JP5741785B2 - Metal fine particle dispersant comprising a highly branched polymer having an amino functional group or an imino functional group at its terminal - Google Patents

Description

  The present invention relates to a metal fine particle dispersant composed of a highly branched polymer having the amino functional group or imino functional group at its terminal, and a composition comprising the metal fine particle dispersant and metal fine particles.

  Metal fine particles having a particle size of several nanometers to several tens of nanometers exhibit various physical and chemical characteristics different from those of bulk metals. For example, as an optical property, it has long been known that a coloring mechanism called plasmon absorption exhibits a unique color depending on the metal type and size, and a solution of metal fine particles is used for colorants such as paints. Yes. In addition, conductive paste, transparent conductive film, high-density recording material, light shielding filter, chemical sensor, catalyst, light guide member, gas barrier material, light scattering / reflecting member, light diffusion member, photosensitive material, photoelectric conversion element Applications to inkjet inks, high dielectric constant materials, fluorescent materials, etc. are expanding.

  As a method for producing such metal fine particles, there are a gas phase method and a liquid phase method, but the liquid phase method is cheaper and it is easier to obtain fine particles having a narrow particle size distribution. In general, the liquid phase method is prepared by reducing metal ions with a reducing agent in a state where an organic dispersant having an affinity for metal is added to a metal salt solution.

As dispersants used in the preparation of metal fine particles by the liquid phase method, citric acid, surfactants, low molecular compounds having thiol groups and amino groups, and high molecular compounds such as polyvinylpyrrolidone and polyethyleneimine have been proposed. .
As an example of a dispersant using a low molecular weight compound, metal fine particles prepared using a thiol compound as a protective colloid can be cited (Patent Document 1). Since the obtained metal fine particles are firmly coated on the surface with a thiol compound, they can be recovered as a powder and redispersed in a solvent. Thus, since the compound having a functional group containing a sulfur atom has a high affinity with the metal surface, it exhibits excellent properties as a dispersant for metal fine particles.
In addition, examples of the dispersant using the polymer compound include metal fine particles prepared using polyvinylpyrrolidone as a protective colloid (Patent Document 2).

In order to use the metal fine particles thus obtained for the above-mentioned various applications, it is necessary to fix the metal fine particles on the substrate. For this reason, additives such as polymer binders, polymerizable monomers, cross-linking agents, and dispersing agents are blended into a solution in which metal fine particles are dispersed in a solvent, and technologies such as spin coating, ink jet, spray, and dip are used. A process such as forming a film on the base material is performed.
For example, a metal fine particle-polymer composite pigment using a methyl methacrylate-acrylic acid random copolymer as a polymer binder and polyethyleneimine as a polymer dispersant is obtained as a pigment insoluble in water or an organic solvent. (Patent Document 3).
In addition, a photo-curable composition containing a polyfunctional acrylic monomer as a polymerizable monomer, using these photopolymerization products as a polymer binder, a low molecular compound having an amino group as a dispersant, and metal fine particles. A light-shielding film for a display device produced by using this has been proposed (Patent Document 4).
Furthermore, a proposal has been made to produce a metal fine particle dispersion without using a solvent by using a monomer having a radical polymerizable double bond as a reaction solvent and reducing metal ions (Patent Document 5).
As an example using a thermosetting polymer binder, metal fine particles obtained using an amine-based polymer dispersant are mixed with a thermosetting resin such as an epoxy resin or a phenol resin to obtain an adhesive paste. An example is disclosed (Patent Document 6).

JP 2003-193118 A JP 2006-299329 A JP 2006-104254 A JP-A-2005-250461 JP 2006-9085 A JP 2003-183616 A

As described above, by adding additives such as a polymerizable monomer and a polymer binder to the dispersion of metal fine particles to form a film-like form on the substrate, the metal fine particles can be used in various applications. Proposed. However, by adding these additives, the metal concentration in the metal fine particle-containing composition is lowered, and as a result, there has been a problem that the performance of the target metal fine particles cannot be sufficiently brought out.
Further, when the amount of the fine particles added is increased in order to bring out the performance of the metal fine particles to a higher level, there is a problem that precipitation occurs without keeping the dispersion state stable.

As a result of intensive studies to achieve the above object, the present inventors have found that a hyperbranched polymer having an amino functional group or an imino functional group introduced at the terminal is excellent in dispersibility of metal fine particles. Further, since this hyperbranched polymer has thermosetting properties, it has been found that by using it as a metal fine particle dispersant, a thin film containing metal fine particles can be obtained without reducing the metal concentration in the metal fine particle-containing composition. The present invention has been completed.
That is, as a first aspect, the present invention has an amino functional group or an imino functional group at the end, and has a weight average molecular weight of 1,000 to 2,000,000 as measured by gel permeation chromatography in terms of polystyrene. The present invention relates to a metal fine particle dispersant characterized by comprising a highly branched polymer.
As a second aspect, the hyperbranched polymer has a monomer A having two or more radical polymerizable double bonds in the molecule, and 5 to 200 mol% of amino functional group or imino functional group with respect to the monomer A. It is related with the metal fine particle dispersing agent as described in a 1st viewpoint which is a hyperbranched polymer obtained by making it superpose | polymerize in presence of the polymerization initiator B which has.
As a 3rd viewpoint, it is related with the metal fine particle dispersing agent as described in a 2nd viewpoint containing the monomer A further.
As a fourth aspect, the metal according to any one of the second aspect and the third aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a heterocyclic amine structure. The present invention relates to a fine particle dispersant.
As a fifth aspect, the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator having a functional group represented by the formula [1], either the second aspect or the third aspect The metal fine particle dispersant according to one item.

(In the formula [1], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, and R ¹ , R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.)
As a sixth aspect, the present invention relates to the fine metal particle dispersant according to the fifth aspect, wherein the polymerization initiator B having an amino functional group or an imino functional group is a polymerization initiator represented by the formula [2].

(In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms. Represents.)
As a seventh aspect, the present invention relates to a metal fine particle dispersant according to any one of the first aspect to the sixth aspect, and a composition containing the metal fine particles.
As an eighth aspect, the present invention relates to the composition according to the seventh aspect, wherein the metal fine particle dispersant is attached or coordinated to the surface of the metal fine particles to form a composite.
As a 9th viewpoint, it is related with the composition as described in the 7th viewpoint or the 8th viewpoint which contains water or an organic solvent further.
As a tenth aspect, the present invention relates to the composition according to the ninth aspect, wherein the metal fine particles are dispersed in water or an organic solvent.
As an eleventh aspect, the present invention relates to the composition according to the ninth aspect, wherein the complex is dispersed in water or an organic solvent.
As a twelfth aspect, the metal fine particles are scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, Seventh aspect to eleventh aspect, which is at least one selected from the group consisting of cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, and bismuth. It is related with the composition as described in any one of viewpoints.
As a thirteenth aspect, the composition according to the twelfth aspect, wherein the metal fine particles are at least one selected from the group consisting of gold, silver, platinum, copper, nickel, ruthenium, rhodium, palladium, osmium, and iridium. About.
As a fourteenth aspect, the present invention relates to the composition according to the thirteenth aspect, wherein the metal fine particles are at least one selected from the group consisting of gold, silver, platinum, and copper.
As a fifteenth aspect, the present invention relates to the composition according to any one of claims 9 to 14, further comprising a crosslinking agent or a photopolymerization initiator soluble in water or an organic solvent.
As a sixteenth aspect, the present invention relates to a thin film obtained from the composition according to any one of the seventh aspect to the fifteenth aspect.
As a 17th viewpoint, it is related with the cured film obtained by heat-processing or light irradiation processing to the thin film obtained from the composition as described in a 15th viewpoint.
Among these, the most preferred embodiment of the present invention has an amino functional group or imino functional group at the end, and has a weight average molecular weight of 1,000 to 2,000,000 as measured by gel permeation chromatography in terms of polystyrene. A dispersant for fine metal particles comprising a certain highly branched polymer, wherein the highly branched polymer contains 5 to 200 mol of monomer A having two or more radical polymerizable double bonds in the molecule. % Hyperbranched polymer obtained by polymerizing in the presence of a polymerization initiator B having an amino functional group or imino functional group,
The monomer A is divinylbenzene,
The polymerization initiator B having the amino functional group or imino functional group is a polymerization initiator represented by the following formula [2], and
The metal fine particle dispersant is at least one selected from the group consisting of gold, silver, platinum and copper.
(In the formula [2], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, and R ¹ Any two or more of R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring, and R ⁴ and R ⁵ each independently represent 1 to 1 carbon atoms. 6 represents an alkyl group.)

The metal fine particle dispersant of the present invention is composed of a highly branched polymer having an amino functional group or imino functional group introduced at the end, has excellent dispersibility of the metal fine particles, and is dispersed in water or an organic solvent without aggregating the metal fine particles. Can do.
In particular, the metal fine particle dispersant of the present invention forms a composite with metal fine particles and is dispersed in water or an organic solvent as the composite, and the metal fine particles can be dispersed in an organic solvent at a high concentration. It is.

The fine metal particle dispersant of the present invention comprises a so-called initiator fragment-incorporated hyperbranched polymer, and has an amino functional group or imino functional group at its end, ie, a functional group that assists or participates in a reaction such as a crosslinking reaction. It consists of a branched polymer.
Therefore, the composition containing the metal fine particles and the metal fine particle dispersant of the present invention is a radical polymerizable double bond derived from the monomer A present in the metal fine particle dispersant (hyperbranched polymer) or a radical polymerizable double bond. In the presence of the monomer A having, a thin film can be easily formed by simply applying it to a substrate without the need for a crosslinking agent or the like, and can be suitably used for various applications. Further, since it is not necessary to use a crosslinking agent or a polymerizable compound as an essential component, the concentration of the metal fine particles in the composition can be kept high, and the performance possessed by the metal fine particles can be sufficiently drawn out to the desired level. It becomes possible.

1 is a diagram showing a ¹ H NMR spectrum of a hyperbranched polymer (HI-DVB) synthesized in Example 1. FIG. 2 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer (HI-DVB) synthesized in Example 1. FIG. FIG. 3 is a diagram showing a ¹ H NMR spectrum of the hyperbranched polymer (HA-DVB) synthesized in the reference example. FIG. 4 shows the ¹³ C NMR spectrum of the hyperbranched polymer (HA-DVB) synthesized in the reference example. FIG. 5 is a view showing a TEM observation image of the gold fine particle composite prepared in Example 2. FIG. 6 is a view showing a TEM observation image of the gold fine particle composite prepared in Example 3. FIG. 7 is a diagram showing a TEM observation image of the silver fine particle composite prepared in Example 4. FIG. FIG. 8 is a view showing a TEM observation image of the gold fine particle composite prepared in Comparative Example 3.

<Metal fine particle dispersant>
Hereinafter, the present invention will be described in more detail.
The metal fine particle dispersant according to the present invention is a highly branched polymer having an amino functional group or an imino functional group at its end, more specifically, a radical polymerizable monomer A having two or more radical polymerizable double bonds in the molecule. Is polymerized in the presence of a polymerization initiator B having an amino functional group or imino functional group of 5 mol% or more and 200 mol% or less with respect to the polymerizable monomer A, and the weight average molecular weight is 1. 2,000 to 2,000,000 hyperbranched polymers.
Since this highly branched polymer has a large number of basic functional groups (amino functional group or imino functional group) that are considered to have high affinity for the metal surface of the fine particles at the terminal, it is highly Dispersibility can be expected, and various skeleton designs, introduction of functional groups, control of molecular weight and distribution, and addition of functions can be performed depending on the combination and conditions of monomer A and initiator B. Have Moreover, by having a branched structure, it also has a high solubility that cannot be seen in a straight chain.

In the present invention, when the weight average molecular weight (hereinafter abbreviated as Mw) of the polymer is less than 1,000, the dispersibility of the metal fine particles may be remarkably lowered or the dispersibility may not be exhibited. If it exceeds 1,000, handling in the dispersion process may become extremely difficult. A highly branched polymer having a weight average molecular weight of 2,000 to 1,000,000 is more preferred.
In addition, the weight average molecular weight in this invention is a measured value (polystyrene conversion) by gel permeation chromatography.

  In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has one or both of a vinyl group and a (meth) acryl group, and particularly a divinyl compound or di ( A meth) acrylate compound is preferred. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of such a monomer A include organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbon:
(A1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene (A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc. (A1-3) aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene , Divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine, etc. (A2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinyl ketones:
(A2-1) vinyl ester; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate, etc. (A2-2) allyl ester; diallyl maleate, diallyl phthalate, Diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc. (A2-3) vinyl ether; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, etc. (A2-4) allyl ether; diallyl ether, diallyloxyethane, tri Allyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc. (A2-5) vinyl ketone; divinyl ketone, diallyl Tons, etc. (A3) (meth) acrylic acid ester:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, alkoxy titanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol Di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy 1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, un Decylenoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide, 1,3-adamantanediol di (meth) acrylate, 1 , 3-Adamantanedimethanol di (meth) acrylate, bisphenol A diethoxydi (meth) acrylate, etc. (A4) Vinyl compounds having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, etc. (A5) Nitrogen-containing vinyl compounds:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide, etc. (A6) silicon-containing vinyl compounds:
Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane (A7) fluorine-containing vinyl compounds such as dietoxydivinylsilane:
1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluorooctane, etc.

  Of these, preferred are the aromatic vinyl hydrocarbons of the group (A1-3), vinyl esters, allyl esters, vinyl ethers, allyl ethers and vinyl ketones of the group (A2), and (meth) acrylic acids of the group (A3). An ester, a vinyl compound having a polyalkylene glycol chain of (A4) group, and a nitrogen-containing vinyl compound of (A5) group. Particularly preferred are divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2), ethylene glycol di (meth) acrylate belonging to group (A3), 1,3-adamantane dimethanol di (meta). ) Acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A diethoxydi (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene and (A5) group Methylenebis (meth) acrylamide. Among these, divinylbenzene, ethylene glycol di (meth) acrylate, and bisphenol A diethoxydi (meth) acrylate are preferable, and divinylbenzene is more preferable.

In the present invention, the polymerization initiator B having an amino functional group or an imino functional group includes an amino group and an amine or imine compound in which a hydrogen atom of ammonia is substituted with a monovalent or divalent hydrocarbon residue, as well as a heterocyclic ring. A polymerization initiator containing an amine.
Examples thereof include primary to tertiary aliphatic amines such as cyclohexylamine, dimethylamine, triethylamine, phenethylamine, and dibenzylamine; primary to tertiary amines such as aniline, dimethylaminopyridine, diphenylamine, and triphenylamine. Tertiary aromatic amines; imines such as methanimine, propan-2-imine, N-methylethaneimine; pyrroline, pyrrolidine, pyrazoline, pyrazolidine, imidazoline, imidazolidine, dihydropyridine, tetrahydropyridine, piperidine, dihydropyrimidine, tetrahydropyrimidine, hexa Such as hydropyrimidine, dihydropyrazine, tetrahydropyrazine, piperazine, morpholine, thiomorpholine, quinuclidine, 1,4-diazabicyclo [2.2.2] octane Cyclic heterocyclic amines; polymerization initiators containing structures such as aromatic heterocyclic amines such as pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, carbazole Is mentioned.

  Therefore, the polymerization initiator having an amino functional group or imino functional group is preferably a polymerization initiator having a heterocyclic amine structure, a polymerization initiator having a functional group represented by the following formula [1], particularly azo And a polymerization initiator.

In the formula [1], R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, or R ¹ , Any two or more of R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring.

  Examples of the functional group represented by the above formula [1] include, but are not limited to, groups represented by the following formulas [A] to [M].

  Examples of the azo polymerization initiator composed of a compound having a functional group represented by the above formulas [A] to [M] include a polymerization initiator represented by the following formula [2].

In the formula [2], R ¹ , R ² and R ³ represent those defined in the formula [1], and R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms. .

Examples of the azo polymerization initiator represented by the formula [2] include compounds shown in the following (1) to (2).
(1) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] -propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and the like.
(2) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, and the like.

Among the azo polymerization initiators, 2,2′-azobis [2-
(2-Imidazolin-2-yl) propane] or 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride is particularly preferred.

  The polymerization initiator B is used in an amount of 5 mol% to 200 mol% with respect to the monomer A, preferably 15 mol% to 200 mol%, more preferably 15 mol% to 170 mol%, still more preferably. Is used in an amount of 50 mol% to 100 mol%.

  The metal fine particle dispersant in the present invention includes a monomer C having at least one radical polymerizable double bond in the molecule in addition to the monomer A having two or more radical polymerizable double bonds in the molecule. And polymerizing in the presence of the polymerization initiator B having the aforementioned amino functional group or imino functional group in an amount of 5 mol% or more and 200 mol% or less with respect to the total mol of the monomer A and the monomer C. The fine metal particle dispersant comprising the resulting highly branched polymer is also targeted.

The monomer C having at least one radical polymerizable double bond in the molecule preferably has at least one of either a vinyl group or a (meth) acryl group.
As such a monomer C, the organic compound shown to the following (C1) thru | or (C3) is illustrated, for example.
(C1) (Meth) acrylic compound:
(C1-1) (meth) acrylic acids; (meth) acrylic acid, itaconic acid, 2-trifluoromethylacrylic acid, 2-ethylacrylic acid, 2-propylacrylic acid, 2-bromomethylacrylic acid, 2-acetamide Acrylic acid, 2-ethylacryloyl chloride, 3,3-dimethyl (meth) acryloyl chloride.
(C1-2) (meth) acrylic acid esters; methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-carboxyethyl (meth) Acrylate, mono-2- (meth) acryloyloxyethyl succinate, bis [2- (meth) acryloyloxyethyl] phosphate, 2- (meth) acryloyloxyethyl acetoacetate, 2-dimethylaminoethyl (meth) acrylate, 2 -Diethylaminoethyl (meth) acrylate, [2- (meth) acryloyloxyethyl] trimethylammonium chloride, 2-isocyanatoethyl (meth) acrylate, 2- [9H-carbazol-9-yl] ethyl (
(Meth) acrylate, vinyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, isobornyl (meth) acrylate Tetrahydrofurfuryl (meth) acrylate, (R) -α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, 2-naphthyl (meth) acrylate, Tylene glycol methyl ether (meth) acrylate, ethylene glycol cyclopentenyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, ethylene glycol (meth) acrylate phosphate, diethylene glycol ethyl ether (meth) acrylate, diethylene glycol 2-ethylhexyl ether ( (Meth) acrylate, dipropylene glycol allyl ether (meth) acrylate, neopentyl glycol methyl ether propoxylate (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, polyethylene glycol phenyl ether (meth) Acrylate, polypropylene glycol Rudi (meth) acrylate, polypropylene glycol methyl ether (meth) acrylate, polypropylene glycol 4-nonylphenyl ether (meth) acrylate, ethyl 2-ethyl acrylate, benzyl 2-ethyl acrylate, ethyl 2-propyl acrylate, benzyl 2-propyl acrylate , Methyl 2-acetamidoacrylate, ethyl cis-2-cyanoacrylate, vinyl crotonate, vinyl cinnamate, isopropyl cinnamate, isobutyl cinnamate, tert-butyl cinnamate, isoamyl cinnamate, ethyl 2-cyano-3,3- Diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate.
(C1-3) Epoxy group-containing (meth) acrylic acid esters; glycidyl (meth) acrylate.
(C1-4) hydroxy group-containing (meth) acrylic acid esters; 2-hydroxyethyl (meth) acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate, 2-hydroxypropyl 2- ( (Meth) acryloyloxyethyl phthalate, caprolactone 2- (meth) acryloyloxyethyl ester hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Methyl 3-hydroxy-2-methylene-butyrate. (C1-5) Halogen-containing (meth) acrylic acid esters; pentabromobenzyl (meth) acrylate, pentabromophenyl (meth) acrylate, methyl 2-bromoacrylate, tert-butyl 2-bromoacrylate, methyl 2-bromomethyl Acrylate, ethyl 2-bromomethyl acrylate.
(C1-6) silicon-containing (meth) acrylic acid esters; ethyl 2-trimethylsilylmethyl acrylate, 3-trimethoxysilylpropyl (meth) acrylate, 2-trimethylsilyloxyethyl (meth) acrylate, 3- [tris (trimethylsiloxy) ) Silyl] propyl (meth) acrylate, trimethylsilyl (meth) acrylate.
(C1-7) Sulfur-containing (meth) acrylic acid esters; 2-methylthioethyl (meth) acrylate.
(C1-8) (meth) acrylamides; (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-tris (hydroxymethyl) methyl ( (Meth) acrylamide N-butoxymethyl (meth) acrylamide, N-isobutyloxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- [3-dimethylaminopropyl] (meth) acrylamide, 3-((meth) Acryloylamino) propyltrimethylammonium chloride, N-tert-butyl (meth) acrylamide, 4- (meth) acryloylmorpholine, N-phenyl (meth) acrylamide, 2-acrylamide glycolic acid, 2-acrylamide 2-methyl-1-propanesulfonic acid.
(C2) (Meth) acrylonitriles:
(Meth) acrylonitrile, 2-chloroacrylonitrile, 1-cyanovinyl acetate.
(C3) Vinyl compound:
(C3-1) styrenes; styrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,4,6-trimethylstyrene, 3
, 4-dimethoxystyrene, 4-benzyloxy-3-methoxystyrene, 4-ethoxystyrene, 4-tert-butylstyrene, 4-tert-butoxystyrene, 4-acetoxystyrene, 2-trifluoromethylstyrene, 3-trimethyl Fluoromethylstyrene, 4-trifluoromethylstyrene, 3,5-bis (trifluoromethyl) styrene, 4-vinylaniline, 4-vinylanisole, N, N-dimethylvinylbenzylamine, 4-vinylbiphenyl, 2-fluoro Styrene, 3-fluorostyrene, 4-fluorostyrene, 2,6-difluorostyrene, 2,3,4,5,6-pentafluorostyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2, 6-dichlorostyrene, 2-bromostyrene, 3- Lomostyrene, 4-bromostyrene, 3-nitrostyrene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, tert-butyl 4-vinylphenyl carbonate, 4-styrenesulfonic acid, 4-vinylphenylboronic acid, α-methylstyrene , Α, 2-dimethylstyrene, 1,3-diisopropenylbenzene, 4-chloro-α-methylstyrene, 2,4-diphenyl-4-methyl-1-pentene, 2-isopropenylaniline, 3-isopropenyl -Α, α-dimethylbenzyl isocyanate, 1-phenyl-1-trimethylsiloxyethylene, α-bromostyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 9-vinylanthracene.
(C3-2) nitrogen-containing heterocyclic vinyl compound; N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 9-vinylcarbazole, 1-vinyl-2-pyrrolidone, N-vinylphthalimide, N-vinylcaprolactone.
(C3-3) Vinyl esters; vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl pivalate, vinyl decanoate, vinyl neodecanoate, vinyl stearate, vinyl benzoate.
(C3-4) vinyl ethers; 4-vinyloxymethylcyclohexylmethyl benzoate, ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 4-vinyloxybutyl benzoate, isobutyl vinyl ether, tert-butyl vinyl ether, tert-pentyl Vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl ether, vinyloxytrimethylsilane, 1,4-butanediol vinyl ether, 1,4-cyclohexanedimethanol vinyl ether, ethylene glycol vinyl ether, ethylene glycol butyl vinyl ether, diethylene glycol vinyl ether, Ethyl 1 -Propenyl ether.
(C3-5) Other vinyl compounds; vinylidene chloride, cis-1,3-dichloro-1-propene, 2-methyl-2-vinyloxirane, vinylcyclopentane, vinylcyclohexane, 4-vinyl-1-cyclohexanone, 5- Vinyl-2-norbornene, vinyl ferrocene, vinyltrimethylsilane, vinyltrimethoxysilane, N-vinylformamide, N-methyl-N-vinylacetamide, vinyl bromide, ethyl vinyl sulfide, methyl vinyl sulfone, vinyl sulfonic acid, vinyl phosphone Acid, trans-4,4′-difluorochalcone.

  Among these compounds, preferred are the compounds described in the above (C1) group, (C2) group, (C3-1) group and (C3-2) group, and particularly preferred are (C1-2). ) Group (meth) acrylic acid esters, (C1-4) group hydroxy (meth) acrylic acid esters, (C3-1) group styrenes and (C3-2) group nitrogen-containing heterocyclic vinyl compounds. More preferred are methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene, 2-vinylnaphthalene, N-vinylimidazole, 2-vinylpyridine, and 1-vinyl-2-pyrrolidone.

The hyperbranched polymer is obtained by polymerizing the aforementioned monomer A in the presence of a predetermined amount of a polymerization initiator B. As the polymerization method, known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, and Examples include bulk polymerization, and among them, solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.

  Examples of organic solvents used here include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, etc. ester or ester ether solvents; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl celloso Ether solvents such as butyl, cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, iso Alcohol solvents such as butanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, ethyl lactate; N, N′-dimethylformamide, N, N′-dimethylacetamide, N -Amide solvents such as methyl-2-pyrrolidone; Sulfoxide solvents such as dimethyl sulfoxide; Aliphatic carboxylic acid solvents such as acetic acid and propionic acid And mixed solvents of two or more thereof.

  Among these, preferred are aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, aliphatic carboxylic acid solvents, and the like. Benzene, toluene, xylene, orthodichlorobenzene, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, dioxane, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol , Tert-butanol, ethylene glycol, propylene glycol monomethyl ether, N, N′-dimethylformamide, N, N′-dimethylacetamide, N-methyl-2-pyrrolidone and An acid, most preferred are n- propanol, n- butanol, ethylene glycol, N, N'-dimethylformamide, N, N'-dimethylacetamide, N- methyl-2-pyrrolidone and acetic acid.

  When the polymerization reaction is performed in the presence of an organic solvent, the content of the organic solvent in the entire polymerization reaction product is preferably 5 to 120 parts by weight, more preferably 10 to 110 parts by weight, with respect to 1 part by weight of the monomer A. Most preferably, it is 30 to 100 parts by mass.

The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N _2.
The polymerization temperature is arbitrary as long as it is not higher than the boiling point of the reaction mixture, but from the viewpoint of polymerization efficiency and molecular weight control, it is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 150 ° C. or lower, more preferably 80 ° C. The temperature is 120 ° C. or lower.
More preferably, the temperature of the polymerization reaction is carried out at a temperature that is 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B, and more specifically, the monomer A (more monomer C if desired), The polymerization reaction is preferably carried out by dropping a solution containing the initiator B and the organic solvent into the organic solvent maintained at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B. It is even more preferable to carry out the polymerization reaction at the reflux temperature of the organic solvent under a reaction pressure.
The reaction time varies depending on the reaction temperature, the types and ratios of the monomer A and the polymerization initiator B, the type of organic solvent, etc., and thus cannot be defined unconditionally, but preferably 30 minutes or more and 720
Minutes or less, more preferably 40 minutes or more and 540 minutes or less.

  More preferably, solution polymerization in an organic solvent is carried out in the presence of a specific acid. Although it is preferable to perform solution polymerization using acetic acid as an organic solvent as described above, it can be said that it is practically difficult to use as a polymerization solvent from the viewpoint of odor and the like. It is desirable to carry out the polymerization in the presence of 100 mol% to 400 mol% with respect to the polymerization initiator B.

The following can be mentioned as an acid which can be used here.
Inorganic acids: hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, etc.
Aromatic carboxylic acids: benzoic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzenepentacarboxylic acid, merit acid, anisic acid, toluic acid, propylbenzoic acid, propoxybenzoic acid, hydroxybenzoic acid, n-octylbenzoic acid Acid, n-octyloxybenzoic acid, hexylbenzoic acid, hexyloxybenzoic acid, heptylbenzoic acid, heptyloxybenzoic acid, ethylbenzoic acid, ethoxybenzoic acid, n-butylbenzoic acid, sec-butylbenzoic acid, tert-butyl Benzoic acid, Butoxybenzoic acid, Bromobenzoic acid, Benzyloxybenzoic acid, Amylbenzoic acid, Amyloxybenzoic acid, Aminobenzoic acid, Acetylbenzoic acid, Acetoxybenzoic acid, Naphthalenecarboxylic acid, Naphthalenedicarboxylic acid, Anthracenecarboxylic acid, Anthracenedi Carboxylic acid, anthraquinone carboxylic acid, anthraquinone dicarboxylic acid, pyrene carboxylic acid, Pi dicarboxylic acid, p- toluenesulfonic acid, and trifluoromethanesulfonic acid.
Aliphatic carboxylic acid: acetic acid, trifluoroacetic acid, valeric acid, undecanoic acid, tridecanoic acid, tricosanoic acid, stearic acid, propionic acid, pentadecanoic acid, pentacosanoic acid, palmitic acid, nonanoic acid, nonadecanoic acid, nonacosanoic acid, octanoic acid , Octacosanoic acid, heptacosanoic acid, heneicosanoic acid, myristic acid, melicinic acid, ligrinoceric acid, lauric acid, hexanoic acid, heptanoic acid, heptadecanoic acid, decanoic acid, serotic acid, butyric acid, behenic acid, arachidic acid, oleic acid, linolenic acid Linoleic acid, erucic acid, elaidic acid, arachidonic acid and the like.
Amino acids: L-valine, L-tryptophan, L-serine, L-proline, L-phenylalanine, L-ornithine, L-leucine, L-isoleucine, L-histidine, L-glutamine, L-cysteine, L-asparagine , L-alanine, L-tyrosine, L-threonine, L-lysine, L-arginine, L-glycine and those whose nitrogen atoms are acetyl protected, butoxycarbonyl protected, carbobenzoxy protected, etc., or these D body etc.

  Among the above acids, the aromatic carboxylic acid group is preferable, and benzoic acid is most preferable.

  When the polymerization is carried out in the presence of an acid, it is preferably neutralized with a base after the completion of the polymerization reaction. Examples of the base used at this time include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide and the like.

  After completion of the polymerization reaction, the obtained hyperbranched polymer is recovered by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

  The average particle diameter of the primary particles of the obtained hyperbranched polymer is preferably 1 nm to 100 nm, more preferably 5 nm to 50 nm.

<Composition Containing Metal Fine Particle Dispersant and Metal Fine Particle>
The present invention also relates to a composition comprising a metal fine particle dispersant comprising the aforementioned hyperbranched polymer and metal fine particles.
In the above composition, the metal fine particle dispersant and the metal fine particles preferably form a composite. Here, the composite means that the hyper-branched polymer, which is a metal fine particle dispersant, coexists in the state of being in contact with or close to the metal fine particles due to the action of the amino functional group or imino functional group, and forms a particulate form. In other words, it is expressed as a composite having a structure in which the amino functional group or imino functional group of the metal fine particle dispersant (hyperbranched polymer) is attached to or coordinated with the metal fine particles.
Therefore, in the “composite” in the present invention, not only the metal fine particles and the metal fine particle dispersant (hyperbranched polymer) are combined to form one composite as described above, but also the metal fine particles and the metal The fine particle dispersant (hyperbranched polymer) may be present independently without forming a bonding portion.

  The metal fine particles can be obtained by adding a reducing agent to an aqueous metal salt solution to reduce metal ions. In the present invention, the complex can be prepared by adding an aqueous solution of a metal salt and a reducing agent to a solution in which the fine metal particle dispersant (highly branched polymer) is dissolved, and reducing metal ions.

The metal used as the metal fine particles is not particularly limited. For example, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium. Palladium, silver, cadmium, indium, tin, antimony, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, and the like. Of these, gold, silver, platinum, copper, nickel, ruthenium, rhodium, palladium, osmium and iridium are preferable, and gold, silver, platinum and copper are particularly preferable.
Examples of the metal salt include chloroauric acid, silver nitrate, copper sulfate, copper nitrate, platinum chloride, Pt (dba) ₂ [dba = dibenzylideneacetone], Pt (cod) ₂ [cod = 1,5-cycloocta Diene], PtMe ₂ (cod), palladium chloride, palladium acetate, palladium nitrate, Pd ₂ (dba) ₃ (CHCl ₃ )], Pd (dba) ₂ , rhodium chloride, rhodium acetate, ruthenium chloride, ruthenium acetate, Ru ( cod) (cot) [cot = cyclooctatriene], iridium chloride, iridium acetate, Ni (cod) _{2 and the} like.

Examples of the method for reducing the metal ion include a method of irradiating light with a high-pressure mercury lamp, a method of adding a compound having a reducing action, and the like. Of these, the method of adding a compound having a reducing action (so-called reducing agent) is advantageous in production because it does not require a special apparatus.
As the above reducing agent, various commonly used ones can be used. For example, alkali metal borohydride salts such as sodium borohydride conventionally used as reducing agents, hydrazine compounds, citric acid or The salt, succinic acid or its salt, ascorbic acid or its salt, etc. can be used.
The addition amount of the reducing agent is preferably 1 to 50 mol with respect to 1 mol of the metal ion. If the amount is less than 1 mol, the reduction is not sufficiently performed, and if it exceeds 50 mol, the stability against aggregation is lowered. More preferably, it is 1.5 to 10 mol.
The average particle diameter of the metal fine particles is preferably 1 to 50 nm, and more preferably 3 to 20 nm.

In the composition of the present invention, particularly in forming the composite, the ratio of the metal salt to the metal fine particle dispersant (hyperbranched polymer) is 20 to 1,000 metal fine particle dispersants per 100 parts by mass of the metal salt. Part by mass is preferred. When the amount is less than 20 parts by mass, the dispersibility of the metal fine particles is insufficient, and when the amount exceeds 1,000 parts by mass, the content of the metal fine particle dispersant not attached to or coordinated with the metal fine particles increases. Problems are likely to occur in the physical properties that express the characteristics of the metal fine particles. More preferably, it is 50 to 500 parts by mass.

The composition may further contain an organic solvent capable of dissolving water or the dispersant (highly branched polymer). In this case, it is desirable that the metal fine particles or the complex formed from the metal fine particles and the metal fine particle dispersant is dispersed in an organic solvent.
Examples of such an organic solvent include tetrahydrofuran (THF), diethyl ether, dimethoxyethane (DME), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, diethylene glycol monoethyl ether, butyl cellosolve, γ-butyrolactone, and the like. Ether compounds, ester compounds such as propylene glycol monomethyl ether acetate (PGMEA), halogenated hydrocarbons such as methylene chloride and chloroform, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N -Amide compounds such as methyl-2-pyrrolidone (NMP), and ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Alcohols such as methanol, ethanol, isopropanol, n-propanol, and ethyl lactate, aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene These organic solvents can be used singly or in combination of two or more.

  The concentration to be dispersed in the solvent is arbitrary. For example, the concentration of the complex is 0.05 to 50% by mass, preferably 0.1 to 40% by mass with respect to the total mass (total mass) of the complex. %.

  Further, the composition may further contain a crosslinking agent or photopolymerization initiator that is soluble in water or an organic solvent.

The crosslinking agent in the present invention is not particularly limited as long as it is a compound having one or more, preferably 1 to 6, polymerizable sites in the molecule. Examples of the polymerizable moiety include an ethylenically unsaturated bond that is a radical polymerizable moiety or a cyclic ether structure such as an epoxy ring or an oxetane ring that is a cationic polymerizable moiety.
Examples of the compound having these polymerizable sites include polyfunctional epoxy compounds.

The polyfunctional epoxy compound is not particularly limited as long as it contains two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Epoxy resin, dimer acid glycidyl ester type epoxy resin, polyalkylene ether type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthol type epoxy resin, naphthalene type An epoxy resin, an alicyclic epoxy resin, a heterocyclic ring-containing epoxy resin, a diglycidyl epoxy resin, a glycidylamine type epoxy resin, a halogenated bisphenol A type epoxy resin, and the like are preferably used. Mixed and used in.
In addition, a compound containing one epoxy group may be contained in a part of the molecule used as a reactive diluent.

  The content of the crosslinking agent in the composition of the present invention is preferably 0.1 to 100 parts by mass, more preferably 1 to 10 parts by mass with respect to 1 part by mass of the metal fine particle dispersant (hyperbranched polymer).

  The photopolymerization initiator is not particularly limited as long as it is a compound that generates an active radical when irradiated with light. For example, a benzoin compound, an α-aminoalkylphenone compound, a thioxanthone compound, an azide compound, a diazo compound, o-quinonediazide compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenones, biscoumarins, biimidazole compounds, organic peroxides, titanocene compounds, thiol compounds, halogenated hydrocarbon compounds, trichloromethyltriazine compounds, or Onium salt compounds such as iodonium salt compounds and sulfonium salt compounds are used. A radical photopolymerization initiator may be used alone or in combination of two or more as required.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.

  Examples of the α-aminoalkylphenone compounds include 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) butan-1-one and the like.

  Examples of the thioxanthone compound include thioxanthone, 1-chlorothioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone. Can do.

  Examples of the azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4′-diazidochalcone, 4,4′-diazidodiphenyl sulfide. 2,6-bis (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidostilbene, and the like.

  Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzeneborofluoride, 1-diazo-4-N, N-dimethylaminobenzene chloride, 1-diazo-4. -N, N-diethylaminobenzeneborofluoride and the like can be mentioned.

  Examples of the o-quinonediazide compounds include 1,2-naphthoquinone-diazide (2) -4-sulfonic acid sodium salt, 1,2-naphthoquinone-diazide (2) -5-sulfonic acid ester, 1,2- Examples thereof include naphthoquinone-diazide (2) -4-sulfonyl chloride.

  Examples of the acylphosphine oxide compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the oxime ester compound include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9. And -ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

Examples of the benzophenones include benzophenone, 4,4′-bis (diethylamino) benzophenone, 1,4-dibenzoylbenzene, 10-butyl-2-chloroacridone, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4 -A benzoyl diphenyl ether, benzyl, etc. can be mentioned.

  Examples of the biscoumarin include 3,3′-carbonylbis (7- (diethylamino) -2H-chromen-2-one) (commercially available from Midori Chemical Co., Ltd. as BC (CAS [63226-13-1]). And the like.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) -1,2′-biphenyl. Examples thereof include imidazole and 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  Examples of the photopolymerization initiator include a known photopolymerization initiator having absorption at 365 nm, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Japan Ltd.). ), Trade name: IRGACURE 369) is preferably used.

  The amount of the photopolymerization initiator used in the composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 1 part by mass of the metal in the metal fine particle composite. is there.

Furthermore, in the composition of the present invention, a general-purpose synthetic resin soluble in the organic solvent may be mixed and combined with the general-purpose synthetic resin. Examples of general-purpose synthetic resin include polyolefin resins such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer); PS (polystyrene) Polystyrene resins such as HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer); polycarbonate resin; Polyvinyl resin; Polyamide resin; (Meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate , PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone, polybutylene succinate, polyethylene succinate / adipate and other polyester resins; polyphenylene ether resins; modified polyphenylene ether resins; polyacetal resins; polysulfone resins; Polyvinyl alcohol resin; polyglycolic acid; modified starch; cellulose acetate, cellulose triacetate; chitin, chitosan; thermoplastic resin such as lignin; phenol resin, urea resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy Examples thereof include thermosetting resins such as resins.
The content of the general-purpose synthetic resin in the composition of the present invention is preferably 5 to 1,000 parts by mass, more preferably 10 to 100 parts by mass with respect to 1 part by mass of the metal fine particle composite.

<Thin film and cured film>
As a specific method for forming a thin film from the composition containing the metal fine particles and the metal fine particle dispersant, the composition containing the metal fine particles and the metal fine particle dispersant is dissolved or dispersed in the aforementioned organic solvent or the like to form a varnish. (Film-forming material), and this is coated and dried on an appropriate base material such as PET, glass, ITO by an appropriate method such as a casting method, a spin coating method, a bar coating method, a roll coating method, or a dip coating method. Thus, a thin film can be formed. Among these coating methods, the spin coating method is preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
The method for drying the solvent is not particularly limited. For example, the solvent may be evaporated in a suitable atmosphere, that is, in an inert gas such as air or nitrogen, in a vacuum, or the like using a hot plate or an oven. Thereby, a thin film having a uniform film formation surface can be obtained. Although a calcination temperature will not be specifically limited if a solvent can be evaporated, It is preferable to carry out at 40-250 degreeC. In this case, two or more stages of temperature changes may be applied for the purpose of developing higher uniform film forming properties or allowing the reaction to proceed on the substrate.

  The thickness of the thin film thus formed is not particularly limited, but is usually 0.01 μm to 50 μm, preferably 0.05 μm to 20 μm.

  In addition, when a crosslinking agent or a photopolymerization initiator is included in the composition, a cured film can be formed by performing heat treatment or light irradiation treatment such as ultraviolet rays after the coating film.

  The thin film or cured film thus obtained is suitable for conductive pastes, transparent conductive films, high-density recording materials, hole injection layers or hole transport layers of organic EL elements, light shielding filters, chemical sensors, catalysts, etc. Can be used.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
(1) GPC (gel permeation chromatography)
Equipment: GPC-101 manufactured by Showa Denko K.K.
Column: Showa Denko LF-804 × 3
Column temperature: 60 ° C
Solvent: NMP with 20 mM LiBr added
Flow rate: 0.6 mL / min Detector: UV (280 nm)
(2) ¹ H NMR spectrum and ¹³ C NMR spectrum Device: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: CDCl ₃
Internal standard: Tetramethylsilane (3) Dynamic light scattering photometer (DLS)
Device: FDLS-3000 manufactured by Otsuka Electronics Co., Ltd.
(4) Transmission electron microscope (TEM)
Apparatus: H-8000 manufactured by Hitachi, Ltd.
(5) Inductively coupled plasma optical emission spectrometer (ICP-OES)
Apparatus: SII Nano Technology Co., Ltd. Vista Pro
(6) Differential thermal balance (TG-DTA)
Equipment: TG-8120 manufactured by Rigaku Corporation
Temperature: Temperature was raised from 25 ° C. to 120 ° C. at 15 ° C./min, held at 120 ° C. for 5 minutes, cooled to 120 ° C. to 25 ° C., and then heated to 700 ° C. at 10 ° C./min.
The weight at 700 ° C. was calculated as the metal weight in the metal fine particles.
(7) Micro shape measuring machine (SURF-CORDER)
Equipment: ET-4000A manufactured by Kosaka Laboratory
(8) Spin coater: Mikasa Corporation MS-A100

Abbreviations represent the following meanings.
DVB: Divinylbenzene (DVB-960 manufactured by Nippon Steel Chemical Co., Ltd.)
AIYP: 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (VA-061 manufactured by Wako Pure Chemical Industries, Ltd.)
MAIB: Dimethyl 2,2′-azobisisobutyrate (MAIB manufactured by Otsuka Chemical Co., Ltd.)
PVP: Polyvinylpyrrolidone (Tokyo Chemical Industry Co., Ltd. K15 (viscosity average molecular weight 10,000))
DMF: N, N-dimethylformamide NMP: N-methyl-2-pyrrolidone

[Example 1]
<Synthesis of hyperbranched polymer (HI-DVB) using DVB and AIYP>
A 500 mL reaction flask was charged with 120 g of n-propanol, and nitrogen was poured for 5 minutes while stirring, and the mixture was heated until n-propanol was refluxed (standard boiling point 97 ° C.).
In a separate 200 mL reaction flask, 2.6 g (20 mmol) of DVB, 3.1 g of AIYP (12 mmol, 62 mol% with respect to DVB), and 120 g of n-propanol were charged, and nitrogen was purged for 5 minutes while stirring. went.
The contents were added dropwise from the 200 mL reaction flask charged with DVB, AIYP and n-propanol into the refluxed n-propanol in the 500 mL reaction flask using a dropping pump over 90 minutes. After completion of dropping, the mixture was aged for 1 hour.
Next, n-propanol was distilled off from this reaction solution using a rotary evaporator, and the resulting residue was dissolved in 26 g of chloroform. This polymer solution was added to 260 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure, and the resulting solid was redissolved in 26 g of chloroform. This polymer solution was added to 260 g of hexane to reprecipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and dried under vacuum to obtain 2.5 g of the desired product (HI-DVB) as a pale yellow powder.
1 and 2 show the measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product.
Shown in
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 47,000, and dispersion degree: Mw / Mn was 13.9. The composition ratio (molar ratio) of DVB and AIYP fragments calculated from the ¹³ C NMR spectrum of this polymer is 1.0: 0.8, and the average particle diameter determined by a dynamic light scattering photometer is 18.4 nm. It was.

[Reference example]
<Synthesis of hyperbranched polymer (HA-DVB) using DVB and MAIB>
A 500 mL reaction flask was charged with 74 g of toluene, and nitrogen was introduced for 5 minutes while stirring, and the mixture was heated until the toluene was refluxed (standard boiling point 111 ° C.).
In another 200 mL reaction flask, 3.9 g (30 mmol) of DVB, 5.5 g of MAIB (24 mmol, 80 mol% with respect to DVB) and 74 g of toluene were charged, and nitrogen was purged for 5 minutes while stirring.
The contents were added dropwise from the 200 mL reaction flask charged with DVB, MAIB and toluene into the refluxing toluene in the 500 mL reaction flask using a dropping pump over 1.5 hours. After completion of dropping, the mixture was aged for 6 hours.
Next, 121 g of toluene was distilled off from this reaction solution using a rotary evaporator and added to 391 g of methanol cooled to 0 ° C. to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 6.1 g of the target product (HA-DVB) as a white powder.
The measurement results of ¹ H NMR and ¹³ C NMR spectra of the obtained target product are shown in FIGS.
Shown in
Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 37,000, and dispersion degree: Mw / Mn was 2.6.

[Example 2]
<Preparation of HI-DVB-gold fine particle composite 1 (HI-DVB-Au-1)>
100 mg of HI-DVB obtained in Example 1 was dissolved in 10 mL of methanol, and 1 mL of 0.2 mol / L chloroauric acid aqueous solution was added with stirring at room temperature (approximately 25 ° C.). The solution instantly became an orange suspension. Furthermore, when 1 mL of 1.0 mol / L sodium borohydride aqueous solution was slowly dripped, the solution gradually changed to dark red. After stirring for 30 minutes, methanol was distilled off under reduced pressure, and then a precipitate was deposited with an aqueous sodium hydroxide solution having a pH of 11. This was recovered by filtration and washed with ion-exchanged water until the pH reached 7. The obtained black solid was vacuum-dried to obtain the intended composite.
This black solid was dispersed in n-propanol so as to be 0.5% by mass, dropped onto a carbon mesh grid, and the dried sample was subjected to TEM observation (see FIG. 5). As shown in FIG. 5, it was confirmed that the HI-DVB-gold fine particle composite was obtained. Moreover, it turned out that the weight ratio of gold | metal | money is 30 mass% by TG-DTA.

[Example 3]
<Preparation of HI-DVB-gold fine particle composite 2 (HI-DVB-Au-2)>
Gold fine particles were synthesized in the same manner as in Example 2 except that the amount of HI-DVB obtained in Example 1 was changed to 50 mg. This black solid was dispersed in n-propanol so as to be 0.5 wt%, dropped onto a carbon mesh grid, and the dried sample was subjected to TEM observation (see FIG. 6). As shown in FIG. 6, it was confirmed that the HI-DVB-gold fine particle composite was obtained. Moreover, it turned out that the weight ratio of gold | metal | money is 41 mass% by TG-DTA. Furthermore, it was 42 mass% in the analysis by ICP-OES.

[Example 4]
<Preparation of HI-DVB-silver fine particle composite (HI-DVB-Ag)>
50 mg of HI-DVB obtained in Example 1 was dissolved in 10 mL of methanol, and 1 mL of 0.4 mol / L silver nitrate aqueous solution was added while stirring at room temperature (approximately 25 ° C.). The solution instantly became a white suspension. Furthermore, when 1 mL of 1.0 mol / L sodium borohydride aqueous solution was slowly dripped, the solution gradually changed to yellow. After stirring for 30 minutes, methanol was distilled off under reduced pressure, and then a precipitate was deposited with an aqueous sodium hydroxide solution having a pH of 11. This was recovered by filtration and washed with ion-exchanged water until the pH reached 7. The obtained black solid was vacuum-dried to obtain the intended composite.
This black solid was dispersed in n-propanol so as to be 0.5% by mass, dropped onto a carbon mesh grid, and the dried sample was subjected to TEM observation (see FIG. 7). As shown in FIG. 7, it was confirmed that a HI-DVB-silver fine particle composite was obtained. Moreover, it turned out that the weight ratio of silver is 48 mass% by TG-DTA. Furthermore, it was 48 mass% also in the analysis by ICP-OES.

[Comparative Example 1]
<Preparation of HA-DVB-gold fine particle composite>
50 mg of HA-DVB obtained in Reference Example was dissolved in 10 mL of tetrahydrofuran,
While stirring at room temperature (approximately 25 ° C.), 1 mL of 0.2 mol / L chloroauric acid aqueous solution was added. The solution was a golden homogeneous solution. Furthermore, when 1 mL of 1.0 mol / L sodium borohydroxide aqueous solution was slowly dripped, only a black precipitate was produced, and the gold fine particles could not be dispersed by HA-DVB.

[Comparative Example 2]
<Preparation of HA-DVB-silver fine particle composite>
The same operation was performed except that a 0.4 mol / L silver nitrate aqueous solution was used instead of the 0.2 mol / L silver chloroauric acid aqueous solution used in Comparative Example 1, but only a black precipitate was formed. The silver fine particles could not be dispersed by -DVB.

[Comparative Example 3]
<Preparation of PVP-gold fine particle composite (PVP-Au)>
50 mg of PVP was dissolved in 10 mL of methanol, and 1 mL of 0.2 mol / L chloroauric acid aqueous solution was added with stirring at room temperature (approximately 25 ° C.). The solution instantly became an orange suspension. Furthermore, when 1 mL of 1.0 mol / L sodium borohydride aqueous solution was slowly dripped, the solution gradually changed to dark red. After stirring for 30 minutes, methanol was distilled off under reduced pressure, and then 100 mL of acetone was added to precipitate a precipitate. This was recovered by filtration and further washed with 100 mL of acetone. The obtained black solid was vacuum-dried to obtain a target PVP-gold fine particle composite.
This black solid was dispersed in n-propanol so as to be 0.5% by mass, and dropped and dried on a carbon mesh grid, and TEM observation was performed. As shown in FIG. 8, it was confirmed that a PVP-gold fine particle composite was obtained. Moreover, it turned out that the weight ratio of gold | metal | money is 62 mass% by TG-DTA.

[Example 5-16]
<Thermal curing of metal fine particle dispersant-metal fine particle composite>
It dissolved in n-propanol so that the density | concentration of the metal fine particle dispersing agent (hyperbranched polymer) -metal fine particle complex shown in Table 1 might be 2.5 mass%. The obtained solution was deposited on a glass substrate (2 × 2 cm) at 800 rpm for 30 seconds using a spin coater, and heat-treated at the temperature and time shown in Table 1. The film thickness at this time was measured (initial film thickness), then the glass substrate was washed with methanol which is a good solvent for the composite, and the film thickness after heating and drying at 80 ° C. for 5 minutes was measured (film after washing) Thickness). The remaining film ratio (%) was determined by (film thickness after cleaning) ÷ (initial film thickness) × 100. The results are shown in Table 1.

[Comparative Example 4-6]
<Thermosetting of PVP gold fine particle composite>
Using the PVP-gold fine particle composite obtained in Comparative Example 3, the remaining film ratio was determined by the same method as in Example 5-16. The results are shown in Table 1.

As shown in Table 1, a thin film composed of a gold fine particle composite using a highly branched polymer having an amino functional group or an imino functional group as a terminal as a metal fine particle dispersant undergoes a curing reaction as the heating temperature increases. The solvent became insoluble in methanol (Examples 5, 6, 9, and 12). Moreover, it was the same tendency also in the silver fine particle composite (Examples 13 to 16). Moreover, in the gold fine particle composite, the progress of the curing reaction was confirmed as the heat treatment time was longer (Examples 6 to 8, 9 to 11).
On the other hand, in the gold fine particle composite using PVP as a dispersant, the progress of the curing reaction could not be confirmed at all (Comparative Examples 4 to 6).

Claims (10)

Dispersing agent for fine metal particles comprising a highly branched polymer having an amino functional group or imino functional group at the end and having a weight average molecular weight of 1,000 to 2,000,000 measured by gel permeation chromatography in terms of polystyrene There,
A polymerization initiator B in which the hyperbranched polymer has a monomer A having two or more radically polymerizable double bonds in the molecule and an amino functional group or imino functional group in an amount of 5 to 200 mol% based on the monomer A. Is a hyperbranched polymer obtained by polymerizing in the presence of
The monomer A is divinylbenzene,
The polymerization initiator B having the amino functional group or imino functional group is a polymerization initiator represented by the following formula [2], and the metal fine particles are selected from the group consisting of gold, silver, platinum and copper. A metal fine particle dispersant which is at least one kind.
(In the formula [2], R ¹ , R ² and R ³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms, and R ¹ Any two or more of R ² and R ³ may be combined with the nitrogen atom to which they are bonded to form a ring, and R ⁴ and R ⁵ each independently represent 1 to 1 carbon atoms. 6 represents an alkyl group.) Furthermore, the metal fine particle dispersing agent of Claim 1 containing the monomer A. A composition comprising the metal fine particle dispersant according to claim 1 and at least one metal fine particle selected from the group consisting of gold, silver, platinum and copper. The composition according to claim 3, wherein the metal fine particle dispersant is attached or coordinated to the surface of the metal fine particles to form a composite. Furthermore, the composition of Claim 3 or Claim 4 containing water or an organic solvent. The composition according to claim 3 , further comprising water or an organic solvent, wherein the metal fine particles are dispersed in water or an organic solvent. The composition according to claim 4 , further comprising water or an organic solvent, wherein the complex is dispersed in water or an organic solvent. Furthermore, the composition as described in any one of Claim 5 thru | or 7 containing the crosslinking agent or photoinitiator soluble in water or an organic solvent. A thin film obtained from the composition according to any one of claims 3 to 8. A cured film obtained by subjecting the thin film according to claim 9 to heat treatment or light irradiation treatment.