CN105164183A - Metal nanoparticle-protecting polymer and metal colloidal solution, and method for producing same - Google Patents
Metal nanoparticle-protecting polymer and metal colloidal solution, and method for producing same Download PDFInfo
- Publication number
- CN105164183A CN105164183A CN201380075890.6A CN201380075890A CN105164183A CN 105164183 A CN105164183 A CN 105164183A CN 201380075890 A CN201380075890 A CN 201380075890A CN 105164183 A CN105164183 A CN 105164183A
- Authority
- CN
- China
- Prior art keywords
- polymkeric substance
- metal nanoparticle
- segment
- poly
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0206—Polyalkylene(poly)amines
Abstract
A metal nanoparticle-protecting polymer includes a polyacetylalkylenimine segment (A) in which 5 to 100 mol% of primary amines in polyalkylenimine are acetylated and 0 to 50 mol% of secondary amines in polyalkylenimine are acetylated, and a hydrophilic segment (B) in a molecule. Also provided are a method for producing the metal nanoparticle-protecting polymer,a metal colloidal solution including a medium and composite bodies dispersed in the medium, each composite body containing a metal nanoparticle protected with the metal nanoparticle-protecting polymer, and a method for producing the metal colloidal solution.
Description
Technical field
The present invention relates to colloidal metal solution and manufacture the method for this colloidal metal solution; described colloidal metal solution uses polymkeric substance as the protective material of metal nanoparticle; described polymkeric substance is the polymkeric substance comprising acetylizad poly (alkylenimines) segment and hydrophilic segment, or for also comprising the polymkeric substance of hydrophobic chain segment except above-mentioned two kinds of segments.The invention still further relates to the method for above-mentioned polymkeric substance and this polymkeric substance of manufacture.
Background technology
Metal nanoparticle is a kind of nanoparticle, has the particle diameter of 1 ~ hundreds of nanometer and sizable specific surface area.The metal nanoparticle with such character causes the concern from various field, and expects very much to use in electronic material, catalyzer, magneticsubstance, optical material, various sensor, coloured material and medical examination.
Printing distributing board and semi-conductor manufacture mainly through photoetching process, and photoetching process comprises the manufacturing step of series of complex.In this case, can the manufacturing technology of print electronic devices noticeable.The manufacturing technology of print electronic devices can comprising: prepare ink composite by being scattered in medium by the metal nanoparticle developed recently, carrying out printing by using ink composite and forming pattern, and by pattern groups dress in a device.
This technology is called printed electronics (printedelectronics).Printed electronics makes to be expected to realize roll-to-roll (roll-to-roll) and manufactures electronic loop pattern and semiconductor element in a large number, and due to this technology be applicable to manufacturing as required, Simplified flowsheet and economizing on resources, therefore bring economical efficiency.Also expect that this technology can be ready for the low cost manufacturing process for display equipment, luminaire, IC tag (RFID) etc.The conductive material ink used in printed electronics can contain the metal nanoparticles such as gold and silver, platinum, copper.For sake of economy and ease for operation, take the lead in having carried out the exploitation of Nano silver grain and the ink containing Nano silver grain.
The silver of nanosize particle form shows the surface energy of sizable specific surface area and increase compared with block silver.Nano silver grain is fuse with one another very strong with the tendency reducing surface energy.As a result, particle is fuse with one another at the temperature far below block silver point.On the one hand, this phenomenon is called quantum size effect (Kub o effect), shows the advantage using Nano silver grain as electro-conductive material.On the other hand, the tendency fuse with one another due to metal nanoparticle is very strong, causes the stability of infringement metal nanoparticle and reduces package stability.In order to by metal nanoparticle stabilization, metal nanoparticle needs by preventing the protective material fused from protecting.
Usually, due to the size of nano material (being generally the compound with nano-grade size), nano material is by special manufacture technics, often expensive.Which suppress the universal of nano material.In order to manufacture metal nanoparticle with low cost, what have advantage is the liquid-phase reduction technique of the specific installation do not needed as vacuum processing chamber.Liquid-phase reduction technique is the technique by making the reductive agent in metallic compound and solvent react to obtain metal nanoparticle.According to known technology, reduction process is carried out when existing and being called as dispersion stabilizer or protectant compound, to control the shape of metal nanoparticle that will generate and particle diameter and to realize stable dispersion state.Protective material be mostly be provided with can with the macromolecular compound (such as referenced patent document 1) of the functional group of metallics coordination (as tertiary amine groups, quaternary ammonium group, the heterocyclic radical with basic nitrogen atom, hydroxyl or carboxyl).
As mentioned above, in order to manufacture the metal nanoparticle of low temperature fusable desired by can expecting to experience, use suitable protective material, this protective material controls the shape of metal nanoparticle and size of particles and makes decentralized stabilization.But protective material plays the effect of resistance components to bulk metal, reduce conductivity.According to the difference of protective material usage quantity, likely cannot show that (ratio resistance of film is 10 to desired low-temperature sintering character
-6the character of ohm-cm level, this film obtains by burning till the conductive ink film of containing metal nanoparticle the temperature range of 100 DEG C to 150 DEG C).From the view point of design electro-conductive material, claimed dose show manufacture small-particle ability, stably disperse the ability of these particles and in sintering process from the ability that particle surface speeds away, thus do not suppress the fusion between metal nanoparticle.From the view point of manufacture metal nanoparticle, claimed dose shows the ability being conducive to refining and be separated the metal nanoparticle generated.Protective material preferably shows these whole abilities.Disclosed protectant example comprises so far: polymer pigment dispersant available on the market is as Solsperse (trade mark; Jie Likang system) and FLOWLEN (trade mark, Chemical Co., Ltd. of common prosperity society system), leading/side chain has pigment affinity groups (amine) and has the polymkeric substance of plural solvation segment and have the multipolymer of polymine segment and polyethylene oxide segment.But these dispersion agents seldom can realize above-mentioned all desired ability, require further improvement (for example, referring to patent documentation 2 to 4).
Citing document
Patent documentation
Patent documentation 1: open No. 2004-346429 of Japanese Unexamined Patent Application
Patent documentation 2: open No. 11-080647 of Japanese Unexamined Patent Application
Patent documentation 3: open No. 2006-328472 of Japanese Unexamined Patent Application
Patent documentation 4: open No. 2008-037884 of Japanese Unexamined Patent Application
Summary of the invention
Technical problem
A kind of metal nanoparticle is the object of the present invention is to provide to protect polymkeric substance; adjust wittingly and impart various character; as controlled the ability of metal nanoparticle, high dispersion stability, good low-temperature sintering and easiness that is refining and separating metal nanoparticle, to show more practical electroconductibility.Further, a kind of colloidal metal solution is also provided and manufactures the method for metal nanoparticle protection polymkeric substance and colloidal metal solution.
Solution
Inventor's open (with reference to patent documentation 4) following binary system polymkeric substance and ternary system polymkeric substance can be used for manufacturing metal nanoparticle, poly (alkylenimines) segment containing polymine in this binary system polymkeric substance is connected with the hydrophilic segment containing polyoxyalkylene chain, and in this ternary system polymkeric substance, hydrophobic chain segment (as epoxy resin) is connected with aforementioned binary system polymkeric substance.But according to the technology disclosed in patent documentation 4, above-mentioned character does not fully realize.Based on further research, contriver finds that the polymkeric substance using the nitrogen-atoms in poly (alkylenimines) segment to be acetylation is effective, so that makes the present invention.
In other words; the invention provides a kind of metal nanoparticle protection polymkeric substance; it comprises poly-ethanoyl alkylene imine segment (A) and hydrophilic segment (B) in molecule; in poly-ethanoyl alkylene imine segment (A); in poly (alkylenimines), the primary amine of 5 ~ 100mol% is acetylation, and in poly (alkylenimines), the secondary amine of 0 ~ 50mol% is acetylation.The present invention also providing the manufacture method of metal nanoparticle protection polymkeric substance, comprising the dispersion colloidal metal solution (this complex body is prepared as protective material by using metal nanoparticle protection polymkeric substance) containing the complex body of metal nanoparticle in media as well and the manufacture method of colloidal metal solution.
The beneficial effect of the invention
The colloidal metal solution that the present invention obtains shows good low-temperature sintering.Because the protection polymkeric substance used in the present invention easily departs from from surfaces of metal nanoparticles at low temperatures, the film therefore by being obtained at easy fired by colloidal metal solution shows good conductivity.Further, about when exist this specifically protection polymkeric substance the metal nanoparticle that obtains, its size is fully little and be monodispersity, and narrow diameter distribution.Thus package stability is also high.This is because the ethanoyl alkylene imine structural unit in protection polymkeric substance protects metal nanoparticle well, and hydrophilic segment in polymkeric substance or hydrophobic chain segment make particle dispersion in medium.Thus, the dispersion state of the not impaired and dispersion of the dispersion stabilization of dispersion stable for extended periods of time in a solvent.
In the present invention; when manufacturing colloidal metal solution; metal nanoparticle is obtained by reduction; ensuing for removing in the refining of impurity and separating step; by adding the such simple operation of lean solvent in the dispersion liquid of complex body, by the just easily sedimentation being separated of metal nanoparticle and the complex body that forms of protection polymkeric substance.This strong association force due to this protection polymkeric substance realizes.Owing to seldom needing complicated step and the setting of accurate condition, therefore the method industrially has advantage.
In addition, the metal nanoparticle in colloidal metal solution obtained in the present invention has large specific surface area, high surface energy and plasmon absorption, and these are characteristics of metal nanoparticle.On top of these properties, can also effectively show dispersion stabilization and package stability, this is because polymer dispersion is self-assembly type.Therefore, colloidal metal solution has required various chemical property, electrical property, the magnetic property such as conductive paste, and may be used for widely in field, as catalyzer, electronic material, magneticsubstance, optical material, various sensor, coloured material and medical examination purposes.
Embodiment
Metal nanoparticle protection polymkeric substance of the present invention is the macromolecular compound with hydrophilic segment (B) and poly-ethanoyl alkylene imine segment (A), in poly-ethanoyl alkylene imine segment (A), in poly (alkylenimines), the primary amine of 5 ~ 100mol% and the secondary amine of 0 ~ 50mol% are acetylation; Or metal nanoparticle of the present invention protection polymkeric substance is the macromolecular compound with poly-ethanoyl alkylene imine segment (A), hydrophilic segment (B) and hydrophobic chain segment (C).The dispersion (colloidal metal solution) with the metal nanoparticle protected by protection polymkeric substance of this structure has high dispersion stability and good conduction property; and display come from metal nanoparticle, the various functions of metallic functionalised dispersant, as painted, catalysis and Electricity Functional.
Poly-ethanoyl alkylene imine segment (A) in protection polymkeric substance of the present invention is acetylation to specific degree.Because the ethanoyl alkylene imine unit in segment can form coordinate bond with metal or metal ion, therefore, poly-ethanoyl alkylene imine segment (A) is segment metal can fixed as nanoparticle.When protecting the metal nanoparticle obtained in the present invention to form complex body with protection polymkeric substance; and when manufacturing in hydrophilic solvent and store complex body; show hydrophilic poly-ethanoyl alkylene imine segment (A) and hydrophilic segment (B) in a solvent owing to having, therefore obtained colloidal metal solution can show excellent dispersion stabilization and package stability.
From the view point of industry manufacture; the simple refining and separation method of complex body is crucial technique; described complex body is by preparing with protection polymkeric substance protection metal nanoparticle, and described metal nanoparticle is by dissolving in media as well or dispersed metallic compounds the metallic compound reduction in medium being obtained.This is refined and separation method preferably includes the sedimentation produced by adding lean solvent (as acetone) in reacted solution.Ethanoyl alkylene imine unit in protection polymkeric substance of the present invention has high polarity, thus promotes that the complex body containing metal nanoparticle associates rapidly.Therefore, while forming the association particle of bulk, easily sedimentation is produced.
Printing or coating metal colloidal solution on substrate, this colloidal metal solution is the dispersion liquid containing metal nanoparticle complex body or the electro-conductive material by using colloidal metal solution to obtain to form conductive ink.In sintering step subsequently, because the coordinate bond between unit and metal is weak, even if therefore protect the ethanoyl alkylene imine unit in polymkeric substance also easily to depart from from surfaces of metal nanoparticles at low temperatures.As a result, good low-temperature sintering is shown.
The particle diameter of the dispersion (complex body) in colloidal metal solution of the present invention not only depends on the molecular weight of used protection polymkeric substance and the polymerization degree of poly-ethanoyl alkylene imine segment (A); also depend on structure and the ratio of components of the constituent of protection polymkeric substance, this constituent is poly-ethanoyl alkylene imine segment (A), following hydrophilic segment (B) and following hydrophobic chain segment (C) namely.
The polymerization degree of poly-ethanoyl alkylene imine segment (A) is not particularly limited.When the polymerization degree is too low, protection polymkeric substance possibly cannot show the ability of enough protection metal nanoparticles.When the polymerization degree is too high, the size of the composite particles be made up of metal nanoparticle and protection polymkeric substance may become excessive, thus reduces package stability.Therefore; in order to improve the crystallized ability of metal nanoparticle and prevent huge dispersed particle; in poly-ethanoyl alkylene imine segment (A), the quantity (polymerization degree) of alkylene imine unit is generally 1 ~ 10; the scope of 000; be preferably 5 ~ 2; the scope of 500, is more preferably the scope of 5 ~ 300.
Poly-ethanoyl alkylene imine segment (A) easily obtains by carrying out acetylize to the alkylene imine part in the precursor construction as poly (alkylenimines) segment.Especially, poly-ethanoyl alkylene imine segment (A) obtains by using acetylizing agent to carry out reacting.The segment be made up of poly (alkylenimines) can be anyly can commercially obtain the segment that maybe can synthesize.From the view point of industrial availability, segment is preferably made up of the polymine of side chain or the PPI of side chain, is more preferably made up of the polymine of side chain.
When using hydrophilic solvent (such as water) to prepare colloidal metal solution, the hydrophilic segment (B) in protection polymkeric substance of the present invention shows with the high-compatibility of solvent and keeps the package stability of colloidal solution.When using hydrophobic solvent, there is the core that strong molecule hydrophilic segment (B) that is interior or Interpolymer Association power contributes to being formed dispersed particle.The polymerization degree of hydrophilic segment (B) is not particularly limited.When using hydrophilic solvent, when the polymerization degree is too low, package stability reduces, and may condense when the polymerization degree is too high.When using hydrophobic solvent, the association force when polymerization degree of hydrophilic segment (B) is too low between dispersed particle becomes not enough, and cannot keep the consistency with solvent when the polymerization degree is too high.From these viewpoints, the polymerization degree of hydrophilic segment (B) is generally 1 ~ 10,000, is preferably 3 ~ 3,000, and, based on the easiness manufactured, be more preferably 5 ~ 1,000.When hydrophilic segment is polyoxyalkylene chain, the polymerization degree is particularly preferably 5 ~ 500.
Hydrophilic segment (B) can be commercially to obtain any segment that maybe can synthesize, that be made up of hydrophilic polymer chain.When using hydrophilic solvent, hydrophilic segment (B) is preferably made up of nonionic polymeric, because can obtain the colloidal solution of high stability.
The example of hydrophilic segment (B) comprises polyoxyalkylene chain (as polyethylene oxide chain and polyoxytrimethylene chain), the polymer chain be made up of polyvinyl alcohol (as polyvinyl alcohol and partly-hydrolysed polyvinyl alcohol), by water-soluble poly (methyl) acrylate (as Poly(Hydroxyethyl Methacrylate), poly hydroxy ethyl acrylate, acrylate and dimethylaminoethyl methacrylate) polymer chain that forms, polyamides base alkylene imine chain containing hydrophilic is (as poly-acetylethylenimine, poly-acetyl propyleneimine, poly-propionyl ethyleneimine and poly-propionyl propyleneimine), and by polyacrylamide (as polyacrylamide, PNIPAM and polyvinylpyrrolidone) polymer chain that forms.Preferred polyoxyalkylene chain among them, because can obtain the colloidal solution of high stability and industrial availability is high.
In the present invention, protection polymkeric substance can contain hydrophobic chain segment (C) further.Especially, when with an organic solvent as when being used for the medium of colloidal metal solution, preferably use polymkeric substance containing hydrophobic chain segment (C) as protective material.
Hydrophobic chain segment (C) can be commercially to obtain any segment that maybe can synthesize, that be made up of the residue of hydrophobic compound.The example of hydrophobic chain segment (C) comprises the segment be made up of the residue of polymkeric substance and the residue of resin, the residue of polymkeric substance is such as: polystyrene type, such as polystyrene, polyvinyltoluene, polychlorostyrene vinyl toluene and poly-bromometllylstyrene, water-soluble poly (methyl) acrylate, such as polymethyl acrylate, polymethylmethacrylate, poly-(2-EHA) and poly-(2-Ethylhexyl Methacrylate), containing the polyamides base alkylene imine class of hydrophobic substituent, such as polyphenyl formyl ethyleneimine, polyphenyl formyl propyleneimine, poly-(methyl) acryloyl ethyleneimine, poly-(methyl) acryloyl propyleneimine, poly-(N-(3-(perfluoro capryl) propionyl) ethyleneimine) and poly-(N-(3-(perfluoro capryl) propionyl) propyleneimine), the residue of resin is such as: epoxy resin, urethane and polycarbonate.Hydrophobic chain segment (C) can form by the residue of single compound or by the residue of the compound obtained by making two or more dissimilar compound react in advance.Hydrophobic chain segment (C) preferably has the structure deriving from epoxy resin; more preferably there is the structure deriving from bisphenol A type epoxy resin because protection polymkeric substance can easily industrially synthesize and the colloidal metal solution obtained thus print or coating time show high-adhesiveness to substrate.
The polymerization degree of hydrophobic chain segment (C) is not particularly limited; if hydrophobic chain segment (C) is polystyrene, poly-(methyl) acrylate, polyamides base alkylene imine etc. containing hydrophobic substituent; then be generally 1 ~ 10; 000; be preferably 3 ~ 3; 000, be more preferably 10 ~ 1,000.When hydrophobic chain segment (C) is made up of the residue of resin (as epoxy resin, urethane, polycarbonate etc.), the polymerization degree is generally 1 ~ 50, is preferably 1 ~ 30, is more preferably 1 ~ 20.
Metal nanoparticle protection polymkeric substance of the present invention reacts to make by making acetylizing agent and precursor compound (I); this precursor compound (I) for having the compound of poly (alkylenimines) segment and hydrophilic segment (B), or for having the compound of poly (alkylenimines) segment, hydrophilic segment (B) and hydrophobic chain segment (C).Or, preparing in the reaction of precursor compound (I) from poly (alkylenimines) segment and hydrophilic segment (B), can acetylizing agent be used.According to any method in these, designed protection polymkeric substance easily can be obtained.Disclosed in patent documentation 4, technique and open No. 2006-213887 of Japanese Unexamined Patent Application can be directly used in manufacture precursor compound (I).
After obtaining precursor compound (I), by the nitrogen-atoms acetylize of the primary amine in poly (alkylenimines) segment and/or secondary amine.Or, the nitrogen-atoms acetylize by the primary amine in poly (alkylenimines) segment and/or secondary amine in the technique of precursor compound (I) is being manufactured by use poly (alkylenimines) segment and hydrophilic segment (B).Acetylization reaction has acetyl structure (CH by adding
3-CO-) acetylizing agent carry out.
Acetylizing agent in general industry can be used as acetylizing agent.The example of acetylizing agent comprises: diacetyl oxide, acetic acid, N,N-DIMETHYLACETAMIDE, ethyl acetate and Mono Chloro Acetic Acid.In these acetylizing agents, from the view point of availability and ease for operation, particularly preferably diacetyl oxide, acetic acid and N,N-DIMETHYLACETAMIDE.
When poly (alkylenimines) segment derives from the polyalkylenimine compounds of side chain, contain primary, secondary and tertiary amine equably or at random.When this poly (alkylenimines) segment and above-mentioned any acetylizing agent react, provide an ethanoyl oxygen to nitrogen-atoms each in primary amine and/or secondary amine, and tertiary amine keeps not being acetylation.In other words, acetylization reaction betides the primary amine higher with used acetylizing agent quantitative reaction and secondary amine.Based on the acetylize ratio of primary amine and secondary amine, the acetylize ratio of acetylization reaction is studied.As a result, find when the secondary amine of 0 ~ 50mol% is acetylation in the primary amine and poly (alkylenimines) segment of 5 ~ 100mol% in poly (alkylenimines) segment, obtain the protection polymkeric substance that there is good electroconductibility, dispersion stabilization and promote the ability refined and be separated.
As mentioned above; compared with alkylene imine unit, the coordinate bond of ethanoyl alkylene imine unit and metal is weak with joint efforts, even if therefore ethanoyl alkylene imine unit also departs from from surfaces of metal nanoparticles at low temperatures swimmingly; as a result, good low-temperature sintering is shown.But gained metal nanoparticle protection polymkeric substance has with the polymer phase using alkylene imine unit to be formed than lower dispersion stabilization (making the ability that metal nanoparticle is stable).Further, dispersion stabilization reduces because of stronger association force.In other words, dispersion stabilization and low-temperature sintering are in shifting relation.Go out to send the above-mentioned acetylizad scope of restriction from the package stability of obtained colloidal metal solution and the viewpoint of the low-temperature sintering of film that formed by colloidal metal solution.
Metal nanoparticle protection polymkeric substance of the present invention also can contain hydrophilic segment (B) except the poly-ethanoyl alkylene imine segment (A) of stable metal nanoparticle except containing, and selectively containing hydrophobic chain segment (C).As mentioned above, hydrophilic segment (B) shows strong association force in hydrophobic solvent, and with the high-compatibility of hydrophilic solvent, and hydrophobic chain segment (C) shows strong association force in hydrophilic solvent, and with the high-compatibility of hydrophobic solvent.Further, can estimate when hydrophobic chain segment (C) is containing aromatic ring, the π-electron in aromatic ring and metal interaction, to help making metal nanoparticle stabilization.
Form the mole number of the polymkeric substance of poly-ethanoyl alkylene imine segment (A) chain and the ratio of the mole number of the polymkeric substance of formation hydrophilic segment (B) chain, i.e. mol ratio (A): (B), is not particularly limited.From the view point of dispersion stabilization and the package stability of obtained colloidal metal solution, this ratio is usually in 1:(1 ~ 100) scope in, preferably in 1:(1 ~ 30) scope in.When protecting polymkeric substance also containing hydrophobic chain segment (C), from the view point of dispersion stabilization and the package stability of obtained colloidal metal solution, form the mole number of the polymkeric substance of poly-ethanoyl alkylene imine segment (A) chain, the ratio of the mole number of the mole number forming the polymkeric substance of hydrophilic segment (B) chain and the polymkeric substance forming hydrophobic chain segment (C) chain, namely, mol ratio (A): (B): (C) is usually in 1:(1 ~ 100): in the scope of (1 ~ 100), preferably in 1:(1 ~ 30): in the scope of (1 ~ 30).Metal nanoparticle of the present invention protects the weight-average molecular weight of polymkeric substance preferably 1, in the scope of 000 ~ 500,000, more preferably 1, in the scope of 000 ~ 100,000.
Protection polymer dispersed of the present invention or be scattered in various medium, for the manufacture of colloidal metal solution.Material as medium is not particularly limited, and dispersion can be oil/water (O/W) system or water/oil (W/O) system.Medium can be selected according to the purposes of the manufacturing process of colloidal metal solution and/or colloidal metal solution.Such as, hydrophilic solvent, hydrophobic solvent, the mixed solvent containing wetting ability and hydrophobic solvent or the mixed solvent as described as follows also containing other solvents except aforementioned solvents can be selected.When using mixed solvent, for O/W system, the amount of hydrophilic solvent being adjusted to and being greater than hydrophobic solvent, for W/O system, the amount of hydrophobic solvent being adjusted to and being greater than hydrophilic solvent.Ratio of mixture depends on the type of used solvent, and thus this ratio of mixture is not particularly limited.Usually, for O/W system, large more than 5 times of the volume ratio hydrophobic solvent of preferred hydrophilic solvent, and for W/O system, large more than 5 times of the volume ratio hydrophilic solvent of preferred hydrophobic solvent.
The example of hydrophilic solvent comprises methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF), acetone, N,N-DIMETHYLACETAMIDE, dimethyl formamide, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, glycol dimethyl ether, Propylene Glycol Dimethyl Ether, methyl-sulphoxide, bisoxirane and N-Methyl pyrrolidone.These can be used alone or and use.
The example of hydrophobic solvent comprises hexane, hexanaphthene, ethyl acetate, butanols, methylene dichloride, chloroform, chlorobenzene, oil of mirbane, anisole, toluene and dimethylbenzene.These can be used alone or and use.
Ethyl acetate, propyl acetate, butylacetate, isobutyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol methyl ether acetate can be comprised with the example of hydrophilic solvent or hydrophobic solvent other solvents used in combination.
Can protect polymer dispersed in medium metal nanoparticle by any method.Usually, by being kept leaving standstill or at room temperature stirring by polymkeric substance, metal nanoparticle can be easily made to protect polymer dispersed.If needed, supersound process or thermal treatment can be carried out.When protecting polymkeric substance to be not easy compatible due to its crystallinity etc. with medium, protection polymer dissolution can be made or after swelling in a small amount of good solvent, make it to be scattered in dispersion medium.In this technique, supersound process or thermal treatment is adopted to be effective.
The mixture of hydrophilic solvent and hydrophobic solvent is by preparations such as any blending means and orders by merging.Due to protection polymkeric substance and all kinds of SOLVENTS consistency, protect the dispersibility of polymkeric substance all according to protecting the type of polymkeric substance, composition and other factors and different, therefore according to object selective solvent ratio of mixture, solvent order, solvent method, mixing condition etc. suitably.
According to the manufacture method of colloidal metal solution of the present invention, metal ion is reduced, to form metal nanoparticle in the solution or dispersion liquid of protection polymkeric substance.The source of metal ion can be metal-salt or metal ion solution.The source of metal ion can be any water miscible metallic compound, such as, and the salt of metallic cation and acidic group negatively charged ion or the acidic group negatively charged ion containing metal.Such as, the metal ion of the metal species had as transition metal is preferably used.
No matter transition metal ion is transition-metal cation (M
n+) or the negatively charged ion (ML be made up of halogen key
x n-), transition metal ion can both swimmingly coordination to form complex compound.In this specification sheets, transition metal refers to 4 ~ 12 races of periodictable and the transition metal in 4 ~ 6 cycles.
The example of transition-metal cation comprises the positively charged ion (M of transition metal
n+), as the positively charged ion of the monovalence of Cr, Co, Ni, Cu, Pd, Ag, Pt, Au etc., divalence, trivalent or tetravalence.The counter anion of metallic cation can be Cl, NO
3, SO
4or the organic anion of carboxylic acid.
The negatively charged ion of metal and halogen complex, such as AgNO
3, AuCl
4, PtCl
4or CuF
6such metallic negatively charged ion (ML
x n-), also can swimmingly coordination to form complex compound.
In these metal ions, preferably silver, gold and platinum ion, because they are spontaneously reduced into nonionic metal nanoparticle under room temperature or heating.When the colloidal metal solution that use obtains is as electro-conductive material, preferably use silver ions, to develop electroconductibility and to prevent the oxidation by film colloidal metal solution printing or coating obtained.
Contained metal species number can be two or more.In this situation, add salt or the ion of various metals at the same time or separately, so that different types of metal ion experiences reduction reaction in media as well and generates different types of metallics.Thus, the colloidal solution containing various metals can be obtained.
In the present invention, reductive agent can be used to carry out reducing metal ion.
Reductive agent can be the reductive agent of any kind.Can select based on the purposes of obtained colloidal metal solution, contained metal species etc.The example of reductive agent comprises hydrogen, boron compound is as sodium borohydride and ammonium borohydride, alcohols is as methyl alcohol, ethanol, propyl alcohol, Virahol, ethylene glycol and propylene glycol, aldehydes is as formaldehyde, acetaldehyde and propionic aldehyde, acids is as xitix, citric acid and Trisodium Citrate, amine is as propylamine, butylamine, diethylamine, dipropyl amine, dimethyl amine, triethylamine, quadrol, Triethylenetetramine (TETA), methylethylolamine, dimethylaminoethanol and trolamine, and hydrazine class is as hydrazine and carbonic acid hydrazine.Among them, due to industrial high availability and ease for operation, preferred sodium borohydride, xitix, Trisodium Citrate, methylethylolamine and dimethylaminoethanol.
In the manufacture method of colloidal metal solution of the present invention, metal ion source is not particularly limited with the usage ratio of protection polymkeric substance.Such as, when the nitrogen-atoms sum forming poly-ethanoyl alkylene imine segment in protection polymkeric substance is set to 100mol, the amount of metal is usually 1 ~ 20; in the scope of 000mol, preferably in the scope of 1 ~ 10,000mol; more preferably in the scope of 50 ~ 7,000mol.
In the manufacture method of colloidal metal solution of the present invention, the medium dispersing or dissolving protection polymkeric substance can mix with metal-salt or solion by any method.Such as, metal-salt or solion can be added in the medium dispersing or dissolving protection polymkeric substance, or also conversely, or can be supplied to different containers by protecting polymkeric substance and metal-salt or solion simultaneously, and mix.Blending means is not particularly limited, and can be to stir.
Reductive agent can be added by any method.Such as, directly reductive agent can be added, or, mix after reductive agent being dissolved or dispersed in the aqueous solution or other solvents.The order of addition of reductive agent is not particularly limited.In advance reductive agent can be added in the protection dispersion liquid of polymkeric substance or solution, or reductive agent is added into together with metal-salt or solion protects in polymkeric substance.After the solution of protection polymkeric substance or dispersion liquid can being mixed with metal-salt or solion in addition, after a few days or several weeks, add reductive agent wherein.
When adding to the medium dispersing or dissolving protection polymkeric substance the metal-salt or its solion that use in manufacture method of the present invention, no matter this system is O/W or W/O, preferably directly or in form of an aqueous solutions adds metal-salt or its solion.When metal ion is silver, gold, palladium, platinum etc., the ethanoyl alkylene imine unit coordination in metal ion and polymkeric substance, then spontaneously reduces under room temperature or heating.Thus under room temperature or heating, metal ion kept static or stir metal ion, can obtain metal nanoparticle and colloidal metal solution, this colloidal metal solution is the dispersion liquid of the complex body of the metal nanoparticle protected by protection polymkeric substance.But in order to reducing metal ion effectively, preferably use reductive agent as described above, colloidal metal solution by keeping ion stable or stirring ion and obtain under room temperature or heating.In this technique, preferably directly use reductive agent or be prepared into the aqueous solution in advance.Carry out the temperature that heats different according to the difference of the type such as protecting polymkeric substance and the metal used, medium, reductive agent type.Generally speaking, temperature is less than 100 DEG C, is preferably less than 80 DEG C.
As the result of reducing metal ions as above, metal nanoparticle is separated out, and meanwhile, the surface of these particles is by making the protection of grain stabilised protection polymkeric substance.Solution after reduction contain impurity (as reductive agent, metal ion counter ion and there is no the protection polymkeric substance of participation protective metal nanoparticle), thus, cannot play a role fully as electro-conductive material.Therefore, the purification step carrying out removing impurity is needed.Because protection polymkeric substance of the present invention has high protective value, lean solvent can be added to solution after the reaction, with the complex body sedimentation effectively making the metal nanoparticle protected by protection polymkeric substance be formed.Can by concentrated or separation by the complex body of sedimentation such as centrifuging.After concentrated, add suitable medium to control non-volatile component (concentration), thus be adapted to the purposes of colloidal metal solution, and the product of gained is used for various uses.
Metal nanoparticle content in colloidal metal solution obtained in the present invention is not particularly limited.But, if content is too low, then can not show the character of the metal nanoparticle in colloidal solution fully.If content or height; the relative weight of the metal nanoparticle then in colloidal solution increases; and due to the balance between the excessive relative weight that can lose metal nanoparticle and the dispersive ability of protection polymkeric substance, the bad stability of colloidal solution therefore can be expected.Further, from the view point of the reducing power of ethanoyl alkylene imine unit in protection polymkeric substance and coordination ability, the non-volatile component content of colloidal metal solution preferably in the scope of 10 ~ 80 quality %, more preferably in the scope of 20 ~ 70 quality %.In order to use colloidal solution to show enough electroconductibility as electro-conductive material, the metal nanoparticle content in non-volatile matter is preferably more than 93 quality %, is more preferably more than 95 quality %.
Metal nano particle diameter contained by non-volatile matter in the colloidal metal solution obtained in the present invention is not particularly limited.In order to make colloidal metal solution show high dispersion stability, metal nanoparticle is preferably the fine particle of particle diameter 1 ~ 70nm, and more preferably particle diameter is 5 ~ 50nm.
Generally speaking, the metal nanoparticle being of a size of tens nanometer has different being excited by surface plasma excimer and the optical absorption of the uniqueness caused according to metal species.Therefore, whether metal is existed with the form of nano_scale particle in the solution, confirm by the plasmon absorption measuring the colloidal metal solution obtained in the present invention.Further, transmission electron microscope (TEM) image of the film obtained by using this solution of cast, can determine particle size and distribution width.
The colloidal metal solution obtained in the present invention keeps stable dispersion for a long time in all types of medium, and thus its purposes is not particularly limited.Find that colloidal metal solution can use in various field, comprise catalyzer, electronic material, magneticsubstance, optical material, various sensor, coloured material and medical examination purposes.The ratio contained due to metal species and its hope also can easily regulate, and therefore can effectively show for the effect desired by its purposes.Further, due to the dispersion of solution stable for extended periods of time, solution can withstand prolonged use and long storage periods, makes solution very useful.Further, about the manufacture method of colloidal metal solution according to the present invention, without the need to step and the setting of accurate condition of complexity, thus in commercial run, tool has great advantage.
Embodiment
By embodiment, the present invention is described in more detail now, but these embodiments do not limit the scope of the invention.Except as otherwise noted, " % " is meant to " quality % ".
The instrumentation and testing method adopted in the following embodiments is as follows:
1h-NMR: the AL300 of Jeol Ltd., 300Hz
Grain diameter measurement: the FPAR-1000 of great Zhong Electronics Co., Ltd
Plasmon absorption spectrum: the UV-3500 of Hitachi, Ltd.
Pass through
1h-NMR confirms the structure of protection polymkeric substance
The protection polymers soln of about 3mL is concentrated, and under reduced pressure finish-drying.NMR residue being dissolved in about 0.8mL measures solvent (deuterochloroform such as containing 0.03% tetramethylsilane), the solution obtained is placed in the NMR measure sample Glass tubing of external diameter 5mm, uses nuclear magnetic resonance absorption spectrum analyzer JEOLJNM-LA300 to obtain
1h-NMR spectrum.Chemical shift δ based on tetramethylsilane as reference material.
By the grain diameter measurement that dynamic light scattering carries out
By a part for purified water dilution colloidal metal solution, and determine size distribution and median size with the FPAR-1000 concentrate system particle analyzer of great Zhong Electronics Co., Ltd.
Metal content measure in the non-volatile matter undertaken by thermogravimetric analysis
The colloidal metal solution of about 1mL is placed in glass sample bottle, and concentrates by heating on boiling water bath under nitrogen gas stream condition.At 50 DEG C, vacuum-drying 8 hours is carried out further to residue, obtains non-volatile matter.To in the aluminium dish of thermogravimetric analysis, add the non-volatile matter that accurate weighing is 2 ~ 10mg.Aluminium dish is placed in EXSTARTG/DTA6300 thermogravimetric analysis/differential thermal analyzer (Seiko Electronics Co., Ltd system), under the condition of air draught, 500 DEG C are heated to from room temperature, to measure the weight loss caused because of heating with the speed of per minute 10 DEG C.Silver content in non-volatile matter is calculated by following equation:
Metal content (%)=100 – weight loss (%)
The measurement of the resistivity of the metallic film obtained from colloidal metal solution
Drip the colloidal metal solution of about 0.5mL on the clean sheet glass top of 2.5 × 5cm, and use No. 8 spreading rods to form film.After film is air-dry, heat 30 minutes with 125 DEG C and 180 DEG C in hot air drying machine, thus film is burnt till in formation.The thickness burning till film is measured with OptelicsC130 true color Laser Scanning Confocal Microscope (Lasertec Inc.), " adopt the test method(s) of the conductive plastic resistance rate of four-point probe ranking method " in accordance with Japanese Industrial Standards (JIS) K7194, use Loresta-EPMCP-T360 low-resistivity tester (Mitsubishi Chemical Ind's system) surface measurements resistivity (ohms per square).Under these conditions, coating thickness keep substantially 0.3 micron constant, calculate volume specific resistance (ohm-cm) based on thickness and surface resistivity (ohms per square) by following equation: volume specific resistance (ohm-cm)=surface resistivity (ohms per square) × thickness (cm)
[synthesis example 1: the synthesis of tosylation poly glycol monomethyl ether (PEGM)]
Under nitrogen atmosphere, stirring and with 30 minutes, the chloroformic solution (30mL) containing 9.6g (50.0mmol) Tosyl chloride is being dropped in the mixing solutions containing 20.0g (10.0mmol) methoxy poly (ethylene glycol) (Mn=2,000), 8.0g (100.0mmol) pyridine and 20mL chloroform under ice-cooled condition.After dropping terminates, the mixture of gained is stirred 4 hours further at 40 DEG C.After reaction terminates, add the chloroform of 50mL with diluting reaction solution.Then, diluted reaction soln is cleaned with the saturated aqueous common salt of 5% aqueous hydrochloric acid of 100mL, the saturated sodium bicarbonate aqueous solution of 100mL and 100mL successively, carries out drying with magnesium sulfate, filter, under reduced pressure concentrate.By the solids hexane cleaning several obtained, filter, under reduced pressure carry out drying at 80 DEG C.As a result, the tosylated product of 22.0g is obtained.
Products therefrom
1the measuring result of H-NMR (AL300, the 300MHz of Jeol Ltd.) is as follows:
1h-NMR (CDCl
3) result:
δ (ppm)=7.8 (d, 2H, J=7.8Hz, tosyl group); 7.3 (d, 2H, J=7.8, tosyl groups); 4.2 (t, 2H, J=4.2Hz; the ortho position of sulphonate), 3.6-3.5 (methylene radical of m, PEGM); 3.4 (methoxyl groups of s, 3H, PEGM chain end); 2.4 (s, 3H, the methyl of tosyl group)
[synthesis example 2: the synthesis of polymine-b-ethylene glycol copolymer]
Under nitrogen atmosphere; at 60 DEG C, the branched polyethylenimine (EPOMINSP200 of Japanese catalyzer Co., Ltd.) of the tolylsulfonyl polyethylene glycol obtained by synthesis example 1 of 19.3g (9.0mmol) and 30.0g (3.0mmol) is dissolved, and mixed by stirring.In the solution of gained, add the salt of wormwood of 0.18g, under the temperature of reaction of 120 DEG C, stir the mixture 6 hours.After reaction terminates, with THF solvent cut product, after removing residue, under reduced pressure concentrate at 30 DEG C.Obtained solid product is dissolved in THF solvent again, and adds heptane in the solution of gained, again make residue sedimentation.By filtering separation residue, under reduced pressure concentrate.As a result, the light yellow solid product (yield: 99%) of 48.1g is obtained.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) and the result of ultimate analysis as follows.
1h-NMR (CDC1
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (methoxyl groups of s, 3H, PEGM chain end), 2.65-2.40 (m, the ethylidene of side chain PEI).
13c-NMR (DMSO-d
6) result:
δ (ppm)=39.9 (s), 41.8 (s), 47.6 (m), 49.5 (m), 52.6 (m), 54.7 (m), 57.8 (m) (being the ethylidene of side chain PEI above), 59.0 (s), 70.5 (m), 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above).
The result of ultimate analysis: C (53.1%), H (10.4%), N (19.1%)
[synthesis example 3: the synthesis of polymine-b-polyoxyethylene glycol-b-bisphenol A epoxide resin]
In the N-N-N,N-DIMETHYLACETAMIDE of 100mL, dissolve EPICLONAM-040-P (the DIC Inc. of 37.4g (20mmol), bisphenol A-type epoxy resin, 933) and the 4-phenylphenol of 2.72g (16mmo1) epoxy equivalent (weight):, the solution to gained adds the ethanolic soln of the 65% ethyl triphenyl phosponium acetate phosphine of 0.52mL.Under nitrogen atmosphere, reaction is carried out 6 hours at 120 DEG C.The product of gained can be cooled and drop in a large amount of water.The a large amount of water of obtained throw out is cleaned.Drying under reduced pressure residue, result obtains modified bisphenol A-type epoxy resin.Product yield is 98%.Pass through
1the integration ratio of epoxy group(ing) is studied in H-NMR measurement.Find to remain 0.95 oxirane ring in each bisphenol A-type epoxy resin molecule, product is the monofunctional epoxy resin with bisphenol A skeleton.
The monofunctional epoxy resin's obtained
1h-NMR (AL300, the 300MHz of Jeol Ltd.) measuring result is as follows:
1h-NMR (CDCl
3) result:
δ(ppm)：7.55～6.75(m)、4.40～3.90(m)、3.33(m)、2.89(m)、2.73(m)、1.62(s)
In methyl alcohol (150mL) solution of 20g (0.8mmol) polymine-b-ethylene glycol copolymer obtained in synthesis example 2, drip acetone (50mL) solution of 3.2g (1.6mmol) modified epoxy under nitrogen atmosphere, mixture is stirred 2 hours at 50 DEG C.After reaction terminates, under reduced pressure distillation is except desolventizing, and under reduced pressure desciccate further.As a result, polymine-b-polyoxyethylene glycol-b-bisphenol A-type epoxy resin is obtained.Yield is 100%.
The product obtained
1h-NMR (AL300, the 300MHz of Jeol Ltd.) measuring result is as follows:
1h-NMR (CDCl
3) result:
δ(ppm)＝7.55～6.75(m)、4.40～3.90(m)、3.57(brs)、3.33(m)、3.25(s)、2.89(m)、2.73(m)、2.65-2.40(m)、1.62(s)。
[embodiment 1: the synthesis of protection polymkeric substance (1-1)]
At the N of 270mL; in N-N,N-DIMETHYLACETAMIDE; under nitrogen atmosphere the side chain of the polyoxyethylene glycol of the tosylation obtained by synthesis example 1 of 19.3g (9.0mmol) and 30.0g (3.0mmol) is gathered acetimide (EPOMINSP200 of Japanese catalyzer Co., Ltd.) dissolving, and add the salt of wormwood of 0.18g wherein.The mixture of gained is stirred 6 hours under the temperature of reaction of 120 DEG C.After reaction terminates, removing solids, under reduced pressure at 70 DEG C of enriched products, adds the mixture of 200mL ethyl acetate and 600mL hexane, thus is precipitated thing to residue.Sediment separate out, and use THF solvent cut.Removing residue, under reduced pressure at 30 DEG C of enriched products.Obtained solid product is dissolved in THF solvent again, and adds heptane wherein, again make residue sedimentation.By filtering separation residue, and under reduced pressure concentrate.As a result, the light yellow solid product (yield: 98%) of 47.8g is obtained.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows.
1h-NMR (CDCl
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (s; 3H; the methoxyl group of PEGM chain end), 3.16 (m, 2H; the methylene radical adjacent with ethanoyl nitrogen); 2.65 ~ 2.40 (m, the ethylidene of side chain PEI), 1.90 (brs; 3H, the ethanoyl of uncle's nitrogen).
13c-NMR (DMSO-d
6) result:
δ (ppm)=22.9 (s) (ethanoyl of uncle's nitrogen); 39.9 (s), 41.8 (s), 47.6 (m), 49.5 (m), 52.6 (m), 54.7 (m), 57.8 (m) (being the ethylidene of side chain PEI above); 59.0 (s), 70.5 (m), 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above), 173.4 (m) (ethanoyl).
Calculate
1because of the integration ratio at the 1.90ppm peak of primary amine generation acetylizad in branched polyethylenimine during H-NMR measures, in known branched polyethylenimine, the primary amine of 11mol% is acetylation.
[embodiment 2: the synthesis of protection polymkeric substance (1-2)]
At the N of 270mL; in N-N,N-DIMETHYLACETAMIDE; under nitrogen atmosphere the branched polyethylenimine (EPOMINSP200 of Japanese catalyzer Co., Ltd.) of the tolylsulfonyl polyethylene glycol obtained by synthesis example 1 of 19.3g (9.0mmol) and 30.0g (3.0mmol) is dissolved, and add the salt of wormwood of 0.18g wherein.The mixture of gained is stirred 6 hours under the temperature of reaction of 140 DEG C.After reaction terminates, removing solids, under reduced pressure at 70 DEG C of enriched products, adds the mixture of 200mL ethyl acetate and 600mL hexane, thus is precipitated thing to residue.Sediment separate out, and use THF solvent cut.Removing residue, under reduced pressure at 30 DEG C of enriched products.Obtained solid product is dissolved in THF solvent again, and adds heptane wherein, again make residue precipitate.By filtering separation residue, and under reduced pressure concentrate.Result obtains the light yellow solid product (yield: 98%) of 48.0g.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows.
1h-NMR (CDCl
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (s; 3H; the methoxyl group of PEGM chain end), 3.16 (m, 2H; the methylene radical adjacent with ethanoyl nitrogen); 2.65 ~ 2.40 (m, the ethylidene of side chain PEI), 1.90 (brs; 3H, the ethanoyl of uncle's nitrogen).
13c-NMR (DMSO-d
6) result:
δ (ppm)=22.9 (s) (ethanoyl of uncle's nitrogen); 39.9 (s); 41.8 (s); 47.6 (m); 49.5 (m); 52.6 (m); 54.7 (m); 57.8 (m) (being the ethylidene of side chain PEI above); 59.0 (s); 70.5 (m), 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above), 173.4 (m) (ethanoyl).
Calculate
1because of the integration ratio at the 1.90ppm peak of primary amine generation acetylizad in branched polyethylenimine during H-NMR measures, in known branched polyethylenimine, the primary amine of 30mol% is acetylation.
[embodiment 3: the synthesis of protection polymkeric substance (1-3)]
In the chloroform of 45g, being dissolved 9.98g (N equivalent: 145mol) by the protection polymkeric substance (1-2) obtained in embodiment 2 (polymine-b-ethylene glycol copolymer that the primary amine of 30mol% is acetylation).In the solution of gained, stir at 30 DEG C the diacetyl oxide adding 1.48g at leisure, to carry out acetylization reaction 2 hours.After reaction terminates, with highly basic process product, the residue obtained thus is filtered.Under reduced pressure enriched product, result obtains the light yellow solid product (yield: 99%) of 10.5g.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows.
1h-NMR (CDCl
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (s; the methoxyl group of 3H, PEGM chain end), 3.16 (m; 2H, the methylene radical adjacent with ethanoyl nitrogen), 2.65 ~ 2.40 (m; the ethylidene of side chain PEI), 2.11 (brs, 3H; the ethanoyl of secondary nitrogen); 1.90 (brs, 3H, the ethanoyl of uncle's nitrogen).
13c-NMR (DMSO-d
6) result:
δ (ppm)=21.4 (s) (ethanoyl of secondary nitrogen); 22.9 (s) (ethanoyl of uncle's nitrogen); 39.9 (s); 41.8 (s); 47.6 (m); 49.5 (m); 52.6 (m); 54.7 (m); 57.8 (m) (being the ethylidene of side chain PEI above), 59.0 (s), 70.5 (m); 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above), 173.4 (m) (ethanoyl).
Calculate
1the integration ratio at the 1.90ppm peak that H-NMR produces because of primary amine acetylizad in branched polyethylenimine and acetylizad secondary amine in measuring respectively and 2.11ppm peak, in known branched polyethylenimine, the primary amine of 58mol% and the secondary amine of 11mol% are acetylation.
[embodiment 4: the synthesis of protection polymkeric substance (1-4)]
In the chloroform of 45g, the protection polymkeric substance (1-2) (polymine-b-ethylene glycol copolymer that the primary amine of 30mol% is acetylation) obtained by embodiment 2 of 9.98g (N equivalent: 145mmol) is dissolved.To the solution of gained, stir at 30 DEG C the diacetyl oxide adding 2.96g at leisure, to carry out acetylization reaction 2 hours.After reaction terminates, with highly basic process product, the residue obtained thus is filtered.Under reduced pressure enriched product, result obtains the light yellow solid product (yield: 98%) of 11.0g.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows:
1h-NMR (CDCl
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (methoxyl groups of s, 3H, PEGM chain end), 3.16 (m, 2H, the methylene radical Ns adjacent with ethanoyl nitrogen), 2.65-2.40 (m,
The ethylidene of side chain PEI), 2.11 (brs, 3H, the ethanoyl of secondary nitrogen), 1.90 (brs, 3H, the ethanoyl of uncle's nitrogen).
13c-NMR (DMSO-d
6) result:
δ (ppm)=21.4 (s) (ethanoyl of secondary nitrogen); 22.9 (s) (ethanoyl of uncle's nitrogen); 39.9 (s); 41.8 (s); 47.6 (m); 49.5 (m); 52.6 (m); 54.7 (m); 57.8 (m) (being the ethylidene of side chain PEI above), 59.0 (s), 70.5 (m); 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above), 173.4 (m) (ethanoyl).
Calculate
1the integration ratio at the 1.90ppm peak that H-NMR produces because of primary amine acetylizad in branched polyethylenimine and acetylizad secondary amine in measuring respectively and 2.11ppm peak, in known branched polyethylenimine, the primary amine of 88mol% and the secondary amine of 22mol% are acetylation.
[embodiment 5: the synthesis of protection polymkeric substance (1-5)]
In the chloroform of 45g, the protection polymkeric substance (1-2) (polymine-b-ethylene glycol copolymer that the primary amine of 30mol% is acetylation) obtained by embodiment 2 of 9.98g (N equivalent: 145mmol) is dissolved.To the solution of gained, stir at 30 DEG C the diacetyl oxide adding 4.44g at leisure, to carry out acetylization reaction 2 hours.After reaction terminates, with highly basic process product, the residue obtained thus is filtered.Under reduced pressure enriched product, result obtains the light yellow solid product (yield: 95%) of 13.7g.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows:
1h-NMR (CDCl
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (s; the methoxyl group of 3H, PEGM chain end), 3.16 (m; 2H, the methylene radical adjacent with ethanoyl nitrogen), 2.65-2.40 (m; the ethylidene of side chain PEI), 2.11 (brs, 3H; the ethanoyl of secondary nitrogen); 1.90 (brs, 3H, the ethanoyl of uncle's nitrogen).
13c-NMR (DMSO-d
6) result:
δ (ppm)=21.4 (s) (ethanoyl of secondary nitrogen); 22.9 (s) (ethanoyl of uncle's nitrogen); 39.9 (s); 41.8 (s); 47.6 (m); 49.5 (m); 52.6 (m); 54.7 (m); 57.8 (m) (being the ethylidene of side chain PEI above), 59.0 (s), 70.5 (m); 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above), 173.4 (m) (ethanoyl).
Calculate
1the integration ratio at the 1.90ppm peak that H-NMR produces because of primary amine acetylizad in branched polyethylenimine and acetylizad secondary amine in measuring respectively and 2.11ppm peak, in known branched polyethylenimine, the primary amine of 96mol% and the secondary amine of 54mol% are acetylation.
[comparative example 1: protection polymkeric substance synthesis (1')]
In the chloroform of 45g, the protection polymkeric substance (1-2) (polymine-b-ethylene glycol copolymer that the primary amine of 30mol% is acetylation) obtained by embodiment 2 of 9.98g (N equivalent: 145mmol) is dissolved.To the solution of gained, stir at 30 DEG C the diacetyl oxide adding 7.40g at leisure, to carry out acetylization reaction 2 hours.After reaction terminates, with highly basic process product, consequent residue is filtered.Under reduced pressure enriched product, result obtains the light yellow solid product (yield: 92%) of 12.0g.
Products therefrom
1h-NMR and
13the result of C-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows:
1h-NMR (CDCl
3) result:
δ (ppm)=3.57 (methylene radical of brs, PEGM), 3.25 (s; the methoxyl group of 3H, PEGM chain end), 3.16 (m; 2H, the methylene radical adjacent with ethanoyl nitrogen), 2.65-2.40 (m; side chain PEI volume ethylidene), 2.11 (brs, 3H; the ethanoyl of secondary nitrogen); 1.90 (brs, 3H, the ethanoyl of uncle's nitrogen).
13c-NMR (DMSO-d
6) result:
δ (ppm)=21.4 (s) (ethanoyl of secondary nitrogen); 22.9 (s) (ethanoyl of uncle's nitrogen); 39.9 (s); 41.8 (s); 47.6 (m); 49.5 (m); 52.6 (m); 54.7 (m); 57.8 (m) (being the ethylidene of side chain PEI above), 59.0 (s), 70.5 (m); 71.8 (s) (being methylene radical and the terminal methoxy group of PEGM above), 173.4 (m) (ethanoyl).
Calculate
1the integration ratio at the 1.90ppm peak that H-NMR produces because of primary amine acetylizad in branched polyethylenimine and acetylizad secondary amine in measuring respectively and 2.11ppm peak, in known branched polyethylenimine, the primary amine of 96mol% and the secondary amine of 98mol% are acetylation.
[embodiment 6: the synthesis of protection polymkeric substance (2-1)]
By 3.2g (1.6mmol) modified epoxy (namely; the monofunctional epoxy resin with bisphenol A skeleton synthesis example 3 is synthesized) acetone (50mL) solution in nitrogen atmosphere, drop to methyl alcohol (150mL) solution of the acetylate (that is, at the protection polymkeric substance (1-3) that embodiment 3 obtains) of 20g (1.25mmol) polymine-b-ethylene glycol copolymer.The mixture of gained is stirred 2 hours at 50 DEG C.After reaction terminates, under reduced pressure distillation is except desolventizing, and drying under reduced pressure product, to obtain poly-ethanoyl ethyleneimine-b-polyoxyethylene glycol-b-bisphenol A type epoxy resin.Yield is 100%.
Products therefrom
1the result of H-NMR (AL300, the 300Hz of Jeol Ltd.) is as follows:
1h-NMR (CDCl
3) result:
δ (ppm)=7.55 ~ 6.75 (m), 4.40 ~ 3.90 (m), 3.57 (brs; the methylene radical of PEGM), 3.33 (m), 3.25 (s; 3H; the methoxyl group of PEGM chain end), 3.16 (m, 2H; the methylene radical adjacent with ethanoyl nitrogen); 2.89 (m), 2.73 (m), 2.65 ~ 2.40 (m; the ethylidene of side chain PEI); 2.11 (brs, 3H, the ethanoyl of secondary nitrogen); 1.90 (brs; 3H, the ethanoyl of uncle's nitrogen), 1.62 (s).
Calculate
1the integration ratio at the 1.90ppm peak that H-NMR produces because of primary amine acetylizad in branched polyethylenimine and acetylizad secondary amine in measuring respectively and 2.11ppm peak, in known branched polyethylenimine, the primary amine of 56mol% and the secondary amine of 12mol% are acetylation.
[embodiment 7: the synthesis of the silver colloidal solution using the protection polymkeric substance (1-1) of embodiment 1 to carry out]
To in the reactor of 1L; the aqueous solution 13.5g and N of protection polymkeric substance (1-1) add pure water 180g successively, being obtained by embodiment 1; N-dimethylaminoethanol 113g (1.27mol), carries out the mixing solutions stirring to prepare protection polymkeric substance and reductive agent.In different containers, 72.0g (0.424mol) Silver Nitrate is dissolved in 120g pure water.The silver nitrate aqueous solution of gained was dropped to reactor with about 30 minutes at 40 DEG C, mixture is stirred 5 hours at 50 DEG C.Reaction terminates and after cooling, adds the lean solvent acetone of 1.9L (about 4 times of reaction mixture volume) wherein, the mixture of gained is stirred 5 minutes, then keeps standing about 1 hour.As a result, the complex body obtaining being made up of Nano silver grain and protection polymkeric substance is separated by sedimentation.After removing supernatant liquor, be separated produced throw out by centrifugal separation.After cleaning with pure water the pasty state throw out separated, again carry out centrifugal.Obtained pasty state throw out is scattered in the pure water of 80g, and the acetone that distillation removing is residual.Under reduced pressure product is concentrated into non-volatile content and becomes about 60%.As a result, obtain the 77.0g silver colloid aqueous solution (be 46.5g as non-volatile matter, yield: 97%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 95.8%.
[embodiment 8: the synthesis of the silver colloidal solution using the protection polymkeric substance (1-2) of embodiment 2 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution 14.2g of the protection polymkeric substance (1-2) obtained by embodiment 2; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 73.0g (be 45.1g as non-volatile matter, yield: 94%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 96.0%.
[embodiment 9: the synthesis of the silver colloidal solution using the protection polymkeric substance (1-3) of embodiment 3 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution 15.5g of the protection polymkeric substance (1-3) obtained by embodiment 3; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 74.0g (be 46.2g as non-volatile matter, yield: 96%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 96.0%.
[embodiment 10: the synthesis of the silver colloidal solution using the protection polymkeric substance (1-4) of embodiment 4 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution 17g of the protection polymkeric substance (1-4) obtained by embodiment 4; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 75.0g (be 45.6g as non-volatile matter, yield: 96%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 96.1%.
[embodiment 11: the synthesis of the silver colloidal solution using the protection polymkeric substance (1-5) of embodiment 5 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution 17.5g of the protection polymkeric substance (1-5) obtained by embodiment 5; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 70.0g (be 45.0g as non-volatile matter, yield: 94%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 96.4%.
[comparative example 2: the synthesis of the silver colloidal solution using the protection polymkeric substance of comparative example 1 (1') to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the protection polymkeric substance aqueous solution 19.9g (1') obtained by comparative example 1; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 70.0g (be 43.6g as non-volatile matter, yield: 91%).The result of thermal analyses (Tg/DTA) represents that the silver content in non-volatile matter is 95.5%.
[embodiment 12: the synthesis of the silver colloidal solution using the protection polymkeric substance (2-1) of embodiment 6 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution 16.9g of the protection polymkeric substance (2-1) obtained by embodiment 6; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 76.0g (be 45.8g as non-volatile matter, yield: 95%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 95.6%.
[comparative example 3: the synthesis of the silver colloidal solution using the compound of synthesis example 2 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution prepared by dissolving the compound 3.5g that obtained by synthesis example 2 in the pure water of 9.5g; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 74.0g (be 45.7g as non-volatile matter, yield: 95%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 96.0%.
[comparative example 4: the synthesis of the silver colloidal solution using the compound of synthesis example 3 to carry out]
In this embodiment; replace except the aqueous solution 13.5g of the protection polymkeric substance (1-1) obtained by embodiment 1 except using the aqueous solution prepared by dissolving the compound 4.1g that obtained by synthesis example 3 in the pure water of 9.5g; operate in the same manner as in embodiment 7; obtain non-volatile content be about 60% silver colloid aqueous solution 77.0g (be 45.5g as non-volatile matter, yield: 95%).Silver content in the result display non-volatile matter of thermal analyses (Tg/DTA) is 95.5%.
To the metallic film by using the silver colloidal solution obtained by embodiment 7 to 12 and comparative example 2 to 4 to prepare, measured resistivity described above and median size.The time spent for the amount of the acetone of settlement treatment and process in building-up process is shown in Table 2.Obtained silver colloidal solution is left standstill 1 week, from the stability evaluating solution in appearance in room temperature (25 to 35 DEG C).Result is shown in table 1 and 2.In table 1, O.L. refers to overload.
Result illustrates; when in the protection polymkeric substance used; primary amine acetylize ratio in poly (alkylenimines) segment be 5 ~ 100mol% and secondary amine acetylize ratio is 0 ~ 50mol% time, show good electric conductivity, dispersion stabilization and the refining and easiness be separated.
Table 1
Table 2
Claims (13)
1. a metal nanoparticle protection polymkeric substance, comprises in molecule:
Poly-ethanoyl alkylene imine segment (A), wherein, in poly (alkylenimines), the primary amine of 5 ~ 100mol% is acetylation and in poly (alkylenimines), the secondary amine of 0 ~ 50mol% is acetylation; And
Hydrophilic segment (B).
2. metal nanoparticle protection polymkeric substance according to claim 1, comprises hydrophobic chain segment (C) further in molecule.
3. metal nanoparticle protection polymkeric substance according to claim 1 and 2, wherein, described hydrophilic segment (B) comprises polyoxyalkylene chain.
4. the metal nanoparticle protection polymkeric substance according to Claims 2 or 3, wherein, described hydrophobic chain segment (C) comprises the structure deriving from epoxy resin.
5. according to any one of Claims 1 to 4 metal nanoparticle protection polymkeric substance, wherein, the unit number of the alkylene imine in described poly-ethanoyl alkylene imine segment (A) 5 ~ 2, in the scope of 500.
6. the metal nanoparticle protection polymkeric substance according to any one of Claims 1 to 5, wherein, described metal nanoparticle protection polymkeric substance has 1,000 ~ 100, the weight-average molecular weight of 000 scope.
7. a manufacture method for metal nanoparticle protection polymkeric substance, comprising:
Make to have the compound of poly (alkylenimines) segment and there is the compound polymerization of hydrophilic segment (B), making the acetylize of alkylene imine unit with acetylizing agent simultaneously.
8. a manufacture method for metal nanoparticle protection polymkeric substance, comprising:
The compound in molecule with poly (alkylenimines) segment and hydrophilic segment (B) is reacted as presoma and acetylizing agent, thus makes the acetylize of alkylene imine unit.
9. a colloidal metal solution, comprising:
Medium; And
Be scattered in the complex body in described medium; each complex body protects polymkeric substance to form by the metal nanoparticle of metal nanoparticle and the described metal nanoparticle of protection; described metal nanoparticle protection polymkeric substance comprises poly-ethanoyl alkylene imine segment (A) and hydrophilic segment (B); in described poly-ethanoyl alkylene imine segment (A), in poly (alkylenimines), the primary amine of 5 ~ 100mol% is acetylation and in poly (alkylenimines), the secondary amine of 0 ~ 50mol% is acetylation.
10. colloidal metal solution according to claim 9, wherein, described metal nanoparticle is Nano silver grain.
11. colloidal metal solutions according to claim 9 or 10, wherein, described metal nanoparticle has the particle diameter of 5 ~ 50nm scope.
The manufacture method of 12. 1 kinds of colloidal metal solutions, comprising:
When there is metal nanoparticle protection polymkeric substance; in media as well reducing metal ions is become metal nanoparticle; described metal nanoparticle protection polymkeric substance comprises poly-ethanoyl alkylene imine segment (A) and hydrophilic segment (B) in molecule; in described poly-ethanoyl alkylene imine segment (A), in poly (alkylenimines), the primary amine of 5 ~ 100mol% is acetylation and in poly (alkylenimines), the secondary amine of 0 ~ 50mol% is acetylation.
The manufacture method of 13. colloidal metal solutions according to claim 12, wherein, described metal nanoparticle is Nano silver grain.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2013/074612 WO2014172856A1 (en) | 2013-04-24 | 2013-04-24 | Metal nanoparticle-protecting polymer and metal colloidal solution, and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105164183A true CN105164183A (en) | 2015-12-16 |
| CN105164183B CN105164183B (en) | 2017-06-30 |
Family
ID=51790986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380075890.6A Active CN105164183B (en) | 2013-04-24 | 2013-04-24 | Metal nanoparticle protects polymer and colloidal metal solution and their manufacture method |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5811430B2 (en) |
| KR (2) | KR101927766B1 (en) |
| CN (1) | CN105164183B (en) |
| TW (1) | TWI613255B (en) |
| WO (1) | WO2014172856A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109195731A (en) * | 2016-05-16 | 2019-01-11 | Dic株式会社 | Metal nanoparticle aqueous dispersions |
| CN112805104A (en) * | 2018-10-12 | 2021-05-14 | 花王株式会社 | Method for producing metal microparticle dispersion |
| CN113795535A (en) * | 2019-03-14 | 2021-12-14 | 路博润先进材料公司 | Polyamine polyester dispersants prepared via anhydride intermediates |
| CN115194171A (en) * | 2022-05-27 | 2022-10-18 | 氢电中科（广州）新能源设备有限公司 | Highly-dispersed platinum nanoparticle solution and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109081948B (en) * | 2017-06-14 | 2020-06-09 | 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 | Hydrophilic solid spherical material, preparation method and application thereof |
| KR102312406B1 (en) * | 2020-07-08 | 2021-10-13 | 유한회사 대동 | Conductive water-based ink composition for screen printing, conductive pattern produced using the same, and conductive device comprising the same |
| KR102552064B1 (en) * | 2020-10-16 | 2023-07-06 | 유한회사 대동 | Conductive water-based ink composition for filling intaglio micropatterns, conductor-filling micropatterns produced using the same, and conductive devices comprising the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1695717A1 (en) * | 2005-02-23 | 2006-08-30 | Ludwig-Maximilians-Universität | Transport of nano-and macromolecular structures into cytoplasm and nucleus of cells |
| JP4026662B1 (en) * | 2006-08-01 | 2007-12-26 | 大日本インキ化学工業株式会社 | Metal nanoparticle dispersion and method for producing the same |
| US20090069435A1 (en) * | 2007-08-10 | 2009-03-12 | Whiteford Jeffery A | Bridged polycyclic compound based compositions for topical applications for pets |
| CN101506307A (en) * | 2006-08-09 | 2009-08-12 | Dic株式会社 | Metal nanoparticle dispersion and process for producing the same |
| CN102066024A (en) * | 2008-06-26 | 2011-05-18 | Dic株式会社 | Silver-containing powder, method for producing the same, conductive paste using the same, and plastic substrate |
| CN103877597A (en) * | 2014-03-19 | 2014-06-25 | 中国人民解放军第二军医大学 | Pegylated polyethyleneimine macromolecular magnetic resonance imaging contrast agent and preparation method of contrast agent |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3594803B2 (en) | 1997-07-17 | 2004-12-02 | 日本ペイント株式会社 | Noble metal or copper colloid solution, method for producing the same, coating composition and resin molded product |
| JP4346510B2 (en) | 1997-07-17 | 2009-10-21 | 日本ペイント株式会社 | Colloidal solution of noble metal or copper, method for producing the same, coating composition and resin molding |
| JP4231307B2 (en) | 2003-03-03 | 2009-02-25 | 田中貴金属工業株式会社 | Metal colloid and catalyst using the metal colloid as a raw material |
| JP4026647B2 (en) | 2005-02-07 | 2007-12-26 | 大日本インキ化学工業株式会社 | Metal-fixed polymer aggregate and method for producing the same |
| JP2006328472A (en) | 2005-05-26 | 2006-12-07 | Mitsui Chemicals Inc | Production method of silver nanoparticle, silver nanoparticle and application thereof |
| JP2007099930A (en) * | 2005-10-05 | 2007-04-19 | Dainippon Ink & Chem Inc | Triblock copolymer and method for producing the same |
-
2013
- 2013-04-24 JP JP2015512999A patent/JP5811430B2/en active Active
- 2013-04-24 CN CN201380075890.6A patent/CN105164183B/en active Active
- 2013-04-24 KR KR1020157023902A patent/KR101927766B1/en active IP Right Grant
- 2013-04-24 KR KR1020177008889A patent/KR20170040368A/en not_active Application Discontinuation
- 2013-04-24 WO PCT/CN2013/074612 patent/WO2014172856A1/en active Application Filing
-
2014
- 2014-04-23 TW TW103114604A patent/TWI613255B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1695717A1 (en) * | 2005-02-23 | 2006-08-30 | Ludwig-Maximilians-Universität | Transport of nano-and macromolecular structures into cytoplasm and nucleus of cells |
| JP4026662B1 (en) * | 2006-08-01 | 2007-12-26 | 大日本インキ化学工業株式会社 | Metal nanoparticle dispersion and method for producing the same |
| CN101506307A (en) * | 2006-08-09 | 2009-08-12 | Dic株式会社 | Metal nanoparticle dispersion and process for producing the same |
| US20090069435A1 (en) * | 2007-08-10 | 2009-03-12 | Whiteford Jeffery A | Bridged polycyclic compound based compositions for topical applications for pets |
| CN102066024A (en) * | 2008-06-26 | 2011-05-18 | Dic株式会社 | Silver-containing powder, method for producing the same, conductive paste using the same, and plastic substrate |
| CN103877597A (en) * | 2014-03-19 | 2014-06-25 | 中国人民解放军第二军医大学 | Pegylated polyethyleneimine macromolecular magnetic resonance imaging contrast agent and preparation method of contrast agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109195731A (en) * | 2016-05-16 | 2019-01-11 | Dic株式会社 | Metal nanoparticle aqueous dispersions |
| CN112805104A (en) * | 2018-10-12 | 2021-05-14 | 花王株式会社 | Method for producing metal microparticle dispersion |
| CN112805104B (en) * | 2018-10-12 | 2023-10-27 | 花王株式会社 | Method for producing metal microparticle dispersion |
| CN113795535A (en) * | 2019-03-14 | 2021-12-14 | 路博润先进材料公司 | Polyamine polyester dispersants prepared via anhydride intermediates |
| CN115194171A (en) * | 2022-05-27 | 2022-10-18 | 氢电中科（广州）新能源设备有限公司 | Highly-dispersed platinum nanoparticle solution and preparation method thereof |
| CN115194171B (en) * | 2022-05-27 | 2023-09-26 | 氢电中科（广州）新能源设备有限公司 | Highly dispersed platinum nanoparticle solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150114552A (en) | 2015-10-12 |
| JP2015525250A (en) | 2015-09-03 |
| KR20170040368A (en) | 2017-04-12 |
| JP5811430B2 (en) | 2015-11-11 |
| TWI613255B (en) | 2018-02-01 |
| TW201441305A (en) | 2014-11-01 |
| WO2014172856A1 (en) | 2014-10-30 |
| KR101927766B1 (en) | 2018-12-12 |
| CN105164183B (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105164183A (en) | Metal nanoparticle-protecting polymer and metal colloidal solution, and method for producing same | |
| US7291292B2 (en) | Preparation of silver particles using thermomorphic polymers | |
| US10000651B2 (en) | Metal nanoparticle composite body, metal colloidal solution, and methods for producing these | |
| CN104470659B (en) | Silver nano-particle and preparation method thereof, silver nano-particle dispersion liquid and form the base material of silver-colored composition | |
| JP3188219B2 (en) | Two-component dispersants for wet milling | |
| CN103338884A (en) | Coated metal microparticle and manufacturing method thereof | |
| CN107614164A (en) | Metallic nano-particle manufacture composition | |
| CN103328135A (en) | Metal particle powder and paste composition using same | |
| WO2012133296A1 (en) | Composite of organic compound and silver core/copper shell nanoparticles and method for producing same | |
| JP7359846B2 (en) | Ink containing metal fine particles | |
| KR102357284B1 (en) | Metal nanoparticle dispersion stabilizer, metal colloidal solution and preparation method thereof | |
| TW202020067A (en) | Aqueous dispersion of metal fine particles | |
| JP5936090B2 (en) | Metal nanoparticle protective polymer, metal colloid solution, and production method thereof | |
| JP2014047364A (en) | Metal nanoparticle protective polymer, metal colloidal solution and manufacturing methods therefor | |
| CN108348884A (en) | The metal dispersion of stability with raising | |
| KR100880095B1 (en) | Dispersing agent of metal nanoparticle composed of polyethylenimine derivative and use hereof | |
| JP7217108B2 (en) | Method for producing water-based fine metal particle dispersion | |
| JP2007301461A (en) | Method for preparing metal colloidal solution and metal colloidal solution | |
| JP2023130600A (en) | Method for producing metal nanoparticles | |
| TW200406272A (en) | Oil phase additive containing nano metal dispersion particles and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |