JP2013229263A - Composition for electrochemical element and electrode for electrochemical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an electrode for an electrochemical element, having high coating film strength and high adhesion with a base material, on the background of problems in the conventional art; an electrode for an electrochemical element, having excellent cycle characteristics even in repeated use and a high-temperature environment; and a composition for an electrochemical element, which has rheology characteristics suitable for coating and is a high solid content, as a composition for forming the electrode for an electrochemical element.SOLUTION: A composition for an electrochemical element includes: a thin film particle containing a graphite oxide; and a dispersion medium.

Description

  The present invention relates to an electrode for an electrochemical element that is tough and excellent in substrate adhesion.

In recent years, various efforts have been made around the world to realize a low-carbon society, and research and development aimed at reducing carbon dioxide gas have attracted attention. In particular, expectations are high for electrochemical elements that are devices that convert chemical energy into electrical energy. In addition, small portable electronic devices such as digital cameras and mobile phones have been widely used, and a small, lightweight and large-capacity storage element is desired as the power source. Various electrochemical elements have been developed for these applications, and in particular, demand for power storage elements such as secondary batteries and capacitors is expanding.

As an energy storage device, energy density, power density, and cycle characteristics are good,
Interest in lithium ion secondary batteries, electric double layer capacitors, hybrid capacitors, etc. is particularly high. Among these, a lithium ion secondary battery having a particularly high energy density is advantageous from the viewpoint of size reduction and weight reduction.

An electrode, which is one of constituent members of an electrochemical element, is formed by forming a layer mainly made of an electrode active material on a current collector. Since it is difficult to form a film only with an electrode active material, for example, a paste obtained by kneading an electrode active material, a conductive additive, a binder, and a dispersion medium is applied to the surface of the current collector and dried. The manufacturing method is disclosed (Patent Document 1, Patent Document 2).

However, in the conventional technique, the adhesion between the current collector and the electrode active material layer is not always sufficient. In an electrochemical device using an electrode having insufficient adhesion between the electrode active material layer and the current collector, the electrochemical characteristics cannot be improved, and the electrode active material is collected as the charge / discharge cycle progresses. There was a problem that performance gradually deteriorated due to gradual removal from the electric body.

In order to solve this problem and improve electrochemical characteristics and durability, methods using various resins as binders have been disclosed (Patent Documents 3 and 4). However, even with the methods of Patent Documents 3 and 4, the effect of improving the adhesion between the electrode active material layer and the current collector is not necessarily sufficient. As described above, when an electrochemical element having an electrode with insufficient adhesion is repeatedly used or exposed to a high temperature environment for a long time, there is a problem that the performance is rapidly deteriorated. Particularly in the secondary battery, the deterioration of the performance was remarkable due to heat generation during charging and discharging.

Further, in the conventional technology, since the binding force between the respective materials such as the electrode active material and the conductive material is not sufficient, the toughness of the electrode active material layer is insufficient. In some cases, the active material gradually dropped from the current collector or cracked. For this reason, the thickness of the electrode active material layer is limited, and there is a problem that the performance per electrode area cannot be improved.

JP-A-11-67213 JP 2002-237305 A JP-A-9-161803 JP 7-226205 A

The present invention has been made against the background of the above-described problems of the prior art, and an object thereof is to provide an electrode for an electrochemical element having high coating strength and high substrate adhesion. It is another object of the present invention to provide an electrode for an electrochemical device that has excellent cycle characteristics even under repeated use and high temperature environments.

Another object of the present invention is to provide an electrochemical device composition having rheological properties suitable for coating and having a high solid content as a composition for forming an electrode for an electrochemical device as described above. To do.

That is, the present invention relates to a composition for an electrochemical device comprising thin film particles containing graphite oxide and a dispersion medium.

The present invention further relates to the composition for an electrochemical device comprising an electrode active material.

The present invention also provides an electrode for an electrochemical element having at least a current collector and a composite material layer, wherein the composite material layer is a layer formed by applying and drying the composition for an electrochemical device. It relates to an electrode.

Further, the present invention is an electrode for an electrochemical device having at least a current collector, a base layer, and a composite layer, wherein the base layer and / or the composite layer is coated with the composition for electrochemical device, The present invention relates to an electrode for an electrochemical element which is a dried layer.

According to the present invention, it is possible to provide an electrode for an electrochemical element that has high coating strength and high substrate adhesion and is excellent in cycle characteristics even under repeated use or high temperature environment. In addition, according to the present invention, it is possible to provide an electrochemical element composition having rheological properties suitable for coating and having a high solid content.

Hereinafter, the electrode for an electrochemical element and the composition for an electrochemical element in the present invention will be described.

Although it does not specifically limit as an electrochemical element in this invention, It is an apparatus which mutually converts a chemical energy and an electrical energy at least. Specific examples include primary batteries, secondary batteries, power storage elements such as capacitors, and power generation elements such as fuel cells.

<Thin film particles>
Hereinafter, the thin film-like particles containing graphite oxide used in the present invention will be described.
Graphite oxide obtained by oxidizing graphite is a particle in which a layer in which carbon atoms are covalently bonded in a planar direction is a single layer or a plurality of layers are overlapped, and is on the edge of the carbon skeleton and / or
Or it is estimated that it has oxygen-containing polar functional groups, such as a phenol group, a quinone group, a carboxyl group, a carbonyl group, an epoxy group, a hydroxyl group, on a plane. Among graphite oxides, those having a small number of layers form thin film-like particles characterized in that the size in the plane direction with respect to the thickness is very large. The thin film particles made of graphite oxide may be used after being chemically and / or physically modified.

(Production method)
As graphite, natural graphite and artificial graphite are used, and expanded graphite produced by expanding these layers can also be used. Examples of natural graphite include scaly graphite, massive graphite, earthy graphite, and the like. Many types of artificial graphite are known depending on the production method thereof, and examples thereof include those obtained by firing and graphitizing graphitizable organic substances such as coal-based coke and petroleum-based coke.

In order to obtain a thin film-like particle having a high ratio of the size in the plane direction to the thickness, it is preferable to use graphite having a developed layer structure. That is, natural graphite and artificial graphite heat-treated particularly at high temperature are preferable raw materials because they have high crystallinity.

In order to obtain thin film-like particles efficiently, it is preferable to use graphite that has been thinned in advance by mechanical treatment or the like. In addition to expanded graphite, graphene plates thinned from several layers to about a dozen layers are commercially available and are preferably used.

Oxidation of graphite causes oxygen-containing polar functional groups such as phenol group, quinone group, carboxyl group, carbonyl group, epoxy group and hydroxyl group to be covalently bonded to graphite. In order to obtain thin film-like particles, it is preferable to introduce oxygen-containing polar functional groups not only on the surface of graphite but also between the layers of graphite.

The method for oxidizing graphite is not particularly limited, and any method that oxidizes a carbon material can be used. Specifically, high temperature treatment in air, sulfuric acid,
Oxidic acids such as nitric acid, chloric acid, permanganic acid, chromic acid, dichromic acid and their salts, peroxy acids such as organic peroxides and peroxomonosulfate, and their known oxidants such as nitrogen dioxide and ozone Or the like can be used. By selecting oxidation conditions according to the crystallinity, particle diameter, layer structure, etc. of the graphite used, thin film particles can be obtained efficiently.

In particular, as a method for oxidizing graphite, since high oxidizing power is required, Brodie method using nitric acid and potassium chlorate, S using nitric acid, sulfuric acid and potassium chlorate.
Taudenmaire method, Hu using sulfuric acid, sodium nitrate and potassium permanganate
The mmers-Offeman method is preferred. The Hummers-Offeman method is particularly preferable because oxidation between graphite layers easily proceeds.

The graphite oxide can be purified as necessary. Although it does not specifically limit as a purification method, Specifically, techniques, such as filtration, decantation, centrifugation, and dialysis, can be used.

The solvent can be exchanged for a dispersion of thin film-like particles containing graphite oxide using the same method as in the purification step described above. For example, when graphite is oxidized by the Hummers-Offeman method, purified water is suitable as a solvent for washing. Therefore, when other solvent is used as a dispersion medium, after washing with purified water to obtain an aqueous dispersion, The method of exchanging the solvent is efficient.

In general, graphite forms thin film-like particles only through an oxidation process and a purification process, but it can be further thinned. Although it does not specifically limit as a thin film formation process, For example, the disperser normally used for pigment dispersion etc. other than ultrasonic irradiation and heat processing can also be used.

Specific examples of the disperser include mixers such as a disper, a homomixer, or a planetary mixer;
Homogenizers such as "Clairemix" manufactured by M Technique or PRIMIX "Fillmix";
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" from Genus, "Starburst" from Sugino Machine, "Nanomizer" from Nanomizer, etc.) "Claire SS-5 from M Technique"
"Silverson mixer" manufactured by Silverson or "Micros" manufactured by Nara Machinery Co., Ltd.
Medialess disperser such as
Other examples include, but are not limited to, a roll mill. Also, a plurality of types of devices can be used in combination.
From the viewpoint of suppressing the destruction of the thin film particles, it is preferable to use a roll mill, homogenizers, or medialess disperser. Further, it is preferable to use a disperser that has been subjected to a metal mixing prevention treatment from the disperser.

(Physical properties)
The thin film-like particles containing graphite oxide preferably contain 30% by weight or more of oxygen element with respect to carbon element. Here, the ratio of oxygen element to carbon element is represented by (weight of oxygen element contained per unit weight ÷ weight of carbon element contained per unit weight),
It shall be expressed in the form of weight percent. The weight of the carbon element and the oxygen element is, for example, an element analyzer by a combustion method (such as “2400 type CHN elemental analysis” manufactured by Perkin Elmer).
Measured in

When the oxygen element is less than 30 weight percent with respect to the carbon element, the introduction amount of the oxygen-containing polar functional group is not sufficient, so that the affinity with other components and / or the dispersion medium in the electrode is reduced, and the electrode composition It may be difficult to mix uniformly in the product. Moreover, there exists a possibility that coating-film adhesiveness and coating-film toughness may be inferior. The oxygen element is preferably contained in an amount of 50 weight percent or more with respect to the carbon element, and more preferably 70 weight percent or more. It has been difficult to produce thin film-like particles containing 200 weight percent or more of oxygen element with respect to carbon element.

The thin film-like particles preferably have a thickness of 0.3 nm or more and less than 50 nm. The thickness is 50n
When it is m or more, the morphological characteristics as a thin film-like particle may be lost, and the flexibility may be lowered. In addition, it was not possible to produce thin film particles having a thickness of less than 0.3 nm.

Moreover, it is preferable that the average aspect-ratio (namely, ratio of the below-mentioned average particle diameter X (average length of the longitudinal direction) with respect to the thickness t) of a thin film-like particle | grain is 20 or more. Average aspect ratio is 2
When it is less than 0, the morphological characteristics as a thin film-like particle are lacking, and flexibility may be reduced. The average aspect ratio is preferably 100 or more, and more preferably 1000 or more. It is difficult to produce thin film-like particles having an average aspect ratio exceeding 100,000, and the dispersion state becomes unstable due to the large particle size, and it may be difficult to uniformly mix the electrode composition.

In the thin film-like particles, the average aspect ratio Z is defined as a value indicating the relationship of thickness t and Z = X / t, where X is the average particle diameter. On a flat substrate (eg cleaved surface of mica mineral)
The diluted dispersion is applied to the solution, the solvent is dried, and the length is measured with an atomic force microscope, the average particle diameter X (average length in the longitudinal direction) is measured, and the height profile is measured to determine the thickness t. Can be sought.

The thin film-like particles can be used after being chemically and physically modified. Specific examples include formation of ion pairs (salt formation) by addition of ion species, polarization or dissociation of ion pairs, formation of covalent bonds with oxygen-containing polar functional groups, and the combination of different materials by adsorption. These methods may be used in combination.

(Content)
The content of the thin film-like particles is 0.1% by weight or more with respect to the electrode active material, 30
It is preferred that it is not more than weight percent. If it is less than 0.1 weight percent, the coating film adhesion and the toughness of the coating film may be inferior. If it exceeds 30 weight percent, the content of the electrode active material in the electrode is reduced, and the weight per electrochemical element is reduced. Performance may be reduced. The addition amount is preferably 0.2 weight percent or more and 20 weight percent or less, and more preferably 0.5 weight percent or more and 10 weight percent or less.

(effect)
Since the thin film-like particles contain an oxygen-containing polar group, it is considered that the thin film particles have an affinity for a highly hydrophilic material such as a current collector, an active material made of an inorganic material, a binder or a dispersant made of a polar resin. Further, since it contains a carbon skeleton, it is considered that it also has an affinity for a highly hydrophobic material such as a carbon material or an active material carrying a carbon material on the surface. That is, the added thin film-like particles can act (for example, adsorb) on each material contained in the electrode, such as an electrode active material, a conductive additive, and a binder, or on the surface of the current collector.

Therefore, as one of the effects of the thin film particles in the electrode, it is considered that the adhesion between the active material and the current collector is improved by the interaction between the oxygen-containing polar functional group of the thin film particles and the current collector. It is done.

Furthermore, since the adhesion between each material contained in the electrode, such as a conductive additive and a binder, is also improved, the electrode film is not easily broken by stress, and the toughness of the electrode film can be improved.

Further, as an effect of the thin film-like particles in the electrode, it is conceivable that the added thin film-like particles act (for example, adsorb) on the surface of the electrode active material to exert a dispersion effect.

Among electrode active materials, in the case of a carbon material or an active material carrying a carbon material on the surface, the hydrophobicity of the particle surface is high, so that it is considered that the dispersion effect by the adsorption action is further improved.

That is, by dispersing a carbon material or an active material in a solvent or water together with the thin film-like particles to form a dispersion, the action (for example, adsorption) of the thin film-like particles proceeds, and the oxygen content of the thin-film particles is contained. It is considered that the polarity of the polar functional group promotes the wetting of the active material surface with respect to the solvent or water, and facilitates the aggregation of the active material.

In addition, the oxygen-containing polar functional group of the thin-film particles interacts with an ionic component such as an amine (for example, ion pair formation (salt formation) by neutralization, ion pair (salt) polarization or dissociation, etc.). Thus, electrostatic repulsion on the surface of the active material is promoted, and it is considered that the dispersion stability of the active material is further increased.

In addition, a resin having an ionic functional group can be used. In that case, an active material is obtained by the interaction (for example, acid-base interaction) between the ionic functional group and the oxygen-containing polar functional group of the thin film-like particle. It is considered that the adhesion between the resin component and the resin component is improved, and the dispersion stability of the active material is further increased. Examples of the ionic functional group include basic functional groups such as amines.

  The effect of these thin film-like particles is also affected by the shape of the particles.

Since the particles are in the form of a thin film, the area of interaction sites per volume is very large. Therefore, it is thought that it can contribute to the adhesiveness and toughness of an electrode, and the dispersibility of a composition effectively, without occupying a big volume, ie, a weight.

Further, when the particles are in a thin film shape, the particles are flexible with respect to bending, and can exist in the electrode film without generating voids between the materials. Therefore, it can be said that it can contribute to the adhesion and toughness of the electrode without occupying a large volume.

On the other hand, since the thin-film particles are composed of a covalent carbon skeleton, they are not easily broken or stretched due to stretching. This feature is considered to greatly contribute to the toughness of the electrode.

<Dispersion medium>
The dispersion medium is not particularly limited. Specifically, alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides,
Examples thereof include phosphoric acid amides, sulfoxides, carboxylic acid esters, phosphoric acid esters, ethers, nitriles, heterocyclic compounds, and water. These can also be mixed and used.

In addition to the dispersion stability of the thin-film particles, the solubility and dispersion stability of various materials described later can be obtained by using a preferable dispersion medium described below.

The dispersion stability of the thin film particles is affected by the electron donating property of the dispersion medium. It is preferable to use a solvent having a large electron-donating effect. In particular, the number of donors of the solvent is 15 Kcal / mol or more, 60 Kc.
A solvent of al / mol or less is preferred. Furthermore, the dispersion stability of the various materials mentioned later was also improved by using the above solvents.

The number of donors is a measure for measuring the electron donating strength of various solvents. As a standard acceptor, 10 ⁻³ M SbCl ₅ in dichloroethane is selected and defined as a reaction molar enthalpy value with a donor. The larger the value, the stronger the electron donating property of the solvent. Also, for some solvents, the donor number is the NaClO ₄ ²³ Na— in the solvent.
Estimated indirectly from NMR chemical shifts. Regarding the number of donors, V.V. Gutman (translated by Otsuki, Okada), “Donor and Acceptor” (Japan Society of Science Publishing Center, 1983). The donor number is 15 Kcal / m, depending on the dielectric constant of the solvent.
If a solvent lower than ol is used, a sufficient dispersion stabilizing effect may not be obtained. Moreover, it seems that there is no remarkable dispersion | distribution improvement effect even if it uses the solvent in which the donor number exceeded 60 Kcal / mol.

As a solvent having a donor number of 15 Kcal / mol or more, for example, methyl alcohol (donor number: 19), ethyl alcohol (20), ethylamine (55), t-butylamine (57), ethylenediamine (55), pyridine (33. 1), acetone (17), formamide (24), N, N-dimethylformamide (26.6), N, N-diethylformamide (30.9), N, N-dimethylacetamide (27.8), N , N-diethylacetamide (32.2), N-methylpyrrolidone (27.3), hexamethylphosphoric triamide (38.8), dimethyl sulfoxide (29.8), ethyl acetate (17.1) trimethyl phosphate (23 ), Tributyl phosphate (23.7), tetrahydrofuran (20.0)
), Isobutyronitrile (15.4), isopropiononitrile (16.1), water (18
. 0) and the like, but are not limited thereto.

In addition, the dispersion stability of the thin film particles was found to be influenced by the hydrogen bonding properties of the dispersion medium. It is preferable to include a solvent having a large hydrogen bonding property, and a solvent having a solubility parameter hydrogen bonding component (SP value (δh)) of 5 (cal / cm ³ ) ^1/2 or more is preferable.
(cal / cm ³ ) ^1/2 or more and 20 (cal / cm ³ ) ^1/2 or less are more preferable. Furthermore, the dispersion stability of the various materials mentioned later was also improved by using the above solvents.

The solubility parameter (SP value) is a value defined as the square root of the cohesive energy density of the liquid. In particular, focusing on the force acting on this SP value between molecules, the London dispersion force component, the force between dipoles CMHansen, K. Skaarup: The idea of dividing into three components: components and hydrogen bonding components:
J. Paint Tech., 39 [511] (1967) and the like.
The SP value (δh) is a parameter for the hydrogen bonding component, and the larger the value, the greater the hydrogen bonding action of the solvent.
Examples of the solvent having a solubility parameter hydrogen bond component (SP value (δh)) of 5 (cal / cm ³ ) ^1/2 or more include aniline (5.0), 2- (2-butoxyethoxy) ethane ( 5.2), diacetone alcohol (5.3), N, N-dimethylformamide (5.
5), 1-pentanol (6.8), 2-ethoxyethanol (7.0), N-methylpyrrolidone (7.2), 1-butanol (7.7), 1-propyl alcohol (8.5) ), Ethanol (9.5), diethylene glycol (9.7), ethanolamine (10.4)
, Methanol (10.9), 1,2-propanediol (11.4), 1,2-ethanediol (12.7), water (16.7), and the like, but are not limited thereto.

A solvent with a large number of donors and a hydrogen bonding component (SP value (δh)) having a solubility parameter has a strong solvating power, and therefore not only promotes polarization of acidic functional groups contained as oxygen-containing polar functional groups, but also various materials. It is speculated that it contributes to the dispersion stability by improving the wettability of the resin and the solubility of the dispersant.
Also, when an oxygen-containing polar functional group interacts with an ionic component such as an amine, the use of a solvent that has a large effect of promoting the polarization or dissociation of an ion pair (salt) can provide good dispersion stability. Seems to be important. Donor number, solubility parameter hydrogen bonding component (SP value (δ
A polar solvent having a large h)) is desirable because it seems to have a high effect of stabilizing the ion pair or its cationic species by solvation. Furthermore, a solvent having a particularly high relative dielectric constant is preferable because it seems to promote dissociation of ion pairs.

From the above, as a dispersion medium suitably used, for example, N, N-dimethylformamide,
Amide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, and dimethyl sulfoxide, water, alcohols, dialkyl ether, tetrahydrofuran , Ethers such as dioxane, amines such as trialkylamine and piperazine, heterocyclic compounds such as pyridine and pyrrole, etc., but are not limited to these, and two or more types may be used in combination. it can.

In the present invention, it is preferable to use a polar solvent having a relative dielectric constant of 15 or more as the dispersion medium. The relative dielectric constant is one of the indices indicating the strength of the polarity of the solvent, and is described in Asahara et al., “Solvent Handbook” (Kodansha Scientific Co., Ltd., 1990).
For example, methyl alcohol (dielectric constant: 33.1), ethyl alcohol (23.8),
2-propanol (18.3), 1-butanol (17.1), 1,2-ethanediol (38.66), 1,2-propanediol (32.0), 1,3-propanediol (
35.0), 1,4-butanediol (31.1), diethylene glycol (31.69)
), 2-methoxyethanol (16.93), 2-ethoxyethanol (29.6), 2
Aminoethanol (37.7), acetone (20.7), methyl ethyl ketone (18.
51), formamide (111.0), N-methylformamide (182.4), N, N
-Dimethylformamide (36.71), N-methylacetamide (191.3), N,
N-dimethylacetamide (37.78), N-methylpropionamide (172.2)
N-methylpyrrolidone (32.0), hexamethylphosphoric triamide (29.6), dimethyl sulfoxide (48.9), sulfolane (43.3), acetonitrile (37.5)
, Propionitrile (29.7), water (80.1) and the like, but are not limited thereto.

In particular, it is preferable to use a polar solvent having a relative dielectric constant of 15 or more and 200 or less, preferably 15 or more and 100 or less, more preferably 20 or more and 100 or less. It is preferable for obtaining dispersion stability.
In a dispersion medium having a relative dielectric constant of less than 15, good dispersion stability of the thin film particles cannot be obtained.
The solubility of materials such as a dispersant described later is remarkably lowered and often a good dispersion cannot be obtained, and even if a solvent having a relative dielectric constant exceeding 200 is used, a remarkable dispersion improvement effect cannot be obtained. There are many cases.

As described above, the use of an acidic functional group contained as an oxygen-containing polar functional group in the thin film-like particle or a solvent having a large effect of accelerating the polarization or dissociation of the acidic functional group of the dispersing agent can provide good dispersion stability. Seems to be important. It is considered that a solvent having a large electron donating property has a strong solvating power for these materials, and therefore promotes polarization of acidic functional groups, and a solvent having a large relative dielectric constant promotes dissociation of polarized acidic functional groups.

Therefore, in order to obtain good dispersion stability, it is possible to use a solvent having a large relative dielectric constant, a solvent having a large donor number, and a solvent having a large solubility parameter hydrogen bond component (SP value (δh)). preferable. It is also preferable to use a solvent having a large relative permittivity, number of donors, and hydrogen bonding components (SP value (δh)) of solubility parameters.

From the environmental load reduction and economic advantages, etc., the solvent discharged in the electrode manufacturing process can be recovered and
When reusing, it is preferable to use a single solvent instead of a mixed solvent. Further, when water is used, there is an advantage that the electrode manufacturing process is simplified, such as the need for explosion-proof equipment and solvent recovery equipment, compared to the case of using an organic solvent.

Furthermore, when adding a dispersant, a conductive additive, an electrode active material, or a binder component, which will be described later, in addition to the influence of the above-mentioned solvent, reactivity with the electrode active material, solubility in the dispersant and the binder component, etc. In consideration of the above, the dispersion medium is selected. It is preferable to select a solvent having high dispersibility, low reactivity with the electrode active material, and high solubility of the dispersant and the binder component.

As the dispersion medium of the present invention, a protic polar solvent and an aprotic polar solvent are preferably used. In order to satisfy the dispersion stability and solubility of other additive components, It is also preferable to use an aprotic polar solvent in combination.

A protic polar solvent is a proton-donating solvent, which has the ability to release protons in the solvent itself, and is considered to be highly effective in stabilizing anionic species by solvation. Preferable protic polar solvents include, for example, alcohols and glycols, amide solvents obtained by monoalkylating nitrogen, such as N-methylformamide, N-methylacetamide, N-methylpropionamide, and water. However, it is not limited to these.

An aprotic polar solvent is a polar solvent that does not have the ability to release protons and does not self-dissociate. Aprotic polar solvents do not cause self-association due to hydrogen bonding, and the solvent itself aggregates. The nature is weak. Therefore, the penetration force to the aggregates of the thin film particles is strong, and a dispersion promoting effect is expected. In addition, since the aprotic polar solvent is weak in cohesiveness of the solvent itself, it has a strong dissolving power and can dissolve various dispersants and resins, so that it has excellent versatility.

Furthermore, since aprotic polar solvents solvate only cationic species, only protons or counter cations in acidic functional groups are solvated. At this time, since the anion side remains bare without being solvated, an effect such as that the action (for example, adsorption) on the surface of the thin film-like particles is hardly inhibited is also expected. Preferred aprotic polar solvents include, for example, N, N-dimethylformamide, N, N-diethylformamide, N, N
Examples thereof include, but are not limited to, amide solvents obtained by dialkylating nitrogen such as dimethylacetamide and N, N-diethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethyl sulfoxide and the like.

From the above, as a dispersion medium that is particularly preferably used, for example, amide solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, and N-methyl Examples include, but are not limited to, pyrrolidone, dimethyl sulfoxide, water, and alcohols.

<Electrode active material>
Although it does not specifically limit as an electrode active material used in this invention, It is a material which gives and receives an electron at least, According to the target electrochemical element, the active material for primary batteries, for secondary batteries Selected from active materials, capacitor active materials, and the like.

Examples of electrode active materials that are particularly preferably used in the present invention include lithium ion secondary battery active materials, electric double layer capacitor active materials, and lithium ion capacitor active materials.

Specific examples of positive electrode active materials for lithium ion secondary batteries include layered lithium nickel composite oxide, lithium cobalt composite oxide, lithium manganese composite oxide, lithium cobalt nickel composite oxide, and lithium nickel. Manganese complex oxide, lithium cobalt nickel manganese complex oxide,
Spinel structure lithium manganese complex oxide,
Examples thereof include lithium iron phosphate, lithium manganese phosphate, lithium cobalt phosphate, lithium iron manganese phosphate and the like, which are lithium transition metal phosphorus-based composite oxides having an olivine structure.

Among these, a lithium transition metal phosphorus-based composite oxide having an olivine structure is a preferable material from the viewpoints of cost and safety.

The negative electrode active material for the lithium ion secondary battery is not particularly limited, but specifically,
Metal Li, its alloys such as tin alloy, silicon alloy, lead alloy, LiXFe ₂ O ₃
, LiXFe ₃ O ₄ , LiXWO ₂ , metal oxides such as lithium titanate, lithium vanadate, and lithium siliconate, conductive polymers such as polyacetylene and poly-p-phenylene, amorphous such as soft carbon and hard carbon Carbonaceous materials such as carbonaceous materials, artificial graphite such as highly graphitized carbon materials, carbonaceous powder such as natural graphite, carbon black, mesophase carbon black, resin-fired carbon material, gas-grown carbon fiber, carbon fiber, etc. Is mentioned.
These negative electrode active materials can be used alone or in combination.

In addition, a composite with a conductive material is also preferably used. Examples of the conductive substance include carbon materials, conductive polymer materials, metals, and the like.

Although it does not specifically limit as an active material for electric double layer capacitors, The above carbonaceous materials can be used and activated carbon is used suitably especially. Specific examples include activated carbon made from phenol, rayon, acrylic, pitch, coconut shell, cotton or the like.
Furthermore, the electric capacity can be increased by subjecting the activated carbon to a surface treatment. For example, a method such as a surface treatment with an organic compound or an inorganic compound, a steam activation treatment, or an alkali activation treatment is preferable.

As the positive electrode active material for lithium ion capacitors, electrode active materials used in electric double layer capacitors can be widely used.

As the negative electrode active material for lithium ion capacitors, electrode active materials used in the negative electrode of lithium ion secondary batteries can be widely used.

<Composition for electrochemical device>
As described above, the composition of the present invention can be used in various electrochemical devices.
Then, the lithium ion secondary battery which is one of the suitable aspects of the composition for electrochemical elements of this invention is demonstrated. Composition for electrochemical device used for lithium ion secondary battery (hereinafter,
The composite ink) has a positive electrode application or a negative electrode application, and the electrode active materials described above are used.

(Conductive aid)
The composite ink can also contain a conductive additive in order to improve the conductivity in the electrode. A carbon material is suitably used as the conductive auxiliary. The carbon material as a conductive auxiliary agent is not particularly limited as long as it is a conductive carbon material, but graphite, carbon black, conductive carbon fiber (carbon nanotube, carbon nanofiber, carbon fiber), fullerene. Etc. 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, and particularly various types such as acetylene black using acetylene gas as a raw material, or 2 More than one type can be used in combination.

As the specific surface area of the carbon black used increases, the number of contact points between the carbon black particles increases, which is advantageous in reducing the internal resistance of the electrode. Specifically, the specific surface area (BET) determined from the adsorption amount of nitrogen 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. When carbon black having a specific surface area of less than 20 m ² / g is used, it may be difficult to obtain sufficient conductivity.
Carbon black exceeding 00 m ² / g may be difficult to obtain with commercially available materials.

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.

It is desirable that the dispersed particle size of the carbon material, which is a conductive additive, in the mixed ink is refined to 0.03 μm or more and 5 μm or less. It may be difficult to produce a composition having a dispersed particle size of the carbon material as the conductive aid of less than 0.03 μm. In addition, when a composition having a dispersed particle diameter of the carbon material as the conductive auxiliary agent exceeding 2 μm is used, problems such as variations in the material distribution of the composite coating film and variations in the resistance distribution of the electrode may occur. .
The dispersed particle size referred to here is a particle size (D50) that is 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution. A particle size distribution meter such as a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.).

Examples of commercially available carbon black include Toka Black # 4300, # 4400,
# 4500, # 5500, etc. (manufactured by Tokai Carbon Co., furnace black), Printex L, etc. (manufactured by Degussa, furnace black), Raven 7000, 5750, 5250,
5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA
, Conductex 975 ULTRA, etc., PUER BLACK100, 115, 2
05 etc. (Columbian made by Furnace Black), # 2350, # 2400B, # 26
00B, # 30050B, # 3030B, # 3230B, # 3350B, # 3400B,
# 5400B etc. (Mitsubishi Chemical Co., Furnace Black), MONARCH1400, 13
00, 900, Vulcan XC-72R, BlackPearls 2000, etc. (Cabot, Furnace Black), Ensaco 250G, Ensaco 260G, En
saco350G, SuperP-Li (manufactured by TIMCAL), Ketjen Black EC
-300J, EC-600JD (manufactured by Akzo), Denka Black, Denka Black HS-
Examples of graphite such as 100, FX-35 (manufactured by Denki Kagaku Kogyo Co., Ltd., acetylene black) include natural graphite such as artificial graphite, flake graphite, lump graphite, and earth graphite, but are not limited thereto. Instead, two or more types may be used in combination.

As the conductive carbon fibers, those obtained by firing from petroleum-derived raw materials are preferable, but those obtained by firing from plant-derived raw materials can also be used. For example, VGCF manufactured by Showa Denko Co., Ltd. manufactured with petroleum-derived raw materials can be mentioned.

(Liquid medium)
Examples of the liquid medium used for the composite ink include alcohols, glycols, cellosolves, amino alcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, Examples thereof include phosphate esters, ethers, nitriles, and water. In particular, by using the above-mentioned preferred dispersion medium, it is possible to obtain the solubility and dispersion stability of various materials in addition to the dispersion stability of the thin film particles.

(Dispersant)
The composite ink may further contain a dispersant in order to alleviate the aggregation of the carbon material, which is an active material and a conductive additive, and to uniformly mix and disperse.

As the dispersant, an organic compound having a basic functional group and / or an acidic functional group is preferably used. These organic compounds not only increase the dispersibility of the electrode active material and material particles such as a conductive additive added as necessary, but can also function as a good binder. By using a specific organic compound as a dispersant, a composite ink excellent in dispersion stability can be provided without impeding conductivity.

An organic compound having a basic functional group and / or an acidic functional group that can be used as a dispersing agent can act or adsorb on the surface of material particles such as an electrode active material and a conductive additive that is added as necessary by the functional group. If it is a thing, the skeleton will not be specifically limited. However, from the viewpoint of battery performance in which electronic conductivity is important, preferred organic compounds having basic functional groups and / or acidic functional groups include acidic resin dispersants (A) and basic resin dispersants. (B
), Amphoteric resin type dispersant (C), various derivatives having a basic functional group, various derivatives having an acidic functional group, and the like.

[Acid Resin Type Dispersant (A)]
As described above, the composite ink can contain the acidic resin dispersant (A) as a dispersant.

The acidic resin dispersant (A) is not particularly limited as long as it is a resin having an acidic functional group. For example, a polyester resin or urethane containing a sulfonic acid group, a carboxyl group, a phosphoric acid group, or the like as the acidic functional group. Resin, urea resin, urethane urea resin, epoxy resin,
Polyamide resin, polyimide resin, or the like can be used.
For example, as the resin having a sulfonic acid group, a formalin condensate of aromatic sulfonic acid or the like can be used. Examples of the formalin condensate of aromatic sulfonic acid include those obtained by condensing benzenesulfonic acid, alkylbenzenesulfonic acid, and naphthalenesulfonic acid (or their alkali metal salts) with formalin.

The acidic resin dispersant (A) includes an ethylenically unsaturated monomer having an aromatic ring (a
Resin-type dispersants obtained by copolymerizing 1), an ethylenically unsaturated monomer (a2) having an acidic functional group, and another ethylenically unsaturated monomer (a4) can be used. . Here, the monomer (a1) is an optional component.

Unless otherwise specified, the ethylenically unsaturated monomer constituting the acidic resin dispersant (A) is 1
The monomer which has one ethylenically unsaturated group in a molecule | numerator is shown.

[About monomer (a1)]
The ethylenically unsaturated monomer (a1) having an aromatic ring is not particularly limited as long as it is a monomer having an aromatic ring, but styrene, α-methylstyrene or benzyl (meth) acrylate can be exemplified. .

In the present specification, “(meth) acryloyl”, “(meth) acrylic acid”, “(
In the case of “meth) acrylate” and “(meth) acryloyloxy”, unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or Or methacrylate "
And “acryloyloxy and / or methacryloyloxy”.

[About monomer (a2)]
The ethylenically unsaturated monomer (a2) having an acidic functional group is not particularly limited as long as it is a monomer having an acidic functional group, but a monomer having a carboxyl group or a monomer having a sulfonic acid group And monomers having a phosphate group.

Here, as a monomer having a carboxyl group, maleic acid, fumaric acid, itaconic acid,
Citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β
-(Meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic Examples thereof include acid, methacrylic acid, crotonic acid, and cinnamic acid. In particular, methacrylic acid and acrylic acid are preferable.

Monomers containing sulfonic acid groups include vinyl sulfonic acid, styrene sulfonic acid, tertiary butyl acrylamide sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, (meth) acrylic acid butyl-4-sulfonic acid, (meta ) Acryloxybenzene sulfonic acid etc. can be illustrated.

Examples of the monomer having a phosphoric acid group include diphenyl (2-acryloyloxyethyl) phosphate, diphenyl (2-methacryloyloxyethyl) phosphate, phenyl (2
-Acrylyloxyethyl) phosphate, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, (meth) acryloyl oxyethyl acid phosphate monoethanolamine salt, 3-chloro-2-acid. Examples thereof include phosphooxypropyl (meth) acrylate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate, acid phosphooxypolyoxypropylene glycol (meth) acrylate, and allyl alcohol acid phosphate.

Only one kind of the acidic group-containing ethylenically unsaturated monomer may be used, but two or more kinds may be used. When two or more types are used, the functional group combination may be a combination of different groups such as a carboxyl group and a sulfonic acid group, a sulfonic acid group and a phosphoric acid group, or a single monomer having the same acidic group such as acrylic acid and methacrylic acid. You may combine 2 or more types from a body.

[About monomer (a4)]
Next, the monomer (a4) other than the above (a1) and (a2) will be described.
Examples of the monomer classified as the other monomer (a4) include a monomer (a6) having no acidic functional group, aromatic ring, and basic functional group, and a (meth) acrylate compound. Are alkyl (meth) acrylates and alkylene glycol (meth) acrylates.

  Specific examples of the monomer (a4) are listed below.

Alkyl (meth) acrylates include alkyl (meth) acrylates having 1 to 22 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, etc. For the purpose of adjustment, an alkyl group-containing acrylate having a C 2-10 alkyl group, more preferably a C 2-8 alkyl group, or a corresponding methacrylate is mentioned.

Examples of the alkylene glycol-based (meth) acrylate include a monoacrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain, such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, or a corresponding monoacrylate. Such as methacrylate, methoxyethylene glycol (meth) acrylate,
Having an alkoxy group at the end, such as methoxydiethylene glycol (meth) acrylate,
Examples thereof include a polyacrylate having a polyoxyalkylene chain or a corresponding monomethacrylate, a polyoxyalkylene acrylate having a phenoxy or aryloxy group at the terminal, or a corresponding methacrylate, such as phenoxyethylene glycol (meth) acrylate.

Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene and the like can be mentioned.

Examples of the nitrogen-containing unsaturated compound include acrylamide unsaturated compounds, (
(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl-
Monoalkylol (meth) acrylamides such as (meth) acrylamide and N, N-di (
Examples include methylol (meth) acrylamides such as methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, and N, N-di (methoxymethyl) acrylamide.

Other unsaturated compounds include, for example, perfluoroalkyl group-containing vinyl monomers such as perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-par Perfluoroalkylalkyl (meth) acrylates having a C1-C20 perfluoroalkyl group such as fluorohexylethyl (meth) acrylate; and perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecyl Perfluoroalkylalkylenes such as ethylene and the like, and silanol group-containing vinyl compounds include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrieth Shishiran, .gamma. (meth) acryloxy propyl trimethoxy silane and the like, more can be mentioned their derivatives etc., may be used a plurality of these groups.

Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate.

Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

Examples of vinyl compounds include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone,
Examples include styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene and the like.

Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like. These can be used alone or in combination of two or more.

(A4) preferably does not contain an ethylenically unsaturated monomer (a3) having a basic functional group, but does not affect the physical properties (preferably (a1), (a2), (a4 ) May be used in a total of 100% by weight, 5% by weight or less).

[About monomer (a3)]
Specific examples of the ethylenically unsaturated monomer (a3) having a basic functional group are given below.
As those having an aliphatic amino group, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) are monomers having one ethylenically unsaturated group in one molecule. Examples of acrylate, N, N-dimethylaminopropyl (meth) acrylate, allylamine, monomers having two ethylenically unsaturated groups in one molecule include diallylamine and diallylmethylamine.
Examples of those having an aromatic amino group include aminostyrene, dimethylaminostyrene, diethylaminostyrene and the like, and those having a nitrogen-containing heterocycle include vinylpyridine, 1-vinylimidazole and the like. It can be illustrated.

[Composition ratio of monomer]
The ratio of the ethylenically unsaturated monomer constituting the acidic resin dispersant (A) is determined by the monomer (
When the sum of a1), (a2), and (a4) is 100,
Ethylenically unsaturated monomer having an aromatic ring (a1): 10 to 80% by weight
Ethylenically unsaturated monomer having an acidic functional group (a2): 20 to 75% by weight
Other ethylenically unsaturated monomers (a4) other than (a1) and (a2): It is preferably 0 to 70% by weight.
More preferably,
(A1) is 10 to 60% by weight, (a2) is 40 to 75% by weight, and (a4) is 0 to 50% by weight.

[Acid value]
When the constituent ratio of the monomer having an acidic functional group in the whole molecule of the acidic resin dispersant (A) is represented by an acid value, the following is preferable. That is, the acid value is 100 mgKOH / g
It is preferably in the range of 800 mgKOH / g or less, more preferably 300 mgKOH
/ G or more and 800 mgKOH / g or less is preferable.

When the acid value is lower than the above range, the dispersion stability of the dispersion is lowered and the viscosity tends to increase. Moreover, when an acid value is higher than the above-mentioned range, the adhesive force of the acidic resin type dispersing agent with respect to each material surface will fall, and there exists a tendency for the storage stability of a dispersion to fall.

The acid value is an acid value (mgK) measured according to the potentiometric titration method of JIS K 0070.
OH / g) is a value in terms of solid content.
The acidic resin dispersant (A) preferably has no amine value, but has an amine value within a range that does not affect the physical properties (preferably 50 mgKOH / g or less, more preferably 20 mgKOH / g or less). It may be.

Further, as the acidic resin dispersant (A), a resin obtained by reacting a vinyl polymer having two hydroxyl groups at one end with tetracarboxylic dianhydride can be used.

Said resin can be manufactured through the following two processes, for example. The first step is the radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, thereby producing a vinyl polymer having two hydroxyl groups at one end. The second step is a step of reacting the vinyl polymer having two hydroxyl groups at one end obtained in the first step with tetracarboxylic dianhydride.

[First step]
The first step is the radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, thereby producing a vinyl polymer having two hydroxyl groups at one end. This is a process for producing a coalescence.

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

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

In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, azo compounds and organic peroxides 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), 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.

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

Examples of the ethylenically unsaturated monomer include the following general ethylenically unsaturated monomers. As a general ethylenically unsaturated monomer, 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, stearyl (meth) acrylate, and lauryl (meth) acrylate;
(Meth) acrylates having an aliphatic ring such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate;
(Meth) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate;
Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (
(Meth) acrylates and (meth) acrylates having an aromatic ring such as phenoxydiethylene glycol (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
N-substituted types such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine (meta ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile;
Styrenes such as styrene and α-methylstyrene;
Ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether,
vinyl ethers such as n-butyl vinyl ether and isobutyl vinyl ether; and
Examples include vinyl acetate and fatty acid vinyls such as vinyl propionate. But,
It is not limited to the said polymer especially, Even if it uses combining 2 or more types, the monomer shown below may be used together as needed.

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

In the vinyl polymer having two hydroxyl groups at one end, among the ethylenically unsaturated monomers exemplified above, benzyl (meth) acrylate is 20% by weight of the whole monomer.
It is preferable to use ˜70% by weight. If the amount is less than 20% by weight, the solvent affinity may be low and the dispersibility may be lowered. If the amount exceeds 70% by weight, the solubility of the dispersant itself in the solvent is improved, so that adsorption to each material is insufficient. Or the viscosity of the composition may increase due to the entanglement of the solvent affinity parts.

The weight average molecular weight of a vinyl polymer having two hydroxyl groups at one end is 1,000.
-10,000 are preferable, and this part becomes an affinity part to the solvent which is a dispersion medium. When the weight average molecular weight of the vinyl polymer is less than 1,000, the effect of steric repulsion by the solvent affinity part is reduced, and it is difficult to prevent aggregation of various materials, and dispersion stability may be insufficient. Moreover, when it exceeds 10,000, the absolute amount of a solvent affinity part will increase, and the dispersibility effect itself may fall. Further, the viscosity of the dispersion may increase.

[Second step]
The second step is a step of reacting the vinyl polymer having two hydroxyl groups at one end obtained in the first step with tetracarboxylic dianhydride.

Assuming that the molar ratio of the vinyl polymer having two hydroxyl groups at one end is α and the molar ratio of tetracarboxylic dianhydride is β, the molecular weight is infinitely large when α = β. In many cases, the target molecular weight is controlled by changing the ratio of α / β when> β or α <β. For example, when α = β + 1, both ends are hydroxyl groups, the molecular weight is not increased any more, and the target resin can be synthesized stably. Meanwhile, β = α + 1
In this case, since both ends become acid anhydride groups and the stability becomes poor, the acid anhydride group can be hydrolyzed to synthesize the desired resin having the end as a carboxyl group.

The tetracarboxylic dianhydride used in the second step reacts with a vinyl polymer having two hydroxyl groups at one end to form an ester bond, and pendant carboxyl groups are formed on the resulting polyester backbone. Can leave. If the acid anhydride group remaining in the product is hydrolyzed, the product of this reaction has 2 or 3 carboxyl groups, and the plurality of carboxyl groups are effective as adsorption sites. .

By reacting a vinyl polymer having two hydroxyl groups at one end with tetracarboxylic dianhydride, a plurality of carboxyl groups bonded to the product function as adsorbing parts to various materials, and vinyl The combined part functions as a solvent affinity part.

As tetracarboxylic dianhydride,
1,2,3,4-butanetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic anhydride 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5,6-tricarboxynorbornane-2-
Acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,
5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetra Aliphatic tetracarboxylic anhydrides such as carboxylic anhydrides; and
Pyromellitic anhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 3, 3 ', 4
, 4′-biphenylsulfonetetracarboxylic acid anhydride, 1,4,5,8-naphthalenetetracarboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3 ′,
4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic acid anhydride 1,2,3,4-furantetracarboxylic anhydride, 4,4′-
Bis (3,4-dicarboxyphenoxy) diphenylsulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis (3
4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, bis ( Phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4'- Diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane anhydride, 9,9-bis (3,4
-Dicarboxyphenyl) fluorenic anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3
4-tetrahydro-1-naphthalene succinic anhydride, and 3,4-dicarboxy-1,
And aromatic tetracarboxylic anhydrides such as 2,3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride.

The tetracarboxylic dianhydride that can be used is not limited to the compounds exemplified above, and any structure may be used as long as it has two carboxylic anhydride groups. Even if these are used alone,
You may use it together. Further, preferably used is an aromatic tetracarboxylic anhydride from the viewpoint of lowering the viscosity of the positive electrode active material dispersion, more preferably a tetracarboxylic anhydride having two or more aromatic rings. . In addition, a compound having one carboxylic anhydride group in the molecule or a compound having three or more can be used in combination.

The catalyst used in the second step may be a known catalyst. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0].
-7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, and the like.

A well-known thing can be used as a polymerization solvent. Examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and N-methylpyrrolidone. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

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

The weight average molecular weight of the obtained resin is preferably 2,000 to 25,000. If the weight average molecular weight is less than 2,000, the stability of the composite ink may decrease. On the other hand, if it exceeds 25,000, the interaction between the resins becomes strong, and the viscosity of the composite ink may increase. The acid value of the obtained resin is preferably 5 to 200 mgKOH / g. More preferably, it is 5 to 150 mg KOH / g, and particularly preferably 5 to 100 mg KO.
H / g. If the acid value is less than 5, the adsorptive capacity may be lowered and there may be a problem in dispersibility.
When it exceeds 0 mgKOH / g, the interaction between the resins becomes strong and the viscosity of the composite ink may increase.

Moreover, as an acidic resin type dispersing agent (A), the polyester-type resin which has an acidic functional group can be used.

Said resin can be manufactured through the following two processes, for example. The first step is a step of producing a polyester having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, and the second step is a polyester having a hydroxyl group at one end. And tetracarboxylic dianhydride.

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

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

As the aliphatic monoalcohol, a branched aliphatic monoalcohol is preferable, for example, 2-
Those having 8 to 20 carbon atoms such as ethylhexanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, and 2-hexyldecanol are preferred.

The monoalcohol has 6 to 30 carbon atoms (more preferably 6 to 2 carbon atoms).
The substituted or unsubstituted aromatic monoalcohol of 5), such as phenol or cumylphenol, can also be used. A saturated aliphatic monoalcohol having an aliphatic group having 1 to 6 carbon atoms and substituted with an aromatic group having 6 to 10 carbon atoms, such as benzyl alcohol, can also be used.

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

Furthermore, monoalcohols that can be used include monoalcohols having one or more ethylenically unsaturated double bonds. Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group, and a (meth) acryloyl group is preferable. These can be compounds having different types of double bonds in one compound.

As the monoalcohol having an ethylenically unsaturated double bond, for example, an unsaturated monoalcohol compound having one, two, or three or more ethylenically unsaturated double bonds can be used. Monoalcohols having one ethylenically unsaturated double bond include (
C1-C8 hydroxyalkyl esters of meth) acrylic acid, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3- Mention may be made of phenoxypropyl acrylate and 1,4-cyclohexanedimethanol mono (meth) acrylate.

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

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

The addition of alkylene oxide is carried out by a known method, for example, 100 to 2 in the presence of an alkali catalyst.
It can be carried out at a temperature of 00 ° C. As a commercial product of the addition polymerization product thus obtained,
There are UNIOX series manufactured by NOF Corporation or BLEMMER series manufactured by NOF Corporation.

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

The monoalcohol that can be used for the production of the polyester-based resin having an acidic functional group is not limited to the above examples, and any compound can be used as long as it is a compound having one hydroxyl group. Even if it uses, two or more types can also be used together.

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

By performing ring-opening polymerization of a lactone using the monoalcohol as an initiator, a polyester having a hydroxyl group at one end and usable for the production of the resin-type dispersant can be obtained. The lactone that can be used in the ring-opening polymerization is preferably a 4-membered ring to 1
It is a 0-membered ring, more preferably a 5-membered to 7-membered lactone, and the ring-constituting carbon atoms can be substituted or unsubstituted. Examples of the substituent of the ring-constituting carbon atom include an alkyl group having 1 to 4 carbon atoms. An unsaturated lactone containing one or more ethylene bonds in the ring or a condensed lactone with an aromatic compound (eg, benzene) can also be used.

Specific examples of suitable lactones include β-butyrolactone, γ-butyrolactone, γ-
Mention may be made of valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone, of which δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone It is preferable to use it in terms of ring-opening polymerizability. Examples of the alkyl substituent include an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group, and the alkyl substituent can be substituted with one or more of these alkyl substituents.

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

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

The number of moles of the lactone added to 1 mole of the monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles.

Examples of the polymerization catalyst for the ring-opening polymerization include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethyl. Quaternary ammonium salts such as ammonium bromide and benzyltrimethylammonium iodide; tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide,
Quaternary phosphonium salts such as tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine Organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate; alkali metal alcoholates such as sodium alcoholate and potassium alcoholate; tertiary amines; organotin compounds; organoaluminum compounds; organotitanate compounds; And zinc compounds such as zinc chloride. The amount of catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 pp.
m.

The ring-opening polymerization reaction can be carried out without a solvent, or an appropriate dehydrated organic solvent can be used. The solvent used in the ring-opening polymerization reaction can be removed by an operation such as distillation after the reaction is completed, or can be used as a part of the battery composition.

The ring-opening polymerization reaction is preferably 100 ° C to 220 ° C, more preferably 110 ° C to 2 ° C.
It is carried out in the range of 10 ° C. If the reaction temperature is less than 100 ° C, the reaction rate is very slow, and if it exceeds 210 ° C, side reactions other than the addition reaction of lactone, such as decomposition of lactone adducts into lactone monomers, formation of cyclic lactone dimers and trimers, etc. are likely to occur. .

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

[Second step]
The second step is a step of reacting the polyester having a hydroxyl group at one end obtained in the first step with tetracarboxylic dianhydride.

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

In particular,
Aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2
, 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3
, 5,6-tricarboxynorbornane-2-acetic dianhydride, and bicyclo [2,2,
2] -alicyclic tetracarboxylic dianhydrides such as oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; and
2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 5- (2,5
-Dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and the like.

Further, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Dianhydride,
3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′
, 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'
-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4, 4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′- Perfluoroisopropylidenediphthalic dianhydride, 3,3
', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m
-Phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid)
-4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-
Diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, etc. Aromatic tetracarboxylic dianhydride of 3,4-dicarboxy-1,2,
Polycyclic compounds such as 3,4-tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Mention may be made of tetracarboxylic dianhydrides.

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

The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride sites in the molecule. These may be used alone or in combination. Furthermore, the tetracarboxylic dianhydride that can be suitably used for the production of a polyester-based resin having an acidic functional group is from the viewpoint of reducing the viscosity of the composite ink,
An aromatic tetracarboxylic dianhydride, more preferably two or more aromatic rings (particularly 2
~ 4) tetracarboxylic dianhydride.

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

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

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

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

Moreover, as acidic resin type dispersing agent (A), resin which has a commercially available acidic functional group can be used.

Although it does not specifically limit as resin which has a commercially available acidic functional group, For example, the following are mentioned. These may be used alone or in combination.
As a resin having an acidic functional group manufactured by Big Chemie, Anti-Terra-U, U
100, 203, 204, 205, Disperbyk-101, 102, 106, 10
7, 110, 111, 140, 142, 170, 171, 174, 180, 2001, B
YK-P104, P104S, P105, 9076, 220S, etc. are mentioned.

As a resin having an acidic functional group manufactured by Nippon Lubrizol, SOLPERSE30
00, 21000, 26000, 36000, 36600, 41000, 41090, 4
3000, 44000, 53095 and the like.

As the resin having an acidic functional group manufactured by Fuka Additives, EFKA4510, 4
530, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5
065, 5066, 5070, 5071 and the like.

As a resin having an acidic functional group manufactured by Ajinomoto Fine Techno Co., Ltd., Ajisper PN411
, And Azisper PA111 and the like.

As a resin having an acidic functional group manufactured by ELEMENTIS, NuosperseFX
-504, 600, 605, FA620, 2008, FA-196, and FA-601
Etc.

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

Examples of the resin having an acidic functional group manufactured by Enomoto Kasei Co., Ltd. include Disparon 2150 and KS-86.
0, KS-873SN, 1831, 1860, PW-36, DA-1200, DA-70
3-50, DA-7301, DA-325, DA-375, DA-234 and the like.

Resins having an acidic functional group manufactured by BASF Japan include JONCRYL 67 and 678.
586, 611, 680, 682, 683, 690, 52J, 57J, 60J, 61J
62J, 63J, 70J, HPD-96J, 501J, 354J, 6610, PDX-
6102B, 7100, 390, 711, 511, 7001, 741, 450, 840,
74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535
PDX-7630, 352J, 252D, 538J7640, 7641, 631, 79
0, 780, 7610 and the like.

Examples of resins having acidic functional groups made by Mitsubishi Rayon include Dianal BR-60, 64,
73, 77, 79, 83, 87, 88, 90, 93, 102, 106, 113, and 1
16 etc. are mentioned.

[About neutralizing agent]
A neutralizing agent can also be added to the acidic resin dispersant (A). When water is used as the dispersion medium, the salt of the acidic functional group is easily dissociated in the aqueous medium by neutralizing part or all of the acidic functional group of the acidic resin type dispersant, and is more easily charged. . Therefore, the surface of the conductive carbon and the surface of the positive and negative electrode active materials adsorbed by the neutralized acidic resin dispersant are charged, and dispersibility is further improved by the repulsion.

Examples of the base used for this neutralization include ammonia, LiOH, NaOH, and K.
Inorganic bases such as OH, and propylamine, isoamylamine, hexylamine, 2
-Ethylhexylamine, 3-ethoxypropylamine, 2-ethylhexyloxypropylamine, 3-lauryloxypropylamine, 3-aminopropanol, dimethylamine, diisopropylamine, 2-piperidineethanol, trimethylamine, ethanolamine, dimethylethanolamine, Methyldiethanolamine, triethanolamine,
And organic bases (amine compounds) such as triethylamine. Dimethylethanolamine, ammonia and NaOH are preferred, more preferably ammonia or N
aOH.

The amount of the base used for the acidic resin type dispersant having an acidic functional group is preferably 0.1 to 10 equivalents, more preferably 0, of the acidic functional group of the acidic resin type dispersant used.
. 8 to 1.2 equivalents.

[Basic resin type dispersant (B)]
As described above, the composite ink can contain the basic resin dispersant (B) as a dispersant.

The basic resin type dispersant (B) is not particularly limited as long as it is a resin having a basic functional group. For example, it is obtained by polymerizing or condensing a monomer having a basic functional group. It is obtained by polymerizing an ethylenically unsaturated monomer (a3) having a functional functional group. One type of monomer having a basic functional group may be used, or a plurality of types may be used in combination.

Further, as the basic resin dispersant (B), an ethylenically unsaturated monomer having an aromatic ring (
Use of a resin-type dispersant obtained by copolymerizing a1), an ethylenically unsaturated monomer (a3) having a basic functional group, and another ethylenically unsaturated monomer (a5) it can. Here, the monomer (a1) or (a5) is an optional component.

Unless otherwise specified, the ethylenically unsaturated monomer constituting the basic resin type dispersant (B) is:
A monomer having one ethylenically unsaturated group in one molecule is shown.

  The description of the monomer (a1) is as described above.

[About monomer (a3)]
The monomer (a3) is not particularly limited as long as it is a monomer having a basic functional group. Monomer (
The explanation of a3) is as described above.

[About monomer (a5)]
Next, other monomers (a5) other than the above (a1) and (a3) will be described.
The monomer classified as the other monomer (a5) includes a monomer (a6) having no acidic functional group, aromatic ring, or basic functional group, and is as described above.
The other monomer (a5) preferably does not contain the ethylenically unsaturated monomer (a2) having an acidic functional group, but is in a range not affecting the physical properties (preferably (a1), (a3 ),
(5% or less in 100% by weight of the total of (a5)). The ethylenically unsaturated monomer (a2) having an acidic functional group is as described above.

[Composition ratio of monomer]
The ratio of the ethylenically unsaturated monomer constituting the copolymer in the basic resin dispersant (B) is 100% by weight of the total of the monomers (a1), (a3) and (a5). If
Ethylenically unsaturated monomer having an aromatic ring (a1): 0 to 30% by weight
Ethylenically unsaturated monomer having basic functional group (a3): 30 to 80% by weight
Other ethylenically unsaturated monomers (a5) other than (a1) and (a3): 0 to 70% by weight are preferable.
More preferably, (a1) is 0 to 30% by weight, (a3) is 50 to 80% by weight, (a5
) Is 0 to 50% by weight.

[Amine number]
When the constituent ratio of the monomer having a basic functional group in the entire molecule of the basic resin type dispersant (B) is represented by an amine value, the following is preferable. That is, the amine value of the basic resin dispersant (B) used is preferably in the range of 110 mgKOH / g or more and less than 1350 mgKOH / g, and more preferably in the range of 250 mgKOH / g or more and less than 1350 mgKOH / g. preferable.

If the amine value of the basic resin dispersant (B) is lower than the above range, the dispersion stability of the dispersion tends to decrease and the viscosity tends to increase. On the other hand, when the amine value is higher than the above range, the adhesion of the basic resin dispersant (B) to the surface of each material is lowered, and the storage stability of the dispersion tends to be lowered.

The amine value is expressed in mg of potassium hydroxide equivalent to perchloric acid required to neutralize all basic nitrogen contained in 1 g of the sample. The measuring method is JIS K 723.
7 (1995) is a value obtained by converting the solid content obtained by the potentiometric titration method.
The above basic resin type dispersant preferably has no acid value, but has an acid value in a range that does not affect physical properties (preferably 50 mgKOH / g or less, more preferably 20 mgKOH / g or less). Also good.

Moreover, as a basic resin type dispersing agent (B), it has an isocyanate group in the both ends formed by reacting the hydroxyl group of the vinyl polymer which has two hydroxyl groups in one terminal area | region, and the isocyanate group of diisocyanate. A resin obtained by reacting an isocyanate group of a urethane prepolymer with a primary and / or secondary amino group of a polyamine and a monoamine can be used.

Said resin can be manufactured through the following three processes, for example. The first step is the radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, thereby producing a vinyl polymer having two hydroxyl groups at one end. In the second step, the vinyl polymer having two hydroxyl groups at one end obtained in the first step and the isocyanate group of diisocyanate obtained in the first step are reacted with isocyanate at both ends. It is a process for producing a urethane prepolymer having a group. The third step is a step of reacting the isocyanate group of the urethane prepolymer having isocyanate groups at both ends produced in the second step with primary and / or secondary amino groups of polyamine and monoamine.

[First step]
The first step is the radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule, thereby producing a vinyl polymer having two hydroxyl groups at one end. This is a process for producing a coalescence.

The compound having two hydroxyl groups and one thiol group in the molecule is not particularly limited as long as it is a compound having two hydroxyl groups and one thiol group in the molecule.
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
-Propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol,
And 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like.

Examples of the ethylenically unsaturated monomer include:
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, and isobornyl (meth) acrylate;
Phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (
(Meth) acrylates and aromatic (meth) acrylates such as phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (
N-substituted (meth) acrylamides such as (meth) acrylamide and acryloylmorpholine;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate; and
Nitriles such as (meth) acrylonitrile are exemplified.

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

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

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. As the polymerization initiator, azo compounds and organic peroxides can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile),
Dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-
Cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile)
And 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate,
Cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t
-Butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5
-Trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

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

[Second step]
In the second step, the vinyl polymer having two hydroxyl groups at one end obtained in the first step is reacted with the isocyanate group of diisocyanate to produce a urethane prepolymer having isocyanate groups at both ends. It is a process to do.

As the diisocyanate, conventionally known ones can be used. For example, aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates,
And alicyclic diisocyanates.

Aromatic-containing diisocyanates include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2 , 6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene and the like.

Aliphatic diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate. , And 2,
Examples include 4,4-trimethylhexamethylene diisocyanate.

Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-.
Examples include diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

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

As described above, the listed diisocyanates are not necessarily limited to these, and two or more kinds can be used in combination.

A method for producing a urethane prepolymer by reacting a hydroxyl group of a vinyl polymer having two hydroxyl groups in one end region with an isocyanate group of a diisocyanate will be described below.

For example, when the number of moles of vinyl polymer is α and the number of moles of diisocyanate is β, α /
When β = α / (α + 1), a urethane prepolymer having an isocyanate group at both ends is theoretically obtained. When α is a positive integer, the molecular weight increases as α increases.

A known catalyst can be used for the synthesis of the urethane prepolymer. Examples thereof include tertiary amine compounds and organometallic compounds.

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

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

Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, and dibutyltin dilaurate (DBTDL).
, Dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate Can be mentioned.

As the non-tin compound, for example,
Titanium-based lead oleate such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride;
Lead systems such as lead 2-ethylhexanoate, lead benzoate, and lead naphthenate;
Iron systems such as iron 2-ethylhexanoate and iron acetylacetonate;
Cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate;
Zinc systems such as zinc naphthenate and zinc 2-ethylhexanoate; and
Zirconium-based compounds such as zirconium naphthenate can be mentioned.

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

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

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

[Third step]
The third step is a step of reacting the isocyanate group of the urethane prepolymer having isocyanate groups at both ends produced in the second step with primary and / or secondary amino groups of polyamine and monoamine.

The polyamine is a compound having at least two primary and / or secondary amino groups, and is used for reacting with an isocyanate group to form a urea bond. A diamine is mentioned as such an amine.

As the diamine having two primary amino groups, known diamines 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-propane Diamine, pentamethylenediamine [alias: 1,5
-Diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane],
Aliphatic diamines such as 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and tolylenediamine;
Alicyclic diamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine; and
Examples include phenylenediamine and aromatic diamines such as xylylenediamine.

In addition, as the diamine having two secondary amino groups, known ones can be used. Specifically, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, and N, N′-di- -Tert-butylethylenediamine and the like can be mentioned.

In addition, as the diamine having primary and secondary amino groups, known diamines can be used.
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], and N-lauryl-1,3-propanediamine [alias: N-lauryl-1]
, 3-diaminopropane or laurylaminopropylamine] and the like.

A polyamine is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group. This urea group becomes an adsorption site. 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, the adsorption to acidic materials This is particularly preferable because of improved properties.

Examples of such polyamines include polyamines having two primary and / or secondary amino groups at both ends as shown below, and further having secondary and / or tertiary amino groups at both ends.

As polyamine,
Methyliminobispropylamine [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias N, N-bis (3-aminopropyl)
Laurylamine], iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, and N,
N'-bisaminopropyl-1,4-butylenediamine, etc. can be mentioned,
Methyliminobispropylamine having two primary amino groups and one tertiary amino group,
And lauryliminobispropylamine is preferable because the reaction with diisocyanate can be easily controlled.

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

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

Polymers having primary and / or secondary amino groups include ethylenically unsaturated monomers having primary amino groups and ethylenically unsaturated monomers having secondary amino groups, such as vinylamine and allylamine monopolymers. Copolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ethyleneimine ring-opening polymers, polycondensates of ethylene chloride and ethylenediamine, and oxazolidone- It is preferably selected from the ring-opening polymers (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is 1 in monomer units based on the polymer.
0-100 weight% is preferable and 20-100 weight% is more preferable. 10% by weight content
If it is above, it is effective in preventing aggregation of each material and suppressing the raise of a 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, and fumaric acid;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, and vinyltoluene;
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid alkylaryl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl esters having functional groups such as glycidyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate;
Dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth)
(Meth) acrylic acid substituted alkyl ester having tertiary amino group such as acrylate;
Alkyl (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and tert-octyl (meth) acrylamide ;
Substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide;
Diene compounds such as 1,3-butadiene and isoprene;
Examples thereof include polymerizable oligomers (macromonomers) such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol; and vinyl cyanide.

The weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) of the polymer having primary and / or secondary amino groups is 300.
It is preferably ˜75,000, more preferably 300 to 20,000, and particularly preferably 500 to 5,000. The weight average molecular weight is 300 to 75,000.
If it is 00, it is effective in suppressing the viscosity increase of a dispersion by preventing aggregation of each material.

As the amine compound, besides the polyamine, a monoamine can also be used. The monoamine is a monoamine compound having one primary amino group or one secondary amino group in the molecule, and the monoamine is used as a reaction terminator in order to suppress excessively high molecular weight in the reaction of diisocyanate and polyamine. Is done. 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, - isopropoxyphenyl propylamine, 3-butoxy-propylamine, 3-isobutoxy-propylamine, 2-ethylhexyloxy propylamine,
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-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebutyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1 -Anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethyl , 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzyl Examples include piperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

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-
Examples include aminopyrrolidine and 3-pyrrolidinol.

Further, 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, and a dispersant. A tertiary amino group having an effect of improving the adsorptive capacity can be introduced into the polymer terminal.

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

These monoamine compounds may be used alone or in combination of two or more. In addition,
The active hydrogen of the urea bond after the reaction between the primary amino group and the isocyanate group has low reactivity, and under the polymerization conditions of the present dispersant, it does not further react with the isocyanate group and the molecular weight does not increase.

In the third step, a urea reaction for obtaining a urethane urea resin, or a polyurethane urea having a primary or secondary amino group at the terminal from a urethane prepolymer, polyamine, and monoamine is:
1) A urethane prepolymer solution is charged into a flask, and polyamine and monoamine (
The method of dripping,
2) A method in which a solution comprising a polyamine, a monoamine, and, if necessary, a solvent is charged into a flask, and a urethane prepolymer solution is dropped,
It is divided roughly into.

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

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

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

The weight average molecular weight (Mw) of the obtained polymer is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, particularly preferably 1,500 to 2.
0,000. If the weight average molecular weight is less than 1,000, the stability of the dispersion may decrease. If the weight average molecular weight exceeds 100,000, the interaction between the resins may increase and the dispersion may increase in viscosity. The amine value of the obtained polymer is preferably 1 to 100 mgKOH / g, more preferably 2 to 50 mgKOH / g, and further preferably 3 to 30.
mgKOH / g.

In addition, as the basic resin type dispersant (B), a polymer (meth) acryloyl group having one or two (meth) acryloyl groups in one end region, and one or more primary and / or two of them. A polyisocyanate containing a primary and / or secondary amino group of a polymer having an amino group obtained by reacting a primary and / or secondary amino group of a polyamine containing a primary amino group with two or more isocyanate groups A resin obtained by reacting with an isocyanate group can be used.

Said resin can be manufactured through the following three processes, for example. The first step is a step of obtaining a polymer having one or two (meth) acryloyl groups in one end region.
The second step comprises a (meth) acryloyl group of the polymer obtained in the first step and a primary and / or secondary amino group of a polyamine containing one or more primary and / or secondary amino groups,
Is a step of obtaining a polymer having an amino group, obtained by reacting In the third step, the primary and / or secondary amino group of the polymer having an amino group obtained in the second step is reacted with an isocyanate group of a polyisocyanate containing two or more isocyanate groups to obtain a resin. It is the process of obtaining.

[First step]

The first step is a step of obtaining a polymer having one or two (meth) acryloyl groups in one end region.

In the first step, the polymer having a (meth) acryloyl group is preferably a polyester or a vinyl polymer. These have good affinity for the solvent and can easily adjust the molecular weight. In addition, the (meth) acryloyl group in one terminal region is preferably an acryloyl group that undergoes a reaction at a relatively low temperature from the viewpoint of reaction control with a primary and / or secondary amino group.

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

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

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.

Lactone can be used without being limited to the above examples, and even when used alone,
Two or more types may be used in combination.

A particularly suitable lactide is lactide (3,6-dimethyl-1,4-dioxane-2,5-
Dione) and glycolide (1,4-dioxane-2,5-dione).

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

The number of moles of lactone and / or lactide polymerized relative 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, the viscosity of the dispersion increases and problems are likely to occur.

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, and benzyltrimethylammonium iodide salt;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide,
Quaternary phosphonium salts such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodide;
Phosphorus compounds such as triphenylphosphine;
Organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate;
Alkali metal alcoholates such as sodium alcoholate and potassium alcoholate;
Tertiary amines such as triethylamine and triphenylamine;
Organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, and dioctyltin oxide;
Organoaluminum compounds such as aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate, aluminum trisacetylacetonate;
Organic titanate compounds such as tetra-n-butyl titanate, the above dimer, tetraisobutyl titanate, tetrastearyl titanate, and diisopropoxy bis (triethanolaminate) titanium; and
Examples thereof include zinc compounds such as zinc chloride.

The amount of the ring-opening polymerization catalyst used is 0 with respect to 100% by weight of the lactone and / or lactide.
. 1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. The amount of catalyst is 3
If it exceeds 000 ppm, the resin may become intensely colored. Conversely, the amount of catalyst used is 0
. If it is less than 1 ppm, the rate of ring-opening polymerization of lactone and / or lactide becomes extremely slow, which may be undesirable.

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

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, phenothiazine and the like are preferable. These can be used alone or in combination
0.01 wt% to 6 wt% with respect to 100 wt% of the alcohol having a (meth) acryloyl group
% By weight, preferably 0.05 to 1.0% by weight.

Polyester 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 (meth) acryloyl It can also be obtained by reacting a compound having a group.

As the compound 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 (meth) acryloyloxyethyl isocyanate.

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

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 , Aliphatic monoalcohols such as cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, and oleyl alcohol;
An aromatic ring-containing monoalcohol such as benzyl alcohol, phenoxyethyl alcohol, and paracumylphenoxyethyl alcohol; and
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2
-Ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene Glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl Pills ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2
Ethyl hexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl Ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-
2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetra Examples include alkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether.

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

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

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, 4,5-epoxypentyl acrylate, and the like.

The polyester 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.
Further, the above-mentioned compound having an epoxy group and (meth) acryloyl group is reacted, and further, a group capable of reacting with a hydroxyl group obtained by ring opening of an epoxy group, a group capable of reacting with a hydroxyl group, and a (meth) acryloyl group It can also be obtained by reacting a compound having In this case, a polyester having two (meth) acryloyl groups in one end region is obtained.

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.

A vinyl polymer having one or two (meth) acryloyl groups in one terminal region is converted into a vinyl polymer having one or two hydroxyl groups in one terminal region and a group capable of reacting with a hydroxyl group ( It can be obtained by reacting a compound having a (meth) acryloyl group.

A vinyl polymer having one or two hydroxyl groups in one end region can be obtained by using an ethylenically unsaturated monomer in the presence of a compound having one or two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of the monomer. Since the thiol group of a compound having one or two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, and a vinyl polymer is synthesized via the S atom, the molecular weight thereof is ethylene. It is easy to adjust the molecular weight of the vinyl polymer within the above range depending on the amount of the compound used relative to the unsaturated monomer, and as a result, the affinity for the solvent can also be suitably adjusted.

Examples of the compound having 1 or 2 hydroxyl groups and 1 thiol group in the molecule include 1 hydroxyl group and 1 hydroxyl group in the molecule such as 1-mercaptoethanol and 2-mercaptoethanol. A compound having a thiol group; and
1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1
, 2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2
-Mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl Examples include compounds having two hydroxyl groups and one thiol group in the molecule such as -1,3-propanediol.

The compound having one or two hydroxyl groups and one thiol group in the molecule is preferably a compound having two hydroxyl groups and one thiol group in the molecule, more preferably 3-mercapto-1,2-propanediol (thioglycerin).

By using a compound having two hydroxyl groups and one thiol group in the molecule, the finally obtained dispersant has an adsorption site having a plurality of amino groups and a plurality of solvent affinity sites. It has an ideal structure.

Examples of the ethylenically unsaturated monomer include:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate,
Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate,
Isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth)
Linear or branched alkyl (meth) acrylates such as acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates and cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, 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, and poly Chi 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, and crotonic acid;
Caprolactone adducts of the above carboxylic acids (addition moles 1-5);
2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (
(Meth) having a carboxyl group such as (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) acrylate
Acrylates;
Styrenes such as styrene and α-methylstyrene;
Vinyls such as vinyl acetate, vinyl propionate, vinyl (meth) acrylate, and allyl (meth) acrylate;
Ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether,
vinyl ethers such as n-butyl vinyl ether and isobutyl vinyl ether;
Examples include (meth) acrylamide and amides having no amino group such as N-vinylformamide; and acrylonitrile having no amino group. These can be used alone or in admixture of two or more.

A compound having one or two hydroxyl groups and one thiol group in the molecule is used as a chain transfer agent, and an ethylenically unsaturated monomer and polymerization start according to the molecular weight of the target vinyl polymer. A vinyl polymer can be obtained by mixing and heating the agent.

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.

In the radical polymerization, 0.001 is arbitrarily added to 100 parts by weight of the ethylenically unsaturated monomer.
Up to 5 parts by weight of a polymerization initiator can be used.

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), and 2,2'-azobis [2- (2-imidazoline-2
-Yl) propane] and other azo compounds and organic peroxides; and
Benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (
2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionylperoxide, and diacetylperoxide These polymerization initiators can be used singly or in combination of two or more.

As the compound 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 (meth) acryloyloxyethyl isocyanate.

The polyester and vinyl polymer can be synthesized without solvent or, if necessary, using a solvent. In the case of solution polymerization, as a polymerization solvent, 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 monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and N-methylpyrrolidone are particularly used. It is not limited to these. These polymerization solvents may be used as a mixture of two or more. The solvent used in the polymerization reaction can be removed by an operation such as distillation after the completion of the reaction, or it can be used as it is as a solvent for the next step or as a part of the product.

[Second step]
The second step comprises a (meth) acryloyl group of the polymer obtained in the first step and a primary and / or secondary amino group of a polyamine containing one or more primary and / or secondary amino groups, Is a step of obtaining a polymer having an amino group, obtained by reacting

A polyamine is a compound having one or more primary and / or secondary amino groups, and a polymer having a (meth) acryloyl group in one terminal region of the primary and / or secondary amine (
Addition reaction to a (meth) acryloyl group produces a polymer having an amino group.
In the third step to be described later, a urea group is generated by reacting a part or all of the primary and / or secondary amine of the polymer having an amino group with the isocyanate group of the polyisocyanate. That is, in the above-mentioned dispersant, an amino group and a urea bond existing in one end region become adsorption sites.
Diamine is mentioned as such a polyamine. In addition, polyamine has 2 at both ends.
In the case of a compound having a single primary and / or secondary amino group and a secondary and / or tertiary amino group other than both ends, the adsorptivity to acidic materials is improved. Is particularly preferred.

As the diamine having two primary amino groups, known diamines 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-propane Diamine, pentamethylenediamine [alias: 1,5
-Diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane],
Aliphatic diamines such as 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and tolylenediamine;
Alicyclic diamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine; and
Examples include phenylenediamine and aromatic diamines such as xylylenediamine.

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

Moreover, as a diamine which has a primary and secondary amino group, a well-known thing can be used, Specifically, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylamino] Ethylamine], N-methyl-1
, 3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,
3-diaminopropane [alias: N-isopropyl-1,3-propanediamine or isopropylaminopropylamine] and N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or lauryl] Aminopropylamine] and the like.

In addition, as the diamine having primary and tertiary amino groups, known diamines can be used. Specifically,
N, N-dimethylethylenediamine [alias: dimethylaminoethylamine], N, N-
Diethylethylenediamine [alias: diethylaminoethylamine], N, N-dimethyl-
1,3-propanediamine [alias: N, N-dimethyl-1,3-diaminopropane or dimethylaminopropylamine] and the like.

As polyamines having two primary and / or secondary amino groups at both ends and having secondary and / or tertiary amino groups at both ends, known ones can be used. In terms of
Methyliminobispropylamine [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias N, N-bis (3-aminopropyl)
Laurylamine], iminobispropylamine [also known as N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, and N,
N'-bisaminopropyl-1,4-butylenediamine, etc. can be mentioned,
Methyliminobispropylamine having two primary amino groups and one tertiary amino group,
In addition, lauryliminobispropylamine is preferable because the reaction with diisocyanate is easily controlled.

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

Further, as the polyamine, a polymer having two or more primary and / or secondary amino groups can also be used.

Polymers having primary and / or secondary amino groups include ethylenically unsaturated monomers having primary amino groups and ethylenically unsaturated monomers having secondary amino groups, such as vinylamine and allylamine monopolymers. Copolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ethyleneimine ring-opening polymers, polycondensates of ethylene chloride and ethylenediamine, and oxazolidone- It is preferably selected from the ring-opening polymers (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is 1 in monomer units based on the polymer.
0-100 weight% is preferable and 20-100 weight% is more preferable. 10% by weight content
If it is above, it is effective in preventing aggregation of each material and suppressing the raise of a 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, and fumaric acid;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, and vinyltoluene;
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid alkylaryl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl esters having functional groups such as glycidyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate;
Dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth)
(Meth) acrylic acid substituted alkyl ester having tertiary amino group such as acrylate;
Alkyl (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and tert-octyl (meth) acrylamide ;
Substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide;
Diene compounds such as 1,3-butadiene and isoprene;
Examples thereof include polymerizable oligomers (macromonomers) such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol; and vinyl cyanide.

The weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) of the polymer having primary and / or secondary amino groups is 300.
It is preferably ˜75,000, more preferably 300 to 20,000, and particularly preferably 500 to 5,000. The weight average molecular weight is 300 to 75,000.
If it is 00, it is effective in suppressing the viscosity increase of the dispersion by preventing aggregation.

As the amine compound, besides the polyamine, a monoamine can also be used. The monoamine is a monoamine compound having one primary amino group or one secondary amino group in the molecule, and the monoamine is too high in the reaction between the polymer obtained in the first step and the polyamine. 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-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3
-Decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropyl Amine, 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-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinebutyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1 -Anilinonaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethyl , 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzyl Examples include piperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

In the second step, one or two (meta) in one end region obtained in the first step
A polymer having an amino group is obtained by an addition reaction of a primary or secondary amino group of a polyamine with a (meth) acryloyl group of a polymer having an acryloyl group. This reaction is generally called the Michael addition reaction. By adjusting the blending of the polymer and polyamine, a structure having a primary or secondary amino group capable of reacting with an isocyanate group can be obtained.

When one polymer molecule having one (meth) acryloyl group in one end region is reacted with one diamine molecule having two primary amino groups, theoretically, one primary amino group One polymer molecule having one secondary amino group is obtained.

In addition, for one polymer molecule having two (meth) acryloyl groups in one end region,
When two diamine molecules having one primary amino group and one secondary amino group are reacted, theoretically, one polymer molecule having four secondary amino groups is obtained.

Further, when n molecules of a polymer having two (meth) acryloyl groups in one terminal region are reacted with (n + 1) molecules of diamine having two primary amino groups, theoretically, the primary amino One polymer molecule having two groups and 2n secondary amino groups is obtained. (N is
It is a positive integer. )

In addition, for n molecules of a polymer having two (meth) acryloyl groups in one end region,
When (n + 1) diamine molecules having two secondary amino groups are reacted, theoretically, one polymer molecule having two secondary amino groups and 2n tertiary amino groups is obtained. (N is a positive integer.)

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

Michael for obtaining a polymer having an amino group from a polymer having one or two (meth) acryloyl groups in one terminal region and a polyamine having one or more primary and / or secondary amino groups The reaction is broadly classified into 1) a method in which the reaction is carried out by charging the whole amount, and 2) a method in which a solution comprising a polyamine and, if necessary, a solvent is charged into a flask and a polymer solution is dropped. The synthesis may be carried out by appropriately selecting a method that allows the reaction to be carried out stably. However, if there is no problem in the reaction, it is preferable to apply the method 2) described above, which makes reaction control (molecular design control) easier.

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

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

[Third step]
In the third step, the primary and / or secondary amino group of the polymer having an amino group obtained in the second step is reacted with an isocyanate group of a polyisocyanate containing two or more isocyanate groups to obtain a resin. It is the process of obtaining.

A primary or secondary amino group of a polymer having an amino group is partially or fully formed as a urea bond by adjusting the amount of polyisocyanate to be reacted, and the rest is present as an amino group in the dispersant. .

In addition, when the polymer 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 adsorbing group for each material. Remains in the dispersant.

For example, when one molecule of diisocyanate is reacted with two molecules of a polymer having one primary amino group and two secondary amino groups, the primary amino group theoretically reacts with the isocyanate group. A dispersant is obtained which forms urea bonds and has 4 secondary amino groups and 2 urea bonds. When it has a maternity leave amino group as a substituent, the dispersant also has a tertiary amino group.

Also, for example, when one molecule of diisocyanate is reacted with two molecules of a polymer having one secondary amino group, theoretically, the secondary amino group reacts with the isocyanate group to form a urea bond. A dispersant is formed that has urea bonds. When it has a maternity leave amino group as a substituent, the dispersant also has a tertiary amino group. The dispersant does not have an amino group having active hydrogen.

Further, for example, a polymer molecule having two primary amino groups and 2n secondary amino groups (m
When m diisocyanate molecules are reacted with +1), theoretically, the primary amino group and the isocyanate group react to form a urea bond, and two primary amino groups and secondary amino groups (2 nm + 2n) And a dispersant having 2 m urea bonds is obtained. When it has a maternity leave amino group as a substituent, the dispersant also has a tertiary amino group. (N and m are positive integers.)

In addition, for example, both ends of a polymer-derived portion obtained by reacting two molecules of a polyamine having one primary amino group and one molecule of a polymer having two (meth) acryloyl groups are used. In the case of reacting m molecules of diisocyanate to (m + 1) polymer molecules having two secondary amino groups, one in each region, theoretically, the above secondary amino group and A dispersant having a total of two secondary amino groups, one at each end region as seen from the polyurea chain, is formed by reacting with an isocyanate group to form a urea bond. (M is a positive integer.)

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

As described above, the molecular weight of the dispersant, the amino group (primary, secondary, and / or tertiary) and the amount of urea bonds are adjusted by changing the reaction ratio between the polymer having amino groups and the polyisocyanate. be able to.

As the polyisocyanate, conventionally known ones can be used, but diisocyanates are preferable from the low viscosity effect of the dispersion, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, and aromatic-aliphatic systems. Diisocyanates, alicyclic diisocyanates, dimers of these diisocyanates (uretodiones), reaction products of these diisocyanate trimers (isocyanurates) and monoalcohols, and reaction products of these diisocyanates and diols (of both end isocyanates) Urethane prepolymer) and the like.

Aromatic diisocyanates include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl terdiisocyanate. -To, dianisidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate,
Examples thereof include naphthylene diisocyanate and 1,3-bis (isocyanatomethyl) benzene.

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

As aromatic-aliphatic diisocyanate, ω, ω′-diisocyanate-1,3-
Dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω ′
-Diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like can be mentioned.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (hereinafter sometimes abbreviated as IPDI), 1,3.
-Cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4
-Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate and the like can be mentioned.

As described above, the listed diisocyanates are not necessarily limited to these, and two or more kinds can be used in combination.

Further, for the purpose of increasing the molecular weight of the dispersant, a polyisocyanate having three or more isocyanate groups in one molecule may be used. An aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic- Aliphatic polyisocyanate and alicyclic polyisocyanate
And the like.

Specifically, as a polyisocyanate having three or more isocyanate groups per molecule,
Isocyanurate of diisocyanate, and diisocyanate trimer such as biuret of diisocyanate, polyol adduct of diisocyanate, copolymer of two or more diisocyanates, aromatic triisocyanate, and polymeric type An aromatic isocyanate oligomer etc. are mentioned.

Examples of the polyisocyanate having three or more isocyanate groups per molecule include isocyanurate of tolylene diisocyanate (hereinafter sometimes abbreviated as TDI),
Isocyanurate of isophorone diisocyanate (hereinafter sometimes abbreviated as IPDI), isocyanurate of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI), hexamethylene diisocyanate (hereinafter referred to as HDI) Isocyanurate body, HDI biuret body, HDI trimethylolpropane (hereinafter sometimes abbreviated as TMP) adduct body, TDI TMP adduct body, TDI / HDI copolymer, etc. 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, and 4,4 '
, 4 ″ -triphenylmethane triisocyanate and the like; and polymer type aromatic isocyanate oligomers such as polymethylene polyphenyl polyisocyanate (also known as MDI oligomer).

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

As described above, the weight average molecular weight (Mw) of the polymer obtained through the three steps is 1,000 to 1.
It is preferably 00,000, more preferably 1,500 to 50,000, particularly preferably 2,000 to 30,000. If the weight average molecular weight is less than 1,000, the stability of the dispersion may decrease. If the weight average molecular weight exceeds 100,000, the interaction between the resins may increase and the dispersion may increase in viscosity. . Further, the amine value of the obtained dispersant is 5 to 5.
It is preferably 100 mgKOH / g, more preferably 10-70 mgKOH / g
More preferably, it is 20-50 mgKOH / g. If the amine value is less than 5 mgKOH / g, the functional groups adsorbing to each material may be insufficient, and it may be difficult to contribute to dispersion of each material. If the amine value exceeds 100 mgKOH / g, aggregation between the materials occurs. Insufficient viscosity lowering effect and defects in the appearance of the coating film may occur.

Further, as the basic resin type dispersant (B), a vinylamide resin can be used. Vinylamide resins are generally known to have an adsorption interaction with anionic species. Strictly speaking, the vinylamide resin does not correspond to a resin having a basic functional group,
Since the pH is slightly basic, it is treated as a resin having a basic functional group in this specification.
The vinylamide resin to be used is not particularly limited, and examples thereof include polyvinylacetamide, polyacrylamide, polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, polyvinylpyrrolidone graft copolymer, and a copolymer of vinylpyrrolidone and a comonomer. Can be mentioned.

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

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

Among the above vinylamide resins, in particular, polyvinylpyrrolidone, vinylpyrrolidone-
A substantially neutral vinylamide resin such as 1-butene copolymer or vinylpyrrolidone-styrene copolymer, or an acid-modified product of polyvinylpyrrolidone treated with an organic acid or an inorganic acid is preferably used.

Further, as the basic resin type dispersant (B), other commercially available resins having basic functional groups can be used. Although it does not specifically limit as resin which has a commercially available basic functional group, For example, the following are mentioned.

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

As a resin having a basic functional group manufactured by Nippon Lubrizol Corporation, SOLPERSE9
000, 13240, 13650, 13940, 17000, 18000, 19000,
20000, 24000SC, 24000GR, 28000, 31845, 32000,
32500, 32600, 33500, 34750, 35100, 35200, 3750
0, 38500, or 39000.

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

As a resin having a basic functional group manufactured by Ajinomoto Fine Techno Co., Ltd., Ajisper PB71
1, Ajisper PB821, or Azisper PB822.

Examples of resins having a basic functional group manufactured by Enomoto Kasei Co., Ltd. include Disparon 1850 and 1860.
Or DA-1401.

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

[About neutralizing agent]
A neutralizing agent may be added to the basic resin type dispersant. By neutralizing some or all of the basic functional groups of the basic resin type dispersant, the salt of the basic functional group is easily dissociated in an aqueous medium, and is more easily charged. Therefore, the surface of the conductive carbon and the surface of the positive and negative electrode active materials on which the neutralized basic resin type dispersant is adsorbed are charged, and dispersibility is further improved by the repulsion.

Examples of the acid used for this neutralization include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrobromic acid, hydroiodic acid, and carboxylic acids, phosphonic acids, sulfonic acids, aromatic hydroxy groups, etc. An organic acid containing

The amount of the acid used for the basic resin type dispersant having a basic functional group is preferably 0.1 to 10 equivalents, more preferably the basic functional group of the basic resin type dispersant used. Is 0.8 to 1.2 equivalents.

[Amotropic resin type dispersant (C)]

As described above, the composite ink can contain the amphoteric resin dispersant (C) as a dispersant. The amphoteric resin type dispersant (C) is not particularly limited as long as it is a resin having an acidic functional group and a basic functional group, but is preferably an ethylenically unsaturated monomer (a1) having an aromatic ring and a carboxyl group. An ethylenically unsaturated monomer (a7) having an amino group and an ethylenically unsaturated monomer (a8) having an amino group as a basic compound And those neutralized with.

The ethylenically unsaturated monomer constituting the amphoteric resin dispersant (C) is, unless otherwise specified,
A monomer having one ethylenically unsaturated group in one molecule is shown.

[About monomer (a1)]
The description of the monomer (a1) is as described above.

[About monomer (a7)]
The ethylenically unsaturated compound (a7) having a carboxyl group is not particularly limited, but maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxy Ethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, croton Examples thereof include acid and cinnamic acid. In particular, methacrylic acid and acrylic acid are preferable.

[About monomer (a8)]
The ethylenically unsaturated monomer (a8) having an amino group is not particularly limited, but dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylamino Examples include styrene.

[About monomer (a9)]
Examples of the monomer (a9) other than (a1), (a7), and (a8) include a monomer (a6) having no acidic functional group, aromatic ring, or basic functional group. , As described above.

[Composition ratio of monomer]
The ratio of the monomers constituting the copolymer in the amphoteric resin type dispersant (C) used is the monomer (
When the total of a1), (a7), (a8), and (a9) is 100% by weight,
5 to 70% by weight of an ethylenically unsaturated monomer (a1) having an aromatic ring,
15 to 60% by weight of ethylenically unsaturated monomer (a7) having a carboxyl group,
1 to 80% by weight of an ethylenically unsaturated monomer having an amino group (a8),
The other monomer (a9) is 0 to 79% by weight.
Preferably, (a1): 20 to 70% by weight, (a7): 15 to 45% by weight, (a8):
1 to 70% by weight, (a9): 0 to 50% by weight.
More preferably, (a1): 30 to 70% by weight, (a7): 15 to 35% by weight, (a8)
: 1 to 40% by weight, (a9): 0 to 40% by weight.

An aromatic ring derived from an ethylenically unsaturated monomer having an aromatic ring (a1) and an amino group derived from an ethylenically unsaturated monomer having an amino group (a8) are mainly adsorbed onto an active material or a carbon material. I guess it will be.

The ethylenically unsaturated monomer (a7) having a carboxyl group has a function of dissolving or dispersing a neutralized copolymer in an aqueous liquid medium.
Then, the copolymer is adsorbed to the active material or the carbon material via an aromatic ring or an amino group, neutralized, and the charge repulsion of the ionized carboxyl group changes the dispersion state of the active material or the carbon material in the aqueous liquid medium. It is considered that it became possible to keep stable.

〔viscosity〕
The molecular weight of the copolymer obtained by copolymerizing the monomers (a1), (a7), (a8), and (a9) is not particularly limited, but the amphoteric resin type dispersant (C) in a 20% solids aqueous solution The viscosity is preferably 5 to 100,000 mPa · s, more preferably 10 to 50,000.
0 mPa · s. When the viscosity of the amphoteric resin dispersant (C) is lower than the predetermined range and the molecular weight of the amphoteric resin dispersant (C) is too high, the electrode active material Or there is a possibility of causing poor dispersion of the carbon material which is a conductive aid.
The viscosity is a value measured at 25 ° C. using a B-type viscometer.

[Acid value]
The copolymer is obtained by copolymerizing the carboxyl group-containing unsaturated compound (a7), and it is preferable that the constituent ratio of the monomer having an anionic functional group in the copolymer is represented by the acid value as follows. That is, the acid value of the copolymer used is 50 mg KOH / g or more 4
It is preferably in the range of not more than 00 mgKOH / g, and further, the acid value is 80 mgKOH
/ G or more and 300 mgKOH / g or less is preferable.
When the acid value of the copolymer used is lower than the above range, the dispersion stability of the dispersion is lowered,
Viscosity tends to increase. Moreover, when the acid value of the copolymer to be used is higher than the above range, the adhesion of the copolymer to the surface of each material is lowered, and the storage stability of the dispersion tends to be lowered.
The acid value of the copolymer is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

[Various derivatives having basic functional groups]
As described above, the composite ink can contain various derivatives having a basic functional group.
Examples of various derivatives having a basic functional group include organic dye derivatives having a basic functional group and triazine derivatives having a basic functional group.

As various derivatives having a basic functional group, a triazine derivative represented by the following general formula (1) or an organic dye derivative represented by the following general formula (6) is preferable.

General formula (1):

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

General formula (2):

General formula (3):

General formula (4):

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

General formula (5):

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

Specific examples of the organic dye residue represented by R ^{1 in the} general formula (1) and R ¹⁰ and R ¹¹ in the general formula (5) include diketopyrrolopyrrole dyes; azo, disazo, polyazo and the like Azo dyes; phthalocyanine dyes; anthraquinone dyes such as diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, and violanthrone; quinacridone dyes; dioxazine dyes; perinone dyes; Thioindigo dyes; isoindoline dyes; isoindolinone dyes; quinophthalone dyes; selenium dyes; and metal complex dyes. In particular, from the viewpoint of enhancing the effect of suppressing short-circuits caused by metals, it is preferable to use organic dye residues that are not metal complex dyes.

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

R ³ and R ⁴ in the general formulas (2) and (3) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, Alternatively, R ³ and R ⁴ are a heterocyclic residue which may have a substituent containing a further nitrogen, oxygen or sulfur atom together.

Y ¹ , Y ² and Y ³ in the general formulas (1) to (5) each independently represent a substituted or unsubstituted alkylene group, alkenylene group or arylene group having 20 or less carbon atoms, preferably Examples thereof include a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group, and an alkylene group which may have a side chain having 10 or less carbon atoms.

General formula (6):

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

General formula (7):

General formula (8):

General formula (9):

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

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

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

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

Specific examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) and the general formulas (6) to (8) include the following.
Dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N- tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, Dihexylamine,
Dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N
-Methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,
2-dimethylpropylamine, N, 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-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N- Dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylamino Ethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid , Lee Nipecotic acid, methyl isonicopetic acid, ethyl isonicopetic acid, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N
-Butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-
Amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

An organic dye derivative having a basic functional group, an anthraquinone derivative having a basic functional group,
A method for synthesizing an acridone derivative having a basic functional group or a triazine derivative having a basic functional group is not particularly limited, and a well-known method can be applied. For example, JP-A-54-62227, JP-A-56-118462, JP-A-5
The method described in JP-A-6-166266, JP-A-60-88185, JP-A-63-305173, JP-A-3-2676, or JP-A-11-199796 is applied. be able to. The disclosure by the above publication is incorporated into a part of this specification by reference.

Various derivatives having a basic functional group, for example, after introducing substituents represented by the following formulas (10) to (13) into an organic dye, anthraquinone, or acridone, react these substituents with an amine component. Can be synthesized.

Formula (10):
-SO ₂ Cl

Formula (11):
-COCl

Formula (12):
-CH ₂ NHCOCH ₂ Cl

Formula (13):
—CH ₂ Cl

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

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

In addition, when introducing the substituent represented by the formula (11), 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 substituents represented by formulas (10) to (13) with the amine component, formulas (10) to (10)
A part of the substituent represented by 13) may be hydrolyzed to replace chlorine with a hydroxyl group. In that case, the substituent represented by the formula (10) is a sulfonic acid group, and the substituent represented by the formula (11) is a carboxylic acid group. Each acid group may remain as a free acid. Alternatively, each may form a salt with a 1-3 valent metal or the above amine.

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

General formula (14):

In general formula (14),
X ¹³ represents —NH—, —O—, —CONH—, —SO ₂ NH—, —CH ₂ NH—, —CH _2.
NHCOCH ₂ NH—, or —X ¹⁴ —Y ⁵ —X ¹⁵ —,
X ¹⁴ represents —NH—, —O—, —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHC.
O— or —NHSO ₂ —,
Each X ¹⁵ is independently —NH— or —O—;
Y ⁵ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
P ¹ is a substituent represented by any ^one of the general formulas (2), (3), and (4),
Q ² represents —O—R ²⁴ , —NH—R ²⁴ , a halogen group, —X ¹ —R ²⁵ , or the general formula (2),
(3) or a substituent represented by either (4),
R ²⁴ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group;
R ²⁵ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the general formula (5).

The triazine derivative having a basic functional group, for example, uses cyanuric chloride as a starting material, and at least one chlorine of cyanuric chloride is represented by general formulas (7) to (9) or general formula (14).
) Is reacted with an amine component (for example, N, N-dimethylaminopropylamine, N-methylpiperazine or the like) that forms the substituent represented by (3), and then the remaining chlorine of cyanuric chloride is reacted with various amines or alcohols. To obtain.

Various derivatives having a basic functional group can be used in combination with other acidic compounds. Examples of the acidic compound include an acidic resin dispersant (A), an inorganic acid, and an organic acid having a molecular weight of 300 or less.

Various derivatives having a basic functional group can be used in combination with the above-mentioned basic resin type dispersant (B) and amphoteric resin type dispersant (C).

[Various derivatives having acidic functional groups]
As described above, the composite ink can include various derivatives having an acidic functional group. Examples of the organic compound having an acidic functional group include one or more derivatives selected from an organic dye derivative having an acidic functional group and a triazine derivative having an acidic functional group.

As various derivatives having an acidic functional group, a triazine derivative represented by the following general formula (15) or an organic dye derivative represented by the following general formula (18) is preferable.

Formula (15):

In general formula (15),
X ¹⁰¹ represents —NH—, —O—, —CONH—, —SO ₂ NH—, —CH ₂ NH—, —CH _2.
NHCOCH ₂ NH—, or —X ¹⁰³ —Y ¹⁰¹ —X ¹⁰⁴ —,
X ¹⁰² and X ¹⁰⁴ are each independently —NH— or —O—;
X ¹⁰³ represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —N
H
SO ₂ −
Y ¹⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ¹⁰¹ is —SO ₃ M, —COOM, or —P (O) (— OM) ₂ ;
M ¹⁰¹ is one equivalent of a monovalent to trivalent cation,
Q ¹⁰¹ represents —O—R ¹⁰² , —NH—R ¹⁰² , a halogen group, —X ¹⁰¹ —R ¹⁰¹ , or —X ^102.
Is a -Y ¹⁰¹ -Z ^101,
R ¹⁰² is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,
n ¹⁰¹ is an integer of 1 to 4,
R ¹⁰¹ is an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or a group represented by the following general formula (16).

Formula (16):

In general formula (16),
X ²⁰¹ is —NH— or —O—;
X ²⁰² and X ²⁰³ each independently represent —NH—, —O—, —CONH—, —SO _2.
N
H—, —CH ₂ NH—, or —CH ₂ NHCOCH ₂ NH—,
R ²⁰¹ and R ²⁰² are each independently an organic dye residue, a substituted or unsubstituted heterocyclic residue, a substituted or unsubstituted aromatic ring residue, or —Y ²⁰¹ —Z ²⁰¹ ,
Y ²⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ²⁰¹ is —SO ₃ M ²⁰¹ , —COOM ²⁰¹ , or —P (O) (— OM ²⁰¹ ) ₂ ;
^M201 is one equivalent of a monovalent to trivalent cation.

Examples of the organic dye residue represented by R ^{101 in the} general formula (15) and R ²⁰¹ and R ²⁰² in the general formula (16) include azo dyes such as diketopyrrolopyrrole dyes, azo, disazo, and polyazo. Dye, phthalocyanine dye, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantron, violanthrone, anthraquinone dye, quinacridone dye, dioxazine dye, perinone dye, perylene dye, thioindigo And dyes such as azo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, and metal complex dyes. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, it is preferable to use an organic dye residue that is not a metal complex dye, among which an azo dye, a diketopyrrolopyrrole dye, a metal-free phthalocyanine dye, The use of quinacridone dyes or dioxazine dyes is preferred because of its excellent dispersibility.

Examples of the heterocyclic residue and aromatic ring residue represented by R ^{101 in the} general formula (15) and R ²⁰¹ and R ²⁰² in the general formula (16) include thiophene, furan, pyridine, pyrazole, pyrrole. Imidazole, isoindoline, isoindolinone, benzimidazolone, benzthiazole, benztriazole, indole, quinoline, carbazole,
Examples thereof include acridine, benzene, naphthalene, anthracene, fluorene, phenanthrene, and anthraquinone. In particular, the use of a heterocyclic residue containing at least one of S, N, and O heteroatoms is preferable because of excellent dispersibility.

Y ^{101 in the} general formula (15) and Y ^{201 in the} general formula (16) each represents a substituted or unsubstituted alkylene group having 20 or less carbon atoms, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group. However, a substituted or unsubstituted phenylene group, biphenylene group, naphthylene group, or alkylene group which may have a side chain having 10 or less carbon atoms is preferable.

Formula (15) substituted or unsubstituted alkyl group represented by R ¹⁰² contained in Q ^101, the alkenyl group is preferably of 20 or less carbon atoms, more preferably having 10 or less carbon atoms Examples thereof include an alkyl group which may have a side chain. In the alkyl group or alkenyl group having a substituent, the hydrogen atom of the alkyl group or alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom, or a bromine atom, a hydroxyl group, or a mercapto group. Is.

M ^{101 in the} general formula (15) and M ^{201 in the} general formula (16) represent one equivalent of a valence of 1 to 3, and are, for example, any one of a hydrogen atom (proton), a metal cation, and a quaternary ammonium cation. Represents. Moreover, when it has two or more M in a dispersing agent structure, M may be only any one of a proton, a metal cation, and a quaternary ammonium cation, and these may be combined.

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

The quaternary ammonium cation is a single compound having a structure represented by the general formula (17) or a mixture.

Formula (17):

In General Formula (17), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted group. An aryl group.

When R ³⁰¹ , R ³⁰² , R ³⁰³ and R ^{304 in the} general formula (17) have a carbon atom, the carbon number is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.

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

General formula (18):

In general formula (18),
X ^401, a direct bond, -NH -, - O -, - CONH -, - SO 2 NH -, - CH 2 NH-
_{, -CH 2 NHCOCH 2 NH -,} - X 402 -Y-, or -X ⁴⁰² -Y-X ⁴⁰³ - a and,
X ⁴⁰² represents —CONH—, —SO ₂ NH—, —CH ₂ NH—, —NHCO—, or —N
H
SO ₂ −
X ⁴⁰³ is —NH— or —O—;
Y ⁴⁰¹ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group composed of 1 to 20 carbon atoms,
Z ⁴⁰¹ is —SO ₃ M ⁴⁰¹ , —COOM ⁴⁰¹ , or —P (O) (— OM ⁴⁰¹ ) ₂ ;
M ⁴⁰¹ is one equivalent of a monovalent to trivalent cation,
R ⁴⁰¹ is an organic dye residue,
n ⁴⁰¹ is an integer of 1 to 4.

Examples of the organic dye residue represented by R ⁴⁰¹ in the general formula (18) include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, and flavantrons. , Antanthrone, Indanthrone, Pyrantron, Biolantron, etc. Anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone And dyes, selenium dyes, and metal complex dyes. The organic dye residue represented by R ₉ includes a light yellow anthraquinone residue that is not generally called a dye. In particular, in order to increase the effect of suppressing the short circuit of the battery due to metal, the use of an organic dye residue that is not a metal complex dye is preferable,
Among them, the use of azo dyes, diketopyrrolopyrrole dyes, metal-free phthalocyanine dyes, quinacridone dyes, or dioxazine dyes is preferable because of excellent dispersibility.

M ^{401 in} the formula of the general formula (18) represents one equivalent of a monovalent to trivalent cation, for example, a hydrogen atom (proton), a metal cation, or a quaternary ammonium cation.
In the case where the dispersant structure has two or more M, M ⁴⁰¹ may be any one of proton, metal cation and quaternary ammonium cation, or a combination thereof.

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

The quaternary ammonium cation is a single compound having a structure represented by the general formula (17) or a mixture.

Formula (17):

In General Formula (17), R ³⁰¹ , R ³⁰² , R ³⁰³ , and R ³⁰⁴ are each independently hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted group. An aryl group.

When R ³⁰¹ , R ³⁰² , R ³⁰³ and R ^{304 in the} general formula (17) have a carbon atom, the carbon number is 1 to 40, preferably 1 to 30, and more preferably 1 to 20. If the carbon number exceeds 40, the conductivity of the electrode may be reduced.

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

Various derivatives having an acidic functional group can be used in combination with other basic compounds. Examples of the basic compound include acidic resin dispersants (B) and (C), inorganic bases, and organic bases.

Moreover, various derivatives having a basic functional group can be used in combination with the acidic resin dispersant (A) described above.

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

[Effect of dispersant]
An organic compound having a basic functional group and / or an acidic functional group used as a dispersant acts (for example, adsorbs) on the surface of each material contained in a mixed ink or electrode such as a conductive additive or an electrode active material. It is considered that it exerts a dispersion effect. That is, it is considered that the polarities of the basic functional groups possessed by the derivatives acting on the surface of each material promote the wetting of the surface of each material with a solvent or water, and the aggregation of each material is easily solved. Among them, electrode active materials,
In the case of carbon-based materials such as conductive aids and materials such as lithium iron phosphate carrying carbon materials, the hydrophobicity of the particle surface is high, which further improves the adsorption effect of various derivatives having basic functional groups. It is thought that the dispersion effect is also exhibited.

Furthermore, when using the resin-type dispersants (A) to (C), the adhesion between the respective materials is also improved through the resin-type dispersant. Improved adhesion,
In addition, it is considered that the electrode film is not easily broken by stress, and the toughness of the electrode film is improved.

In addition, when a dispersant having a basic functional group is used, the basic functional group possessed by various dispersants interacts with the acidic functional group possessed by the thin film-like particle of the present invention (for example, formation of ion pairs by neutralization (production) Salt) and ion pair (salt) polarization or dissociation, etc.), the electrostatic repulsion of each material is promoted, and the dispersion stability of each material is considered to further increase.

(binder)
The composite ink may further contain a binder in order to bind particles such as a conductive additive and other active materials.

Examples of the binder include acrylic resin, polyurethane resin, polyester resin,
Phenolic resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, formaldehyde resin, silicone resin, fluororesin, cellulose resin such as carboxymethylcellulose, synthetic rubber such as styrene-butadiene rubber and fluororubber, polyaniline, polyacetylene, etc. And high molecular compounds containing fluorine atoms such as polyvinylidene fluoride, polyvinyl fluoride, and tetrafluoroethylene. Further, modified products, mixtures, copolymers, and aqueous emulsions of these resins may be used. These binders can be used alone or in combination.

Specifically, 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. Examples thereof include a copolymer contained as a structural unit.

As specific examples of materials that can be used as the binder, a binder composition (D) containing crosslinked resin fine particles and a polymer compound having a fluorine atom will be described in detail below.

[Binder composition containing crosslinked resin fine particles (D)]
A binder composition (D) containing crosslinked resin fine particles can be used for the composite ink. The cross-linked resin fine particles indicate resin fine particles having an internal cross-linked structure (three-dimensional cross-linked structure)
It is important that the particles are cross-linked inside. When the cross-linked resin fine particles have a cross-linked structure, the electrolytic solution elution resistance can be secured, and the effect can be enhanced by adjusting the cross-linking inside the particles. Further, when the cross-linked resin fine particles contain a specific functional group, it is possible to contribute to adhesion with the current collector or the electrode. Furthermore, the composition for secondary battery electrode formation excellent in flexibility can be obtained by adjusting the quantity of a crosslinked structure and a functional group. However, for the purpose of adjusting the flexibility of the binder, cross-linking of particles (inter-particle cross-linking) can be used together, but in this case, since a cross-linking agent is added later, the electrolyte solution of the cross-linking agent component In some cases, leakage of the electrode and variations in electrode fabrication may occur. For this reason, it is necessary to use a crosslinking agent to such an extent that the electrolyte solution resistance is not impaired.

Examples of the crosslinked resin fine particles used in the composite ink include resin fine particles obtained by emulsion polymerization of an ethylenically unsaturated monomer in water in the presence of a surfactant with a radical polymerization initiator. The crosslinked resin fine particles can be obtained by emulsion polymerization of an ethylenically unsaturated monomer selected from the following monomer groups (D1) and (D2).

Among the ethylenically unsaturated monomers constituting the crosslinked resin fine particles described below (d1),
(D3) indicates a monomer having one ethylenically unsaturated group in one molecule unless otherwise specified.

[Regarding monomer group (D1)]
The monomer group (D1) includes an ethylenically unsaturated monomer (d1) having a monofunctional or polyfunctional alkoxysilyl group, and a monomer having two or more ethylenically unsaturated groups in one molecule ( d
2) at least one monomer selected from the group consisting of 0.1 to 5% by weight in the ethylenically unsaturated monomer used for emulsion polymerization.

The functional group (alkoxysilyl group, ethylenically unsaturated group) of the monomer contained in the monomer group (D1) is a self-crosslinking reactive functional group, and is mainly used for particle internal crosslinking during particle synthesis. Has the effect of forming. Electrolytic solution resistance can be improved by sufficiently carrying out internal crosslinking of the particles. Therefore, it is possible to obtain crosslinked resin fine particles by using a monomer contained in the monomer group (D1). In addition, by sufficiently carrying out particle crosslinking, the resistance to electrolytic solution can be improved.

Monomer having one ethylenically unsaturated group and alkoxysilyl group in one molecule (d1
), For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ
-Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-methacryloxymethyl Trimethoxysilane, γ-acryloxymethyltrimethoxysilane,
Examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and vinylmethyldimethoxysilane.

As the monomer (d2) having two or more ethylenically unsaturated groups in one molecule, for example,
Allyl (meth) acrylate, 1-methylallyl (meth) acrylate, 2-methylallyl (meth) acrylate, 1-butenyl (meth) acrylate, 2-butenyl (meth) acrylate, (meth) acrylic acid 3- Butenyl, 1,3-methyl-3-butenyl (meth) acrylate, 2-chloroallyl (meth) acrylate, 3-chloroallyl (meth) acrylate, o-allylphenyl (meth) acrylate, (meth) acrylic acid 2- (allyloxy) ethyl, (
Allyl lactyl (meth) acrylate, citronellyl (meth) acrylate, geranyl (meth) acrylate, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, diallyl maleate, diallyl itaconic acid, vinyl (meth) acrylate, croton Vinyl acid, vinyl oleate, vinyl linolenate, 2- (2'-vinyloxyethoxy) (meth) acrylic acid
Ethylenically unsaturated group-containing (meth) acrylic acid esters such as ethyl; ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri (meth) Trimethylolpropane acrylate,
Pentaerythritol tri (meth) acrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1
, 1-trishydroxymethylpropanetriacrylic acid and other polyfunctional (meth) acrylic acid esters; divinylbenzene, divinyl such as divinyl adipate; diallyls such as diallyl isophthalate, diallyl phthalate and diallyl maleate Can be mentioned.

The purpose of the alkoxysilyl group or the ethylenically unsaturated group in the monomer (d1) or the monomer (d2) is to introduce a crosslinked structure into the particles by self-condensation or polymerization mainly during the polymerization. However, a part of it may remain inside or on the surface after polymerization. The remaining alkoxysilyl group or ethylenically unsaturated group contributes to interparticle crosslinking of the binder composition. In particular, an alkoxysilyl group is preferable because it has an effect of improving adhesion to the current collector.

The monomer contained in the monomer group (D1) is used in an amount of 0.1 to 5% by weight in the whole ethylenically unsaturated monomer (100% in total) used for emulsion polymerization. To do. Preferably it is 0.5 to 3 weight%. When the monomer contained in the monomer group (D1) is less than 0.1% by weight, the particles are not sufficiently crosslinked, and the resistance to the electrolytic solution is deteriorated. If it exceeds 5% by weight,
There is a problem in polymerization stability at the time of emulsion polymerization, or a problem in storage stability even if polymerization is possible.

[Regarding monomer group (D2)]
The monomer group (D2) includes an ethylenically unsaturated monomer (d3) other than the monomers (d1) and (d2).
) And is used in an amount of 95 to 99.9% by weight in the ethylenically unsaturated monomer used for emulsion polymerization.

The monomer (d3) is not particularly limited as long as it is a monomer having an ethylenically unsaturated group other than the monomers (d1) and (d2).
Monomer (d4) having one ethylenically unsaturated group and monofunctional or polyfunctional epoxy group in one molecule, one ethylenically unsaturated group and monofunctional or polyfunctional amide group in one molecule And at least one monomer selected from the group consisting of a monomer (d6) having one ethylenically unsaturated group and a monofunctional or polyfunctional hydroxyl group in one molecule (d5) body,
In addition, monomers (d7) having an ethylenically unsaturated group other than the monomers (d1), (d2), and (d4) to (d6) can be used.
By using the monomers (d4) to (d6), an epoxy group, an amide group, or a hydroxyl group can be left in or on the surface of the cross-linked resin fine particles. The physical properties of can be improved. As for the monomers (d4) to (d6), the functional groups of the monomers (d4) to (d6) are likely to remain inside or on the surface even after the particle synthesis, and the adhesion effect to the current collector is large even in a small amount.
Moreover, a part of them may be used for the crosslinking reaction, and by adjusting the degree of crosslinking of these functional groups, it is possible to balance the resistance to electrolytic solution and the adhesion.

Examples of the monomer (d4) having one ethylenically unsaturated group and a monofunctional or polyfunctional epoxy group in one molecule include glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate. Etc.

Examples of the monomer (d5) having one ethylenically unsaturated group and a monofunctional or polyfunctional amide group in one molecule include, for example, a primary amide group-containing ethylenically unsaturated monomer such as (meth) acrylamide. N-methylol acrylamide, N, N-di (methylol) acrylamide, alkylol (meth) acrylamides such as N-methylol-N-methoxymethyl (meth) acrylamide; N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide,
Monoalkoxy (meth) acrylamides such as N-butoxymethyl- (meth) acrylamide and N-pentoxymethyl- (meth) acrylamide; N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethyl Methacrylamide, N,
N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethyl methacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N- Di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N,
Dialkoxy (meth) acrylamides such as N-di (pentoxymethyl) acrylamide and N-methoxymethyl-N- (pentoxymethyl) methacrylamide; N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide Dialkylamino (meth) acrylamides such as N, N-dimethylacrylamide, N
And dialkyl (meth) acrylamides such as N-diethylacrylamide; keto group-containing (meth) acrylamides such as diacetone (meth) acrylamide.

Examples of the monomer (d6) having one ethylenically unsaturated group and a monofunctional or polyfunctional hydroxyl group in one molecule include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, 2- (
Examples include meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol.

A part of the functional groups of the monomers contained in the monomers (d4) to (d6) may react during particle polymerization and be used for intraparticle crosslinking. Monomers contained in the monomers (d4) to (d6) are
0.1 to 20 in the entire ethylenically unsaturated monomer (100% by weight in total) used for emulsion polymerization
It is characterized by being used by weight%. Preferably it is 1 to 15 weight%, Most preferably, it is 2 to 10 weight%. When the amount of the monomers (d4) to (d6) in the whole ethylenically unsaturated monomers (100% by weight in total) used for the emulsion polymerization is less than 0.1% by weight, the inside of the particles after polymerization or on the surface The amount of remaining functional groups is reduced, and cannot sufficiently contribute to the improvement of the adhesion of the current collector.
On the other hand, if it exceeds 20% by weight, there will be a problem in the polymerization stability at the time of emulsion polymerization, or even if it can be polymerized, there will be a problem in the storage stability.

The monomer (d7) is not particularly limited as long as it is a monomer other than the monomers (d1), (d2), (d4) to (d6) and has an ethylenically unsaturated group, For example, a monomer (d8) having one ethylenically unsaturated group and an alkyl group having 8 to 18 carbon atoms in one molecule
And a monomer (d9) having one ethylenically unsaturated group and a cyclic structure in one molecule. When the monomer (d8) and / or the monomer (d9) is used for emulsion polymerization as the monomer (d7) (the monomer (d7) includes other monomers). The monomers (d8) and (d9) are all monomers having an ethylenically unsaturated group ((
(d1), (d2), (d4) to (d6) and (d7)) are preferably contained in a total amount of 30 to 95% by weight. It is preferable to use the monomer (d8) or the monomer (d9) because the particle stability at the time of particle synthesis and the resistance to electrolytic solution are excellent. If it is less than 30% by weight, the electrolyte solution resistance may be adversely affected. If it exceeds 95% by weight, the stability during particle synthesis will be adversely affected, or even if synthesis is possible, the temporal stability of the particles will be impaired. There is a case.

Examples of the monomer (d8) having one ethylenically unsaturated group and an alkyl group having 8 to 18 carbon atoms in one molecule include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and myristyl. (Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

Examples of the monomer (d9) having one ethylenically unsaturated group and a cyclic structure in one molecule include alicyclic ethylenically unsaturated monomers and aromatic ethylenically unsaturated monomers. It is done. Examples of the alicyclic ethylenically unsaturated monomer include cyclohexyl (meth) acrylate,
Examples of the aromatic ethylenically unsaturated monomer include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like.
Examples thereof include styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, allylbenzene, ethynylbenzene and the like.

Examples of the monomer (d7) other than the monomer (d8) and monomer (d9) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
alkyl group-containing ethylenically unsaturated monomers such as n-butyl (meth) acrylate, pentyl (meth) acrylate and heptyl (meth) acrylate; nitrile group-containing ethylenically unsaturated monomers such as (meth) acrylonitrile; Fluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-
Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) Perfluoroalkyl group-containing ethylenic group having a C1-C20 perfluoroalkyl group such as acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Unsaturated monomers; perfluorobutylethylene, perfluorohexylethylene,
Perfluoroalkyl group-containing ethylenically unsaturated compounds such as perfluoroalkyl, perfluorodecylethylene, and other perfluoroalkyl groups; polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meta ) Acrylate, propoxy polyethylene glycol (meth) acrylate, n-butoxy polyethylene glycol (meth) acrylate, n-pentoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (Meth) acrylate, ethoxypolypropylene glycol (meth) ac Rate, propoxypolypropylene glycol (meth) acrylate, n-butoxypolypropylene glycol (meth) acrylate, n-pentoxypolypropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypoly Ethylenically unsaturated compounds having a polyether chain such as tetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate; lactone modification (meta ) Ethylenically unsaturated compounds having a polyester chain such as acrylate; Noethylmethyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, and trimethyl-3- ( Quaternary ammonium base-containing ethylenically unsaturated compounds such as 1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride; vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate Fatty acid vinyl compounds such as vinyl palmitate and vinyl stearate; vinyl ether ethylenically unsaturated monomers such as butyl vinyl ether and ethyl vinyl ether; 1-hexene, 1-octene, 1-decene, 1-dodecene, 1- Te Α-olefinic ethylenically unsaturated monomers such as tradecene and 1-hexadecene; allyl monomers such as allyl acetate and allyl cyanide; vinyl monomers such as vinyl cyanide, vinylcyclohexane and vinylmethylketone; acetylene And ethynyl monomers such as ethynyltoluene.

Examples of the monomer (d7) other than the monomer (d8) and the monomer (d9) include:
Maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester,
Carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; Tertiary butyl group-containing ethylenically unsaturated monomers such as tertiary butyl (meth) acrylate; Vinylsulfonic acid Sulfonic acid group-containing ethylenically unsaturated monomers such as styrene sulfonic acid; phosphoric acid group-containing ethylenically unsaturated monomers such as (2-hydroxyethyl) methacrylate acid phosphate; diacetone (meth) acrylamide, acrolein , N-vinylformamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate and other keto group-containing ethylenically unsaturated monomers ( 1 in 1 molecule And ethylenically unsaturated groups, a monomer having a keto group).

When a keto group-containing ethylenically unsaturated monomer is used as the monomer (d7), a polyfunctional hydrazide compound having two or more hydrazide groups capable of reacting with a keto group as a crosslinking agent is mixed with the binder composition. A tough coating film can be obtained by crosslinking between a keto group and a hydrazide group. This has excellent electrolytic solution resistance and binding properties. Furthermore, since it is possible to achieve both durability and flexibility in a high temperature environment due to repeated charge / discharge and heat generation, a long-life non-aqueous secondary battery with reduced discharge capacity reduction in the charge / discharge cycle is obtained. Can do.

Further, among the monomers (d7), an ethylenically unsaturated monomer having a carboxyl group, a tertiary butyl group (tertiary butanol is removed by heat to form a carboxyl group), a sulfonic acid group, and a phosphoric acid group. The resin fine particles obtained by copolymerization of the body have the effect of improving the physical properties such as the adhesion of the current collector, while the functional groups remain in the particles and on the surface even after polymerization, and at the same time agglomeration during synthesis Can be prevented, and the stability of the particles after synthesis may be maintained.

A part of the carboxyl group, tertiary butyl group, sulfonic acid group, and phosphoric acid group may react during polymerization and be used for intraparticle crosslinking. When using a monomer containing a carboxyl group, a tertiary butyl group, a sulfonic acid group, and a phosphoric acid group, the total amount of ethylenically unsaturated monomers used in the emulsion polymerization (100% by weight in total) is 0.00. The content is preferably 1 to 10% by weight, more preferably 1 to 5% by weight. Carboxyl group,
If the monomer containing a tertiary butyl group, a sulfonic acid group, and a phosphoric acid group is less than 0.1% by weight, the stability of the particles may be deteriorated. On the other hand, when the content exceeds 10% by weight, the hydrophilicity of the binder composition becomes too strong, and the electrolytic solution resistance may deteriorate. Furthermore, these functional groups may react during drying and be used for cross-linking within or between particles.

For example, a carboxyl group can react with an epoxy group during polymerization and drying to introduce a crosslinked structure into the resin fine particles. Similarly, a tertiary butyl group can react with an epoxy group in the same manner as described above since tertiary butyl alcohol is generated and a carboxyl group is formed when heat of a certain temperature or higher is applied.

These monomers (d7) are used in combination of two or more of the monomers listed above in order to adjust the polymerization stability and glass transition temperature of the particles, as well as the film formability and film properties. Can be used. Further, for example, by using (meth) acrylonitrile in combination, there is an effect that rubber elasticity is exhibited.

[Characteristics of cross-linked resin particles]
{Glass-transition temperature}
The glass transition temperature (hereinafter also referred to as Tg) of the crosslinked resin fine particles is -30 to 70 ° C.
Is preferable, and -20-30 degreeC is further more preferable. When Tg is less than −30 ° C., the binder excessively covers the electrode active material, and the impedance tends to increase. Moreover, when Tg exceeds 70 ° C., the flexibility and adhesiveness of the binder become poor, and the adhesion of the electrode active material to the current collector,
The formability of the electrode may be inferior. The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

The measurement of the glass transition temperature by DSC (differential scanning calorimeter) can be performed as follows. About 2 mg of resin obtained by drying the cross-linked resin fine particles is weighed on an aluminum pan, the test container is set on a DSC measurement holder, and the endothermic peak of the chart obtained under a temperature rising condition of 10 ° C./min is read. The peak temperature at this time is defined as the glass transition temperature.

{Particle structure}
Further, the particle structure of the crosslinked resin fine particles may be a multi-layer structure, so-called core-shell particles. For example, it is possible to localize a resin in which a monomer having a functional group is mainly polymerized in the core part or the shell part, or to provide a difference in Tg or composition between the core and the shell, thereby improving the curability and drying. Property, film formability, and mechanical strength of the binder can be improved.

{Particle size}
The average particle diameter of the crosslinked resin fine particles is 10 from the viewpoint of the binding property of the electrode active material and the stability of the particles.
It is preferably ˜500 nm, and more preferably 30 to 250 nm. Further, when a large amount of coarse particles exceeding 1 μm are contained, the stability of the particles is impaired, so that the coarse particles exceeding 1 μm are preferably at most 5% by weight. In addition,
An average particle diameter here represents a volume average particle diameter, and can be measured by the dynamic light scattering method.

The average particle diameter can be measured by the dynamic light scattering method as follows. The cross-linked resin fine particle dispersion is diluted with water 200 to 1000 times depending on the solid content. About 5 dilutions
ml is injected into a cell of a measuring apparatus [Microtrack manufactured by Nikkiso Co., Ltd.], and after measuring the refractive index conditions of the solvent and resin according to the sample, measurement is performed. The peak of the volume particle size distribution data (histogram) obtained at this time is defined as the average particle size.

[Uncrosslinked compound (E) added to polymerized resin fine particles]
In addition to the crosslinked resin fine particles, the binder composition containing the crosslinked resin fine particles further includes an uncrosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group. And at least one uncrosslinked compound (E) selected from the group consisting of the containing compounds [hereinafter sometimes referred to as compound (E)].

The “uncrosslinked functional group-containing compound” which is the compound (E) is an internal cross-linked structure (three-dimensional cross-linked structure) of the cross-linked resin fine particles as in the monomers included in the monomer group (C1). Unlike the compound that forms the resin, it is a compound that is added after the resin fine particles are subjected to emulsion polymerization (polymer formation) (does not participate in the internal cross-linking of the resin fine particles). That is, “uncrosslinked” means that it is not involved in the formation of the internal crosslinked structure (three-dimensional crosslinked structure) of the crosslinked resin fine particles.

The cross-linked resin fine particles have a cross-linked structure to ensure the resistance to electrolyte, and the compound (
By using E), at least one functional group selected from an epoxy group, an amide group, a hydroxyl group, and an oxazoline group in the compound (E) may contribute to adhesion to the current collector or the electrode. it can. Furthermore, the binder composition for secondary battery electrodes excellent in flexibility can be obtained by adjusting the amount of the crosslinked structure and functional group.

The cross-linked resin fine particles need to be cross-linked inside the particles. Electrolytic solution resistance can be ensured by appropriately adjusting the crosslinking inside the particles. further,
At least one uncrosslinked selected from the group consisting of an uncrosslinked epoxy group-containing compound, an uncrosslinked amide group-containing compound, an uncrosslinked hydroxyl group-containing compound, and an uncrosslinked oxazoline group-containing compound on the functional group-containing crosslinked resin fine particles By adding the compound (E), an epoxy group, an amide group, a hydroxyl group or an oxazoline group acts on the current collector, and the adhesion to the current collector or the electrode can be effectively improved. Since the functional group contained in the compound (E) is stable by heat during long-term storage or electrode production, the effect of adhesion to the current collector is large even when used in a small amount.
Furthermore, it is excellent in storage stability. The compound (E) may react with the functional group in the cross-linked resin fine particles for the purpose of adjusting the flexibility and the electrolytic solution resistance of the binder. When the functional group in the compound (E) is excessively used for the reaction, the functional group capable of interacting with the current collector or the electrode is decreased. For this reason, the reaction between the crosslinked resin fine particles and the compound (E) needs to be at a level that does not impair the adhesion to the current collector or the electrode. In addition, when a part of the functional group contained in the compound (E) is used for the crosslinking reaction [
In the case where the compound (E) is a polyfunctional compound], the balance between the electrolytic solution resistance and the adhesiveness can be balanced by adjusting the degree of crosslinking of these functional groups.

{Uncrosslinked epoxy group-containing compound}
As an uncrosslinked epoxy group-containing compound, for example, glycidyl (meth) acrylate,
Epoxy group-containing ethylenically unsaturated monomers such as 3,4-epoxycyclohexyl (meth) acrylate; radicals obtained by polymerizing ethylenically unsaturated monomers including the epoxy group-containing ethylenically unsaturated monomers Polymeric resin; ethylene glycol diglycidyl ether,
Polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N
Polyfunctional epoxy compounds such as' -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane; bisphenol A-epichlorohydrin type epoxy resin, bisphenol F-epi Examples thereof include epoxy resins such as chlorohydrin type epoxy resins.

Among epoxy group-containing compounds, epoxy resins such as bisphenol A-epichlorohydrin type epoxy resin, bisphenol F-epichlorohydrin type epoxy resin,
A radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an epoxy group-containing ethylenically unsaturated monomer is preferred. The epoxy resin can be expected to have a synergistic effect of improving the electrolytic solution resistance by having a bisphenol skeleton and improving the adhesion of the current collector by a hydroxyl group contained in the skeleton. In addition, the radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an epoxy group-containing ethylenically unsaturated monomer has a higher adhesion to the current collector by having more epoxy groups in the resin skeleton. In addition, by being a resin,
The effect of improving the resistance to electrolytic solution can be expected as compared with the monomer.

{Uncrosslinked amide group-containing compound}
As an uncrosslinked amide group-containing compound, for example, a primary amide group-containing compound such as (meth) acrylamide; N-methylolacrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meta) ) Alkyrol (meth) acrylamide compounds such as acrylamide; N-methoxymethyl- (meth) acrylamide, N
Monoalkoxy (meth) acrylamide compounds such as ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide; N, N-di (
Methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide ,
N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide N-methoxymethyl-N-
Dialkoxy (meth) acrylamide compounds such as (pentoxymethyl) methacrylamide; Dialkylamino (meth) acrylamide compounds such as N, N-dimethylaminopropylacrylamide and N, N-diethylaminopropylacrylamide; N, N-
Dialkyl (meth) acrylamide compounds such as dimethylacrylamide and N, N-diethylacrylamide; keto group-containing (meth) such as diacetone (meth) acrylamide
Acrylamide group-containing ethylenically unsaturated monomers such as acrylamide compounds; radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including the amide group-containing ethylenically unsaturated monomers, etc. Can be mentioned.

Among the amide group-containing compounds, radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including amide group-containing ethylenically unsaturated monomers such as acrylamide are particularly preferable. By having more amide groups in the resin skeleton, it is possible to improve the current collector adhesion, and by using the resin, the effect of improving the resistance to electrolytic solution compared to the monomer can be expected.

{Uncrosslinked hydroxyl-containing compound}
Examples of the uncrosslinked hydroxyl group-containing compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate 4-hydroxyvinylbenzene, 1
A hydroxyl group-containing ethylenically unsaturated monomer such as ethynyl-1-cyclohexanol or allyl alcohol; a radical polymerization system obtained by polymerizing an ethylenically unsaturated monomer containing the hydroxyl group-containing ethylenically unsaturated monomer Resin; ethylene glycol, diethylene glycol, 1,
3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-
Straight chain aliphatic diols such as hexanediol; branched chain aliphatic diols such as propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2,2-diethyl-1,3-propanediol; And cyclic diols such as 1,4-bis (hydroxymethyl) cyclohexane.

Among the hydroxyl group-containing compounds, radical polymerization resins obtained by polymerizing ethylenically unsaturated monomers including a hydroxyl group-containing ethylenically unsaturated monomer or cyclic diols are particularly preferable. The radical polymerization resin obtained by polymerizing ethylenically unsaturated monomers including hydroxyl group-containing ethylenically unsaturated monomers improves current collector adhesion by having more hydroxyl groups in the resin skeleton. In addition, the resin can be expected to have an effect of improving the resistance to electrolytic solution compared to the monomer. Moreover, cyclic diols can be expected to have an effect of improving the resistance to electrolytic solution by having a cyclic structure in the skeleton.

{Uncrosslinked oxazoline group-containing compound}
Examples of the uncrosslinked oxazoline group-containing compound include 2′-methylenebis (2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′-ethylenebis (
4-methyl-2-oxazoline), 2,2′-propylenebis (2-oxazoline), 2
, 2′-tetramethylenebis (2-oxazoline), 2,2′-hexamethylenebis (2
-Oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p
-Phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2′-p-phenylenebis (4-phenyl-2-oxazoline), 2,2
'-M-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4'-dimethyl-2-)
Oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (4- Methyl-2-oxazoline), 2,2′-bis (2-oxazoline), 2,2
Contains' -bis (4-methyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline), and oxazoline group Examples include radical polymerization resins.

Among oxazoline group-containing compounds, in particular, phenylene bis-type oxazoline compounds such as 2′-p-phenylenebis (2-oxazoline), or ethylenically unsaturated monomers containing an oxazoline group-containing ethylenically unsaturated monomer A radical polymerization resin obtained by polymerizing is preferred. The phenylenebis type oxazoline compound has an effect of improving the resistance to electrolytic solution by having a phenyl group in the skeleton. In addition, a radical polymerization resin obtained by polymerizing an ethylenically unsaturated monomer containing an oxazoline group-containing ethylenically unsaturated monomer has a current collector adhesion by having more oxazoline groups in the resin skeleton. In addition, by using a resin, the resistance to an electrolytic solution can be improved as compared with a monomer.

{Addition amount of compound (E), molecular weight}
The compound (E) is preferably added in an amount of 0.1 to 50 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the solid content of the crosslinked resin fine particles. When the addition amount of the compound (E) is less than 0.1 parts by weight, the amount of the functional group contributing to the adhesion of the current collector is reduced,
In some cases, the current collector cannot sufficiently contribute to improving the adhesion. On the other hand, if it exceeds 50 parts by weight, the binder performance may be adversely affected such as leakage of the compound (E) into the electrolyte. Furthermore, two or more types of compounds (E) can be used in combination.

The molecular weight of the compound (E) is not particularly limited, but the weight average molecular weight is 1,000 to 1,000.
It is preferably 10,000, and more preferably 5,000 to 500,000.
If the weight average molecular weight is less than 1,000, the adhesion effect to the current collector may not be sufficient, and if the weight average molecular weight exceeds 1,000,000, the viscosity of the compound may increase. There may be a case where handling properties at the time of electrode preparation are deteriorated. In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Furthermore, the compound (E) may be a compound that dissolves in a solvent or a compound that disperses.

[Polymer compound having fluorine atom]
The composite ink can also contain a polymer compound having a fluorine atom in the molecule as a binder. Examples of the polymer compound having a fluorine atom in the molecule include polyvinylidene fluoride, polyvinyl fluoride, and polytetrafluoroethylene resin.

Examples of commercially available vinylidene fluoride polymers include KF polymer W # 1100, #
1300, # 1700, # 7200, # 7300, # 9100, # 9200, # 9300
(Manufactured by Kureha), Kyner 721, 741, 761, 461, 301F, HSV900,
Kyner flex 2851, 2801, 2821 (manufactured by Arkema), Solef 1013,
1015, 21216, 31508, 6020 (manufactured by Solvay Solexis) and the like, but are not limited thereto.

The weight average molecular weight of the vinylidene fluoride polymer is preferably 3,000 to 1,000,000, more preferably 10,000 to 1,000,000. When the molecular weight is less than 3,000, the binding property is poor. Therefore, increasing the binder ratio in the electrode mixture layer to improve the binding property decreases the capacity. Adhesiveness with an electric body may be reduced. When the molecular weight exceeds 1,000,000, the solubility becomes low, and it may be difficult to obtain a composition having suitable properties.

Among vinylidene fluoride resins, it is preferable to include a vinylidene fluoride resin having an acidic functional group. Hereinafter, the vinylidene fluoride resin having an acidic functional group will be described.

Polyvinylidene fluoride resin having an acidic functional group is not particularly limited,
Japanese Patent Publication No. 52-24959, Japanese Patent Application Laid-Open No. 58-136605, Japanese Patent Application Laid-Open No. 2-604, Japanese Patent Application Laid-Open No. 6-172452, Japanese Patent Application Laid-Open No. 2004-049475, Japanese Patent No. 312.
The compound can be synthesized with reference to a method disclosed in Japanese Patent No. 1943 or Japanese Patent No. 3784494. The disclosure by the above publication is incorporated as part of the present specification. Hereinafter, specific methods for preparing the resin will be exemplified.

For example, a polyvinylidene fluoride-based resin having a sulfonic acid group is a homopolymer (homopolymer) of vinylidene fluoride, a monomer having fluorine other than vinylidene fluoride and vinylidene fluoride, and other non-fluorine-containing monomers. It can be obtained by sulfonating a copolymer (copolymer) with at least one monomer selected from the group consisting of monomers. Examples of the monomer having fluorine other than vinylidene fluoride include trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether. The other monomer is a monomer copolymerizable with vinylidene fluoride, and examples thereof include ethylene, chloroethylene, propylene, alkyl (meth) acrylate, and styrene. For sulfonation, for example, hydrogen in a polymerized unit in a polyvinylidene fluoride resin is converted into a sulfonic acid group by a sulfonating agent such as concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, amidosulfuric acid, sulfur trioxide, or triethyl phosphate complex. This is done by replacing.

For example, the polyvinylidene fluoride resin having a carboxyl group was selected from the group consisting of vinylidene fluoride, a monomer having a carboxyl group, a monomer having fluorine other than vinylidene fluoride, and another monomer having no fluorine. It can be obtained by copolymerizing with one or more monomers.

Examples of the monomer having a carboxyl group include unsaturated monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid, and unsaturated dibasic acids such as itaconic acid, maleic acid, and citraconic acid (and their monovalent acids). Ester) and the like.

Examples of the fluorine-containing monomer include trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.

The other monomer is a monomer copolymerizable with vinylidene fluoride, and examples thereof include ethylene, chloroethylene, propylene, alkyl (meth) acrylate, and styrene.

Examples of commercially available carboxyl group-containing polyvinylidene fluoride resins include KF polymers W # 9100, W # 9200, and W # 9300 (manufactured by Kureha).

For example, the polyvinylidene fluoride resin having a phosphate group was selected from the group consisting of vinylidene fluoride, a monomer having a phosphate group, a monomer having fluorine other than vinylidene fluoride, and another monomer having no fluorine. It can be obtained by copolymerizing with one or more monomers.

Examples of the monomer having a phosphoric acid group include alkylene oxide-modified phosphoric acid (meth) acrylate, alkylene oxide-modified di (meth) acrylate, alkylene oxide-modified tri (meth) acrylate, alkylene oxide-modified alkoxyphosphoric acid (meth) acrylate, and alkylene oxide-modified. Examples include alkoxyphosphate di (meth) acrylates, adducts obtained by reacting (meth) acrylates containing a glycidyl group and phosphoric acid.

Examples of the fluorine-containing monomer include trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether. The other monomer is a monomer copolymerizable with vinylidene fluoride. For example, ethylene, chloroethylene, propylene, (
Examples include alkyl (meth) acrylate and styrene.

Further, the polyvinylidene fluoride resin having a phosphoric acid group is obtained by causing phosphoric acid, phosphorous pentoxide, phosphorus oxychloride, polyphosphoric acid, or orthophosphoric acid, etc., which are phosphorylating agents to act on the polyvinylidene fluoride resin having a hydroxyl group. It can be obtained as an ester. The polyvinylidene fluoride-based resin having a hydroxyl group is one kind selected from the group consisting of vinylidene fluoride, a monomer having a hydroxyl group, a monomer having fluorine other than vinylidene fluoride, and another monomer having no fluorine It can be obtained by copolymerizing the above monomers.

Monomers having a hydroxyl group include (meth) acrylates and allyl ethers, and (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-2-ethylhexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Examples include penta (meth) acrylate, glycidyl methacrylate- (meth) acrylic acid adduct, 1,1,1-trimethylolpropane, or di (meth) acrylic acid ester of glycerol.

Examples of allyl ethers having a hydroxyl group include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoacrylate, dipropylene glycol monoacrylate, and tripropylene glycol monoacrylate. , Polypropylene glycol monoacrylate, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane Diallyl ether, glycerol monoallyl ether, glycerol Allyl ether, pentaerythritol monoallyl ether, pentaerythritol triallyl ether, pentaerythritol diallyl ether, and the like.

Examples of the fluorine-containing monomer include trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ether.

The other monomer is a monomer copolymerizable with vinylidene fluoride, and examples thereof include ethylene, chloroethylene, propylene, alkyl (meth) acrylate, and styrene.

The weight average molecular weight of the polyvinylidene fluoride resin having an acidic functional group is 3,000 to 1.
1,000,000 are preferable, and 10,000 to 1,000,000 are more preferable. When the molecular weight is small, the resistance as a binder may decrease. In addition, 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, and the workability is lowered and the mixture component may be aggregated.

As the polymer compound having a fluorine atom, a commercially available polyvinyl fluoride resin or a commercially available polytetrafluoroethylene resin can also be used.
Examples of commercially available polyvinyl fluoride resins include Tedlar (manufactured by DuPont).
Examples of commercially available polytetrafluoroethylene resins include PTFE30-J (Mitsui / DuPont Fluorochemical), etc.
Although each is mentioned, it is not limited to these.

The weight average molecular weight of polyvinyl fluoride and polytetrafluoroethylene is 10,000.
00 to 1,000,000 is preferred. When the molecular weight of the resin used is small, the resistance of the binder tends to decrease. On the other hand, when the molecular weight is increased, the resistance of the binder is improved, but not only the viscosity of the binder itself is increased and workability is lowered, but also works as a flocculant,
There is a tendency for the mixture components to undergo significant aggregation.

Furthermore, a film forming aid, an antifoaming agent, a leveling agent, a preservative, a pH adjuster, a viscosity adjuster, and the like can be blended in the composite ink as necessary.

(Adjusting composite ink)
The viscosity of the composite ink depends on the coating method, but in the range of 30 to 90% by weight of solid content, 100m
It is preferable to set it to Pa · s or more and 30,000 mPa · s or less.
It is preferable that the active material is contained as much as possible within the viscosity range that can be applied. For example, the ratio of the active material to the solid content of the composite ink is preferably 80% by weight or more and 99% by weight or less.
Moreover, it is preferable that the ratio of the thin-film-like particle | grains which occupy for material ink solid content is 0.1 to 15 weight%.
When the conductive assistant is included, the proportion of the conductive assistant in the solid ink solid content is preferably 0.1 to 15% by weight.
When the binder is included, the ratio of the binder to the solid ink solid content is 0.1 to 15
It is preferable that it is weight%.

Such a composite ink can be obtained by various methods.
A case of a mixed ink containing an active material, thin film particles, a conductive additive, a binder, and an aqueous liquid medium will be described as an example.
For example,
(1) An aqueous dispersion of an active material containing an active material, thin film particles and an aqueous liquid medium can be obtained, and a conductive additive and a binder can be added to the aqueous dispersion to obtain a composite ink.
The conductive auxiliary agent and the binder can be added simultaneously, or after adding the conductive auxiliary agent, the binder may be added, or vice versa.
(2) An aqueous dispersion of a conductive additive containing a conductive additive, thin film particles and an aqueous liquid medium can be obtained, and an active material and a binder can be added to the aqueous dispersion to obtain a composite ink.
The active material and the binder can be added simultaneously, or after the active material is added, the binder may be added, or vice versa.
(3) An aqueous dispersion of an active material containing an active material, thin film particles, a binder, and an aqueous liquid medium can be obtained, and a conductive additive can be added to the aqueous dispersion to obtain a composite ink.
(4) An aqueous dispersion of a conductive additive containing a conductive additive, thin film particles, a binder, and an aqueous liquid medium can be obtained, and an active material can be added to the aqueous dispersion to obtain a composite ink.
(5) An active material, thin film particles, a conductive aid, a dispersant, a binder, and an aqueous liquid medium can be mixed almost simultaneously to obtain a mixed ink.
The method for producing the composite ink is not limited to the above, and a dispersant or the like can be blended as necessary.

(Disperser / Mixer)
As an apparatus used for obtaining the composite ink, a disperser or a mixer that is usually used for pigment dispersion or the like as described in the thinning process can be used.
Moreover, as the disperser, it is preferable to use a disperser that has been subjected to a metal contamination 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 metal agitator and vessel surface are treated with tungsten carbide spraying or resin coating. Is preferably used. As the media, it is preferable to use glass beads, ceramic beads such as 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. Further, in the case of a positive or negative electrode active material in which particles are easily broken or crushed by a strong impact, a medialess disperser such as a roll mill or a homogenizer is preferable to a media type disperser.

<Underlayer forming composition>
As described above, the composition for an electrochemical element of the present invention can be used as a composition ink, as well as a composite ink.
The composition for forming the underlayer contains a conductive additive, thin film particles, and an aqueous liquid medium. Furthermore, a dispersing agent and a binder can also be contained. About each component, it is the same as that of the case of compound ink.
The ratio of the carbon material as a conductive additive to the total solid content of the composition used for the electrode underlayer is 5
% By weight or more and 95% by weight or less is preferable, and 10% by weight or more and 90% by weight or less is more preferable. If the carbon material that is the conductive auxiliary agent is small, the conductivity of the underlayer may not be maintained. On the other hand, if the carbon material that is the conductive auxiliary agent is too large, the resistance of the coating film may be reduced. In addition, the appropriate viscosity of the electrode underlayer ink depends on the electrode underlayer ink coating method, but generally 10 mP
It is preferable to set it as a * s or more and 30,000 mPa * s or less.

<Electrodes for electrochemical devices>
Of the composition for an electrochemical element of the present invention, the composite ink can be applied to a current collector and dried to form a composite layer, whereby a secondary battery electrode can be obtained.
Alternatively, the composition for forming an underlayer in the composition for an electrochemical element of the present invention is formed by forming an underlayer on a current collector, providing a composite layer on the underlayer, and forming an electrode for a secondary battery. It can also be obtained. The composite material layer provided on the base layer may be formed using the above-described composite material inks (1) to (5) of the present invention, or may be formed using other composite material inks.

(Current collector)
The material and shape of the current collector used for the electrode are not particularly limited, and those suitable for various secondary batteries can be appropriately selected.
For example, examples of the material of the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel. In the case of a lithium ion battery, aluminum is particularly preferable as the positive electrode material, and copper is preferable as the negative electrode material.
In general, a flat foil is used as the shape, but a roughened surface, a perforated foil, or a mesh current collector can also be used.

There is no restriction | limiting in particular as a method of apply | coating a mixture ink and the composition for base layer formation on a collector, A well-known method can be used.
Specifically, die coating method, dip coating method, roll coating method,
Doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method, electrostatic coating method, etc. can be mentioned, and the drying method is left drying, blower dryer, hot air dryer, infrared heating However, the present invention is not limited to these.
Moreover, you may perform the rolling process by a lithographic press, a calender roll, etc. after application | coating. 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. When the base layer is provided, the total thickness of the base layer and the composite layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more, 30
0 μm or less.

<Electrochemical element>
An electrochemical element can be obtained by using the above electrode for at least one of a positive electrode and a negative electrode.
Electrochemical elements include lithium ion secondary batteries, secondary batteries such as alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, lithium air secondary batteries, capacitors such as electric double layer capacitors and lithium ion capacitors. An electrolyte solution, a separator and the like that are conventionally known can be appropriately used.

(Electrolyte)
A case of a lithium ion secondary battery will be described as an example. As the electrolytic solution, an electrolyte containing lithium dissolved in a non-aqueous solvent is used.
As the _{electrolyte, 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 LiBP,
Although h ₄ and the like without limitation.

The non-aqueous solvent is not particularly limited.
Carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and 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, and 1,2-dibutoxyethane;
Esters such as methyl formate, methyl acetate, and methyl propionate;
Dimethylsulfoxide, and sulfoxides such as sulfolane; and
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 polymer electrolyte that is held in a polymer matrix and made into a gel. 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, and a polysiloxane having a polyalkylene oxide segment.

(separator)
Examples of the separator include, but are not limited to, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyamide nonwoven fabric and those obtained by subjecting them to a hydrophilic treatment.

(Battery structure / configuration)
The structure of the lithium ion secondary battery using the composition 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, a paper type, a cylindrical type, a button type, It can be made into various shapes 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,% represents% by weight.

The following measuring instruments were used for the analysis.
CHN elemental analysis; Perkin Elmer 2400 type CHN elemental analysis TEM (transmission electron microscope); Hitachi High-Technology HF2000
・ AFM (Atomic Force Microscope); SPI3800N manufactured by SII Nanotechnology

<Synthesis of thin film particles>
A mixed solution consisting of 7.5 g of sodium nitrate, 345 mL of sulfuric acid and 45 g of potassium permanganate was prepared, and after adding 10 g of natural graphite in an ice bath, stirring was continued at room temperature for 5 days. The obtained liquid was dropped into 1000 mL of 5% aqueous sulfuric acid solution in an ice bath, 30 g of hydrogen peroxide was added, and the mixture was stirred at room temperature for 2 hours. The obtained liquid was centrifuged, and the resulting precipitate was diluted with purified water, and then washed by cross-flow filtration using an ultrafiltration membrane to obtain an aqueous dispersion of thin film particles. The solid content ratio in this dispersion was 0.5%. Concentration was performed by centrifugation to obtain an aqueous dispersion (a) having a solid content ratio of 5%.

<Evaluation of thin film particles>
When the dispersion of thin film particles was dried in an oven and elemental analysis of the resulting solid was performed,
Oxygen was 45%, carbon was 42%, and hydrogen was 3%. Also, the dispersion is dripped and dried to produce TE.
When observed by M, the size in the plane direction was 5 μm or more. Moreover, when observed with AFM, the thickness was 5 nm or less.

<Preparation of thin-film particle dispersion>
An aqueous dispersion having a solid content ratio of 5% in the form of thin film particles is concentrated by centrifugation, and NMP (N-methyl-
The operation of diluting with 2-pyrrolidone) was repeated three times to obtain an NMP dispersion (b) having a solid content ratio of 5%.

<Aqueous composition>
[Example 1]
Acetylene black (Denka Black HS-100) 1 as a carbon material that is a conductive aid
0 part, 40 parts of aqueous dispersion (a) of thin film-like particles (2 parts as solids), 10 parts of aqueous solution or aqueous dispersion of resin-type dispersant (1) shown in Table 1 (2 parts as solids) ), 40 parts of water was mixed in a mixer, and further dispersed in a sand mill to obtain a carbon material dispersion (1) for an electrochemical device.

[Examples 2 to 4]
As shown in Table 1, except that the resin-type dispersants (2) to (4) were used, the carbon material dispersions for electrochemical devices (2) to (2) to Example 2 to 4 in the same manner as in Example 1. (4) was obtained.

[Comparative Example 1]
Acetylene black (Denka Black HS-100) 1 as a carbon material that is a conductive aid
0 parts, 10 parts of an aqueous solution or dispersion of the resin-type dispersant (1) (2 parts as a solid content), and 40 parts of water were mixed and dispersed in the same manner as in Example 1 to produce an electrochemical element A carbon material dispersion (5) was obtained.

(Determining the degree of dispersion)
The degree of dispersion of the carbon material dispersions (1) to (5) for electrochemical devices was determined by determination with a grind gauge (according to JIS K5600-2-5).
It was found that when the compositions for electrochemical elements of Examples 1 to 4 of the present invention were used, all of them were excellent in dispersibility of the carbon material which is a conductive additive and suitable for practical use. On the other hand, Comparative Example 1 has low dispersibility and is not suitable for practical use. From this, it can be seen that by using the composition for an electrochemical device of the present invention, a uniform carbon material dispersion for an electrochemical device having excellent dispersibility can be obtained.

St: Styrene AA: Acrylic acid DM: Dimethylamino methacrylate HEMA: 2-hydroxyethyl methacrylate

<Positive electrode ink>, <Positive electrode>
[Example 5]
With respect to 50 parts of the carbon material dispersion for electrochemical devices (1) prepared in Example 1 (5 parts as acetylene black solid content), 45 parts of LiFePO ₄ as a positive electrode active material, binder (1) shown in Table 3 ( 60% aqueous dispersion) 8.3 parts and 50 parts of water were mixed to prepare a mixture ink for a secondary battery electrode for a positive electrode. The dispersity of the composite ink was determined in the same manner as the dispersity of the carbon material dispersion described above.
And after apply | coating this mixed-material ink for secondary battery electrodes for positive electrodes on the 20-micrometer-thick aluminum foil used as a collector using a doctor blade, it dried by heating under reduced pressure and the thickness of an electrode was 100 micrometers.
It adjusted so that it might become m.
Furthermore, the rolling process by roll press was performed and the positive electrode from which thickness becomes 85 micrometers was produced.

[Examples 6 to 11], [Comparative Example 2]
As shown in Table 4, positive electrode secondary materials were obtained in the same manner as in Example 5 except that the carbon material dispersions (2) to (5) for electrochemical devices and the binders (1) to (4) shown in Table 3 were used. A mixed ink for battery electrodes and a positive electrode were obtained.

The dispersities of the composite inks of Examples 5 to 11 and Comparative Example 2 were determined in the same manner as in Example 1. Moreover, the softness | flexibility and adhesiveness of the electrode were evaluated with the following method.
(Electrode flexibility)
The electrode produced above was formed into a strip shape and wound so that the current collector side was in contact with a metal rod having a diameter of 3 mm, and cracks on the electrode surface that occurred during winding were determined by visual observation. The one that does not crack is more flexible.

(Electrode adhesion)
Using the knife, the incision from the surface of the electrode to the depth reaching the current collector was cut into 6 grids in the vertical and horizontal directions at intervals of 2 mm. An adhesive tape was applied to the cut and immediately peeled off, and the degree of the active material falling off was determined by visual judgment.

When the composition for electrochemical elements of the present invention of Examples 5 to 11 is used, the carbon material or the active material which is a conductive auxiliary agent is uniformly dispersed in the composite ink, so the dispersibility of the composite ink It has been found that the flexibility and adhesion of the electrode are good and suitable for practical use. On the other hand, Comparative Example 2 is not suitable for practical use because of the low dispersibility of the composite ink and the flexibility and adhesion of the electrodes. This is because when the composition for an electrochemical device of the present invention is used, the carbon material or the active material, which is a conductive auxiliary agent, is uniformly dispersed in the mixture ink, and adhesion between the materials is maintained. it is conceivable that.

<Negative electrode ink>, <Negative electrode>
[Example 12]
With respect to 10 parts of the carbon material dispersion for electrochemical devices (1) prepared in Example 1 (1 part as an acetylene black solid content), 96 parts of artificial graphite as a negative electrode active material, binder (1) (
60 parts of an aqueous dispersion) 5 parts and 90 parts of water were mixed to prepare a composite ink for a secondary battery electrode for a negative electrode.
This negative electrode mixture ink was applied onto a copper foil having a thickness of 20 μm serving as a current collector using a doctor blade, and then dried by heating under reduced pressure so that the thickness of the electrode was adjusted to 100 μm. A rolling process using a roll press was performed to produce a negative electrode having a thickness of 85 μm.

[Examples 13 to 18], [Comparative Example 3]
As shown in Table 4, the negative electrode secondary material was obtained in the same manner as in Example 12 except that the carbon material dispersions (2) to (5) for electrochemical devices and the binders (1) to (4) shown in Table 3 were used. A mixture ink for battery electrodes and a negative electrode were obtained.

The dispersity of the composite inks of Examples 12 to 18 and Comparative Example 3 and the flexibility and adhesion of the electrodes were evaluated in the same manner as in Example 5.

When the composition for an electrochemical element of Examples 12 to 18 of the present invention is used, the carbon material or the active material as the conductive auxiliary agent is uniformly dispersed in the composite ink. It has been found that the flexibility and adhesion of the electrode are good and suitable for practical use. On the other hand, Comparative Example 3 has low dispersibility of the mixed material ink and flexibility and adhesion of the electrode, and is not suitable for practical use. This is because when the composition for an electrochemical device of the present invention is used, the carbon material or the active material, which is a conductive auxiliary agent, is uniformly dispersed in the mixture ink, and adhesion between the materials is maintained. it is conceivable that.

<NMP-based composition>, <Positive electrode ink>, <Positive electrode>

[Example 19]
45 parts of LiFePO ₄ , 2.5 parts of acetylene black (Denka Black HS-100), 2.5 parts of PVDF (polyvinylidene fluoride) (KF polymer W # 1100), 5 parts of NMP dispersion (b) of thin film particles, And 45 parts of NMP were added and kneaded with a planetary mixer to prepare a mixture ink, and a positive electrode was obtained in the same manner as in Example 5.

[Examples 20 to 31]
Except for adding 0.5 parts of the acidic resin dispersants (A) to (L) shown in Tables 5 to 7, a mixture ink for positive electrode secondary battery electrode and a positive electrode were obtained in the same manner as in Example 19. .

[Example 32]
Instead of KF polymer W # 1100, a mixture ink for positive electrode secondary battery electrode and a positive electrode were obtained in the same manner as in Example 19 except that KF polymer W # 9300 was used.

[Comparative Example 4]
A mixture ink for positive electrode secondary battery electrode and a positive electrode were obtained in the same manner as in Example 19 except that 10 parts of NMP was used instead of 10 parts of the NMP dispersion (b) of thin film particles.

For Examples 20 to 32 and Comparative Example 4, the dispersity of the composite ink, the flexibility of the electrode, and the adhesion were evaluated in the same manner as in Example 5.
When the compositions for electrochemical devices of Examples 20 to 32 of the present invention were used, the carbon material or the active material, which is a conductive additive, was uniformly dispersed in the composite ink, so the dispersibility of the composite ink It has been found that the flexibility and adhesion of the electrode are good and suitable for practical use. On the other hand, Comparative Example 4 has low dispersibility of the composite ink and flexibility and adhesion of the electrode, and is not suitable for practical use. This is because when the composition for an electrochemical device of the present invention is used, the carbon material or the active material, which is a conductive auxiliary agent, is uniformly dispersed in the mixture ink, and adhesion between the materials is maintained. it is conceivable that.

As described above, since the composition for an electrochemical device of the present invention contains thin film particles containing graphite oxide, the dispersibility is improved by the thin film particles acting on the surface of the carbon material or the electrode active material. Conceivable. In addition, an electrode using the composition for an electrochemical element of the present invention is considered to have high substrate adhesion because the oxygen-containing polar functional group of the thin film particles interacts with the current collector. Further, the presence of the thin film-like particles can improve the adhesion between the materials in the electrode, and thus is considered to have high coating strength.

From the foregoing description, it will be apparent that a wide variety of different embodiments may be constructed without departing from the spirit and scope of the invention, and the invention is not limited to that particular, except as limited in the claims. It is not limited by the embodiment.

Claims (4)

A composition for an electrochemical device comprising thin film particles containing graphite oxide and a dispersion medium. The composition for an electrochemical element according to claim 1, further comprising an electrode active material. An electrochemical device electrode having at least a current collector and a composite material layer, wherein the composite material layer is a layer formed by applying and drying the composition for an electrochemical device according to claim 1 or 2. Element electrode. An electrode for an electrochemical device having at least a current collector, a base layer, and a composite layer, wherein the base layer and / or the composite layer is coated with the composition for an electrochemical device according to claim 1, An electrode for an electrochemical element, which is a dried layer.