JP2009099561A - Conductive particle dispersion composition, conductive paste and printed wiring board using the same, and method for manufacturing conductive particle dispersion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive particle dispersion composition that is excellent in dispersion stability of conductive particles and allows formation of a homogeneous and high-conductivity hardened material, a method for manufacturing the conductive particle dispersion composition by a simple process, and a printed wiring board having a homogeneous and high-conductivity conductive layer. <P>SOLUTION: The conductive particle dispersion composition includes each component shown in the following (A)-(C). The conductive particle dispersion composition is used in conductive paste, conductive ink, and printed wiring boards. The manufacturing method is used for manufacturing the conductive particle dispersion composition. (A) A conductive particle configured such that an average particle size obtained by particle sizing using a dynamic light scattering method is 0.02-20 μm and a content on the basis of the total mass of a nonvolatile component included in the conductive particle dispersion composition is 30-95 mass% (B) A hardening compound having a functional group that forms an interaction with the conductive particle. (C) A solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductive particle dispersion composition, a conductive paste using the same, a printed wiring board, and a method for producing a conductive particle dispersion composition.

  Conventionally, various conductive particle dispersion compositions represented by conductive pastes and conductive inks are known in the field of electric / electronic circuit formation technology. For example, wiring formation materials for printed wiring boards, multilayer substrates It is used as an interlayer conduction material, a bonding material for mounting parts, and the like. Such a conductive particle dispersion composition is required to have a dispersion stability of the conductive particles contained in the composition in order to maintain high conductivity and stability.

  As the conductive particle dispersion composition, for example, a conductive paste formed by dispersing conductive metal filler (conductive particles) in a composition containing an epoxy resin using diallyl phthalate or triallyl isocyanurate is disclosed. (See Patent Documents 1 and 2). However, the conductive paste described in these patent documents does not have sufficient dispersibility stability of the conductive metal filler in the composition.

  In addition, the surface of metal particles used as conductive particles is surface-treated with a coupling agent, etc., thereby improving the interaction between the dispersant and the metal particles and improving the dispersion stability of the conductive particle dispersion composition. There is also a known method (see Patent Document 3). However, in order to carry out the surface treatment, there is a problem that a further process is required and the process becomes complicated.

Thus, it is required to easily obtain a conductive particle dispersion composition having high dispersion stability. However, at present, such a conductive particle dispersion composition and a production method thereof have not been provided yet. is there.
JP 2007-142147 A JP 2007-141648 A JP 2004-183060 A

An object of this invention is to provide the electroconductive particle dispersion composition which is excellent in the dispersion stability of electroconductive particle, has high electroconductivity, and can form homogeneous hardened | cured material.
Another object of the present invention is to provide a printed wiring board having a highly conductive and homogeneous conductive layer.
Furthermore, the present invention provides a production method capable of producing a conductive particle dispersion composition that is excellent in dispersion stability of conductive particles, has high conductivity, and can form a homogeneous cured product in a simple process. With the goal.

  Means for solving the above-mentioned problems are as follows.

<1> A conductive particle dispersion composition comprising the components shown in the following (A) to (C).
(A) The average particle size obtained by particle size measurement by the dynamic light scattering method is 0.02 μm to 20 μm, and the content based on the total mass of the nonvolatile components contained in the conductive particle dispersion composition is 30% to 95% by weight of conductive particles (B) A curable compound having a functional group capable of forming an interaction with the conductive particles (C) Solvent

<2> The conductive particle dispersion composition according to <1>, further comprising (D) another curable compound having a molecular structure different from the component (B).

<3> The curable compound contained as the component (B) is a functional group different from a functional group capable of interacting with the conductive particles, and reacts with each other by applying energy. Or a functional group capable of reacting the curable compound with another curable compound contained as the component (D). Particle dispersion composition.

<4> Other curable compounds contained as the component (D) are selected from the group consisting of acrylate compounds, epoxy compounds, isocyanate compounds, and compounds having functional groups capable of reacting with these compounds. The conductive particle dispersion composition according to <2> or <3>, which is a molecular compound.

<5> The conductive particles contained as the component (A) are selected from the group consisting of gold, platinum, silver, palladium, indium, copper, nickel, iron, zinc, bell, lead, and bismuth, The conductive particle-dispersed composition according to any one of <1> to <4>, wherein the conductive particle-dispersed composition is an alloy made of these metals or particles containing oxides of these metals.

<6> The functional group capable of forming an interaction with the conductive particles contained in the curable compound contained as the component (B) is a functional group capable of adsorbing a metal, a functional group having a positive charge, Functional group having a structure capable of dissociating into negative charge, functional group having a negative charge, functional group having a structure capable of dissociating into a negative charge, nonionic polar group capable of interacting with conductive particles, conductivity Selected from the group consisting of functional groups capable of forming a chelation or multidentate structure with particles, functional groups capable of inclusion of conductive particles, and functional groups that interact with a solvent in which a metal is retained as crystal water. The conductive particle dispersion composition according to any one of the above items <1> to <5>, wherein

<7> The curable compound contained as the component (B) is a copolymer including a unit represented by the following formula (1) and a unit represented by the following formula (2). The conductive particle dispersion composition according to any one of <1> to <6>.

In Formula (1) and Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z each independently represent a single atom. Represents a bond or a substituted or unsubstituted divalent organic group, ester group, amide group or ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group; To express.

<8> The conductive material according to any one of <1> to <7>, wherein the curable compound contained as the component (B) has a weight average molecular weight of 2,000 to 500,000. Particle dispersion composition.

<9> The conductive material according to any one of <1> to <8>, further comprising (E) a compound selected from a polymerization initiator, a curing agent, and a curing accelerator. Particle dispersion composition.

<10> The conductive particle dispersion composition according to any one of <1> to <9>, wherein the conductive particle dispersion composition can be cured by energy application.

<11> The conductive particle dispersion composition according to any one of <1> to <10>, which is a conductive paste.

<12> A printed wiring board having a conductive layer using the conductive particle dispersion composition according to any one of <1> to <11>.

<13> A method for producing a conductive particle dispersion composition comprising at least a first step of kneading or predispersing a mixture containing the components shown in the following (A), (B), and (C): .
(A) The average particle size obtained by particle size measurement by the dynamic light scattering method is 0.02 μm to 20 μm, and the content based on the total mass of the nonvolatile components contained in the conductive particle dispersion composition is 30% by mass to 95% by mass of conductive particles (B) A curable compound having a functional group capable of forming an interaction with the conductive particles (C) Solvent <14> After the first step, the following (D) Performing the 2nd process of adding a component, The manufacturing method of the electroconductive particle dispersion composition as described in said <13> characterized by the above-mentioned.
(D) Another curable compound having a molecular structure different from the component (B).

ADVANTAGE OF THE INVENTION According to this invention, the electroconductive particle dispersion composition which is excellent in the dispersion stability of electroconductive particle, has high electroconductivity, and can form a homogeneous hardened | cured material can be provided.
Moreover, according to this invention, the printed wiring board which has high electroconductivity and a homogeneous conductive layer can be provided.
Furthermore, according to the present invention, there is provided a production method capable of producing a conductive particle dispersion composition having excellent dispersion stability of conductive particles, high conductivity and capable of forming a homogeneous cured product in a simple process. can do.

  Hereinafter, the present invention will be described in detail.

[Conductive particle dispersion composition]
The conductive particle dispersion composition of the present invention is characterized by containing the components shown in the following (A) to (C).
(A) The average particle size obtained by particle size measurement by the dynamic light scattering method is 0.02 μm to 20 μm, and the content based on the total mass of the nonvolatile components contained in the conductive particle dispersion composition is 30% to 95% by weight of conductive particles (B) A curable compound having a functional group capable of forming an interaction with the conductive particles (C) Solvent

  In the following, the conductive particles contained as the component (A) are appropriately referred to as “specific conductive particles”, and the curable compound contained as the component (B) is appropriately designated as “specific curing”. It is referred to as a “chemical compound”.

  The conductive particle dispersion composition of the present invention has excellent dispersion stability of the conductive particles by having the above configuration. Therefore, even when the conductive particle dispersion composition of the present invention is stored for a long period of time, its fluidity is not impaired, and the conductive particles in the composition are settled or separated. The resulting aggregate formation is also effectively suppressed.

  The effect of suppressing the formation of aggregates exhibited by the conductive particle dispersion composition of the present invention can be achieved by applying the composition to a conductive paste or conductive ink, which is a preferred embodiment thereof, to form a wiring on a wiring board, or a multilayer wiring. When used for filling pores formed when conducting interlayer conduction of a substrate, it is possible to form a conductive layer having high conductivity and homogeneity.

  The conductive particle dispersion composition of the present invention may further be referred to as (D) another curable compound having a molecular structure different from the component (B) (hereinafter simply referred to as “other curable compound”). ) Is preferably contained.

  Here, in the present specification, the “curable compound” means a compound such as a monomer, a macromonomer, an oligomer, or a polymer that can contribute to the curing reaction, specifically, the curable compounds or The conductive particle dispersion composition can be cured by a polymerization reaction, a crosslinking reaction or the like between the curable compound and another compound.

  Furthermore, the electroconductive particle dispersion composition of the present invention further contains other components (for example, a polymerization initiator, a curing agent, a curing accelerator, etc.) other than the components (A) to (D) as desired. May be. Hereinafter, the constituent elements of the conductive particle dispersion composition of the present invention will be sequentially described.

<(A) Specific conductive particles>
In the conductive particle dispersion composition of the present invention, (A) the average particle size obtained by particle size measurement by the dynamic light scattering method is 0.02 μm to 20 μm, and is contained in the conductive particle dispersion composition. The electroconductive particle (specific electroconductive particle) whose content on the basis of the total mass of a component is 30 mass%-95 mass% is contained.

  The specific conductive particle in the present invention is preferably a metal, an alloy composed of two or more metals, or a particle containing a metal oxide. More preferably, the specific conductive particle is made of a metal selected from the group consisting of gold, platinum, silver, palladium, indium, copper, nickel, iron, zinc, bell, lead, tin, and bismuth. It is an alloy or a particle containing an oxide of these metals. Among these, particularly from the viewpoint of conductivity, the specific conductive fine particles are preferably particles containing gold, silver, copper, nickel, zinc, and tin.

  The specific conductive particles may be used alone or in combination of two or more.

  The average particle diameter of the specific conductive particles is 0.02 μm to 20 μm, and 0.02 μm to 0.2 μm is preferable from the viewpoint of ensuring conductivity when the conductive particle dispersion composition is sintered at a low temperature. 0.02 μm to 0.1 μm is more preferable

  The average particle diameter of the specific conductive particles in the present specification is a value obtained by measuring the particle diameter by a dynamic light scattering method.

  The content of the specific conductive particles in the conductive particle dispersion composition is 30 to 95% by mass based on the total mass of nonvolatile components contained in the conductive particle dispersion composition from the viewpoint of conductivity. . Content of specific electroconductive particle can be suitably designed in the said range according to the application object of the said composition.

For example, if the conductive particle dispersion composition is applied to a conductive paste which is a preferred embodiment thereof, the content of the specific conductive particles is based on the total mass of nonvolatile components contained in the conductive paste. As, it is 30-95 mass%, and 50-95 mass% is more preferable. Further, when the conductive particle dispersion composition is applied to a conductive ink that is one of the embodiments of the conductive paste, the content of the specific conductive particles is the non-volatile component contained in the conductive ink. Based on the total mass, it is 30 to 95% by mass, and more preferably 30 to 80% by mass.
In addition, the detail of the suitable aspect of the electroconductive particle dispersion composition of this invention, such as an electroconductive paste and the electroconductive ink which is one of the aspects, is mentioned later.

<(B) Specific curable compound>
The conductive particle dispersion composition of the present invention contains a curable compound (specific curable compound) having a functional group capable of forming an interaction with the conductive particles as the component (B).

  The specific curable compound has a functional group (hereinafter, appropriately referred to as “interactive group”) capable of forming an interaction with the conductive particle in the molecule, and the conductive particle of the present invention. The dispersion composition functions as a dispersant.

  That is, in the conductive particle dispersion composition of the present invention, the interaction group of the specific curable compound forms an interaction with the specific conductive particle, whereby the specific conductive particle has the interaction. It is considered that excellent dispersion stability of the conductive particles is exhibited in the composition by adsorbing the functional group and, as a result, the specific curable compound is adsorbed on the surface of the specific conductive particles.

  The interactive group possessed by the specific curable compound is preferably a functional group capable of adsorbing a metal. As such an interactive group, from the viewpoint of the function it has, a functional group having a positive charge, a functional group having a structure capable of dissociating into a positive charge, a functional group having a negative charge, Functional groups with a structure that can be dissociated to charge, nonionic polar groups that can interact with conductive particles, functional groups that can form chelation or multidentate structures with conductive particles, and conductive particles can be included And functional groups selected from the group consisting of functional groups that interact with a solvent in which a metal is held as crystal water, and more specifically, the following functional groups.

Examples of the functional group having a positive charge or having a structure capable of dissociating into a positive charge include an ammonium group, a phosphonium group, an imino group, a nitrogen-containing heterocycle, and the like.
Examples of the functional group having a negative charge or having a structure that can be dissociated into a negative charge include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a phosphonic acid group. Examples of the nonionic polar group that can be used include a hydroxyl group, an amide group, a sulfonamide group, an alkoxy group, a cyano group, a urethane group, and a thiol group.

  The functional group capable of having a chelation or multidentate structure with the conductive particle is a functional group that does not generate a proton due to dissociation of the functional group and can be coordinated by interaction with the conductive particle by intermolecular force. Is mentioned. Specific examples of such functional groups include nitrogen-containing heterocycles such as ether groups, thioether groups, cyano groups, trialkylamine groups, pyrrole, pyrrolidone, imidazole and pyridine, and oxygen-containing heterocycles such as furan and pyran. And those containing a sulfur-containing heterocycle such as thiophene and thiopyran, among which a nitrogen-containing functional group, an oxygen-containing functional group, and a sulfur-containing functional group are preferable, and specifically, a pyridyl group, cyano Those containing a group, an ether group or a thioether group are particularly preferred.

More preferable examples of the interactive group possessed by the specific curable compound in the present invention include those described above, for example, a group capable of coordinating with conductive particles, a nitrogen-containing functional group, a sulfur-containing functional group, An oxygen-containing functional group, a phosphorus-containing functional group, a group containing a halogen atom; an unsaturated ethylene group, and the like. More specifically, imide group, pyridine group, tertiary amino group, ammonium group, pyrrolidone group, amidino group, triazine ring, triazole ring, benzotriazole group, benzimidazole group, quinoline group, pyridine group, pyrimidine group, A group containing an alkylamine group structure such as a pyrazine group, a nazoline group, a quinoxaline group, a purine group, a triazine group, a piperidine group, a piperazine group, a pyrrolidine group, a pyrrole group, a pyrazole group, an aniline group or a trialkylamine group, an isocyanuric structure Nitrogen-containing functional groups such as containing groups, nitro groups, nitroso groups, azo groups, diazo groups, azide groups, cyano groups, cyanate groups (R—O—CN); phenolic hydroxyl groups, hydroxyl groups, carbonate groups, ether groups, carbonyls Group containing ester group, ester group, furan group, pyran group, N-oxide structure Oxygen-containing functional groups such as a group containing an S-oxide structure and a group containing an N-hydroxy structure; a thiophene group, a thiopyran group, a thiol group, a thiocyanuric acid group, a benzthiazole group, a mercaptotriazine group, a thioether group, a thioxy group, a sulfoxide Sulfur-containing functional groups such as groups, sulfone groups, sulfite groups, groups containing sulfoximine structures, groups containing sulfoxynium salt structures, groups containing sulfonic acid ester structures; such as phosphate groups, phosphoramide groups, phosphine groups, etc. Examples thereof include phosphorus-containing functional groups; groups containing halogen atoms such as chlorine and bromine; and unsaturated ethylene groups. Moreover, an imidazole group, a urea group, a thiourea group, etc. may be sufficient if it is a mode which shows non-dissociation by the relationship with an adjacent atom or atomic group. Furthermore, as the interactive group, for example, a functional group having a complex-forming structure such as an inclusion compound, cyclodextrin, or crown ether may be used.
Among them, since it has high polarity and high interaction with conductive particles, it is preferably a nitrogen-containing functional group, an oxygen-containing functional group, or a sulfur-containing functional group, and a pyridyl group, a cyano group, and an ether group, A thioether group is more preferable, an ether group (more specifically, a structure represented by —O— (CH ₂ ) _n —O— (n is an integer of 1 to 5)), and a cyano group are more preferable, and cyano The group is particularly preferred.

  Moreover, the dissociation group or nonionic polar group included in the functional groups listed above may take a form in which the conductive particles can be included by arranging a plurality of these groups. In the present invention, a functional group capable of taking such a form is referred to as a functional group capable of including conductive particles.

  Examples of the functional group that interacts with the solvent in which the metal is retained as crystal water include interaction with water coordinated to the metal by a dissociation group or a nonionic polar group included in the functional groups listed above. To be included.

  The specific curable compound has a functional group as listed above as an interactive group, thereby forming a salt with the metal particle, multidentate coordination with the metal particle, metal salt dispersion, inclusion of the metal particle, ion The property of adsorbing the conductive particles can be exhibited by injection or ion exchange.

  The specific curable compound is a functional group different from the above-described interactive group and can react with the curable compound by applying energy, or the curable compound and the component (E) described later It is preferable to further have a functional group capable of reacting with another curable compound contained as a curable compound.

  By having a functional group as described above, the specific curable compound reacts with each other or with another curable compound contained as the component (E) to form a conductive cured product. sell. As described above, the conductive particle dispersion composition of the present invention is a composition having excellent dispersion stability of conductive particles. Therefore, when the conductive particle dispersion composition of the present invention is cured, a cured product is formed while the uniform dispersion state of the conductive particles in the composition is maintained. A homogeneous cured product can be formed.

  As the functional group capable of reacting the specific curable compounds with each other by applying energy and the functional group capable of reacting the specific curable compound with another curable compound contained as the component (D), for example, a vinyl group And functional groups such as ethylene addition polymerizable unsaturated groups (polymerizable groups) such as allyl groups and (meth) acryl groups, epoxy groups, isocyanate groups, phenolic hydroxyl groups, amino groups, acid anhydrides, mercapto groups, and the like. It is done.

  The specific curable compound may be in any form of a monomer, an oligomer, a macromonomer, and a polymer. Among them, a polymer is preferably used from the viewpoint of dispersion stability.

  As a polymer which is a specific curable compound, the polymer which has a polymeric group and an interactive group is mentioned, for example. Such polymers include homopolymers and copolymers obtained using monomers having an interactive group, and ethylene addition polymerizable unsaturated groups (such as vinyl, allyl, and (meth) acryl groups) as polymerizable groups ( The polymer having a polymerizable group) is preferably introduced, and the polymer having the polymerizable group and the interactive group is preferably a polymer having a polymerizable group at least at the main chain terminal or side chain. Those having a polymerizable group are more preferred.

  In the polymer having a polymerizable group and an interactive group, the unit derived from the monomer having an interactive group is a polymer having a polymerizable group and an interactive group from the viewpoint of interaction formation with conductive particles. It is preferable to contain in the range of 50-95 mol%, and it is more preferable to contain in the range of 40-80 mol%.

  Moreover, when obtaining the polymer which has a polymeric group and an interactive group, you may synthesize | combine using another monomer other than the monomer which has the said interactive group. As the other monomer, a general polymerizable monomer may be used, and examples thereof include a diene monomer and an acrylic monomer.

Such a polymer having a polymerizable group and an interactive group can be synthesized as follows.
As synthesis methods, i) a method in which a monomer having an interactive group and a monomer having a polymerizable group are copolymerized, and ii) a monomer having an interactive group and a monomer having a double bond precursor are copolymerized. And then introducing a double bond by treatment with a base or the like, iii) reacting a polymer having an interactive group with a monomer having a polymerizable group to introduce a double bond (introducing a polymerizable group) ) Method. From the viewpoint of synthesis suitability, ii) a method in which a monomer having an interactive group and a monomer having a double bond precursor are copolymerized, and then a double bond is introduced by treatment with a base or the like, iii This is a method of introducing a polymerizable group by reacting a polymer having an interactive group with a monomer having a polymerizable group.

  As the monomer having an interactive group used for the synthesis of a polymer having a polymerizable group and an interactive group, the same monomers as those having the above interactive group can be used. A monomer may be used individually by 1 type and may use 2 or more types together.

Examples of the monomer having a polymerizable group to be copolymerized with a monomer having an interactive group include allyl (meth) acrylate and 2-allyloxyethyl methacrylate.
Examples of the monomer having a double bond precursor include 2- (3-chloro-1-oxopropoxy) ethyl methacrylate, 2- (3-bromo-1-oxopropoxy) ethyl methacrylate, and the like.

  Furthermore, the polymerizability used for introducing an unsaturated group by utilizing a reaction with a functional group such as a carboxyl group, an amino group or a salt thereof, a hydroxyl group, and an epoxy group in a polymer having an interactive group. Examples of the monomer having a group include (meth) acrylic acid, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-isocyanatoethyl (meth) acrylate.

  The weight average molecular weight of the polymer having an interactive group used as the specific curable compound is preferably 2000 or more and 500,000 or less, and more preferably 10,000 or more and 300,000 or less.

  As the polymer applied as the specific curable compound, for example, a unit represented by the following formula (1) and a copolymer containing a unit represented by the following formula (2) (hereinafter referred to as “specific polymerization” as appropriate). As a suitable example, it is referred to as “adhesive polymer”.

In the above formulas (1) and (2), R ^{1 to} R ⁵ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z are each independently A single bond, a substituted or unsubstituted divalent organic group, an ester group, an amide group, or an ether group; L ¹ and L ² each independently represent a substituted or unsubstituted divalent organic group; To express.

When R ^{1 to} R ⁵ are substituted or unsubstituted alkyl groups, examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the substituted alkyl group include methoxy And a methyl group, an ethyl group, a propyl group, and a butyl group substituted with a group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, and the like.
R ¹ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.
R ³ is preferably a hydrogen atom.
R ⁴ is preferably a hydrogen atom.
R ⁵ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a hydroxy group or a bromine atom.

When X, Y and Z are a substituted or unsubstituted divalent organic group, the divalent organic group includes a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group. Is mentioned.
As the substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an ethylene group, a propylene group, a butylene group, or these groups are substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, or the like. Those are preferred.
The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom or the like.
Among _{them, - (CH 2) n -} (n is an integer of 1 to 3) are preferred, more preferably -CH ₂ -.

L ¹ is preferably a divalent organic group having a urethane bond or a urea bond, more preferably a divalent organic group having a urethane bond, and among them, one having a total carbon number of 1 to 9 is preferable. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1.
More specifically, the structure of L ¹ is preferably a structure represented by the following formula (1-1) or formula (1-2).

In the above formula (1-1) and formula (1-2), R ^a and R ^b each independently represent two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom. A divalent organic group formed by using, preferably a substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group, ethylene oxide group, diethylene oxide group, triethylene oxide group, tetraethylene oxide group, di- Examples include a propylene oxide group, a tripropylene oxide group, and a tetrapropylene oxide group.

L ² is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. The group obtained by combining the alkylene group and the aromatic group may further be via an ether group, an ester group, an amide group, a urethane group, or a urea group. Among them, L ² preferably has 1 to 15 total carbon atoms, and particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^2.
Specifically, a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, and those groups substituted with a methoxy group, a hydroxy group, a chlorine atom, a bromine atom, a fluorine atom, etc., The group which combined these is mentioned.

  As the specific polymerizable polymer, the unit represented by the formula (1) is preferably a unit represented by the following formula (3).

In the above formula (3), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and Z represents a single bond, a substituted or unsubstituted divalent organic group. Represents an ester group, an amide group, or an ether group, W represents an oxygen atom, or NR (R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted C 1-5 substituent. And L ¹ represents a substituted or unsubstituted divalent organic group.

R ¹ and R ² in the formula (3) are synonymous with R ¹ and R ² in the formula (1), and preferred examples are also the same.

Z in Formula (3) has the same meaning as Z in Formula (1), and preferred examples are also the same.
Further, ^{L 1} in the formula (3) also has the same meaning as ^{L 1} in Formula (1), and preferred examples are also the same.

  As the specific polymerizable polymer, the unit represented by the formula (3) is preferably a unit represented by the following formula (4).

In Formula (4), R ¹ and R ² each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, and V and W each independently represent an oxygen atom or NR (R Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms), and L ¹ represents a substituted or unsubstituted divalent organic group. Represents.

R ¹ and R ² in the formula (4) are synonymous with R ¹ and R ² in the formula (1), and preferred examples are also the same.

L ¹ in Formula (4) has the same meaning as L ¹ in Formula (1), and the preferred examples are also the same.

In Formula (3) and Formula (4), W is preferably an oxygen atom.
In Formulas (3) and (4), L ¹ is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, and a divalent organic group having a urethane bond. Of these, those having 1 to 9 carbon atoms in total are particularly preferred.

  Moreover, as a specific polymerizable polymer, it is preferable that the unit represented by the said Formula (2) is a unit represented by following formula (5).

In Formula (5), R ⁵ represents a hydrogen atom or a substituted or unsubstituted alkyl group, U represents an oxygen atom, or NR ′ (R ′ represents a hydrogen atom or an alkyl group, preferably , A hydrogen atom, or an unsubstituted alkyl group having 1 to 5 carbon atoms.), L ² represents a substituted or unsubstituted divalent organic group.

R ⁵ in Formula (5) has the same meaning as R ¹ and R ² in Formula (1), and is preferably a hydrogen atom.

L ² in formula (5) has the same meaning as L ² in formula (1), and is preferably a linear, branched, or cyclic alkylene group, an aromatic group, or a group obtained by combining these. .
In particular, in the formula (5), the linking site with the cyano group in L ² is preferably a divalent organic group having a linear, branched, or cyclic alkylene group. The organic group preferably has 1 to 10 carbon atoms.
As another preferred embodiment, it is preferable that the linkage site to the cyano group in L ² in Formula (5) is a divalent organic group having an aromatic group, and among them, the divalent organic group However, it is preferable that it is C6-C15.

The specific polymerizable polymer is configured to include units represented by the formulas (1) to (5), and is a polymer having a polymerizable group and a cyano group in the side chain.
This specific polymerizable polymer can be synthesized, for example, as follows.

Examples of the polymerization reaction when synthesizing the specific polymerizable polymer include radical polymerization, cationic polymerization, and anionic polymerization. From the viewpoint of reaction control, radical polymerization or cationic polymerization is preferably used.
The specific polymerizable polymer is 1) when the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain, and 2) introduced into the polymerization form and side chain forming the polymer main chain. The synthesis method differs depending on whether the polymerization form of the polymerizable group is the same.

1) When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain When the polymerization form forming the polymer main chain is different from the polymerization form of the polymerizable group introduced into the side chain 1-1) An embodiment in which the polymer main chain is formed by cationic polymerization and the polymerization form of the polymerizable group introduced into the side chain is radical polymerization, and 1-2) the polymer main chain is formed by radical polymerization. There is a mode in which the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization.

1-1) A mode in which polymer main chain formation is performed by cationic polymerization, and a polymerization form of a polymerizable group introduced into a side chain is radical polymerization. In the present invention, polymer main chain formation is performed by cationic polymerization, and a side chain is formed. Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into the radical polymerization is radical polymerization include the following compounds.

-Monomers used to form polymerizable group-containing units As monomers used to form polymerizable group-containing units used in this embodiment, vinyl (meth) acrylate, allyl (meth) acrylate, 4- ( (Meth) acryloylbutane vinyl ether, 2- (meth) acryloylethane vinyl ether, 3- (meth) acryloylpropane vinyl ether, (meth) acryloyloxydiethylene glycol vinyl ether, (meth) acryloyloxytriethylene glycol vinyl ether, (meth) acryloyl 1st ter Pioneer, 1- (meth) acryloyloxy-2-methyl-2-propene, 1- (meth) acryloyloxy-3-methyl-3-butene, 3-methylene-2- (meth) acryloyloxy-norbornane, 4,4′-ethylidene diphenol di (meth) acrylate, methacrolein di (meth) acryloyl acetal, p-((meth) acryloylmethyl) styrene, allyl (meth) acrylate, 2- (bromomethyl) vinyl acrylate, 2- (Hydroxymethyl) allyl acrylate and the like.

Monomers used to form cyano group-containing units Monomers used to form cyano group-containing units used in this embodiment include 2-cyanoethyl vinyl ether, cyanomethyl vinyl ether, 3-cyanopropyl vinyl ether, 4-cyanobutyl Vinyl ether, 1- (p-cyanophenoxy) -2-vinyloxy-ethane, 1- (o-cyanophenoxy) -2-vinyloxy-ethane, 1- (m-cyanophenoxy) -2-vinyloxy-ethane, 1- ( p-cyanophenoxy) -3-vinyloxy-propane, 1- (p-cyanophenoxy) -4-vinyloxy-butane, o-cyanobenzyl vinyl ether, m-cyanobenzyl vinyl ether, p-cyanobenzyl vinyl ether, allyl cyanide, allyl cyanoacetic acid And the following compounds.

Polymerization methods include general cation polymerization methods described in Experimental Chemistry Course “Polymer Chemistry”, Chapter 2-4 (p74) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu, Chapter 7 (p195). Can be used. In the cationic polymerization, proton acids, metal halides, organometallic compounds, organic salts, metal oxides and solid acids, and halogens can be used as initiators. As possible initiators, the use of metal halides and organometallic compounds is preferred.
Specifically, boron trifluoride, boron trichloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, tin bromide, phosphorus pentafluoride, antimony chloride, molybdenum chloride, tungsten chloride, iron chloride, Examples include dichloroethylaluminum, chlorodiethylaluminum, dichloromethylaluminum, chlorodimethylaluminum, trimethylaluminum, trimethylzinc, and methylgrineer.

1-2) A mode in which polymer main chain formation is performed by radical polymerization and the polymerization form of the polymerizable group introduced into the side chain is cationic polymerization In the present invention, polymer main chain formation is performed by radical polymerization, and the side chain Examples of the monomer used in an embodiment in which the polymerization form of the polymerizable group introduced into is cationic polymerization include the following compounds.

-Monomer used for forming polymerizable group-containing unit The same monomers as those used for forming the polymerizable group-containing unit mentioned in the embodiment 1-1) can be used.

Monomers used to form cyano group-containing units Monomers used to form cyano group-containing units used in this embodiment include cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 3-cyanopropyl ( (Meth) acrylate, 2-cyanopropyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 5-cyanopentyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 7-cyano Hexyl (meth) acrylate, 8-cyanohexyl (meth) acrylate, 2-cyanoethyl- (3- (bromomethyl) acrylate), 2-cyanoethyl- (3- (hydroxymethyl) acrylate), p-cyanophenyl (meth) ) Acrylate, o-cyanophenyl (meth) acrylate, m-cyanophenyl (meth) acrylate, 5- (meth) acryloyl-2-carbonitryl-norbornene, 6- (meth) acryloyl-2-carbonitryl-norbornene, 1 -Cyano-1- (meth) acryloyl-cyclohexane, 1,1-dimethyl-1-cyano- (meth) acrylate, 1-dimethyl-1-ethyl-1-cyano- (meth) acrylate, o-cyanobenzyl (meta ) Acrylate, m-cyanobenzyl (meth) acrylate, p-cyanobenzyl (meth) acrylate, 1-cyanocycloheptyl acrylate, 2-cyanophenyl acrylate, 3-cyanophenyl acrylate, vinyl cyanoacetate, 1-cyano-1- Cyclopropanecarboxylic acid vinyl , Allyl cyanoacetate, allyl 1-cyano-1-cyclopropanecarboxylate, N, N-dicyanomethyl (meth) acrylamide, N-cyanophenyl (meth) acrylamide, allyl cyanomethyl ether, allyl-o-cyanoethyl ether, allyl -M-cyanobenzyl ether, allyl-p-cyanobenzyl ether and the like.
A monomer having a structure in which a part of hydrogen of the monomer is substituted with a hydroxyl group, an alkoxy group, a halogen, a cyano group, or the like can also be used.

Polymerization methods include general radical polymerization methods described in Experimental Chemistry Course “Polymer Chemistry” Chapter 2-2 (p34) and “Experimental Methods for Polymer Synthesis” written by Takayuki Otsu Chapter 5 (p125). Can be used. As the initiator for radical polymerization, a high-temperature initiator that requires heating at 100 ° C. or higher, a normal initiator that starts by heating at 40 to 100 ° C., a redox initiator that starts at a very low temperature, and the like are known. In general, an initiator is preferred from the viewpoint of stability of the initiator and ease of handling of the polymerization reaction.
Usual initiators include benzoyl peroxide, lauroyl peroxide, peroxodisulfate, azobisisobutyronitrile, azovir-2,4-dimethylvaleronitrile.

2) When the polymerization form forming the polymer main chain is the same as the polymerization form of the polymerizable group introduced into the side chain Polymerization form forming the polymer main chain and the polymerization form of the polymerizable group introduced into the side chain Are the same, 2-1) both are cationic polymerization, and 2-2) both are radical polymerization.

2-1) Both are aspects of cationic polymerization In both aspects of cationic polymerization, as the monomer having a cyano group, the same monomers as those used for forming the cyano group-containing unit mentioned in the aspect of 1-1) are used. Can be used.
From the viewpoint of preventing gelation during polymerization, a polymer having a cyano group is synthesized in advance, and then the polymer and a compound having a cationic polymerizable group (hereinafter referred to as “reactive compound” as appropriate). It is preferable to use a method in which a cationically polymerizable group is introduced into the side chain.

In addition, it is preferable that the polymer which has a cyano group has a reactive group as shown below for reaction with a reactive compound.
Moreover, it is preferable that the polymer having a cyano group and the reactive compound are appropriately selected so as to be a combination of the following functional groups.
Specific combinations include (polymer reactive group, functional group of reactive compound) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, Benzyl halide), (hydroxyl group, carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, halogenated benzyl) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), etc. be able to.

Here, specifically, the following compounds can be used as the reactive compound.
That is, allyl alcohol, 4-hydroxybutane vinyl ether, 2-hydroxyethane vinyl ether, 3-hydroxypropane vinyl ether, hydroxytriethylene glycol vinyl ether, 1st terpionol, 2-methyl-2-propenol, 3-methyl-3-butenol, 3 -Methylene-2-hydroxy-norbornane, p- (chloromethyl) styrene.

2-2) Aspect in which both are radical polymerizations In a mode in which both are radical polymerizations, the synthesis method includes i) a method of copolymerizing a monomer having a cyano group and a monomer having a polymerizable group, ii) a cyano group A method of copolymerizing a monomer having a monomer and a monomer having a double bond precursor and then introducing a double bond by treatment with a base or the like; iii) reacting a polymer having a cyano group with a monomer having a polymerizable group And introducing a double bond (introducing a polymerizable group). From the viewpoint of synthesis suitability, ii) a method in which a monomer having a cyano group and a monomer having a double bond precursor are copolymerized and then a double bond is introduced by treatment with a base or the like, iii) cyano In this method, a polymer having a group and a monomer having a polymerizable group are reacted to introduce a polymerizable group.

  Examples of the monomer having a polymerizable group used in the synthesis method i) include allyl (meth) acrylate and the following compounds.

  Examples of the monomer having a double bond precursor used in the synthesis method ii) include compounds represented by the following formula (a).

In the above formula (a), A is an organic group having a polymerizable group, R ^{1 to} R ³ are each independently a hydrogen atom or a monovalent organic group, and B and C are removed by elimination reaction. This is a leaving group, and the elimination reaction referred to here is one in which C is extracted by the action of a base and B is eliminated. B is preferably eliminated as an anion and C as a cation.
Specific examples of the compound represented by the formula (a) include the following compounds.

  Further, in the synthesis method of ii), in order to convert the double bond precursor into a double bond, as shown below, a method for removing the leaving groups represented by B and C by elimination reaction, That is, a reaction in which C is extracted by the action of a base and B is eliminated is used.

  Preferred examples of the base used in the elimination reaction include alkali metal hydrides, hydroxides or carbonates, organic amino compounds, and metal alkoxide compounds. Preferred examples of alkali metal hydrides, hydroxides or carbonates include sodium hydride, calcium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, Examples include potassium hydrogen carbonate and sodium hydrogen carbonate. Preferable examples of the organic amine compound include trimethylamine, triethylamine, diethylmethylamine, tributylamine, triisobutylamine, trihexylamine, trioctylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N- Methyldicyclohexylamine, N-ethyldicyclohexylamine, pyrrolidine, 1-methylpyrrolidine, 2,5-dimethylpyrrolidine, piperidine, 1-methylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, 1,4-dimethyl Piperazine, quinuclidine, 1,4-diazabicyclo [2,2,2] -octane, hexamethylenetetramine, morpholine, 4-methylmorpholine, pyridine, picoline, 4-dimethylaminopyridine, Cytidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N, N'-dicyclohexylcarbodiimide (DCC), diisopropylethylamine, Schiff base, and the like. Preferable examples of the metal alkoxide compound include sodium methoxide, sodium ethoxide, potassium t-butoxide and the like. These bases may be used alone or in combination of two or more.

  Examples of the solvent used for adding (adding) the base in the elimination reaction include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate , Ethyl lactate, water and the like. These solvents may be used alone or in combination of two or more.

  The amount of the base used may be equal to or less than the equivalent to the amount of the specific functional group (the leaving group represented by B or C) in the compound, or may be equal to or more than the equivalent. Moreover, when an excess base is used, it is also a preferred form to add an acid or the like for the purpose of removing the excess base after the elimination reaction.

The polymer having a cyano group used in the synthesis method of iii) includes a monomer used for forming the cyano group-containing unit mentioned in the above embodiment 1-2) and a reactive group for introducing a double bond. It is synthesized by radical polymerization of the monomer having it.
Examples of the monomer having a reactive group for introducing a double bond include monomers having a carboxyl group, a hydroxyl group, an epoxy group, or an isocyanate group as the reactive group.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, itaconic acid, vinyl benzoate, Aronics M-5300, M-5400, M-5600 manufactured by Toagosei, acrylic ester PA, HH manufactured by Mitsubishi Corporation, and Kyoeisha Chemical Co., Ltd. Examples thereof include light acrylate HOA-HH manufactured by Nakamura Chemical Co., Ltd., NK ester SA, A-SA, and the like.
As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1- (meth) acryloyl- 3-hydroxy-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl)-(meth) acrylate, methyl ester of 2- (hydroxymethyl)-(meth) acrylate, 3-chloro-2-hydroxypropyl (meth) ) Acrylate, 3,5-dihydroxypentyl (meth) acrylate, 1-hydroxymethyl-4- (meth) acryloylmethyl-cyclohexane, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1-methyl-2-acryl Iroxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 1-methyl-2-acryloyloxyethyl-2-hydroxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxy-3 -Chloropropyl phthalic acid, Aronics M-554, M-154, M-555, M-155, M-158, manufactured by Toagosei Co., Ltd., Bremer PE-200, PE-350, manufactured by NOF Corporation PP-500, PP-800, PP-1000, 70PEP-350B, 55PET800, lactone-modified acrylate having the following structure can be used.
_{CH 2 = CRCOOCH 2 CH 2 [} OC (= O) C 5 H 10] n OH
(R = H or Me, n = 1-5)

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and cyclomers A and M manufactured by Daicel Chemical.
As the monomer having an isocyanate group, Karenz AOI and MOI manufactured by Showa Denko can be used.
The polymer having a cyano group used in the synthesis method iii) may further contain a third copolymer component.

In the synthesis method of iii), the monomer having a polymerizable group to be reacted with a polymer having a cyano group varies depending on the type of the reactive group in the polymer having a cyano group, but has the following combinations of functional groups: Can be used.
That is, (reactive group of polymer, functional group of monomer) = (carboxyl group, carboxyl group), (carboxyl group, epoxy group), (carboxyl group, isocyanate group), (carboxyl group, benzyl halide), (hydroxyl group) , Carboxyl group), (hydroxyl group, epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, benzyl halide) (isocyanate group, hydroxyl group), (isocyanate group, carboxyl group), (epoxy group, carboxyl group), etc. Can be mentioned.
Specifically, the following monomers can be used.

In the specific polymerizable polymer, when L ¹ in Formula (1), Formula (3), or Formula (4) is a divalent organic group having a urethane bond, the following synthesis method (hereinafter, It is preferably synthesized by the synthesis method A).
That is, the synthesis method A uses a polymer having a hydroxyl group in a side chain and a compound having an isocyanate group and a polymerizable group in at least a solvent, and adds the isocyanate group to the hydroxyl group, thereby adding L ¹ It is characterized by forming a urethane bond inside.

Here, as the polymer having a hydroxyl group in the side chain used in the synthesis method A, the monomer used for forming the cyano group-containing unit mentioned in the above embodiment 1-2) and the hydroxyl group-containing listed below A copolymer with (meth) acrylate is preferred. Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 1- (meth) acrylate. ) Acrylyl-3-hydroxy-adamantane, hydroxymethyl (meth) acrylamide, 2- (hydroxymethyl)-(meth) acrylate, methyl ester of 2- (hydroxymethyl)-(meth) acrylate, 3-chloro-2-hydroxy Propyl (meth) acrylate, 3,5-dihydroxypentyl (meth) acrylate, 1-hydroxymethyl-4- (meth) acryloylmethyl-cyclohexane, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1- Tyl-2-acryloyloxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 1-methyl-2-acryloyloxyethyl-2-hydroxypropylphthalic acid, 2-acryloyloxyethyl- 2-hydroxy-3-chloropropylphthalic acid, Allonics M-554, M-154, M-555, M-155, M-158 manufactured by Toagosei Co., Ltd., Bremer PE-200 manufactured by NOF Corporation PE-350, PP-500, PP-800, PP-1000, 70PEP-350B, 55PET800, and lactone-modified acrylates having the following structures can be used.
_{CH 2 = CRCOOCH 2 CH 2 [} OC (= O) C 5 H 10] n OH (R = H or Me, n = 1~5)
In addition, the polymer which has a hydroxyl group in the side chain used for the synthesis method A may further contain a third copolymer component.

Among the polymers having a hydroxyl group in the side chain as described above, from the viewpoint of synthesizing a polymer having a high molecular weight, the bifunctional acrylate produced as a by-product when synthesizing a hydroxy group-containing (meth) acrylate was removed as a raw material. It is preferable to use a polymer synthesized using raw materials. As the purification method, distillation and column purification are preferred. More preferably, it is preferably synthesized using a hydroxyl group-containing (meth) acrylate obtained by sequentially performing the following steps (1) to (4).
(1) Step (2) for dissolving a mixture containing hydroxyl group-containing (meth) acrylate and bifunctional acrylate by-produced when synthesizing the hydroxyl group-containing (meth) acrylate in water (2) obtained aqueous solution A step of separating the layer containing the first organic solvent and the bifunctional acrylate from the aqueous layer after adding the first organic solvent that separates from the water (3) In the aqueous layer, the hydroxyl group-containing A step of dissolving a compound having higher water solubility than (meth) acrylate (4) A step of adding a second organic solvent to the aqueous layer, extracting the hydroxyl group-containing (meth) acrylate, and then concentrating it.

The mixture used in the step (1) includes a hydroxyl group-containing (meth) acrylate and a bifunctional acrylate that is an impurity by-product when the hydroxyl group-containing (meth) acrylate is synthesized. It corresponds to a general commercial product of hydroxyl group-containing (meth) acrylate.
In the step (1), this commercial product (mixture) is dissolved in water to obtain an aqueous solution.

In the step (2), a first organic solvent that separates from water is added to the aqueous solution obtained in the step (1). Examples of the first organic solvent used here include ethyl acetate, diethyl ether, benzene, toluene and the like.
Thereafter, the layer (oil layer) containing the first organic solvent and the bifunctional acrylate is separated from the aqueous solution (aqueous layer).

In the step (3), a compound having higher water solubility than the hydroxyl group-containing (meth) acrylate is dissolved in the aqueous layer separated from the oil layer in the step (2).
Compounds having higher water solubility than the hydroxyl group-containing (meth) acrylate used here include alkali metal salts such as sodium chloride, sodium chloride and potassium chloride, and alkaline earth metal salts such as magnesium sulfate and calcium sulfate. An inorganic salt or the like is used.

In the step (4), the second organic solvent is added to the aqueous layer to extract the hydroxyl group-containing (meth) acrylate, followed by concentration and isolation.
Examples of the second organic solvent used here include ethyl acetate, diethyl ether, benzene, toluene and the like. The second organic solvent may be the same as or different from the first organic solvent described above.
For the concentration in the step (4), drying with anhydrous magnesium sulfate, distillation under reduced pressure, or the like is used.

The isolate containing the hydroxyl group-containing (meth) acrylate obtained by sequentially performing the steps (1) to (4) described above has a bifunctional acrylate in the total mass of 0.1% by mass or less. It is preferable to include. That is, through the steps (1) to (4), the bifunctional acrylate that is an impurity is removed from the mixture, and the hydroxyl group-containing (meth) acrylate is purified.
A more preferable range of the content of the bifunctional acrylate is 0.05% by mass or less in the total mass of the isolate, and the smaller the better.
By using such a purified hydroxyl group-containing (meth) acrylate, the bifunctional acrylate that is an impurity is less likely to affect the polymerization reaction, so that a specific polymerizable polymer having a weight average molecular weight of 20000 or more is synthesized. Can do.

  The hydroxy group-containing (meth) acrylate used in the step (1) is a hydroxyl group-containing (meth) acrylate used when synthesizing a polymer having a hydroxyl group in the side chain used in the synthesis method A described above. Those listed can be used. Among them, a monomer having a primary hydroxyl group is preferable from the viewpoint of reactivity to isocyanate, and further, from the viewpoint of increasing the polymerizable group ratio per unit weight of the polymer, a hydroxyl group containing a metal having a molecular weight of 100 to 250 (meta ) Acrylate is preferred.

  Moreover, as a compound which has an isocyanate group and a polymeric group used for the synthesis method A, 2-acryloyloxyethyl isocyanate (Karenz AOI, Showa Denko KK), 2-methacryloxy isocyanate (Karenz MOI, Showa Denko) Etc.).

Moreover, as a solvent used for the synthesis method A, those having an SP value (calculated by the Okitsu method) of 20 to 23 MPa ^1/2 are preferable. Specifically, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diester are used. Acetate, methyl acetoacetate, ethyl acetoacetate, 1,2,3-triacetoxy-propane, cyclohexanone, 2- (1-cyclohexenyl) cyclohexanone, propionitrile, N-methylpyrrolidone, dimethylacetamide, acetylacetone, acetophenone, triacetin 1,4-dioxane, dimethyl carbonate and the like.
Among them, from the viewpoint of synthesizing a high molecular weight substance, an ester solvent is more preferable, and diacetate solvents such as ethylene glycol diacetate and diethylene glycol diacetate, and dimethyl carbonate are more preferable.
Here, the SP value of the solvent in the present invention is calculated by the Okitsu method (Toshinao Okitsu, “Journal of the Adhesion Society of Japan” 29 (3) (1993)). Specifically, the SP value is calculated by the following formula. ΔF is a value described in the literature.
SP value (δ) = ΣΔF (Molar Attraction Constants) / V (molar volume)

In the specific polymerizable polymer synthesized as described above, the ratio of the polymerizable group-containing unit and the cyano group-containing unit is preferably in the following range with respect to the entire copolymerization component.
That is, the polymerizable group-containing unit is preferably contained in an amount of 5 mol% to 50 mol%, more preferably 5 mol% to 40 mol%, based on the entire copolymer component. If it is 5 mol% or less, the reactivity (curability and polymerizability) is lowered, and if it is 50 mol% or more, it is easily gelled during synthesis and is difficult to synthesize.
Moreover, it is preferable that a cyano group containing unit is contained by 5-95 mol% with respect to the whole copolymerization component from an adsorptive viewpoint with respect to electroconductive particle, More preferably, it is 10-95 mol%.

  The specific polymerizable polymer may contain other units in addition to the cyano group-containing unit and the polymerizable group-containing unit. As the monomer used for forming the other unit, any monomer can be used as long as it does not impair the effects of the present invention.

Specific examples of monomers used to form other units include acrylic resin skeleton, styrene resin skeleton, phenol resin (phenol-formaldehyde resin) skeleton, melamine resin (melamine and formaldehyde polycondensate) skeleton, Urea resin (polycondensate of urea and formaldehyde) skeleton, polyester resin skeleton, polyurethane skeleton, polyimide skeleton, polyolefin skeleton, polycycloolefin skeleton, polystyrene skeleton, polyacryl skeleton, ABS resin (polymer of acrylonitrile, butadiene, styrene) Skeleton, polyamide skeleton, polyacetal skeleton, polycarbonate skeleton, polyphenylene ether skeleton, polyphenylene sulfide skeleton, polysulfone skeleton, polyether sulfone skeleton, polyarylate skeleton, polyether Ether ketone skeleton, include monomers capable of forming a main chain skeleton of the polyamide-imide skeleton.
Further, these main chain skeletons may be cyano group-containing units or main chain skeletons of polymerizable group-containing units.

However, when the polymerizable group is introduced by reacting with the polymer as described above, a small amount of reactive portion remains when it is difficult to introduce 100%, so this becomes the third unit. There is a possibility.
Specifically, when the polymer main chain is formed by radical polymerization, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl Unsubstituted (meth) acrylates such as (meth) acrylate and stearyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, Halogen-substituted (meth) acrylic esters such as 2-chloroethyl (meth) acrylate, ammonium group-substituted (meth) acrylic esters such as 2- (meth) acryloyloxyethyltrimethylammonium chloride, butyl (meth) acrylamide, Iso (Meth) acrylamides such as propyl (meth) acrylamide, octyl (meth) acrylamide, dimethyl (meth) acrylamide, styrenes such as styrene, vinylbenzoic acid, p-vinylbenzylammonium chloride, N-vinylcarbazole, vinyl acetate, Vinyl compounds such as N-vinylacetamide and N-vinylcaprolactam, and dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-ethylthio-ethyl (meth) acrylate, (meth) acrylic acid, 2 -Hydroxyethyl (meth) acrylate etc. can be used.
Moreover, the macromonomer obtained using the monomer of the said description can also be used.

  When the polymer main chain is formed by cationic polymerization, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethylene glycol vinyl ether, di (ethylene glycol) vinyl ether, 1,4-butanediol vinyl ether, 2-chloroethyl vinyl ether, 2 -Vinyl ethers such as ethylhexyl vinyl ether, vinyl acetate, 2-vinyloxytetrahydropyran, vinyl benzoate, vinyl butyrate, styrenes such as styrene, p-chlorostyrene, p-methoxystyrene, allyl alcohol, 4-hydroxy-1- Terminal ethylenes such as butene can be used.

The weight average molecular weight of the specific polymerizable polymer is preferably from 2,000 to 500,000, and more preferably from 10,000 to 300,000.
In particular, from the viewpoint of polymerization sensitivity, the weight average molecular weight of the specific polymerizable polymer is preferably 20000 or more.

The polymerization degree of the specific polymerizable polymer is preferably 10-mer or higher, more preferably 20-mer or higher. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.
The preferable ranges of the molecular weight and the degree of polymerization described here are also preferable ranges for a polymer having a polymerizable group and an interactive group other than the specific polymerizable polymer used in the present invention.

Specific examples of the specific polymerizable polymer are shown below, but are not limited thereto.
In addition, as for the weight average molecular weight of these specific examples, all are the range of 3000-100000.

Here, for example, in the compound 2-2-11 of the specific example described above, acrylic acid and 2-cyanoethyl acrylate are dissolved in, for example, N-methylpyrrolidone, and the polymerization initiator is, for example, azoisobutyronitrile ( AIBN) can be used for radical polymerization, and then glycidyl methacrylate can be synthesized by addition reaction using a catalyst such as benzyltriethylammonium chloride and a polymerization inhibitor such as tertiary butylhydroquinone. it can.
Further, for example, the compound 2-2-19 in the specific example described above is prepared by dissolving the following monomers and p-cyanobenzyl acrylate in a solvent such as N, N-dimethylacrylamide, and polymerizing such as dimethyl azoisobutyrate. It can be synthesized by performing radical polymerization using an initiator and then dehydrochlorinating using a base such as triethylamine.

  The compound having a polymerizable group and an interactive group such as a specific polymerizable polymer may have a polar group in addition to the polymerizable group and the interactive group.

  The specific curable compound may be used alone or in combination of two or more.

  As content of the specific sclerosing | hardenable compound in the electroconductive particle dispersion composition of this invention, it is preferable that it is 5-70 mass% on the basis of the total mass of the non-volatile component contained in an electroconductive particle dispersion composition. .

<(C) Solvent>
The conductive particle dispersion composition of the present invention contains a solvent as the component (C).
The solvent that can be used is (B) a specific curable compound that is an essential component contained in the conductive particle dispersion composition, and (E) another curable compound that can be contained as an optional component. There is no particular limitation. A solvent can be used individually or in combination of 2 or more types.

  Examples of the solvent that can be used include alcohol solvents such as methanol, ethanol, propanol, 1-methoxy-2-propanol, isopropyl alcohol, and glycerin, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, and tetrahydrofuran. , Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ether solvents such as tetrahydrofuran, nitrile solvents such as acetonitrile and propyronitrile, formamide, N-methyl-2-pyrrolidone, Amide solvents such as N, N-dimethylacetamide and N, N-dimethylformamide, methyl acetate, ethyl acetate, butyl acetate, Acetic acid esters such as isopropyl acid, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolves such as cellosolve, butylcellosolve, carbitols such as carbitol, butylcarbitol, toluene, xylene, benzene, naphthalene, hexane And aromatic hydrocarbons such as cyclohexane, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and the like.

  Among these solvents, when a specific polymerizable polymer is used, amide, ketone, nitrile, and carbonate solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propio Nitrile, N-methylpyrrolidone and dimethyl carbonate are preferred.

  Moreover, if the conductive particle dispersion composition containing the specific polymerizable polymer is applied to a usage mode such as coating, it is preferable to use a solvent having a boiling point of 50 to 150 ° C. for ease of handling. In addition, these solvents may be used alone or in combination.

  The content of the solvent in the conductive particle dispersion composition of the present invention can be appropriately designed depending on the application mode of the composition, but about 10 to 90% by mass is appropriate.

<(D) Other curable compound>
The conductive particle dispersion composition of the present invention preferably contains another curable compound having a molecular structure different from the component (B).

  Other curable compounds that the conductive particle dispersion composition of the present invention may contain as the component (D) include acrylate compounds, epoxy compounds, isocyanate compounds, and compounds having functional groups that can react with these compounds. A compound selected from the group consisting of: The other curable compound may be in the form of a monomer, oligomer, macromonomer, or polymer.

  The acrylate compound that can be used as the other curable compound means a compound having at least one (meth) acryloyl group in the molecule. For example, vinyl (meth) acrylate, allyl (meth) acrylate, 4- (meth) Acryloylbutane vinyl ether, 2- (meth) acryloylethane vinyl ether, 3- (meth) acryloylpropane vinyl ether, (meth) acryloyloxydiethylene glycol vinyl ether, (meth) acryloyloxytriethylene glycol vinyl ether, (meth) acryloyl 1st terpionol, 1- (meth) acryloyloxy-2-methyl-2-propene, 1- (meth) acryloyloxy-3-methyl-3-butene, 3-methylene-2- (meth) acryloyloxy-norbornane, 4,4 -Ethylidene diphenol di (meth) acrylate, methacrolein di (meth) acryloyl acetal, p-((meth) acryloylmethyl) styrene, allyl (meth) acrylate, 2- (bromomethyl) vinyl acrylate, 2- (hydroxymethyl) And allyl acrylate.

  The epoxy compound that can be used as the other curable compound means a compound having at least one epoxy group in the molecule, such as a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak. Type epoxy resin, alkylphenol novolac type epoxy resin, biphenol F type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanate Examples thereof include nurate and alicyclic epoxy resin. As such an epoxy compound, a commercially available product can be used. For example, Epicoat 806 (jER806), Epicoat 828, Epicoat 807, Epicoat 4004P, Epicoat 152, Epicoat 154, Epicoat YX4000 (above, Japan Epoxy Resins Co., Ltd.) Epichron 840, Epicron 857, Epicron 830 (manufactured by Dainippon Ink & Chemicals, Inc.);

  As another curable compound, a compound having both functions of the above-mentioned epoxy compound and acrylate compound, that is, a compound having at least one (meth) acryloyl group and an epoxy group in the molecule (hereinafter referred to as “epoxy acrylate compound”) May be collectively referred to as “.”.

  Examples of the epoxy acrylate compound that can be used in the present invention include (meth) acrylic mono-, di-, poly-, and epoxy compounds having a main skeleton structure such as bisphenol type, resorcin type, phthalic acid type, glycol type, and phenol type. The thing etc. which added the acid are mentioned. As such an epoxy acrylate compound, a commercially available product can be used, for example, Neopole 8414, Neopole 8101, Neopole 8400, Neopole 8260 (manufactured by Nippon Yupica Co., Ltd.); Denacol DA-111, Denacol DA-141 , Denacol DA-250 (manufactured by Nagase ChemteX Corporation);

  The isocyanate compound that can be used as the other curable compound means a compound having at least one isocyanate group in the molecule, for example, TDI adduct type, TDI polymerization type, XDI type, IPDI type, HDI type, polyisocyanate type. Isocyanate compounds such as As such an isocyanate compound, a commercially available product can be used, for example, Takenate D-101A, Takenate 102, Takenate 103, Takenate 110, Takenate 120, Takenate 140 (above, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), etc. Is mentioned.

  As the compound having a functional group capable of reacting with the other curable compound described above, it means a compound having a functional group having a nucleophilicity such as a carboxyl group, an amino group or a hydroxyl group in the molecule, for example, polyallylamine, Examples include polyacrylic acid, polymethacrylic acid, polyester polyol, acrylic polyol, polyurethane polyol, and the like. Commercially available products may be used as such compounds, and examples thereof include tomide and fujicure (manufactured by Fuji Kasei Kogyo Co., Ltd.); Takelac series (Mitsui Chemical Polyurethane Co., Ltd.) and the like.

  Other curable compounds may be used alone or in combination of two or more.

  As content of the other sclerosing | hardenable compound in the electroconductive particle dispersion composition of this invention, it is 0-60 mass% on the basis of the total mass of the non-volatile component contained in an electroconductive particle dispersion composition. Preferably, it is 0-50 mass%, More preferably, it is 0-40 mass%.

<(E) Polymerization initiator, curing agent, and curing accelerator>
The conductive particle dispersion composition of the present invention may further contain a compound selected from a polymerization initiator, a curing agent, and a curing accelerator as the component (E).

-Polymerization initiator-
The polymerization initiator is appropriately selected according to the functional group possessed by the coexisting (B) specific curable compound and (D) other curable compound used in combination, if desired. Examples thereof include the following compounds. .

  As the polymerization initiator, for example, a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator and the like can be used. From the viewpoint of ease of handling and reactivity, a radical polymerization initiator and a cationic polymerization initiator are used. Are preferred, and radical polymerization initiators are more preferred. Further, the polymerization initiator may have a function of a thermal polymerization initiator, a photopolymerization initiator, or both.

  Specific examples of the polymerization initiator that can be contained as the component (E) include, for example, benzoyl peroxide (BPO), t-butylperoxy-2-ethylhexanate (PBO), Peroxide initiators such as di-t-butyl peroxide (PBD), t-butyl peroxyisopropyl carbonate (PBI), n-butyl 4,4, bis (t-butylperoxy) valerate (PHV), etc. 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis ( 2-methylpropane), 2,2′-azobis (2-methylbutane), 2,2′-azobis (2-methylpentane), 2,2′-azobis (2,3-dimethylbutane) ), 2,2′-azobis (2-methylhexane), 2,2′-azobis (2,4-dimethylpentane), 2,2′-azobis (2,3,3-trimethylbutane), 2, 2'-azobis (2,4,4-trimethylpentane), 3,3'-azobis (3-methylpentane), 3,3'-azobis (3-methylhexane), 3,3'-azobis (3 4-dimethylpentane), 3,3′-azobis (3-ethylpentane), dimethyl-2,2′-azobis (2-methylpropionate), diethyl-2,2′-azobis (2-methylpropio) And azo initiators such as di-tert-butyl-2,2′-azobis (2-methylpropionate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane -1 on It can be used. Further, the photopolymerization initiator may be a low molecule or a polymer, and generally known ones can be used.

  The content of the polymerization initiator in the conductive particle dispersion composition of the present invention is preferably 0 to 10% by mass based on the total mass of nonvolatile components contained in the conductive particle dispersion composition, More preferably, it is 0-5 mass%.

-Curing agent and / or curing accelerator-
If necessary, a curing agent and / or a curing accelerator can be added to the conductive particle dispersion composition of the present invention in order to advance the curing of the composition.
For example, as a curing agent and / or a curing accelerator when an epoxy compound is contained in the polymerization initiation layer, in the polyaddition type, an aliphatic polyamine, an alicyclic polyamine, an aromatic polyamine, polyamide, an acid anhydride, phenol, Examples of catalyst types such as phenol novolac, polymercaptan, compounds having two or more active hydrogens include aliphatic tertiary amines, aromatic tertiary amines, imidazole compounds, Lewis acid complexes, and the like.

Also, those that start curing by heat, light, moisture, pressure, acid, base, etc. include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyamidoamine, mensendiamine, isophoronediamine, N-amino. Ethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4 -Aminocyclohexyl) methane, m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, dicyandiamide, adipic dihydrazide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylteto Hydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), Methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride, polyazeline acid anhydride, phenol novolak, xylylene novolak, bis A novolak, triphenylmethane novolak, biphenyl novolak, dicyclopentadiene phenol novolak, terpene phenol novolak, polymercaptan Polysulfide, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol-tri-2-ethylhexyl Lurate, benzyldimethylamine, 2- (dimethylaminomethyl) phenol 2-methylimidazole, 2-ethyl-4-methylimidazole 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl- 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-diamino-6- (2-methylimidazolyl- (1))-ethyl S-triazine, BF ₃ monoethylamine complex, Lewis acid complex, organic acid Examples include hydrazide, diaminomaleonitrile, melamine derivatives, imidazole derivatives, polyamine salts, amine imide compounds, aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, triallyl selenium salts, ketimine compounds and the like.

  These curing agents and / or curing accelerators are 0 to 0 of the remaining non-volatile components from which the solvent is removed from the viewpoint of the coating properties of the conductive particle dispersion composition, the adhesion to the substrate to which the composition is applied, and the like. It can be added up to about 50% by mass.

<(F) Other ingredients>
-Surfactant-
A surfactant may be added to the conductive particle dispersion composition as necessary. The surfactant is not particularly limited as long as it is soluble in a solvent. Examples of such a surfactant include an anionic surfactant such as sodium n-dodecylbenzenesulfonate and n-dodecyltrimethylammonium chloride. Cationic surfactants such as these, polyoxyethylene nonylphenol ether (commercially available products include, for example, Emulgen 910, manufactured by Kao Corporation), polyoxyethylene sorbitan monolaurate (commercially available products such as “Tween” 20 "), and nonionic surfactants such as polyoxyethylene lauryl ether.

-Plasticizer-
If necessary, a plasticizer can be added to the conductive particle dispersion composition. Usable plasticizers include general plasticizers such as phthalates (dimethyl ester, diethyl ester, dibutyl ester, di-2-ethylhexyl ester, dinormal octyl ester, diisononyl ester, dinonyl ester, diisodecyl ester). Ester, butyl benzyl ester), adipic acid ester (dioctyl ester, diisononyl ester), azelain san dioctyl, sebacin sun ester (dibutyl ester, dioctyl ester) tricresyl phosphate, acetyl citrate tributyl, epoxidized soybean oil, trimellit High boiling solvents such as trioctyl acid, chlorinated paraffin, dimethylacetamide, and N-methylpyrrolidone can also be used.

-Polymerization inhibitor-
A polymerization inhibitor may be added to the conductive particle dispersion composition as necessary. As the polymerization inhibitor that can be used, hydroquinones such as hydroquinone, ditertiary butyl hydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, phenols such as p-methoxyphenol and phenol, Nitrosamines such as benzoquinones, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy free radical), free radicals such as 4-hydroxy TEMPO, phenothiazines, N-nitrosophenylhydroxyamine, and aluminum salts thereof Catechols can be used.

-Other ingredients-
Further, rubber components (for example, CTBN), flame retardants (for example, phosphorus flame retardants), diluents and thixotropic agents, pigments, antifoaming agents, leveling agents, coupling agents, etc. It may be added.
May be.

(Characteristics of conductive particle dispersion composition)
The conductive particle dispersion composition of the present invention is a composition that can be cured by applying energy. Application of energy that can be applied to the conductive particle dispersion composition of the present invention can be carried out by irradiation with radiation such as heating and exposure, and a combination of both.

  As a method for imparting energy to the conductive particle dispersion composition, for example, light irradiation with a UV lamp, visible light, or the like, heating with a hot plate, or the like is possible.

  Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Further, g-line, i-line, deep-UV light, and high-density energy beam (laser beam) are also used.

  Specific examples generally used include direct image-like recording using a thermal recording head, scanning exposure using an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.

  The time required for energy application varies depending on the use of the conductive particle dispersion composition, but is usually between 10 seconds and 5 hours.

In the case of performing the application of energy by the exposure, the exposure power, because to easily proceed the graft polymerization, addition, in order to suppress the decomposition of the produced graft ^polymer, of 500mJ / cm ² ~5000mJ / cm 2 A range is preferable.
In addition, when a polymer having an average molecular weight of 20,000 or more and a polymerization degree of 200 or more is used as a compound having a polymerizable group and an interactive group, graft polymerization proceeds easily with low energy exposure, and thus the generated graft Degradation of the polymer can be further suppressed.

(Use of conductive particle dispersion composition)
The conductive particle dispersion composition of the present invention having the above characteristics is suitable as a conductive paste. The conductive particle dispersion composition of the present invention can also be applied to conductive paints, electromagnetic wave shielding paints, paints that give a metal texture, and the like.
Here, the conductive paste means a paste obtained by mixing conductive particles such as silver, carbon, copper and the like at a high concentration with a viscous binder.
Moreover, conductive ink is mentioned as one of the aspects of an electrically conductive paste. The conductive ink can be applied as an ink in an inkjet method or the like.

  A conductive paste formed by applying the conductive particle dispersion composition of the present invention, and a conductive ink as one embodiment thereof are used for wiring formation materials for wiring boards, interlayer conduction materials for multilayer boards, and mounting components. It is suitable as a bonding material.

[Printed wiring board]
The printed wiring board of the present invention is characterized by having a conductive layer formed using the conductive particle dispersion composition of the present invention. The printed wiring board of the present invention can be provided with a highly conductive and homogeneous conductive layer by using the conductive particle dispersion composition of the present invention as a material for the conductive layer.

  The printed wiring board of the present invention is, for example, a printed wiring board described in each publication such as JP 2007-142147 A, JP 2007-142147 A, JP 2007-141648 A, JP 2006-202604 A, and the like. Instead of the conductive paste used for forming the conductive layer of the printed wiring board, the conductive particle dispersion composition of the present invention can be applied.

[Method for producing conductive particle dispersion composition]
The method for producing a conductive particle dispersion composition of the present invention is a method suitable for the production of the conductive particle dispersion composition of the present invention described above, and (A) specific conductive particles and (B) specific curability. It has at least a first step of kneading or predispersing a mixture containing a compound and (C) a solvent.

  By carrying out the first step, the specific conductive particles and the interactive groups are firmly formed due to the interaction between the specific conductive particles and the interactive group of the specific curable compound. Adsorb. As described above, the specific curable compound contributes as a dispersant for the specific conductive particles, and the strong adsorption between the specific conductive particles and the interactive group is in the obtained conductive particle dispersion composition. The dispersion stability of the specific conductive particles can be significantly improved.

In the manufacturing method of the electroconductive particle dispersion composition of this invention, it is preferable to perform the 2nd process of adding said (D) other sclerosing | hardenable compound, after performing a said 1st process.
In the second step, other components such as a curing agent and a polymerization initiator can be added in addition to other curable compounds.

  By performing the second step after performing the first step, it is possible to add another curable compound without impairing the dispersion stability of the specific conductive particles.

  As a method for producing the conductive particle dispersion of the present invention, any known dispersion method and mixing method can be applied.

  As described above, according to the method for producing a conductive particle dispersion composition of the present invention, a conductive particle dispersion composition that is excellent in dispersion stability of conductive particles, has high conductivity, and can form a homogeneous cured product. Can be manufactured by a simple process.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

[Example 1]
In the following manner, “conductive paste (1)” which is the conductive particle dispersion composition of the present invention is obtained.

<Conductive paste (1)>
Silver particles (average particle diameter: 5 μm, (A) specific conductive particles) 80 parts by mass Curing compound B 20 parts by mass (the following structure, weight average molecular weight: 60,000, (B) specific curable compound)
-Bis F-type epoxy compound 20 parts by mass (Epicoat 806, manufactured by Japan Epoxy Resin Co., Ltd., (D) Other curable compounds)
Epoxy acrylate compound 10 parts by mass (Neopol 8414, manufactured by Nippon Iupika Co., Ltd., 65% DEGDMA solution,
(D) Other curable compound)
・ Dicyandiamide (curing agent) 2 parts by mass ・ Propylene glycol monomethyl ether ((C) solvent) 20 parts by mass

Half of silver particles, curable compound B, and propylene glycol monomethyl ether are previously mixed by stirring with a stirrer, and then bis-F type epoxy compound, epoxy acrylate compound, and dicyandiamide are blended in the above composition ratio, and stirred. After that, it is kneaded with a three-roll mill and pasted.
In this way, the conductive paste (1) of Example 1 is obtained.

[Example 2]
In Example 1, the curable compound B was changed from 20 parts by weight to 40 parts by weight, and the bis-F type epoxy compound and the epoxy acrylate compound were not used. Further, instead of 2 parts by weight of dicyandiamide, 2-benzyl-2 A conductive paste (2) of the example is obtained in the same manner as in the example 1 except that 2 parts by mass of -dimethylamino-1- (4-morpholinophenyl) -butan-1-one is used.

[Comparative Example 1]
In Example 1, the conductive paste (3) of the comparative example is obtained in the same manner as in Example 1 except that the epoxy acrylate compound is changed from 10 parts by mass to 20 parts by mass without using the curable compound B.

  Each of the following evaluations is performed using the conductive pastes (1) to (3). The evaluation results are shown in Table 1 below.

1. Evaluation of Adhesiveness between Electrode and Substrate Using each of the conductive pastes (1) to (3), 100 μm on a polyimide film (trade name: Kapton 500H, manufactured by Toray DuPont Co., Ltd., thickness: 125 μm). An electrode pattern having a stripe pattern with a width is prepared, and the adhesion between the electrode and the substrate is evaluated by a tape peeling method according to JIS K5400 using a cellophane adhesive tape defined in JIS Z1522. The evaluation criteria are as follows.
-Evaluation criteria-
○: The electrode pattern is not completely peeled. Δ: The electrode is not peeled off, but a part of the electrode is lifted. ×: The electrode is peeled off.

2. Evaluation of Line Shape Using each of the conductive pastes (1) to (3), a polyimide film (trade name: Kapton 500H, manufactured by Toray DuPont Co., Ltd., thickness: 125 μm) was placed on a dispenser (Musashi Engineering ( After forming a line of L / S = 300 μm at SHOTmini), heating at 200 ° C. is performed.
The shape of the obtained line is observed with a microscope, and it is observed and evaluated whether there is any variation or twist in the line width, or any protrusion due to the aggregate of conductive particles on the line. The evaluation criteria are as follows.
-Evaluation criteria-
○: Line width variation or twist, no line due to conductive particle agglomeration △: Line width variation, gap, or line due to conductive particle agglomeration ×: Line width Unevenness due to dispersion, twisting, or agglomeration of conductive particles on the line

3. Conductivity Evaluation Each of the conductive pastes (1) to (3) was placed on a polyimide film (trade name: Kapton 500H, manufactured by Toray DuPont Co., Ltd., thickness: 125 μm) and dispenser (Musashi Engineering Co., Ltd.). The film is applied so as to form a 5 cm square pattern with a thickness of 50 μm.
The volume resistivity in the formed pattern is measured and evaluated according to JIS K6911. The evaluation criteria are as follows.
-Evaluation criteria-
○: Non-resistance is less than 1 × 10 ⁻³ Δ: Non-resistance is 1 × 10 ⁻³ or more and less than 5 × 10 ⁻³ ×: Non-resistance is 5 × 10 ⁻³ or more

4). Evaluation of Storage Stability The conductive pastes (1) to (3) are stored in a refrigerator at 10 ° C. and evaluated according to the following evaluation criteria.
-Evaluation criteria-
○: Maintains fluidity that can withstand use after one month or more from the start of storage, and does not cause sedimentation or separation of conductive particles. Δ: Maintains fluidity that can withstand use until the second week after the start of storage. Keeping, and no sedimentation or separation of conductive particles occurs ×: Within one week, fluidity drop that cannot be used, sedimentation and separation of conductive particles occur

  As shown in Table 1, the conductive pastes (1) and (2) obtained in Examples 1 and 2 were evaluated for any of adhesion between the electrode and the substrate, line shape, conductivity, and storage stability. It can be confirmed that it is also excellent. On the other hand, it can be seen that the conductive paste (3) obtained in Comparative Example 1 is inferior in any of the above evaluations in comparison with the conductive pastes (1) and (2).

  From the above results, the conductive pastes (1) and (2), which are the conductive particle dispersion composition of the present invention, are excellent in dispersion stability of the conductive particles. It can be seen that a highly conductive and homogeneous conductive layer (cured product) can be obtained.

Claims (14)

Each of the components shown in the following (A) to (C) is contained, and a conductive particle dispersion composition.
(A) The average particle size obtained by particle size measurement by the dynamic light scattering method is 0.02 μm to 20 μm, and the content based on the total mass of the nonvolatile components contained in the conductive particle dispersion composition is 30% to 95% by weight of conductive particles (B) A curable compound having a functional group capable of forming an interaction with the conductive particles (C) Solvent   The conductive particle dispersion composition according to claim 1, further comprising (D) another curable compound having a molecular structure different from that of the component (B).   The curable compound contained as the component (B) is a functional group different from the functional group capable of forming an interaction with the conductive particles, and the functional group capable of reacting the curable compounds with each other by applying energy. The conductive particle dispersion composition according to claim 2, further comprising a group or a functional group capable of reacting the curable compound with another curable compound contained as the component (D). object.   The other curable compound contained as the component (D) is a polymer compound selected from the group consisting of acrylate compounds, epoxy compounds, isocyanate compounds, and compounds having functional groups capable of reacting with these compounds. The conductive particle dispersion composition according to claim 2, wherein the composition is a conductive particle dispersion composition.   The conductive particles contained as the component (A) are metals selected from the group consisting of gold, platinum, silver, palladium, indium, copper, nickel, iron, zinc, bells, lead, tin, and bismuth, these The conductive particle-dispersed composition according to any one of claims 1 to 4, wherein the conductive particle-dispersed composition is an alloy made of any of the above metals or particles containing an oxide of these metals.   The functional group capable of forming an interaction with the conductive particles contained in the curable compound contained as the component (B) is a functional group capable of adsorbing a metal and has a positive charge or dissociates into a positive charge. Functional groups having a structure that can be negatively charged or having a structure that can be dissociated to a negative charge, nonionic polar groups that can interact with conductive particles, chelation with a conductive particle It is selected from the group consisting of a functional group capable of taking a coordinated structure, a functional group capable of including conductive particles, and a functional group that interacts with a solvent in which a metal is held as crystal water. The conductive particle dispersion composition according to any one of claims 1 to 5. The curable compound contained as the component (B) is a copolymer including a unit represented by the following formula (1) and a unit represented by the following formula (2). The conductive particle dispersion composition according to any one of claims 1 to 6.

[In Formula (1) and Formula (2), R ^{1 to} R ⁵ each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group, and X, Y, and Z each independently represent: Represents a single bond or a substituted or unsubstituted divalent organic group, ester group, amide group, or ether group, and L ¹ and L ² each independently represents a substituted or unsubstituted divalent organic group; Represents. ]   8. The conductive particle dispersion composition according to claim 1, wherein a weight average molecular weight of the curable compound contained as the component (B) is 2000 or more and 500,000 or less. object.   The conductive particle dispersion composition according to any one of claims 1 to 8, further comprising (E) a compound selected from a polymerization initiator, a curing agent, and a curing accelerator. object.   It can harden | cure by energy provision, The electroconductive particle dispersion composition of any one of Claims 1-9 characterized by the above-mentioned.   It is an electroconductive paste, The electroconductive particle dispersion composition of any one of Claims 1-10 characterized by the above-mentioned.   The printed wiring board which has a conductive layer using the electroconductive particle dispersion composition of any one of Claims 1-11. The manufacturing method of the electroconductive particle dispersion composition which has at least the 1st process of knead | mixing or predispersing the mixture containing each component shown to following (A), (B), and (C).
(A) The average particle size obtained by particle size measurement by the dynamic light scattering method is 0.02 μm to 20 μm, and the content based on the total mass of the nonvolatile components contained in the conductive particle dispersion composition is 30% to 95% by weight of conductive particles (B) A curable compound having a functional group capable of forming an interaction with the conductive particles (C) Solvent The method for producing a conductive particle dispersion composition according to claim 13, wherein after the first step is performed, a second step of adding the following component (D) is performed.
(D) Another curable compound having a molecular structure different from the component (B).