JP6051929B2 - Secondary battery electrode forming composition, secondary battery electrode, and secondary battery - Google Patents

Description

The present invention is a lithium-ion secondary battery electrode-forming composition, and an electrode for a lithium ion secondary battery obtained by using the composition, and to a lithium ion secondary battery obtained by using the electrode.

  In recent years, small portable electronic devices such as digital cameras and mobile phones have been widely used. These electronic devices have always been required to minimize the volume and reduce the weight, and the batteries to be mounted are also required to be small, light, and have a large capacity. In addition, in a large-sized secondary battery for use in automobiles or the like, it is desired to realize a large-sized secondary battery instead of a conventional lead storage battery. In recent years, from the viewpoint of resource depletion and environmental problems, the use of a secondary battery as a power source, such as a hybrid vehicle or an electric vehicle, has been studied.

  In order to meet such demands, development of secondary batteries such as lithium ion secondary batteries and alkaline secondary batteries, for example, development of composite inks used for forming a composite layer has been actively conducted. There is also an interest in a composition for forming an underlayer used for forming an underlayer of a composite material layer.

An important characteristic required for the composite ink used for forming the electrode and the composition for forming the underlayer includes uniformity in which the active material and the conductive additive that are particles are appropriately dispersed.
This is because the dispersion state of the active material and the conductive additive in the composite ink and the dispersion state of the conductive additive in the composition for forming the underlayer are the distribution state and particles of the active material and the conductive additive in the composite layer. This is because they affect the physical properties of the electrode, and thus the battery performance.

Therefore, dispersion of the active material and the conductive auxiliary agent is an important issue. In particular, carbon materials with excellent electrical conductivity (conducting aids) have a strong cohesive force due to their large structure and specific surface area, and should be uniformly mixed and dispersed, whether in the composite ink or in the composition for forming the underlayer. Is difficult.
And if the dispersibility and particle size control of the carbon material that is the conductive auxiliary agent is insufficient, the internal resistance of the electrode cannot be reduced because a uniform conductive network is not formed, and as a result, the performance of the electrode material is sufficient. The problem of being unable to withdraw.

  Moreover, when not only the conductive assistant but also the dispersion of the active material in the composite ink is insufficient, partial aggregation occurs in the composite layer formed from such a composite ink. In addition, resistance distribution occurs on the electrode due to partial aggregation, current concentration occurs when used as a battery, and problems such as partial heat generation and deterioration may occur.

  Patent Documents 1 to 3 describe examples in which a resin-type dispersant is used as a dispersant. When these resin-type dispersants are used, they act as a dispersant for both the active material and the conductive additive, and a mixed ink in which the respective particles are uniformly mixed is obtained. However, the battery capacity decreased in the long-term cycle characteristics. Moreover, electrolyte solution tolerance was inadequate.

In the above method, as a result of uniformly dispersing the particles of the active material and the conductive auxiliary agent, a good particle network is formed. However, as a result, it is difficult to maintain the interparticle contact between the active material and the active material, between the active material and the conductive aid, or between the conductive aid and the conductive aid for a long time in charge and discharge in contact with the electrolytic solution. It is thought that it has been. The electrode underlayer forming composition also has the same problem regarding the formation of a conductive path by particle contact between the conductive auxiliary agent and the conductive auxiliary agent.

On the other hand, the use of a silane compound is known in order to increase the strength of the electrode film and the adhesion to the current collector.

Patent Documents 4 and 5 describe examples in which the strength of the film is improved by adding a silane coupling agent. In these examples, sufficient effects could not be obtained unless a large amount of coupling agent was added. Moreover, electrolyte solution tolerance was inadequate.

Patent Documents 6 to 9 give examples in which irreversible capacity is suppressed by surface treatment and cycle characteristics are improved. Although these methods can form interparticle contact, the process for surface treatment becomes complicated. For example, after mixing an active material and a coupling agent solution, a plurality of processes such as surface treatment by drying by heating, impregnation of an electrode having a mixture layer in a coupling agent solution, and drying by heating are performed. I need it. From the viewpoint of industrialization and cost, a simpler method has been demanded. Moreover, even if these methods were used, the electrolyte solution resistance of the composite material layer was not sufficient.

Patent Documents 10 and 11 describe a method of treating a silane coupling agent only in a slurry mixing step, but the dispersion of particles is insufficient, so that the electrolyte solution resistance of the mixture layer is insufficient. Met.

JP 2010-97816 A JP 2010-97817 A JP2011-70908A JP 7-326346 A JP-A-8-96801 JP-A-8-111243 JP 11-354104 A JP2008-235030 JP 2002-367610 A JP2007-18874 JP-A-2005-293942

An object of the present invention is to provide an electrode forming composition for forming a lithium ion secondary battery, which is excellent in dispersibility of an active material and a conductive additive. Furthermore, by forming a composite material layer or an electrode underlayer having high resistance to electrolyte solution (hereinafter, the composite material layer or the electrode base layer may be collectively referred to as an electrode layer in this specification), long-term charging is achieved. An object of the present invention is to provide an electrode for a lithium ion secondary battery excellent in discharge cycle characteristics.

One or more resin-type dispersants (C) selected from the group consisting of a resin having an acidic functional group, a resin having a basic functional group, and a nonionic resin, and a silane coupling agent (D) And the composition for forming a lithium ion secondary battery electrode in which the active material (A) and the conductive additive (B) are dispersed.

The present invention relates to at least one of an active material (A) or a conductive auxiliary agent (B), a polyvinylidene fluoride resin (C ^A1 ) having an acidic functional group, a polyvinyl resin (C ^A2 ) having an acidic functional group, an acidic Polyester resin having a functional group (C ^A3 ), Disperbyk-111 (manufactured by Big Chemie) (C ^A4 ), a polyvinyl resin having a basic functional group (C ^B1 ), a polyester resin having a basic functional group (C ^B2 ), Azisper PB821 (Ajinomoto Fine Techno Co., Ltd.) (C ^B3 ), polyvinyl alcohol resin (C ^C1 ), polyvinyl acetal resin (C ^C2 ), and polyvinylamide resin (C ^C3 ) The present invention relates to a composition for forming a lithium ion secondary battery electrode comprising the resin-type dispersant (C) and a silane coupling agent (D).

Moreover, this invention relates to the said composition for lithium ion secondary battery electrode formation in which a silane coupling agent (D) has a reactive functional group.

Further, the present invention is an electrode comprising a current collector and at least one layer of a composite material layer or an electrode base layer, wherein the composite material layer or the electrode base layer is for forming the lithium ion secondary battery electrode. The present invention relates to an electrode for a lithium ion secondary battery which is formed from a composition.

Further, the invention relates to a battery having a positive electrode and the negative electrode and the electrolyte, to the positive electrode or at least one of a lithium ion secondary battery is an electrode for the lithium ion secondary battery of the negative electrode.

By this invention, the composition for electrode formation which was excellent in the dispersibility of an active material and a conductive support agent was able to be provided. Furthermore, a composite material layer or an electrode base layer having a high resistance to electrolyte solution can be formed, and an electrode for a lithium ion secondary battery excellent in long-term charge / discharge cycle characteristics can be provided.
This is because an active material or a conductive aid is used by using one or more resin-type dispersants selected from the group consisting of a resin having an acidic functional group, a resin having a basic functional group, and a nonionic resin. Aggregation is loosened and uniformly dispersed, and the silane coupling agent is allowed to act in such a state.
At this time, the fine particles acted on by the silane coupling agent can form a larger number of inter-particle contacts, and as a result, an electrode layer having a very strong inter-particle contact can be formed. It is done. This is a very remarkable effect as compared with the case where the particles are acted in an insufficiently dispersed state, and the effect can be obtained even with a smaller amount of the silane coupling agent. The electrode layer formed from such an electrode-forming composition also has improved electrolyte resistance, and is considered to have contributed to the improvement of battery performance in a long-term cycle test.

An electrode for a lithium ion secondary battery can be obtained by various methods. For example, on the surface of a current collector such as a metal foil,
(1) an ink-like composition containing an active material and a liquid medium (hereinafter referred to as composite ink),
(2) a mixed ink containing an active material, a conductive additive and a liquid medium;
(3) a mixed ink containing an active material, a binder and a liquid medium;
(4) A mixed ink containing an active material, a conductive additive, a binder, and a liquid medium,
It can be used to form a composite layer and obtain an electrode.

  Alternatively, an underlayer is formed on the surface of a current collector such as a metal foil using a composition for forming an underlayer containing a conductive additive and a liquid medium, and the above-mentioned composite ink ( An electrode can also be obtained by forming a composite layer using 1) to (4) or other composite ink.

  As described in the background art, in any case, the dispersion state of the active material and the conductive additive in the composite ink and the composition for forming the underlayer, and the active material in the mixture layer and the underlayer In addition, the distribution state of the conductive aid affects the battery performance.

A resin having an acidic functional group, a resin having a basic functional group, and a nonionic resin (C) (hereinafter, may be simply referred to as a resin-type dispersant in this specification) are an active material or a conductive assistant. Acts as a dispersing agent by reducing the aggregation of the agent. Moreover, a silane coupling agent (D) adsorb | sucks to the surface of an active material or a conductive support agent, and provides interparticle contact.

Thus, the composite layer obtained from the composite ink that achieves both uniform dispersion and appropriate interparticle contact, or the base layer obtained from the base layer forming composition has high electrolyte resistance and improved battery characteristics. To do.

Therefore, the composition for forming a lithium ion secondary battery electrode of the present invention can be used as a composite ink that requires an active material or as a composition for forming an underlayer that does not require an active material.

First, the resin type dispersant (C) which is a dispersant in the present invention will be described. The resin-type dispersant (C) is selected from the group consisting of a resin having an acidic functional group, a resin having a basic functional group, and a nonionic resin.

<Resin having an acidic functional group>
Examples of the resin having an acidic functional group in the present invention include the following four types of C ^{A1 to} C ^A4 . C ^{A1 to} C ^A3 are preferable from the viewpoint of dispersibility.
(1) Polyvinylidene fluoride resin having an acidic functional group (C ^A1 )
(2) Polyvinyl resin having an acidic functional group (C ^A2 )
(3) Polyester resin having an acidic functional group (C ^A3 )
(4) Other commercially available resins having acidic functional groups (C ^A4 )
Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

<Polyvinylidene fluoride-based resin having acidic functional group (C ^A1 )>
The polyvinylidene fluoride-based resin (C ^A1 ) having an acidic functional group is not particularly limited, but includes Japanese Patent Publication Nos. 52-24959, 58-136605, and 2-604. It can be synthesized with reference to Kaihei 6-172451, WO2004-049475, Japanese Patent No. 3121943, or Japanese Patent No. 3784494.

Specific examples are shown below. However, a monomer represents an ethylenically unsaturated monomer. 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 fluorine-free resins. 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 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 monomer having fluorine and other monomers include the same ones as those used for the polyvinylidene fluoride resin having a sulfonic acid group.

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 phosphoric acid group was selected from the group consisting of vinylidene fluoride, a monomer having a phosphoric acid 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 thereof include adducts obtained by reacting alkoxyphosphoric acid di (meth) acrylate and (meth) acrylate containing glycidyl group with phosphoric acid.

Examples of the monomer having fluorine and other monomers include the same ones as those used for the polyvinylidene fluoride resin having a sulfonic acid group.

Further, the polyvinylidene fluoride resin having a phosphoric acid group is obtained by causing a phosphoric acid, phosphorous pentoxide, phosphorus oxychloride, polyphosphoric acid, or orthophosphoric acid, etc., as phosphorylating agents to act on the polyvinylidene fluoride resin having a hydroxyl group. Can also be obtained.

The polyvinylidene fluoride-based resin having a hydroxyl group is at least one 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 with a monomer.

Monomers having a hydroxyl group include (meth) acrylates and allyl ethers, and (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 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 penta (meth) acrylate, glycidyl methacrylate- (meth) acrylic acid adduct, , 1,1-trimethylol propane or glycerol di (meth) acrylic acid ester.

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, 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 diallyl Ether, pentaerythritol monoallyl ether, pentaerythritol triallyl ether, pentaerythritol diallyl ether, and the like.

Examples of the monomer having fluorine and other monomers include the same ones as those used for the polyvinylidene fluoride resin having a sulfonic acid group.

The weight average molecular weight of the polyvinylidene fluoride-based resin (C ^A1 ) having an acidic functional group in the present invention is preferably 3,000 to 1,000,000. More preferably, it is 5,000-500,000. The acid value is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g.

<Polyvinyl resin (C ^A2 ) having an acidic functional group>
Examples of the method for synthesizing the polyvinyl resin (C ^A2 ) having an acidic functional group in the present invention include a method through the following first step and second step.
(First step): A step of obtaining a vinyl polymer (a ¹ ) having two hydroxyl groups at one end by radical polymerization.
(Second step): A step of reacting the vinyl polymer (a ¹ ) having two hydroxyl groups at one end obtained in the first step with tetracarboxylic dianhydride (b ¹ ).

<First Step of Polyvinyl Resin (C ^A2 ) Having Acid Functional Group>
The first step is radical polymerization of an ethylenically unsaturated monomer (m) in the presence of a compound (s) having two hydroxyl groups and one thiol group in the molecule as shown in the following general formula (1). In this step, a vinyl polymer (a ¹ ) having two hydroxyl groups at one end is produced. The thiol group of the compound (s) having two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, and ends of the vinyl polymer site (M) where the ethylenically unsaturated monomer (m) is polymerized. A vinyl polymer (a ¹ ) in which two hydroxyl groups are introduced via S atoms is synthesized.

General formula (1)

(Compound having two hydroxyl groups and one thiol group in the molecule (s))
Examples of the compound (s) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 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, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like. However, it is not limited to these.

Z ⁰ in the general formula (1) is a residue obtained by removing the hydroxyl group and the thiol group from the compound (s) having two hydroxyl groups and one thiol group in the molecule.

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

In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (m). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), and 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane] and the like. However, it is not limited to these.

Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. However, it is not limited to these. These polymerization initiators can be used alone or in combination of two or more.

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

(Ethylenically unsaturated monomer (m))
Examples of the ethylenically unsaturated monomer (m) include the following general ethylenically unsaturated monomers. Common ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl Alkyl (meth) acrylates such as (meth) acrylate, t-butyl (meth) acrylate, 2-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;
(Meth) acrylates having an aromatic ring such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and 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;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, and vinyltoluene; styrenes such as;
And 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. Two or more types may be combined.

In the present invention, among the ethylenically unsaturated monomers (m) exemplified above, methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate and benzyl (meth) acrylate are included. It is preferred to use. When these are used, it is possible to achieve both adsorption to the active material and conductive additive and solvent affinity, which is preferable as a dispersant. Furthermore, you may use together the monomer shown below as needed.

As one of the ethylenically unsaturated monomers (m), an ethylenically unsaturated monomer having a carboxyl group may 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 ( The addition mole number can be selected from 1 to 5), caprolactone adduct of methacrylic acid (addition mole number is 1 to 5), or the like.

Moreover, you may use together the ethylenically unsaturated monomer which has a hydroxyl group as an ethylenically unsaturated monomer (m). Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3, or 4) -hydroxybutyl (meth) ) Hydroxyalkyl (meth) acrylates such as acrylate, cyclohexanedimethanol mono (meth) acrylate, and glycerol (meth) acrylate;
N- (hydroxyalkyl) (meth) such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, and N- (2-hydroxybutyl) (meth) acrylamide Acrylamides;
Hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, and 2- (or 3- or 4-) hydroxybutyl vinyl ether;
And hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and 2- (or 3-, or 4-) hydroxybutyl allyl ether. However, it is not limited to these.

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

In the present invention, together with the ethylenically unsaturated monomer (m) exemplified above, an ethylenically unsaturated monomer having a blocked isocyanate group, an ethylenically unsaturated monomer having an oxetane group, and t- The vinyl polymer (a ¹ ) may be produced using an ethylenically unsaturated monomer selected from at least one of ethylenically unsaturated monomers having a butyl group.

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

In the present invention, an unsaturated bond may be introduced into the vinyl polymer (a ¹ ). As a method for introducing an unsaturated bond, a method in which a hydroxyl group is introduced into a vinyl polymer (a ¹ ) and an ethylenically unsaturated monomer having an isocyanate group is reacted later, in a vinyl polymer (a ¹ ) A method of reacting an ethylenically unsaturated monomer having an epoxy group after the introduction of a carboxyl group into the vinyl polymer, introducing an epoxy group into the vinyl polymer (a ¹ ), and then having an ethylenic unsaturated group having a carboxyl group Examples include a method of reacting monomers.

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

In the present invention, the weight average molecular weight in terms of polystyrene by GPC of the vinyl polymer having two hydroxyl groups at one end (a ¹ ) is preferably 1,000 to 10,000. The weight average molecular weight of the vinyl polymer (a ¹ ) is the use weight, reaction temperature, reaction of the compound (s) having two hydroxyl groups and one thiol group in the molecule relative to the ethylenically unsaturated monomer (m). It is easy to adjust the time, the weight of the polymerization initiator used as necessary, the kind of the polymerization solvent used as necessary, and the ethylenically unsaturated monomer (m) concentration during the polymerization.

<Second Step of Polyvinyl Resin (C ^A2 ) Having Acid Functional Group>
As shown in the following general formula (2), the second step for obtaining a polyvinyl resin (C ^A2 ) having an acidic functional group is a vinyl polymer having two hydroxyl groups at one end obtained in the first step. In this step, the coalescence (a ¹ ) is reacted with tetracarboxylic dianhydride (b ¹ ).

General formula (2)

Assuming that the molar ratio of the vinyl polymer (a ¹ ) having two hydroxyl groups at one end is α ^A2 and the molar ratio of the tetracarboxylic dianhydride (b ¹ ) is β ^A2 , in theory, α ^A2 = β ^A2 Since the molecular weight becomes infinitely large, the ratio of α ^A2 / β ^A2 is often changed to α ^A2 > β ^A2 or α ^A2 <β ^A2 to control the target molecular weight. For example, when α ^A2 = β ^A2 +1, both ends are hydroxyl groups, the molecular weight is not increased any more, and a polyvinyl resin (C ^A2-1 ) having an acidic functional group is obtained. On the other hand, in the case of β ^A2 = α ^A2 +1, both ends become acid anhydride groups, which are hydrolyzed to obtain a polyvinyl resin (C ^A2-2 ) having an acidic functional group with the ends being carboxyl groups. .

(Tetracarboxylic dianhydride (b ¹ ))
The tetracarboxylic dianhydride (b ¹ ) used in the present invention is represented by the following general formulas (3) to (5) and reacts with a vinyl polymer (a ¹ ) having two hydroxyl groups at one end. Form the main chain. X ⁰ of the present invention is a reaction residue after the reaction of tetracarboxylic dianhydride (b ¹ ) with a vinyl polymer (a ¹ ) having two hydroxyl groups at one end.

General formula (3)

General formula (4)

General formula (5)

Y ⁰ is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, the following general formula (6) or the following general formula (7). Represented by either

General formula (6)

General formula (7)

As tetracarboxylic dianhydride (b ¹ ) used in the present invention, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride Product, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3- Aliphatic acids such as methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Tet Dianhydride;
And pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4 , 4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-di Ruboxyphenoxy) 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 Anhydride, 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] fluorenic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene And acid dianhydrides and aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

The tetracarboxylic dianhydride (b ¹ ) used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride as represented by the general formulas (3) to (5). Moreover, you may use together the compound which has one carboxylic anhydride group in a molecule | numerator, and the compound which has 3 or more.

As the catalyst used in the second step of the polyvinyl resin (C ^A2 ) having an acidic functional group that can be used in the present invention, a known catalyst can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and 1 , 5-diazabicyclo- [4,3,0] -5-nonene.

The polyvinyl resin (C ^A2 ) having an acidic functional group that can be used in the present invention can be produced using only the raw materials listed so far, but there are problems such as high viscosity and non-uniform reaction. In order to avoid this, it is preferable to use a solvent. As the solvent to be used, known solvents can be used. Examples 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-methyl-2-pyrrolidone. The solvent used in the reaction may be removed by an operation such as distillation after completion of the reaction, or may be used as a part of the product as it is.

The polyvinyl resin (C ^A2 ) having an acidic functional group that can be used in the present invention is reacted with a vinyl polymer (a ¹ ) having two hydroxyl groups at one end and a tetracarboxylic dianhydride (b ¹ ). Can be obtained. Tetracarboxylic acid dianhydride (b ¹⁾ an acid anhydride group and a vinyl polymer in (a ¹⁾ the molar ratio of the hydroxyl group in the molar ratio alpha ^A2 of the vinyl polymer (a ^1), a tetracarboxylic acid When the molar ratio of the dianhydride (b ¹ ) is β ^A2 , β ^A2 / α ^A2 = 0.3 to 1.2 is preferable, and β ^A2 / α ^A2 = 0.5 to 1.0 is more preferable. Most preferably, β ^A2 / α ^A2 = 0.6 to 0.8. When the reaction is carried out with β ^A2 / α ^A2 > 1, the remaining acid anhydride group may be hydrolyzed with a necessary amount of water.

The reaction temperature in the second step of the polyvinyl resin (C ^A2 ) having an acidic functional group is 80 ° C. to 180 ° C., preferably 90 ° C. to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when it is 180 ° C. or higher, the carboxyl group may undergo an esterification reaction. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption. However, when the acid value of the polyester (c ¹ ) is in the range of 5 to 200, or the hydroxyl value is The reaction may be stopped when entering the range of 20-200.

The weight average molecular weight of the polyvinyl resin (C ^A2 ) having an acidic functional group in the present invention is preferably 2,000 to 25,000, more preferably 5,000 to 15,000. The acid value is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g.

<Polyester resin having acidic functional group (C ^A3 )>
The polyester resin (C ^A3 ) having an acidic functional group is represented by the following general formula (8). The production method includes, for example, a first step of producing a polyester (c ¹ ) having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, and a polyester having a hydroxyl group at one end (c ¹ ) and a second step of reacting tetracarboxylic dianhydride (b ² ).

General formula (8)

X ¹ is a tetravalent tetracarboxylic acid compound residue, X ² is a lactone residue, X ³ is a monoalcohol residue, m is 2 or 3, and n is an integer of 1 to 50 And t is (4-m).

<First step of polyester-based resin (C ^A3 ) having acidic functional group>
<Monoalcohol>
The monoalcohol that can be used for the production of the polyester-based resin (C ^A3 ) having an acidic functional group is not particularly limited as long as it is a compound having one hydroxyl group. The aliphatic monoalcohol is, for example, preferably a linear or branched substituted or unsubstituted saturated aliphatic monoalcohol having 1 to 30 carbon atoms (more preferably 1 to 25 carbon atoms), or a carbon atom. Examples thereof include substituted or unsubstituted saturated alicyclic monoalcohols having 1 to 30 (more preferably 1 to 25 carbon atoms). Examples of the substituent of the saturated aliphatic monoalcohol or saturated alicyclic monoalcohol include a carboxyl group.

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

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

As the monoalcohol, a substituted or unsubstituted aromatic monoalcohol having 6 to 30 carbon atoms (more preferably 6 to 25 carbon atoms), for example, phenol or cumylphenol may be used. Moreover, you may use the saturated aliphatic monoalcohol which has a C1-C6 aliphatic group part and was substituted by the C6-C10 aromatic group, for example, benzyl alcohol.

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

Furthermore, in the production of the polyester-based resin (C ^A3 ) having an acidic functional group, a monoalcohol having one or more ethylenically unsaturated double bonds may be used as the monoalcohol. Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

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. Examples of monoalcohols having one ethylenically unsaturated double bond include hydroxyalkyl esters of (meth) acrylic acid having 1 to 8 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate and the like can be mentioned.

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

Alcohols 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 end is ether Polyalkylene glycol that has been converted to an ester may also be used for the production of a polyester-based resin (C ^A3 ) having an acidic functional group. As the alkylene oxide used for the addition polymerization, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, or a mixture of two or more thereof is used. be able to. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. The addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, and particularly preferably 5 to 100 in one molecule.

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

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

The monoalcohol that can be used for the production of the polyester-based resin (C ^A3 ) having an acidic functional group is not limited to the above examples, and any compound can be used as long as it is a compound having one hydroxyl group. These may be used alone or in combination of two or more.

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

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

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

The number of moles of the lactone added per mole of the monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles. The lactone may be used without being limited to the above examples, and may 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 to a dehydrating tube and a condenser and under a nitrogen stream. . When a low-boiling monoalcohol is used as the monoalcohol, it can be reacted 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.

As the polymerization catalyst for the ring-opening polymerization, known ones can be used without limitation, for example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide. Quaternary ammonium salts such as tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetraphenylphosphonium iodide;
Phosphorus compounds such as triphenylphosphine; organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate; alkali metal alcoholates such as sodium alcoholate and potassium alcoholate; triethylamine, and triphenylamine Tertiary amines; organotin compounds such as dibutyltin dilaurate, dibutyltin oxide, and dioctyltin oxide; aluminum alkyl acetoacetate / diisopropylate, aluminum bisethylacetoacetate / monoacetylacetonate, aluminum trisacetylacetonate Organoaluminum compounds;
Examples thereof include organic titanate compounds such as tetra-n-butyl titanate, the dimer, tetraisobutyl titanate, tetrastearyl titanate, and diisopropoxy bis (triethanolaminate) titanium; and zinc compounds such as zinc chloride. The catalyst is used in an amount of 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm.

The ring-opening polymerization reaction may be carried out without a solvent, or an appropriate dehydrated organic solvent may be used. The solvent used in the ring-opening polymerization reaction may be removed by an operation such as distillation after the completion of the reaction, or may be used as it is as a part of the electrode forming composition of the present invention.

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

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

<Second step of polyester-based resin (C ^A3 ) having acidic functional group>
The polyester-based resin (C ^A3 ) having an acidic functional group used in the present invention includes a hydroxyl group of a polyester (c ¹ ) having a hydroxyl group at one end obtained in the first step, and a tetracarboxylic dianhydride (b ² ) is preferably obtained through a second step.

As the tetracarboxylic dianhydride (b ² ) used for obtaining the polyester resin (C ^A3 ) having an acidic functional group used in the present invention, a polyvinyl resin (C) having an acidic functional group used in the present invention. ^The same tetracarboxylic dianhydride (b ¹ ) used in obtaining ^A2 ) can be used.

X ¹ in the general formula (8) is a reaction residue after the tetracarboxylic dianhydride (b ² ) has reacted with the hydroxyl group of the polyester (c ¹ ) having a hydroxyl group at one end, and the general formula ( It is a residue after the tetracarboxylic dianhydride represented by 3) to (5) has reacted.

In the general formula (8), n is preferably an integer of 1 to 50, more preferably an integer of 2 to 20, and most preferably an integer of 4 to 16. In the general formula (8), when at least one of n and t is 2 or more, the plurality of X ² and X ³ present in the general formula (8) are all the same group, Multiple types of groups may be included.

X ² is a hexamethylene group, a pentamethylene group, an alkyl-substituted hexamethylene group, or the like, and X ³ is an aliphatic alkyl group having 8 to 20 carbon atoms, or a terminal ether having a molecular weight of 200 to 1500, or And ester polyoxyalkylene (alkylene moiety having 2 to 4 carbon atoms) groups.

The reaction ratio in the second step is the ratio of the number of moles β ^A3 of the anhydrous ring of tetracarboxylic dianhydride (b ² ) to the number of moles α ^A3 of the hydroxyl group of the polyester (c ¹ ) having a hydroxyl group at one end, that is, α ^A3 / β ^A3 is preferably 0.5 <α ^A3 / β ^A3 <1.2, more preferably 0.7 <α ^A3 / β ^A3 <1.1, most preferably α ^A3 / β ^3A = 1. It is. When reacting with α ^A3 / β ^A3 <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.

In the second step, a catalyst may be used. 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 second steps may be performed without solvent, or an appropriate dehydrated organic solvent may be used. After completion of the reaction, the solvent used in the reaction may be removed by an operation such as distillation, or may be used as it is as a part of the electrode forming composition of the present invention.

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.

The weight average molecular weight of the polyester-based resin (C ^A3 ) having an acidic functional group in the present invention is preferably 2,000 to 25,000, more preferably 5,000 to 15,000. The acid value is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g.

The resin having an acidic functional group is not limited to the above-described C ^{A1 to} C ^A3 , but other polyvinyl-based, polyurethane-based, polyester-based, polyether-based, formalin condensate, silicone-based, and these And a composite polymer. Furthermore, two or more kinds of resins having these acidic functional groups can be used in combination.

<Resins with other commercially available acidic functional groups (C ^4A )>
Although it does not specifically limit as resin ( ^C4A ) which has a commercially available acidic functional group, For example, the following are mentioned .

The resin having manufactured by BYK-Chemie acidic functional groups, Disperbyk - 11 1, and the like.

<Resin having a basic functional group>
Examples of the resin having a basic functional group in the present invention include the following three types of C ^{B1 to} C ^B3 . From the viewpoint of dispersibility, C ^B1 and C ^B2 are preferable.
(1) Polyvinyl-based resin (C ^B1 ) having a basic functional group
(2) Polyester resin having a basic functional group (C ^B2 )
(3) Other commercially available resins having basic functional groups (C ^B3 )
Moreover, as a preferable basic functional group, a 1-3 grade amino group is mentioned.

<Polyvinyl resin having basic functional group (C ^B1 )>
Examples of the method for synthesizing the polyvinyl resin (C ^B1 ) having a basic functional group in the present invention include (C ^B1-1 ) and (C ^B1-2 ) synthesized by the following two methods. It is done.

<Polyvinyl resin having basic functional group (C ^B1-1 )>
Examples of the method for synthesizing the polyvinyl resin (C ^B1-1 ) having a basic functional group in the present invention include a method through the following first step, second step, and third step.
(First step): A step of obtaining a vinyl polymer (a ¹ ) having two hydroxyl groups at one end by radical polymerization.
(Second Step): a vinyl polymer having two hydroxyl groups at one end obtained in the first step with (a ^1), by reacting a polyisocyanate (d ^1), the urethane prepolymer (e ¹⁾ Obtaining step.
(Third step): The urethane prepolymer (e ¹ ) obtained in the second step is reacted with the polyamine (f ¹ ) to obtain a polyvinyl resin (C ^B1-1 ) having a basic functional group. Process.

<First Step of Polyvinyl Resin (C ^B1-1 ) Having Basic Functional Group>
The first step for obtaining a polyvinyl-based resin (C ^B1-1 ) having a basic functional group is the same as the first step for synthesizing the polyvinyl-based resin (C ^A2 ) having an acidic functional group of the present invention. Yes, through the process shown in general formula (1). The same applies to materials that can be used.

<Second Step of Polyvinyl Resin (C ^B1-1 ) Having Basic Functional Group>
(Polyisocyanate (d ¹ ))
The polyisocyanate (d ¹ ) used in the second step for obtaining the polyvinyl resin (C ^B1-1 ) having a basic functional group of the present invention is a compound having two or more isocyanate groups in the molecule. . As the compound having two isocyanate groups in the molecule, conventionally known compounds can be used. For example, aromatic-containing diisocyanates, aliphatic-containing diisocyanates, araliphatic-containing diisocyanates, and alicyclic-containing diisocyanates, these Examples include diisocyanate dimers (uretdione), reaction products of these diisocyanate trimers (isocyanurate) and monoalcohol, reaction products of these diisocyanates and diols (urethane prepolymers of both terminal isocyanates), and the like. However, it is not limited to these. These may be used alone or in combination of two or more.

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 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the araliphatic diisocyanate include 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.

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.

Examples of compounds having three or more isocyanate groups in one molecule include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic-aliphatic polyisocyanates, and alicyclic polyisocyanates. Can be mentioned.

Examples of the polyisocyanate having three or more isocyanate groups per molecule include the above-mentioned diisocyanate isocyanurate and diisocyanate trimers such as the diisocyanate biuret, the diisocyanate polyol adduct, and two or more of the above diisocyanates. Examples thereof include a copolymer, an aromatic triisocyanate, and a polymer type aromatic isocyanate oligomer.

Specifically, isocyanurate of tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), isocyanurate of isophorone diisocyanate (hereinafter sometimes abbreviated as IPDI), 4,4′-diphenylmethane diisocyanate. (Hereinafter sometimes abbreviated as MDI) isocyanurate, hexamethylene diisocyanate (hereinafter sometimes abbreviated as HDI), isocyanurate, HDI biuret, HDI trimethylolpropane (hereinafter referred to as “MDI”). TMP may be abbreviated as TMP.) Diisocyanate modifications such as adducts, TMP adducts of TDI, and TDI / HDI copolymers; 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, and 4,4 ', 4''-triphenyl Examples thereof include aromatic triisocyanates such as methane triisocyanate and polymer type aromatic isocyanate oligomers such as polymethylene polyphenyl polyisocyanate (also known as MDI oligomer).

The polyisocyanate (d ¹ ) used in the present invention is preferably 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate).

(Urethane prepolymer (e ¹ ))
The urethane prepolymer (e ¹ ), which is a component for obtaining a polyvinyl resin (C ^B1-1 ) having a basic functional group in the present invention, is a vinyl polymer (a ¹ ) having two hydroxyl groups at one end. It is obtained by reacting the hydroxyl group of and the isocyanate group of polyisocyanate (d ¹ ).

In the synthesis of the urethane prepolymer (e ¹ ), a known catalyst can be used, and examples thereof include a tertiary amine compound and an organometallic compound.

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

Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

Non-tin compounds include, for example, titanium series such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead series such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate, Iron systems such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt systems such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc systems such as zinc naphthenate and zinc 2-ethylhexanoate, and And zirconium series such as zirconium naphthenate.

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 may be used alone or in combination.

The organometallic compound catalyst used in the synthesis of the urethane prepolymer (e ¹ ) significantly accelerates the reaction even in the further reaction with the polyamine (f ¹ ) described later.

A known solvent is preferably used for the synthesis of the urethane prepolymer (e ¹ ). The use of a solvent serves to facilitate reaction control.

Examples of the solvent used in the synthesis of the urethane prepolymer (e ¹ ) include ethyl acetate, n-butyl acetate, isobutyl acetate, N-methyl-2-pyrrolidone, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, Propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether and the like are used, but are not particularly limited thereto.

In view of the solubility of the urethane, such as the solubility of the urethane prepolymer (e ¹ ) and the boiling point of the solvent, ethyl acetate, N-methyl-2-pyrrolidone, toluene, methyl ethyl ketone, diethylene glycol diethyl ether, or a mixed solvent thereof is particularly preferable. .

Further, the concentration in the urethane prepolymer reaction system when using a solvent is preferably 30 to 95% by weight from the viewpoint of reaction control in terms of the solid content concentration of the urethane prepolymer, and from the viewpoint of viscosity control. More preferably, it is 40 to 90% by weight.

There are various urethanization reactions in which the urethane prepolymer (e ¹ ) is produced by reacting the hydroxyl group of the vinyl polymer (a ¹ ) having two hydroxyl groups at one end with the isocyanate group of the polyisocyanate (d ¹ ). Is possible.
(1) Method of reacting by charging the whole amount (2) After adding a vinyl polymer (a ¹ ) having two hydroxyl groups at one end and, if necessary, a solvent into a flask and adding polyisocyanate (d ¹ ) dropwise, The method is roughly classified into a method of adding a catalyst as necessary, but (2) is preferable when the reaction is precisely controlled.

The reaction temperature for obtaining the urethane prepolymer (e ¹ ) is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed in the presence of a catalyst at 50 to 110 ° C. for 1 to 20 hours.

Compounding ratio of the vinyl polymer having two hydroxyl groups at one end (a ¹⁾ a polyisocyanate (d ¹⁾ is an integer alpha ^B1 a molar ratio of vinyl polymer having two hydroxyl groups at one end (a ¹⁾ When the molar ratio β ^B1 of the polyisocyanate (d ¹ ) is β ^B1 = α ^B1 +1, a urethane prepolymer (e ¹ ) having an isocyanate group at both ends is theoretically obtained. Since the minimum of α ^B1 is 1, the blending molar ratio β ^B1 / α ^B1 is 2 or less.

If the polyisocyanate (d ¹ ) is further increased, all isocyanate groups in the mixture of urethane prepolymer (e ¹ ) and excess polyisocyanate (d ¹ ) can be designed to react with the polyamine (f ¹ ). Excess polyisocyanate (d ¹ ) can be incorporated into the polyvinyl resin (C ^B1-1 ) having a basic functional group of the present invention. When synthesizing the urethane prepolymer (e ¹ ) of the present invention, it is preferable to add excess polyisocyanate so as not to leave a vinyl polymer (a ¹ ) having two hydroxyl groups at one end.

Therefore, the compounding molar ratio of the polyisocyanate (d ¹ ) to the vinyl polymer (a ¹ ) having two hydroxyl groups at one end is 1.01 to 3.3 from the viewpoint of the productivity of the urethane prepolymer (e ¹ ). 00 is preferable, and 1.30 to 2.30 is more preferable from the viewpoint of the balance between the adsorption site and the solvent affinity site of the polyvinyl resin (C ^B1-1 ) having a basic functional group as the final synthesized product. .50 to 2.00 is most preferable.

<The 3rd process of polyvinyl resin (C ^B1-1 ) which has a basic functional group>
(Polyamine (f ¹ ))
The polyamine (f ¹ ) used in the third step for obtaining the polyvinyl resin (C ^B1-1 ) having a basic functional group of the present invention is a compound having at least two primary and / or secondary amino groups. Yes, it reacts with the isocyanate group of the urethane prepolymer (e ¹ ) to form a urea bond. Examples of such polyamine (f ¹ ) include various diamines.

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-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2- Aliphatic diamines such as dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, and tolylenediamine;
Cycloaliphatic diamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine; and
Examples thereof include aromatic diamines such as phenylenediamine and xylylenediamine. However, it is not limited to these.

Further, as the diamine having two secondary amino groups, known ones can be used, specifically,
N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-di-tert-butylethylenediamine and the like can be mentioned. However, it is not limited to these.

In addition, as the diamine having primary and secondary amino groups, known ones can be used. Specifically,
N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylamino Propylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3- Propanediamine or isopropylaminopropylamine], and N-lauryl-1,3-propanediamine [also known as N-lauryl-1,3-diaminopropane or laurylaminopropylamine]. However, it is not limited to these.

The polyamine (f ¹ ) of the present invention is a compound having at least two primary and / or secondary amino groups, and the polyamine (f ¹ ) has two primary and / or secondary amino groups at both ends, Furthermore, a compound having a secondary and / or tertiary amino group other than both ends may be used. Examples of such compounds include the following, specifically:
Methyliminobispropylamine [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias N, N-bis (3-aminopropyl) laurylamine], iminobispropylamine [alias] N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, and the like. Can do. However, it is not limited to these.

Methyliminobispropylamine and lauryliminobispropylamine having two primary amino groups and one tertiary amino group are preferable because they can easily control the reaction with diisocyanate.

In addition, iminobispropylamine having two primary amino groups and one secondary amino group is an adsorption site and solvent affinity of a polyvinyl resin (C ^B1-1 ) having a basic functional group as a final product. It is preferable from the viewpoint of the balance of the parts.

Furthermore, as the polyamine (f ¹ ) of the present invention, a polymer having two or more primary and / or secondary amino groups may 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, ring-opening polymers of ethyleneimine, polycondensates of ethylene chloride and ethylenediamine, 2- It is preferably selected from ring-opening polymers of oxazolidone (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer.

Examples of the ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group or an ethylenically unsaturated monomer having a secondary amino group include the above-described ethylenically unsaturated monomers. What was illustrated by (m) is mentioned.

Furthermore, a monoamine may be used in combination with the polyamine (f ¹ ) used in the present invention. The monoamine is a monoamine compound having one primary amino group or one secondary amino group in the molecule, and the monoamine is too high in the reaction of the polyisocyanate (d ¹ ) and the polyamine (f ¹ ). 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 a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

As the monoamine, conventionally known monoamines can be used. Specifically, aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-amino Tridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino -2-methylpro , 3-amino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine , 3-lauryloxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n- Propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine 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 Rubenzene, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzyl Examples include piperidine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, and diphenylamine.

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

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

Moreover, 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.

Examples of the diamine having a primary or secondary amino group and a tertiary amino group include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, and N, N. A diamine having a primary amino group and a tertiary amino group, such as 1,2,2-tetramethyl-1,3-propanediamine; 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. In addition, the active hydrogen of the urea bond after the primary amino group and the isocyanate group react with each other has low reactivity, and under the polymerization conditions of the dispersant of the present invention, it does not further react with the isocyanate group and the molecular weight does not increase. .

In the third step for obtaining the polyvinyl resin (C ^B1-1 ) having a basic functional group of the present invention, the urea reaction by the urethane prepolymer (e ¹ ) and the polyamine (f ¹ ) is performed in the following two methods. It is divided roughly into.
(1) A method of preparing a urethane prepolymer (e ¹ ) solution in a flask and dropping polyamine (f ¹ ),
(2) A method in which a solution comprising a polyamine (f ¹ ) and, if necessary, a solvent is charged into a flask, and a urethane prepolymer (e ¹ ) solution is dropped.

The synthesis is carried out with a stable reaction. If there is no problem in the reaction, the method (1) which is easy to operate is preferred. The temperature of the urea reaction of the present invention is preferably 100 ° C. or lower. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a polyvinyl resin (C ^B1-1 ) having a basic functional group having a predetermined molecular weight and structure.

Further, the urethane prepolymer (e ^1), and polyamines (f ^1), mixing ratio of the monoamine to be added if necessary is not particularly limited and is selected arbitrarily according to the application and required performance.

The end point of the reaction is judged from the disappearance of the isocyanate peak by the measurement of isocyanate% due to titration and IR measurement.

The weight average molecular weight (Mw) of the polyvinyl resin (C ^B1-1 ) having a basic functional group of the present invention is preferably 1,000 to 100,000, more preferably 1,500 to 50,000. Particularly preferred is 2,000 to 30,000. Moreover, it is preferable that the amine value of the obtained polymer is 1-100 mgKOH / g, More preferably, it is 2-70 mgKOH / g, More preferably, it is 10-50 mgKOH / g.

<Polyvinyl resin having basic functional group (C ^B1-2 )>
On the other hand, as a method of synthesizing a polyvinyl resin (C ^B1-2 ) having a basic functional group in the present invention, methods including the following first step, second step, third step, and fourth step may be mentioned. It is done.
(First step): A step of obtaining a vinyl polymer (a ² ) having one or two hydroxyl groups at one end by radical polymerization.
(Second Step): a vinyl polymer having one or two hydroxyl groups at one end obtained in the first step the (a ^2), a compound having a group and (meth) acryloyl groups capable of reacting with a hydroxyl group (g ¹⁾ or the like is reacted with the steps of obtaining at one end of the (meth) vinyl polymer having an acryloyl group (a ^3).
(Third step): A vinyl polymer (a ³ ) having a (meth) acryloyl group at one end obtained in the second step and a polyamine (f ² ) are reacted to give a vinyl polymer having an amino group (h ¹ ) obtaining.
(Fourth step): A vinyl polymer (h ¹ ) having an amino group obtained in the third step and a polyisocyanate (d ² ) are reacted to form a polyvinyl resin (C ^{B1- 2} ) obtaining.

<First Step of Polyvinyl Resin (C ^B1-2 ) Having Basic Functional Group>
The first step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group is carried out in the presence of a compound (s ² ) having one or two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of an ethylenically unsaturated monomer (m ¹ ). The thiol group of the compound (s ² ) having one or two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, and the vinyl polymer (a ² ) is synthesized via the S atom. The molecular weight can be easily adjusted by the amount of the compound (s ² ) having one or two hydroxyl groups and one thiol group in the molecule relative to the ethylenically unsaturated monomer (m ¹ ). As a result, the affinity for the solvent can also be suitably adjusted.

As a compound (s ² ) having one or two hydroxyl groups and one thiol group in the molecule, for example, one hydroxyl group and one thiol group are contained in the molecule such as 1-mercaptoethanol and 2-mercaptoethanol. And the compound (s) having two hydroxyl groups and one thiol group in the molecule as described above. In the present invention, the compound (s) having two hydroxyl groups and one thiol group in the molecule is preferable, and 3-mercapto-1,2-propanediol is more preferable.

The ethylenically unsaturated monomer (m ¹ ) used in the first step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group is the aforementioned polyvinyl resin (C ¹ ) having an acidic functional group. The same thing as the ethylenically unsaturated monomer (m) used at the 1st process at the time of synthesize ^| combining ^A2 ) can be used. In addition, other fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate are used. Also good.

The compound (s ² ) having one or two hydroxyl groups and one thiol group is used in a bulk polymerization of 0.8 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (m). Alternatively, solution polymerization is preferably performed. More preferably, it is 1.5-15 weight part, More preferably, it is 2-9 weight part, Especially preferably, it is 5-9 weight part.

As the solvent that can be used in the case of solution polymerization, the same solvents as those exemplified in the synthesis of the polyvinyl resin (C ^A2 ) having an acidic functional group can be used.

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. A polymerization initiator may be used in the polymerization, and the polymerization initiator that can be used is the same as that used in the first step of the polyvinyl resin (C ^A2 ) having an acidic functional group described above. Things.

<Second Step of Polyvinyl Resin (C ^B1-2 ) Having Basic Functional Group>
(Compound having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group (g ¹ ))
As the compound (g ¹ ) having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group, used in the second step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group of the present invention. A compound having an isocyanate group and a (meth) acryloyl group is preferred, and examples thereof include 2- (meth) acryloyloxyethyl isocyanate. Furthermore, in the second step, when a compound having an isocyanate group and a (meth) acryloyl group is used as the compound (g ¹ ) having a group capable of reacting with a hydroxyl group and a (meth) acryloyl group, the urethane prepolymer described above is used. A known catalyst used in the synthesis of the polymer (e ¹ ) can be used.

Furthermore, when polymerizing a compound (g ¹⁾ having a group and (meth) acryloyl groups capable of reacting with hydroxyl group, adding a radical polymerization inhibitor, the reaction is preferably carried out in a stream of dry air. As the radical polymerization inhibitor, known ones can be used without limitation, and examples thereof include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, and phenothiazine. Is preferred. These may be used alone or in combination within a range of 0.01% to 6% by weight, preferably 0.05% to 1.0% by weight, based on 100% by weight of the compound having a (meth) acryloyl group. .

Further, the vinyl polymer having one or two hydroxyl groups at one terminal (a ^2), by reacting a compound having one dibasic acid anhydride group, a vinyl polymer having a carboxyl group at one end Next, a compound having a (meth) acryloyl group and a group capable of reacting with a hydroxyl group with respect to a hydroxyl group obtained by reacting a compound having an epoxy group and a (meth) acryloyl group and then ring opening of the epoxy It can also be obtained by reacting (g ¹ ). In this case, the vinyl polymer (a ³ ) having a (meth) acryloyl group at one end has two (meth) acryloyl groups at one end.

The compound having one dibasic acid anhydride group may be any compound as long as it is a compound having 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, and 4, Examples include 5-epoxypentyl acrylate.

<The 3rd process of polyvinyl resin (C ^B1-2 ) which has a basic functional group>
(Vinyl polymer having an amino group (h ¹ ))
In the third step for obtaining the polyvinyl resin (C ^B1-2 ) having a basic functional group of the present invention, a vinyl polymer having a (meth) acryloyl group at one end obtained in the second step (a ³ ) Of (meth) acryloyl group and the amino group of polyamine (f ² ) are reacted to obtain a vinyl polymer (h ¹ ) having an amino group. This is a reaction in which an amino group is added to a (meth) acryloyl group, and is generally called a Michael addition reaction. By adjusting the blend of the vinyl polymer (a ³ ) having a (meth) acryloyl group at one end and the polyamine (f ² ), a vinyl polymer (h ¹ ) having an amino group capable of reacting with an isocyanate group is obtained. It is done.

The polyamine (f ² ) used in the third step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group is a compound having one primary and / or secondary amino group in the molecule. There are compounds having two or more primary and / or secondary amino groups in the molecule. Examples of the compound having one primary and / or secondary amino group include those exemplified in the monoamine described in the third step for obtaining a polyvinyl resin (C ^B1-1 ) having a basic functional group.

As the compound having two or more primary and / or secondary amino groups, polyamine (f ¹ ) described in the third step for obtaining a polyvinyl resin (C ^B1-1 ) having a basic functional group may be used. What was illustrated is mentioned.

Examples of the reaction in the third step for obtaining the polyvinyl resin (C ^B1-2 ) having a basic functional group of the present invention include the following general formulas (9) to (12).

For example, as shown in the following general formula (9), for one polymer (a ³ ) molecule having one (meth) acryloyl group at one end, one monoamine molecule is used as an example of polyamine (f ² ). When reacted, one molecule of vinyl polymer (h ¹ ) having one primary and / or secondary amino group is obtained.

General formula (9)

X ⁴ is a portion of the vinyl polymer (a ³ ) having a (meth) acryloyl group at one end, excluding the (meth) acryloyloxy group, and X ⁵ is a primary and / or secondary amino group of monoamines. R ⁰ is a hydrogen atom or a methyl group, and R ¹ is a hydrogen atom or an alkyl group.

For example, the polyamine (f ² ) having two primary amino groups per molecule of the polymer (a ³ ) having one (meth) acryloyl group at one end as shown in the following general formula (10) When one molecule is reacted, theoretically, one molecule of vinyl polymer (h ¹ ) having one primary amino group and one secondary amino group is obtained.

General formula (10)

X ⁴ is a portion of the vinyl polymer (a ³ ) having a (meth) acryloyl group at one end, excluding the (meth) acryloyloxy group, and X ⁶ is a polyamine (f ² ) having two primary classes. It is a portion excluding the amino group, and R ⁰ is a hydrogen atom or a methyl group.

For example, as shown in the following general formula (11), one molecule of the polymer (a ³ ) having two (meth) acryloyl groups at one end has one primary amino group and one secondary amino group. When ^two molecules of polyamine (f ² ) are reacted, theoretically, one molecule of vinyl polymer (h ¹ ) having four secondary amino groups is obtained.

Formula (11)

X ⁴ is a portion excluding the (meth) acryloyloxy group in the vinyl polymer (a ³ ) having two (meth) acryloyl groups at one end, and X ⁶ is a polyamine (f ² ) , A portion excluding primary and secondary amino groups, R ⁰ is a hydrogen atom or a methyl group, and R ² represents an alkyl group.

For example, as shown in the following general formula (12), two primary amino groups or two secondary amino groups 2 per molecule n ^{0 of the} vinyl polymer (a ³ ) having two (meth) acryloyl groups at one end. Molecule (n ⁰ +1) molecules of polyamine (f ² ) having one molecule, theoretically, molecule 1 of vinyl polymer (h ¹ ) having two primary amino groups and 2n ⁰ secondary amino groups Or one molecule of vinyl polymer (h ¹ ) having two or two secondary amino groups and 2n ⁰ tertiary amino groups.

Formula (12)

X ⁴ is a portion excluding the (meth) acryloyloxy group in the vinyl polymer (a ³ ) having two (meth) acryloyl groups at one end, and X ⁶ is a polyamine (f ² ) , R ⁰ is a hydrogen atom or a methyl group, R ¹ is a hydrogen atom or an alkyl group, and n ⁰ is a positive integer.

The above general formulas (9) to (12) are the cases where the primary amino group has a higher reactivity than the secondary amino group, and therefore the reaction is preferentially performed. For example, even if the primary amino group remains, the secondary amino group may react first. Therefore, in some cases, a vinyl polymer (h ¹ ) having an amino group having a structure different from that expected may be obtained. However, since the above addition reaction proceeds almost quantitatively, most of the purpose is the purpose. A vinyl polymer (h ¹ ) having an amino group having a structure as described above is obtained, and there is no problem in the subsequent reaction and the function as a dispersant.

Michael addition for obtaining a vinyl polymer (h ¹ ) having an amino group from a vinyl polymer (a ³ ) having one or two (meth) acryloyl groups at one end and a polyamine (f ² ) The reaction is roughly divided into the following two methods.
(1) A method of reacting by charging the whole amount,
(2) A method in which a solution comprising polyamine (f ² ) and, if necessary, a solvent is charged into a flask, and a vinyl polymer (a ³ ) solution having a (meth) acryloyl group at one end is dropped.
The synthesis is carried out with a stable reaction, but if there is no problem in the reaction, the method (2) that allows easy reaction control (molecular design control) is preferred.

The temperature of the Michael addition reaction of the present invention 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. If the temperature is higher than 70 ° C., it is difficult to control the reaction rate.

Moreover, the compounding ratio of the vinyl polymer (a ³ ) having a (meth) acryloyl group at one end and the polyamine (f ² ) is not particularly limited, and is arbitrarily selected depending on the use and required performance. The end point of the reaction is judged by measuring the amine% due to titration.

<Fourth Step of Polyvinyl Resin (C ^B1-2 ) Having Basic Functional Group>
The fourth step for obtaining a polyvinyl-based resin (C ^B1-2 ) having a basic functional group is a primary or secondary amino group of a vinyl polymer (h ¹ ) having an amino group and two or more isocyanates. It is obtained by reacting an isocyanate group of a polyisocyanate (d ² ) having a group. The primary or secondary amino group of the vinyl polymer (h ¹ ) having an amino group partially or entirely forms a urea bond by adjusting the amount of the polyisocyanate (d ² ) to be reacted, Present as an amino group in the dispersant.

Moreover, when the vinyl polymer (h ¹ ) 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 is dispersed as it is. Remains in the agent.

In the fourth step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group, the polyisocyanate (d ² ) used is a polyvinyl resin (C ^B1-1 ) having a basic functional group. The same polyisocyanate (d ¹ ) used in the second step for obtaining the above can be used.

Examples of the reaction in the fourth step for obtaining the polyvinyl resin (C ^B1-2 ) having a basic functional group of the present invention include the following general formulas (13) to (15).

For example, as shown in the following general formula (13), one molecule of polyisocyanate (d ² ) is reacted with two molecules of vinyl polymer (h ¹ ) having one primary and / or secondary amino group. In this case, theoretically, the primary and / or secondary amino group reacts with the isocyanate group to obtain a polyvinyl resin (C ^B1-2 ) having a urea bond.

Formula (13)

X ⁴ is a precursor of a vinyl polymer (h ¹ ) having one primary and / or secondary amino group, and among the vinyl polymers (a ³ ) having a (meth) acryloyl group at one end, ( It is a portion excluding the (meth) acryloyloxy group. X ⁵ is a portion of the monoamine, which is a precursor of the vinyl polymer (h ¹ ) having one primary and / or secondary amino group, excluding the primary and / or secondary amino group. X ⁷ is a portion of the polyisocyanate (d ² ) excluding the isocyanate group. R ⁰ is a hydrogen atom or a methyl group.

For example, as shown in the following general formula (14), one molecule of polyisocyanate (d2) is reacted with two molecules of vinyl polymer (h ¹ ) having one primary amino group and one secondary amino group. In this case, theoretically, the primary amino group reacts with the isocyanate group to form a urea bond, and a polyvinyl resin (C ^B1-2 ) having two secondary amino groups and two urea bonds is obtained.

General formula (14)

X ⁴ is a vinyl polymer (a ³ ) having a (meth) acryloyl group at one end, which is a precursor of a vinyl polymer (h ¹ ) having one primary amino group and one secondary amino group, This is a portion excluding the (meth) acryloyloxy group. X ⁶ is a precursor of a vinyl polymer (h ¹ ) having one primary amino group and one secondary amino group, and the primary amino group is excluded from the polyamine (f ² ) having two primary amino groups. Part. X ⁷ is a portion of the polyisocyanate (d ² ) excluding the isocyanate group. R ⁰ is a hydrogen atom or a methyl group.

For example, as in the following general formula (15), a vinyl polymer (h ¹ ) having two primary amino groups and 2n ⁰ secondary amino groups, or two secondary amino groups and 2n ⁰ tertiary amino groups to vinyl polymer or molecule n ¹ +1 single (h ¹⁾ having, when reacted with ^one molecule n of the polyisocyanate (d ^2), and theoretically, primary or secondary amino group by the reaction with isocyanate groups to form a urea bond, a primary amino group two and secondary amino groups ^{2n 0 n} 1 + ²ⁿ 0 or a polyvinyl resin with ^one urea bond 2n ^{(C B1-2)} or a two A polyvinyl resin (C ^B1-2 ) having two secondary amino groups, 2 tertiary amino groups 2n ⁰ n ¹ + 2n ⁰ and ¹ urea bond 2n is obtained.

General formula (15)

X ⁴ is a vinyl polymer (h ¹ ) having two primary amino groups and 2n ⁰ secondary amino groups, or a vinyl polymer (h ¹ ) having two secondary amino groups and 2n ⁰ tertiary amino groups. It is a portion excluding the (meth) acryloyloxy group in the vinyl polymer (a ³ ) having two (meth) acryloyl groups at one end, which is any precursor. X ⁶ is a vinyl polymer (h ¹ ) having two primary amino groups and 2n ⁰ secondary amino groups, or a vinyl polymer (h ¹ ) having two secondary amino groups and 2n ⁰ tertiary amino groups. It is a part of the polyamine (f ² ) having two primary amino groups or two secondary amino groups, which is any precursor, excluding the amino group. X ⁷ is a portion of the polyisocyanate (d ² ) excluding the isocyanate group. X ⁸ is a vinyl polymer (h ¹ ) having two primary amino groups and 2n ⁰ secondary amino groups, or a vinyl polymer (h ¹ ) having two secondary amino groups and 2n ⁰ tertiary amino groups. It is the part except the site | part which has an amino group among any. R ¹ is a hydrogen atom or an alkyl group. n ⁰ and n ¹ are each independently a positive integer.

Theoretically, in the above three examples, the primary amino group has a higher reactivity than the secondary amino group, so that the primary amino group always reacts preferentially. Even if it remains, the secondary amino group may react first. Therefore, in some cases, a polyvinyl resin (C ^B1-2 ) having a structure different from that expected may be obtained. However, since the reaction proceeds almost quantitatively, most of the structure is the target structure. Thus, a polyvinyl resin (C ^B1-2 ) having a basic functional group is obtained, and there is no problem in the function as a dispersant.

The reaction of an amino group-containing vinyl polymer (h ¹ ) and polyisocyanate (d ² ) is roughly classified into the following two methods.
(1) When reacting with the entire amount charged.
(2) A method in which a vinyl polymer (h ¹ ) solution having an amino group is charged into a flask and polyisocyanate (d ² ) is dropped.
(2) is preferable when the reaction is precise.

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

The compounding ratio of equivalents of vinyl polymer having an amino group (h ¹⁾ for the polyisocyanate (d ²⁾ is an amino group (primary and secondary amino groups) equivalent of the vinyl polymer having an amino group (h ¹⁾ Assuming that the isocyanate group equivalent of γ ^B1 and polyisocyanate (d ² ) is δ ^B1 , δ ^B1 / γ ^B1 is 0.25 to 1.00, and it is preferable to react all of the isocyanate groups with amino groups. .35 to 0.9 is more preferable, and 0.5 to 0.8 is most preferable.

When the said compounding equivalent ratio is smaller than 0.25, the quantity of the urea bond in the polyvinyl-type resin (C ^B1-2 ) which is a final product will decrease, and dispersibility may worsen. On the other hand, if the blending equivalent ratio is larger than 1.00, an isocyanate group having a high reaction activity remains, which reacts with water and the like, resulting in a high molecular weight and a high viscosity, which is not preferable. When the blending equivalent is 1.00, for example, in the reaction of a vinyl polymer having two amino groups (h ¹ ) and a polyisocyanate having two isocyanate groups (d ² ), theoretically, Since molecular weight becomes infinite, molecular weight control may be difficult.

Furthermore, it is preferable that a primary amino group and / or a secondary amino group be present in the dispersant skeleton in addition to the tertiary amino group and the urea bond, since the balance between the adsorptivity and the solvent affinity site is improved. Thus, by changing the reaction ratio between the vinyl polymer (h ¹ ) having an amino group and the polyisocyanate (d ² ), the molecular weight of the polyvinyl resin (C ^B1-2 ) and the amino group (primary, secondary) And / or tertiary) and the amount of urea linkages can be adjusted.

The weight average molecular weight (Mw) of the polyvinyl resin (C ^B1-2 ) having a basic functional group of the present invention is preferably 1,000 to 100,000, more preferably 1,500 to 50,000. Particularly preferred is 2,000 to 30,000. Moreover, it is preferable that the amine value of the obtained polymer is 1-100 mgKOH / g, More preferably, it is 2-70 mgKOH / g, More preferably, it is 10-50 mgKOH / g.

<Polyester-based resin having basic functional group (C ^B2 )>
Examples of the method for synthesizing the polyester-based resin (C ^B2 ) having a basic functional group in the present invention include a method through the following first step, second step, and third step.
(First step): Ring-opening polymerization of lactone and / or lactide using a monoalcohol having a (meth) acryloyl group as an initiator to obtain an ester polymer (c ² ) having a (meth) acryloyl group at one end Process.
(Second step): The ester polymer (c ² ) having a (meth) acryloyl group at one end obtained in the first step and the polyamine (f ³ ) are reacted to form an ester polymer having an amino group (h ² ) obtaining.
(Third step): A polyester-based resin (C ^B2 ) having a basic functional group obtained by reacting the ester polymer (h ² ) having an amino group obtained in the third step with polyisocyanate (d ³ ). Obtaining.

<First step of polyester-based resin (C ^B2 ) having basic functional group>
(Monoalcohol having (meth) acryloyl group)
In the first step for obtaining a polyester resin having a basic functional group of the present invention, the monoalcohol having a (meth) acryloyl group used as an initiator is not particularly limited. Hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, and the like are mentioned, from the viewpoint of hydroxyl reactivity, 4- It is preferable to use one or more selected from the group consisting of hydroxybutyl acrylate and 2-hydroxyethyl acrylate.

(Lactone and / or lactide)
On the other hand, the lactone and / or lactide is not particularly limited. As the lactone, for example, the same lactone as that used for obtaining a polyester resin (C ^A3 ) having an acidic functional group can be used.

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

General formula (16)

R ² and R ³ are each independently a hydrogen atom or a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms, and R ⁴ and R ⁵ are each independently , A hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched alkyl group having 1 to 9 carbon atoms.

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

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

The number of moles of lactone and / or lactide polymerized per mole of monoalcohol having a (meth) acryloyl group as an initiator is preferably in the range of 3 to 60 moles, more preferably 10 to 40 moles, most preferably 15 to 30 moles.

A well-known thing can be used for the polymerization catalyst in the said ring-opening polymerization. For example, the thing similar to the polymerization catalyst used in order to obtain the polyester-type resin (C ^A3 ) which has an acidic functional group can be used.

The lactone and / or lactide ring-opening polymerization temperature is 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. If the reaction temperature is less than 100 ° C, the reaction rate may be very slow. If the reaction temperature exceeds 220 ° C, side reactions other than the addition reaction of lactone and / or lactide, for example, depolymerization of lactone adducts to lactone monomers, cyclic lactones In some cases, dimer or trimer formation is likely to occur.

(Radical polymerization inhibitor)
When polymerizing a monoalcohol having a (meth) acryloyl group as an initiator, it is preferable to add a radical polymerization inhibitor and carry out the reaction under a dry air flow. Known radical polymerization inhibitors can be used. For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, and phenothiazine are preferable. These may be used alone or in combination within a range of 0.01% to 6% by weight, preferably 0.05% to 1.0% by weight, based on 100% by weight of the alcohol having a (meth) acryloyl group. .

In the present invention, the first step mentioned as an example of the method for synthesizing the polyester-based resin (C ^B2 ) having a basic functional group may be, for example, the following three steps.

(1) An ester polymer 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 A method of reacting a compound having a group.
(2) A compound having one dibasic acid anhydride group in an ester polymer 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 To obtain an ester polymer having a carboxyl group at one end, then reacting a compound having an epoxy group and a (meth) acryloyl group, and further, with respect to the hydroxyl group obtained by ring opening of the epoxy, A method of reacting a group capable of reacting with a hydroxyl group and a compound having a (meth) acryloyl group.
(3) An ester polymer 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, and then an epoxy group and (meth) A method of reacting a compound having an acryloyl group and further reacting a compound having a (meth) acryloyl group and a group capable of reacting with the hydroxyl group with respect to a hydroxyl group obtained by ring opening of an epoxy group.

In the case of (2) and (3), the ester polymer (c ² ) having a (meth) acryloyl group at one end has two (meth) acryloyl groups at one end.

(Monoalcohol without (meth) acryloyl group)
As the monoalcohol having no (meth) acryloyl group, any compound may be used as long as it is a compound having one hydroxyl group.

For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1- Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol , Aliphatic monoalcohols such as 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, and oleyl alcohol;
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, Ethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol Mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, Tripropylene glycol monomer Ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl Ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl A And alkylene glycol monoalkyl ethers such as tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

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 examples thereof include 2- (meth) acryloyloxyethyl isocyanate.

There is no restriction ^| limiting in particular as a compound which has one dibasic acid anhydride group, The thing similar to what was illustrated at the 2nd process for obtaining the polyvinyl-type resin (C ^B1-2 ) which has a basic functional group is used. Can be used.

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

(Monocarboxylic acid without (meth) acryloyl group)
Examples of monocarboxylic acids having no (meth) acryloyl group 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.

<Second Step of Polyester Resin (C ^B2 ) Having Basic Functional Group>
(Ester polymer having an amino group (h ² ))
The second step for obtaining a polyester-based resin (C ^B2 ) having a basic functional group of the present invention is an ester polymer (c ² ) having a (meth) acryloyl group at one end obtained in the first step. The (meth) acryloyl group and the amino group of the polyamine (f ³ ) are reacted to obtain an ester polymer (h ² ) having an amino group. This is a reaction in which an amino group is added to a (meth) acryloyl group, and is generally called a Michael addition reaction. By adjusting the blend of the ester polymer (c ² ) having a (meth) acryloyl group at one end and the polyamine (f ³ ), an ester polymer (h ² ) having an amino group capable of reacting with an isocyanate group is obtained. It is done.

The polyamine (f ³ ) used in the second step for obtaining a polyester-based resin (C ^B2 ) having a basic functional group is a compound having one or more primary and / or secondary amino groups in the molecule. ^Yes , the same polyamine (f ² ) used in the third step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group can be used.

The Michael addition reaction in the second step for obtaining the polyester-based resin (C ^B2 ) having a basic functional group of the present invention is the third for obtaining a polyvinyl-based resin (C ^B1-2 ) having a basic functional group. The reaction is the same as in the process. Therefore, for example, reactions such as the above general formulas (9) to (12) can be mentioned.

In the above general formulas (9) to (12), a vinyl polymer (a ³ ) having a (meth) acryloyl group at one end and an ester polymer (c ² ) having a (meth) acryloyl group at one end. When the polyamine (f ² ) is changed to the polyamine (f ³ ), an ester polymer (h ² ) having an amino group can be obtained instead of the vinyl polymer (h ¹ ) having an amino group.

Regarding the reaction method, reaction conditions, and end point determination in the second step for obtaining a polyester-based resin (C ^B2 ) having a basic functional group, a polyvinyl-based resin (C ^B1-2 ) having a basic functional group is also used. It can carry out similarly to the 3rd process for obtaining.

<Third step of polyester resin (C ^B2 ) having basic functional group>
The third step for obtaining a polyester-based resin (C ^B2 ) having a basic functional group includes a primary or secondary amino group of the ester polymer (h ² ) having an amino group obtained in the second step; It is obtained by reacting an isocyanate group of a polyisocyanate (d ³ ) having two or more isocyanate groups. The primary or secondary amino group of the ester polymer (h ² ) having an amino group partially or entirely forms a urea bond by adjusting the amount of the polyisocyanate (d ³ ) to be reacted, and the rest Present as an amino group in the dispersant.

The polyisocyanate (d ³ ) used in the third step for obtaining a polyester-based resin (C ^B2 ) having a basic functional group is a compound having two or more isocyanate groups in the molecule. it can be the same as the polyisocyanate used in the fourth step to obtain a polyvinyl resin (C ^B1-2) having a group (d ^2).

The reaction between the amino group and the isocyanate group in the third step for obtaining the polyester-based resin (C ^B2 ) having a basic functional group of the present invention is performed by using a polyvinyl resin (C ^B1-2 ) having a basic functional group. It is the same reaction as the fourth step for obtaining. Therefore, for example, reactions such as the above general formulas (13) to (15) can be mentioned.

In the above general formulas (13) to (15), the vinyl polymer (h ¹ ) having an amino group is changed to the ester polymer (h ² ) having an amino group, and the polyisocyanate (d ² ) is changed to a polyisocyanate (d If each is changed to ³ ), a polyester resin (C ^B2 ) having a basic functional group is obtained instead of the polyvinyl resin (C ^B1-2 ) having a basic functional group.

Method of reaction in the third step for obtaining a polyester resin (C ^B2 ) having a basic functional group, reaction conditions, and blending ratio of polyisocyanate (d ³ ) to ester polymer (h ² ) having an amino group Can be carried out in the same manner as in the fourth step for obtaining a polyvinyl resin (C ^B1-2 ) having a basic functional group.

Further, the polyester resin (C ^B2 ) having a basic functional group preferably has a weight average molecular weight (Mw) of 1,000 to 100,000, more preferably 1,500 to 50,000, particularly preferably. Is 2,000 to 30,000. Moreover, it is preferable that the amine value of the obtained polymer is 1-100 mgKOH / g, More preferably, it is 2-70 mgKOH / g, More preferably, it is 10-50 mgKOH / g.

The resin having a basic functional group is not limited to the above-mentioned C ^B1 and C ^B2 , but other polyvinyl-based, polyurethane-based, polyester-based, polyether-based, formalin condensate, silicone-based, and These composite polymers are exemplified. Furthermore, two or more kinds of resins having these basic functional groups can be used in combination.

<Resin having other basic functional groups (C ^B3 )>
Although it does not specifically limit as resin (C ^B3 ) which has a commercially available basic functional group, For example, the following are mentioned .

The resin having a Ajinomoto Fine-Techno Co. of the basic functional group include AJISPER PB82 1 or the like.

<Nonionic resin>
Examples of the nonionic resin in the present invention include the following three types of C ^{C1 to} C ^C3 . From the viewpoint of dispersibility, C ^C2 and C ^C3 are preferable.
(1) Polyvinyl alcohol resin (C ^C1 )
(2) Polyvinyl acetal resin (C ^C2 )
(3) Polyvinylamide resin (C ^C3 )

<Polyvinyl alcohol resin (C ^C1 )>
There is no restriction | limiting in particular about the manufacturing method of the polyvinyl alcohol resin ( ^CC1 ) used for this invention, The polyvinyl alcohol resin synthesize | combined by the well-known method and a commercially available thing can also be used.

Examples of the method for producing the polyvinyl alcohol resin (C ^C1 ) used in the present invention include a method for saponifying a polyvinyl ester obtained by polymerizing a vinyl ester. Examples of vinyl esters include, for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate and the like.
Alternatively, polyvinyl alcohol can also be obtained by decomposing these homopolymers or copolymers using vinyl ethers such as t-butyl vinyl ether, trimethylsilyl vinyl ether, and benzyl vinyl ether.

Further, it may be a modified polyvinyl alcohol resin obtained by copolymerizing other monomers when polymerizing polyvinyl ester or polyvinyl ether. Examples of other monomers include olefins such as ethylene, propylene, 1-butene and isobutene;
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) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, (meth) acrylamidopropyldimethylamine or a salt thereof, N- (Meth) acrylamides such as methylol (meth) acrylamide;
N-vinylamides such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone;
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether;
Nitriles such as (meth) acrylonitrile; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated carboxylic acids such as maleic acid and itaconic acid Examples thereof include acids and unsaturated carboxylic acid esters which are esters thereof; vinylsilyl compounds such as vinyltrimethoxysilane; and the like.
In the modified polyvinyl alcohol resin, the amount of modification with other monomers is preferably 20 mol% or less, more preferably 10 mol% or less among all monomers constituting the modified polyvinyl alcohol resin.

Examples of the saponification catalyst used when saponifying the polyvinyl ester to obtain the polyvinyl alcohol resin (C ^C1 ) include alkali catalysts and acid catalysts, and conventionally known ones can be used. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, ammonia, sodium methylate and the like. Examples of the acid catalyst include sulfuric acid, hydrochloric acid, P-toluenesulfonic acid and the like. The degree of saponification of the polyvinyl alcohol resin (C ^C1 ) is preferably 70 mol% or more, and more preferably 80 mol% or more.

Although it does not restrict | limit especially as a commercially available polyvinyl alcohol resin ( ^CC1 ), For example, the following are mentioned. These may be used alone or in combination.

Examples of the polyvinyl alcohol resin manufactured by Nippon Synthetic Chemical Co., Ltd. include Gohsenol NH-26, NH-18, NM-14, AH-17, A-300, GM-14L, GL-05, and KL-05.

Examples of polyvinyl alcohol resins manufactured by Denki Kagaku Kogyo include Denkapoval K-05, K-17C, K-24E, H-12, B-05, and B-17.

Examples of the polyvinyl alcohol resin manufactured by Kuraray include POVAL PVA-103, 105, 117, 205, 217, 405 and 420.

<Polyvinyl acetal resin (C ^C2 )>
There is no restriction | limiting in particular about the manufacturing method of the polyvinyl acetal resin ( ^CC2 ) used for this invention, The polyvinyl acetal resin synthesize | combined by the well-known method and a commercially available thing can also be used.

Examples of the method for producing the polyvinyl acetal resin (C ^C2 ) used in the present invention include a method of reacting the polyvinyl alcohol resin with an aldehyde to acetalize. Examples of aldehydes used for the acetalization include acetaldehyde, n-butyraldehyde, propionaldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-heptylaldehyde, and n-octylaldehyde. Aliphatic aldehydes such as n-nonylaldehyde and n-decylaldehyde;
Aromatic aldehydes such as benzaldehyde and cinnamaldehyde are exemplified. These aldehydes may be used alone or in combination of two or more. In particular, n-butyraldehyde which is excellent in acetalization reaction is preferable.

It does not specifically limit as an acid catalyst used for acetalization, Any of an organic acid and an inorganic acid may be used, for example, an acetic acid, paratoluenesulfonic acid, nitric acid, a sulfuric acid, hydrochloric acid etc. are mentioned. Of these, hydrochloric acid is preferred.

The degree of acetalization of the polyvinyl acetal resin (C ^C2 ) obtained by the method of the present invention is preferably 40 to 80 mol%, more preferably 50 to 80 mol%. Further, the residual amount of vinyl ester units is preferably 0.1 to 20 mol%, and the residual amount of vinyl alcohol units is preferably 10 to 45 mol%. The acetalization degree, the remaining vinyl ester units, and the remaining amount of vinyl alcohol units are in proportion to the total vinyl monomer units.

Although it does not restrict | limit especially as a commercially available polyvinyl acetal resin ( ^CC2 ), For example, the following are mentioned. These may be used alone or in combination.

As the polyvinyl acetal resin manufactured by Sekisui Chemical Co., Ltd., ESREC BL-1, BL-10, BM-1, BM-S, BH-3, BH-S, BX-L, BX-1, KS-10, and KS-5 etc. are mentioned.

Examples of the polyvinyl acetal resin manufactured by Denki Kagaku Kogyo include Denkabutyral # 3000-1, # 3000-K, and # 4000-2.

Examples of the polyvinyl acetal resin manufactured by Kuraray include MOWITAL B16H, B20H, B30T, B30H, B30HH, B45M, and B60T.

<Polyvinylamide resin (C ^C3 )>
In the present invention, the polyvinylamide resin (C ^C3 ) is not particularly limited. For example, polyvinylacetamide, polyacrylamide, polyvinylpyrrolidone, alkylated polyvinylpyrrolidone, polyvinylpyrrolidone graft copolymer, and vinylpyrrolidone and ethylene And a copolymer with a polymerizable unsaturated monomer.

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

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

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

Although it does not restrict | limit especially as a commercially available polyvinylpyrrolidone resin, For example, the following are mentioned. These may be used alone or in combination.

Examples of polyvinylpyrrolidone manufactured by BASF include Luvitec K-17, K-30, and K-90.

Examples of polyvinylpyrrolidone manufactured by ISP Japan include K-15, K-30, and K-120.

Examples of polyvinyl pyrrolidone manufactured by Nippon Shokubai include K-30, K-85 and K-90.

<Silane coupling agent (D)>
Next, the silane coupling agent (D) in this invention is demonstrated. The silane coupling agent (D) used in the present invention is represented by the following general formula (17).

Formula (17)

Y ¹ is —CH ₃ , —C ₂ H ₅ , — (CH ₂ ) ₂ CH ₃ , —CH (CH ₃ ) CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CH ₂ CH (CH ₃ ) _2. , — (CH ₂ ) ₆ CH ₃ , — (CH ₂ ) ₇ CH ₃ , — (CH ₂ ) ₉ CH ₃ , —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , — (CH ₂ ) _{2 CF 3, -CH = CH 2,} -CH 2 CH = CH 2, -C 6 H 5, -C 6 H 4 -CH = CH 2, -C 3 H 6 COOC (CH 3) = CH 2, -C _{3 H 6 COOCH = CH 2,} -C 3 H 6 NH 2, -C 3 H 6 NHC 2 H 4 NH 2, -C 3 H 6 NHC 6 H 5, -C 3 H 6 N = C (CH 3) _{C 4 H 9, -C 3 H} 6 NHC 2 H 4 NH 2 CH-C 6 H 4 -CH = CH 2, -C 3 H _{6 SH, -C 3 H 6 NCO} , -C 3 H 6 NHCONH 2, -C 3 H 6 NHCOOC 2 H 5, -C 3 H 6 NHCH 2 CH = CH 2, -C 3 H 6 NHC 2 H 4 NHCH ₂ CH═CH ₂ , —C ₃ H ₆ NHC ₂ H ₄ NHCH ₂ COOH, —C ₃ H ₆ NHCOCH═CHCOOH, —C ₃ H ₆ S (CH ₂ ) ₂ COOH, and the following formulas (18) to ( The substituent shown in any of 22) is represented.

General formula (18)

General formula (19)

General formula (20)

Formula (21)

General formula (22)

X ^{9 to} X ²⁰ in the general formulas (17) to (20) are each independently —Cl, —CH ₃ , —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , or —OC ₂ H ₅ OCH. ₃ is represented.

Among these, in the present invention, a silane coupling having a reactive functional group is preferable, and examples of the reactive functional group include an amino group, an epoxy group, a mercapto group, an isocyanate group, a vinyl group, an acryloyl group, and a (meth) acryloyl group. Ureido groups, carboxyl groups, and the like, preferably amino groups, epoxy groups, mercapto groups, isocyanate groups, and functional groups represented by general formulas (18) to (20).

As specific structures, Y ¹ in the general formula (17) is —OCH ₃ , —OC ₂ H ₅ , —CH═CH ₂ , —CH ₂ CH═CH ₂ , —C ₆ H ₄ —CH. _{= CH 2, -C 3 H 6} COOC (CH 3) = CH 2, -C 3 H 6 COOCH = CH 2, -C 3 H 6 NH 2, -C 3 H 6 NHC 2 H 4 NH 2, -C _{3 H 6 NHC 6 H 5,} -C 3 H 6 NHC 2 H 4 NH 2 CH-C 6 H 4 -CH = CH 2, -C 3 H 6 SH, -C 3 H 6 NCO, -C 3 H 6 _{NHCONH 2, -C 3 H 6 NHCH} 2 CH = CH 2, -C 3 H 6 NHC 2 H 4 NHCH 2 CH = CH 2, -C 3 H 6 NHC 2 H 4 NHCH 2 COOH, -C 3 H 6 NHCOCH = _CHCOOH, -C _{3 H} 6 S CH ₂₎ a ₂ COOH, and the general formula (18) to (22).

Furthermore, it is more preferable that X ^{9 to} X ²⁰ in the general formulas (17) to (20) are each independently any of —CH ₃ , —OCH ₃ , and —OC ₂ H ₅ .

Next, the active material (A) and the conductive additive (B) used in the present invention will be described. As described above, the composition for forming a lithium ion secondary battery electrode of the present invention can be used in any application, a composite ink for forming a composite layer and a composition for forming a base layer for forming a base layer.

<Active material (A)>
The positive electrode active material for the lithium ion secondary battery is not particularly limited, but metal oxides capable of doping or intercalating lithium ions, metal compounds such as metal sulfides, and conductive polymers are used. be able to.
Examples thereof include transition metal oxides such as Fe, Co, Ni, and Mn, composite oxides with lithium, and inorganic compounds such as transition metal sulfides. Specifically, transition metal oxide powders such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , layered structure lithium nickelate, lithium cobaltate, lithium manganate, spinel structure lithium manganate, etc. Examples thereof include composite oxide powders of lithium and transition metals, lithium iron phosphate materials that are phosphate compounds having an olivine structure, transition metal sulfide powders such as TiS ₂ and FeS, and the like.
In addition, conductive polymers such as polyaniline, polyacetylene, polypyrrole, and polythiophene can also be used. Moreover, you may mix and use said inorganic compound and organic compound.

The negative electrode active material for the lithium ion secondary battery is not particularly limited as long as it can be doped or intercalated with lithium ions. For example, metal Li, alloys thereof such as tin alloys, silicon alloys, lead alloys, etc., Li _X Fe ₂ O ₃ , Li _X Fe ₃ O ₄ , Li _X WO ₂ , lithium titanate, lithium vanadate, silicon Metal oxides such as lithium oxide, conductive polymers such as polyacetylene and poly-p-phenylene, amorphous carbonaceous materials such as soft carbon and hard carbon, artificial graphite such as highly graphitized carbon materials, or natural Examples thereof include carbonaceous powders such as graphite, carbon black, mesophase carbon black, resin-fired carbon materials, air-growth carbon fibers, and carbon fibers. These negative electrode active materials can be used alone or in combination.

  The size of these active materials (A) is preferably in the range of 0.05 to 100 μm, and more preferably in the range of 0.1 to 50 μm. And it is preferable that the dispersed particle diameter of the active material (A) in compound-material ink is 0.5-20 micrometers. 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.).

<Conductive aid (B)>
Next, the carbon material (B) which is a conductive support agent will be described.
The carbon material (B), which is a conductive aid in the present invention, 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 and the like 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. Ordinarily oxidized carbon black, hollow carbon and the like can also be used.

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

As the specific surface area of the carbon black used increases, the 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, and carbon black of more than 1500 m ² / g may be difficult to obtain from commercially available materials. is there.

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

It is desirable that the dispersed particle size in the composite ink of the carbon material (B), which is a conductive additive, be 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 size of the carbon material as the conductive auxiliary agent exceeding 2 μm is used, there may be problems such as variations in the material distribution of the composite coating film and variations in the resistance distribution of the electrodes. .
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 (Tokai Carbon Co., Furnace Black), Printex L and the like (Degussa Co., Furnace Black), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, etc., Conductex SC ULTRA, Conductex 975 ULTRA, etc., PUER BLACK100, 115, 205, etc. (manufactured by Colombian, Furnace Black), # 2350, # 2400B, # 2600B, # 30050B, # 3030B, # 3030B, # 3030B 3350B, # 3400B, # 5400B, etc. (Mitsubishi Chemical Corporation, furnace black), MONARCH1400, 1300, 900, VulcanXC-7 2R, BlackPearls2000, etc. (Cabot, Furnace Black), Ensaco 250G, Ensaco 260G, Ensaco 350G, 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. They may be used in combination of two or more.

  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.

Examples of the liquid medium that may be used in the battery composition of the present invention (hereinafter sometimes referred to as a solvent or a solvent in the present specification) include alcohols, glycols, cellosolves, amino alcohols, amines, and the like. , Ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, phosphoric acid esters, ethers and nitriles.

Among these, it is preferable to use a polar solvent having a relative dielectric constant of 15 or more. 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 (3 .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), and the like, but are not limited thereto.

  In particular, the use of 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 is excellent in dispersibility of the active material and the conductive assistant. It is preferable.

  The solvent is selected in view of reactivity with the active material, solubility in the binder resin, and the like. It is preferable to select a solvent having high dispersibility, low reactivity with the active material, and high solubility of the binder resin.

  Furthermore, from the viewpoint of reducing environmental burdens and economic advantages, when recovering and reusing the solvent discharged in the electrode manufacturing process, it is preferable to use a single solvent instead of a mixed solvent.

  As the solvent satisfying the relative permittivity, the reactivity with the active material, and the solubility of the binder resin and having versatility in a single use, an amide solvent is preferable, and in particular, N, N-dimethylformamide, It is preferable to use an amide aprotic non-aqueous solvent such as N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide.

<Composite ink>
A description will be given of a composite ink essentially comprising an active material, which is one of the preferred embodiments of the composition for forming a lithium ion secondary battery electrode of the present invention. There exist positive mix ink or negative mix ink as compound ink, and as already demonstrated, there are various modes as shown in the following (1) to (4), respectively.
(1) A composite ink containing an active material (A), a resin-type dispersant (C), a silane coupling agent (D), and a liquid medium.
(2) A composite ink further containing a conductive additive (B) in (1).
(3) A composite ink further containing a binder in (1).
(4) The composite ink further containing the conductive additive (B) and a binder in (1).

  The composite ink of the present invention can further contain a binder. The binder in the present invention is used for binding particles such as an active material and a conductive auxiliary agent, and the effect of dispersing the particles in a solvent is small.

Examples of the binder used in the electrode forming composition of the present invention include ethylene, propylene, vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylonitrile, styrene, and the like. Polymer or copolymer containing as a structural unit: polyurethane resin, polyester resin, phenol resin, epoxy resin, phenoxy resin, urea resin, melamine resin, alkyd resin, acrylic resin, formaldehyde resin, silicone resin, fluorine resin; carboxymethylcellulose Such cellulose resins; rubbers such as styrene-butadiene rubber and fluororubber; and conductive resins such as polyaniline and polyacetylene. Moreover, the modified body and mixture of these resin, and a copolymer may be sufficient. These binders may be used alone or in combination of two or more. In particular, it is preferable to use a polymer compound containing a fluorine atom in the molecule, for example, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene, etc. from the viewpoint of resistance.

In the composite ink of the present invention, these binders can be used alone or in combination of two or more for the purpose of controlling the viscosity of the composite ink or assisting the formation of a film of the composite layer.

  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.

Although it depends on the coating method, the viscosity of the composite ink is preferably 100 mPa · s or more and 30,000 mPa · s or less in the range of 30 to 90% by weight of the solid content.
It is preferable that the active material (A) is contained as much as possible within the viscosity range that can be applied. For example, the proportion of the active material (A) in the solid ink solid content is 80 wt% or more and 99 wt% or less. Is preferred.

When the composite ink of this invention contains a conductive support agent (B), it is preferable that the ratio of the conductive support agent (B) to solid composite ink solid content is 0.1 to 15 weight%.

  In the present invention, the proportion of the resin-type dispersant (C) in the composite ink is 0.1 to 15% by weight with respect to the total weight of the active material (A) and the conductive additive (B). Preferably there is. More preferably, it is 0.1 to 10 weight%, More preferably, it is 0.1 to 5 weight%.

  In the present invention, the proportion of the silane coupling agent (D) in the composite ink is 0.001 to 5.0 weight with respect to the total weight of the active material (A) and the conductive auxiliary agent (B). % Is preferred. More preferably, it is 0.003-1.0 weight%, More preferably, it is 0.005-0.10 weight%.

  Moreover, when the compound ink of this invention contains a binder, it is preferable that the ratio of the binder to the compound ink solid content is 0.1 to 15 weight%. More preferably, it is 1 to 8% by weight.

  Such a composite ink can be obtained by various methods. Regarding the method for producing the composite ink of the present invention, the active material (A), the conductive auxiliary agent (B), the resin-type dispersant (C), the silane coupling agent (D) and the liquid which are (4) described above. A composite ink containing a medium will be described as an example. For example,

(4-1) An active material dispersion containing an active material (A), a resin-type dispersant (C), and a liquid medium is obtained, and a conductive additive (B) and a silane coupling agent (D) are added to the dispersion. A binder ink can be added to obtain a composite ink.
You may add a conductive support agent (B), a silane coupling agent (D), and a binder in any order. Further, two or more materials may be mixed in advance and then added to the active material dispersion.

(4-2) Conductive auxiliary agent dispersion containing conductive additive (B), resin-type dispersant (C) and liquid medium is obtained, and active material (A) and silane coupling agent (D) are obtained in the dispersion. A binder ink can be added to obtain a composite ink.
The active material (A), the silane coupling agent (D), and the binder may be added in any order. Moreover, after mixing 2 or more materials previously, you may add to the said conductive support agent dispersion.

(4-3) An active material dispersion containing an active material (A), a resin-type dispersant (C), a silane coupling agent (D), a binder, and a liquid medium is obtained, and a conductive additive (B ) To obtain a composite ink.

(4-4) A conductive auxiliary agent dispersion containing a conductive auxiliary agent (B), a resin-type dispersant (C), a silane coupling agent (D), a binder, and a liquid medium is obtained, and an active material ( A) can be added to obtain a composite ink.

(4-5) An active material dispersion containing an active material (A), a resin-type dispersant (C), a silane coupling agent (D), and a liquid medium is obtained, while a conductive auxiliary agent (B) and a resin are obtained. A conductive auxiliary agent dispersion containing a mold dispersant (C), a silane coupling agent (D), and a liquid medium is obtained, and the active material dispersion, the conductive auxiliary agent dispersion, and a binder are mixed and mixed. Ink can be obtained.

(4-6) Mixing the active material (A), the conductive additive (B), the resin-type dispersant (C), the silane coupling agent (D), the binder and the liquid medium almost simultaneously to obtain a composite ink. Can do.

(Disperser / Mixer)
As an apparatus used for obtaining the composite ink, a disperser or a mixer which is usually used for pigment dispersion or the like can be used.
For example, mixers such as dispersers, homomixers, or planetary mixers; homogenizers such as “Clearmix” manufactured by M Technique, or “fillmix” manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill (Shinmaru Enterprises "Dynomill", etc.), Attritor, Pearl Mill (Eirich "DCP Mill", etc.), or Coball Mill, etc .; Media type dispersers; Wet Jet Mill (Genus, "Genus PY", Sugino Media-less dispersers such as “Starburst” manufactured by Machine, “Nanomizer” manufactured by Nanomizer, etc., “Claire SS-5” manufactured by M Technique, or “MICROS” manufactured by Nara Machinery; or other roll mills, etc. Although The present invention is not limited to these. 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 surface of the metal agitator and vessel is 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.

<Composition for forming electrode underlayer>
As described above, the composition for forming a lithium ion secondary battery electrode of the present invention can also be used as a composition for forming an electrode base layer (hereinafter sometimes referred to as electrode base layer ink in the present specification).
The underlayer-forming composition contains a conductive additive (B), a resin-type dispersant (C), a silane coupling agent (D), and a liquid medium. Furthermore, a binder can also be contained.

In the electrode underlayer ink of the present invention, the proportion of the conductive auxiliary agent (B) in the electrode underlayer ink solid content is preferably 5 to 95% by weight. More preferably, it is 10 to 90% by weight.

  Moreover, in this invention, it is preferable that the ratio of the resin type dispersing agent (C) which occupies in electrode base layer ink is 0.5 to 100 weight% with respect to the weight of a conductive support agent (B). More preferably, it is 1-30 weight%, More preferably, it is 2-10 weight%.

  Moreover, in this invention, it is preferable that the ratio of the silane coupling agent (D) which occupies in electrode base layer ink is 0.001-10.0 weight% with respect to the weight of a conductive support agent (B). More preferably, it is 0.003 to 5.0% by weight, further preferably 0.005 to 2.0% by weight, and most preferably 0.005 to 0.1% by weight.

  Moreover, when the electrode underlayer ink of this invention contains a binder, it is preferable that the ratio of the binder to electrode underlayer ink solid content is 0.1 to 90 weight%. More preferably, it is 1 to 80% by weight. More preferably, it is 10 to 70% by weight.

As an apparatus used for obtaining the electrode underlayer ink, the same apparatus as that used for the composite ink can be used. Moreover, although the appropriate viscosity of electrode base layer ink is based on the coating method of electrode base layer ink, generally it is preferable to set it as 10 mPa * s or more and 30,000 mPa * s or less.

<Electrode>
Of the composition for forming a lithium ion secondary battery electrode of the present invention, a mixture ink is coated on a current collector and dried to form a mixture layer, thereby obtaining an electrode for a lithium ion secondary battery. . Alternatively, the base layer forming composition of the lithium ion secondary battery electrode forming composition of the present invention is coated and dried on a current collector to form a base layer, and a composite material is formed on the base layer. A layer may be provided to obtain an electrode for a lithium ion secondary battery. The composite material layer provided on the base layer may be formed using the above-described composite material inks (1) to (4) 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 for the current collector include metals and alloys such as aluminum, copper, nickel, titanium, and stainless steel. 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. Specific examples include die coating method, dip coating method, roll coating method, doctor coating method, knife coating method, spray coating method, gravure coating method, screen printing method or electrostatic coating method, and the like. Examples of methods that can be used include standing drying, blower dryers, hot air dryers, infrared heaters, and far-infrared heaters, but are not particularly limited thereto.

  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 underlayer is provided, the total thickness of the underlayer and the composite layer is generally 1 μm or more and 500 μm or less, preferably 10 μm or more and 300 μm or less.

<Secondary battery>
A secondary battery can be obtained by using the above electrode for at least one of a positive electrode and a negative electrode. Secondary batteries include lithium ion secondary batteries, sodium ion secondary batteries, magnesium secondary batteries, alkaline secondary batteries, lead storage batteries, sodium sulfur secondary batteries, lithium air secondary batteries, etc. Conventionally known electrolyte solutions, separators, and the like for secondary batteries can be used as appropriate.

(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 LiBPh ₄ etc. but are not limited to.

  Although it does not specifically limit as a non-aqueous solvent, For example, carbonates, such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylmethyl carbonate, and diethyl carbonate; γ-butyrolactone, γ-valerolactone, and γ- Lactones such as octanoic lactone; tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,2-methoxyethane, 1,2-ethoxyethane, and 1,2 -Glymes such as dibutoxyethane; esters such as methyl formate, methyl acetate, and methyl propionate; sulfoxides such as dimethyl sulfoxide and sulfolane; and nitriles such as acetonitrile. It is below. 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, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” represents “part by weight”. The polymerization average molecular weight (Mw) of the resin having an acidic functional group and the resin having a basic functional group is a weight average molecular weight in terms of polystyrene measured using HLC-8320GPC (manufactured by Tosoh Corporation) as a device. The acid value in the resin having an acidic functional group 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. When acid value titration was difficult, the acid value was calculated by the following method. According to Japanese Patent No. 3784494, introduction of an acidic functional group was confirmed by FT-IR. Next, assuming that the ratio of the absorption intensity matches the ratio of the number of functional groups per unit weight, the absorption intensity (near 764 cm ⁻¹ ) derived from the resin skeleton and the absorption corresponding to the acidic functional group (in the case of a sulfonic acid group) 1180cm around ^-1, around 1750 cm ^-1 in the case of a carboxylic acid group, a phosphoric acid group calculates the acidic functional groups per unit weight from the ratio of the intensity variation of 940cm around ^-1), which, in terms of the acid value did. The amine value in the resin having a basic functional group is the total amine value (mg KOH / g) measured according to the method of ASTM D 2074.

<Preparation of resin having acidic functional group>
<Polyvinylidene fluoride-based resin having acidic functional group (C ^A1 )>
[Synthesis of polyvinylidene fluoride-based resin (A1-1) having a sulfonic acid group]
Preparation of a polyvinylidene fluoride resin having a sulfonic acid group was in accordance with Japanese Patent No. 3784494. That is, 100 g of polyvinylidene fluoride resin was dispersed in 400 mL of chloroform in a 1 L separable flask, and 100 mL of chlorosulfonic acid was added dropwise with stirring, followed by heating to reflux for 2 hours. Thereafter, the reaction solution was poured into ice water, the solid matter was filtered off, washed with water and dried to obtain a polyvinylidene fluoride resin (A1-1) having a sulfonic acid group having a weight average molecular weight of about 10,000. As the polyvinylidene fluoride resin, a homopolymer of 1,1-difluoroethylene synthesized by a known method was used. The acid value was 9 mgKOH / g.

[Synthesis of Polyvinylidene Fluoride Resin Having Phosphoric Acid Group (A1-2)]
A polyvinylidene fluoride-based resin having a hydroxyl group was synthesized according to Japanese Patent Laid-Open No. 6-172452. That is, 1040 g of ion-exchanged water, 0.8 g of methyl cellulose, 2.5 g of ethyl acetate, 4 g of diisopropyl peroxydicarbonate, 396 g of vinylidene fluoride and 4 g of 2-hydroxyethyl acrylate were charged in a 2 L autoclave and suspended at 28 ° C. for 47 hours. Turbid polymerization was performed. After the polymerization was completed, the polymer slurry was dehydrated, washed with water, and dried at 80 ° C. for 20 hours to obtain a polymer.

Next, 100 g of the above hydroxyl group-containing polyvinylidene fluoride resin is dispersed in 400 mL of chloroform in a 1 L separable flask equipped with a nitrogen gas introduction tube and a condenser, and the content is 116% orthophosphoric acid while stirring under nitrogen. After mixing 100 g of polyphosphoric acid, the mixture was heated to reflux for 2 hours. Thereafter, the reaction solution was poured into ice water, solid matter was filtered off, washed with water, and dried to obtain a polyvinylidene fluoride resin (A1-2) having a phosphate group having a weight average molecular weight of about 10,000. The acid value was 11 mgKOH / g.

<Polyvinyl resin (C ^A2 ) having an acidic functional group>
[Synthesis of Polyvinyl Resin (A2-1) Having Carboxyl Group]
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 100 parts of n-butyl methacrylate and 100 parts of benzyl methacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic dianhydride, 231 parts of N-methyl-2-pyrrolidone and 0.40 part of 1,8-diazabicyclo- [5,4,0] -7-undecene as catalyst were added, Reacted for hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyvinyl resin (A2-1) solution having a carboxyl group with a solid content of 50%. The obtained polyvinyl resin (A2-1) had a weight average molecular weight (Mw) of 8,500 and an acid value of 43 mgKOH / g.

[Synthesis of Polyvinyl Resin (A2-2) Having Carboxyl Group]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 180 parts of methyl methacrylate and 20 parts of methacrylic acid and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.1 part of 2,2′-azobisisobutyronitrile was dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 19 parts of pyromellitic dianhydride, 231 parts of N-methyl-2-pyrrolidone and 0.40 part of 1,8-diazabicyclo- [5,4,0] -7-undecene as catalyst were added, Reacted for hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated to obtain a polyvinyl resin (A2-2) solution having a carboxyl group with a solid content of 50%. The obtained polyvinyl resin (A2-2) had a weight average molecular weight (Mw) of 8,600 and an acid value of 93 mgKOH / g.

<Polyester resin having acidic functional group (C ^A3 )>
[Synthesis of Polyester Resin (A3-1) Having Carboxyl Group]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of dibutyltin oxide as a catalyst. After substitution, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic dianhydride was added and reacted at 120 ° C. for 2 hours to obtain a polyester resin (A3-1) having a carboxyl group. . The obtained polyester resin (A3-1) was a white wax-like solid at room temperature, the weight average molecular weight (Mw) was 2,500, and the acid value was 49 mgKOH / g.

[Synthesis of Polyester Resin Having Carboxyl Group (A3-2)]
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 111.4 parts of methoxy PEG 400 (one-end methoxylated polyethylene glycol; molecular weight 400), 127.1 parts of ε-caprolactone, δ-valerolactone 111. After 5 parts and 0.1 part of dibutyltin oxide as a catalyst were charged and replaced with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 41.0 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at 120 ° C. for 2 hours to have a carboxyl group. A polyester resin (A3-2) was obtained. The obtained polyester resin (A3-2) was a pale yellow transparent liquid at room temperature, the weight average molecular weight (Mw) was 4,800, and the acid value was 43 mgKOH / g.

<Resin having other commercially available acidic functional groups (C ^A4 )>
A4-1: Disperbyk-111 (manufactured by Big Chemie); resin having an acidic functional group, acid value of 129 mgKOH / g.

<Polyvinyl resin having basic functional group (C ^B1 )>
[Synthesis of Polyvinyl Resin (B1-1) Having Amino Group]
<Synthesis of vinyl polymer ( ^a1-1 )>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 500 parts of n-butyl methacrylate, 28 parts of 3-mercapto-1,2-propanediol, and 528 parts of N-methyl-2-pyrrolidone. And replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., and 0.50 part of 2,2′-azobisisobutyronitrile was added, followed by reaction for 7 hours. After confirming that 95% had reacted by solid content measurement, it was cooled to room temperature, and a 50% solid content solution of a vinyl polymer (a ^1-1 ) having a weight average molecular weight of 4800 and having two hydroxyl groups at one end was obtained. Obtained.

<Synthesis of Polyvinyl Resin (B1-1)>
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 1056 parts of a 50% solid solution of vinyl polymer (a ^1-1 ), 115.1 parts of isophorone diisocyanate, and dibutyltin dilaurate 0 as a catalyst .12 g was charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 3 hours, then cooled to 40 ° C., 25.5 parts of iminobispropylamine, 16.7 parts of di-n-butylamine, N-methyl-2- The mixture was added dropwise to 492.0 parts of pyrrolidone over 30 minutes, reacted for another 1 hour, and then cooled to room temperature to complete the reaction. The solid content was adjusted to 40%, and a pale yellow transparent solution of an amino group-containing polyvinyl resin (B1-1) was obtained. The obtained polyvinyl resin (B1-1) had a weight average molecular weight of 21,600 and an amine value of 17.4 mgKOH / g.

[Synthesis of Polyvinyl Resin (B1-2) Having Amino Group]
<Synthesis of vinyl polymer (a ^3-1 ) having two acryloyl groups at one end>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 400 parts of methyl methacrylate, 100 parts of butyl acrylate, and 100 parts of N-methyl-2-pyrrolidone and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and a solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved in 27.5 parts of 3-mercapto-1,2-propanediol was added. Reacted for 10 hours. After confirming that 95% had reacted by solid content measurement, 427 parts of N-methyl-2-pyrrolidone was added for dilution, and then 32.6 parts of 2-acryloyloxyethyl isocyanate and 1 part of dibutyltin dilaurate under a dry air flow. Then, 0.3 part of methylhydroquinone was added, and the mixture was further heated and stirred for 2 hours, further adjusted to a solid content of 50% by weight, and a vinyl polymer having a weight average molecular weight of 4500 and having two acryloyl groups at one end (a ³ A solid content 50% by weight solution of ^-1 ) was obtained.

<Synthesis of polyvinyl resin (B1-2)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 27.8 parts of iminobispropylamine and 184 parts of N-methyl-2-pyrrolidone and heated to 50 ° C. to give a vinyl polymer (a ^3-1 ) 700 parts of a 50 wt% solid content solution was added dropwise over 30 minutes, and after another 1 hour of reaction, a mixture of 15.7 parts of isophorone diisocyanate and 121 parts of N-methyl-2-pyrrolidone was added for 30 minutes. The reaction mixture was added dropwise over a period of 2 hours, reacted for 2 hours, added with N-methyl-2-pyrrolidone, adjusted to a solid content of 30% by weight, and having a basic functional group with a weight average molecular weight of 15200 and an amine value of 94 mgKOH / g. A solid content 30% by weight solution of the resin (B1-2) was obtained.

<Polyester-based resin having basic functional group (C ^B2 )>
[Synthesis of polyester resin having amino group (B2-1)]
<Synthesis of an ester polymer ( ^c2-1 ) having an acryloyl group at one end>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 20.8 parts of 4-hydroxybutyl acrylate and 379 parts of ε-caprolactone, 0.1 part of dibutyltin oxide as a catalyst, hydroquinone as a polymerization inhibitor 1 part was charged, heated and stirred at 120 ° C. for 4 hours under a stream of dry air, the reaction was completed after confirming that 95% had reacted by solid content measurement, and diluted by adding 171 parts of N-methyl-2-pyrrolidone. Furthermore, the solid content was adjusted to 70% by weight to obtain a 70% by weight solid content solution of an ester polymer (c ^2-1 ) having an weight average molecular weight of 6500 and having an acryloyl group at one end.

<Synthesis of polyester resin (B2-1)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 18.9 parts of iminobispropylamine and 248 parts of N-methyl-2-pyrrolidone and heated to 50 ° C. to produce an ester polymer (c ^2-1 ) 571 parts of a 70 wt% solid content solution was added dropwise over 30 minutes, and the reaction was further continued for 1 hour. Then, a mixed solution of 16.0 parts of isophorone diisocyanate and 112 parts of N-methyl-2-pyrrolidone was added for 30 minutes. The polyester having a basic functional group having a weight average molecular weight of 13,000 and an amine value of 36 mgKOH / g is prepared by adding N-methyl-2-pyrrolidone and adjusting to a solid content of 30% by weight. A 30% by weight solid content solution of the resin (B2-1) was obtained.

[Synthesis of polyester resin having amino group (B2-2)]
<Synthesis of polyester resin (B2-2)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 23.9 parts of methyliminobispropylamine and 248 parts of N-methyl-2-pyrrolidone and heated to 50 ° C. to produce an ester polymer ( c ^2-1) having a solid content of 70 wt% solution 571 parts was added dropwise over 30 minutes, the reaction was conducted for 1 hour, 18.3 parts of isophorone diisocyanate, the N- methyl-2-pyrrolidone 207 parts mixture of 30 Add dropwise over a minute, react for 2 hours, add N-methyl-2-pyrrolidone to adjust the solid content to 30% by weight, and have a basic functional group with a weight average molecular weight of 27000 and an amine value of 41 mgKOH / g. A solid content solution of 30% by weight of polyester resin (B2-2) was obtained.

<Resin having other basic functional group (C ^B3 )>
B3-1: Azisper PB821 (manufactured by Ajinomoto Fine Techno Co.); resin having an amino group, amination 10 mgKOH / g.

<Nonionic resin>
<Polyvinyl alcohol resin (C ^C1 )>
C1-1: Kuraray pobar 420 (manufactured by Kuraray); polyvinyl alcohol resin, saponification degree 79 mol%.

<Polyvinyl acetal resin (C ^C2 )>
C2-1: ESREC BX-1 (manufactured by Sekisui Chemical Co., Ltd.); polyvinyl acetal resin, degree of acetalization 66 mol%, vinyl alcohol unit 33 mol%,

<Polyvinylamide resin (C ^C3 )>
C3-1: PVP K-30 (manufactured by ISP Japan); polyvinylpyrrolidone, weight average molecular weight of about 40,000 to 80,000.

Table 1 shows silane coupling agents used in Examples and Comparative Examples.

<Dispersion>
[Example 1]
10 parts of acetylene black (Denka Black HS-100) as a conductive assistant, 0.5 part of polyvinylidene fluoride resin (A1-1) having a sulfonic acid group in terms of solid content, and the silane coupling agent S shown in Table 1 -01 0.1 part Furthermore, N-methyl-2-pyrrolidone was added so that the solid content in the dispersion would be 10% by weight, and the solid content was adjusted and mixed in a mixer. Subsequently, it put into the sand mill and disperse | distributed and the dispersion 1 was obtained.

[Examples 2 to 7]
Dispersions 2 to 7 of Examples 2 to 7 were obtained in the same manner as in Example 1 using the conductive assistant, resin type dispersant, and silane coupling agent shown in Table 2, respectively.

[Comparative Example 1]
The silane coupling agent S was changed by changing Denka Black HS-100 to Super-PLi and polyvinylidene fluoride resin (A1-1) having a sulfonic acid group to polyvinyl resin (A2-1) having a carboxyl group. Dispersion 8 was obtained in the same manner as in Example 1 except that -01 was not added.

[Comparative Example 2]
In the same manner as in Example 1 except that the silane coupling agent S-01 was changed to the silane coupling agent S-06 shown in Table 1 and the polyvinylidene fluoride resin (A1-1) was not added. Dispersion 9 was obtained.

[Comparative Example 3]
The same method as in Example 1 except that the polyvinylidene fluoride resin (A1-1) was changed to a polyester resin (B2-1) having an amino group and the silane coupling agent S-01 was not added. Dispersion 10 was obtained.

(Dispersion degree determination of dispersion)
For determining the degree of dispersion of the conductive additive in the dispersion, a dynamic light scattering type particle size distribution meter ("Microtrack UPA" manufactured by Nikkiso Co., Ltd.) is used. When the ratio was integrated, the particle diameter (D50) at 50% was determined.
The evaluation results of the dispersion are shown in Table 2. The numbers in the table indicate the size of the coarse particles. The smaller the value, the better the dispersibility and the more uniform the dispersion.

HS-100: Acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Super-P Li: Furnace Black (manufactured by TIMCAL)

As shown in Table 2, it was confirmed that the dispersion using the resin type dispersant (C) was excellent in dispersibility of the conductive assistant and was a dispersion in which the conductive assistant was uniformly dispersed.

<Positive electrode mixture ink, negative electrode mixture ink>
[Example 8]
With respect to 50 parts of dispersion 1 prepared in Example 1 (5 parts as a conductive additive), 90 parts of LiFePO ₄ as a positive electrode active material and 4.7 parts of binder (KF polymer W1100: manufactured by Kureha, polyvinylidene fluoride) N-methyl-2-pyrrolidone was added and further mixed so that the solid content of the mixture ink was 60%, whereby positive electrode mixture ink 1 was prepared.

[Examples 16, 17, 19, 20, 22, 25, comparative examples 4, 5, 10]
A positive electrode mixture ink 9, 10, 12, 13, 15, 18, 21, 22 and a negative electrode mixture ink 4 were obtained in the same manner as in Example 8 except that the materials shown in Table 3 were used.

[Example 28]
Negative electrode composite material as in Example 8, except that 50 parts of dispersion 1 was changed to 30 parts, 90 parts of LiFePO ₄ to 93 parts of artificial graphite as a negative electrode active material, and 4.7 parts of binder to 3.82 parts. Ink 1 was obtained.

[Example 9]
As a positive electrode active material, 90 parts of LiFePO ₄ , 5 parts of Denka Black HS-100, 0.25 parts of a polyvinyl resin (A2-2) having a carboxyl group, 0.05 of a silane coupling agent S-06 described in Table 1 Part, binder (KF polymer W1100: manufactured by Kureha, polyvinylidene fluoride) 4.70 parts, N-methyl-2-pyrrolidone is added and further mixed so that the solid content of the mixture ink is 60% A positive electrode mixture ink 2 was obtained.

[Example 10]
Silane coupling agent S-06 Positive electrode mixture ink 3 was obtained in the same manner as in Example 9, except that 0.05 part was changed to 0.10 part and the binder 4.70 part was changed to 4.65 part.

[Example 11]
3. Polyvinyl resin (A2-2) having a carboxyl group is added to polyvinylidene fluoride resin (A1-2) having a phosphoric acid group, 0.05 part of silane coupling agent S-06 is added to 0.08 part, and binder 4. A positive electrode mixture ink 4 was obtained in the same manner as in Example 9 except that 70 parts were changed to 4.67 parts.

[Example 12]
Silane coupling agent S-06 Positive electrode mixture ink 5 was obtained in the same manner as in Example 9, except that 0.05 part was changed to 0.06 part and binder was changed to 4.69 part.

[Example 13]
Polyvinyl resin having carboxyl group (A2-2) is converted to polyester resin having carboxyl group (A3-2), 0.05 part of silane coupling agent S-06 is 0.03 part, and binder is 4.70 parts. The positive electrode mixture ink 6 was obtained in the same manner as in Example 9 except that the amount was changed to 4.72 parts.

[Example 14]
Silane coupling agent S-06 Positive electrode mixture ink 7 was obtained in the same manner as in Example 9, except that 0.05 part was changed to 0.01 part and the binder 4.70 part was changed to 4.74 part.

[Example 15]
Silane coupling agent S-06 Positive electrode mixture ink 8 was obtained in the same manner as in Example 9, except that 0.05 part was changed to 0.005 part and the binder 4.70 part was changed to 4.745 part.

[Examples 18, 21, 23, 24, 26, 29]
Positive electrode mixture inks 11, 14, 16, 17, 19 and negative electrode mixture ink 2 were obtained in the same manner as in Example 9 except that the materials shown in Table 3 were used.

[Example 27]
A silane cup is added to 0.25 parts of a carboxyl group-containing polyvinyl resin (A2-2) and 0.15 parts of a carboxyl group-containing polyester resin (A3-1) and 0.10 parts of a polyvinyl acetal resin (C2-1). A positive electrode mixture ink 20 was obtained in the same manner as in Example 9, except that the ring agent S-06 was changed to the silane coupling agent S-04, respectively.

[Comparative Example 6]
LiFePO ₄ was changed to LiCoO ₂ , the carboxyl group-containing polyvinyl resin (A2-2) was changed to a carboxyl group-containing polyester resin (A3-1), and the binder 4.70 parts was changed to 4.75 parts. A positive electrode mixture ink 23 was obtained in the same manner as in Example 9 except that the coupling agent S-06 was not added.

[Comparative Example 7]
The silane coupling agent S-06 was changed to the silane coupling agent S-01, the binder 4.70 parts was changed to 4.95 parts, and the polyvinyl resin (A2-2) having a carboxyl group was not added. In the same manner as in Example 9, a positive electrode mixture ink 24 was obtained.

[Comparative Example 8]
LiFePO ₄ was changed to LiNi _1/3 Mn _1/3 Co _1/3 O ₂ , silane coupling agent S-06 was changed to silane coupling agent S-04, and binder was changed from 4.70 parts to 4.95 parts. A positive electrode mixture ink 25 was obtained in the same manner as in Example 9 except that the polyvinyl resin (A2-2) having a carboxyl group was not added.

[Comparative Example 9]
90 parts of LiFePO _{4 is} 93 parts of artificial graphite, 5 parts of Denka Black HS-100 is 3 parts, polyvinyl resin (A2-2) having a carboxyl group and 0.25 parts of polyester resin (B2- 1) A negative electrode mixture ink 3 was prepared in the same manner as in Example 9 except that 0.15 part was changed to 4.75 part of binder and 3.85 parts of silane coupling agent S-06 was not added. Obtained.

(Determination of dispersion degree of compound ink)
The degree of dispersion of the positive electrode mixture ink and the negative electrode mixture ink was determined by determination with a grind gauge (according to JISK5600-2-5). Table 3 shows the evaluation results of the degree of dispersion of the composite ink.

<Positive electrode, negative electrode>
And after apply | coating this positive mix ink on the 20-micrometer-thick aluminum foil used as a collector using a doctor blade, it dried under reduced pressure and adjusted so that the thickness of an electrode might be set to 100 micrometers. Furthermore, the rolling process by roll press was performed and the positive electrode from which thickness becomes 85 micrometers was produced.

  In the case of the negative electrode mixture ink, after applying using a doctor blade on a copper foil having a thickness of 20 μm to be a current collector, adjusting the thickness of the electrode to 80 μm by drying under reduced pressure, A rolling process using a roll press was performed to produce a negative electrode having a thickness of 70 μm.

(Electrode electrolyte resistance)
The obtained positive electrode or negative electrode was punched to a diameter of 16 mm, immersed in a mixed solvent in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio), and stored at 60 ° C. for 1 week. Thereafter, the electrode was taken out, and the degree of collapse of the composite layer was determined from the change in the weight of the composite layer before and after immersion. The smaller the change in weight, the higher the electrolyte solution resistance of the composite layer. The evaluation results are shown in Table 3.
A: “Weight change before and after immersion is less than 4%.”
○: “Weight change before and after immersion is 4% or more and less than 8%.”
Δ: “Weight change before and after immersion is 8% or more and less than 15%.”
×: “Weight change before and after immersion is 15% or more.”

<Coin-type battery>
Next, the obtained positive electrode or negative electrode was punched into a diameter of 16 mm as a working electrode, and a metal lithium foil was used as a counter electrode. LiPF ₆ in a working solvent, a counter electrode, a separator (porous polypropylene film) inserted between the working electrode and the working electrode, and an electrolyte (a mixed solvent in which ethylene carbonate and diethyl carbonate are mixed at a ratio of 1: 1 (volume ratio)) A non-aqueous electrolyte solution having a concentration of 1M dissolved therein. The coin-type battery was used in a glove box substituted with argon gas, and a predetermined battery characteristic evaluation was performed after the coin-type battery was produced.

(Cycle characteristics)
About the obtained coin-type battery, charging / discharging measurement was performed using the charging / discharging apparatus (SM-8 by Hokuto Denko).
When the active material to be used was LiFePO ₄ , constant current charging was continued to a charge end voltage of 4.2 V at a charging current of 1.0 mA. After the battery voltage reached 4.2 V, constant current discharge was performed at a discharge current of 1.0 mA until the discharge end voltage of 2.0 V was reached. These charging / discharging cycles are defined as one cycle, and 50 cycles of charging / discharging are repeated to obtain “discharge capacity maintenance rate = discharge capacity at the 50th cycle / discharge capacity at the first cycle”, depending on the discharge capacity maintenance rate as follows: Judged. The evaluation results are shown in Table 3.
A: “Discharge capacity maintenance ratio is 95% or more. Particularly excellent.”
○: “Discharge capacity maintenance rate is 90% or more and less than 95%. No problem”
Δ: “Discharge capacity maintenance rate is 80% or more and less than 90%. Usable.”
×: “Discharge capacity maintenance rate is less than 80%.

Further, when the active material used is LiCoO ₂ , it is the same as LiFePO ₄ except that the charge current is 1.6 mA, the charge end voltage is 4.3 V, the discharge current is 1.6 mA, and the discharge end voltage is 2.8 V. Cycle characteristics can be measured.

Further, when the active material used is LiMn ₂ O ₄ , LiFePO ₄ is used except that the charge current is 1.0 mA, the charge end voltage is 4.3 V, the discharge current is 1.0 mA, and the discharge end voltage is 3.0 V. Cycle characteristics can be measured as in the case.

When the active material used is LiNi _1/3 Mn _1/3 Co _1/3 O ₂ , the charging current is 1.9 mA, the charging end voltage is 4.3 V, the discharging current is 1.9 mA, and the discharge end voltage is 3. Except for 0 V, cycle characteristics can be measured in the same manner as LiFePO ₄ .

Further, when the active material used is artificial graphite, it is the same as LiFePO ₄ except that the charging current is 1.8 mA, the charging end voltage is 0.1 V, the discharging current is 1.8 mA, and the discharging end voltage is 2.0 V. Cycle characteristics can be measured.

When the active material used is Li ₄ Ti ₅ O ₁₂ , LiFePO ₄ is used except that the charging current is 1.0 mA, the charging end voltage is 1.0 V, the discharging current is 1.0 mA, and the discharging end voltage is 2.0 V. The cycle characteristics can be measured in the same manner as in.

LFP: LiFePO ₄
LCO: LiCoO ₂
LMO: LiMn ₂ O ₄ ,
NMC: LiNi _1/3 Mn _1/3 Co _1/3 O ₂
LTO: Li ₄ Ti ₅ O ₁₂

As shown in Table 3, it was confirmed that the compositions for forming lithium ion secondary battery electrodes in Examples 8 to 29 of the present invention were uniform compositions excellent in dispersibility of the conductive assistant and the active material. .

However, the composite ink formed using only the resin-type dispersant (C) cannot maintain the interparticle contact when the composite layer is formed, although each particle is uniformly dispersed. It is considered that the electrolytic solution resistance and cycle characteristics of the material layer were lowered and sufficient battery characteristics were not obtained.

On the other hand, the composite ink formed using only the silane coupling agent (D) had a large particle size and agglomerates remained. Therefore, it is considered that partial aggregation occurred in the composite material layer, and the deterioration was promoted by the resistance distribution and current concentration caused by the aggregation.

On the other hand, it has been clarified that the electrode for a lithium ion secondary battery having a composite layer formed from the composition for forming a lithium ion secondary battery electrode of the present invention is excellent in electrolyte resistance and cycle characteristics. .

In the lithium ion secondary battery electrode or lithium ion secondary battery using the composition for forming a lithium ion secondary battery electrode of the present invention, it is presumed as follows that the electrolytic solution resistance and cycle characteristics are improved. Yes. Improved dispersibility of active materials and conductive additives by using one or more resin-type dispersants selected from the group consisting of resins having acidic functional groups, resins having basic functional groups, and nonionic resins Let
And in the state where the aggregation of the active material and the conductive auxiliary agent is loosened and the particles are uniformly dispersed, the silane coupling agent is efficiently adsorbed to the active material and the conductive auxiliary agent. It is presumed that the contact between particles became stronger. Surprisingly, it is believed that the composite layer that maintains strong inter-particle contact has improved resistance to the electrolyte, thereby improving long-term cycle characteristics.

<Electrode base layer ink>
[Example 30]
20 parts of the dispersion 1 prepared in Example 1 and 20 parts of an N-methyl-2-pyrrolidone solution (solid content 10%) of a binder (KF polymer W1100: manufactured by Kureha, polyvinylidene fluoride) were mixed, A formation ink was obtained.

The electrode underlayer ink was applied onto an aluminum foil having a thickness of 20 μm serving as a current collector using a doctor blade, and then dried by heating to form an underlayer so that the thickness was 5 μm. Next, the positive electrode mixture ink 18 of Example 25 was applied on the underlayer, and a positive electrode for a lithium ion secondary battery having an underlayer was obtained in the same manner as the above-described positive electrode.

[Example 31]
100 parts of acetylene black (Denka Black HS-100) as a conductive assistant, 5.0 parts of polyvinyl resin (A2-1) having a carboxyl group, 0.05 parts of silane coupling agent S-04 described in Table 1 N- 895 parts of methyl-2-pyrrolidone was mixed in a mixer, and further dispersed in a sand mill to obtain Dispersion 11. When the degree of dispersion was measured in the same manner as the dispersion, the particle size was 0.502 μm.
An electrode underlayer ink was obtained in the same manner as in Example 30 except that the dispersion 1 was changed to the dispersion 11, and predetermined battery characteristic evaluation was performed.

[Example 32, Comparative Examples 11 and 12]
Table 4 shows the dispersion and cause material ink to be used, respectively, in the same manner as in Example 30, a positive electrode for a lithium ion secondary battery having a base layer, and an anode for a lithium ion secondary battery having a base layer respectively A coin-type battery was prepared in the same manner as the above-described positive electrode and negative electrode, and predetermined battery characteristic evaluation was performed.

As shown in Table 4, good results were obtained with the electrode for a lithium ion secondary battery having the composite layer of the present invention and the electrode underlayer of the present invention. In addition, the lithium ion secondary electrode having the electrode underlayer of the present invention had high electrolytic solution resistance, and the cycle characteristics were also good (Example 32). This is because the base layer has high electrolytic solution resistance, and in the charge / discharge cycle evaluation, the conductivity and the contact with the composite layer were maintained, so that the battery characteristics compared to the case without the base layer (Comparative Example 9). Is estimated to have improved. On the other hand, in Comparative Example 11, the battery characteristics were deteriorated as compared with the case without the underlayer (Example 25). About this, since the electrolyte solution resistance of the underlayer is not sufficient, the underlayer gradually collapsed during the charge / discharge cycle evaluation, and contact between the composite layer and the current collector could not be obtained. It is thought that caused.

Claims (4)

At least one of the active material (A) or the conductive auxiliary agent (B), a polyvinylidene fluoride resin (C ^A1 ) having an acidic functional group, a polyvinyl resin (C ^A2 ) having an acidic functional group, and having an acidic functional group Polyester resin (C ^A3 ), Disperbyk-111 (manufactured by Big Chemie) (C ^A4 ), polyvinyl resin (C ^B1 ) having a basic functional group, polyester resin (C ^B2 ) having a basic functional group , Addispar One or more resin-type dispersions selected from the group consisting of PB821 (Ajinomoto Fine Techno Co., Ltd.) (C ^B3 ), polyvinyl alcohol resin (C ^C1 ), polyvinyl acetal resin (C ^C2 ), and polyvinylamide resin (C ^C3 ) The composition for lithium ion secondary battery electrode formation containing an agent (C) and a silane coupling agent (D). The composition for forming a lithium ion secondary battery electrode according to claim 1, wherein the silane coupling agent (D) has a reactive functional group. An electrode comprising a current collector and at least one layer of a composite material layer or an electrode base layer, wherein the composite material layer or the electrode base layer is for forming a lithium ion secondary battery electrode according to claim 1 or 2. An electrode for a lithium ion secondary battery, which is formed from a composition. A battery having a positive electrode and the negative electrode and the electrolyte, the positive electrode or at least one of a lithium ion secondary battery is a lithium ion secondary battery electrode according to claim 3, wherein said negative electrode.