JP2006156068A - Conductive particulate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive particulate that reconciles high flexibility and hardness. <P>SOLUTION: In the conductive particulate, an organic polymer particulate (B) coated with an inorganic compound, preferably, a metal oxide or nonmetal complex compound, more preferably, silicon oxide, having a shell of the inorganic compound (A) and a core of an organic polymer (b), is coated with a conductive metal (C). Preferably, the inorganic compound (A) and the organic polymer (b) are chemically bonded, the conductive metal (C) has an average coating thickness of 0.01 μm to 10 μm, and the conductive particulate has a number average particle size of 0.1 μm to 60 μm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to conductive fine particles in which the surface of an organic polymer fine particle coated with an inorganic compound is coated with a metal, and an anisotropic conductive material using the same. More specifically, the present invention relates to conductive fine particles having both flexibility and hardness.

Conductive fine particles are widely used as the main constituent material of anisotropic conductive materials such as anisotropic conductive films, conductive pastes, conductive adhesives, conductive adhesives, etc. by mixing with binder resin etc. Yes.
As an important characteristic required for the conductive fine particles used for the anisotropic conductive material, high flexibility is required. This is to increase the contact area in the crimped state and to reduce the resistivity of the connection site. On the other hand, high hardness is required as a characteristic of the conductive fine particles. This is because the restoration rate is increased and long-term reliability is ensured. There was a problem that these two characteristics conflicted.

As conductive fine particles that simultaneously satisfy these contradictory characteristics, conductive fine particles comprising a flexible core and a shell harder than the core have been proposed (Patent Document 1). However, this shell has a high glass transition temperature (hereinafter abbreviated as Tg) of the resin, and there is a problem that the restoration rate is not sufficient and the long-term reliability is inferior.
On the contrary, conductive fine particles composed of a shell having flexibility and a core harder than the shell have been proposed (Patent Document 2). However, this has a problem that the shell part has flexibility and is inferior in rigidity, so that the restoration rate is inferior and the reliability cannot be secured.

JP-A-11-209714 JP-A-8-193186

  The present invention has been made in view of the above situation, and has been made for the purpose of providing conductive fine particles having both high flexibility and hardness.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is characterized in that organic polymer fine particles (B) coated with an inorganic compound (A) as a shell and organic polymer (b) as a core are coated with a conductive metal (C). The conductive fine particles (D) to be used, and the anisotropic conductive material using the same.

  The conductive fine particles of the present invention have the effect that the resistance value is reduced by having high flexibility, and the restoration rate is high and the reliability is excellent by having high hardness.

   The present invention is characterized in that organic polymer fine particles (B) coated with an inorganic compound (A) as a shell and organic polymer (b) as a core are coated with a conductive metal (C). And conductive fine particles.

The inorganic compound (A) may be any of a natural product (A1), a modified product (A2) of a natural product, and a synthetic product (including a purified product) (A3).
These shapes are spherical, needle-like (fiber-like), layer-like (plate-like), or film-like, but from the viewpoint of hardness, a film-like is preferred.

  Examples of natural products (A1) include limestone (heavy calcium carbonate), quartz, silica (silica), wollastonite, gypsum, asbestos, apatite, magnetite, zeolite and clay.

Examples of the modified natural product (A2) include those obtained by modifying clay with an organic compound (organized clay). Examples of the organic clay include clay modified with an organic cation (organic cation) (clay cation exchanged with an organic cation) and the like.
There are no particular limitations on the organic method, and any known method can be used.

  Examples of synthetic products (including purified products) (A3) include metals, metal compounds, other composites (metal composite compounds, non-metal compounds, non-metal composite compounds, etc.), and carbides with organic substances as precursors. It is done.

  As the metal, any metal that is solid at room temperature or higher (20 to 250 ° C.) can be used. In the periodic table of elements, metals in groups 1 to 16 (zinc, aluminum, molybdenum, tungsten, zirconium, Barium, manganese, cobalt, calcium, gold, silver, chromium, titanium, iron, platinum, copper, lead, nickel, etc.), nickel-copper, cobalt-nickel, copper-palladium, iron-bismuth, etc. Also, alloys (solid solution) such as aluminum-magnesium can be used.

  Examples of the metal compound include group 1 to group 16 metal oxides (titanium oxide, zinc oxide, aluminum oxide, chromium oxide, manganese oxide, molybdenum oxide, tungsten oxide, vanadium oxide, tin oxide, oxidation in the periodic table of elements. Iron (including magnetic iron oxide) and indium oxide), metal hydroxides (aluminum hydroxide, gold hydroxide, magnesium hydroxide, etc.), metal sulfides (copper sulfide, sodium sulfide, lead sulfide, nickel sulfide and sulfide) Platinum), metal halides (calcium fluoride, tin fluoride, potassium fluoride, etc.), metal carbides (calcium carbide, titanium carbide, iron carbide, sodium carbide, etc.), metal nitrides (aluminum nitride, chromium nitride, nitridation) Germanium, cobalt nitride, etc.), metal carbonates [calcium carbonate (light calcium carbonate), hydrogen carbonate] Lucium, sodium hydrogen carbonate (bicarbonate) and iron carbonate, etc.], metal sulfates (aluminum sulfate, cobalt sulfate, sodium hydrogen sulfate, copper sulfate, nickel sulfate, barium sulfate, etc.) and other metal salts [titanate (titanate) Barium, magnesium titanate, potassium titanate, etc.), borate (aluminum borate, zinc borate, etc.), phosphate (calcium phosphate, sodium phosphate, magnesium phosphate, etc.), aluminate (yttrium aluminate (YAG), etc.) ) And nitrates (sodium nitrate, iron nitrate, lead nitrate, etc.)] and the like.

  Examples of other composites include metal composite compounds, nonmetal compounds, and nonmetal composite compounds. Examples of the metal composite include ferrite, silver ion supported zeolite, lead zirconate titanate (PZT), zirconia and the like. Examples of the nonmetallic compound include alum, zeolite, silicon oxide (including silica, silicate, glass, and glass fiber), silicon nitride, silicon carbide, and silicon sulfide. Examples of the non-metallic composite compound include alumina fiber, cement, zonotlite, and MOS (manufactured by Ube Industries).

  Examples of the carbide having an organic substance as a precursor include carbon black, carbon nanotube, graphite, activated carbon, bamboo charcoal, charcoal, and fullerene.

  Of these, metal oxides and non-metal composites are preferable from the viewpoint of film forming properties, more preferably titanium oxide and silicon oxide, and particularly preferably silicon oxide. .

  The content (% by weight) of the inorganic compound (A) is preferably 0.1 to 20, more preferably 0.5 to 15, particularly preferably 1 to 10, based on the weight of the organic polymer (b). . Within this range, the compatibility between the hardness and the flexibility is further improved.

In the present invention, the organic polymer (b) is not particularly limited, and may be a thermoplastic resin or a thermosetting resin.
For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicone resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like can be given.
Of these, polyester, polyurethane resin, epoxy resin, and polyamide resin are preferable. More preferred are polyurethane resins and polyester resins.

  Moreover, as an organic polymer (b), it is preferable to have a reactive functional group which reacts with an inorganic compound (A) from an adhesive viewpoint with the inorganic compound (A) used as a shell.

  Although it does not specifically limit as a reactive functional group, An alkoxy silyl group, a silanol group, a hydroxyl group, an amino group, an epoxy group, a carboxy group, an isocyanate group, a thiol group etc. are mentioned. Of these, an alkoxysilyl group and a silanol group are preferable, and an alkoxysilyl group is more preferable.

  The method for introducing the functional group into the organic polymer (b) is not particularly limited. However, the method for imparting the functional group to the terminal of the organic polymer, or reacting the compound having the reactive functional group with the organic polymer (b). Examples thereof include a method of introducing, a method of blending the compound having a reactive functional group with the organic polymer (b), and the like. Among these, a method of introducing a compound having a reactive functional group by reacting with the organic polymer (b) from the viewpoint of adhesion is preferable.

  The polyurethane resin is usually a resin obtained by polyaddition reaction of polyisocyanate (b1) and an active hydrogen-containing compound.

  (B1) includes diisocyanates and trifunctional or higher polyfunctional isocyanates; for example, aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), 18 aliphatic polyisocyanates, alicyclic polyisocyanates having 6 to 15 carbon atoms, araliphatic polyisocyanates having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane groups, carbodiimide groups, allophanate groups, burettes) Group, uretdione group, uretoimine group, isocyanurate group, modified product containing oxazolidone group) and a mixture of two or more thereof.

  Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4. '-And / or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl- 4,4'-diisocyanatodiphenylmethane, crude MDI [crude diaminodiphenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; trifunctional of diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight)] A mixture of the above with polyamine]; polyaryl polyiso Aneto], 1,5-naphthylene diisocyanate, 4,4 ', 4 "- triphenylmethane triisocyanate, include m- and p- isocyanatophenyl sulfonyl isocyanate.

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Lysine diisocyanate (2,6-diisocyanatomethylcaproate), bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexa Noate.

  Specific examples of the alicyclic polyisocyanate include, for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl). ) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate and α, α, α ', α'-tetramethylxylylene diisocyanate.

  Examples of modified polyisocyanates include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, burette-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI. Modified products of isocyanate and mixtures of two or more thereof [for example, combined use of modified MDI and urethane-modified TDI (isocyanate group-containing pre-organic polymer)] are included.

  Among these, preferred are aliphatic and cycloaliphatic polyisocyanates, particularly HDI, IPDI, and hydrogenated MDI, which are less likely to discolor due to aging.

  The active hydrogen-containing compound includes a low-molecular polyfunctional active hydrogen-containing compound (b2) and a polymer polyol (b3).

  (B2) includes a low molecular polyol (b21) and a low molecular polyamine (b22).

As (b21), the OH equivalent [number average molecular weight per hydroxyl group (measured by gel permeation chromatography (hereinafter abbreviated as GPC) or titration method)] is less than 300 (preferably 30 to 250), 2 to 10 valence. Or more (preferably 2-3 valence) polyol can be used.
Specific examples of (b21) include dihydric alcohols such as aliphatic diols [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, etc.), branched diols (propylene glycol, neopentyl glycol, 3-methyl 1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1, 3- or 2,3-butanediol and the like], and diol having a cyclic group (for example, those described in JP-B No. 45-1474; 1,4-bis (hydroxymethyl) cyclohexane, m- or p-xylyl) Renglycol, dihydric phenol [(poly) oxyalkylene group such as bisphenol A Ter (alkylene having 2 to 4 carbon atoms, etc.); trivalent to 10-valent or higher polyhydric alcohol, such as alkane polyol (glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc., and their intermolecular or molecular Internal dehydrates [dipentaerythritol, polyglycerol (degree of polymerization 2 to 8), sorbitan, etc.], saccharides and derivatives thereof (glycosides) (sucrose, methyl glucoside, etc.); and their alkylene oxides (hereinafter abbreviated as AO). C2-C10 or more, for example, what is mentioned in manufacture of the below-mentioned (b32)] low molar adduct; and a mixture of these 2 or more types.
Of these, polyhydric alcohols are preferred, and glycerin and pentaerythritol are more preferred.

(B22) includes diamines having an amine equivalent (number average molecular weight per active hydrogen atom-containing amino group) of less than 300 (preferably 30 to 250) and trifunctional or higher polyfunctional amines; ), Which is a polyamine in which the isocyanate group in (b1) is replaced by an amino group. Specifically, diamines such as aliphatic diamines [ethylene diamine, hexamethylene diamine, etc.], alicyclic diamines [4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3, 3′-dimethyldicyclohexyl, diaminocyclohexane, isophoronediamine, etc.], aromatic diamine [diethyltoluenediamine, etc.], araliphatic diamine [xylylenediamine, α, α, α ′, α′-tetramethylxylylenediamine, etc.] A heterocyclic diamine (such as piperidine); a polyfunctional amine having 3 to 6 or more valences, such as polyalkylene (having 2 to 6 carbon atoms) polyamine (such as diethylenetriamine and triethylenetetramine), polyphenylmethane polyamine (formaldehyde and aniline) A condensation product of Mixtures of two or more of these and the like.
Of these, preferred are polyfunctional amines, and particularly preferred are diethylenetriamine and triethylenetetramine.

As the polymer polyol (b3), a polyol having an OH equivalent [number average molecular weight per hydroxyl group] of 300 or more (preferably 300 to 10,000) or 2 or more (preferably 2 to 3) is used. Can be used.
(B3) includes polyester polyol (b31), polyether polyol (b32), and mixtures of two or more thereof.

Examples of (31) include condensed polyester polyol (b311) (by polycondensation of polyol and polycarboxylic acid), polylactone polyol (b312) (one obtained by ring-opening polymerization of a lactone monomer using a polyol as an initiator). Polycarbonate polyol (b313) [by reaction of polyol and alkylene (2 to 4 carbon atoms) carbonate (such as ethylene carbonate), phosgenation or transesterification with diphenyl carbonate]; and mixtures of two or more of these It is done.

As the polyol in (b311), (b312), and (b313), one or more of low molecular polyols [for example, (b21) described above] and / or polyether polyols [for example (a32)] can be used.

The polycarboxylic acids in (b311) include polycarboxylic acids and their ester-forming derivatives.
Specific examples include aliphatic polycarboxylic acids [polycarboxylic acids having 2 to 6 functional groups and 3 to 30 carbon atoms such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, hexa Hydrophthalic acid, etc.], aromatic polycarboxylic acids [polycarboxylic acids having 2 to 6 functional groups and 8 to 30 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, trimellit Acid, pyromellitic acid, etc.]; these ester-forming derivatives [acid anhydrides, lower alkyl (carbon number 1-4) esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc.): for example, maleic anhydride Acid, phthalic anhydride, dimethyl terephthalate, etc.]; and mixtures of two or more thereof.
Of these, aliphatic polycarboxylic acids are preferred.

  Examples of the lactone monomer in (b312) include lactones having 3 to 17 carbon atoms (preferably 4 to 12), such as γ-butyrolactone, ε-caprolactone, γ-valerolactone, and mixtures of two or more thereof.

  (B32) includes those having a structure in which AO is added to a compound having two or more active hydrogen atoms.

  Examples of the compound having an active hydrogen atom include low-molecular polyols (for example, (b21) above); divalent phenols [for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), monocyclic phenols (catechol, hydroquinone, etc.) )]; Amines [primary monoamines such as alkyl or alkenyl amines (1 to 20 carbon atoms), anilines, alkanolamines (2 to 4 carbon atoms of the hydroxyl alkyl group) (such as those mentioned in the terminators below), polyamines such as (B22), heterocyclic polyamines such as piperazine, aminoalkyl (2 to 4 carbon atoms) piperazine (such as aminoethylpiperazine)] and the like.

  As AO, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- and 2,3-butylene oxide, styrene oxide, carbon number 5 -10 or more α-olefin oxides, epichlorohydrin, and combinations of two or more thereof (block and / or random addition).

  Among these, preferred are those obtained by adding AO (particularly PO) to divalent phenols (particularly bisphenols).

  In this case, the OH equivalent of (b3) is preferably 300 to 10,000, more preferably 500 to 5,000, and particularly preferably 1,000 to 3,000 from the viewpoint of Tg.

  The production of the polyurethane resin can be carried out by an ordinary method, in which the active hydrogen-containing compound and (b1) are all reacted together (one-shot method), and some of these reaction components are reacted in advance. Examples thereof include a method (prepolymer method) in which a multistage reaction is performed via an isocyanate group or a hydroxyl group-terminated urethane pre-organic polymer (b0). Preferred is a prepolymer method, particularly a method of reacting an isocyanate group-terminated urethane prepolymer (b0) and (b2) (extending agent and / or cross-linking agent) and / or a terminator.

The isocyanate group-terminated urethane prepolymer (b0) is preferably formed by the reaction of (b1) with (b3) and optionally (b2). In this case, the equivalent ratio of (b1) to (b2) and (b3) is usually 0.1 to 0.8 equivalent, preferably 0.2 to 0.6, relative to (b1) 1 equivalent. The equivalent amount (b3) is usually 0.05 to 0.7 equivalent, preferably 0.1 to 0.5 equivalent.
The isocyanate group content in (b) is usually 0.5 to 10% by weight, preferably 1.5 to 6% by weight.

  Examples of the extender include the diols mentioned in the above (b21), the diamines mentioned in (b22), their ketimine compounds, for example, the above amines and ketones having 3 to 8 carbon atoms [acetone, methyl ethyl ketone, methyl isobutyl ketone (hereinafter, Abbreviated as MIBK) and the like], and water. A ketimine compound is preferred.

  Examples of the crosslinking agent include the polyhydric alcohols mentioned in (b21) and the polyfunctional amines mentioned in (b22) (diethylenetriamine, triethylenetetramine, etc.).

  Examples of the terminator include monoamines having 1 or 2 hydroxyalkyl groups having 2 to 4 carbon atoms, and aliphatic monoamines having no hydroxyl group.

Monoamines having one or two hydroxyalkyl groups include monoalkanolamines [monoethanolamine, monopropanolamine, etc.]; dialkanolamines [diethanolamine, dipropanolamine, etc.] and mixtures of two or more thereof. .
Of these, dialkanolamine is preferable, and diethanolamine and dipropanolamine are particularly preferable.

Aliphatic monoamines having no hydroxyl group include alicyclic monoamines [(mono- and di-cycloalkyl (5 to 18 carbon atoms) such as cyclopentylamine, cyclohexylamine, etc.], aliphatic monoamines [mono-and Di-alkyl or alkenyl (C1-C20) amines such as methylamine, ethylamine, propylamine, butylamine, octylamine, 2-ethylhexylamine, nonylamine, oleylamine, N-methylbutylamine, diethylamine, dibutylamine and the like] and A mixture of two or more of these may be mentioned.
Among these, preferred are aliphatic monoamines having no hydroxyl group, and particularly preferred are butylamine, octylamine, 2-ethylhexylamine, and dibutylamine.

The charging ratio of the extender, the terminator, and the crosslinking agent to the urethane prepolymer (b0) is appropriately selected within a range in which a polyurethane resin having a predetermined number average molecular weight is formed. For example, the equivalent ratio of the extender to 1 equivalent of isocyanate group in (b0) is preferably 0.05 to 0.8 equivalent, more preferably 0.1 to 0.6 equivalent. Moreover, the equivalent ratio of the terminator is usually 0 to 0.2 equivalent, preferably 0.05 to 0.1 equivalent, and the equivalent ratio of the crosslinking agent is usually 0.1 to 0.8 equivalent, preferably 0. .2 to 0.6 equivalents.
In addition, the total equivalent ratio of the extender + termination agent + crosslinking agent to 1 equivalent of the isocyanate group in (b0) is preferably 0.1 to 2.3 equivalents, more preferably 0.3 to 1.7 equivalents. .

When the organic polymer (b) in the present invention is a polyester resin, examples thereof include polycondensates of polycarboxylic acids and polyols, compounds having carboxyl groups and hydroxyl groups in the same molecule, or polycondensates of anhydrides thereof.
Examples of the polycarboxylic acids include those described in the above (b311). Of these, preferred are aliphatic polycarboxylic acids (especially succinic acid, maleic acid, adipic acid, azelaic acid, sebacic acid) and aromatic polycarboxylic acids (especially phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride). Dimethyl terephthalate, etc.).
These polycarboxylic acids can be used as one kind or a mixture of two or more kinds.
Moreover, when making it bridge | crosslink in a polyesterification reaction process, trifunctional or more polycarboxylic acid (For example, trimellitic acid, pyromellitic acid, etc.) can be used together.

As the polyol, a low molecular polyol and / or a polyether polyol can be used.
Examples of the low molecular polyol include the above-mentioned (b2). Preferred are dihydric alcohols such as aliphatic diols (especially ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.), branched diols (propylene glycol, neopentyl glycol), bisphenol A (Poly) oxyalkylene ether (alkylene group having 2 to 4 carbon atoms).

As the polyether polyol, the above-mentioned (b32) may be mentioned. Preferred are low molecular polyols (especially aliphatic diols) with addition of AO (especially PO).

  The number average molecular weight of these polyether polyols is preferably 1,000 to 20,000. Moreover, these low molecular weight and polyether polyols can be used by 1 type, or 2 or more types of mixtures.

  In the case of crosslinking in the polyesterification reaction step, a tri- or higher functional polyol (for example, a tri- to 10-valent polyhydric alcohol among those described in the above (b21)) may be used in combination.

  Examples of the compound having a carboxyl group and a hydroxyl group in the same molecule or an anhydride thereof include (b312) described above. Preference is given to γ-butyrolactone, ε-caprolactone, and mixtures thereof.

  Moreover, when using trifunctional or more than polycarboxylic acid and / or polyol, it is 0.01-10 weight% normally with respect to the total weight of polycarboxylic acid and polyol, Preferably it is 0.03-5 weight% 3 or more functional groups are used.

The temperature during the polycondensation of the polyester resin is usually 100 to 300 ° C, preferably 130 to 220 ° C. The atmosphere during the polymerization is desirably performed in the presence of an inert gas such as nitrogen.
The equivalent ratio of polycarboxylic acids and polyols during polymerization is an equivalent ratio of carboxylic acid / hydroxyl group, and preferably 1 / 0.7 to 1 / 1.1.
The acid value after polycondensation is preferably 10 or less.

When the organic polymer (b) of the present invention is a polyamide resin, examples thereof include polycondensates of polycarboxylic acids and polyamines, compounds having a carboxyl group and an amino group in the same molecule, or polycondensates of anhydrides thereof.
Examples of the polycarboxylic acids include the polycarboxylic acids described in the above (b311). Of these, aliphatic polycarboxylic acids (especially maleic acid, adipic acid, azelaic acid) and aromatic polycarboxylic acids (especially phthalic acid, terephthalic acid, dimethyl terephthalate, etc.) are preferred.
These polycarboxylic acids can be used as one kind or a mixture of two or more kinds.

Examples of the polyamine include those described in the above (b22). Of these, preferred are aliphatic diamines (hexamethylenediamine, 1,5-pentanediamine, etc.) and araliphatic diamines (xylylenediamine, etc.). These polyamines can be used alone or in a mixture of two or more.
Specific examples of the compound having a carboxylic acid group and an amino group in the same molecule or an anhydride thereof include amino acids having 2 to 30 carbon atoms such as ε-aminoundecanoic acid, lauryl lactam, enanthractam, ε-caprolactam and the like. Examples thereof include lactams having 4 to 10 carbon atoms.

  In the case of crosslinking in the polyamidation reaction step, a tri- or higher functional polycarboxylic acid (for example, trimellitic acid, pyromellitic acid, etc.) is used in combination, or a tri- or higher functional polyamine [for example, described in (b22) above] 3 to 6 or more polyfunctional amines may be used in combination.

  Moreover, when using polycarboxylic acids and / or polyamines having three or more functional groups, usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the polycarboxylic acids and polyamines. It is.

  The polyamide resin can be obtained by polycondensation of the above polycarboxylic acids and polyamines. The temperature during polycondensation is usually 120 to 300 ° C, preferably 150 to 220 ° C. The atmosphere during the polymerization is desirably performed in the presence of an inert gas such as nitrogen. The equivalent ratio of polycarboxylic acids and polyamines at the time of polymerization is an amine / hydroxyl equivalent ratio, preferably 1 / 0.7 to 1 / 1.1. The amine value after condensation polymerization is preferably 10 or less.

  When the organic polymer (b) is an epoxy resin, aromatic, heterocyclic, alicyclic and aliphatic polyepoxides (the number of epoxy groups is 2 to 4, the epoxy equivalent is 70 to 4,000 eq / g) polymer and cured product.

Examples of the aromatic polyepoxide include glycidyl ethers of polyhydric phenols and glycidyl aromatic polyamines.
Examples of glycidyl ethers of polyphenols include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, and tetrachlorobisphenol A. Diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl di Glycidyl ether, phenol or cresol novolac tree A glycidyl ether of fat, a diglycidyl ether obtained from the reaction of 2 mol of bisphenol A and 3 mol of epichlorohydrin, a polyglycidyl ether of polyphenol obtained by the condensation reaction of phenol and glycoxal, glutaraldehyde, or formaldehyde, and Examples thereof include polyglycidyl ethers of polyphenols obtained by condensation reaction of resorcin and acetone.
Examples of the glycidyl aromatic polyamine include N, N-diglycidylaniline and N, N, N ′, N′-tetraglycidyldiphenylmethanediamine. Furthermore, in the present invention, as the aromatic system, a diglycidyl urethane compound obtained by addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate and glycidol, a glycidyl group-containing polyurethane (pre) polymer obtained by reacting the two reactants with a polyol. And diglycidyl ethers of bisphenol A alkylene oxide (ethylene oxide or propylene oxide) adducts.

  Heterocyclic systems include trisglycidyl melamine.

  Alicyclics include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ale, 3,4-epoxy-6-methyl. Cyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3,4-epoxy-6-methylcyclohexylmethyl) Butylamine is mentioned. Moreover, as an alicyclic type | system | group, the nuclear hydrogenation thing of the said aromatic polyepoxide is also included.

Aliphatics include polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, and glycidyl aliphatic amines.
As the polyglycidyl ether of polyhydric alcohol, the polyglycidyl ether of (b21), for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl. And ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether.
Examples of the polyglycidyl ester of polycarboxylic acid include the polyglycidyl ester of (b311), for example, a (co) polymer of diglycidyl adipate and glycidyl (meth) acrylate.
Examples of the glycidyl aliphatic amine include the polyglycidylated product of (b22), for example, N, N, N ′, N′-tetraglycidylhexamethylenediamine.

  As a method for producing an epoxy resin, a method of ring-opening polymerization of the above polyepoxide using a catalyst (an alkaline inorganic compound such as alkali hydroxide, a quaternary ammonium salt, a Lewis acid, etc.) and a polyamine [as described above] (B22) aliphatic polyamine or aromatic polyamine, etc.] and a method of curing by ring-opening and crosslinking.

  The vinyl resin is an organic polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. Examples of vinyl monomers include the following (1) to (10).

(1) Vinyl hydrocarbon: (1-1) Aliphatic vinyl hydrocarbon: Alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-other than the above Olefin and the like; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden etc.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbon (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products, for example, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene , Isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

  (2) Carboxyl group-containing vinyl monomers and salts thereof: C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their anhydrides and monoalkyl (C1-C24) esters such as (meth) Acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester Carboxyl group-containing vinyl monomers such as cinnamic acid.

  (3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesterified products and salts thereof: Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfone Acids; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid; sulfo (hydroxy) alkyl- (meth) acrylates or (meth) acrylamides such as sulfopropyl (meth) acrylates, 2-hydroxy -3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2- Hydroxypropane sulfonic acid, 2- (me ) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene) Butylene: single, random, or block) mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.] and polyoxyethylene polycyclic phenyl ether sulfate.

  (4) Phosphoric acid group-containing vinyl monomers and salts thereof: (meth) acryloyloxyalkyl (C1-C24) phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (Meth) acryloyloxyalkyl (C1-24) phosphonic acids, for example 2-acryloyloxyethylphosphonic acid.

  Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

  (5) Hydroxyl group-containing vinyl monomers: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, black Tyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer: (6-1) Amino group-containing vinyl monomer: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinyl Pyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole These salts and the like.
(6-2) Amide group-containing vinyl monomers: (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (Meth) acrylamide, cinnamic amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, N-vinylpyrrolidone and the like.
(6-3) Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(6-4) Quaternary ammonium cationic group-containing vinyl monomers: tertiary such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diallylamine and the like Quaternized amine group-containing vinyl monomers (quaternized with quaternizing agents such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
(6-5) Nitro group-containing vinyl monomers: nitrostyrene and the like.

  (7) Epoxy group-containing vinyl monomers: glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, and the like.

  (8) Halogen element-containing vinyl monomers: vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene, and the like.

(9) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones: (9-1) Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate , Vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched, having 2 to 8 carbon atoms) A chain or alicyclic group), a dialkyl maleate (two alkyl groups are straight-chain, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) aryl Roxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (Molecular weight 300) Mono (meth) acrylate, polypropylene glycol (Molecular weight 5 00) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols : Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]
(9-2) Vinyl (thio) ether, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxy butadiene, vinyl 2- Butoxyethyl ether, 3,4-dihydro1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl 2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene, (9-3) vinyl ketones such as vinyl Methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfone such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyls Lufon, divinyl sulfoxide, etc.

  (10) Other vinyl monomers: isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

  Examples of the copolymer of vinyl monomers include organic polymers obtained by copolymerizing any of the above monomers (1) to (10) with a binary or higher number in any proportion. For example, styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer Examples thereof include styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid, divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like.

Examples of the method for producing the organic polymer (b) include a method in which a crosslinking agent is used in the polymerization reaction step as described above, and a method in which a crosslinking agent is further added to each resin after polymerization to perform crosslinking.
As the crosslinking agent after polymerization, known ones can be used. For example, when a carboxyl group is present as a functional group in the resin, polyepoxide [for example, the above-described polyepoxide, preferably aromatic such as bisphenol A diglycidyl ether, trisglycidyl, etc. Heterocyclic systems such as melamine, alicyclic systems such as vinylcyclohexene dioxide, and aliphatic systems such as polyethylene glycol diglycidyl ether, glycidyl (meth) acrylate (co) polymers] and melamine resins [trimethylolmelamine, hexa Methylol melamine, methoxytrimethylol melamine and mixtures thereof] and the like.
When the reactive functional group in the organic polymer (b) is a hydroxyl group, examples of the crosslinking agent include the aforementioned polycarboxylic acids, polyisocyanate (b1), and the melamine resin. When the reactive functional group is an epoxy group, the above-described polycarboxylic acids are exemplified.

  The method for obtaining the organic polymer fine particles (B) coated with the inorganic compound of the present invention is not particularly limited. For example, the organic polymer fine particles (B0) composed of the organic polymer (b) are prepared, and the inorganic compound (A) is added thereto. For example, a method of coating the surface.

The method for obtaining the organic polymer fine particles (B0) of the present invention in the form of fine particles (beads) is not particularly limited, but includes the following (1) to (4).
(1) When the organic polymer (b) is a polyaddition or condensation resin such as a polyamide resin, a polyester resin, a polyurethane resin, or an epoxy resin, the precursor (monomer, oligomer, etc.) of (b), or (b) The following emulsifier is dissolved in a solvent (X) solution of the precursor (which is preferably a liquid. It may be liquefied by heating), and then water is added to perform phase inversion emulsification and polymerization.
(2) An organic polymer (b) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) was dissolved in the solvent (X). Add the poor solvent (Y) to the resin solution, or add the poor solvent (Y) to the resin solution obtained by dissolving the organic polymer (b) in the solvent (X), or dissolve it in the solvent (X) in advance. The organic polymer (b) particles are precipitated by cooling the solution of the organic polymer (b) and dispersed in water.
(3) Dissolved in a solvent (X) containing an organic polymer (b) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) A method in which the organic polymer (b) solution is dispersed in an aqueous medium in the presence of the following dispersant, and the solvent is removed by heating or decompression.
(4) The organic polymer (b) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) was dissolved in the solvent (X). A method of phase inversion emulsification by adding water after dissolving the following emulsifier in the organic polymer (b) solution.
Among the above methods, the method (1) is most preferable.

The solvent (X) is used for the purpose of dissolving the resin and needs to be able to uniformly dissolve the organic polymer (b).
Specific examples include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone, di-n-butyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; Amide solvents such as dimethylformamide and dimethylacetamide; Sulfoxide solvents such as dimethylsulfoxide, and heterocyclic compound systems such as N-methylpyrrolidone Agent, and a mixed solvent of two or more thereof. Of these, preferred are aromatic hydrocarbon solvents, and more preferred are toluene and xylene.

The poor solvent (Y) is used for the purpose of precipitating the resin, and the solubility of the organic polymer (a) is required to be 1% by weight or less at 25 ° C.
Specific examples include aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane; methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, Halogen solvents such as perchloroethylene; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone A solvent and a mixed solvent of two or more of these may be mentioned. Of these, preferred are aliphatic hydrocarbon solvents, and more preferred are n-hexane and n-heptane.

  In the above methods (1) to (4), as the emulsifier or dispersant used, a known surfactant (S), water-soluble organic polymer (T) and the like can be used. Moreover, a solvent (U) etc. can be used together as an auxiliary agent for emulsification or dispersion.

  As the surfactant (S), anionic surfactant (S-1), cationic surfactant (S-2), amphoteric surfactant (S-3), nonionic surfactant (S-4) and the like. Is mentioned. The surfactant (S) may be a combination of two or more surfactants.

  Examples of the anionic surfactant (S-1) include carboxylic acid or a salt thereof, a sulfate ester salt, a salt of carboxymethylated product, a sulfonate salt, and a phosphate ester salt.

  Examples of carboxylic acids or salts thereof include saturated or unsaturated fatty acids having 8 to 22 carbon atoms or salts thereof. Specifically, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. , Oleic acid, linoleic acid, ricinoleic acid and a mixture of higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like. Examples of the salt include salts of sodium, potassium, ammonium, alkanolamine and the like.

  Examples of sulfate salts include higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms) and higher alkyl ether sulfate esters salts (1 to 10 moles of ethylene oxide of aliphatic alcohols having 8 to 18 carbon atoms). Sulfates of adducts), sulfated oils (natural unsaturated oils or unsaturated waxes that have been neutralized by sulfation), sulfated fatty acid esters (sulfurized lower alcohol esters of unsaturated fatty acids) And sulphated olefins (sulphated and neutralized olefins having 12 to 18 carbon atoms). Examples of the salt include sodium salt, potassium salt, ammonium salt, and alkanolamine salt. Specific examples of higher alcohol sulfates include octyl alcohol sulfate, decyl alcohol sulfate, lauryl alcohol sulfate, stearyl alcohol sulfate, alcohols synthesized using Ziegler catalysts (for example, ALFOL 1214: CONDEA's sulfate ester salt, alcohols synthesized by the oxo method (for example, Dovanol 23, 25, 45: Mitsubishi Yuka, Tridecanol: Kyowa Hakko, Oxocol 1213, 1215, 1415: Nissan Chemical, Diadol 115 -L, 115H, 135: manufactured by Mitsubishi Chemical); specific examples of higher alkyl ether sulfates include lauryl alcohol ethylene oxide 2-mol adduct sulfate, octyl alcohol ethylene Oxide 3-mole adduct sulfate ester; Specific examples of sulfated oils include sodium, potassium, ammonium, alkanolamine salts sulfated fatty acids of castor oil, peanut oil, olive oil, rapeseed oil, beef tallow, sheep fat, etc. Specific examples of the ester include sodium, potassium, ammonium, and alkanolamine salts of sulfates such as butyl oleate and butyl ricinoleate; specific examples of the sulfated olefin include Typol (manufactured by Shell).

  Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms and a carboxymethylated salt of an ethylene oxide 1 to 10 mol adduct of an aliphatic alcohol having 8 to 16 carbon atoms. It is done. Specific examples of salts of carboxymethylated products of aliphatic alcohols include octyl alcohol carboxymethylated sodium salt, decyl alcohol carboxymethylated sodium salt, lauryl alcohol carboxymethylated sodium salt, dovanol 23 carboxymethylated sodium salt, tridecanol Specific examples of salts of carboxymethylated sodium salt of carboxymethylated product of aliphatic alcohol ethylene oxide 1-10 mol adduct include octyl alcohol ethylene oxide 3 mol adduct carboxymethylated sodium salt, lauryl alcohol ethylene oxide 4 Mole adduct carboxymethylated sodium salt, dovanol 23 ethylene oxide 3 mol adduct carboxymethylated sodium salt, tridecanol ethylene oxide Such as 5 mole adduct carboxymethylated sodium salt.

  Examples of the sulfonate include (d1) alkylbenzene sulfonate, (d2) alkylnaphthalene sulfonate, (d3) sulfosuccinic acid diester type, (d4) α-olefin sulfonate, (d5) Igepon T type, (d6 ) Other sulfonates of aromatic ring-containing compounds. Specific examples of alkylbenzene sulfonate include sodium dodecylbenzene sulfonate; specific examples of alkyl naphthalene sulfonate; sodium dodecyl naphthalene sulfonate; specific examples of sulfosuccinic acid diester type include di-2 sulfosuccinic acid di-2 -Ethylhexyl ester sodium salt and the like. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether, styrenated phenol sulfonate, and the like.

  Examples of phosphoric acid ester salts include (e1) higher alcohol phosphoric acid ester salts and (e2) higher alcohol ethylene oxide adduct phosphoric acid ester salts.

  Specific examples of higher alcohol phosphoric acid ester salts include lauryl alcohol phosphoric acid monoester disodium salt, lauryl alcohol phosphoric acid diester sodium salt; specific examples of higher alcohol ethylene oxide adduct phosphoric acid ester salts include oleyl alcohol ethylene oxide 5 mol adduct phosphate monoester disodium salt.

  Examples of the cationic surfactant (S-2) include a quaternary ammonium salt type and an amine salt type.

  The quaternary ammonium salt type is obtained by a reaction between a tertiary amine and a quaternizing agent (an alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, dimethyl sulfate; ethylene oxide, etc.) For example, lauryl trimethyl ammonium chloride, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride (benzalkonium chloride), cetyl pyridinium chloride, polyoxyethylene trimethyl ammonium chloride, stearamide ethyl diethyl Examples include methylammonium methosulfate.

  As amine salt type, primary to tertiary amines are inorganic acids (hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, etc.) or organic acids (acetic acid, formic acid, oxalic acid, lactic acid, gluconic acid, adipic acid, alkylphosphoric acid, etc.) It is obtained by neutralizing with For example, the primary amine salt type includes inorganic or organic acid salts of higher aliphatic amines (higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine); Examples include fatty acid (stearic acid, oleic acid, etc.) salts and the like. Examples of the secondary amine salt type include inorganic acid salts or organic acid salts such as ethylene oxide adducts of aliphatic amines. Examples of the tertiary amine salt type include aliphatic amines (triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), ethylene oxides of aliphatic amines (2 moles). Above) Adducts, alicyclic amines (N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine, 1,8-diazabicyclo (5,4,0) -7-undecene, etc.) , Inorganic acid salts or organic acid salts of nitrogen-containing heterocyclic aromatic amines (4-dimethylaminopyridine, N-methylimidazole, 4,4′-dipyridyl, etc.); triethanolamine monostearate, stearamide ethyl diethyl methyl ethanol Examples include inorganic acid salts or organic acid salts of tertiary amines such as amines.

  The amphoteric surfactant (S-3) used in the present invention includes a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric interface. Examples of the surfactant include amphoteric surfactants and amino acid-type amphoteric surfactants and betaine-type amphoteric surfactants.

Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. Examples of amphoteric surfactants having an amino group and a carboxyl group include compounds represented by the following general formula.
[R—NH— (CH ₂ ) n —COO] mM [wherein R is a monovalent hydrocarbon group; n is usually 1 or 2; m is 1 or 2; M is a hydrogen atom, an alkali metal atom, an alkali An earth metal atom, an ammonium cation, an amine cation, an alkanolamine cation and the like. Specific examples include, for example, alkylaminopropionic acid type amphoteric surfactants (such as sodium stearylaminopropionate and sodium laurylaminopropionate); alkylaminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate), and the like. It is done.

  Betaine-type amphoteric surfactants are amphoteric surfactants having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule. For example, alkyldimethylbetaine (stearyl) represented by the following general formula: Dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, etc.), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyl dihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.) etc. are mentioned.

  Furthermore, examples of the imidazoline type amphoteric surfactant include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine.

  Examples of other amphoteric surfactants include glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; pentadecylsulfotaurine and the like Examples include sulfobetaine-type amphoteric surfactants.

  Examples of the nonionic surfactant (S-4) include alkylene oxide addition type nonionic surfactants and polyvalent alcohol type nonionic surfactants.

  Alkylene oxide addition type nonionic surfactants include polyalkylene glycols obtained by adding alkylene oxide directly to higher alcohols, higher fatty acids or alkylamines, or by adding alkylene oxides to glycols. It is obtained by reacting a higher fatty acid with a higher fatty acid, adding an alkylene oxide to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or adding an alkylene oxide to a higher fatty acid amide.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Of these, preferred are ethylene oxide and random or block adducts of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is preferably 10 to 50 moles, and 50 to 100% by weight of the alkylene oxide is preferably ethylene oxide.

  Specific examples of the alkylene oxide addition type nonionic surfactant include oxyalkylene alkyl ethers (for example, octyl alcohol ethylene oxide addition product, lauryl alcohol ethylene oxide addition product, stearyl alcohol ethylene oxide addition product, oleyl alcohol ethylene oxide addition product). , Lauryl alcohol ethylene oxide propylene oxide block adduct, etc.); polyoxyalkylene higher fatty acid ester (eg, stearyl acid ethylene oxide adduct, lauric acid ethylene oxide adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (For example, polyethylene glycol lauric acid diester, polyethylene glycol oleic acid diester, polyethylene glycol Polyoxyalkylene alkylphenyl ether (eg, nonylphenol ethylene oxide adduct, nonylphenol ethylene oxide propylene oxide block adduct, octylphenol ethylene oxide adduct, bisphenol A ethylene oxide adduct, dinonylphenol ethylene oxide addition) Polyoxyalkylene alkylamino ether and (for example, laurylamine ethylene oxide adduct, stearylamine ethylene oxide adduct, etc.); polyoxyalkylene alkyl alkanolamide (for example, Hydroxyethyl lauric acid amide ethylene oxide adduct, hydroxypropyl oleic acid Ethylene oxide adducts of bromide, ethylene oxide adducts of dihydroxy ethyl lauric acid amide, etc.) and the like.

  Examples of the polyhydric alcohol type nonionic surfactant include polyhydric alcohol fatty acid esters, polyhydric alcohol fatty acid ester alkylene oxide adducts, polyhydric alcohol alkyl ethers, and polyhydric alcohol alkyl ether alkylene oxide adducts.

  Specific examples of polyhydric alcohol fatty acid esters include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dioleate, sucrose monostearate, etc. Is mentioned. Specific examples of the polyhydric alcohol fatty acid ester alkylene oxide adduct include ethylene glycol monooleate ethylene oxide adduct, ethylene glycol monostearate ethylene oxide adduct, trimethylolpropane monostearate ethylene oxide propylene oxide random adduct, sorbitan mono Examples include laurate ethylene oxide adduct, sorbitan monostearate ethylene oxide adduct, sorbitan distearate ethylene oxide adduct, sorbitan dilaurate ethylene oxide propylene oxide random adduct, and the like. Specific examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside, lauryl glycoside and the like. Specific examples of polyhydric alcohol alkyl ether alkylene oxide adducts include sorbitan monostearyl ether ethylene oxide adduct, methylglycoside ethylene oxide propylene oxide random adduct, lauryl glycoside ethylene oxide adduct, stearyl glycoside ethylene oxide propylene oxide random adduct Etc.

  Examples of the water-soluble organic polymer (T) include cellulosic compounds (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and saponified products thereof), gelatin, starch, dextrin, gum arabic, Chitin, chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing organic polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide of polyacrylic acid) Partially neutralized product, sodium acrylate-acrylic acid ester copolymer), styrene-maleic anhydride copolymer hydroxide Sodium (partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

The solvent (U) used in the present invention is used for the purpose of imparting dispersion stability, and may be added to an aqueous medium as needed during emulsification dispersion. The solvent (U) needs to have a solubility in water of 1% by weight or more. Among the solvent (X) and the poor solvent (Y), those having a solubility in water of 1% by weight or more can be used as the solvent (U).
Specific examples include ester solvents such as ethyl acetate, butyl acetate, and methoxybutyl acetate; ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve, and butyl cellosolve; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and t-butanol; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide, N-methylpyrrolidone And the like, and a mixed solvent of two or more of these. Of these, preferred are ketone solvents, and more preferred are acetone and methyl ethyl ketone.

The total amount of the surfactant (S) and the water-soluble organic polymer (T) is usually 0.1 to 5% based on the weight of the organic polymer (b) (hereinafter, unless otherwise specified,% is% by weight). Represented), preferably 0.2 to 4%. Further, the dispersant is preferably 0.01 to 5%, more preferably 0.1 to 3% based on the weight of water. If it is 0.01 to 5%, resin fine particles having a preferable average particle diameter are easily obtained. Moreover, the usage-amount of the dispersing agent solution which consists of a dispersing agent and water with respect to the weight of an organic polymer (b) becomes like this. Preferably it is 50 to 1,000%, More preferably, it is 100 to 1,000%. If it is 50 to 1,000%, the dispersion state of the organic polymer (b) tends to be good, and resin fine particles having a preferable average particle diameter are easily obtained. If necessary, the organic polymer (b) may be heated to 40 to 60 ° C. in order to reduce the viscosity.
The amount of the solvent (U) added is preferably from 0.1 to 20%, more preferably from 0.5 to 5%, based on the weight of the organic polymer (b).

  As a method for dispersing (b) in water containing a dispersant in the above methods (1) and (4), a known method such as a high-speed shearing method, a friction method, a high-pressure jet method, or an ultrasonic method is preferably used. A disperser can be used. Of these, a more preferable method is a high-speed shearing method. When a high-speed shearing disperser is used, the number of rotations is preferably 1,000 to 30,000 rpm, more preferably 2,000 to 10,000 rpm. The dispersion time is preferably 0.1 to 5 minutes. If the rotation speed and dispersion time are within these ranges, resin fine particles having a preferable average particle diameter can be easily obtained.

The reaction time between the precursor and the extender in the method (1) is not particularly limited, and is appropriately selected according to the reactivity and reaction temperature. For example, when the reaction temperature is 30 ° C., it is usually 1 hour to 40 hours, preferably 5 hours to 20 hours.
In the manufacturing method of this invention, reaction temperature is 0-50 degreeC normally, Preferably it is 20-40 degreeC.

The dispersion is filtered or separated using a known equipment such as a filter press, a spatula filter, a centrifuge, and the resulting fine particles are dried to obtain the organic polymer fine particles (B0) of the present invention.
The obtained fine particles can be dried using a known facility such as a circulating dryer, a spray dryer or a fluidized bed dryer.

  The number average particle diameter of the organic polymer fine particles (B0) obtained by the above production method is preferably 0.1 μm or more, more preferably 0.5 μm or more, and preferably 60 μm or less from the viewpoint of conductivity. More preferably, it is 20 μm or less.

  The particle shape of the organic polymer fine particles (B0) of the present invention may be indefinite or spherical, but preferably contains 50% or more of spherical particles from the viewpoint of fluidity at room temperature. Here, the term “spherical” refers to particles having a major axis / minor axis ratio in the range of 1.0 to 1.5.

The method for coating the surface of the organic polymer fine particles (B0) with the inorganic compound (A) is not particularly limited. For example, a method by electroless plating, a method using a sol-gel reaction of metal alkoxide, a method of wet coating metal fine particles , Vacuum deposition, ion plating, ion sputtering and the like. From the viewpoint of film formability, a method utilizing a sol-gel reaction of metal alkoxide is preferable.
Examples of the method of coating with silicon oxide include a method in which an alkoxysilane compound is absorbed in an organic polymer fine particle (B0) and then the alkoxysilane compound is condensed, and the surface of the organic polymer fine particle (B0) is a silane such as vinyltriethoxysilane. For example, a sol-gel method may be used after introducing a polysiloxane structure on the particle surface by treatment with a coupling agent.
Among these, from the viewpoint of the denseness of the shell layer, a method of treating with a silane coupling agent to introduce a polysiloxane structure on the particle surface and then performing a sol-gel method is preferable.

  The average coating thickness of the inorganic compound (A) layer in the organic polymer fine particles (B) is preferably 0.01 μm to 10 μm, more preferably 0.1 μm to 5 μm, still more preferably 0.1 μm from the viewpoint of specific gravity. 3 μm to 1 μm.

  The conductive fine particles of the present invention can be obtained by preparing organic polymer fine particles (B) coated with an inorganic compound and then coating the surface of (B) with a conductive metal (C).

As the conductive metal (C) in the present invention, a conductive metal can be used, for example, chromium, iron, copper, cobalt, nickel, zinc, tin, gold, silver, aluminum, and alloys of two or more thereof. Can be used.
Among these, nickel, copper, aluminum, silver, gold, and alloys thereof are preferable from the viewpoint of conductivity. Silver is more preferable from the viewpoint of oxidizing properties.

  The method for coating the organic polymer fine particles (B) with the conductive metal (C) is not particularly limited. For example, a method by electroless plating, a method by electroplating, a method for coating metal fine particles, vacuum deposition, ion plating, Examples of the method include ion sputtering. Of these, the electroless plating method is preferred.

  In the method for coating the metal fine particles, the number average particle diameter of the metal fine particles is preferably 1 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, more preferably 100 nm or less from the viewpoint of conductivity. is there.

  The process of forming a metal plating layer (conductive layer) by an electroless plating method is generally divided into an etching process, an activation process, and an electroless plating process, but the etching process is not necessarily required.

  The etching step is a step of forming irregularities on the surface of the organic polymer fine particles (B) to improve the adhesion of the metal plating layer (conductive layer). The etching solution used in the etching step is not particularly limited, and examples thereof include an alkaline aqueous solution such as a caustic soda aqueous solution and an acid aqueous solution such as an aqueous chromic acid solution. These etching liquids may be used independently and 2 or more types may be used together.

  The activation step is a step of activating the catalyst layer while forming a catalyst layer on the surface of the organic polymer fine particle (B) that has undergone the etching step or the surface of the organic polymer fine particle (B) that has not undergone the etching step. is there. Activation of the catalyst layer promotes metal deposition in the electroless plating process. The catalyst used in the activation step is not particularly limited, and examples thereof include an alkali catalyst (alkali catalyst) such as a commercially available amine complex-based catalyst. These catalysts may be used independently and 2 or more types may be used together.

  The electroless plating step is a step of coating the surface of the organic polymer fine particles (B) on which the catalyst layer is formed with a conductive metal (C). By immersing the organic polymer fine particles (B) on which the catalyst layer is formed in an electroless metal plating solution, a conductive metal (C) layer is formed on the surface of the organic polymer fine particles (B).

For example, when an Ag plating layer is formed on the surface of resin fine particles, the catalyst layer of resin fine particles is reduced with a reducing agent such as dimethylaminoborane and then immersed in an electroless Ag plating solution, or a catalyst layer is formed. After immersing the organic polymer fine particles (B) in an electroless Ag plating solution, an Ag plating layer can be formed on the surface of the organic polymer fine particles (B) by adding a reducing agent and reducing.

  The average coating thickness of the conductive metal (C) layer in the conductive fine particles is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 2 μm, and still more preferably 0.1 μm to 10 μm from the viewpoint of specific gravity. 1 μm.

  The number average particle diameter of the conductive fine particles by the light scattering method is preferably 0.1 μm or more, more preferably 0.5 μm or more, preferably 60 μm or less, more preferably 20 μm or less from the viewpoint of conductivity. is there.

  The particle shape of the conductive fine particles of the present invention may be indefinite or spherical, but preferably contains 50% or more of spherical particles from the viewpoint of powder flowability at room temperature. Here, the term “spherical” refers to particles having a major axis / minor axis ratio in the range of 1.0 to 1.5.

  An anisotropic conductive material can be produced by dispersing the conductive fine particles of the present invention in a binder (E).

As the binder (E), known thermosetting resins and thermoplastic resins can be used.
As a thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, etc. are mentioned, for example.
Examples of the thermoplastic resin include polyolefin resins, acrylate resins, and polystyrene resins.
Examples of the polyolefin resin include polyethylene, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylic acid ester copolymer.
Examples of the acrylate resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate.
Examples of the polystyrene resin include polystyrene, styrene-acrylic acid ester copolymer, SB type styrene-butadiene block copolymer, styrene-isoprene block copolymer, and block organic polymers such as these water additives. It is done.
Among these, from the viewpoint of adhesion to the conductive metal (B), a thermosetting resin is preferable, and an epoxy resin is particularly preferable.
Mw by GPC (measurement conditions: temperature 40 ° C., tetrahydrofuran solvent, polystyrene conversion) of (E) is usually 1,000 to 2,000,000, preferably 3,000 to 1,000,000.

  The amount of the conductive fine particles used is preferably 50 to 150% by weight based on the weight of the binder (E), and more preferably 80 to 120% by weight from the viewpoint of conductivity.

A solvent (H) can be used for the anisotropic conductive material of this invention as needed.
As (H), water, C4-C30 aliphatic hydrocarbon, C6-C18 aromatic hydrocarbon, C1-C18 alcohol, C3-C18 ketone, C3-C3 36 esters, ethers having 4 to 18 carbon atoms, halogenated hydrocarbons having 1 to 12 carbon atoms, and mixtures thereof.
Examples of the aliphatic hydrocarbon include hexane, octane, and paraffin oil.
Examples of the aromatic hydrocarbon include benzene, toluene and xylene.
Examples of the alcohol include methanol, isopropyl alcohol and butanol.
Examples of the ketone include acetone, methyl ethyl ketone, and isobutyl methyl ketone.
Examples of the ester include ethyl acetate, butyl acetate, and methyl propionate.
Examples of ethers include diethyl ether, dibutyl ether and tetrahydrofuran.
Examples of the halogenated hydrocarbon include chloroform, methylene dichloride, ethylene dichloride, and the like.
When (H) is used, the amount of (H) used is usually 0.1 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the total of the conductive fine particles and (E). Particularly preferred is 20 to 60 parts by weight.

In addition to the conductive fine particles (E) and (H), other components can be added to the anisotropic conductive material as necessary.
Examples of other components include an antifoaming agent, a leveling agent, a viscosity modifier, a dispersant, and a stabilizer.
When other components are used, the amount of the other components is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the total of the conductive fine particles and (E). Particularly preferred is 1 to 10 parts by weight.

The anisotropic conductive material can be obtained by uniformly mixing and dispersing conductive fine particles and a binder (E).
For uniform mixing / dispersing, for example, a three-roll, bead mill, disper mill, high-pressure homogenizer, kneader or planetary mixer can be used. The mixing / dispersing temperature is usually 5 to 100 ° C., and the mixing / dispersing time is usually 5 minutes to 10 hours.

  The hardness of the conductive fine particles is preferably 10% K value of 1000 to 15000 MPa, more preferably 2000 to 10,000 MPa, from the viewpoint of non-damage of the electrode.

The 10% K value is a smooth indenter made of a diamond cylinder having a diameter of 50 μm, using a fine compression tester (PCT-200, manufactured by Shimadzu Corporation) in accordance with Japanese Patent Publication No. 6-503180. It is measured by compressing at the end face under the conditions of a compression rate of 0.27 g / sec and a maximum test excess of 10 g, and a 10% K value can be obtained from the following formula.
K = (3 / √2) · F · S-3 / (2 · R) −1/2
F: Load value in 10% compression deformation of particles (kg)
S: Compression displacement (mm) in 10% compression deformation of particles
R: radius of particle (mm)

    The conductive fine particles of the present invention are formed by coating organic polymer fine particles (B) coated with an inorganic compound (A) as a shell and organic polymer (b) as a core with a conductive metal (C), It has the characteristics of having both high flexibility and hardness.

  The conductive fine particles of the present invention are used as a main constituent material of various anisotropic conductive materials, and are used when electrically connecting two opposing substrates and electrode terminals. The anisotropic conductive material to be contained is also included in the present invention.

  The anisotropic conductive material is not particularly limited as long as conductive fine particles are dispersed in an insulating binder resin. An anisotropic conductive film, anisotropic conductive paste, anisotropic conductive ink, etc. Is included.

  An anisotropic conductive film is obtained by, for example, adding a solvent to a binder in which conductive fine particles are dispersed to form a solution, casting the solution on a release film to form a film, and evaporating the solvent from the film. It can be wound on a roll. In use, the film can be unwound together with the release film, placed on the electrode to be bonded, and the counter electrode can be superimposed on the electrode and heated to compress the film.

  An anisotropic conductive paste is obtained, for example, by adding a solvent to a binder in which conductive fine particles are dispersed to form a paste, put this in a suitable dispenser, and apply it to a desired thickness on the electrode to be connected, A counter electrode can be overlaid on this, and heated and pressed to cure the resin, thereby allowing connection.

  The anisotropic conductive ink can be obtained, for example, by adding a solvent to a binder in which conductive fine particles are dispersed so as to have a viscosity suitable for printing. The connection can be established by evaporating the solvent and superposing the counter electrode on top of this to heat-compress.

Examples Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. In the following, parts and% indicate parts by weight and% by weight, respectively.

The number average particle size, 10% K value, and metal layer average coating thickness were measured by the following methods.
<Number average particle diameter> The number average particle diameter was measured with a laser scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) using toluene as a solvent.
<10% K value> Using a micro-compression tester (PCT-200, manufactured by Shimadzu Corporation), the obtained resin fine particles were measured on a smooth indenter end face made of a diamond cylinder having a diameter of 50 μm, a compression rate of 0.27 g / sec, and a maximum test. It measured by compressing under the condition of excess weight 10g, and 10% K value was calculated | required from said formula.
<Metal layer average coating film thickness> Conductive fine particles 0.5g was precisely weighed and dissolved in 10ml of 30% nitric acid aqueous solution. The silver content WAg was measured with 0.01 MEDTA standard solution using -PAN as an indicator, and the silver plating layer thickness was calculated by the following formula.
Silver plating layer thickness (μm) = (ρ _P × W _Ag × D) / {6 × ρ _Ag × (100−W _Ag )}
ρ _P : Specific gravity of resin fine particles ρ _Ag : Specific gravity of silver W _Ag : Silver content (%) D: Number average particle diameter (μm) of resin fine particles

Example 1
<Manufacture of silica-coated polyurethane fine particles (B-1)>
1,000 parts of toluene is added to 650 parts of polyethylene terephthalate (number average molecular weight 2,000, acid value 0.2), 142 parts of diphenylmethane diisocyanate is added, and the mixture is refluxed with toluene at 120 ° C. for 5 hours. After the reaction (isocyanate group content 3.2%), the mixture was cooled to room temperature, 35 parts of ethylenediamine, 10 parts of an amino silane coupling agent (KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) was added at 60 ° C. After reacting for 5 hours, toluene was distilled off under reduced pressure to obtain a polyurethane resin having hydroxyl groups at both ends and having urethane and urea bonds. 400 parts of the obtained resin, 12 parts of yellow iron oxide, and 380 parts of ethyl acetate were mixed and dispersed while being added dropwise to 2000 parts of a previously prepared 0.5% aqueous polyvinyl alcohol solution. The obtained resin was taken out of the water by filter paper filtration and dried with a circulating air dryer at 40 ° C. to obtain polyurethane fine particles (B0-1) (number average particle diameter 1.5 μm).
100 parts of the above-mentioned polyurethane fine particles (B0-1) are put into a 1 liter flask, and 75 parts of methanol, 25 parts of water, 2 parts of tetraethoxysilane, and 10 parts of 25% ammonia water are added to the flask, and the temperature of the liquid exceeds 30 hours. It was well dispersed using sonic vibration. The particles obtained after filtration and washing were again subjected to the same treatment with the same treatment liquid as the tetraethoxysilane liquid. The contents were washed by filtration and then dried at 120 ° C. for a whole day and night to obtain silica-coated polyurethane fine particles (B-1).

<Production of silver-coated conductive polyurethane fine particles (C-1)>
Etching was performed by dispersing 10 g of the obtained silica-coated polyurethane fine particles (B-1) in a pre-dip solution for powder plating (Okuno Pharmaceutical Co., Ltd.) and stirring at 30 ° C. for 30 minutes. After washing with water, the solution was added to 100 ml of a Pd catalyst containing 1% by weight of palladium sulfate and stirred at 30 ° C. for 30 minutes to adsorb palladium ions to the particles. The particles were collected by filtration and washed with water, and then added to a 0.5% by weight dimethylamine borane solution (adjusted to pH 6.0) to obtain organic polymer fine particles having activated Pd.
Distilled water (500 ml) was added to the obtained Pd-activated resin fine particles, and sufficiently dispersed using an ultrasonic processor to obtain a fine particle suspension. While stirring this suspension at 50 ° C., an electroless plating solution (pH adjusted to 7.5) consisting of 50 g / L of silver sulfate, 40 g / L of sodium hypophosphite, and 50 g / L of citric acid is gradually added. It was added and electroless silver plating was performed. When the metal coating layer became approximately 0.10 μm, the addition of the electroless plating solution was stopped, and after replacing with alcohol, vacuum-dried to obtain silver-coated conductive urethane fine particles (C-1) (Ag plating) Layer thickness: 0.24 μm, number average particle size: 2.4 μm, 10% K value: 4855).

Example 2
<Production of silica-coated polyester fine particles (B-2)>
To 450 parts of bisphenol A ethylene oxide (EO) 2 mol adduct (BPE-20T manufactured by Sanyo Kasei Kogyo Co., Ltd.), 242 parts of terephthalic acid and 28 parts of trimellitic anhydride are added, and 3 parts of dibutyltin oxide is added as a catalyst. The reaction was carried out at 230 ° C. for 10 hours (acid value 0.5, number average molecular weight 5000). This was taken out into a vat at 150 ° C. and cooled to room temperature to obtain a polyester resin. 400 parts of the obtained resin, 10 parts of an amino-based silane coupling agent (KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) and 380 parts of ethyl acetate are mixed to form an oil phase. 20 parts of an emulsifier (Calibon B (manufactured by Sanyo Chemical Industries)) is dissolved in 800 parts of ion-exchanged water to obtain an aqueous phase. While the aqueous phase was stirred at 8,000 rpm with a TK homomixer, the oil phase was added and stirred for 3 minutes. Next, this mixed liquid was transferred to a reaction vessel equipped with a stir bar and a thermometer, and the temperature was raised to distill off ethyl acetate. The resulting resin dispersion was removed from the water by filtration with a filter paper, and a circulating dryer at 40 ° C. To obtain polyester fine particles (B0-2) (number average particle diameter 2.7 μm).
100 parts of the above polyester fine particles are put into a 1 liter flask, 75 parts of methanol, 25 parts of water, 2 parts of tetraethoxysilane, and 10 parts of 25% ammonia water are added thereto, and ultrasonic vibration is used for 2 hours at a liquid temperature of 30 degrees. And well dispersed. The particles obtained after filtration and washing were again subjected to the same treatment with the same treatment liquid as the tetraethoxysilane liquid. The contents were washed by filtration and then dried at 120 ° C. for a whole day and night to obtain silica-coated polyester fine particles (B-2).

<Production of silver-coated conductive polyester fine particles (C-2)>
Silver-coated conductive polyester fine particles (C-2) were obtained by the same operation as in Example 1 except that the silica-coated polyester fine particles (B0-2) were used (Ag plating layer thickness: 0.22 μm, number average particle diameter). 3.6 μm, 10% K value: 4550).

Example 3
<Manufacture of silica-coated epoxy fine particles (B-3)>
In a reaction vessel equipped with a stir bar and a thermometer, 47 parts of a styrenated phenol polyethylene oxide adduct (Eleminol HB-12, Sanyo Chemical Industries) and bisphenol A diglycidyl ether (Epicoat 828, Yuka Shell) 232 The part was added and dissolved uniformly. Water was added dropwise to the reaction vessel with stirring. When 38 parts of water was added, the system emulsified milky white. Further, 224 parts of water was added dropwise to obtain an emulsion. After heating this and raising the temperature in the system to 70 ° C., a solution in which 20 parts of ethylenediamine and 10 parts of an amino silane coupling agent (KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved in 446 parts of water was 70. It was added dropwise over 2 hours while maintaining the temperature. After dropping, the reaction and aging were carried out at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain an aqueous epoxy resin dispersion. Subsequently, the obtained resin dispersion was taken out of the water by filtration with a filter paper and dried with a circulating dryer at 40 ° C. to obtain epoxy fine particles (B0-3) (number average particle diameter 1.8 μm).
100 parts of the above epoxy fine particles are put into a 1 liter flask, 75 parts of methanol, 25 parts of water, 2 parts of tetraethoxysilane and 10 parts of 25% aqueous ammonia are added thereto, and ultrasonic vibration is used for 2 hours at a liquid temperature of 30 degrees. And well dispersed. The particles obtained after filtration and washing were again subjected to the same treatment with the same treatment liquid as the tetraethoxysilane liquid. The contents were washed by filtration and then dried at 120 ° C. for a whole day and night to obtain silica-coated epoxy fine particles (B-3).

<Production of silver-coated conductive epoxy fine particles (C-3)>
A silver-coated conductive epoxy fine particle (C-3) was obtained in the same manner as in Example 1 except that the silica-coated epoxy fine particle (B-3) was used (Ag plating layer thickness: 0.25 μm, number average particle diameter). 2.8 μm, 10% K value: 4060).

Example 4
<Production of silica-coated polyamide fine particles (B-4)>
100 parts of isophthalic acid chloride, 90 parts of hexamethylenediamine, 10 parts of an amino silane coupling agent (KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) and 120 parts of MEK are added and dissolved to obtain an oil phase. 10 parts of emulsifier (Calibon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filtration with filter paper and dried with a circulating dryer at 40 ° C. to obtain polyamide fine particles (B0-4) (number average particle diameter 1.7 μm). ).
100 parts of the above-mentioned polyamide fine particles (B0-4) are put into a 1 liter flask, and 75 parts of methanol, 25 parts of water, 2 parts of tetraethoxysilane, and 10 parts of 25% ammonia water are added to the flask, and the temperature of the liquid exceeds 30 hours. It was well dispersed using sonic vibration. The particles obtained after filtration and washing were again subjected to the same treatment with the same treatment liquid as the tetraethoxysilane liquid. The contents were washed by filtration and then dried at 120 ° C. for a whole day and night to obtain silica-coated polyamide fine particles (B-4).

<Production of silver-coated conductive polyamide fine particles (C-4)>
Silver-coated conductive polyamide fine particles (C-4) were obtained by the same operation as in Example 1 except that silica-coated polyamide fine particles (B-4) were used (Ag plating layer thickness: 0.25 μm, number average particle diameter). 2.5 μm, 10% K value: 4200).

Comparative Example 1 <Production of silver-coated conductive polyurethane fine particles (C′-1)>
Silver-coated conductive polyurethane fine particles (C′-1) were obtained by the same operation as in Example 1 except that the polyurethane fine particles (B0-1) obtained in Example 1 were used (Ag plating layer thickness: 0. 0). 19 μm, number average particle size 1.8 μm, 10% K value: 3520).

Comparative Example 2 <Production of silver-coated conductive polyester fine particles (C′-2)>
Silver-coated conductive polyester fine particles (C′-2) were obtained by the same operation as in Example 1 except that the polyester fine particles (B0-2) obtained in Example 2 were used (Ag plating layer thickness: 0. 19 μm, number average particle size 2.9 μm, 10% K value: 3820).

Comparative Example 3 <Production of silver-coated conductive epoxy fine particles (C′-3)>
In a reaction vessel equipped with a stir bar and a thermometer, 47 parts of a styrenated phenol polyethylene oxide adduct (Eleminol HB-12, Sanyo Chemical Industries) and bisphenol A diglycidyl ether (Epicoat 828, Yuka Shell) 232 The part was added and dissolved uniformly. Water was added dropwise to the reaction vessel with stirring. When 38 parts of water was added, the system emulsified milky white. Further, 224 parts of water was added dropwise to obtain an emulsion. After heating this and raising the temperature in the system to 70 ° C., a solution obtained by dissolving 20 parts of diethylenetriamine and 10 parts of an amino-based silane coupling agent (KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) in 446 parts of water was prepared. It was added dropwise over 2 hours while maintaining the temperature. After dropping, the reaction and aging were carried out at 70 ° C. for 5 hours and at 90 ° C. for 5 hours to obtain an aqueous epoxy resin dispersion. Subsequently, the obtained resin dispersion was taken out from the water by filtration with a filter paper and dried with a circulating dryer at 40 ° C. to obtain epoxy fine particles (B0′-3) (number average particle size 2.2 μm).
Silver-coated conductive polyester fine particles (C′-3) were obtained by the same operation as in Example 1 except that the epoxy fine particles (B0′-3) were used (Ag plating layer thickness: 0.19 μm, number average particles). Diameter 2.4 μm, 10% K value: 11820).

Comparative Example 4 <Production of silver-coated conductive polyamide fine particles (C′-4)>
100 parts of isophthalic acid chloride, 80 parts of hexamethylenediamine, 15 parts of diethylenetriamine, 10 parts of an amino silane coupling agent (KBM-9103 manufactured by Shin-Etsu Chemical Co., Ltd.) and 120 parts of MEK are added and dissolved to make an oil phase. 10 parts of emulsifier (Calibon B (Sanyo Chemicals)) is dissolved in 800 parts of ion-exchanged water, and this is used as an aqueous phase. The aqueous phase and the oil phase are mixed and dispersed under the condition of 4000 rpm × 1 minute using a homomixer. The volume average particle diameter of the oil droplets was 20 μm. This dispersion is reacted at 60 ° C. for 10 hours. After completion of the reaction, the obtained spherical resin was taken out of the water by filtration with filter paper and dried with a circulating dryer at 40 ° C. to obtain polyamide fine particles (B0′-4) (number average particle size 1. 9 μm).
Silver-coated conductive polyamide fine particles (C′-4) were obtained by the same operation as in Example 1 except that the above-mentioned polyamide fine particles (B0-4) were used (Ag plating layer thickness: 0.21 μm, number average particle diameter). 2.1 μm, 10% K value: 9220).

  The conductive fine particles (C-1 to 4, C-1 ′ to 4 ′) obtained above were evaluated for powder resistivity, contact resistance value when used as an anisotropic conductive material, and long-term reliability. It was. The results are shown in Table 1.

<Powder resistivity (× 10 ⁻⁴ Ω · cm)>
A 20 g sample was compressed at a press pressure of 500 kgf and measured with a Loresta AP and Loresta PD-41 type (both manufactured by Mitsubishi Chemical).

<Contact resistance value (Ω)>
Conductive fine particles (C-1 to 4, C-1 ′ to 4 ′) are mixed with an epoxy adhesive (SE-4500, manufactured by Furukawa Chemical Co., Ltd.) at a rate of 5 wt%, and dispersed thoroughly with a homogenizer. An isotropic conductive material was produced.
This anisotropic conductive material was applied on a glass substrate having a width of 300 μm and on which an ITO electrode was formed, and the same glass substrate was stacked thereon so that the ITO electrode became a cloth. This was heated at 160 ° C. for 30 minutes while applying a pressure of 30 kg / cm ² , followed by pressure-curing and curing, then conductive fine particles (C-1 to 4, C-1 ′ to 4 ′) present at the intersection of ITO. The contact resistance value was measured by the 4-terminal method. The number of conductive fine particles present at the intersecting portion was counted with an optical microscope, and the obtained contact resistance value was divided by this number to obtain the contact resistance value per conductive fine particle.

<Reliability test>
In the above contact resistance measurement, an anisotropic conductive material is pressure-cured and cured on a glass substrate on which an ITO electrode is formed, and then a pressure of 20 kg / cm ² is applied for 30 minutes and then the pressure is released for 100 minutes. After repeating, the contact resistance value of the conductive fine particles (C-1 to 4, C-1 ′ to 4 ′) present at the portion where the ITO intersects was measured by the four-terminal method. The number of conductive fine particles present at the intersecting portion was counted with an optical microscope, and the obtained contact resistance value was divided by this number to obtain the contact resistance value per conductive fine particle.
Resistance change rate (%) = (contact resistance value after repetition−initial contact resistance value) × 100 / initial contact resistance value

  In Examples 1 to 4 using the inorganic compound-coated organic polymer fine particles of the present invention, high conductivity was exhibited and the reliability was excellent. In contrast, in Comparative Examples 1 to 4 using organic polymer fine particles not coated with an inorganic compound, Comparative Examples 1 and 2 having high flexibility are inferior in reliability, and in Comparative Examples 3 and 4 having high rigidity, conductivity is low. It became inferior result.

The conductive fine particles of the present invention can be both hard and flexible by using organic polymer fine particles coated with an inorganic compound, and are excellent in conductivity and reliability. Because of these characteristics, they are useful as anisotropic conductive materials such as anisotropic conductive films, conductive pastes, conductive adhesives, and conductive adhesive materials.

Claims (7)

Conductive fine particles, wherein the organic polymer fine particles (B) covered with an inorganic compound having an inorganic compound (A) as a shell and an organic polymer (b) as a core are covered with a conductive metal (C). The conductive fine particles according to claim 1, wherein the inorganic compound (A) is a metal oxide or a non-metal composite. The conductive fine particles according to claim 1 or 2, wherein the inorganic compound (A) is silicon oxide. The conductive fine particles according to claim 1, wherein the inorganic compound (A) and the organic polymer (b) are chemically bonded. The conductive fine particles according to claim 1, wherein the conductive metal (C) has an average coating thickness of 0.01 μm or more and 10 μm or less. The conductive fine particles according to any one of claims 1 to 5, wherein the number average particle diameter is 0.1 µm or more and 60 µm or less. An anisotropic conductive material comprising the conductive fine particles according to claim 1.