyst ink composition in combination with the above-described uniform dispersion effect.

  The resin having a basic functional group is not limited to the above-described three types, and other than the three types, polyvinyl type, polyurethane type, polyester type, polyether type, formalin condensate, silicone type, and These composite polymers are exemplified. Furthermore, two or more kinds of resins having these basic functional groups can be used in combination.

<Other resins having basic functional groups>
Although it does not specifically limit as resin which has a commercially available basic functional group, For example, the following are mentioned.

  As the resin having a basic functional group manufactured by Big Chemie, Disperbyk-108, 109, 112, 116, 130, 161, 162, 163, 164, 166, 167, 168, 180, 182, 183, 184, 185, 2000, 2001, 2050, 2070, 2150, or BYK-9077.

  As a resin having a basic functional group manufactured by Nippon Lubrizol, SOLPERSE 9000, 13240, 13650, 13940, 17000, 18000, 19000, 20000, 24000SC, 24000GR, 28000, 31845, 32000, 32500, 32600, 33500, 34750, 35100, 35200, 37500, 38500, or 39000.

  As the resin having a basic functional group manufactured by Efka Additives, EFKA4008, 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403 4406, 4500, 4550, 4560, 4570, 4580, or 4800.

  Examples of the resin having a basic functional group manufactured by Ajinomoto Fine-Techno Co., Ltd. include Ajisper PB711, Azisper PB821, or Azisper PB822.

  Examples of the resin having a basic functional group manufactured by Enomoto Kasei Co., Ltd. include Disparon 1850, 1860, or DA-1401.

  Examples of the resin having a basic functional group manufactured by Kyoeisha Chemical include Floren DOPA-15B and Floren DOPA-17.

<Pigment derivative having acidic functional group (II-1)>
The catalyst paste composition of the present invention includes an organic dye derivative having an acidic functional group and an anthraquinone having an acidic functional group as an organic compound having an acidic functional group in order to obtain good dispersion and dispersion stability of the carbon-based catalyst material. One or more derivatives selected from a derivative, an acridone derivative having an acidic functional group, or a triazine derivative having an acidic functional group may be contained.

  In particular, use of a triazine derivative represented by the following formula (27) or an organic dye derivative represented by the following formula (30) is preferable.

In equation (27),
X ¹⁰¹ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹⁰³ -Y ¹⁰¹ -X ¹⁰⁴ - a and,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ _{is, -CONH -, - SO 2 NH} -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Y ¹⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,

Z ¹⁰¹ is —SO ₃ M, —COOM, or —P (O) (— OM) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ is —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ¹⁰² —Y ¹⁰¹ —Z ¹⁰¹ ,
R ¹⁰² is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following formula (28).

In formula (28),
X ²⁰¹ is —NH— or —O—;
X ^202, and X ²⁰³ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or —Y ²⁰¹ —Z ²⁰¹ ,
Y ²⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
^M201 is one equivalent of a monovalent to trivalent cation.

Examples of the organic dye residue represented by R ^{101 of} formula (27) and R ²⁰¹ and R ²⁰² of formula (28) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, Phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, anthanthrone, indanthrone, pyranthrone, violanthrone and other anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes , Isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complex dyes, and the like. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, The use of a quinacridone dye or a dioxazine dye is preferable because of excellent dispersibility.

Examples of the heterocyclic residues and aromatic ring residues represented by R ^{101 in} formula (27) and R ²⁰¹ and R ²⁰² in formula (28) include thiophene, furan, pyridine, pyrazole, pyrrole, imidazole. , Isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole, acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, or anthraquinone. In particular, the use of a heterocyclic residue containing at least one of S, N, and O heteroatoms is preferable because of excellent dispersibility.

Y ^{101 in} formula (27) and Y ^{201 in} formula (28) represent a substituted or unsubstituted alkylene group, alkenylene group or arylene group having 20 or less carbon atoms, preferably a substituted or unsubstituted phenylene group or biphenylene. Group, a naphthylene group, or an alkylene group which may have a side chain having 10 or less carbon atoms.

The substituted or unsubstituted alkyl group or alkenyl group represented by R ¹⁰² contained in Q ^{101 of} formula (27) is preferably one having 20 or less carbon atoms, more preferably the side having 10 or less carbon atoms. Examples thereof include an alkyl group which may have a chain. In the alkyl group or alkenyl group having a substituent, the hydrogen atom of the alkyl group or alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom, or a bromine atom, a hydroxyl group, or a mercapto group. Is.

M ²⁰¹ of M ¹⁰¹ of the formula (27) (28) represents one equivalent of a monovalent to trivalent cation, e.g., hydrogen atom (proton) represents any metal cation, or a quaternary ammonium cation . Moreover, when it has two or more M in a dispersing agent structure, M may be only any one of a proton, a metal cation, or a quaternary ammonium cation, and these may be combined.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the formula (29) or a mixture.

In Formula (29), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are any of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group It is.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ^{304 in} formula (29) may be the same or different. In addition, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the number of carbon atoms is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

In equation (30),
X ^401, a direct bond, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH -, - X 402 -Y-, or -X ⁴⁰² - Y- ^X403-
X ⁴⁰² _{is, -CONH -, - SO 2 NH} -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
X ⁴⁰³ is —NH— or —O—;
Y ⁴⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ⁴⁰¹ is —SO ₃ M ⁴⁰¹ , —COOM ⁴⁰¹ , or —P (O) (— OM ⁴⁰¹ ) ₂ ;
M ⁴⁰¹ is one equivalent of a monovalent to trivalent cation,
R ⁴⁰¹ is an organic dye residue,
n ⁴⁰¹ is an integer of 1 to 4.

Examples of the organic dye residue represented by R ⁴⁰¹ in the formula (30) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, Anthraquinone dyes such as anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes Examples thereof include dyes, selenium dyes, and metal complex dyes. The organic dye residue represented by R ₉ includes a light yellow anthraquinone residue that is not generally called a dye. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, The use of a quinacridone dye or a dioxazine dye is preferable because of excellent dispersibility.

M ^{401 in} the formula of formula (30) represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation. Further, when two or more ^Ms are included in the dispersant structure, M ⁴⁰¹ may be any one of proton, metal cation and quaternary ammonium cation, or a combination thereof.

  Examples of the metal include lithium, sodium, potassium, calcium, barium, magnesium, aluminum, nickel, and cobalt.

  The quaternary ammonium cation is a single compound having a structure represented by the formula (29) or a mixture.

In Formula (29), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are any of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group It is.

R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ^{304 in} formula (29) may be the same or different. In addition, when R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ have a carbon atom, the number of carbon atoms is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.

  Specific examples of the quaternary ammonium include dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, hydroxyethylammonium, dihydroxyethylammonium, 2-ethylhexylammonium, dimethylaminopropylammonium, laurylammonium, and stearylammonium. However, it is not limited to these.

  The method for synthesizing the dispersing agent is not particularly limited. For example, Japanese Patent Publication No. 39-28884, Japanese Patent Publication No. 45-11026, Japanese Patent Publication No. 45-29755, Japanese Patent Publication No. 64-5070. It can synthesize | combine by the method described in gazette or Unexamined-Japanese-Patent No. 2004-217842. The disclosure by the above publication is incorporated as part of the present specification.

  As one of the effects of the various derivatives having an acidic functional group, it is considered that the added derivative exerts a dispersion effect by acting (for example, adsorbing) on the surface of the carbon-based catalyst material.

  That is, at least one derivative selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group (hereinafter sometimes abbreviated as “derivative having an acidic functional group” or “derivative”). Is completely or partially dissolved in a solvent or water, and a carbon-based catalyst material is added and mixed in the solution. As a result, the action (for example, adsorption) of these derivatives on the carbon-based catalyst material proceeds, and the solvent on the surface of the carbon-based catalyst material depends on the polarity of the acidic functional group possessed by the derivative that acts on the surface of the carbon-based catalyst material (for example, adsorption). Alternatively, it is considered that wetting with water is promoted and the carbon-based catalyst material is easily agglomerated.

  In addition, by interacting the acidic functional group possessed by the above derivative with a cation component such as amine (for example, formation of ion pairs by neutralization (salt formation) and polarization or dissociation of ion pairs (salts)), It is considered that electrostatic repulsion on the surface of the carbon-based catalyst material is promoted, and the dispersion stability of the carbon-based catalyst material is further increased.

  In addition, due to the interaction (for example, acid-base interaction) between the acidic functional group of the derivative and the basic functional group of the resin having the basic functional group, the adhesion between the carbon-based catalyst material and the resin component is improved. In addition to the improvement, it is considered that the dispersion stability of the carbon-based catalyst material is further increased.

  Furthermore, since the adhesion between the carbon-based catalyst material and the hydrogen ion conductive polymer as the binder component is also improved through the resin having the basic functional group, it is prepared by coating and transferring as a catalyst ink composition. In addition to the adhesion to the solid polymer electrolyte membrane when the electrode membrane assembly for a fuel cell is used, it is considered that the hydrogen ion conductivity to the catalytic active point of the carbon-based catalyst material is also improved.

<II-2. Resin having acidic functional group> The catalyst paste composition of the present invention contains a resin having an acidic functional group in order to obtain good dispersion and dispersion stability of the carbon-based catalyst material. Preferred acidic functional groups are a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The resin having an acidic functional group is preferably the following three types of resins (H1) to (H3) from the viewpoint of dispersion stability.

  The resin having an acidic functional group binds carbon-based catalyst materials, or binds to a hydrogen ion conductive polymer film as a catalyst ink layer when the carbon-based catalyst material is a catalyst ink composition. Also functions as a binder. The resin having an acidic functional group is selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group. By using in combination with one or more selected derivatives, the dispersion stability of the carbon-based catalyst material and the coating properties when used as a catalyst ink composition and the adhesion to the hydrogen ion conductive solid electrolyte membrane are further improved. be able to. The hydrogen ion conductive solid electrolyte membrane often uses a polymer having the same structure as the hydrogen ion conductive polymer used for the binder of the catalyst ink composition, but at least has a high affinity with the hydrogen ion conductive polymer. preferable. A typical example is a Nafion electrolyte membrane.

  That is, an organic dye derivative having a basic functional group acting (for example, adsorbing) on the surface of a carbon-based catalyst material, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, or a triazine having a basic functional group Interaction between basic functional group of derivative and acidic functional group of resin having acidic functional group (for example, acid-base interaction), organic dye derivative having basic functional group, anthraquinone having basic functional group A derivative, an acridone derivative having a basic functional group, or a triazine derivative having a basic functional group and a resin having an acidic functional group interact with each other (for example, acid-base interaction) and adsorb to the surface of the carbon-based catalyst material. . As a result, the adsorption of the resin having an acidic functional group to the surface of the carbon-based catalyst material is promoted, and the adhesion between the carbon-based catalyst material and the resin component is improved. It is considered that the dispersion stability of the material is improved. In addition, the adhesion between the carbon-based catalyst material and the hydrogen ion conductive polymer as the binder component and the hydrogen ion conductivity to the catalytic active point of the carbon-based catalyst material are also improved. For example, the amount of binder used is reduced. Can also be expected. Hereinafter, resins (H1) to (H3) suitable as resins having an acidic functional group in the present invention will be described.

<Polyvinyl resin (H1) having acidic functional group>
As shown in the formula (31), the first step for producing the polyvinyl resin (H1) having an acidic functional group is a compound (s) having two hydroxyl groups and one thiol group in the molecule. Is a step of radically polymerizing the ethylenically unsaturated monomer (m) to produce a vinyl polymer (a) having two hydroxyl groups at one end. The thiol group of the compound (s) having two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, and the solvent-affinity vinyl polymer site (ethylenically unsaturated monomer (m)) is polymerized ( A vinyl polymer (a) in which two hydroxyl groups are introduced via S atoms at the terminal of M) is synthesized.

  Examples of the compound (s) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto- 1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propane Examples include diol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

  A compound (s) having two hydroxyl groups and one thiol group in the molecule is adjusted with the ethylenically unsaturated monomer (m), optionally in accordance with the molecular weight of the target vinyl polymer (a). A vinyl polymer (a) can be obtained by mixing and heating a polymerization initiator. Preferably, bulk polymerization or solution polymerization is performed using 1 to 30 parts by weight of the compound (s) having a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is 40 to 150 ° C., preferably 50 to 110 ° C., and the reaction time is 3 to 30 hours, preferably 5 to 20 hours.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (m). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), and 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like.

  Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and N-methyl are used as polymerization solvents. Pyrrolidone or the like is used, but is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

  Examples of the ethylenically unsaturated monomer (m) include the following general ethylenically unsaturated monomer (m1). Common ethylenically unsaturated monomers (m1) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) Alkyl (meth) acrylates such as acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate; cyclohexyl (meth) acrylate , (Meth) acrylates having an aliphatic ring such as isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; (meth) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate; (Meth) acrylates having aromatic rings such as (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate; methoxypolypropylene glycol (meth) acrylate, and ethoxypolyethylene glycol Alkoxypolyalkylene glycol (meth) acrylates such as (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye N-substituted (meth) acrylamides such as acetone (meth) acrylamide and acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate, and N, N- Amino group-containing (meth) acrylates such as ethylaminoethyl (meth) acrylate; nitriles such as (meth) acrylonitrile; styrenes such as styrene and α-methylstyrene; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n -Vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate. However, it is not particularly limited to the above polymer, and two or more types may be used in combination, or the following monomers may be used in combination as required.

  As one of the ethylenically unsaturated monomers (m), a carboxyl group-containing ethylenically unsaturated monomer (m2) can be used in combination. Examples of the ethylenically unsaturated monomer (m2) having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, and caprolactone of acrylic acid. One type or two or more types can be selected from an adduct (addition mole number is 1 to 5), a caprolactone adduct of methacrylic acid (addition mole number is 1 to 5), and the like.

  In this invention, it is preferable to use 20 to 70 weight% of benzyl (meth) acrylate among the ethylenically unsaturated monomer (m) illustrated above. If it is less than 20% by weight, the solvent affinity becomes low, and sufficient steric repulsion effect cannot be obtained, and the pigment dispersibility may be lowered. If it exceeds 70% by weight, the solubility of the dispersant itself in the solvent may be reduced. In order to improve, the adsorption | suction to a pigment may become inadequate, or the viscosity of a pigment composition may become high by the entanglement of solvent affinity parts.

  In the present invention, the ethylenically unsaturated monomer (m3) having a blocked isocyanate group, the ethylenically unsaturated monomer having an oxetane group, together with the ethylenically unsaturated monomer (m) exemplified above. A vinyl polymer (a) can be produced using an ethylenically unsaturated monomer selected from at least one of a body (m4) and an ethylenically unsaturated monomer (m5) having a t-butyl group. I can do it. By using these monomers, the crosslinkable functional groups (blocked isocyanate group, oxetane group, and t-butyl group, respectively) in the monomer are crosslinked by heating, so that the catalyst ink composition according to the present invention is used. When used as an electrode membrane assembly, the chemical resistance, solvent resistance, heat resistance, and alkali resistance can be further improved after thermosetting by hot pressing.

  Examples of the ethylenically unsaturated monomer (m3) having a blocked isocyanate group include Karenz MOI-BM and Karenz MOI-BP (manufactured by Showa Denko). Examples of the ethylenically unsaturated monomer (m4) having an oxetane group include ETERNACOLL OXMA (manufactured by Ube Industries). Examples of the ethylenically unsaturated monomer (m5) having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

  The blocked isocyanate group of the monomer is more preferable because it crosslinks with the hydroxyl group when used in combination with the hydroxyl group, and the oxetane group is more preferable because it crosslinks with the carboxyl group when used in combination with the carboxyl group. When used together with a group, it undergoes a crosslinking reaction with a hydroxyl group, and when used together with an oxetane group, a crosslinking reaction occurs with an oxetane group.

  In the case of combining carboxyl groups, in the curable dispersant, a carboxyl group derived from tetracarboxylic dianhydride (b) can be used as a curable site, but an ethylenically unsaturated monomer having a carboxyl group is ethylenic. By using together as an unsaturated monomer (m2), a carboxyl group can be easily introduced into the curable dispersant.

  Examples of the ethylenically unsaturated monomer (m2) having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, and caprolactone of acrylic acid. One type or two or more types can be selected from an adduct (addition mole number is 1 to 5), a caprolactone adduct of methacrylic acid (addition mole number is 1 to 5), and the like.

  Moreover, when combining a hydroxyl group, a hydroxyl group can also be introduce | transduced into a curable dispersing agent by using together the ethylenically unsaturated monomer (m6) which has a hydroxyl group as an ethylenically unsaturated monomer.

As the ethylenically unsaturated monomer (m6) having a hydroxyl group, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used.
2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3, or 4) -hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and glycerol ( Hydroxyalkyl (meth) acrylates such as meth) acrylate; N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (2-hydroxybutyl) (meta) ) N- (hydroxyalkyl) (meth) acrylamides such as acrylamide; 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, and 2- (or 3- or 4-) hydroxybutyl vinyl ether Hydroxy And alkylalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and 2- (or 3-, or 4-) hydroxybutyl allyl ether. It is done.

  Also, ethylenic unsaturation obtained by adding alkylene oxide or lactone to the above hydroxyalkyl (meth) acrylates, N- (hydroxyalkyl) (meth) acrylamides, hydroxyalkyl vinyl ethers, and hydroxyalkyl allyl ethers. A monomer can also be used as an ethylenically unsaturated monomer having a hydroxyl group used in the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and a combination system of two or more of these are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  In the present invention, an unsaturated bond can be introduced into the vinyl polymer (a). As a method for introducing an unsaturated bond into the vinyl polymer (a), a hydroxyl group is introduced into the vinyl polymer (a), and then an ethylenically unsaturated monomer (m7) having an isocyanate group is reacted. A method, a method of introducing a carboxyl group into the vinyl polymer (a), and then reacting an ethylenically unsaturated monomer having an epoxy group (m8); an epoxy group being introduced into the vinyl polymer (a); And a method of reacting an ethylenically unsaturated monomer (m2) having a carboxyl group later.

  Examples of the ethylenically unsaturated monomer (m7) having an isocyanate group include Karenz MOI (2-methacryloyloxyethyl isocyanate manufactured by Showa Denko) and Karenz AOI (2-acryloyloxyethyl isocyanate manufactured by Showa Denko). . Examples of the ethylenically unsaturated monomer (m8) having an epoxy group include glycidyl (meth) acrylate and cyclomer M100 (3,4-epoxycyclohexyl (meth) acrylate manufactured by Daicel Chemical Industries).

  As shown in the following formula (32), the second step for producing a polyvinyl resin (H2) having an acidic functional group is a vinyl polymer having two hydroxyl groups at one end obtained in the first step. This is a step of reacting the union (a) with the tetracarboxylic dianhydride (b).

  Assuming that the molar ratio of the vinyl polymer (a) having two hydroxyl groups at one end is α and the molar ratio of the tetracarboxylic dianhydride (b) is β, the molecular weight is theoretically infinite when α = β. Therefore, it is often the case that α> β or α <β is changed to change the α / β ratio to control the target molecular weight. For example, when α = β + 1, both ends are hydroxyl groups, the molecular weight is not increased any more, and a polyvinyl resin (H2-1) having an acidic functional group can be synthesized stably. On the other hand, when β = α + 1, both ends become acid anhydride groups and the stability is deteriorated. Therefore, the acid anhydride group is hydrolyzed to have a polyvinyl resin (H2 -2) can be synthesized.

  Next, each component in the 2nd manufacturing process of the polyvinyl resin (H2) which has an acidic functional group is demonstrated.

The tetracarboxylic dianhydride (b) used in the present invention reacts with a vinyl polymer (a) having two hydroxyl groups at one end to form an ester bond, and on the resulting polyester main chain Pendant carboxyl groups can be left. If the acid anhydride group remaining in the product of formula (32) is hydrolyzed, the product of this reaction has 2 or 3 carboxyl groups in the X ₁ moiety in the structural formula. The plurality of carboxyl groups are effective as adsorption sites on the carbon-based catalyst material.

However, when only one carboxyl group is bonded to X ⁰ , it is not preferable because high dispersibility, fluidity, and storage stability are not exhibited. X ⁰ in the present invention is a reaction residue after the tetracarboxylic dianhydride (b) has reacted with the vinyl polymer (a) having two hydroxyl groups at one end. Preferably, it is a reaction residue after the tetracarboxylic dianhydride represented by the following formula (33) or formula (34) has reacted with the vinyl polymer (a) having a hydroxyl group.

  In the above formula (33), k is 1 or 2.

In the above formula (34), Q ⁰ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, the following formula (35) or It is group represented by (36).

In the present invention, a vinyl polymer (a) having two hydroxyl groups at one end is reacted with tetracarboxylic dianhydride (b) to bind to X ⁰ in the product in the above formula (32). A plurality of carboxyl group parts function as adsorbing parts for the carbon-based catalyst material, and a vinyl polymer part functions as a solvent affinity part.

  The weight average molecular weight of the vinyl polymer (a) having two hydroxyl groups at one end is preferably 1,000 to 10,000, and this part becomes an affinity part for the solvent as a dispersion medium. When the weight average molecular weight of the vinyl polymer (a) is less than 1,000, the effect of steric repulsion due to the solvent affinity portion is reduced, and it becomes difficult to prevent aggregation of the carbon-based catalyst material, and the dispersion stability is insufficient. There is a case. On the other hand, if it exceeds 10,000, the absolute amount of the solvent affinity part increases, and the dispersibility effect itself may be lowered. Furthermore, the viscosity of the catalyst paste composition may increase.

  The vinyl polymer (a) can easily adjust the molecular weight to the above range, and also has good affinity for the solvent. As explained in the first step of the polyvinyl resin (H1) having an acidic functional group, the weight average molecular weight of the vinyl polymer (a) having two hydroxyl groups at one end is determined by the ethylenically unsaturated monomer. Use of compound (s) having two hydroxyl groups and one thiol group in the molecule for (m), reaction temperature, reaction time, used as needed for ethylenically unsaturated monomer (m) It can be controlled by the weight of the polymerization initiator used, the type of polymerization solvent used as required, and the ethylenically unsaturated monomer (m) concentration during polymerization.

  Examples of the tetracarboxylic dianhydride (b) include 1,2,3,4-butanetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5,6-tricarboxy Norbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides, and aliphatic tetracarboxylic anhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic anhydride; and pyromelli Toic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 3 , 3 ′, 4,4′-biphenylsulfonetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid anhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid Anhydride, 1,2,3,4-furantetracarboxylic anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (tri Phenylphthalic acid anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4 ′ -Diphenylmethane anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic anhydride, 9,9-bis [4- ( 3,4-dicarboxyphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic anhydride, and 3,4-dicarboxy-1, And aromatic tetracarboxylic anhydrides such as 2,3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride.

  The tetracarboxylic dianhydride (b) that can be used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic acid anhydride represented by the formula (34) or the formula (35) from the viewpoint of reducing the viscosity of the catalyst paste composition, A tetracarboxylic anhydride having two or more aromatic rings is preferred. Further, a compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.

  The catalyst used in the second step of preparing the polyvinyl resin (H1) having the acidic functional group may be a known catalyst. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and 1 , 5-diazabicyclo- [4.3.0] -5-nonene.

  The polyvinyl resin (H1) having an acidic functional group that can be used in the present invention can be produced using only the above raw materials, but avoids problems such as high viscosity and non-uniform reaction. Therefore, it is preferable to use a solvent. A well-known thing can be used as a solvent. Examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and N-methylpyrrolidone. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

  The polyvinyl resin (H1) having an acidic functional group that can be used in the present invention is obtained by reacting a vinyl polymer (a) having two hydroxyl groups at one end and a tetracarboxylic dianhydride (b). can get. The molar ratio of the acid anhydride group in the tetracarboxylic acid anhydride (b) to the hydroxyl group in the vinyl polymer (a) is such that the molar ratio of the vinyl polymer (a) is α, and the tetracarboxylic dianhydride ( When the molar ratio of b) is β, 2β / 2α = β / α = 0.3 to 1.2 is preferable, more preferably β / α = 0.5 to 1.0, and most preferably β / α. = 0.6 to 0.8. When the reaction is carried out with β / α> 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water and used. If it is less than 0.3, the acid anhydride residue that is an adsorbing part to the carbon-based catalyst material may be decreased, and the acid value of the resin may be decreased. On the other hand, when the ratio exceeds 1.2, the polyester has a high molecular weight, and when used as a catalyst paste composition, the interaction between the resins becomes strong and the viscosity may increase.

  The reaction temperature in the second step of the polyvinyl resin (H1) having an acidic functional group is 80 ° C. to 180 ° C., preferably 90 ° C. to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when it is 180 ° C. or higher, the carboxyl group undergoes an esterification reaction, which may cause a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but when the acid value of the polyester is in the range of 5 to 200, or the hydroxyl value is 20 to 200. The reaction may be stopped when entering the range.

  The weight average molecular weight of the obtained polyvinyl resin (H2) having an acidic functional group is preferably 2,000 to 25,000. If the weight average molecular weight is less than 2,000, the stability of the catalyst paste composition may decrease. On the other hand, when it exceeds 25,000, the interaction between resins becomes strong, and the viscosity of the catalyst paste composition may increase. Moreover, as for the acid value of the obtained polyvinyl-type resin (H1) which has an acidic functional group, 5-200 mgKOH / g is preferable. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g. If the acid value is less than 5, the adsorptive ability to the carbon-based catalyst material may be reduced, and there may be a problem in dispersibility. If the acid value exceeds 200 mgKOH / g, the interaction between the resins becomes strong and the viscosity of the catalyst paste composition. May be higher.

<Polyester resin having acidic functional group (H2)>
As long as the polyester-based resin (H2) having an acidic functional group that can be used in the present invention has a structure represented by the following formula (1), its chemical structure and production method are not particularly limited. The production method includes, for example, a first step of producing a polyester having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, a polyester having a hydroxyl group at one end, a tetra A method comprising a second step of reacting carboxylic dianhydride is preferred.

Formula (37):
^{_{(HOOC-) m -R 21 - (}} - COO - [- R 23 -COO-] n -R 22) t

In the above formula (37), R ²¹ is a tetravalent tetracarboxylic acid compound residue, R ²² is a monoalcohol residue, R ²³ is a lactone residue, and m is 2 or 3 Where n is an integer from 1 to 50 and t is (4-m).

In the present invention, preferred compounds as polyester resin (H3) having an acidic functional group represented by the above formula (37), R ²¹ is a group represented by the later-described formula (38) - (42), R ²² is an aliphatic alkyl group having 8 to 20 carbon atoms, or a terminal ether group or ester polyoxyalkylene (alkylene moiety having 2 to 4 carbon atoms) group having a molecular weight of 200 to 1500, and R ²³ is , A hexamethylene group, a pentamethylene group, or an alkyl-substituted hexamethylene group, m is 2 or 3, n is an integer of 3 to 20, and t is (4-m) It is a certain resin.

In the polyester resin (H3) having an acidic functional group represented by the above formula (37), R ²¹ is preferably any one of groups represented by the following formulas (38) to (40).

In the above formula (40), A ⁰ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ). ₂ − is a group represented by the following formula (41) or (42).

  The monoalcohol that can be used for the production of the polyester-based resin (H2) having an acidic functional group is not particularly limited as long as it is a compound having one hydroxyl group. The aliphatic monoalcohol is, for example, preferably a linear or branched substituted or unsubstituted saturated aliphatic monoalcohol having 1 to 30 carbon atoms (more preferably 1 to 25 carbon atoms), or a carbon atom. Examples thereof include substituted or unsubstituted saturated alicyclic monoalcohols having 1 to 30 (more preferably 1 to 25 carbon atoms). Examples of the substituent of the saturated aliphatic monoalcohol or saturated alicyclic monoalcohol include a carboxyl group.

  Examples of aliphatic monoalcohols are methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, 4-methyl-2-pentanol. 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2- Examples include octyl decanol, 2-octyl decanol, 2-hexyl decanol, behenyl alcohol, and oleyl alcohol. Examples of the alicyclic monoalcohol include cyclohexanol.

  As the aliphatic monoalcohol, a branched aliphatic monoalcohol is preferable, and examples thereof include 8 to 20 carbon atoms such as 2-ethylhexanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, and 2-hexyldecanol. Are preferred.

  As the monoalcohol, a substituted or unsubstituted aromatic monoalcohol having 6 to 30 carbon atoms (more preferably 6 to 25 carbon atoms), for example, phenol or cumylphenol can be used. A saturated aliphatic monoalcohol having an aliphatic group having 1 to 6 carbon atoms and substituted with an aromatic group having 6 to 10 carbon atoms, such as benzyl alcohol, can also be used.

  Furthermore, as the monoalcohol, a monoalkylene glycol monoether having a hydroxyl group at one end or a polyalkylene glycol monoether having a hydroxyl group at one end can be used. As these monoalkylene glycol monoethers or polyalkylene glycol monoethers, preferably, mono or polyethylene glycol or mono or polypropylene glycol alkyl monoethers having 1 to 8 carbon atoms can be mentioned. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene Glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, trie Lenglycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, triethylene glycol Propylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetra Ethylene glycol monob Chill ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl Mention may be made of alkylene glycol monoalkyl ethers such as ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

  Furthermore, examples of the monoalcohol that can be used for the production of the polyester-based resin (H2) having an acidic functional group include monoalcohols having one or more ethylenically unsaturated double bonds. Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group, and a (meth) acryloyl group is preferable. These can be compounds having different types of double bonds in one compound.

  As the monoalcohol having the ethylenically unsaturated double bond, for example, an unsaturated monoalcohol compound having one, two, or three or more ethylenically unsaturated double bonds can be used. Examples of monoalcohols having one ethylenically unsaturated double bond include hydroxyalkyl esters of (meth) acrylic acid having 1 to 8 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate and the like can be mentioned.

  Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate or glycerin di (meth) acrylate. Examples of the monoalcohol having three ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having five ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate. be able to.

  Alcohol obtained by addition polymerization of alkylene oxide starting from the hydroxyl group of the aliphatic monoalcohol, aromatic monoalcohol, and monoalcohol having an ethylenically unsaturated double bond exemplified above, that is, one terminal is Etherified or esterified polyalkylene glycol can also be used for the production of a polyester-based resin (H2) having an acidic functional group. As the alkylene oxide used for the addition polymerization, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, or a mixture of two or more thereof is used. be able to. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. The addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, and particularly preferably 5 to 100 in one molecule.

  The addition of alkylene oxide can be carried out by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. Commercially available products of the addition polymerization product thus obtained include Nippon Oil & Fats Uniox series or Nippon Oil & Fats Bremer series.

  Specifically, UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-1000, PP -500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET series, 30PPT -800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, and 10APB-500B.

  The monoalcohol that can be used for the production of the polyester-based resin (H2) having an acidic functional group is not limited to the above examples, and any compound can be used as long as it is a compound having one hydroxyl group. These can be used alone or in combination of two or more.

  Among the above monoalcohols, for example, 4-methyl-2-pentanol, isopentanol, isooctanol, 2-ethylhexanol, isononanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, or 2-hexyldecanol By using a branched aliphatic monoalcohol such as polyalkylene glycol having a hydroxyl group at one end, the crystallinity is lowered and may become liquid at room temperature. It is preferable in terms of compatibility.

  By performing ring-opening polymerization of a lactone using the monoalcohol as an initiator, a polyester having a hydroxyl group at one end and usable for the production of the resin-type dispersant can be obtained. The lactone that can be used in the ring-opening polymerization is preferably a 4-membered to 10-membered ring, more preferably a 5- to 7-membered lactone, and the ring-constituting carbon atom is substituted or unsubstituted. Can be. Examples of the substituent of the ring-constituting carbon atom include an alkyl group having 1 to 4 carbon atoms. Also, an unsaturated lactone containing one or more ethylene bonds in the ring, or a condensed lactone with an aromatic compound (for example, benzene) can be used.

  Specific examples of suitable lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. Of these, δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone is preferably used from the viewpoint of ring-opening polymerizability. Examples of the alkyl substituent include an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group, and the alkyl substituent can be substituted with one or more of these alkyl substituents.

  The lactone can be used without being limited to the above examples, and can be used alone or in combination of two or more. When two or more types are used in combination, the crystallinity is lowered and may become liquid at room temperature, which is preferable in terms of workability and compatibility with other resins.

  The ring-opening polymerization of the monoalcohol and the lactone can be carried out in a known manner, for example, by charging the monoalcohol, the lactone, and the polymerization catalyst into a reactor connected with a dehydrating tube and a condenser, and under a nitrogen stream. . When a low-boiling monoalcohol is used as the monoalcohol, the reaction can be performed under pressure using an autoclave. Moreover, when using the compound which has an ethylenically unsaturated double bond as said monoalcohol, it is preferable to add a polymerization inhibitor and to react in the flow of dry air.

  The number of moles of the lactone added to 1 mole of the monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles. If the number of added moles is less than 1 mole, the effect of dispersing the carbon-based catalyst material cannot be obtained, and if it exceeds 50 moles, the molecular weight becomes too large, and the dispersibility of the carbon-based catalyst material and the catalyst ink composition It causes a decrease in fluidity.

  Examples of the polymerization catalyst for the ring-opening polymerization include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethyl. Quaternary ammonium salts such as ammonium bromide and benzyltrimethylammonium iodide; tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, Benzyltrimethylphosphonium bromide Quaternary phosphonium salts such as benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate Organic carboxylates such as sodium alcoholates, alkali metal alcoholates such as sodium alcoholates and potassium alcoholates; tertiary amines; organotin compounds; organoaluminum compounds; organotitanate compounds; and zinc compounds such as zinc chloride . The catalyst is used in an amount of 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When the catalyst amount is 3000 ppm or more, the polyester resin (H3) having an acidic functional group is intensely colored, which adversely affects the stability of the product. On the contrary, if the amount of the catalyst used is 0.1 ppm or less, the rate of ring-opening polymerization of the cyclic ester is extremely slow, which is not preferable.

  The ring-opening polymerization reaction can be carried out without a solvent, or a suitable dehydrated organic solvent can be used. The solvent used in the ring-opening polymerization reaction can be used after removal of the reaction by an operation such as distillation.

  The ring-opening polymerization reaction is preferably carried out in the range of 100 to 220 ° C, more preferably 110 to 210 ° C. If the reaction temperature is less than 100 ° C., the reaction rate is very slow, and if it exceeds 210 ° C., side reactions other than the addition reaction of lactone, such as decomposition of lactone adducts into lactone monomers, formation of cyclic lactone dimers and trimers, etc. .

  The radical polymerization inhibitor used when using a monoalcohol having an ethylenically unsaturated double bond is hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol. And phenothiazine are preferable, and these can be used alone or in combination, and the amount used is preferably 0.01% to 6%, more preferably 0.05% to 1.0%. .

  The polyester-based resin (H2) having an acidic functional group used in the present invention reacts a hydroxyl group of a polyester having a hydroxyl group at one end obtained in the first step with a tetracarboxylic dianhydride. It is preferable to obtain by (second step).

  Examples of tetracarboxylic dianhydrides used in the second step include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and heterocyclic tetracarboxylic acids. Mention may be made of acid dianhydrides and polycyclic tetracarboxylic dianhydrides.

  Specifically, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3 -Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, Fats such as 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Cyclic tetracarboxylic dianhydride; and 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2- It can be mentioned heterocyclic tetracarboxylic acid anhydrides such as carboxylic acid dianhydride.

  Further, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4 , 4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis 3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) Diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) Phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′- Diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarbo) Ciphenyl) fluorene dianhydride, aromatic tetracarboxylic dianhydride such as 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy- 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, etc. Of polycyclic tetracarboxylic dianhydrides.

  As the aromatic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride having two or more aromatic rings is particularly preferable, and in particular, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride. Products, ethylene glycol ditrimellitic anhydride ester, and 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride.

  The tetracarboxylic dianhydride that can be used for the production of the polyester-based resin (H2) having an acidic functional group is not limited to the compounds exemplified above, and any one having two carboxylic anhydride moieties in the molecule. Such a structure may be used. These may be used alone or in combination. Furthermore, the tetracarboxylic dianhydride that can be suitably used for the production of the polyester-based resin (H2) having an acidic functional group is an aromatic tetracarboxylic dianhydride from the viewpoint of reducing the viscosity of the catalyst paste composition. And more preferably tetracarboxylic dianhydride having two or more aromatic rings (particularly 2 to 4).

  The reaction ratio in the second step is the ratio of the number of moles <N> of the anhydrous ring of the tetracarboxylic acid anhydride to the number of moles <H> of the hydroxyl group of the polyester having a hydroxyl group at one end [<H> / <N>] is preferably 0.5 <H> / <N> <1.2, more preferably 0.7 <H> / <N> <1.1, and most preferably <H> / <N> = 1. When the reaction is performed with <H> / <N> <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.

  A catalyst may be used in the second step. As the catalyst, tertiary amine compounds include, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, and 1,8-diazabicyclo- [5.4.0] -7-undecene, Examples include 1,5-diazabicyclo- [4.3.0] -5-nonene.

  Both the first step and the second step may be performed without a solvent, or an appropriate dehydrated organic solvent may be used. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

  The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the half-esterified product again forms a cyclic anhydride, making it difficult to complete the reaction.

In the above formula (1), n is preferably an integer of 1 to 30, more preferably an integer of 2 to 20. In the above formula (1), when at least one of n and t is 2 or more, the plurality of R ²³ present in the above formula (1) are all the same group or a plurality of groups. Can be included.

  The resin having an acidic functional group is not limited to only the above two types (H1) to (H2), and other than the two types, polyvinyl, polyurethane, polyester, polyether, formalin condensate, Silicone-based and composite polymers thereof may be used. Furthermore, two or more kinds of resins having these acidic functional groups can be used in combination.

<Resins (H3) having other commercially available acidic functional groups>
Although it does not specifically limit as resin which has a commercially available acidic functional group, For example, the following are mentioned. These may be used alone or in combination.
As the resin having an acidic functional group manufactured by Big Chemie, Anti-Terra-U, U100, 203, 204, 205, Disperbyk-101, 102, 106, 107, 110, 111, 140, 142, 170, 171, 174 180, 2001, BYK-P104, P104S, P105, 9076, and 220S.

  Examples of the resin having an acidic functional group manufactured by Nippon Lubrizol include SOLPERSE 3000, 21000, 26000, 36000, 36600, 41000, 41090, 43000, 44000, and 53095.

  Examples of the resin having an acidic functional group manufactured by Efka Additives include EFKA4510, 4530, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, and 5071.

  Examples of the resin having an acidic functional group manufactured by Ajinomoto Fine Techno Co. include Ajisper PN411 and Azisper PA111.

  Examples of the resin having an acidic functional group manufactured by ELEMENTIS include Nuosperse FX-504, 600, 605, FA620, 2008, FA-196, and FA-601.

  Examples of the resin having an acidic functional group manufactured by Lion Corporation include Politi A-550 and Politi PS-1900.

  As resins having an acidic functional group manufactured by Enomoto Kasei Co., Ltd., Disparon 2150, KS-860, KS-873SN, 1831, 1860, PW-36, DA-1200, DA-703-50, DA-7301, DA-325 DA-375, DA-234, and the like.

  Examples of the resin having an acidic functional group manufactured by BASF Japan include JONCRYL67, 678, 586, 611, 680, 682, 683, 690, 52J, 57J, 60J, 61J, 62J, 63J, 70J, HPD-96J, 501J, 354J, 6610, PDX-6102B, 7100, 390, 711, 511, 7001, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630, 352J, 252D, 538J7640, 7641, 631, 790, 780, and 7610.

  Examples of the resin having an acidic functional group manufactured by Mitsubishi Rayon include Dianal BR-60, 64, 73, 77, 79, 83, 87, 88, 90, 93, 102, 106, 113, and 116. .

<Catalyst ink composition for fuel cells>
The proportions of the carbon-based catalyst material, the dispersant, and the hydrogen ion conductive polymer or the water repellent material contained in the catalyst ink composition of the present invention are not limited and can be appropriately selected within a wide range.

  The method for preparing the catalyst ink composition is not particularly limited. In the preparation, each component may be dispersed at the same time, or after dispersing the catalyst paste composition, a hydrogen ion conductive polymer component or a water repellent material may be added. It can be optimized by polymer or water repellent material and solvent type. However, if a catalyst paste composition is prepared first and then a hydrogen ion conductive polymer or a water repellent material is added later to prepare a catalyst ink composition, it can greatly contribute to cost reduction such as shortening of dispersion time.

  For example, in the catalyst ink composition of the present invention, the dispersant is 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, and the hydrogen ion conductive polymer with respect to 100 parts by weight of the carbon-based catalyst material. 10 to 300 parts by weight, preferably 20 to 250 parts by weight, and the water repellent material is 5 to 100 parts by weight, preferably 10 to 90 parts by weight.

<Hydrogen ion conductive polymer>
Hydrogen ion conducting polymers are known. Examples of the hydrogen ion conductive polymer include fluorinated ion exchange resins such as perfluorosulfonic acid, olefin resins and polyimide resins into which strongly acidic functional groups such as sulfonic acid groups are introduced. For example, by introducing a fluorine atom having a high electronegativity, it is chemically very stable, a sulfonic acid group has a high degree of detachment, and high ionic conductivity can be realized. Specific examples of such hydrogen ion conductive polymers include “Nafion” manufactured by DuPont, “Flemion” manufactured by Asahi Glass Co., Ltd., “Aciplex” manufactured by Asahi Kasei Co., Ltd., “ Gore Select "and the like. Usually, the hydrogen ion conductive polymer is used as an alcohol aqueous solution containing about 5 to 30% by weight of the polymer. As the alcohol, for example, methanol, propanol, ethanol diethyl ether and the like are used.

<Water repellent material>
Any water-repellent material may be used as long as it has good drainage of excess water, which reacts with oxygen and hydrogen ions in the catalyst layer on the cathode side to generate water, and does not hinder gas diffusibility. The surface tension of the water repellent material is preferably lower than the surface tension of water (about 72 dyn / cm). For example, fluorine resin, polypropylene, and polyethylene can be used, and among them, fluorine resin is preferable. Examples of the fluororesin include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

<Solvent>
As a solvent, if it is a solvent with high affinity with water or water, it will not specifically limit. In particular, alcohol can be preferably used. As such an alcohol, for example, a monohydric alcohol or a polyhydric alcohol having a boiling point of about 80 to 200 ° C. can be used, and an alcohol solvent having 4 or less carbon atoms is preferable. Specific examples include 1-propanol, 2-propanol, 1-butanol, 2-butanol, and t-butanol. Alcohol is used individually by 1 type or in mixture of 2 or more types. Among these monohydric alcohols, 2-propanol, 1-butanol and t-butanol are preferable. Specifically, the polyhydric alcohol is preferably, for example, propylene glycol, ethylene glycol or the like, particularly propylene glycol, from the viewpoint of compatibility with the hydrogen ion conductive polymer and the problem of drying efficiency when used as a catalyst ink composition. preferable.

<Catalyst layer for fuel cell and electrode membrane assembly for fuel cell>
The catalyst layer for a fuel cell may be formed by directly applying and drying the catalyst ink composition to an electrode substrate (carbon paper or the like), and removing the catalyst ink composition from a Teflon (registered trademark) sheet or the like. It may be formed by preparing a catalyst layer transfer sheet formed by coating and drying on a possible transfer sheet (base material) and then transferring it to a solid polymer electrolyte membrane.

  When the catalyst layer for a fuel cell is produced by applying the catalyst ink composition to a transfer sheet (such as a Teflon (registered trademark) sheet) or directly applying to the electrode substrate and then drying, A normal coating method can be used. The coating method is not particularly limited, and for example, general methods such as knife coater, bar coater, blade coater, spray, dip coater, spin coater, roll coater, die coater, curtain coater, and screen printing can be used. Applicable.

  After coating, the coating film (fuel cell catalyst layer) is formed by drying. A drying temperature is about 40-120 degreeC normally, Preferably it is about 75-95 degreeC. The drying time is usually about 5 minutes to 2 hours, preferably about 30 minutes to 1 hour, although it depends on the drying temperature. The thickness of the fuel cell catalyst layer after coating and drying is usually about 5 μm to 80 μm, preferably about 10 μm to 70 μm.

  The pressure level in transferring the above fuel cell catalyst layer to the solid polymer electrolyte membrane is usually about 0.5 Mpa to 20 Mpa, preferably about 1 Mpa to 10 Mpa, in order to avoid transfer failure. Further, it is preferable to heat the pressure surface during this pressure operation in order to avoid transfer failure. The heating temperature is usually 200 ° C. or lower, preferably about 120 to 150 ° C., in order to avoid damage or modification of the solid polymer electrolyte membrane.

  The electrode membrane assembly for a fuel cell in the present invention is formed by adhering a fuel cell catalyst layer to one or both sides of a hydrogen ion conductive solid polymer electrolyte membrane, and further, It means what electrode base materials, such as paper, have adhered and comprised.

As a method for producing an electrode membrane assembly for a fuel cell, a fuel cell catalyst layer previously formed on an electrode substrate is bonded to one or both sides of a solid polymer electrolyte membrane by thermocompression bonding. The fuel cell electrode may be prepared by forming a catalyst layer for a fuel cell previously formed on a transfer substrate on a solid polymer electrolyte membrane by transfer and then thermocompression-bonding the electrode substrate. A membrane assembly may be produced. At this time, the electrode base material on which the fuel cell catalyst layer is formed in advance can be used.

In the fuel cell electrode membrane assembly described above, the pressure level when thermocompression bonding between the electrode substrate, the fuel cell catalyst layer, and the solid polymer electrolyte membrane is usually about 0.1 Mpa to 100 Mpa, preferably 1 Mpa to About 20 Mpa is good. The heating temperature is usually 200 ° C. or lower, preferably about 120 to 150 ° C., in order to avoid damage or modification of the solid polymer electrolyte membrane.

The electrode membrane assembly of the present invention may include a microporous layer on the side of the catalyst layer that contacts the electrode substrate. This layer is handled as a part of the catalyst layer, or is also called a water repellent layer or MPL (micro porous layer), in addition to uniform gas supply to the catalyst layer and improved conductivity. It has the role of improving the drainage of water generated during power generation on the cathode side. The water-repellent layer or MPL can be formed, for example, by applying a carbon material or a carbon-based catalyst material and an ink composition containing a water-repellent material onto a carbon paper substrate and firing at about 300 ° C. The catalyst paste composition can also be suitably used.

<Solid polymer electrolyte membrane>
Examples of the solid polymer electrolyte membrane include perfluorosulfonic acid-based fluorine ion exchange resins. By introducing a fluorine atom having a high electronegativity, it is chemically very stable, the degree of sulfonic acid group dissociation is high, and high ionic conductivity can be realized. Specific examples of such a hydrogen ion conductive polymer electrolyte include “Nafion” manufactured by DuPont, “Flemion” manufactured by Asahi Glass Co., Ltd., “Aciplex” manufactured by Asahi Kasei Co., Ltd., and Gore manufactured by Gore. Examples include films formed using “Gore Select” or the like. The thickness of the electrolyte membrane is usually about 20 μm to 250 μm, preferably about 20 μm to 80 μm.

<Electrode substrate (gas diffusion layer)>
The electrode base material is well known, and various electrode base materials constituting a fuel electrode or an air electrode can be used. The electrode base material may be any material having conductivity, but preferably carbon paper made of carbon fiber.
The electrode substrate is also called a gas diffusion layer or GDL and is porous or fibrous so that gas can pass and diffuse so that oxygen in the air can be taken in on the cathode side and hydrogen can be taken in on the anode side. It is preferable. Furthermore, since it is necessary to take in and out electrons, a conductive material must be used. Usually used are carbon paper base materials and the like.

<Transfer substrate>
The transfer substrate is a film substrate for applying a catalyst ink composition to form a fuel cell catalyst layer and transferring the catalyst layer on the transfer substrate to a solid polymer electrolyte membrane such as Nafion. As the transfer substrate, a polymer film that is inexpensive and easily available is preferable, and polytetrafluoroethylene, polyimide, polyethylene terephthalate, and the like are more preferable. The thickness of the transfer substrate is usually about 6 μm to 100 μm, preferably about 10 μm to 50 μm, more preferably about 15 μm to 30 μm, from the viewpoints of handleability and economy.

<Fuel cell>
Since the fuel cell of the present invention is superior in dispersibility of the fuel cell catalyst paste composition and the fuel cell catalyst ink composition as compared with the conventional fuel cell, the carbon-based catalyst material can be suitably brought into contact with a gas such as oxygen gas. Thus, the oxygen reduction potential and the oxygen reduction current density (sometimes simply referred to as current density) are improved, and the coating unevenness and pinholes are small, so that the durability is excellent.

  Below, an example of the method of evaluating the performance of a fuel cell is shown. A fuel cell electrode membrane assembly is used as a sample of 4 cm square, and two gaskets are sandwiched from both sides thereof, then two separators which are graphite plates are sandwiched, and two current collector plates are further attached from both sides to produce a single cell. . Battery characteristics are measured by supplying humidified oxygen gas from the cathode (air electrode) side and supplying humidified hydrogen gas from the anode (fuel electrode) side.

  As described above, the fuel cell catalyst layer produced using the fuel cell catalyst paste composition or fuel cell catalyst ink composition of the present invention is likely to come into contact with a gas such as oxygen gas. As a result, there are advantages that the oxygen reduction potential and current density are improved, coating unevenness and pinholes are small, and durability is excellent. Therefore, the fuel cell produced using the fuel cell catalyst layer and the fuel cell electrode membrane assembly of the present invention is more economical and cost superior than the conventional fuel cell, and the catalyst is poisoned. It has the advantage that it is excellent in durability.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

  Regarding the dispersant, “one kind selected from the group consisting of an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, an acridone derivative having a basic functional group, and a triazine derivative having a basic functional group” Hereinafter, the description of “the derivative” may be abbreviated as “derivative having a basic functional group”. In addition, the description of “one or more derivatives selected from the group consisting of an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group” is hereinafter abbreviated as “a derivative having an acidic functional group”. There is. Furthermore, the description of “various derivatives having basic functional groups” or “various derivatives having acidic functional groups” may be abbreviated as “derivatives having basic functional groups or acidic functional groups”.

  The “polymerization average molecular weight (Mw)” of the resin having an acidic functional group is a polystyrene equivalent value measured using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus.

  In addition, “polymerization average molecular weight (Mw)” of a resin having a basic functional group uses HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, SUPER-AW3000 as a column, and 30 mM triethylamine as an eluent. And it is the polystyrene conversion value obtained by measuring using the N, N- dimethylformamide solution of 10 mM LiBr.

  The acid value was measured based on "JIS K 2501-2003 Petroleum products and lubricants-Neutralization number test method". The sample was dissolved in a titration solvent in which xylene and dimethylformamide (1 + 1) were mixed, and titrated with a 0.1 mol / L potassium hydroxide / ethanol solution by potentiometric titration, and the inflection point on the titration curve was taken as the end point. The acid value was calculated from the titration amount to the end point of the potassium hydroxide solution. The amine value is a measured value obtained by the method of ASTM D 2074.

<Dispersant>
<Compound having a basic functional group: a derivative having a basic functional group>
Dispersants A to O shown in Tables 1 to 4, and more specifically classified as follows.
Organic pigment derivatives having basic functional groups: A, B, C, D, E, H
Anthraquinone derivatives having basic functional groups: F, L
・ Acridone derivatives having basic functional groups: G
Triazine derivatives having basic functional groups: H, I, J, K, L, M, N, O

<Compound without basic functional group and acidic functional group>
Dispersants P and Q shown in Table 5 are used for comparison in the present invention.

<Compound having basic functional group: resin having basic functional group>
Resin having basic functional group Polymer G1 type G1-1: Polyvinyl polymer having amino group; weight average molecular weight 13500, amine value 27.5 mg KOH / g.
G1-2: Polyvinyl polymer having an amino group; the weight average molecular weight is 21600, and the amine value is 17.4 mg KOH / g.
G1-3: Polyvinyl polymer having an amino group; weight average molecular weight 11900, amine value 25.2 mg KOH / g.

  The preparation methods of the polymers G1-1 to G1-3 are as follows.

<Preparation of Vinyl Resin Polymer G1-1 Having Amino Group>
<Synthesis of vinyl polymer A1-1>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 500 parts of methyl methacrylate, 28 parts of thioglycerol, and 528 parts of N-methyl-2-pyrrolidone, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of AIBN was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature, and a 50% solid content solution of vinyl polymer A-1 having a weight average molecular weight of 4200 and having two free hydroxyl groups in one end region was obtained. Obtained.

<Synthesis of Polymer G1-1>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 1022 parts of a 50% solid content solution of vinyl polymer A1-1, 45.2 parts of isophorone diisocyanate, and 0.11 g of dibutyltin dilaurate as a catalyst Charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C., reacted for 3 hours, cooled to 40 ° C., and mixed with 30% in a mixed solution of 26.7 parts iminobispropylamine and 363.3 parts N-methyl-2-pyrrolidone. The mixture was added dropwise over a period of minutes, and the reaction was further continued for 1 hour, followed by cooling to room temperature to complete the reaction. The solid content was adjusted to 40% to obtain a pale yellow transparent solution of the polymer G1-1. The weight average molecular weight of the polymer G1-1 was 13500, and the amine value was 27.5 mg KOH / g.

<Preparation of Vinyl Resin Polymer G1-2 Having Amino Group>
<Synthesis of vinyl polymer A1-2>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 500 parts of n-butyl methacrylate, 28 parts of thioglycerol, and 528 parts of N-methyl-2-pyrrolidone were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of AIBN was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature, and a 50% solid content solution of vinyl polymer A1-2 having a weight average molecular weight of 4800 and having two free hydroxyl groups in one end region was obtained. Obtained.

<Synthesis of Polymer G1-2>
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 1056 parts of a 50% solid solution of vinyl polymer (A1-2), 115.1 parts of isophorone diisocyanate, and dibutyltin dilaurate as a catalyst 0. 12 g was charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C., reacted for 3 hours, cooled to 40 ° C., 25.5 parts of iminobispropylamine, 11.5 parts of 2-amino-2-methyl-propanol, N -Methyl-2-pyrrolidone The mixture was added dropwise to 492.0 parts of a mixed solution over 30 minutes, reacted for another 1 hour, and then cooled to room temperature to complete the reaction. The solid content was adjusted to 40% to obtain a pale yellow transparent solution of polymer G1-2. The weight average molecular weight of the polymer G1-2 was 21600, and the amine value was 17.4 mg KOH / g.

<Preparation of vinyl-based resin polymer G1-3 having amino group>
<Synthesis of vinyl polymer A1-3>
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 400 parts of methyl methacrylate, 100 parts of butyl acrylate, 56 parts of thioglycerol, and 556 parts of N-methyl-2-pyrrolidone. Replaced. The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of AIBN was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature, and a 50% solid content solution of vinyl polymer A1-3 having a weight average molecular weight of 3000 and having two free hydroxyl groups in one end region was obtained. Obtained.

<Synthesis of Polymer G1-3>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 1112 parts of a 50% solid solution of vinyl polymer A1-3, 230.2 parts of isophorone diisocyanate, and 0.13 g of dibutyltin dilaurate as a catalyst Charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C., reacted for 3 hours, cooled to 40 ° C., 56.4 parts of methyliminobispropylamine, 33.4 parts of dibutylamine, and N-methyl-2-pyrrolidone. The mixture was added dropwise to 757.9 parts of the mixture over 30 minutes, and the reaction was further continued for 1 hour, followed by cooling to room temperature to complete the reaction. The solid content was adjusted to 40% to obtain a pale yellow transparent solution of polymer G1-3. The weight average molecular weight of the polymer G1-3 is 11900, and the amine value is 25.2 mg.
KOH / g.

Resin having basic functional group Polymer G2 type G2-1: Polyester polymer having amino group; weight average molecular weight 13000, amine value 36 mgKOH / g.
G2-2: Polyester polymer having an amino group; weight average molecular weight 27000, amine value 41 mgKOH / g.
G2-3: Polyvinyl polymer having an amino group; weight average molecular weight 15200, amine value 94 mgKOH / g.

The preparation methods of the polymers G2-1 to G2-3 are as follows. <Preparation of polyester polymer G2-1 having an amino group>
<Synthesis of polyester A2-1 having an acryloyl group at one end>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 20.8 parts of 4-hydroxybutyl acrylate and 379 parts of ε-caprolactone, 0.1 part of monobutyltin (IV) oxide as a catalyst, and as a polymerization inhibitor 0.1 part of hydroquinone was added, heated and stirred at 120 ° C. for 4 hours under a dry air flow, and the reaction was terminated after confirming that 95% had reacted by solid content measurement, and 171 parts of N-methyl-2-pyrrolidone was added. Further, the solid content was adjusted to 70% by weight to obtain a 70% solids solution of polyester A2-1 having a weight average molecular weight of 6500 and one acryloyl group at one end.

<Synthesis of Polymer G2-1>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 18.9 parts of iminobispropylamine and 248 parts of N-methyl-2-pyrrolidone were charged and heated to 50 ° C. to obtain polyester A2-1. 571 parts of a 70 wt% solid solution was added dropwise over 30 minutes, and after further reaction for 1 hour, a mixed solution of 16.0 parts of isophorone diisocyanate and 112 parts of N-methyl-2-pyrrolidone was added dropwise over 30 minutes, The reaction was further continued for 2 hours, N-methyl-2-pyrrolidone was added to adjust the solid content to 30% by weight, and a solid content 30% by weight solution of polymer G2-1 having a weight average molecular weight of 13,000 and an amine value of 36 mgKOH / g. Got.

<Preparation of polyester polymer G2-2 having an amino group>
<Synthesis of Polymer G2-2>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 23.9 parts of methyliminobispropylamine and 248 parts of N-methyl-2-pyrrolidone and heated to 50 ° C. to obtain polyester A2-1. 571 parts of a 70% by weight solids solution was added dropwise over 30 minutes, and the reaction was continued for another hour, followed by dropwise addition of a mixture of 18.3 parts isophorone diisocyanate and 207 parts N-methyl-2-pyrrolidone over 30 minutes. The mixture was further reacted for 2 hours, N-methyl-2-pyrrolidone was added to adjust the solid content to 30% by weight, and the solid content of the polymer G2-2 having a weight average molecular weight of 27,000 and an amine value of 41 mgKOH / g was 30% by weight. A solution was obtained.

<Preparation of vinyl polymer G2-3 having amino group>
<Synthesis of vinyl polymer A2-2 having an acryloyl group at one end>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 400 parts of methyl methacrylate, 100 parts of butyl acrylate, and 100 parts of N-methyl-2-pyrrolidone and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and a solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved in 27.5 parts of 3-mercapto-1,2-propanediol was added. Reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement, diluted with 427 parts of N-methyl-2-pyrrolidone, and then 32.6 parts of acryloyloxyethyl isocyanate, 1 part of DBTDL, 3 parts was added, and the mixture was further heated and stirred for 2 hours. Further, the solid content was adjusted to 50% by weight, and the solid content of vinyl polymer A2-2 having a weight average molecular weight of 4500 and having two acryloyl groups at one end was 50. A weight percent solution was obtained.

<Synthesis of Polymer G2-3>
Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 27.8 parts of iminobispropylamine and 184 parts of N-methyl-2-pyrrolidone were charged and heated to 50 ° C. to be vinyl polymer A2- 500 parts of a 70% by weight solid content solution of 2 was added dropwise over 30 minutes, and after another 1 hour of reaction, a mixed solution of 15.7 parts of isophorone diisocyanate and 121 parts of N-methyl-2-pyrrolidone was added dropwise over 30 minutes. The mixture was further reacted for 2 hours, N-methyl-2-pyrrolidone was added to adjust the solid content to 30% by weight, and the solid content of polymer G2-3 having a weight average molecular weight of 15200 and an amine value of 94 mgKOH / g was 30%. % Solution was obtained.

-Resin G3 having a basic functional group other than the polymers G1 and G2
G3-1: Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd., resin having amino group G3-2: SOLPERSE24000GR, manufactured by Nippon Lubrizol Co., Ltd., resin having amino group

-Vinylamide resin G3-3: PVP K-30 (trade name, manufactured by ISP Japan): polyvinylpyrrolidone (abbreviated as PVP), weight average molecular weight of about 40,000 to 80,000.
G3-4: PNVA GE191 (manufactured by Showa Denko KK, trade name): poly N-vinylacetamide (abbreviated as PNVA) weight average molecular weight of about 1 to 30,000.

<Compound having acidic functional group: Derivative having acidic functional group>
Dispersants Da to Ds shown in Tables 6 to 10, and more specifically classified as follows. Organic dye derivatives having acidic functional groups: Da, Dk, Dl, Dm, Dn, Do, Dp, Dq, Dr, Ds Triazine derivatives having acidic functional groups: Da, Db, Dc, Dd, De, Df, Dg, Dh, Di, Dj, Dp, Dr

  Derivative Dm having acidic functional group: At the time of preparation of the catalyst paste composition, 1 equivalent of ammonia was added to the sulfonic acid form (no salt formation) to obtain an ammonium salt product.

  Derivative Ds having acidic functional group: During preparation of the catalyst paste composition, 1 equivalent of ammonia was added to the sulfonic acid form (no salt formation) to obtain an ammonium salt product.

<Acid compound: inorganic acid, organic acid having a molecular weight of 300 or less>
For inorganic acids and organic acids having a molecular weight of 300 or less, the compounds shown in Table 11 described later were added according to the composition shown in Table 11.

<Acid compound: resin having an acidic functional group>
・ Polyvinyl resin H1 type with acidic functional group
<Preparation of Polyvinyl Resin H1-1 Having Carboxyl Group>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic anhydride, 231 parts of N-methyl-2-pyrrolidone and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was heated at 120 ° C. for 7 hours. Reacted. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and a polyvinyl resin H1-1 solution having a carboxyl group with a solid content of 50% was obtained. The obtained polyvinyl resin H1-1 had a weight average molecular weight (Mw) of 8,500 and an acid value of 43 mgKOH / g.

<Preparation of Polyvinyl Resin H1-2 Having Carboxyl Group>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 180 parts of methyl methacrylate and 20 parts of methacrylic acid and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic anhydride, 231 parts of N-methyl-2-pyrrolidone and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was heated at 120 ° C. for 7 hours. Reacted. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, the reaction was terminated, and a polyvinyl resin H1-2 solution having a carboxyl group with a solid content of 50% was obtained. The obtained polyvinyl resin H1-2 had a weight average molecular weight (Mw) of 8,600 and an acid value of 93 mgKOH / g.

<Preparation of Polyvinyl Resin H1-3 Having Carboxyl Group>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 160 parts of ethyl acrylate, 30 parts of methyl methacrylate, and 10 parts of methacrylic acid, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic anhydride, 231 parts of N-methyl-2-pyrrolidone and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and the mixture was heated at 120 ° C. for 7 hours. Reacted. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. Thus, a polyvinyl resin H2-3 solution having a carboxyl group with a solid content of 50% was obtained. The obtained polyvinyl resin H1-3 had a weight average molecular weight (Mw) of 8,400 and an acid value of 70 mgKOH / g.

-Polyester resin H2 type having acidic functional group <Preparation of polyester resin H2-1 having carboxyl group>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added, and it was made to react at 120 degreeC for 2 hours, and the polyester-type resin (H2-1) which has a carboxyl group was obtained. The obtained polyester resin H2-1 was a white wax-like solid at room temperature.

<Preparation of polyester-based resin H2-2 having a carboxyl group>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 169.0 parts of methoxy PEG 400 (one-end methoxylated polyethylene glycol; molecular weight 400), 96.4 parts of ε-caprolactone, 84. of δ-valerolactone. 6 parts and 0.1 part of monobutyltin (IV) oxide as a catalyst were charged and replaced with nitrogen gas, and then heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 62.2 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at 120 ° C. for 2 hours to have a carboxyl group. Polyester resin H2-2 was obtained. The obtained polyester resin H2-2 was a pale yellow transparent liquid at room temperature.

Resin H3H3-1 having a functional group other than the above H1 to H2 types: Disperbyk-111 (manufactured by Big Chemie, trade name): Resin having a phosphate group H3-2: Aqualon EC N100 ethylcellulose (manufactured by Hercules) H3- 3: Carboxymethylcellulose (CMC1380 manufactured by Daicel Finechem) <Production example of carbon-based catalyst material> [Production example 1: Preparation of carbon-based catalyst material X1]
Using polyvinyl pyridine (manufactured by Aldrich: Mw: 60,000) as a starting material, 10 g of polyvinyl pyridine iron (II) complex is obtained, and 10 g of this ketjen black EC300 (manufactured by Lion Corporation) is dry-mixed in a mortar for 20 minutes. Then, it was baked in an electric furnace under a nitrogen atmosphere (0.5 L / min) at 800 ° C. for 1 hour (temperature rising 1.5 hours). The fired product was dry-ground with a mortar and classified with a 150 mesh sieve. Furthermore, in order to remove the metal, stirring and decantation were repeated three times in 37% hydrochloric acid, and finally heat treatment was performed in an electric furnace under a nitrogen atmosphere (0.5 L / min) at 700 ° C. for 1 hour (temperature rising 2 hours). And then dry-pulverized and classified with 150 mesh to obtain a carbon-based catalyst material X1.

[Production Example 2: Preparation of carbon-based catalyst material X2]
13.1 g of metal-free phthalocyanine which is a nitrogen-containing compound is mixed with 10 g of furfuryl alcohol which is a precursor of furan resin, 10 g of 1M-hydrochloric acid is added, and this mixture is heated at 80 ° C. in an oven to thereby add phthalocyanine-containing furan. A resin was obtained. This was further heat-treated in a nitrogen atmosphere in an oven at a rate of 10 ° C./min from room temperature and kept at 1000 ° C. for 1 hour. As a result, a carbonized product of a phthalocyanine-containing furan resin was obtained. This carbonized product was pulverized with a planetary ball mill (manufactured by Lecce, PM100) to obtain a carbon-based catalyst material X2 having an average particle diameter of 0.1 μm doped with 13.4 mol% of nitrogen atoms.

[Production Example 3: Preparation of carbon-based catalyst material X3]
Iron phthalocyanine (manufactured by Sanyo Pigment) and Ketjen black (EC-300J by Lion) were weighed at a weight ratio of 1: 1 and dry-mixed in a mortar to obtain a precursor.
The precursor powder was filled into an alumina crucible and heat-treated at 700 ° C. for 2 hours in a nitrogen atmosphere in an electric furnace to obtain a carbon-based catalyst material X3.

[Production Example 4: Preparation of carbon-based catalyst material X4]
Cobalt phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) and Ketjen black (EC-600JD manufactured by Lion Corporation) were weighed at a weight ratio of 0.5: 1 and dry-mixed in a mortar to obtain a precursor.
The precursor powder was filled into an alumina crucible and heat-treated at 800 ° C. for 2 hours in a nitrogen atmosphere in an electric furnace to obtain a carbon-based catalyst material X4.

<Preparation of catalyst paste composition> [Example 1-1]
8 parts by weight of carbon-based catalyst material X1, 71.96 parts by weight of butanol (manufactured by Kishida Chemical Co., Ltd.) as a solvent, 0.04 parts by weight of polyvinylpyrrolidone PVP K-30 (manufactured by ISP Japan) as a dispersant (carbon-based catalyst material) The catalyst paste composition 1 of the present invention (solid content concentration: 10% by weight) is prepared by mixing and stirring with a disper (Primix, TK homodisper). did.

[Example 2-1 to Example 108-1]
A catalyst paste composition was prepared in the same manner as in Example 1-1 except that the types and compositions of the carbon-based catalyst material, the solvent, and the dispersant were changed to Tables 11, 12, 13 and 14.

[Comparative Examples 1-1 to 8-1 Preparation of catalyst paste composition]
A catalyst paste composition was prepared in the same manner as Example 1-1 except that the dispersant was not used.

[Comparative Examples 9-1 to 13-1 Preparation of Catalyst Paste Composition]
A catalyst paste was prepared in the same manner as in Example 1-1 except that the dispersants P and Q having no basic and acidic functional groups described in Table 5 were used as the dispersant, and the addition amounts described in Table 12 were used. A composition was prepared.

[Comparative Examples 14-1 to 17-1 Preparation of Catalyst Paste Composition]
A catalyst paste composition was prepared in the same manner as in Example 1-1 except that the following comparative resin was used as a dispersant.
Comparative resin: PTFE 30-J (Mitsui / Dupont Fluoro Chemical Co.): 60% polytetrafluoroethylene (PTFE) aqueous dispersion

<Evaluation of catalyst paste composition>

The dispersibility of the catalyst paste composition was evaluated by viscosity and particle size.
The viscosity was measured using an E type viscometer (“RE80 type viscometer” manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 50 rpm and a temperature of 25 ° C.
For the particle size, the volume particle size distribution was measured using a dynamic light scattering particle size distribution meter ("MICROTRACK UPA" manufactured by Nikkiso Co., Ltd.), and the volume ratio of the particles from the fine particle size was integrated. The average particle size (D ₅₀ ) at which it sometimes becomes 50% was taken as the particle size.
Tables 15 and 16 show the results of evaluation of dispersibility of the catalyst ink composition. The lower the viscosity and the smaller the particle size, the better the dispersibility.

[Example 1-2 Preparation of catalyst ink composition]
To the catalyst paste composition obtained in Example 1-1, 20 parts by weight of a 20 wt% Nafion solution (hydrogen ion conductive polymer, manufactured by DuPont, solvent: water and 1-propanol) was added, and a disper ( Catalyst ink composition (solid content concentration 12% by weight, catalyst ink composition 100% by weight carbon-based catalyst material and hydrogen ion conductive polymer by stirring and mixing with Primix Co., Ltd., TK homodisper) (Total ratio) was prepared.

[Example 2-2 to Example 108-2, Comparative Example 1-2 to Comparative Example 17-2]
The catalyst paste composition obtained in Example 1-1 was changed to the catalyst paste composition obtained in Example 2-1 to Example 108-1 and Comparative Example 1-1 to Comparative Example 17-1, respectively. Were prepared in the same manner as in Example 1-2 to prepare catalyst ink compositions, respectively.

<Evaluation of catalyst ink composition>
The catalyst ink composition was evaluated by the following electrochemical evaluation, storage stability evaluation, and dispersibility evaluation.

(Electrochemical evaluation)
Electrochemical evaluation of the catalyst ink composition was carried out using an RRDE-3A rotating leading electrode device to measure an oxygen reduction start potential (oxygen reduction potential) and an oxygen reduction current (current value) by linear sweep voltammetry measurement. The measurement procedure of linear sweep voltammetry is shown below. The catalyst ink composition was diluted with ethanol, and a measurement sample was prepared so that the solid content concentration was 1% by weight. 5 μL of this sample was collected, applied on the glassy carbon of the rotating electrode, and dried in a saturated water vapor atmosphere. The dried rotating electrode was used as a working electrode, the Ag / AgCl electrode was used as a reference electrode, and a platinum wire was used as a counter electrode, and the baseline was measured by degassing with nitrogen gas in 0.5 M sulfuric acid as an electrolyte for 30 minutes. Then it was degassed with oxygen for 30 minutes. The measurement was performed in the range of 0.8 V vs Ag / AgCl to -0.2 V vs Ag / AgCl at a sweep speed of 5 mV / s and a rotation speed of 2000 rpm. The oxygen reduction potential was read when the oxygen reduction current density was 10 μA / cm ² , and the oxygen reduction current density was read when the oxygen reduction potential was 0.05V. All voltages were converted to potentials based on a reversible hydrogen electrode.

  The results of electrochemical evaluation of the catalyst ink composition are shown in Table 17 and Table 18. The higher the oxygen reduction potential and the higher the oxygen reduction current value density, the better the oxygen reduction catalytic ability.

(Storage stability evaluation)
The storage stability of the catalyst ink composition was determined by measuring the viscosity immediately after preparation (initial viscosity) and the viscosity after storage at 50 ° C. for 3 days (time-dependent viscosity), and the rate of change in viscosity (time-dependent viscosity / initial viscosity). Evaluated by. The viscosities were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “RE80 viscometer”) at a rotation speed of 50 rpm and a temperature of 25 ° C.

  Tables 17 and 18 show the results of the storage stability evaluation of the catalyst ink composition. The smaller the viscosity change rate, the better the storage stability. In addition, in the catalyst ink composition of the present invention, no occurrence of precipitates was observed, no increase in viscosity was observed even after storage at 20 ° C. for 3 months, and the coating property after storage was good, It was confirmed that a uniform coating film was obtained.

(Dispersibility evaluation)
The dispersibility was determined by a grind gauge (according to JIS K5600-2-5), and the particle size of the catalyst ink composition was determined. When there was no aggregate of 30 μm or more, the dispersibility was evaluated as good. The catalyst ink compositions of the present invention were all 10 to 20 μm and the dispersibility was good, whereas the catalyst ink compositions obtained in Comparative Examples 1-2 to 17-2 were all 30 μm or more. The aggregate was confirmed, and it was confirmed that the dispersibility was inferior.

<Creation of fuel cell catalyst layer>
[Example 1-3 Preparation of catalyst layer 1 for fuel cell]
The catalyst ink composition obtained in Example 1-2 was applied onto a Teflon (registered trademark) film with a doctor blade so that the basis weight of the carbon-based catalyst material after drying was 2 mg / cm ² , and the atmosphere Then, the catalyst layer 1 for a cathode fuel cell of the present invention was produced by drying at 95 ° C. for 15 minutes.

[Example 2-3 to Example 108-3, Comparative Example 1-3 to Comparative Example 17-3]
The catalyst ink composition obtained in Example 1-2 was changed to the catalyst ink composition obtained in Example 2-2 to Example 108-2 and Comparative Example 1-2 to Comparative Example 17-2, respectively. The cathode fuel cell catalyst layer 1 was prepared in the same manner as in Example 1-3.

(Evaluation of coatability) The fuel cell catalyst layer was evaluated by the following coatability evaluation. The fuel cell catalyst layer 1 formed on the Teflon (registered trademark) film was observed with a video microscope VHX-900 (manufactured by Keyence Corporation) at a magnification of 500 times, and coating unevenness (unevenness: evaluated by the density of the catalyst layer) ) And pinholes (evaluated by the presence or absence of defects on which the catalyst layer is not applied) were determined according to the following criteria. The results are shown in Table 21 and Table 22.
(village)
○: The density of the catalyst layer is not confirmed (good).
(Triangle | delta): Although there are 2-3 shades of a catalyst layer, it is a very small area | region (it is satisfactory practically).
X: A large number of shades of the catalyst layer is confirmed, or one or more of the stripes having a length of 5 mm or more (defective).
(Pinhole)
○: No pinholes are confirmed (good).
Δ: There are 2 to 3 pinholes but they are very small (defect).
X: Many pinholes are confirmed, or one or more pinholes having a diameter of 1 mm or more (very poor).

[Fabrication of anode fuel cell catalyst layer 4]
Here, a method for producing a catalyst layer for an anode fuel cell used for producing an electrode membrane assembly for a fuel cell will be described below.
Instead of the carbon-based catalyst material, platinum catalyst-supporting carbon 4 parts by weight (manufactured by Tanaka Kikinzoku Co., Ltd., 46% platinum), butanol (made by Kishida Chemical Co., Ltd.) 56 parts by weight as a solvent, and water 20 parts by weight are dispersed (primics, A catalyst paste composition (solid content concentration 4% by weight) was prepared by stirring and mixing with a TK homodisper. Next, 20 parts by weight of a 20 wt% Nafion solution (hydrogen ion conductive polymer, manufactured by DuPont, solvent: water and 1-propanol) was added and stirred with a disper (Primix, TK homodisper). A catalyst ink composition having a solid content concentration of 8% by weight and a catalyst ink composition of 100% by weight was prepared by mixing. The resulting catalyst ink composition had a basis weight of platinum catalyst-carrying carbon of 0. A catalyst layer 4 for an anode fuel cell was produced by coating on a Teflon (registered trademark) film so as to be .46 mg / cm ^2, and drying for 15 minutes at 95 ° C. in an air atmosphere.

[Example 1-4 Production of fuel cell electrode membrane assembly]
The cathode fuel cell catalyst layer 1 and the anode fuel cell catalyst layer 4 prepared in Example 1-3 were adhered to both surfaces of a solid polymer electrolyte membrane (Nafion 212, manufactured by DuPont, film thickness 50 μm). Then, after sandwiching at 150 ° C. and 5 MPa, the Teflon (registered trademark) film was peeled off. Next, the electrode base material (gas diffusion layer GDL, carbon paper made of carbon fiber, TGP-H-090, manufactured by Toray Industries, Inc.) is further adhered from both sides, and the fuel cell electrode membrane assembly (GDL / Catalyst layer / solid polymer electrolyte membrane / catalyst layer / GDL).

[Example 2-4 to Example 108-4, Comparative Example 1-4 to Comparative Example 17-4]
Instead of the fuel cell catalyst layer 1 produced in Example 1-3, the fuel cell catalyst layer obtained in Example 2-3 to Example 108-3 and Comparative Example 1-3 to Comparative Example 17-3, respectively. A fuel cell electrode membrane assembly was produced in the same manner as in Example 1-4, except that the number was changed to 1.

  The fuel cell electrode membrane assemblies (GDL / catalyst layer / solid polymer electrolyte membrane / catalyst layer / GDL) of the present invention prepared in Examples 1-4 to 108-4 were cracked in the catalyst layer after transfer. A uniform electrode film without any chipping was formed. On the other hand, the fuel cell electrode membrane assemblies produced in Comparative Examples 1-4 to 17-4 all had poor conditions such as cracks and chipping during transfer.

[Example 1-5 Production of fuel cell (single cell)]
The fuel cell electrode membrane assembly obtained in Example 1-4 was used as a 4 cm square sample, sandwiched between two gaskets from both sides and then two separators, which were graphite plates, and two current collector plates from both sides. A fuel cell (single cell) was prepared by mounting. The measurement was carried out by Auto PEM series “PEFC evaluation system” manufactured by Toyo Technica. The cell characteristics were measured by supplying humidified oxygen gas from the cathode (air electrode) side and supplying humidified hydrogen gas from the anode (fuel electrode) side.

[Example 2-5 to Example 108-5, Comparative Example 1-5 to Comparative Example 17-5]
Instead of the electrode membrane assembly for fuel cell of Example 1-4 used in Example 1-5, Example 2-4 to Example 108-4 and Comparative Example 1-4 to Comparative Example 17-4, respectively A single cell of the fuel cell was produced in the same manner as in Example 1-5, except that the electrode membrane assembly for a fuel cell was changed.

(Evaluation of fuel cell (single cell))
The battery performance was evaluated by measuring the current-voltage characteristics of the single cells produced in Example 1-5 to Example 108-5 and Comparative Example 1-5 to Comparative Example 17-5. The results are shown below. In the single cell produced in Example 1-5, the open circuit voltage was 0.85 V and the short-circuit current density was 1000 mA / cm ^{2. Even} in the single cells produced in Examples 2-5 to 108-5, the open circuit voltage was 0. They were 8V-0.85V and short circuit current density 600-1200mA / cm < ² >. In contrast, the single cell produced in Comparative Example 1-5～17-5, open voltage 0.7V～0.77V, was short-circuit current density ^{400mA / cm 2 ~600mA / cm 2} .

<Method for Directly Applying to Gas Diffusion Layer to Create Fuel Cell Catalyst Layer>
Hereinafter, a method for preparing a fuel cell catalyst layer by directly applying the catalyst ink composition of the present invention to a gas diffusion layer will be described.

[Example 1-1B Preparation of catalyst paste composition]
A catalyst paste composition having a solid concentration of 20% by weight was obtained in the same manner as in Example 1-1, except that in Example 1-1, butanol was changed to 31.96 parts by weight.

[Example 2-1B to Example 108-1B]
In Example 2-1 to Example 108-1, except that butanol was changed to 31.96 parts by weight, in the same manner as Example 2-1 to Example 108-1, the solid content concentration was 20% by weight, respectively. The catalyst paste composition was obtained.

[Comparative Example 1-1B to Comparative Example 17-1B]
In Comparative Example 1-1 to Comparative Example 17-1, except that butanol was changed to 31.96 parts by weight, a catalyst paste composition having a solid content concentration of 20% by weight was obtained in the same manner as Example 1-1B. However, precipitation occurred and a catalyst paste composition could not be obtained. As a result of trying to increase the solid content concentration, the carbon-based catalyst material seems to have agglomerated and sedimented.

[Example 1-2B Preparation of catalyst ink composition]
To the catalyst paste composition prepared in Example 1-1B, 20 parts by weight of a 20% by weight Nafion solution (hydrogen ion conductive polymer, manufactured by DuPont, solvent: water and 1-propanol) was further added. Catalyst ink composition (carbon-based catalyst material and hydrogen ion conductive polymer when solid content concentration is 20% by weight and catalyst ink composition is 100% by weight by stirring and mixing with Primix, TK homodisper) (Total ratio) was prepared. The viscosity was 104 mPa · s.

[Example 2-2B to Example 108-2B]
Except for changing the catalyst paste composition obtained in Example 1-1B to the catalyst paste composition obtained in Example 2-1B to Example 108-1B, respectively, the same as in Example 1-2B, In each case, a catalyst ink composition was prepared. All the viscosities were 80 to 120 mPa · s.

[Example 1-3B Production of catalyst layer 2 for fuel cell]
The catalyst ink composition obtained in Example 1-2B was dried with a doctor blade so that the basis weight of the carbon-based catalyst material after drying was 2 mg / cm ² (carbon paper made of carbon fiber, TGP- H-090, manufactured by Toray Industries, Inc.) and dried in an air atmosphere at 95 ° C. for 15 minutes to produce a catalyst layer 2 for a cathode fuel cell of the present invention. A good fuel cell catalyst layer 2 could be formed with no coating unevenness and no dripping from the carbon paper.

[Example 2-3B to Example 108-3B]
Except for changing the catalyst ink composition obtained in Example 1-2B to the catalyst ink composition obtained in Example 2-2B to Example 108-2B, respectively, in the same manner as in Example 1-3B, respectively. Then, a catalyst layer 2 for a cathode fuel cell was prepared.

[Example 1-4B Production of electrode membrane assembly for fuel cell]
Using the cathode fuel cell catalyst layer 2 (catalyst ink composition fixed to carbon paper) and the anode fuel cell catalyst layer 4 prepared in Example 1-3B, a solid polymer electrolyte membrane (Nafion 212, DuPont) was used. After being held at 150 ° C. and 5 Mpa so as to be in contact with the film thickness of 50 μm, the Teflon (registered trademark) film on the anode side is peeled off, and the electrode substrate (carbon made of carbon fiber) is further peeled off from the anode side. Paper, TGP-H-090, manufactured by Toray Industries, Inc.), that is, gas diffusion layer GDL, and electrode membrane assembly for fuel cell of the present invention (GDL / catalyst layer / solid polymer electrolyte membrane / catalyst layer / GDL) Was made.

[Example 2-4B to Example 108-4B]
Instead of the fuel cell catalyst layer 2 of Example 1-3B, it was the same as Example 1-4B, except that the fuel cell catalyst layer 2 obtained in Example 2-3B to Example 108-3B was used. Thus, an electrode membrane assembly for a fuel cell was produced.

[Example 1-5B Production of Fuel Cell]
The fuel cell electrode membrane assembly obtained in Example 1-4B was used as a sample of 4 cm square, sandwiched between two gaskets from both sides and then two separators as graphite plates, and two current collector plates from both sides. A fuel cell (single cell) was prepared by mounting. The measurement was carried out by Auto PEM series “PEFC evaluation system” manufactured by Toyo Technica. The cell characteristics were measured by supplying humidified oxygen gas from the cathode (air electrode) side and supplying humidified hydrogen gas from the anode (fuel electrode) side.

[Example 2-5B to Example 108-5B]
Instead of the electrode membrane assembly for fuel cell of Example 1-4B used in Example 1-5B, it was changed to the electrode membrane assembly for fuel cell obtained in Example 2-4B to Example 108-4B, respectively. Except for the above, a fuel cell was fabricated in the same manner as in Example 1-5B.

<Fuel cell single cell evaluation>
About the single cell produced in Example 1-5B-Example 108-5B, the battery performance was evaluated by measuring a current-voltage characteristic, respectively. The results are shown below. In the single cell manufactured in Example 1-5B, the open-circuit voltage is 0.87 V and the short-circuit current density is 1200 mA / cm ^{2. Even} in the single cells manufactured in Examples 2-5B to 108-5B, the open-circuit voltage is It was 0.8 V to 0.88 V, and the short circuit current density was 700 to 1400 mA / cm ² .

[Example 1-2C Preparation of catalyst ink composition containing water repellent material]
To the catalyst paste composition obtained in Example 1-1, a 20 wt% PTFE dispersion (PTFE 30-J; manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd., 60% polytetrafluoroethylene aqueous dispersion was diluted with ion-exchanged water. 20 parts by weight, and a catalyst ink composition containing a water-repellent material (solid content concentration: 12% by weight, catalyst ink composition) The total proportion of the carbon-based catalyst material and the water-repellent material was 100% by weight. The viscosity was 24 mPa · s. The viscosity after the lapse of 3 days was 26 mPa · s.

[Example 2-2C to Example 108-2C]
A catalyst containing a water repellent material having a solid content concentration of 12% by weight, respectively, in the same manner as in Example 2-1 to Example 108-1, except that the 20% by weight Nafion dispersion was changed to a 20% by weight PTFE dispersion. An ink composition was obtained. All the viscosities were 20 to 30 mPa · s. Further, the viscosity after 3 days did not change greatly, and the viscosity change rate was 130% or less, and the storage stability was good.

[Comparative Example 1-2C to Comparative Example 17-2C]
A catalyst ink composition containing a water-repellent material in the same manner as in Example 1-2C except that in Comparative Example 1-1 to Comparative Example 17-1, the 20 wt% Nafion dispersion solution was changed to a 20 wt% PTFE dispersion solution. I got a thing. The viscosities were all 25 to 60 mPa · s, which was slightly higher than those of Examples 2-2C to 108-2C. In addition, a large change was observed in the viscosity after the lapse of 3 days, the rate of change in viscosity was 180% or more, and some sedimentation was also observed.

[Example 1-3C Fabrication of fuel cell catalyst layer 5 (water repellent layer)]
The catalyst ink composition containing the water-repellent material obtained in Example 1-2C was subjected to an electrode substrate (made of carbon fiber) by a doctor blade so that the basis weight of the carbon-based catalyst material after drying was 1 mg / cm ^2. This was coated on carbon paper, TGP-H-090, manufactured by Toray Industries, Inc., and baked in an air atmosphere at 300 ° C. for 60 minutes to produce a cathode fuel cell catalyst layer 5 of the present invention. A good fuel cell catalyst layer 5 could be formed without uneven coating.

[Example 1-3C to Example 108-3C]
Example 1 except that the catalyst ink composition containing the water repellent material obtained in Example 1-2C was changed to the water repellent catalyst ink composition obtained in Example 2-2C to Example 108-2C, respectively. Cathode fuel cell catalyst layers 5 were prepared in the same manner as in 3C.

[Comparative Examples 1-3C to Comparative Example 17-3C]
Example 1 except that the catalyst ink composition containing the water repellent material obtained in Example 1-2C was changed to the water repellent catalyst ink composition obtained in Comparative Example 1-2C to Comparative Example 17-2C, respectively. Cathode fuel cell catalyst layers 5 were prepared in the same manner as in 3C. The obtained catalyst layer had many coating unevenness and cracks. .

[Example 1-4C Production of electrode membrane assembly for fuel cell]
The cathode fuel cell catalyst layer 1 and the anode fuel cell catalyst layer 4 prepared in Example 1-3 were adhered to both surfaces of a solid polymer electrolyte membrane (Nafion 212, manufactured by DuPont, film thickness 50 μm). Then, after sandwiching at 150 ° C. and 5 MPa, the Teflon (registered trademark) film was peeled off. Next, an electrode substrate (gas diffusion layer GDL, carbon paper made of carbon fiber, TGP-H-090, manufactured by Toray Industries, Inc.) was closely attached to the anode side, and Example 1-3C was prepared on the cathode side. The fuel cell electrode membrane assembly (GDL / catalyst layer / solid polymer electrolyte membrane / catalyst layer / GDL) of the present invention was produced by closely contacting the cathode fuel cell catalyst layer 5.

[Example 2-4C to Example 108-4C]
Instead of the fuel cell catalyst layer 1 produced in Example 1-3, the fuel cell catalyst layer 1 obtained in Example 2-3 to Example 108-3 was changed, respectively, and on the cathode side, Example except that the fuel cell catalyst layer 5 obtained in Example 2-3C to Example 108-3C was adhered in place of the cathode fuel cell catalyst layer 5 produced in Example 1-3C. In the same manner as in 1-4C, a fuel cell electrode membrane assembly was produced.

[Comparative Examples 1-4C to Comparative Example 17-4C]
Instead of the fuel cell catalyst layer 1 produced in Example 1-3, the fuel cell catalyst layer 1 obtained in Comparative Example 1-3 to Example 17-3 was changed, respectively. Example except that the fuel cell catalyst layer 5 obtained in Comparative Example 1-3C to Comparative Example 17-3C was adhered in place of the cathode fuel cell catalyst layer 5 produced in Example 1-3C. In the same manner as in 1-4C, a fuel cell electrode membrane assembly was produced.

  The fuel cell electrode membrane assemblies (GDL / catalyst layer / solid polymer electrolyte membrane / catalyst layer / GDL) of the present invention prepared in Examples 1-4C to 108-4C were cracked in the catalyst layer after transfer. A uniform electrode film without any chipping was formed. On the other hand, all of the fuel cell electrode membrane assemblies produced in Comparative Examples 1-4C to 17-4C were in a poor state such as cracking or chipping during transfer.

[Example 1-5C Production of fuel cell (single cell)]
The fuel cell electrode membrane assembly obtained in Example 1-4C was used as a sample of 4 cm square, and sandwiched between two gaskets from both sides and then two separators as graphite plates, and two current collector plates from both sides. A fuel cell (single cell) was prepared by mounting. The measurement was carried out by Auto PEM series “PEFC evaluation system” manufactured by Toyo Technica. The cell characteristics were measured by supplying humidified oxygen gas from the cathode (air electrode) side and supplying humidified hydrogen gas from the anode (fuel electrode) side.

[Example 2-5C to Example 108-5C, Comparative Example 1-5C to Comparative Example 17-5C]
Instead of the electrode membrane assembly for fuel cell of Example 1-4C used in Example 1-5C, Example 2-4C to Example 108-4C and Comparative Example 1-4C to Comparative Example 17-4C were used, respectively. A single cell of the fuel cell was produced in the same manner as in Example 1-5C, except that the electrode membrane assembly for a fuel cell was changed.

(Evaluation of fuel cell (single cell))
The battery performance was evaluated by measuring the current-voltage characteristics of the single cells prepared in Example 1-5C to Example 108-5C and Comparative Example 1-5C to Comparative Example 17-5C. The results are shown below. In the single cell produced in Example 1-5C, the open circuit voltage was 0.88 V and the short circuit current was 1200 mA / cm ^{2. Even} in the single cells produced in Examples 2-5C to 108-5C, the open circuit voltage was 0.81 V. It was -0.88V and the short circuit current was 800-1400mA / cm < ² >. In contrast, the single cell produced in Comparative Example 1-5C～17-5C, open voltage 0.7～0.77V, were both the short-circuit current 300mA ^/ cm ² ~600mA ^/ cm 2 and low performance.

Claims (8)

A catalyst paste composition for a fuel cell, comprising a non-platinum-based carbon-based catalyst material in which a catalytic active site is a carbon atom in the vicinity of a heteroatom introduced at an edge of the carbon material surface, and a dispersant Fuel whose dispersant is a dispersant selected from the group consisting of resins having basic functional groups, resins having acidic functional groups, pigment derivatives having basic functional groups, pigment derivatives having acidic functional groups, and mixtures thereof A battery catalyst paste composition . Resin having a resin and / or an acidic functional group having a basic functional group, polyvinyl resin or polyester resin in which claim 1 for a fuel cell catalyst paste composition. Pigment derivative having a pigment derivative and / or an acidic functional group having a basic functional group, an organic dye derivative, an anthraquinone derivative, according to claim 1 which is acridone derivatives, triazine derivatives and pigment derivative selected from the group consisting of mixtures The catalyst paste composition for fuel cells as described. A fuel cell catalyst ink composition comprising the fuel cell catalyst paste composition according to any one of claims 1 to 3 , and at least one of a hydrogen ion conductive polymer or a water repellent material. A catalyst layer for a fuel cell formed from the catalyst ink composition for a fuel cell according to claim 4 . A water repellent layer for a fuel cell formed from the catalyst ink composition for a fuel cell according to claim 4 . A fuel cell electrode membrane assembly comprising a solid polymer electrolyte membrane, at least one of a fuel cell catalyst layer according to claim 5 or a water repellent layer for fuel cell according to claim 6, and a gas diffusion layer. . A fuel cell comprising the electrode membrane assembly for a fuel cell according to claim 7 .