JP5369667B2 - Positive electrode mixture paste for lithium secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stabilize diffusion of a positive electrode active material without limiting conductivity of the positive electrode active material in a positive electrode mixture paste for a lithium secondary battery, and improve binding force between a battery material powder and a binder constituent, as well as to improve performance of a battery produced by using this. <P>SOLUTION: The positive electrode mixture paste for a lithium secondary battery includes: one or more kinds of derivatives selected from a 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; a resin having a basic functional group; and a positive electrode active material. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a positive electrode mixture paste used for producing a positive electrode constituting a lithium secondary battery and a method for producing the same. In addition, the present invention is a lithium secondary comprising an electrode having excellent discharge characteristics or charge characteristics at a large current, cycle characteristics, and conductivity of an electrode mixture, and a small contact resistance between the electrode current collector and the electrode mixture. It relates to batteries.

  In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. These electronic devices have always been required to minimize the volume and reduce the weight, and the batteries to be mounted are also required to be small, light, and have a large capacity. Also, in large-sized secondary batteries for automobiles and the like, it is desired to realize a large-sized nonaqueous electrolyte secondary battery instead of the conventional lead-acid battery.

  In order to meet such demands, lithium secondary batteries are being actively developed. As an electrode of a lithium secondary battery, a positive electrode in which an electrode mixture composed of a positive electrode active material containing lithium ions, a conductive additive, an organic binder, and the like is fixed to the surface of a metal foil current collector, and a lithium ion A negative electrode is used in which an electrode mixture composed of a removable negative electrode active material, a conductive additive, an organic binder, and the like is fixed to the surface of a current collector of a metal foil.

  In general, as the positive electrode active material, lithium transition metal composite oxides such as lithium cobaltate, lithium manganate, or lithium nickelate are used, but these have low electronic conductivity and are not used alone. Sufficient battery performance cannot be obtained. Therefore, attempts have been made to improve the conductivity by reducing the internal resistance of the positive electrode by adding a carbon material such as carbon black (for example, acetylene black) as a conductive additive. In addition, in order to efficiently reduce internal resistance with a smaller amount of carbon black, both the positive electrode active material and the conductive auxiliary carbon material are required to be uniformly mixed at a finer level in the electrode. . In particular, reducing the internal resistance of the electrode is very important in enabling discharge with a large current and improving charge and discharge efficiency.

  However, the positive electrode active material, which is an inorganic component having high hydrophilicity, and the carbon material such as carbon black, which has high hydrophobicity, are greatly different from each other in physical properties on the particle surface, and as such, can be uniformly dispersed and mixed in the positive electrode mixture paste. This makes it difficult to achieve the maximum performance of the positive electrode active material and the carbon material that is the conductive additive, and a high improvement in battery performance cannot be expected. Also, if the dispersion of the positive electrode active material and the conductive additive in the positive electrode mixture is insufficient, a resistance distribution occurs on the electrode plate due to partial aggregation, and the current concentrates when used as a battery, Inconveniences such as partial heat generation and deterioration may occur.

  In addition, when a positive electrode mixture layer is formed on a current collector such as a metal foil, the charge and discharge are repeated many times, and the interface between the current collector and the positive electrode mixture layer or the positive electrode active material and the conductive material inside the positive electrode mixture. There is a problem in that the adhesion at the auxiliary agent interface is deteriorated and the battery performance is lowered. This is because the positive electrode active material and the positive electrode mixture layer repeatedly expand and contract by lithium ion doping and dedoping in charge and discharge, and the positive electrode mixture layer and the current collector interface, and the positive electrode active material and the conductive auxiliary agent. It is considered that local shear stress is generated at the interface and the adhesion at the interface is deteriorated. Also in this case, if the dispersion of the positive electrode active material and the conductive additive is insufficient, the decrease in adhesion becomes significant. This is presumably because the presence of coarse aggregated particles makes it difficult to relieve stress.

  In lithium secondary batteries, the dispersion of a carbon material that is an active material and a conductive auxiliary agent is one of the important points. Patent Documents 1 and 2 describe examples in which a surfactant is used as a dispersant when dispersing an active material and carbon black in a solvent. However, since the surfactant has a weak adsorption force to the particle surface, the amount of the surfactant added must be increased in order to obtain good dispersion stability. As a result, the amount of the active material that can be contained is small. Battery capacity will decrease. Further, if the surfactant is not sufficiently adsorbed on the particles, the active material and the carbon material are aggregated. Further, a general surfactant has a remarkably low dispersion effect in an organic solvent as compared with dispersion in an aqueous solution.

  Patent Document 3 discloses a method of improving the dispersion state by adding a dispersion resin when the negative electrode active material and carbon black are dispersed in water. However, with this method, although the dispersibility of the active material and carbon black is improved, the dispersion resin having a large molecular weight coats the particle surface, so that the conductive network is likely to be hindered and the resistance of the electrode is increased. In addition, the effect of improving the dispersion of the active material and carbon black may be offset.

  In addition to the improvement in the dispersibility of the electrode material, an important factor for improving the charge / discharge efficiency is an improvement in the wettability of the electrode with respect to the electrolytic solution. Since the electrode reaction occurs at the contact interface between the electrode material surface and the electrolytic solution, it is important that the electrolytic solution penetrates into the electrode and the electrode material is well wetted. As a method of promoting the electrode reaction, a method of increasing the surface area of the electrode by using a fine active material or a conductive assistant has been studied, but the actual contact area is difficult to increase because of poor wettability to the electrolyte. There is a problem that it is difficult to improve battery performance.

As a method for improving the wettability of the electrode, Patent Document 4 discloses a method of improving the wettability by adsorbing a surfactant such as a higher fatty acid alkali salt to the negative electrode active material and carbon powder. As described above, surfactants are often not sufficiently dispersed in a non-aqueous system, and a uniform electrode coating film cannot be obtained. In these examples, the total performance including the dispersibility of the electrode material was insufficient.
JP-A-63-236258 JP-A-8-190912 JP-T-2006-51679 gazette JP-A-6-60877

In the positive electrode mixture paste for a lithium secondary battery, the present invention aims to stabilize the dispersion without inhibiting the conductivity of the positive electrode active material, to improve the wettability of the positive electrode active material with respect to the electrolyte, It aims at improving the battery performance of the battery produced using the battery composition of invention.

This object is achieved, and one or more derivative selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, and a positive electrode active material, the a comprising at for a lithium secondary battery positive electrode material mixture paste,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
This is solved by a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

  The present invention also relates to a compound in which a vinyl polymer (A1) having two hydroxyl groups in one terminal region constituting the polymer (G1) has two hydroxyl groups and one thiol group in the molecule ( The present invention relates to the positive electrode material mixture paste for a lithium secondary battery, which is obtained by radical polymerization of an ethylenically unsaturated monomer (a12) in the presence of a11).

  Further, the present invention is characterized in that the polymer (A2) having one or two (meth) acryloyl groups in one end region constituting the polymer (G2) contains a vinyl polymer or polyester. The present invention relates to a positive electrode mixture paste for a lithium secondary battery.

  Moreover, this invention relates to the said positive mix paste for lithium secondary batteries whose positive electrode active material is lithium iron phosphate.

  The present invention further relates to the positive electrode mixture paste for a lithium secondary battery comprising a binder component other than a resin having a basic functional group.

  The present invention also relates to the positive electrode material mixture paste for a lithium secondary battery, wherein the binder component is a polymer compound containing a fluorine atom in the molecule.

  The present invention further relates to the above-mentioned positive electrode mixture paste for a lithium secondary battery comprising a solvent.

  The present invention further relates to the above-mentioned positive electrode mixture paste for a lithium secondary battery comprising a carbon material as a conductive agent.

Furthermore, the present invention may comprise a combination of one or more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, a conductive additive A method for producing a positive electrode mixture paste for a lithium secondary battery in which a carbon material is dispersed in a solvent ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
It is related with the manufacturing method of the positive mix paste for lithium secondary batteries which is resin which has 1 or more types of basic functional groups chosen from the group which consists of.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

Further, the present invention may comprise a combination of one or more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, the positive electrode active material And a carbon material as a conductive auxiliary, and a method for producing a positive electrode mixture paste for a lithium secondary battery, which is co-dispersed in a solvent ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
It is related with the manufacturing method of the positive mix paste for lithium secondary batteries which is resin which has 1 or more types of basic functional groups chosen from the group which consists of.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

Further, the present invention may comprise a combination of one or more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, the positive electrode active material And a method for producing a positive electrode mixture paste for a lithium secondary battery in which a carbon material as a conductive additive and a binder component are co-dispersed in a solvent ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
It is related with the manufacturing method of the positive mix paste for lithium secondary batteries which is resin which has 1 or more types of basic functional groups chosen from the group which consists of.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

Further, the present invention may comprise a combination of one or more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, the positive electrode active material And a dispersion formed by dispersing in a solvent, and a method for producing a positive electrode material paste for a lithium secondary battery, in which a carbon material as a conductive additive is mixed ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
It is related with the manufacturing method of the positive mix paste for lithium secondary batteries which is resin which has 1 or more types of basic functional groups chosen from the group which consists of.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

Further, the present invention may comprise a combination of one or more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, the positive electrode active material And a dispersion formed by dispersing in a solvent, a carbon material as a conductive auxiliary agent, and a binder component, a method for producing a positive electrode mixture paste for a lithium secondary battery ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
It is related with the manufacturing method of the positive mix paste for lithium secondary batteries which is resin which has 1 or more types of basic functional groups chosen from the group which consists of.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

Furthermore, a positive electrode active material that has been previously treated with one or more treatment agents selected from the group consisting of organic dye derivatives having basic functional groups, triazine derivatives having basic functional groups, and resins having basic functional groups A method for producing a positive electrode mixture paste for a lithium secondary battery using
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
It is related with the manufacturing method of the positive mix paste for lithium secondary batteries which is resin which has 1 or more types of basic functional groups chosen from the group which consists of.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}

Furthermore, the present invention is a lithium secondary battery comprising a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium, The present invention relates to a lithium secondary battery in which the positive electrode mixture layer is formed using the positive electrode mixture paste for a lithium secondary battery.

  Furthermore, this invention relates to the lithium secondary battery formed using the said positive mix paste for lithium secondary batteries.

  According to a preferred embodiment of the present invention, a battery composition having excellent dispersion stability can be obtained without inhibiting the conductivity of the conductive additive. Furthermore, by using the positive electrode mixture paste for a lithium secondary battery according to a preferred embodiment of the present invention for an electrode such as a lithium secondary battery, the electrode active material and the conductive additive are uniformly distributed in the electrode mixture. When mixed, the adhesion between the electrode current collector and the electrode mixture, the adhesion between the active material and the conductive additive, and the wettability of the electrode mixture with respect to the electrolyte are improved, thereby reducing the internal resistance of the electrode. In addition, the charging and discharging efficiency can be improved, and the battery performance can be improved comprehensively.

For the composition for a battery according to the present invention will be described in detail below.

<Various derivatives having basic functional groups>
Examples of the derivative having a basic functional group in the present invention include an organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group, and a basic group functional group as shown by the following general formula (1). One or more selected from the group consisting of an acridone derivative having a triazine derivative having a basic functional group.

  General formula (1):

[In general formula (1),
P ⁰ is an m ⁰ valent organic dye residue, an anthraquinone skeleton, an acridone skeleton, or a triazine skeleton,
L ⁰ is a substituent having a basic functional group,
m ⁰ is an integer of 1 to 4. ]

  In particular, use of a triazine derivative represented by the following general formula (2) or an organic dye derivative represented by the general formula (7) is preferable.

  General formula (2):

{Formula (2) Medium X ¹⁰¹ is, -NH -, or -X ¹⁰² -Y ¹⁰¹ -X ¹⁰³ - a and,
X ¹⁰² _{is, -CONH -, -SO 2 NH -} , or -NHSO ₂ - and is,
X ¹⁰³ is, -NH - a is,
Y ¹⁰¹ is composed of 1 to 20 carbon atoms, an arylene group,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH— R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is hydrogen atom, alkyl group, or an aryl group,
R ¹⁰¹ is a group represented by the organic dye residue, heterocyclic residue, an aromatic ring residue, or the following general formula (6),
ⁿ¹⁰¹ is an integer of 1-4.

  General formula (3):

  General formula (4):

  General formula (5):

[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct binding, or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ — ,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, also an arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ each independently hydrogen atom, an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , And R ¹⁰⁸ is hydrogen atom,
R ¹⁰⁹ is an alkyl group . ]

[In general formula (6),
T is, -X ¹⁰⁸ - is R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is, -NH - a and,
X ¹⁰⁸ is —NH— ;
Y ¹⁰³ is composed of 1 to 20 carbon atoms, an alkylene group,
R ¹¹⁰ is an organic dye residue, heterocyclic residue, also an aromatic ring residue. ]}

[In general formula (6),
T is, -X ¹⁰⁸ -R ^110, or a W ^101,
U is, -X ¹⁰⁹ -R ^111, or W is ^102,
W ¹⁰¹ and W ¹⁰² are each independently —O—R ¹²⁰ , —NH—R ¹²⁰ , a halogen group, or a substituent represented by any one of the general formulas (3), (4), or (5) Group,
R ¹²⁰ is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent,
X ¹⁰⁷ is —NH— or —O—.
X ^108, and X ¹⁰⁹ each independently, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-, or a -CH ₂ NHCOCH ₂ NH-,
Y ¹⁰³ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which has 1 to 20 carbon atoms,
R ¹¹⁰ and R ¹¹¹ are each independently an organic dye residue, a heterocyclic residue which may have a substituent, or an aromatic ring residue which may have a substituent. ]]

R ¹⁰¹ in formula (2), and, as the organic pigment residues represented by R ¹¹⁰ in formula (6), For example, diamino-di-anthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone , and anthraquinone-based coloring element such violanthrone; Ru include dioxazine color element.

R ¹⁰¹ in formula (2), and, as the heterocyclic residues and aromatic ring residues represented by R ¹¹⁰ in formula (6), For example, triazine down, benzimidazolonyl down, Karubazo Le, benzene, anthraquinone, and the like. These heterocyclic ring residues and aromatic ring residues are alkyl groups (methyl group, ethyl group, butyl group, etc. ), halogens (chlorine, bromine, fluorine, etc.), phenyl groups (alkyl groups, amino groups, alkyl groups). an amino group, a nitro group, a hydroxyl group, which may have an alkoxy group, or substituted with a halogen or the like but it may also) substituents such.

Formula (3) and (4) in the R ^103, and R ¹⁰⁴ each independently are hydrogen atom, or an alkyl group.

Y ¹⁰¹ , Y ¹⁰² , and Y ¹⁰³ in the general formulas (2) to (6) each independently represent an alkylene group or an arylene group which may have a substituent having 20 or less carbon atoms. Includes a phenylene group which may have a substituent , or an alkylene group which may have a side chain having 10 or less carbon atoms.

  General formula (7):

{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
ⁿ¹⁰² is an integer of 1 to 4,
R ¹¹² is an organic dye residue, heterocyclic residue, also is an aromatic ring residue.

  General formula (8):

  General formula (9):

  General formula (10):

[In the general formulas (8) to (10),
X ¹¹⁰ _{is, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, or -CH ₂ - der is,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or R ¹¹³ and further nitrogen together with the R ^114, or oxygen atom including heterocyclic residue,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ , And R ¹¹⁸ is hydrogen atom,
R ¹¹⁹ is an alkyl group . ]}

Examples of the organic dye residue represented by R ¹¹² in the general formula (7) include diketopyrrolopyrrole dyes; azo dyes such as azo, disazo, and polyazo; phthalocyanine dyes;
Diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone,
Indanthrone, pyranthrone, and anthraquinone dyes such as violanthrone; Ru mentioned quinacridone color element or the like.

As the heterocyclic residue, and an aromatic ring residue represented by R ¹¹² in formula (7), For example, anthraquinone and acridone, and the like. These heterocyclic residues and aromatic ring residue is a nitro group, hydroxyl group, halogen (chlorine, bromine, and fluorine, etc.), as well as, a phenyl group (an alkyl group, an amino group, an alkylamino group, a nitro group, hydroxyl, which may have an alkoxy group, and substituents of good not), or the like which may be substituted by halogen or the like.

R ¹¹³ in the general formulas (8) and (9) And R ¹¹⁴ each independently represents an alkyl group or R ^113. And R ¹¹⁴ and a further nitrogen together, or oxygen atom is including heterocyclic residue.

Examples of amine components used to form the substituents represented by the general formulas (3) to (5) and the general formulas (7) to (9) include:
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-pipecoline, 2,4-rupetidin, 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- methyl homopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, and 1-cyclopentyl piperazine and the like.

  As a method of 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 having a basic functional group according to the present invention. Although there is no particular limitation, JP-A 54-62227, JP-A 56-118462, JP-A 56-166266, JP 60-88185, JP It can be synthesized by the method described in JP-A-63-305173, JP-A-3-2676, JP-A-11-199796 or the like.

  For example, after introducing substituents represented by the formulas (11) to (14) into an organic dye, anthraquinone, or acridone, these substituents and amine components (for example, N, N-dimethylaminopropylamine, N- Synthesizing by reacting methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazin-2-ylamino] aniline). Can do.

General formula (11):
-SO ₂ Cl

Formula (12):
-COCl

General formula (13):
-CH ₂ NHCOCH ₂ Cl

General formula (14):
—CH ₂ Cl

  For example, when introducing the substituent represented by the formula (11), an organic dye, anthraquinone, or acridone is dissolved in chlorosulfonic acid and reacted with a chlorinating agent such as thionyl chloride. The number of substituents represented by the formula (11) to be introduced into the organic dye, anthraquinone, or acridone can be controlled by conditions such as the reaction temperature and reaction time.

  In addition, when the substituent represented by the formula (12) is introduced, first, an organic dye having a carboxyl group, anthraquinone, or acridone is synthesized by a known method, and then thionyl chloride or the like in an aromatic solvent such as benzene. And the like, and the like.

  During the reaction of the substituent represented by formula (11) to formula (14) with the amine component, a part of the substituent represented by formula (11) to formula (14) is hydrolyzed and chlorine is substituted with a hydroxyl group. There are things to do. In that case, the substituent represented by the formula (11) is a sulfonic acid group, and the substituent represented by the formula (12) is a carboxylic acid group. Or a salt with the above amine.

When the organic dye is an azo dye, a substituent represented by the general formulas (8) to (10) or the following general formula (15) is previously introduced into the diazo component or the coupling component, and then coupled. An azo organic dye derivative can also be produced by carrying out the reaction.
Formula (15):

{In general formula (15),
X ¹¹³ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - CH 2 NHCOCH 2 NH-, or -X ¹¹⁴ -Y ¹⁰⁵ -X ¹¹⁵ - a and,
X ¹¹⁴ is, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH -, - NHCO-, or -NHSO ₂ - and is,
Each X ¹¹⁵ is independently —NH— or —O—;
Y ¹⁰⁵ is an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent, which is composed of 1 to 20 carbon atoms,
P ¹ is a substituent represented by any of the above general formulas (3), (4), or (5), and Q ² is —O—R ¹²⁴ , —NH—R ¹²⁵ , a halogen group, — X ¹⁰¹ -R ¹²⁵ , or a substituent represented by any of the above general formulas (3), (4), or (5),
R ¹²⁴ is a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent,
R ¹²⁵ represents an organic dye residue, a heterocyclic residue which may have a substituent, an aromatic ring residue which may have a substituent, or a group represented by the general formula (6). is there. }

  In addition, the triazine derivative having a basic functional group of the present invention, for example, using cyanuric chloride as a starting material, and adding at least one chlorine of cyanuric chloride to the above general formulas (8) to (10) or general formula (15) Reacting the amine component (eg, N, N-dimethylaminopropylamine, N-methylpiperazine, etc.) that forms the indicated substituents, and then reacting the remaining chlorine of cyanuric chloride with various amines, alcohols, etc. Obtained by.

  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 active material surface. Among the positive electrode active materials, in the case of lithium iron phosphate carrying a carbon material, since the particle surface has high hydrophobicity, the adsorption action effect of various derivatives having basic functional groups is further improved, and the dispersion effect is also exhibited. Conceivable.

  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 active material in the solution, the action (for example, adsorption) of these derivatives proceeds to the active material, and the polarity of the basic functional group of the derivative that acts on the surface of the active material (for example, adsorption) It is considered that wetting of the active material surface with respect to the solvent is promoted, and the aggregation of the active material is easily solved. Moreover, the dispersion stability of the active material can be further increased by using in combination with a basic resin described later.

  Furthermore, in the case of a resin having a basic functional group, which will be described later, it is adsorbed to the active material by the interaction of the basic functional group, thereby improving the adhesion with the resin component and the active material due to the steric hindrance effect of the basic resin. It is considered that the dispersion stability of the resin further increases.

Furthermore, since the adhesiveness between the active material and the polymer compound having a fluorine atom as a binder component is improved through the resin having the basic functional group, the active material in the electrode current collector or electrode mixture It is thought that the adhesion to the surface is improved.

<Resin having a basic functional group>
The battery composition of the present invention contains a resin having a basic functional group. A preferred basic functional group is a primary to tertiary amino group. The resin having a basic functional group is preferably one or more two types selected from the group consisting of the polymer (G1) and the polymer (G2) described below from the viewpoint of dispersion stability.

  The resin having the basic functional group binds the electrode active material and the carbon material as the conductive auxiliary agent, or binds the electrode active material and the carbon material as the conductive auxiliary agent to the collector electrode. 1 selected from 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 Dispersion stability of an active material by using in combination with a derivative having a basic functional group of more than one species (hereinafter sometimes simply referred to as “derivative having a basic functional group” or “basic derivative”). And the adhesiveness of an electrode mixture layer can be improved.

  That is, the basic functional group of the basic derivative acts on the surface of the active material (for example, adsorbs), and at the same time, the adsorption of the basic functional group of the resin having the basic functional group to the active material surface is promoted. It is considered that the adhesion with the resin component is improved and the dispersion stability of the active material is improved by repulsion due to the steric hindrance of the resin. Further, since the adhesion between the active material and the polymer compound containing a fluorine atom in the molecule as the binder component is also improved, it can be expected that the amount of the binder used is reduced.

  In the present application, when expressed as “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy”, unless otherwise specified, It is intended to represent “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy”.

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

  The vinyl polymer site grafted to the side chain derived from the vinyl polymer (A) has excellent affinity with a wide range of active material carrier and dispersion medium, functions as a solvent affinity site, and the urea binding site of the main chain is It functions as an adsorbing group on the active material surface. Furthermore, an amino group can be introduced into the main chain in order to further improve the adsorptivity.

  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 binder resin or the like active material carrier and the solvent that is the dispersion medium, and is represented by the following general formula (16).

  Formula (16):

[In General Formula (16),
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, or 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. The compound (a11) is preferably obtained by bulk polymerization or solution polymerization using 0.5 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (a12), more preferably 1 to 20 parts. Part by weight, more preferably 2 to 15 parts by weight, particularly preferably 2 to 10 parts by weight. The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. If the amount is less than 0.5 part by weight, the molecular weight of the vinyl polymer portion is too high, and the absolute amount increases as the affinity portion for the active material carrier and the solvent, and the dispersibility effect itself may be reduced. If it exceeds 30% by weight, the molecular weight of the vinyl polymer part is too low, and as an affinity site for the active material carrier and the solvent, the effect of steric repulsion is lost, and it is difficult to suppress aggregation of the active material. Become.

<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), or 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 or the like is 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)>
As the ethylenically unsaturated monomer (a12), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, or isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, or phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate or oxetane (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate;
N-substituted type (meta) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile are included.

In addition, as a monomer that can be used in combination with the acrylic monomer,
Styrenes such as styrene or α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or
Examples include vinyl acetate or fatty acid vinyls such as 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, etc.>
In the present invention, among the ethylenically unsaturated monomers (a12) exemplified above, methyl methacrylate is preferably used from the viewpoint of dispersibility and resistance, and from the viewpoint of affinity with the active material carrier and the dispersion medium. More preferably, methyl methacrylate and butyl methacrylate or t-butyl methacrylate are used 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. Moreover, 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 30% of the ethylenically unsaturated monomer (a12). It preferably occupies 100% by weight, more preferably 50-100% 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 active material dispersibility becomes better. The copolymerization site of methyl methacrylate and butyl methacrylate or t-butyl methacrylate has high compatibility with the binder resin and dispersion solvent while maintaining basic physical properties such as dispersibility.

  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 active 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. Further, the viscosity of the dispersion may increase.

  When the weight average molecular weight is 500 to 30,000, it is advantageous to suppress an increase in viscosity of the active material dispersion by preventing aggregation of the active 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 from the following calculation for calculating the glass transition temperature. To do.

1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
W1 to Wn indicate the weight fraction of each monomer used, and Tg1 to Tgn indicate the glass transition temperature of each homopolymer obtained from each monomer (unit: absolute temperature “K”). Show.

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, or 1,3-bis (isocyanate methyl) 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 or 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, or 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, or 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 constituent element of the polymer (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 form 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- Aliphatic diamines such as dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, or tolylenediamine;
Cycloaliphatic diamines such as isophorone diamine or dicyclohexylmethane-4,4′-diamine; or
Examples thereof include aromatic diamines such as phenylenediamine and 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, N, N′-di-tert-butylethylenediamine and the like can be mentioned.

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 methylamino Propylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3- Propanediamine or isopropylaminopropylamine], or N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine].

  The polyamine of the present invention 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 an active material adsorption site. However, 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 at both ends. In particular, it is preferable because the adsorptivity to the active material is increased.

  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 [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias N, N-bis (3-aminopropyl) laurylamine], iminobispropylamine [alias] N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, etc. Can
Methyliminobispropylamine and lauryliminobispropylamine having two primary amino groups and one tertiary amino group are preferable because they can easily control the reaction with diisocyanate.

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

  As the polyamine (D1) of the present invention, 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. When the content is 10% by weight or more, it is effective for preventing aggregation of the active material and suppressing an increase in viscosity.

As an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group or an ethylenically unsaturated monomer having a secondary amino group, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, or vinyltoluene;
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid alkylaryl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a functional group such as glycidyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a tertiary amino group such as dimethylaminoethyl (meth) acrylate or dimethylaminopropyl (meth) acrylate;
Alkyl (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, or tert-octyl (meth) acrylamide ;
Substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide or dimethylaminopropyl (meth) acrylamide;
Diene compounds such as 1,3-butadiene or isoprene;
Polymerizable oligomers (macromonomers) such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, or one-end methacryloylated polyethylene glycol; or
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 active material dispersion by preventing aggregation of the active material.

<< monoamine (E1) >>
As the amine compound that is a constituent element of the polymer (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 a polar functional group 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. Specifically,
Aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-amino Hexane, 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-methylpropane, 3-amino-1-propene, 3-amino Methyl heptane, -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, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic Acid Isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric 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-amino Anthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o -Aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenacylamine, p- Examples include methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, or 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.

As an aliphatic monoamine compound having only a secondary amino group,
Dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethyl Propylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, etc. are mentioned.

  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 active material can be introduced into the polymer terminal of the dispersant.

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

  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 of the present invention, 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)>
In the synthesis of the urethane prepolymer (C1), a known catalyst (F1) can be used, and examples thereof include a tertiary amine compound and an organometallic compound.

As the tertiary amine compound, for example,
Examples include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like.

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

Examples of tin compounds include:
Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyl Examples thereof include tin ethoxide, dioctyl tin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethylhexanoic acid tin.

Examples of non-tin compounds include:
Titanium-based lead oleate such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride;
Lead systems such as lead 2-ethylhexanoate, lead benzoate, or lead naphthenate;
Iron systems such as iron 2-ethylhexanoate and iron acetylacetonate;
Cobalt-based benzoate or cobalt 2-ethylhexanoate, etc .;
Zinc-based such as zinc naphthenate or zinc 2-ethylhexanoate; or
Zirconium-based compounds such as zirconium naphthenate can be mentioned.

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

  A catalyst such as the tertiary amine compound or organometallic compound 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:
Use 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, or diethylene glycol diethyl ether However, it is not limited to these.

  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.

<Composite conditions>
Various methods can be used for the urethanization reaction to produce urethane prepolymer (C1) by reacting the hydroxyl group of vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of diisocyanate (B1). It is. 1) When the reaction is carried out in the whole amount, 2) The vinyl polymer (A) having two hydroxyl groups in one end region, and if necessary, the solvent is charged into the flask, and after adding the diisocyanate (B1) dropwise, it is necessary. Depending on the method of adding the catalyst, the method 2) is preferred when the reaction is precisely controlled. 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 at 50 to 110 ° C. for 1 to 20 hours in the presence of a catalyst.

  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 diisocyanate is further increased, all 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). This design allows excess diisocyanate (B1) to be incorporated into the dispersant molecules of the present invention. In the case of synthesizing a normal urethane prepolymer (C1), in order not to leave a polyol, in many cases, an excess polyisocyanate is blended in anticipation of chain extension by the polyamine in the next step. Excessive diisocyanate (B1) -derived polymer structural units and excess diisocyanate (B1) hydrolyzate-derived impurities often adversely affect active material dispersibility and stability over time.

  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, from the viewpoint of the design of the dispersant that is the final product (the balance between the active material adsorption site and the solvent affinity site), 1.30 to 2.30 are more preferable, and the active using the dispersant that is the final product is preferable. From the viewpoint of dispersion stability of the substance dispersion, 1.50 to 2.00 is most preferable. If the blending molar ratio is too small, the final product dispersant has a high molecular weight, the active material dispersion using the dispersant, and the viscosity of the mixture paste or ink using the dispersant increases, which causes practical problems. . Moreover, as mentioned above, when the blending molar ratio is larger than 2.00, the diisocyanate (B1) having no vinyl polymer part derived from the vinyl polymer (A1) and the urethane part derived therefrom increase, and the dispersion performance of the active material is increased. Serious adverse effects.

<< Production method and synthesis conditions of polymer (G1) having basic functional group >>
The polymer (G1) having a basic functional group constituting the composition of the present invention,
It has two hydroxyl groups in one terminal region formed by radical polymerization of ethylenically unsaturated monomer (a12) in the presence of compound (a11) having two hydroxyl groups and one thiol group in the molecule. A first step of producing a vinyl polymer (A1);
A urethane prepolymer (C1) having isocyanate groups at both ends is prepared by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups at one end region with the isocyanate group of diisocyanate (B1). The second step,
And a third step of reacting the isocyanate group of the urethane prepolymer (C1) having isocyanate groups at both ends with the primary and / or secondary amino groups of the polyamine (D1) and monoamine (E2). it can.

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) A method in which a solution comprising a polyamine (D1) and a monoamine (E1) and, if necessary, a solvent is charged into a flask, and a urethane prepolymer (C1) solution is dropped.
It is divided roughly into.

  The synthesis is carried out with a stable reaction. If there is no problem in the reaction, the method 1) which is easy to operate is preferred. The temperature of the urea reaction of the present invention is preferably 100 ° C. or lower. 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 from the disappearance of the isocyanate peak by the measurement of isocyanate% due to titration and 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. If the weight average molecular weight is less than 1,000, the stability of the active material dispersion may be reduced. If the weight average molecular weight exceeds 100,000, the interaction between the resins becomes strong and the viscosity of the active material dispersion increases. There is a case. 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 active material and the adsorbing functional group may be insufficient, which may make it difficult to contribute to the active material dispersion. If the amine value exceeds 100 mgKOH / g, aggregation of the active materials occurs. Insufficient viscosity lowering effect and defects in the appearance of the coating film may occur.

<Polymer 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 active material adsorptive site having a binding site. The active material adsorption site having the amino group and the urea binding site can be dispersed and stabilized.

<< 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, fluidity, 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 advances 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, or 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, such as -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.

  In the production method of the present invention, the lactone can be used without being limited to the above examples, and may be used alone or in combination of two or more.

As the lactide, those represented by the following general formula (17) are preferable (including glycolide).
Formula (17):

[In general formula (17),
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. ]

  In the production method of the present invention, 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, lactone is preferably used 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 an active material, the viscosity of the dispersion becomes high, causing a problem.

[Ring-opening polymerization catalyst]
As the ring-opening polymerization catalyst, any known catalyst can be used without limitation.
Quaternary ammonium such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, or benzyltrimethylammonium iodide salt;
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 or tetraphenylphosphonium iodide;
Phosphorus compounds such as triphenylphosphine;
Organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, or sodium benzoate;
Alkali metal alcoholates such as sodium alcoholate and potassium alcoholate;
Tertiary amines such as triethylamine or triphenylamine;
Organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, or dioctyltin oxide;
Organoaluminum compounds such as aluminum alkyl acetoacetate diisopropylate, aluminum bisethyl acetoacetate monoacetylacetonate, or aluminum trisacetylacetonate;
An organic titanate compound such as tetra-n-butyl titanate, said dimer, tetraisobutyl titanate, tetrastearyl titanate, or diisopropoxy bis (triethanolaminate) titanium; or
Examples thereof include 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 very slow. If the reaction 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, cyclic lactones In some cases, dimer or trimer formation is likely to occur.

[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. For example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, or 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.

  Polyester (A21) has a dibasic acid anhydride group on 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. It was obtained by reacting a polyester having a carboxyl group at one end obtained by reacting a compound having one with a compound having an epoxy group and a (meth) acryloyl group, and further opening the epoxy group. It can also be obtained by reacting a group capable of reacting with a hydroxyl group and a compound having the (meth) acryloyl group. 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, or oleyl alcohol;
An aromatic ring-containing monoalcohol such as benzyl alcohol, phenoxyethyl alcohol, or paracumylphenoxyethyl alcohol; or
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, Ethylene 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 glycol mono-2-ethylhexyl ether, Tripropylene glycol monomer 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, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl A And alkylene glycol monoalkyl ethers such as tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

[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 acid anhydride, phthalic acid anhydride, naphthalene-1,2-dicarboxylic acid anhydride, naphthalene-2,3-dicarboxylic acid anhydride, anthracene-1,2-dicarboxylic acid anhydride, or 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, or 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, or 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 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 without (meth) acryloyl group]
The monocarboxylic acid having no (meth) acryloyl group may be any compound as long as it is a compound having a carboxyl group and having no (meth) acryloyl 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 reactive group with a 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 having one or two hydroxyl groups and one thiol group in the molecule (s)]
Examples of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule include 1 hydroxyl group in the molecule such as 1-mercaptoethanol or 2-mercaptoethanol. A compound having one thiol group (s1); or
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, The compound (s2) which has two hydroxyl groups and one thiol group in molecules, such as 3-propanediol or 2-mercaptoethyl-2-ethyl-1,3-propanediol, is mentioned.

  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 active material adsorption site having a plurality of amino groups and a plurality of solvent affinities. And an ideal structure having a sex part.

[Ethylenically unsaturated monomer (a21)]
As the ethylenically unsaturated monomer (a21), for example,
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) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
Unsaturated carboxylic acids such as acrylic acid, acrylic acid dimer, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or crotonic acid;
Caprolactone adducts (1 to 5 addition moles) of the carboxylic acid;
2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide (Meth) acrylates having a carboxyl group such as modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
Styrenes such as styrene and α-methylstyrene;
Vinyls such as vinyl acetate, vinyl propionate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Amides having no amino group, such as (meth) acrylamide or N-vinylformamide; or
Examples include acrylonitrile having no amino group. 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 general formula (18). The amount of the ethylenically unsaturated monomer (a22) represented by the following general formula (18) is preferably 20% by weight to 100% by weight with respect to the whole ethylenically unsaturated monomer (a21), -70 wt% is more preferred. When the monomer represented by the general formula (18) is used, the solvent affinity is improved and the carbon dispersibility is improved. If it is less than 20% by weight, the effect of improving the solvent affinity is insufficient.
General formula (18):

[In General Formula (18), R ⁵ is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

[Amount of compound (s) used]
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. When the temperature exceeds 150 ° C., it becomes difficult to control the molecular weight such as an increase in the molecular weight.

[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 ( 4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2′-azobis [2- (2-imidazolin-2-yl)
Azo compounds such as propane] and organic peroxides; or
Benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneo Organic peroxides such as decanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide, etc., and polymerization initiators thereof Can be used alone or in combination of two or more.

[Compound having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group (a24)]
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. .

[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, or N-methylpyrrolidone is used, but is 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 as part of a product.

<Polyamine (B2)>
The polyamine (B2) of the present invention is a compound having one or more primary and / or secondary amino groups, and the polymer (A2) in which the primary and / or secondary amine has a (meth) acryloyl group in one terminal region. To the (meth) acryloyl group, to produce 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, in the dispersant of the present invention, the amino group and urea bond existing in one end region serve as the active material adsorption site. 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 active material is increased.

As the diamine (b21) having two primary amino groups, known ones can be used.
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- Aliphatic diamines such as dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, or tolylenediamine;
Cycloaliphatic diamines such as isophorone diamine or dicyclohexylmethane-4,4′-diamine; or
Examples thereof include aromatic diamines such as phenylenediamine and 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, or N, N′-di-tert-butylethylenediamine can be used.

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 methylamino Propylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3- Propanediamine or isopropylaminopropylamine], or N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine].

Moreover, as diamine (b21) which has a primary and tertiary amino group, a well-known thing can be used, Specifically,
N, N-dimethylethylenediamine [alias: dimethylaminoethylamine], N, N-diethylethylenediamine [alias: diethylaminoethylamine], or 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. Yes, specifically
Methyliminobispropylamine [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias N, N-bis (3-aminopropyl) laurylamine], iminobispropylamine [alias] N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, etc. Can
Methyliminobispropylamine and lauryliminobispropylamine having two primary amino groups and one tertiary amino group are preferable because they can easily control the reaction with diisocyanate.

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

  As the polyamine (B2) of the present invention, 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. When the content is 10% by weight or more, it is effective for preventing aggregation of the active material and suppressing an increase in viscosity.

As an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group or an ethylenically unsaturated monomer having a secondary amino group, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, or vinyltoluene;
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid alkylaryl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a functional group such as glycidyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a tertiary amino group such as dimethylaminoethyl (meth) acrylate or dimethylaminopropyl (meth) acrylate;
Alkyl (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, or tert-octyl (meth) acrylamide ;
Substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide or dimethylaminopropyl (meth) acrylamide;
Diene compounds such as 1,3-butadiene or isoprene;
Polymerizable oligomers (macromonomers) such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, or one-end methacryloylated polyethylene glycol; or
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 the viscosity increase of the dispersion by preventing aggregation of the active material.

《Monoamine》
In addition to the polyamine (B2), a monoamine can also be used as the amine compound constituting the dispersant of the present invention. 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 ones can be used, specifically,
Aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-amino Hexane, 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-methylpropane, 3-amino-1-propene, 3-amino Methyl heptane, -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, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic Acid Isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric 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-amino Anthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o -Aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenacylamine, p- Examples include methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, or diphenylamine.

<< Amino group-containing polymer (C2) >>
As shown in the following general formula (19), the polymer (C2) having an amino group has a primary or secondary amino group of polyamine (B2) having 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 a group. 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.

  General formula (19):

[In General Formula (19), X ¹ is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ¹ is a primary and secondary amino group in the polyamine (B2). R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom or an alkyl group. ]

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

  Formula (20):

[In the general formula (20), X ¹ is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a polyamine (B2) excluding the primary amino group. And R ⁶ is a hydrogen atom or a methyl group. ]

  For example, as shown in the following general formula (21), one primary amino group and secondary amino group per molecule of the polymer (A2) having two (meth) acryloyl groups in one end region When two molecules of the diamine (B2) having one are reacted, one molecule of the polymer (C2) having four secondary amino groups is theoretically obtained.

  Formula (21):

[In General Formula (21), X ² is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a primary and secondary amino group in the polyamine (B2). R ⁶ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group. ]

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

  Formula (22):

[In General Formula (22), X ² is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a polyamine (B2) excluding the primary amino group. And R ⁶ is a hydrogen atom or a methyl group, and n is a positive integer. ]

  Further, for example, as shown in the following general formula (23), a diamine having two secondary amino groups for n molecules of the polymer (A2) having two (meth) acryloyl groups in one terminal region ( When (2 + 1) molecules of B2) are reacted, theoretically, one molecule of polymer (C2) having 2 secondary amino groups and 2n tertiary amino groups is obtained. (N is a positive integer.)

  Formula (23):

[In General Formula (23), X ² is a portion of the polymer (A2) excluding the (meth) acryloyloxy group, and Y ² is a 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. ]

  The above four examples are the cases where the primary amino group has a higher reactivity than the secondary amino group, and therefore the primary amino group always reacts preferentially. Actually, the primary amino group depends on the reaction conditions and the like. Even if it remains, since the secondary amino group may react first, a polymer (C2) having a structure different from the expected one may be obtained, but the above addition reaction is almost stoichiometric. In most cases, the polymer (C2) having the desired structure is obtained, and there is no problem in the subsequent reaction and the function as a final dispersant.

<Composite 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 addition reaction to obtain the union (C2) is: 1) a method in which the reaction is carried out by adding the whole amount, 2) a solution comprising polyamine (B2) and, if necessary, a solvent is placed in a flask, and the polymer (A2) solution is added dropwise. It is roughly divided into how to do. The synthesis is carried out with a stable reaction, but if there is no problem in the reaction, the method 2) is preferred because the reaction control (molecular design control) is easy.

  The temperature of the Michael reaction of the present invention 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 is 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 depending on the application and required performance. The end point of the reaction is judged by measuring the amine% due to titration.

<< Dispersant with amino group and urea bond >>
The polymer (G2) having a basic functional group constituting the composition of the present invention is a dispersant having an amino group and a urea bond, and the primary or secondary amino group of the polymer (C2) having an amino group. And an isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups. 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.

  In addition, 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 remains as an active material adsorbing group. As it remains in the dispersant.

For example, as shown in the following general formula (24), one molecule of diisocyanate (D2) was reacted with two molecules of polymer (C2) having one primary amino group and two secondary amino groups. In this case, theoretically, the primary amino group reacts with the 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 general formula (24) have a tertiary amino group derived from the polyamine (B2) and / or the polymer (C2), the dispersant also has a tertiary amino group.

  General formula (24):

[In General 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 ¹ and W ² are In the polyamine (B2) which is a precursor of the polymer (C2), the primary and secondary amino groups are excluded, R ⁶ is a hydrogen atom or a methyl group, and Z ¹ is a polyisocyanate ( This is a portion excluding the isocyanate group in D2). ]

Further, for example, when one molecule of diisocyanate (D2) is reacted with two molecules of polymer (C2) having one secondary amino group as shown in the following general formula (25), theoretically, 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 general 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. The dispersant does not have an amino group having active hydrogen.

  Formula (25):

[In General Formula (25), 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 a polymer ( In the polyamine (B2) which is a precursor of C2), it is a portion excluding a primary amino group, R ⁶ is a hydrogen atom or a methyl group, and Z ¹ is an isocyanate among polyisocyanates (D2). This is the part excluding the group. ]

Further, for example, as shown in the following general formula (26), the molecule (m + 1) of the polymer (C2) having two primary amino groups and 2n secondary amino groups, which is a product of the general formula (25). ), When m molecules of diisocyanate (D2) are reacted, theoretically, a primary amino group and an isocyanate group react to form a urea bond, and two primary amino groups and secondary amino groups ( A dispersant having 2 nm + 2n) and 2 m urea bonds is obtained. When Y ² in the following general formula (15) 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.)

  General formula (26):

[In the general 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 ² is a polymer ( In the polyamine (B2) which is a precursor of C2), it is a portion excluding the primary amino group, and W ⁴ is a portion excluding the site having an amino group in the polymer (C2), and R ⁶ 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 general formula (27), two molecules of a polyamine (B2) having one primary amino group and one molecule of a polymer (A2) having two (meth) acryloyl groups For each molecule (m + 1) of the polymer (C2) having two, in total, one secondary amino group in each terminal region as seen from the part derived from the polymer (A2) obtained by the reaction When m molecules of diisocyanate (D2) are reacted, theoretically, the secondary amino group and the isocyanate group react to form a urea bond, and when viewed from the polyurea chain, A dispersant having two primary amino groups, one in total, is obtained. (M is a positive integer.)

  Formula (27):

[In the general formula (27), 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 a polyamine (B2 ), A portion excluding the primary amino group, W ⁵ is a portion of the polymer (C2) excluding the portion having an amino group, and 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. ]

  The above four examples are the cases where the primary amino group has a higher reactivity than the secondary amino group, and therefore the primary amino group always reacts preferentially. Actually, the primary amino group depends on the reaction conditions and the like. Even if it remains, the secondary amino group may react first, so in some cases a dispersant with a structure different from the expected one may be obtained, but the above reaction proceeds almost stoichiometrically. Therefore, 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) used in the present invention, conventionally known ones can be used, but diisocyanates are preferred from the low viscosity effect of the dispersion. For example, aromatic diisocyanate (d21), Aliphatic diisocyanates (d22), aromatic-aliphatic diisocyanates (d23), alicyclic diisocyanates (d24), dimers of these diisocyanates (uretodiones), trimers of these diisocyanates (isocyanurates) and mono Examples include a reaction product with alcohol or a reaction product of these diisocyanate and diol (urethane prepolymer of both terminal isocyanates).

  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, or 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, or 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, or 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, or 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). Body, HDI biuret body, HDI trimethylolpropane (hereinafter sometimes abbreviated as TMP) adduct body, TDI TMP adduct body, or diisocyanate modified product such as TDI / HDI copolymer;
An aromatic triisocyanate such as 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, or 4,4 ', 4 "-triphenylmethane triisocyanate;
And polymer type aromatic isocyanate oligomers such as polymethylene polyphenyl polyisocyanate (also known as MDI oligomer).

<Composite 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, 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 of the present invention 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 is 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 preferably from 0.25 to 1.00, and all of the isocyanate groups are preferably reacted with an amino group having active hydrogen, From the viewpoint of the design (dispersion of the active material adsorption site and the solvent affinity site) of the dispersant that is the final product, 0.35 to 0.9 is more preferable, and the dispersion using the dispersant that is the final product is preferable. From the viewpoint of dispersion stability, 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.

  Furthermore, when a primary amino group and / or a secondary amino group (amino group having active hydrogen) is present in the dispersant skeleton in addition to the tertiary amino group and the urea bond, the adsorptivity to the active material is improved and the solvent affinity is increased. The balance with the sex site is also improved, and the dispersibility and its stability over time are also improved.

  Further, when too many amino groups having active hydrogen remain, the amount of active material adsorption is exceeded, causing problems such as reaction with the acryloyl group of a polyfunctional monomer added when preparing resist ink.

  Therefore, it is preferable to mix appropriately so that an amino group having active hydrogen remains.

  That is, as described above, when the compounding equivalent ratio is 0.35 to 0.9, preferably 0.5 to 0.8, a tertiary amino group, a urea bond, an amino group having active hydrogen, and a 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. When,
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in the one end region and the primary of the polyamine (B2) containing one or more primary and / or secondary amino groups And / or a secondary amino group, a second step of producing a polymer (C2) having an amino group, and
A third step of reacting the primary and / or secondary amino group of the polymer (C2) having an amino group with the isocyanate group of the polyisocyanate (D2) containing at least two isocyanate groups;
It can manufacture by the manufacturing method containing.

  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 active material dispersion may be lowered, and if it exceeds 100,000, the interaction between the resins becomes strong and the dispersion may be thickened. is there. 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 active material and the adsorbing functional group may be insufficient, which may make it difficult to contribute to dispersion. If the amine value exceeds 100 mgKOH / g, aggregation of the active materials occurs, and viscosity is increased. Insufficient lowering effects and defects in the appearance of the coating film may occur.

<Positive electrode active material>
Although it does not specifically limit as a positive electrode active material used by this invention, Metal compounds, such as a metal oxide which can dope or intercalate lithium ion, a metal sulfide, a conductive polymer, etc. can be used. . Examples thereof include transition metal oxides such as Ti, Fe, Co, Ni, and Mn, composite oxides of the transition metal and lithium, and inorganic compounds such as sulfides of the transition metal.

In particular,
Transition metal oxide powders such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , or TiO ₂ ;
A composite oxide powder of lithium and a transition metal such as lithium nickelate, lithium cobaltate, lithium manganate having a layered structure, or lithium manganate having a spinel structure;
A lithium iron phosphate material which is a phosphate compound having an olivine structure; and
Examples thereof include transition metal sulfide powders such as TiS ₂ and FeS.

  In addition, a conductive polymer such as polyaniline, polyacetylene, polypyrrole, or polythiophene can also be used.

  Moreover, you may mix and use said inorganic compound and organic compound.

As the specific surface area of the positive electrode active material used increases, the number of contact points between the positive electrode active material particles increases, which is advantageous in reducing the internal resistance of the positive electrode. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is 0.1 m ² / g or more and 150 m ² / g or less, preferably 1 m ² / g or more and 120 m ² / g or less, more preferably 1.5 m ² / g or more, 100 m ² / g
It is desirable to use: When a positive electrode active material having a specific surface area of less than 0.1 m ² / g is used, it may be difficult to obtain sufficient conductivity, and a positive electrode active material having a specific surface area of more than 150 m ² / g may not be easily manufactured. .

In addition, the particle size of the positive electrode active material to be used is preferably 0.01 to 500 μm, particularly preferably 0.05 to 100 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.

Among positive electrode active materials, lithium iron phosphate having an olivine structure is a preferable material from the viewpoints of cost and safety.

Since lithium iron phosphate having a simple olivine structure has very low electronic conductivity compared to lithium cobaltate or the like, it is difficult to obtain excellent battery characteristics. Therefore, in order to improve the electron conductivity, a method is adopted in which a conductive material such as a carbon material is supported on the particles or the primary particle diameter is reduced.

The carbon material-supported lithium iron phosphate is not particularly limited.
No. 92308, Japanese Patent Application Laid-Open No. 2003-292309, and the like can be produced.

For example, ferrous phosphate octahydrate (Fe ₃ PO ₄ ) ₂ · 8H ₂ O) and lithium phosphate (Li
₃ PO ₄ ) is mixed so that the element ratio of lithium and iron is 1: 1, and a carbon material (for example, acetylene black, ketjen black, etc.) that is a conductive substance, or is fired An organic compound that is decomposed to become a carbon material is further added so that the carbon material component is 0.1 to 50% by weight in the final product, and after pulverizing and mixing with a dry pulverizer or the like, under an inert gas atmosphere, It is obtained by firing at 600 ° C. for several hours and pulverizing the obtained fired product.

<Negative electrode active material>
Although it does not specifically limit as a negative electrode active material used for the lithium secondary battery formed using the positive mix paste of this invention, A lithium ion can be doped or intercalated,
Metallic lithium;
Metal alloys such as lithium alloys, tin alloys, or silicon alloys;
A metal oxide of lithium and metal such as Li _x Fe ₂ O ₃ , Li _x Fe ₃ O ₄ , or Li _x WO ₂ ;
Conductive polymers such as polyacetylene or poly-p-phenylene; or
Amorphous carbonaceous material such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon material, carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, gas-grown carbon fiber, or A carbon-based material such as carbon fiber is used.

<Binder>
The positive electrode mixture paste of the present invention can further contain a binder component other than the resin having a basic functional group.

  Binders used include ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal, vinyl pyrrolidone, etc. Polymer or copolymer containing as a structural unit; polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, acrylic resin, formaldehyde resin, silicone resin, fluorine resin; carboxymethyl cellulose Cellulose resins such as: rubbers such as styrene-butadiene rubber and fluororubber; conductive resins such as polyaniline and polyacetylene. Moreover, the modified body and mixture of these resin, and a copolymer may be sufficient. In particular, the use of a polymer compound containing a fluorine atom in the molecule, for example, polyvinylidene fluoride, polyvinyl fluoride, or tetrafluoroethylene, is preferable from the viewpoint of resistance.

  Moreover, as for the weight average molecular weight of these resin as a binder, 10,000-1,000,000 are preferable. When the molecular weight is small, the resistance of the binder may decrease. When the molecular weight is increased, the resistance of the binder is improved, but the viscosity of the binder itself is increased and the workability is lowered.

<Solvent>
The positive electrode mixture paste of the present invention can further contain a solvent. Examples of the solvent include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphorus Examples thereof include acid amides, sulfoxides, carboxylic acid esters, phosphate esters, ethers, nitriles, and water.

  In order to obtain the solubility of the binder resin component and the dispersion stability of the carbon material which is a conductive additive, it is preferable to use a highly polar solvent.

  For example, N-methyl-2-pyrrolidone, an amide solvent obtained by dialkylating nitrogen such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, or N, N-diethylacetamide , Hexamethylphosphoric triamide, dimethyl sulfoxide, and the like, but are not limited thereto. Two or more types can be used in combination.

<Carbon material as conductive aid>
The positive electrode material mixture paste of the present invention can further contain a carbon material as a conductive auxiliary, and the carbon material is not particularly limited as long as it is a carbon material having conductivity, for example, graphite, Carbon materials such as carbon black, carbon nanotubes, carbon nanofibers, carbon fibers, or fullerenes can be used alone or in combination of two or more. From the viewpoint of conductivity, availability, and cost, it is preferable to use carbon black.

  Carbon black is a furnace black produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially ketjen black using ethylene heavy oil as a raw material. Channel black that has been rapidly cooled and precipitated, thermal black obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, or various types such as acetylene black using acetylene gas as a raw material alone, or Two or more types can be used in combination. Ordinarily oxidized carbon black, hollow carbon and the like can also be used.

  The oxidation treatment of carbon is performed by treating the carbon with a high temperature in the air, or further treating it with nitric acid, nitrogen dioxide, ozone, or the like, for example, phenol group, quinone group, carboxyl group, or This is a treatment for directly introducing (covalently bonding) an oxygen-containing polar functional group such as a carbonyl group to the carbon surface, and is generally performed to improve the dispersibility of carbon. However, since it is common for the conductivity of carbon to fall, so that the introduction amount of a functional group increases, it is preferable to use the carbon which has not been oxidized.

As the specific surface area of the carbon black used increases, the contact point between the carbon black particles increases, which is advantageous for lowering the internal resistance of the electrode. Specifically, the specific surface area (BET) determined from the amount of nitrogen adsorbed is 20 m ² / g or more and 1500 m ² / g or less, preferably 50 m ² / g or more and 1500 m ² / g or less, more preferably 100 m ^2. / G or more and 1500 m ² / g or less are desirable. If carbon black having a specific surface area of less than 20 m ² / g is used, it may be difficult to obtain sufficient conductivity, and carbon black of more than 1500 m ² / g may be difficult to obtain from commercially available materials. is there.

  Further, the particle size of the carbon black to be used is preferably 0.005 to 1 μm, particularly preferably 0.01 to 0.2 μm in terms of primary particle size. However, the primary particle diameter here is an average of the particle diameters measured with an electron microscope or the like.

Examples of commercially available carbon black include
Tokai Carbon # 4300, # 4400, # 4500, # 5500 and other furnace black made by Tokai Carbon Co.,
Furnace Black made by Degussa such as Printex L,
Raven 7000, 5750, 5250, 5000 ULTRA III, and 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc.
# 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B or # 5400B furnace black manufactured by Mitsubishi Chemical Corporation,
MONARCH 1400, 1300, 900, Vulcan XC-72R, or Black, manufactured by Cabot, such as Black Pearls 2000,
Furnace black manufactured by TIMCAL, such as Ensaco 250G, Ensaco 260G, Ensaco 350G, or SuperP-Li,
Ketjen Black EC-300J, Akzo Ketjen Black such as EC-600JD, or
Examples thereof include acetylene black manufactured by Denki Kagaku Kogyo Co., Ltd. such as Denka Black, Denka Black HS-100, or FX-35, but are not limited thereto.

<Use of the present invention>
The positive electrode mixture paste of the present invention is a composition that is an active material dispersion comprising the above-described derivative having a basic functional group, a resin having a basic functional group, a positive electrode active material, and a solvent. It is preferable to use it as a positive electrode mixture paste containing a carbon material as a conductive additive and a binder component.

  The ratio of the active material to the total solid content in the positive electrode mixture paste is preferably 80% by weight or more and 98.5% by weight or less. Moreover, the ratio of the solid content which combined the derivative | guide_body which has a basic functional group in the total solid content in a positive mix paste, the resin which has a basic functional group, and the carbon material as a conductive support agent, 0.5 weight% or more and 19 weight% or less are preferable. The proportion of the binder component (resin component other than the resin having a basic functional group) in the total solid content in the positive electrode mixture paste is preferably 1% by weight or more and 10% by weight or less. The proper viscosity of the positive electrode mixture paste depends on the method of applying the electrode mixture paste, but generally it is preferably 100 mPa · s or more and 30,000 mPa · s or less.

  In the positive electrode mixture paste, the carbon material particles as the conductive auxiliary agent can be uniformly coordinated and adhered around the positive electrode active material, and excellent conductivity and adhesion can be imparted to the positive electrode mixture layer. Further, since the conductivity is improved, the amount of the carbon material added as a conductive auxiliary agent can be reduced, so that the amount of the positive electrode active material added can be relatively increased, and the capacity which is a large characteristic of the battery can be increased. Can be bigger.

  Furthermore, since the positive electrode mixture paste of the present invention has very little aggregation of the positive electrode active material and the carbon material (conducting aid), a uniform coating film with high smoothness can be obtained when applied to a current collector. The adhesion between the current collector and the positive electrode mixture is improved. In addition, since a derivative having a basic functional group and a resin having a basic functional group act on the active material surface (for example, adsorption), the surface of the positive electrode active material such as a lithium transition metal composite oxide and a carbon material Conductive auxiliary agent) The interaction with the surface becomes stronger, and the adhesion between the positive electrode active material and the carbon material (conductive auxiliary agent) compared to the case where a derivative having a basic functional group and a resin having a basic functional group are not used. Will improve.

<The manufacturing method of the positive mix paste of this invention>
Next, the manufacturing method of the composition of this invention is demonstrated.

  The positive electrode mixture paste of the present invention includes, for example, a derivative having a basic functional group, a resin having a basic functional group, and a positive electrode active material dispersed in a solvent. It can manufacture by mixing the carbon material as an agent, or an additional binder component (resin components other than resin which has a basic functional group). The order of addition of each component is not limited to this. Moreover, you may add a solvent further as needed.

  In the above production method, a derivative having a basic functional group and a resin having a basic functional group are completely or partially dissolved in a solvent, and an active material is added to and mixed in the solution. And a resin having a basic functional group is preferably dispersed in a solvent while acting (for example, adsorbing) on the surface of the active material. The concentration of the active material in the dispersion at this time is preferably 10% by weight or more and 98% by weight or less, more preferably 15% by weight or more, although it depends on the specific surface area and the amount of surface functional groups of the active material used. 95% by weight or less. When the concentration of the active material is too low, the production efficiency is deteriorated, and when the concentration of the active material is too high, the viscosity of the dispersion is remarkably increased, and the dispersion efficiency and the handleability of the dispersion may be lowered.

  The addition amount of the derivative having a basic functional group is determined by the specific surface area of the active material used. Generally, the derivative having a basic functional group is 0.05 to 40 parts by weight, preferably 0.1 to 35 parts by weight, more preferably 100 parts by weight of the active material. 0.2 parts by weight or more and 30 parts by weight or less. If the addition amount is small, a sufficient dispersion effect cannot be obtained, and even if added excessively, a significant dispersion improvement effect may not be obtained.

  In addition, when dispersing the active material in the solvent, it is preferable to add a derivative having a basic functional group and a resin having a basic functional group. The amount of the resin having a basic functional group added when dispersing the active material is preferably 0.1 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the active material, 100 parts by weight or less is more preferable.

  In addition, as a device for dispersing the basic functional group-derived derivative and the basic functional group-containing resin in a solvent while acting (for example, adsorbing) the active material, a dispersion usually used for pigment dispersion or the like is used. The machine can be used.

For example,
Mixers such as dispersers, homomixers, or planetary mixers;
Homogenizers such as “Clairemix” manufactured by M Technique, or “Fillmix” of PRIMIX;
Media type dispersers such as paint conditioners (manufactured by Red Devil), ball mills, sand mills (such as “Dynomill” manufactured by Shinmaru Enterprises), attritors, pearl mills (such as “DCP mill” manufactured by Eirich), or coball mills;
Wet jet mills ("Genus PY" manufactured by Genus, "Starburst" manufactured by Sugino Machine, "Nanomizer" manufactured by Nanomizer, etc.) "Claire SS-5" manufactured by M Technique, or "MICROS" manufactured by Nara Machinery Co., Ltd. Medialess dispersers such as; or
In addition, although a roll mill etc. are mentioned, it is not limited to these.

  Further, as the disperser, it is preferable to use a disperser that has been subjected to a metal mixing prevention treatment from the disperser.

  For example, when using a media-type disperser, a disperser in which the agitator and vessel are made of a ceramic or resin disperser, or the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. And as a medium, it is preferable to use ceramic beads, such as glass beads, zirconia beads, or alumina beads. Moreover, also when using a roll mill, it is preferable to use a ceramic roll. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.

  In addition, as a method for adding an additional binder component (a resin component other than a resin having a basic functional group), a group consisting of the organic dye derivative having the basic functional group and the triazine derivative having a basic functional group. While stirring the dispersion formed by dispersing one or more derivatives selected from the above, a resin having a basic functional group, and a carbon material as a conductive additive in a solvent, an additional binder component (basic functional group) A resin component other than a resin having a group) may be added and dissolved in a solid state. In addition, a method in which an additional binder component (a resin component other than a resin having a basic functional group) is dissolved in a solvent in advance and mixed with the dispersion can be used. Further, after adding an additional binder component (a resin component other than a resin having a basic functional group) to the dispersion, the dispersion treatment may be performed again using the dispersion apparatus.

  As a method for adding the positive electrode active material, one or more derivatives selected from the group consisting of the above organic dye derivatives having basic functional groups and triazine derivatives having basic functional groups, and resins having basic functional groups And a positive electrode active material dispersed in a solvent, and a carbon material as a conductive additive is added and dispersed while stirring. In addition, a solvent containing one or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group and a triazine derivative having a basic functional group, a resin having a basic functional group, and a positive electrode active material When being dispersed, a part or all of the carbon material as a conductive aid can be added simultaneously to perform co-dispersing treatment. In addition, as the apparatus for performing mixing and dispersion at this time, the above-described dispersion apparatus used for ordinary pigment dispersion or the like can be used.

  The dispersed particle diameter of the positive electrode active material is desirably 15 μm or less, preferably 10 μm or less, and more preferably 8 μm or less. When the dispersed particle diameter exceeds 15 μm, the battery characteristics may be unstable due to defects or unevenness of the electrode coating film.

  As described above, the positive electrode mixture paste of the present invention is usually produced, distributed, and used as a dispersion (liquid) containing a solvent or a paste. This includes at least one derivative selected from the group consisting of a conductive auxiliary agent, an active material, an organic dye derivative having a basic functional group, and a triazine derivative having a basic functional group, a resin having a basic functional group, , Even when mixed in a dry powder state, it is difficult to uniformly act on the conductive auxiliary agent or active material. By dispersing the conductive auxiliary agent or active material in a solvent by a liquid phase method, the conductive auxiliary agent Or at least one active material, an organic dye derivative having a basic functional group, and one or more derivatives selected from the group consisting of triazine derivatives having a basic functional group, and a resin having a basic functional group, It is because it can be made to act. Moreover, as described below, when an electrode mixture layer is formed on a current collector, it is preferable to apply a liquid dispersion as uniformly as possible and dry it.

  However, for example, a dispersion produced by a liquid phase method may be considered as a dry powder by once removing the solvent for reasons such as transportation cost. And it can also be considered that this dry powder is redispersed with an appropriate solvent and used to form an electrode mixture layer. Therefore, the positive electrode mixture paste of the present invention is not limited to a liquid dispersion, and may be a composition in a dry powder state.

<Lithium secondary battery>
Next, a lithium secondary battery using the composition of the present invention will be described.

The lithium secondary battery includes a positive electrode having a positive electrode mixture layer on a current collector, a negative electrode having a negative electrode mixture layer on the current collector, and an electrolyte containing lithium. An electrode base layer may be formed between the positive electrode mixture layer and the current collector or between the negative electrode mixture layer and the current collector.

  For the electrode, the material and shape of the current collector to be used are not particularly limited, and as the material, a metal or an alloy such as aluminum, copper, nickel, titanium, or stainless steel is used. Copper is preferred as the negative electrode material. In general, a flat foil is used as the shape, but a roughened surface, a perforated foil shape, and a mesh shape can also be used.

  The electrode mixture layer can be formed on the current collector by directly applying the above-mentioned positive electrode mixture paste on the current collector and drying the electrode mixture layer, and after forming the electrode underlayer on the current collector. And a method of applying an agent paste and drying. In addition, when the positive electrode mixture layer is formed on the electrode base layer, after applying the electrode base paste on the current collector, the positive electrode mixture paste may be repeatedly applied in a wet state and dried. good. The thickness of the electrode mixture layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.

  There is no restriction | limiting in particular about the coating method, A well-known method can be used. Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a spray coating method, a gravure coating method, a screen printing method, and an electrostatic coating method. Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating.

<Electrolyte>
As the electrolytic solution constituting the lithium secondary battery of the present invention, an electrolyte containing lithium is dissolved in a non-aqueous solvent. As electrolytes, LiBF ₄ , LiClO ₄ , LiPF ₆ , LiAsF ₆ , LiSbF ₆ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, LiC ₄ F ₉ SO ₃ , Li (CF ₃ SO ₂ ) ₃ C , LiI, LiBr, LiCl, LiAlCl, LiHF ₂ , LiSCN, or LiBPh _4, but are not limited thereto.

The non-aqueous solvent is not particularly limited.
Carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate;
Lactones such as γ-butyrolactone, γ-valerolactone, and γ-octanoic lactone;
Glymes such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, or 1,2-dibutoxyethane;
Esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide or sulfolane; or
Nitriles such as acetonitrile are exemplified. These solvents may be used alone or in combination of two or more.

Furthermore, the electrolyte solution may be a gelled polymer electrolyte held in a polymer matrix. Examples of the polymer matrix include, but are not limited to, an acrylate resin having a polyalkylene oxide segment, a polyphosphazene resin having a polyalkylene oxide segment, or a polysiloxane having a polyalkylene oxide segment.

  The structure of the lithium secondary battery using the positive electrode mixture paste of the present invention is not particularly limited, but is usually composed of a positive electrode and a negative electrode, and a separator provided as necessary, and is a paper type, cylindrical type, button type Various shapes can be formed according to the purpose of use, such as a laminated type.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. When measuring the particle size distribution of the active material, a particle size analyzer FPAR1000 (manufactured by Otsuka Electronics Co., Ltd.) was used. The particle diameter (D50), that is, the dispersed particle diameter was determined. Further, the dispersed particle sizes of the active material dispersion and the electrode mixture paste were determined by determination with a grind gauge (according to JIS K5600-2-5). The viscosity of the active material dispersion was measured at 25 ° C. at a rotation speed of 1 rad / sec using a cone plate viscometer using a cone plate having a diameter of 60 mm and an angle of 0 ° 59 min.

Hereinafter, one or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group and a triazine derivative having a basic functional group are abbreviated as derivatives having a basic functional group.

  In addition, hereinafter, the polymerization average molecular weight (Mw) of the resin having a basic functional group is HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, SUPER-AW3000 as a column, 30 mM triethylamine and 10 mM as an eluent. It is the weight average molecular weight of polystyrene conversion measured using N, N-dimethylformamide of LiBr.

  The amine value is the total amine value (mg KOH / g) measured according to the method of ASTM D 2074.

  The active materials, derivatives having basic functional groups, and resins having basic functional groups used in Examples and Comparative Examples are shown below.

<Positive electrode active material>
LiCoO ₂ : lithium cobalt oxide HLC-17 (Honjo Chemical Co., Ltd.);
Average primary particle size 2.5 μm, specific surface area 0.54 m ² / g.
LiMn ₂ O ₄ : lithium manganate CELLSEED S-LM (Nippon Chemical Industry Co., Ltd.)
Average primary particle size 12.0 μm, specific surface area 0.48 m ² / g.
LiNiO ₂ : lithium nickelate (Honjo Chemical Co.);
Average primary particle size 9.0 μm, specific surface area 0.3 m ² / g.
LiFePO ₄ : lithium iron phosphate (manufactured by TIANJIN STL ENERG Y TECHNOLOGY); average primary particle size 0.2 μm, specific surface area 15 m ² / g.

<Carbon black>
Denka Black HS-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.): Acetylene black, primary particle size 48 nm, specific surface area 48 m ² / g

<Derivatives (A) to (O) having basic functional groups>
-Dye derivatives having basic functional groups: (A) to (E)
・ Triazine derivatives having basic functional groups, others: (F) to (O)

<Resin having a basic functional group>
・ Polymer (G1) type with basic functional group

[Preparation of vinyl resin having amino group (G1-1)]
<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 the solid content of vinyl polymer (a-1) having a weight average molecular weight of 4200 and having two free hydroxyl groups in one end region was 50%. A solution was 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 solution of vinyl polymer (A1-1), 45.2 parts of isophorone diisocyanate, and dibutyltin dilaurate as a catalyst 0. 11 g was 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 having amino group (G1-2)]
<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 the solid content of vinyl polymer (A1-2) having a weight average molecular weight of 4800 and having two free hydroxyl groups in one end region was 50%. A solution was 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 the 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 resin having amino group (G1-3)]
<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 the solid content of vinyl polymer (A1-3) having a weight average molecular weight of 3000 and having two free hydroxyl groups in one end region was 50%. A solution was 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 dibutyltin dilaurate as a catalyst 0. 13 g was 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 the polymer (G1-3). The weight average molecular weight of the polymer (G1-3) was 11900, and the amine value was 25.2 mg KOH / g.
・ Polymer (G2) type with basic functional group

[Preparation of polyester polymer (G2-1) having amino group]
<Synthesis of polyester (A2-1) having 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 Charge 0.1 part of hydroquinone, heat and stir for 4 hours at 120 ° C. under a dry air flow, and confirm that 95% of the reaction has been confirmed by solid content measurement. The reaction is terminated, and 171 parts of N-methyl-2-pyrrolidone is added. Further, the solution was adjusted to a solid content of 70% by weight to obtain a 70% solid solution of polyester (A2-1) having a weight average molecular weight of 6500 and having one acryloyl group at one end.

<Synthesis of polymer (G2-1)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 18.9 parts of iminobispropylamine and 248 parts of N-methyl-2-pyrrolidone and heated to 50 ° C. to obtain polyester (A2-1 ) 70% by weight solid solution of 571) was added dropwise over 30 minutes and the reaction was continued for another hour, followed by dropwise addition of a mixture of 16.0 parts isophorone diisocyanate and 112 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 (G2-1) having a weight average molecular weight of 13,000 and an amine value of 36 mgKOH / g A 30 wt% solution was obtained.
[Preparation of polyester polymer having amino group (G2-2)]

<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- 571 parts of a 70% by weight solid content solution of 1) was added dropwise over 30 minutes and reacted for another hour, and then a mixture of 18.3 parts of isophorone diisocyanate and 207 parts of N-methyl-2-pyrrolidone was added over 30 minutes. The solution was added dropwise, reacted for another 2 hours, N-methyl-2-pyrrolidone was added to adjust the solid content to 30% by weight, and the solid of polymer (G2-2) having a weight average molecular weight of 27000 and an amine value of 41 mgKOH / g A 30 wt% solution was obtained.

[Synthesis of vinyl polymer having amino group (G2-3)]
<Synthesis of vinyl polymer (A2-2) having 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, and further heated and stirred for 2 hours, further adjusted to a solid content of 50% by weight, a solid of a vinyl polymer (A2-2) having a weight average molecular weight of 4500 and having two acryloyl groups at one end A 50% by weight solution was obtained.

<Synthesis of polymer (G2-3)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 27.8 parts of iminobispropylamine and 184 parts of N-methyl-2-pyrrolidone and heated to 50 ° C. to give a vinyl polymer (A2 -2) 500 parts of a solid 70% by weight solution was added dropwise over 30 minutes and the reaction was continued for another hour, and then a mixture of 15.7 parts of isophorone diisocyanate and 121 parts of N-methyl-2-pyrrolidone was added over 30 minutes. Of the polymer (G2-3) having a weight average molecular weight of 15200 and an amine value of 94 mgKOH / g. A 30 wt% solids solution was obtained.

<Binder>
-KF polymer W # 1100 (manufactured by Kureha):
Polyvinylidene fluoride (PVDF), weight average molecular weight of about 280,000

<Preparation of positive electrode active material surface-treated with resin having basic functional group>
In accordance with the composition and treatment method shown in Table 5, the surface treatment of the positive electrode active material with a resin having a basic functional group was performed. The amount of the resin having a basic group is expressed in terms of solid content.

[Surface treatment positive electrode active material (1)]
Lithium cobaltate (LiCoO ₂ , HLC-17, average primary particle size 2.5 μm, specific surface area 0.54 m ² / g, manufactured by Honjo Chemical Co., Ltd.) 100 parts as a positive electrode active material, basic derivative (A) 0.1 Part, 0.5 part of basic dispersion resin (G1-1) solution (solid content: 0.2 part), and 25 parts of N-methyl-2-pyrrolidone (NMP) were charged, treated with two rolls, and dried. Thus, a surface-treated positive electrode active material (1) was obtained.

[Surface treatment positive electrode active material (2)]
In a kneader, 100 parts of lithium manganate (LiMn ₂ O ₄ , CELLSEED S-LM, average primary particle size 12.0 μm, specific surface area 0.48 m ² / g, manufactured by Nippon Chemical Industry Co., Ltd.), which is a positive electrode active material, basic A derivative (E) 0.3 part, a basic dispersion resin (G1-2) solution 0.25 part (solid content 0.1 part), and 25 parts of N-methyl-2-pyrrolidone (NMP) were charged and kneaded. Went. The obtained processed product was dried and pulverized to obtain a surface-treated positive electrode active material (2).

[Surface treatment positive electrode active material (3)]
To a kneader, lithium iron phosphate (LiFePO ₄ , average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) 100 parts as a positive electrode active material, basic derivative (I) 0.5 Part, 0.5 part of basic dispersion resin (G1-3) solution (solid content 0.2 part), and 43 parts of N, N-dimethylformamide (DMF) were charged and kneaded. The obtained treated product was added to 1000 parts of hexane and stirred, and then the aggregate was collected by filtration, dried and pulverized to obtain a surface-treated positive electrode active material (3).

[Surface treatment positive electrode active material (4)]
Lithium iron phosphate (LiFePO ₄ , average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY Co., Ltd.) 100 parts as a positive electrode active material, basic derivative (M) 1.5 Part, 1.67 parts (0.5 part solids) of a resin (G2-1) having a basic functional group is dissolved in 15 parts of N-methyl-2-pyrrolidone (NMP) and crushed with a dry jet mill The surface-treated positive electrode active material (4) was obtained by processing while drying.

[Surface treatment positive electrode active material (5)]
Lithium iron phosphate as a positive electrode active material (LiFePO ₄ , average primary particle size 0.2 μm, specific surface area 15 m ² / g, manufactured by TIANJIN STL ENERGY TECHNOLOGY) 100 parts, basic derivative (B) 1.0 part, base Surface dispersion resin (G2-2) 3.33 parts (solid content 1.0 part) and N-methyl-2-pyrrolidone (NMP) 25 parts, treated with two rolls and dried A treated positive electrode active material (5) was obtained.

<Evaluation of wettability of positive electrode active material with and without surface treatment>
Various positive electrode active materials not treated with the dispersant and various positive electrode active materials treated with the dispersant were dried under reduced pressure at 80 ° C. for 10 hours. Subsequently, the dried product was pulverized with an agate mortar and further dried under reduced pressure at 80 ° C. for 12 hours. The obtained dried product was again pulverized in an agate mortar, and then loaded with 500 kgf / cm ² with a tablet molding machine (Specac) to produce a positive electrode active material pellet (diameter 10 mm, thickness 0.5 mm). did. A droplet in which ethylene carbonate and diethyl carbonate were mixed 1: 1 was dropped on this pellet with a microsyringe, and the time for the droplet to penetrate the pellet was measured. This measurement was performed 5 times for each sample, and those whose average permeation time was less than 1 second was “◎”, those that were 1 second or more and less than 5 seconds were “◯”, 5 seconds or more and 10 seconds. Those that were less than “Δ” were those that were 10 seconds or longer, and “x”. The results of the wettability evaluation of the positive electrode active material are shown in Table 1.

≪Preparation of positive electrode active material dispersion≫
[Positive electrode active material dispersion (1)]
In a container, as a solvent, 26.4 parts of N-methyl-2-pyrrolidone, 0.1 part of a basic derivative (C), 3.5 parts of a basic dispersion resin (G1-1) solution (1.4 parts of solid content) ) And mixed and stirred to completely or partially dissolve the derivative. Next, 70 parts of lithium cobaltate LiCoO ₂ was added as a positive electrode active material and dispersed with a homogenizer as a medialess disperser to obtain a positive electrode active material dispersion (1).

[Adjustment of Positive Electrode Active Material Dispersions (2) to (8)]
Positive electrode active material dispersions (2) to (8) were obtained by the same method as the adjustment of the positive electrode active material dispersion (1) so as to have the composition shown in Table 6.

[Positive electrode active material dispersion (9)]
In a container, as a solvent, 28.84 parts of N-methyl-2-pyrrolidone, 0.44 part of basic derivative (N), 0.23 part of 30% resin (G2-2) having a basic functional group (solid) 0.07 part min) was mixed and stirred to completely or partially dissolve the resin. Next, 70.49 parts of the surface-treated positive electrode active material (3) was added and dispersed with a homogenizer as a medialess disperser to obtain a positive electrode active material dispersion (9).
[Preparation of positive electrode active material dispersion (10)]
A positive electrode active material dispersion (10) was obtained according to the composition shown in Table 6 in the same manner as in the preparation of the positive electrode active material dispersion (9).

[Positive electrode active material dispersion (11)]
In a container, 29.22 parts of purified water as a solvent, binder 2, that is, 0.78 part of 60% polytetrafluoroethylene PTFE aqueous dispersion (PTFE, 30-J, manufactured by Mitsui / DuPont Fluorochemical) (solid content 0) .47 parts) was added and mixed and stirred to completely or partially dissolve the resin. Next, 70 parts of lithium iron phosphate LiFePO ₄ as a positive electrode active material was added and dispersed with a homogenizer as a medialess disperser to obtain a positive electrode active material dispersion (11).

[Preparation of positive electrode active material dispersion (12)]
As a solvent, 30 parts of N-methyl-2-pyrrolidone and 70 parts of lithium iron phosphate LiFePO ₄ were added to a container and dispersed with a homogenizer as a medialess disperser to obtain a positive electrode active material dispersion (12).

In Table 6, abbreviations are as shown below.
Basic resin: Resin having basic functional group Basic derivative: Derivative having basic functional group PTFE: Polytetrafluoroethylene (aqueous dispersion)
NMP: N-methyl-2-pyrrolidone

[Dispersion evaluation of positive electrode active material dispersions (1) to (12)]
Table 7 shows the results of dispersion evaluation of the obtained positive electrode active material dispersions (1) to (12).

It shows about the material described in Table 1 and 2, and the material used by the Example and the comparative example. ≪Positive electrode active material≫
LiCoO ₂ : lithium cobalt oxide HLC-17 (manufactured by Honjo Chemical Co.); average primary particle size 2.5 μm, specific surface area 0.54 m ² / g.
LiMn ₂ O ₄ : lithium manganate CELLSEED S-LM (Nippon Chemical Industry Co., Ltd.); average primary particle size 12.0 μm, specific surface area 0.48 m ² / g.
LiNiO ₂ : lithium nickelate (Honjo Chemical Co.); average primary particle size 9.0 μm, specific surface area 0.3 m ² / g.
LiFePO ₄ : lithium iron phosphate (manufactured by TIANJIN STL ENERGY TECHNOLOGY); average primary particle size 0.2 μm, specific surface area 15 m ² / g.

≪Resin having basic functional group≫
<Resin polymer having basic functional group (G1) type>
G1-1: Polyvinyl polymer having an 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.

<Resin polymer having basic functional group (G2) type>
G2-1: Polyester polymer having an 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.

<Resin (H) having basic functional group other than (G1) and (G2) types>
H1: Azisper PB821 (manufactured by Ajinomoto Fine Techno); resin having amino group H2: SOLPERSE24000GR (manufactured by Nippon Lubrizol); resin having amino group

≪Binder≫
PVDF: KF polymer W # 1100 (manufactured by Kureha); polyvinylidene fluoride (PVDF), weight average molecular weight of about 280,000.
PTFE: PTFE 30-J (manufactured by Mitsui DuPont Fluorochemical Co.); 60% polytetrafluoroethylene (PTFE) aqueous dispersion.

≪Carbon black for conductive aid≫
HS-100: Denka Black HS-100 (manufactured by Denki Kagaku Kogyo); acetylene black, primary particle size 48 nm, specific surface area 48 m ² / g.

≪Preparation of positive electrode mixture paste for lithium secondary battery≫
As described below, using positive electrode active material dispersions (1) to (12), the carbon black, a binder, and a solvent, positive electrode mixture pastes (1) to (12) and comparative positive electrode mixture paste (1 ) To (2) were adjusted.

[Example 1]
Positive electrode active material dispersion (1) For 64.286 parts, 1.536 parts of polyvinylidene fluoride (PVDF, KF polymer W # 11000, manufactured by Kureha) as a binder and N-methyl-2-pyrrolidone 31. After mixing 678 parts with a planetary mixer, 2.5 parts of Denka Black HS-100 was added as a conductive aid, and further kneaded with a planetary mixer to obtain a positive electrode mixture paste (1) [solid content: 50% , Solid content composition weight ratio: positive electrode active material / carbon black / others (derivative having basic functional group and resin + binder) = 90/5/5]. The results are shown in Table 8.

[Examples 2 to 9, Comparative Example 2]
In the same manner as in Example 1, according to the composition of Table 8, positive electrode mixture pastes (2) to (10) and comparative positive electrode mixture paste (2) [solid content: 50%, solid content composition weight ratio: positive electrode Active material / carbon black / others (derivative and resin having a basic functional group + binder) = 90 /
5/5] was obtained. Examples 7 and 8 are reference examples.

[Example 10]
For positive electrode active material dispersion (10) 64.286 parts, as binder, 2.613 parts of 60% polytetrafluoroethylene PTFE aqueous dispersion (PTFE 30-J, manufactured by Mitsui & DuPont Fluorochemicals) (solid content) 1.568 parts) and 30.601 parts of purified water using a planetary mixer, and then adding 2.5 parts of Denka Black HS-100 as a conductive aid, and further kneading with a planetary mixer. A paste (10) [solid content: 50%, solid content composition weight ratio: positive electrode active material / carbon black / others (derivative having basic functional group and resin + binder) = 90/5/5] was obtained.

[Comparative Example 1]
Comparative positive electrode mixture paste (1) [solid content: 50%, solid content composition weight ratio: positive electrode active] according to the composition of Table 4 in the same manner as in Example 10 except that the positive electrode active material dispersion (11) was used. Substance / carbon black / others (resin having a basic functional group + binder) = 90/5/5].

Positive electrode mixture pastes (1) to (10) and comparative positive electrode mixture pastes (1) and (2)
Table 8 shows the evaluation results of dispersion stability (initial and dispersion particle diameter after 3 days at 50 ° C.). Examples 7 and 8 are reference examples.

  In Table 8, abbreviations are as follows.

Basic resin: Resin having basic functional group Basic derivative: Derivative having basic functional group PVDF: Polyvinylidene fluoride PTFE: Polytetrafluoroethylene (aqueous dispersion)
NMP: N-methyl-2-pyrrolidone

<Preparation of negative electrode mixture paste for lithium secondary battery>
After mixing 5 parts of polyvinylidene fluoride PVDF (KF polymer W # 1100, manufactured by Kureha) and 100 parts of N-methyl-2-pyrrolidone with 2 parts of carbon black HS-100 with a high-speed disper, 93 parts of mesophase carbon (MCMB 6-28, average particle size 5 to 7 μm, specific surface area 4 m ² / g made by Osaka Gas Chemical Co., Ltd.) was added as a substance and kneaded by a planetary mixer, and a negative electrode mixture paste (solid content: 50%) , Solid content composition weight ratio: negative electrode active material / carbon black / others (dispersion resin having basic functional group + binder) = 93/2/5).

≪Lithium secondary battery positive electrode characteristics evaluation≫
[Examples 1-10, Comparative Examples 1-2]
<Preparation of positive electrode for lithium secondary battery>
The positive electrode mixture pastes (1) to (10) prepared earlier and the comparative positive electrode mixture pastes (1) to (2) were applied on a 20 μm thick aluminum foil serving as a current collector using a doctor blade. Then, it heat-dried under reduced pressure and performed the rolling process by a roll press etc., and produced the 50-micrometer-thick positive mix layer. (See Table 4)

<Preparation of negative electrode for lithium secondary battery>
The negative electrode mixture paste prepared above was applied onto a copper foil having a thickness of 20 μm to be a current collector using a doctor blade, and then dried by heating under reduced pressure, and subjected to a rolling treatment by a roll press or the like, and having a thickness of 50 μm. A negative electrode mixture layer was prepared.

<Assembly of lithium secondary battery positive electrode evaluation cell>
A separator made of a porous polypropylene film between the working electrode and the counter electrode (# 2400, manufactured by Celgard Co., Ltd.) with the positive electrode fabricated previously punched out to a diameter of 9 mm and used as a working electrode and a metal lithium foil (thickness 0.15 mm) as a counter electrode Is inserted and laminated, filled with an electrolyte (nonaqueous electrolyte in which LiPF ₆ is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate in a ratio of 1: 1), and a bipolar metal cell (Hosen) (HS flat cell). The cell was assembled in a glow box substituted with argon gas, and after the cell was assembled, predetermined battery characteristics were evaluated.

<Assembly of lithium secondary battery negative electrode evaluation cell>
A separator made of a porous polypropylene film between the working electrode and the counter electrode (# 2400, manufactured by Celgard Co., Ltd.) with the negative electrode prepared previously punched out to a diameter of 9 mm and used as a working electrode, and a metallic lithium foil (thickness 0.15 mm) as a counter electrode Is inserted and laminated, filled with an electrolyte (nonaqueous electrolyte in which LiPF ₆ is dissolved at a concentration of 1 M in a mixed solvent of ethylene carbonate and diethyl carbonate in a ratio of 1: 1), and a bipolar metal cell (Hosen) (HS flat cell). The cell was assembled in a glow box substituted with argon gas, and after the cell was assembled, predetermined battery characteristics were evaluated.

<Characteristic evaluation of lithium secondary battery positive electrode>
[Charge / Discharge Cycle Characteristics Examples 1 to 10, Comparative Examples 1 to 2]
The produced battery evaluation cell was fully charged at a constant current and constant voltage charge (upper limit voltage 4.2 V) at a room temperature (25 ° C.) with a charge rate of 0.2 C and 1.0 C, and at a constant current at the same rate as during charging. Charge / discharge for discharging to a discharge lower limit voltage of 3.0V is defined as one cycle (charge / discharge interval rest time 30 minutes), and this cycle is performed for a total of 20 cycles to evaluate charge / discharge cycle characteristics (Evaluation apparatus: SM-8 manufactured by Hokuto Denko Co., Ltd.) ) Moreover, the cell after evaluation was decomposed | disassembled and the external appearance of the electrode coating film was confirmed visually.
The evaluation results are shown in Table 9 . Examples 7 and 8 are reference examples.

[Direct Current Internal Resistance Measurement Examples 1 to 10, Comparative Examples 1 to 2]
The produced battery evaluation cell was charged at a constant current and a constant voltage at a room temperature (25 ° C.) and a charge rate of 0.2 C (
The battery voltage was measured after discharging for 5 seconds at a constant current of 0.1C, 0.2C, 0.5C, and 1.0C. The voltage value was plotted against the current value, and the slope of the obtained linear relationship was defined as the internal resistance. The evaluation results are shown in Table 9, and are shown as relative values when the measured internal resistance value of Example 1 is 100. Examples 7 and 8 are reference examples.

As can be seen from Tables 5 to 9, in the examples, by using a derivative having a basic functional group and a dispersion resin, the dispersibility of the positive electrode active material was improved. Dispersibility and stability over time were improved. Further, as compared with the comparative example, a tendency of lowering the internal resistance was observed, and the battery capacity and the 20 cycle capacity maintenance rate were improved.

Claims (16)

One or more derivatives selected from the group consisting of an organic dye derivative having a basic functional group and a triazine derivative having a basic functional group, a resin having a basic functional group, and a positive electrode active material. A positive electrode material paste for a secondary battery,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
Resin der having one or more basic functional group selected from the group consisting of Ru lithium secondary battery positive electrode material mixture paste.

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
A vinyl polymer (A1) having two hydroxyl groups in one terminal region constituting the polymer (G1) is present in the presence of a compound (a11) having two hydroxyl groups and one thiol group in the molecule. , ethylenically unsaturated monomer (a12) the characterized by comprising by radical polymerization of claim 1, wherein the lithium secondary battery positive electrode material mixture paste. Polymers having one or two (meth) acryloyl groups in one terminal region constituting the polymer (G2) (A2) is a vinyl polymer, or according to claim 1, comprising a polyester Positive electrode mixture paste for lithium secondary battery. The positive electrode active material is lithium iron phosphate. The positive electrode material mixture paste for a lithium secondary battery according to any one of claims 1 to 3 . Furthermore, the positive mix paste for lithium secondary batteries in any one of Claims 1-4 containing binder components other than resin which has a basic functional group. The positive electrode mixture paste for a lithium secondary battery according to claim 5 , wherein the binder component is a polymer compound containing a fluorine atom in the molecule. The positive electrode mixture paste for a lithium secondary battery according to any one of claims 1 to 6 , further comprising a solvent. Furthermore, comprising a carbon material as a conductive additive according to claim 1-7 or wherein the lithium secondary battery positive electrode material mixture paste. Dispersing one and more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, and the positive electrode active material, the solvent A method for producing a positive electrode mixture paste for a lithium secondary battery , comprising:
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
A method for producing a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
And one or more derivative selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, and a positive electrode active material, a conductive additive A method of producing a positive electrode material mixture paste for a lithium secondary battery, wherein the carbon material is co-dispersed in a solvent ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
A method for producing a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
And one or more derivative selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, and a positive electrode active material, a conductive additive A method for producing a positive electrode mixture paste for a lithium secondary battery, wherein the carbon material and a binder component are co-dispersed in a solvent ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
A method for producing a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
Dispersing one and more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, and the positive electrode active material, the solvent And a dispersion material obtained by mixing a carbon material as a conductive additive with a positive electrode material mixture paste for a lithium secondary battery ,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
A method for producing a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
1 or a more derivatives selected from the group consisting of a triazine derivative having an organic dye inductive element and basic functional group having a basic functional group, and a resin having a basic functional group, and a positive electrode active material dispersed in a solvent A method of producing a positive electrode mixture paste for a lithium secondary battery, in which a carbon material as a conductive additive and a binder component are mixed with the dispersion obtained by:
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
A method for producing a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
Organic dye induction having a basic functional group, triazine derivatives having a basic functional group, and one or more processing agents selected from the group consisting of a resin having a basic functional group, the pre-treated positive electrode active material a method according to claim 9-13 or described lithium secondary battery positive electrode material mixture paste used,
The organic dye derivative having a basic functional group is an organic dye derivative represented by the following general formula (7),
The triazine derivative having a basic functional group is a triazine derivative represented by the following general formula (2),
A resin having a basic functional group is
The urethane prepolymer (C1) having an isocyanate group at both ends formed by reacting the hydroxyl group of the vinyl polymer (A1) having two hydroxyl groups in one end region with the isocyanate group of the diisocyanate (B1). An isocyanate group;
A primary and / or secondary amino group of an amine compound containing at least a polyamine (D1);
A polymer (G1) having an amine value of 1 to 100 mgKOH / g obtained by reacting
The (meth) acryloyl group of the polymer (A2) having one or two (meth) acryloyl groups in one terminal region and the primary of the polyamine (B2) having one or more primary and / or secondary amino groups And / or a secondary amino group, and a primary and / or secondary amino group of a polymer (C2) having an amino group obtained by reacting, and
An isocyanate group of a polyisocyanate (D2) having two or more isocyanate groups;
A polymer (G2) having an amine value of 5 to 100 mgKOH / g obtained by reacting
A method for producing a positive electrode mixture paste for a lithium secondary battery, which is a resin having one or more basic functional groups selected from the group consisting of:

General formula (7):
{In general formula (7),
Z is at least one selected from the group represented by the following general formulas (8), (9), and (10),
n ¹⁰² is an integer from 1 to 4,
R ¹¹² is an organic dye residue, a heterocyclic residue or an aromatic ring residue;
The organic dye residue is a diketopyrrolopyrrole dye, an azo dye, a phthalocyanine dye, an anthraquinone dye or a quinacridone dye,
A heterocyclic residue is an acridone residue;
The aromatic ring residue is an anthraquinone residue.
General formula (8):
General formula (9):
General formula (10):
[In the general formulas (8) to (10),
X ¹¹⁰ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, or —CH ₂ —,
v ¹ is an integer from ¹ to 10,
R ¹¹³ , And R ¹¹⁴ are each independently an alkyl group, or a heterocyclic residue containing an additional nitrogen or oxygen atom together with R ¹¹³ and R ¹¹⁴ ,
R ¹¹⁵ , R ¹¹⁶ , R ¹¹⁷ And R ¹¹⁸ is a hydrogen atom,
R ¹¹⁹ is an alkyl group. ]}

General formula (2):
{In general formula (2)
X ¹⁰¹ is —NH—, or —X ¹⁰² —Y ¹⁰¹ —X ¹⁰³ —,
X ¹⁰² _{is, -CONH -, - SO 2 NH-} , or -NHSO ₂ - and it is,
X ¹⁰³ is —NH—,
Y ¹⁰¹ is an arylene group composed of 1 to 20 carbon atoms,
P is a substituent represented by any of the following general formulas (3), (4), or (5),
Q is —O—R ¹⁰² , —NH—R ¹⁰² , —X ¹⁰¹ —R ¹⁰¹ , or a substituent represented by any of the following general formulas (3), (4), or (5),
R ¹⁰² is a hydrogen atom, an alkyl group, or an aryl group,
R ¹⁰¹ is an organic dye residue, a heterocyclic residue, an aromatic ring residue, or a group represented by the following general formula (6),
The organic dye residue is an anthraquinone dye or a dioxazine dye,
The heterocyclic residue is a triazine residue, a benzimidazolone residue, or a carbazole residue,
The aromatic ring residue is a benzene residue or an anthraquinone residue,
n ¹⁰¹ have an integer of 1 to 4.

General formula (3):
General formula (4):
General formula (5):
[In the general formulas (3) to (5),
X ¹⁰⁴ is a direct bond or -X ¹⁰⁵ -Y ¹⁰² -X ¹⁰⁶ - a and,
X ¹⁰⁵ is —NH— or —O—.
X ¹⁰⁶ is a direct bond, —SO ₂ —, or —CH ₂ NHCOCH ₂ —,
Y ¹⁰² is composed of 1 to 20 carbon atoms, an alkylene group, or arylene group,
v is an integer from 1 to 10,
R ¹⁰³ And R ¹⁰⁴ are each independently a hydrogen atom or an alkyl group,
R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ And R ¹⁰⁸ is a hydrogen atom,
R ¹⁰⁹ is an alkyl group. ]

General formula (6):
[In general formula (6),
T is -X ¹⁰⁸ -R ^110,
U is W ¹⁰² ,
W ¹⁰² is a substituent represented by the general formula (5),
X ¹⁰⁷ is a -NH-,
X ¹⁰⁸ is —NH—;
Y ¹⁰³ is an alkylene group composed of 1 to 20 carbon atoms,
R ¹¹⁰ is a heterocyclic residue;
A heterocyclic residue is a benzimidazolone residue. ]}
A lithium secondary battery comprising: a positive electrode having a positive electrode mixture layer on a current collector; a negative electrode having a negative electrode mixture layer on the current collector; and an electrolyte containing lithium, wherein the positive electrode mixture layer A lithium secondary battery formed by using the positive electrode mixture paste for a lithium secondary battery according to claim 8 . Claims 10-14 or claim 15 lithium secondary battery according made is formed using the produced lithium secondary battery positive electrode material mixture paste by the method according.