JP2013060637A - Complex of organic compound and nano copper particle, complex of organic compound and nano copper oxide (i) particle, and method for manufacturing them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a complex of a compound and a nano copper oxide (I) particle or a nano copper particle, the complex having an effect of supressing particle growth in reducing a copper compound in a liquid phase to produce the nano particles and capable of stably dispersing the nanoparticles in a medium.SOLUTION: A complex includes a nano particle, and a compound represented by formulas (1)-(2): [X-(OCHCHR)-O-CH-CH(OH)-CH-S-]Y (1) and [X-(OCHCHR)-O-CH-CH(OH)-CH-S-R'-]Z (2) [wherein, X represents an alkyl group; R represents H or a methyl group; n represents 2-100; Y represents a group having a valency of 2-4 and a hydrocarbon group or a group including hydrocarbon groups linked with O, S or NHR"; m represents 2-4; R' represents an alkylcarbonyloxy group; Z represents a group having a valency of 2-6 and a hydrocarbon group; a group including hydrocarbon groups linked with O, S or NHR" or an isocyanuric acid-N,N',N"-triethylene group, and l represents 2-6].

Description

  The present invention relates to a composite of a polythioether organic compound having a plurality of sulfide (C—S—C) groups in a molecule and nano copper particles or nano copper (I) particles. Furthermore, using a thioether-containing organic compound as a metal colloid protective agent, reducing the copper compound in the presence thereof, a composite of an organic compound and nano-copper particles, a composite of an organic compound and nano-copper (I) particles It relates to a manufacturing method.

  The formation of the wiring pattern of the electronic circuit is currently produced through a complicated process based exclusively on photolithography, but a nanomaterial that has been developed in recent years is dispersed in some medium to form a coating composition, Development of coating-type electronic device manufacturing technology is also progressing, in which this is patterned into various devices using various printing techniques. Such a technique is called printable electronics, but this method has the possibility that an electronic circuit can be mass-produced by a roll-to-roll process, economy on demand, simplification of processes, and resource saving. It is expected as an innovative technology that can completely change the manufacturing method of electronic devices from the viewpoint of performance. Since the coating material can be prepared by inking nano metal particles or nano metal oxide particles, it is no exaggeration to say that the basic material in printable electronics is nano metal (or nano metal oxide) particles. . From such a viewpoint, the development of nano silver particles and nano copper particles as conductive materials is very active, especially nano copper particles and semiconductor characteristics that are less likely to cause disconnection due to migration when the raw material is inexpensive and printed wiring is used. The nano copper oxide (I) particle which has has great expectation.

  On the other hand, high integration of electronic devices and high-density mounting of electronic circuits are technologies that are constantly being pursued from the viewpoint of miniaturization of devices and energy savings. . For example, for mounting, the line width and the space between lines are several tens of μm, the thickness is 10 μm or less, etc. In addition, for use in semiconductor nanopatterning, a line width of about 30 nm is formed. There must be. Therefore, in order to achieve this with printable electronics, the nano metal particles to be used need to have a diameter of 10 to 20 nm or less.

  The industrial utility value of copper is not limited to conductive members. For example, copper (I) oxide is a p-type semiconductor used for rectifiers and the like in the old days, and has often been used for elementary solar cell experiments (for example, see Non-Patent Documents 1 and 2). If this is converted into nanoparticles, not only will it lead to the provision of coating materials for metal oxide p-type semiconductors that are still in the search process, but the Kubo effect (quantum size effect / It is expected that a unique phenomenon that cannot be observed in bulk particles due to the electronic effect) will be observed, and its practical application should be greatly studied.

  In addition, copper (I) oxide is a material that has attracted attention as an economical solar cell that substitutes for an inorganic material that is of concern for toxicity and has a low environmental load (see, for example, Non-Patent Documents 3, 4, and 5). . From such a point of view, research on homojunction type solar cells and metal oxide thin film solar cells that are structured and interface-controlled at the nano level is also being promoted (see, for example, Patent Documents 1 and 2).

  Although it is a nano copper / nano copper (I) particle attracting attention, there are many unsolved problems in its practical application. In other words, a synthesis method that controls the particle size at the nanometer level, dispersion stabilization, suppression of properties that are very easily oxidized and disproportionated, and lowering the fusion temperature of nano copper particles when used as a conductive material It is also an important issue.

  As a method for producing nano-copper particles, a copper compound (oxide, halide, carboxylate, etc.) is synthesized by reducing and synthesizing with a reducing agent such as hydrazine hydrate in the presence of a metal colloid protective agent. Phase reduction methods are common. When the starting material is a copper (II) compound, partial reduction to monovalent copper is possible by selecting the type and conditions of the reducing agent, and the reduced copper is produced via the copper (I) compound intermediate. The method to do can be adopted. If the copper (I) intermediate obtained in the process is colloidal and the particle size can be controlled at the nanometer level, it can itself be applied as a coating-type semiconductor material. Moreover, it becomes easy to suppress the enlargement of particles in the subsequent reduction step to zero-valent copper.

  For example, a method for producing fine copper particles in two stages by controlling the particle size of copper (I) oxide using a noble metal seed (seed crystal) and subsequently reducing with hydrazine hydrate is described. (For example, see Patent Document 3). In addition, copper (II) acetate and silver acetate are reduced with a hydroxylamine compound, and the nano silver particles produced in advance are used as seeds to obtain fine nano copper oxide (I), followed by nano copper particles. A production method in which the reduction is performed in two stages is also provided (for example, see Patent Document 4).

  As a method for controlling copper (I) oxide to a small particle size without using a seed, there is an attempt to control the field of particle growth by a fluid engineering method. For example, it has been reported that copper oxide (I) having a thickness of about 15-20 nm can be produced by a technique using a laminar flow region in a microreactor as a reaction field (see, for example, Patent Document 5).

  However, these methods have several drawbacks. First, the former two require an expensive noble metal seed for particle size control. In the method described in Patent Document 3, since the selection of the protective agent is limited, the obtained particle size is as large as about 300 nm, which is not a method for controlling the particle size of fine particles. Further, since the noble metal seed is added, it is always obtained as multi-component metal particles (for example, silver core copper shell type particles), and it is a disadvantage that a material having the property of pure copper element cannot be obtained. This is fatal when the nano copper (I) oxide particles are applied as a metal oxide semiconductor. In addition, whether all the precious metal fine particles added as seeds are combined with copper particles (for example, core-shell structure) depends on the manufacturing conditions and the purification results, and each single particle may be mixed. Therefore, it is easy to produce performance variations. On the other hand, although the fluid engineering method does not have the disadvantage of becoming multi-component particles, the flow rate setting for maintaining laminar flow formation in the microreactor is delicate, and the condition must be maintained within a specific setting range. Therefore, mass production can be dealt with only by preparing a large number of reactors, which is very inefficient.

  There is also a method using a microemulsion as a reaction field (see, for example, Patent Document 6). In this method, first, a complex is prepared from copper acetate (I) and an organic amine compound, and this is used as a solution of alcohols. A process is required. This is added to a w / o microemulsion prepared from water, an organic solvent and a surfactant, and fine copper oxide (I) is prepared by decomposing the complex in it. The copper acetate is difficult to obtain and is difficult to operate.

Maruyama, Tani, Production Research, 1951, 3 (10), 362-366 Rai, Sol. Cells 1988, 25, 265-272 Taro Toyoda et al. , Acc. Chem. Res. 2009, 42, 1848-1857 Choi et al. , J .; Phys. Chem. Lett. 2010, 1,266-267 Yong et al. , J .; Am. Chem. Soc. 2009, 131, 3756-3761

JP 2007-019460 A JP 2007-2335040 A Japanese Patent Laid-Open No. 04-116109 JP 2008-019461 A JP 2006-096569 A JP 2011-001213 A

  In view of the above circumstances, the problem of the present invention is that a particle growth inhibitory effect (capping effect) essential for producing fine nano copper (I) particles and nano copper particles by reducing a copper compound in a liquid phase. A composite of an organic compound (that is, a metal colloid protective agent) that can stably disperse the produced nanoparticles in a medium, and the nanocopper particles and nanocopper oxide (I) particles. In particular, it is to provide a composite containing nano copper (I) particles having a narrow particle size distribution of 10 nm or less or nano copper fine particles of 20 nm or less. Furthermore, it is providing the simple manufacturing method of those.

  In order to solve the above problems, a metal colloid protective agent having high capping ability and dispersion stabilizing ability is designed, and the particle size of nano copper oxide (I) or nano copper particles is controlled and synthesized to 10 to 20 nm or less. It is necessary.

  As a result of diligent research, the present inventors have been protected with an organic compound by allowing a reducing agent to act on a copper compound in the presence of an organic compound having a specific structure containing a plurality of thioether groups (sulfide bonds) in the molecule. Found that nano-copper oxide (I) particles and nano-copper particles having a uniform and very small particle diameter were obtained, and that the obtained particle / organic compound composite maintained a stable dispersion state in a medium for a long period of time. The present invention has been completed.

  That is, the present invention provides a thioether-containing organic compound (A) having a structure represented by the following general formula (1) or general formula (2) containing two or more thioether groups in the molecule by reaction with a polyvalent thiol compound. And a composite of an organic compound and nanocopper particles, or an organic compound and nanocopper oxide (I) particles, characterized by containing nanocopper particles (B) or nanocopper particles (I) particles (C) And provide a complex.

[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—] _m Y (1)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—R′—] _l Z (2)
[X in the formula (1) and (2) is an alkyl group of _C 1 -C _8, R is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, R May be the same or different for each repeating unit, and Y is a divalent to tetravalent group in which a carbon atom is directly bonded to a sulfur atom, and is a C ₁ -C ₄ saturated carbonization Two or three hydrogen groups or C ₁ -C ₄ saturated hydrocarbon groups are connected by —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). It is a group. M in Formula (1) is an integer of 2-4. R ′ in the formula (2) is a C _{2 to} C ₅ alkylcarbonyloxy group, Z is a divalent to hexavalent group in which a carbon atom is directly bonded to a sulfur atom, and C _{2 to} C ₆ saturated hydrocarbon groups and C ₂ -C ₆ saturated hydrocarbon groups are —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). ~ 3 linked groups, or isocyanuric acid-N, N ', N "-triethylene group, and l is an integer of 2-6.]

  Furthermore, the present invention provides an organic compound and a nano copper particle that reduce a copper compound in the presence of the thioether-containing organic compound (A) having the structure represented by the general formula (1) or the general formula (2). The present invention also provides a method for producing a composite or a composite of an organic compound and nano-copper (I) particles.

The dispersion of the composite of the organic compound and nano-copper particles of the present invention and the composite of the organic compound and nano-copper (I) particles can ensure dispersion stability for 3 months or more under airtight and refrigerated storage. It is a dispersion. The average particle diameter of the nano copper (I) particles and the nano copper particles is controlled to 5 to 20 nm, and a reducing agent (for example, glucose) is added to the dispersion of the nano copper (I) particle composite, After forming into a film, a copper film having a volume resistivity of about 10 ⁻⁴ Ωcm is easily manufactured by heating at, for example, 300 ° C. for 30 minutes under an inert gas atmosphere (for example, under a nitrogen gas atmosphere). Can do. Moreover, the coating film manufactured from the nano copper particle composite is heated to about 10 ⁻⁵ Ωcm by heating at 250 ° C. for 30 minutes under an inert gas atmosphere (for example, under an argon atmosphere containing 3% hydrogen). A copper film having a volume resistivity can be easily produced. Therefore, a composite liquid of the organic compound of the present invention and nano-copper particles, and a dispersion of a composite of organic compound and nano-copper oxide (I) particles are A conductive ink and a semiconductor ink used for printable electronics, or a conductive bonding agent and a heat conductor can be provided. In addition, a semiconductor film having photoresponsiveness can be formed from a dispersion of a complex with nano copper (I) particles.

It is an ultraviolet-visible absorption spectrum of the dispersion liquid of the composite of the organic compound and nano copper particles obtained in Example 1. 2 is a wide-angle X-ray diffraction spectrum of a dispersion of a composite of an organic compound and nanocopper particles obtained in Example 1. It is a transmission electron microscope image of the composite_body | complex of the organic compound and nano copper particle which were obtained in Example 3. FIG. 2 is a transmission electron microscope image of nanocopper particles obtained in Comparative Example 1. FIG. It is a transmission electron microscope image of nano copper (I) oxide obtained in Example 13. 2 is a wide-angle X-ray diffraction spectrum of a nanocopper film before firing (6 days after film formation) obtained in Application Example 1. 2 is a wide-angle X-ray diffraction spectrum of a nanocopper film before firing (the day after film formation) obtained in Comparative Application Example 1. 4 is a wide-angle X-ray diffraction spectrum of a nano-copper (I) oxide film before firing obtained in Application Example 2. It is a wide-angle X-ray-diffraction spectrum of the membrane | film | coat obtained by baking the nano copper (I) membrane | film | coat obtained by the application example 2 in 3% hydrogen containing argon.

Hereinafter, the present invention will be described in detail.
[Thioether-containing organic compound (A)]
Nano copper particles or nano copper (I) particles, for example, the required particle size and distribution when used as a printable electronics material, dispersion stability, and low resistance due to low-temperature fusion phenomenon for nano copper particles Therefore, it is necessary to design a colloid protective agent that exhibits a high capping effect and a dispersion stabilizing effect. For this purpose, an organic compound having both an adsorbing group having an appropriate affinity for the surface of copper (I) oxide particles or copper particles and a functional group having an affinity for the medium is required.

  Appropriate affinity adsorption means that it is well adsorbed on the surface of metal particles in the medium, but is easily detached from the particles when dried and does not hinder the adhesion between the particles. Unless a compound exhibiting such properties is used as a colloid protective agent, a uniform semiconductor film composed of copper (I) oxide particles and a highly conductive copper thin film by low-temperature sintering cannot be realized.

  As an affinity group for the metal surface, a thiol group (-SH) is frequently used, but this forms a strong bond such as a thiolate with the metal, and is inferior in detachability. Thus, as a result of diligent search, it was found that a sulfur functional group-containing compound of the thioether type (RSR ′) is suitable in terms of the balance between affinity and detachment, and this is used as an adsorbing group on the metal surface. Selected.

  It is understood that such an adsorption phenomenon reaches a dynamic adsorption equilibrium where the adsorption rate and the desorption rate are the same under the conditions used. In other words, in the case of a colloid protective agent having only one adsorption functional group, focusing on a single molecule, there are cases where it is adsorbed on the particle surface and when it is not adsorbed. Will be shown. Therefore, if there are a plurality of adsorptive functional groups in the molecule, the probability that any one of the adsorbing groups is on the particle is increased, and a high adsorptivity as a whole is exhibited. From such considerations, it was considered that when a compound having a plurality of thioether structures in the molecule was used as a colloid protective agent, the dispersion stabilization of the composite of nanocopper particles or nanocopper (I) oxide particles would be excellent. The number of thioether functional groups is preferably 2 to 6 from the viewpoint of handling and dispersion stability.

  In the present invention, as the functional group contributing to the dispersion stability of the composite containing nano copper particles or nano copper (I) oxide particles, a chain functional group having ethylene glycol and propylene glycol as repeating units is selected. did. The number of repetitions is usually 2 to 100, and in particular 7 to 50 (with a molecular weight of about 300 to 2000) is more preferable because of excellent dispersion stability.

  One end of the chain-like functional group having ethylene glycol and propylene glycol as a repeating unit as described above is a non-reactive group, and when used as a production method, industrial availability, and a protective agent From the viewpoint of dispersion stability, it is a linear or branched alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of stability in an aqueous medium. .

The polymer which the inventor has selected as a protective agent for the nano copper particles or the nano copper oxide (I) particles has the structure represented by the following general formula (1) or general formula (2).
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—] _m Y (1)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—R′—] _l Z (2)
[X in the formula (1) and (2) is an alkyl group of _C 1 -C _8, R is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, R May be the same or different for each repeating unit, and Y is a divalent to tetravalent group in which a carbon atom is directly bonded to a sulfur atom, and is a C ₁ -C ₄ saturated carbonization Two or three hydrogen groups or C ₁ -C ₄ saturated hydrocarbon groups are connected by —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). It is a group. M in Formula (1) is an integer of 2-4. R ′ in the formula (2) is a C _{2 to} C ₅ alkylcarbonyloxy group, Z is a divalent to hexavalent group in which a carbon atom is directly bonded to a sulfur atom, and C _{2 to} C ₆ saturated hydrocarbon groups and C ₂ -C ₆ saturated hydrocarbon groups are —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). ~ 3 linked groups, or isocyanuric acid-N, N ', N "-triethylene group, and l is an integer of 2-6.]

Among these, Y has a structure containing ether (C—O—C) and thioether (C—S—C) as a partial structure, and R ′ represents a methylene carboxy group (—CH ₂ COO—) or an ethylene carboxy group ( a -CH ₂ CH ₂ COO-), those wherein Z is an ethylene group, 2-ethyl-2-methylene-1,3-diyl, 2,2-bis-methylene-1,3-diyl Is most suitable as a protective agent for nano copper particles / nano copper (I) oxide particles.

  The thioether-containing organic compound (A) of the present invention is specifically a compound obtained by reacting an epoxide having polyethylene glycol or polypropylene glycol with a polyvalent thiol compound. As the polyvalent thiol compound, a compound having a structure represented by the general formula (1) and the general formula (2) can be easily obtained by using a compound as shown below.

[Method for producing thioether-containing organic compound (A)]
As described above, the protective agent used in the present invention is a compound having a structure represented by the general formula (1) and the general formula (2). The method for synthesizing this organic compound (A) will be described in detail below.

  As a method for easily synthesizing the thioether-containing organic compound (A), the polyether compound (a1) having a glycidyl group at the terminal and the thiol compound (a2) may be reacted. The polyether compound (a1) having the glycidyl group at the end can be represented by the following general formula.

(In the formula, X is a C _{1 to} C ₈ alkyl group, R is a hydrogen atom or a methyl group, n is an integer indicating the number of repetitions of 2 to 100, and R is independent for each repeating unit. They may be the same or different.)

  As a method for synthesizing the polyether compound (a1) having a glycidyl group at the terminal, polyethylene / propylene glycol monomethyl ether may be converted into alkoxide using potassium tertiary butoxide, and this may be condensed with epichlorohydrin.

  The target thioether-containing organic compound (A) can be obtained by opening the terminal oxirane ring of the polyether compound (a1) having a glycidyl group at the terminal by nucleophilic attack of the SH group of the thiol compound (a2). it can. Various activation methods are known for this reaction, but a method using a tetraalkylammonium fluoride which is excellent in the yield of the compound (A) and the regioselectivity of the reaction as a catalyst is preferable (Penso et al., Synthesis). 1994, 34-36). By applying this method, a thioether-containing organic compound that can be used in the present invention without any special purification after the reaction of the polyether compound (a1) having a glycidyl group at the terminal and the thiol compound (a2). (A) can be obtained with good yield.

[Composite of organic compound and nano copper (I) oxide particles]
The complex of the organic compound of the present invention and nano-copper (I) particles contains the above-mentioned thioether-containing organic compound (A) and nano-copper (I) particles having a nanometer order particle size. In particular, nano-copper oxide (I) particles having an average particle diameter of about 10 nm are coated with the thioether-containing organic compound (A) to form a particulate composite as a whole.

  Measurement of the particle size and particle size distribution of a complex of an organic compound and nano copper (I) oxide particles can be performed with a transmission electron microscope image (hereinafter referred to as TEM). In addition, the shape of the complex of the organic compound and nano copper (I) oxide particles can be similarly observed by TEM. Measurement of the particle diameter and its distribution in the particulate composite can also be performed by a dynamic light scattering method in combination with TEM observation.

  When the particle diameter of 100 composites is determined by TEM and the average particle diameter (primary particle diameter) is calculated, it is approximately 5 to 20 nm, preferably 5 to 15 nm. Even when nano copper particles are produced, a fine one of about 20 to 40 nm is obtained. The average particle size obtained by the dynamic light scattering method is larger than the particle size obtained by TEM observation and is about 100 nm.

  In addition, for a non-volatile material obtained by drying a complex of an organic compound and nano-copper oxide (I) particles after purification, which will be described later, a thermogravimetric analyzer is used to determine the weight loss rate when this is ignited. When measured by (TG / DTA method), this can be regarded as the content of the organic compound in the complex. As a content rate of the thioether containing organic compound (A) calculated | required in this way, what is 2-15 mass% is suitable as a material used for various application methods.

  According to wide-angle X-ray diffraction of a film formed by applying the composite to a substrate such as a glass slide and drying, it can be confirmed that the metal particles constituting the composite consist only of monovalent copper oxide. The content of I) can be considered to be obtained by subtracting the content of the organic compound measured by the TG / DTA method from the weight of the nonvolatile material.

[Composite of organic compound and nano copper particles]
The composite of the organic compound and nanocopper particles of the present invention contains the above-mentioned thioether-containing organic compound (A) and nanocopper particles having a particle diameter of the order of nanometers. Nano copper particles having an average particle diameter of 20 nm are coated with the thioether-containing organic compound (A) to form a particulate composite as a whole.

  Measurement of the particle size and particle size distribution of the nanocopper particles can be performed by TEM and dynamic light scattering as in the case of the complex of the organic compound and nanocopper oxide (I) particles. By the DTA method, the organic compound content in the non-volatile material can be measured. What is 2-15 mass% as a content rate of the thioether containing organic compound (A) calculated | required in this way is suitable when using a composite_body | complex or its dispersion as an electroconductive material.

  According to wide-angle X-ray diffraction, it can be confirmed that the metal particles constituting the composite are composed only of zero-valent reduced copper, and the content of copper (0) is an organic content measured by the TG / DTA method from the weight of nonvolatiles. It can be considered that the content of the compound is subtracted.

[Composite of organic compound and nano-copper (I) particles, production method of composite of organic compound and nano-copper particles]
The method for producing a composite of an organic compound and nano-copper oxide (I) particles of the present invention and a composite of an organic compound and nano-copper particles is a bivalent compound in the presence of the above-mentioned thioether-containing organic compound (A). It has the process of mixing a copper ion compound with a solvent, and the process of reduce | restoring a copper ion, It is characterized by the above-mentioned.

As the divalent copper ion compound, generally available copper compounds can be used, and sulfates, nitrates, carboxylates, carbonates, chlorides, acetylacetonate complexes and the like can be used. When obtaining a complex with zero-valent nano copper particles, it may be produced from a divalent compound or may be produced from a monovalent compound, or it may have water or crystal water. When producing a composite containing nano copper (I) oxide particles, a divalent copper compound may be partially reduced. Specifically, if expressed excluding crystal water, CuSO ₄ , Cu (NO ₃ ) ₂ , Cu (OAc) ₂ , Cu (CH ₃ CH ₂ COO) ₂ , Cu (HCOO) ₂ , CuCO ₃ , CuCl _{3 2} , Cu ₂ O, C ₅ H ₇ CuO _{2 and the} like. Further, basic salts obtained by heating the above salts or exposing them to a basic atmosphere, such as Cu (OAc) ₂ .CuO, Cu (OAc) ₂ .2CuO, Cu ₂ Cl (OH) _3, etc. Most preferably, it can be used. These basic salts may be prepared within the reaction system, or those prepared separately outside the reaction system may be used. Further, a general method can be applied in which ammonia or an amine compound is added to form a complex to ensure solubility and then used for the reduction.

  These copper ion compounds are dissolved or mixed in a medium in which the thioether-containing organic compound (A) is previously dissolved or dispersed. The medium that can be used at this time depends on the structure of the organic compound (A) to be used, but when a complex is prepared using the polyethylene glycol-based organic compound (A), water, ethanol, acetone , Ethylene glycol, diethylene glycol, glycerin and mixtures thereof are preferably used, and water-ethylene glycol mixtures are particularly preferred. On the other hand, when the polypropylene glycol organic compound (A) is used, glyme solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, butyl diethylene glycol acetate and the like can be used.

  The concentration of the thioether-containing organic compound (A) in various media is preferably adjusted to a range of 0.3 to 10% by mass from the viewpoint of easy control of the subsequent reduction reaction.

  The divalent copper ion compound is added to the medium prepared above in a lump or dividedly and mixed. In the case of using a medium that is difficult to dissolve, a method in which the medium is dissolved in a small amount of a good solvent in advance and then added to the medium may be used.

  The proportion of the thioether-containing organic compound (A) and the copper ion compound to be mixed is preferably appropriately selected according to the protective ability of the thioether-containing organic compound (A) in the reaction medium. It is preferably prepared in the range of 1 mmol to 30 mmol (about 2 to 60 g when a polymer having a molecular weight of 2000 is used) as the thioether-containing organic compound (A) per 1 mol of the compound, and particularly preferably in the range of 5 to 30 mmol.

  Subsequently, copper ions are reduced using various reducing agents. As reducing agents, hydrazine compounds, hydroxylamine and its derivatives, metal hydrides, phosphinates, aldehydes, enediols, hydroxyketones, etc., promote the copper reduction reaction at temperatures from ice-cold temperature to 80 ° C or lower. It is preferable that the compound can be a copper mirror or a complex with less precipitate formation.

  Specifically, it is a strong reducing agent such as hydrazine hydrate, asymmetric dimethylhydrazine, aqueous hydroxylamine, sodium borohydride and the like. Since these have the ability to reduce the copper compound to zero valence, the divalent and monovalent copper compounds are reduced copper and are suitable for producing a composite of an organic compound and nano-copper particles. In addition, when obtaining nano copper (I) oxide particles, hydrazine hydrate, asymmetric dimethylhydrazine, or an aqueous hydroxylamine solution is slowly added after the addition equivalent is suppressed to about 1 / 4-fold mole. Alternatively, partial reduction is performed using ascorbic acid, acetaldehyde, hydroxyacetone, N, N-diethylhydroxylamine or the like. These reducing agents may be used alone or in combination.

  Conditions suitable for the reduction reaction vary depending on the copper compound used as a raw material, the type of reducing agent, the presence or absence of complexation, the medium, and the type of the thioether-containing organic compound (A). For example, when copper (II) acetate is reduced with sodium borohydride in an aqueous system, zero-valent nano copper particles can be prepared even at a temperature of about ice cooling. On the other hand, when hydrazine hydrate is used, the reaction is slow at room temperature, and a smooth reduction reaction occurs only after heating to about 60 ° C. Further, when complexed with ammonia, the redox potential of the complex ion becomes more noble, so that a higher temperature of about 20 ° C. is required. In determining the reaction conditions, monitoring is essential. The color change of the reaction system is important information, but the completion of the reaction can be detected by the disappearance of the color of the ammine copper ion generated by adding concentrated aqueous ammonia to the reaction solution or the ultrafiltration filtrate of the reaction solution. . Further, according to a copper ion test paper (Merck Quant 1.10003, Merck), a semi-quantitative reaction rate can be known. The reduction reaction is carried out until the completion of the reaction while performing such monitoring, but when copper acetate is reduced in an ethylene glycol / water system, a reaction time of about 2 hours at 60 ° C. is required. When the reduction reaction is thus completed, a reaction mixture containing a composite of an organic compound and nanocopper particles or a composite of an organic compound and nanocopper (I) oxide particles is obtained.

[Method for producing dispersion]
After the reduction reaction, a step of removing a copper compound residue, a reducing reagent residue, an excess thioether-containing organic compound (A) and the like is provided as necessary. In particular, if there is a large amount of the excess thioether-containing organic compound (A), there is a possibility that the nanocopper oxide (I) particles contained in the composite or the fusion between the nanocopper particles may be inhibited. When used as a conductive material or the like, a purification step excluding these is essential. For the purification of the complex, reprecipitation, centrifugal sedimentation or ultrafiltration can be applied, and the reaction mixture containing the resulting complex is washed with a washing solvent such as water, ethanol, acetone and a mixture thereof. The aforementioned impurities can be washed away. In particular, the purification of nano copper (I) oxide particles is easy to perform centrifugal sedimentation because the amount of reducing agent as a complexing agent is smaller than that of a reaction mixture containing a complex with nano copper particles.

  In the final stage of purification, instead of adding a washing solvent to the composite, a solvent that is suitable for the purpose of use is added and the medium is exchanged to obtain a dispersion in which the composite is dispersed in the medium selected according to the purpose. Can be prepared. For example, when water, ethanol and a mixture thereof are added, a dispersion that can be easily dried is obtained, which is suitable as a conductive material.

  In addition, after substituting with water or ethanol, water such as toluene, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, etc., a solvent having a boiling point higher than ethanol is added, followed by distilling off the water or ethanol to obtain a nonpolar solvent It can also be a dispersion. In this case, application to an inkjet printing method or the like can be achieved.

  The concentration of the dispersion can be variously prepared depending on the purpose of use, and it is required to be about 5 to 40% by mass for general coating and about 20 to 80% by mass for inkjet printing. What is necessary is just to adjust and adjust the addition amount of to the density | concentration. The composite dispersion prepared in this way is stable for 3 months regardless of the preparation concentration if stored in a closed container.

[Copper (I) oxide film, copper film production method]
When the obtained dispersion of the composite is applied to a substrate with a bar coater (No. 8) or the like and dried in an inert gas or air, a stable film is formed. The copper (I) oxide film was heated at 300 ° C. for 30 minutes in a 3% hydrogen mixed argon gas atmosphere. The copper film was heated in an inert gas atmosphere at 300 ° C. for 30 minutes or in a 3% hydrogen mixed argon gas atmosphere at 250 ° C. for 30 minutes, and then measured for resistivity and film thickness to evaluate the conductivity of the thin film. Thus, evaluation as a conductive material was performed.

  As the reducing atmosphere, hydrogen, alcohol vapor such as carbon monoxide, ethylene glycol, glycerin, and a mixture thereof can be used. In the case of using alcohol vapor, heating at about 250 to 300 ° C. is required, so that hydrogen and carbon monoxide are more preferable because the heating temperature is slightly lower.

  The substrate is not particularly limited as long as it can withstand the firing temperature, but glass and polyimide film can be used for this purpose.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass.

Measurement of ¹ H-NMR About 20 mg of the compound to be measured was dissolved in about 0.8 mL of 0.03% tetramethylsilane-containing deuterated chloroform, and this was put into a glass NMR measurement sample tube with an outer diameter of 5 mm, and JEOL JNM-LA300 A ¹ H-NMR spectrum was obtained by a type nuclear magnetic resonance absorption spectrum measuring apparatus. The chemical shift value δ was expressed using tetramethylsilane as a reference substance.

Measurement of UV-Vis Absorption Spectra Add about 1 mL of the dispersion of ethylene glycol to about 10 mL of ethylene glycol and shake, and immediately use an MV-2000 type photodiode array type UV-Vis absorption spectrum measuring device manufactured by JASCO Corporation. The ultraviolet-visible absorption spectrum was measured by sweeping from 400 nm to 800 nm in 0.1 second.

Measurement of electrical resistivity of copper thin film About the obtained film, surface resistivity (Ω / □) was measured using a Loresta-GP MCP-T610 type low resistivity meter (manufactured by Mitsubishi Chemical Corporation) and JIS K7194 “Conductive plastic” ”Resistivity test by 4-probe method”. The volume resistivity (Ωcm) was calculated from the following equation from the thin film thickness (cm) and the surface resistivity (Ω / □).

Volume resistivity (Ωcm) = Surface resistivity (Ω / □) × Thickness (cm)
The thickness of the film was measured using a 1LM15 scanning laser microscope (manufactured by Lasertec Corporation).

Measurement of particle size and particle size distribution Transmission electron microscope (TEM) observation Dilute a small amount of dispersion with purified water and immediately drop one drop onto a copper grid with a collodion film for electron microscope observation. This is JEM-2200FS type. Microscopic observation was performed using a transmission electron microscope (acceleration voltage 200 kV, manufactured by JEOL Ltd.), and the particle diameter was measured from the obtained photographic image.

Particle size distribution measurement by dynamic light scattering method A part of the dispersion was diluted with ethylene glycol, and the particle size distribution and average particle size were measured with an FPAR-1000 type concentrated particle size analyzer (Otsuka Electronics Co., Ltd.). . At this time, the measurement was performed at 25 ° C., and the medium was analyzed with a refractive index of 1.4306 and a viscosity of 17.4 cP.

Wide-angle X-ray diffraction method Dispersion: The dispersion was filled in a liquid sample holder, and the intensity of the diffracted X-ray with respect to the diffraction angle (2θ) was immediately measured using RINT TTR2 (50 kv, 300 mA, manufactured by Rigaku Corporation).

  Copper film: A glass slide with a copper film is cut to an appropriate size and placed on a sample stage. Immediately using RINT TTR2 (50 kv, 300 mA, manufactured by Rigaku Corporation), the intensity of diffracted X-rays with respect to the diffraction angle (2θ) is measured. Measured and recorded.

Content of copper / copper (I) oxide by thermal analysis (thermogravimetric analysis (TG / DTA method)) About 1 mL of the obtained dispersion was placed in a glass sample bottle, heated and concentrated in a nitrogen stream on warm water, and the residue further increased to 40 A dried product was obtained by vacuum drying at 8 ° C. for 8 hours, and approximately 5 mg of this dried product was precisely measured on an aluminum pan for thermogravimetric analysis, and an EXSTAR TG / DTA6300 type differential thermogravimetric analyzer (manufactured by Seiko Instruments Inc.). ) And heated at a rate of 10 ° C. per minute from room temperature to 500 ° C. under a nitrogen stream, and the weight loss rate with heating was measured.The content of copper or copper (I) oxide was as follows: Calculated.

  Content rate (%) = 100-weight reduction rate (%)

  Synthesis Example 1 Polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 2000)

  To 1000 g of dehydrated toluene, potassium t-butoxide (100.8 g, 0.8983 mol) was added and stirred. To this mixture was added a toluene (2000 g) solution of polyethylene glycol monomethyl ether (molecular weight 2000, 600 g) at room temperature. It was added dropwise over time. After stirring for 2 hours at room temperature, the temperature was raised to 40 ° C. and stirring was continued for 2 hours. Epichlorohydrin (168 g, 1.82 mol) was added dropwise to the mixture at the same temperature, and the mixture was stirred at 40 ° C. for 5.5 hours. The reaction mixture was filtered, and the filtrate was concentrated. The residue obtained was dissolved again by adding chloroform, and this was washed 5 times with water. The chloroform layer was decolorized by adding dry alumina, the alumina was filtered, and the filtrate was concentrated. The concentrated residue was purified by reprecipitation with toluene / n-hexane, and the resulting solid was collected and dried under reduced pressure to obtain 507.0 g of the title compound (yield 82%).

¹ H-NMR (deuterated chloroform): δ = 3.9-3.4 (m, polyethylene glycol chain, etc.), 3.43 (dd, 1H, J = 6.0, 5.7 Hz, -oxirane ring adjacent methylene One of hydrogen), 3.38 (s, 3H, PEG terminal methoxy group), 3.16 (m, 1H, oxirane ring methine hydrogen), 2.79 (m, 1H, oxirane ring terminal methylene hydrogen), 2.61 (m, 1H, oxirane ring terminal methylene hydrogen).

  Synthesis Example 2 Polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400)

  96 g of the title compound was obtained by operating in the same manner as in Synthesis Example 1 except that polyethylene glycol monomethyl ether (molecular weight: 400, 90 g) was used instead of polyethylene glycol monomethyl ether (molecular weight: 2000, 600 g) of Synthesis Example 1. 94%).

¹ H-NMR (deuterated chloroform): δ = 3.9-3.4 (m, polyethylene glycol chain, etc.), 3.55 (dd, 1H, J = 6.0, 5.7 Hz, oxirane ring adjacent methylene hydrogen 1), 3.38 (s, 3H, PEG terminal methoxy group), 3.17 (m, 1H, oxirane ring methine hydrogen), 2.79 (m, 1H, oxirane ring terminal methylene hydrogen), 2 61 (m, 1H, oxirane ring terminal methylene hydrogen).

Synthesis Example 3 Thioether-containing organic compound (A-1)
Ethylene bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylpropionate)
(Ring-opening addition compound of polyethylene glycol methyl glycidyl ether (polyethylene glycol chain molecular weight 2000) with ethylene glycol bis (mercaptopropionate))

To the polyethylene glycol methyl glycidyl ether (molecular weight of methoxypolyethylene glycol 2000, 5.01 g) obtained in Synthesis Example 1, ethylene glycol bis (mercaptopropionate) (325 mg, 1.23 mmol) and 1 mol / L tetrabutylammonium After adding a fluoride / tetrahydrofuran solution (121 μL, 0.12 mmol), the temperature was raised, and the mixture was stirred at 70 to 75 ° C. for 1 hour. After cooling, 50 mL of water and 50 mL of ethyl acetate were added to this mixture and stirred well, followed by liquid separation for standing. Thereafter, the aqueous layer was further washed twice with ethyl acetate (50 mL). When sodium sulfate was added to the aqueous layer, an oily substance was precipitated, and this was extracted with methylene chloride (50 mL × 3 times). The methylene chloride layer was collected, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain 4.29 g of the title thioether-containing organic compound (A-1) (yield: about 81%). ^{From 1} H-NMR, the purity required no special purification.

¹ H-NMR (deuterated chloroform): δ = 4.32 (t, 4H, ester adjacent ethylene group), 3.9-3.4 (m, polyethylene glycol chain, etc.), 3.38 (s, 6H, PEG Terminal methoxy group), 2.83 (m, 4H, thiol compound side S adjacent methylene group), 2.66 (m, 8H, polyether compound side S adjacent methylene group, ester carbonyl group α-position methylene group).

Synthesis Example 4 Thioether-containing organic compound (A-2)
Ethylene = bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl acetate)
(Ring-opening addition compound of polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400) with ethylene glycol bis (mercaptoacetate))

Polyethylene glycol methyl glycidyl ether (molecular weight 400, 5.02 g of methoxypolyethylene glycol) obtained in Synthesis Example 2 was added to bis (mercaptoacetic acid) ethylene glycol (1.11 g, 5.30 mmol) and 1 mol / L tetrabutylammonium fluoride. A solution of tetrahydrofuran / tetrahydrofuran (0.53 mL, 0.53 mmol) was added, and the mixture was stirred at room temperature for 1 hour. To this mixture, 50 mL of water and 50 mL of ethyl acetate were added and stirred well, followed by liquid separation for standing. Thereafter, the aqueous layer was further washed twice with ethyl acetate (50 mL). When sodium sulfate was added to the aqueous layer, an oily substance was precipitated, and this was extracted with methylene chloride (50 mL × 3 times). The methylene chloride layer was collected, dried over anhydrous sodium sulfate, and concentrated to dryness to obtain 5.35 g of the title thioether-containing organic compound (A-2) (yield: about 87%). ^{From 1} H-NMR, the purity required no special purification.

¹ H-NMR (deuterated chloroform): δ = 4.33 (t, 4H, ester adjacent ethylene group), 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.38 (s, 6H, PEG Terminal methoxy group), 3.33 (s, 4H, thiol compound side S adjacent methylene group), 2.75 (m, 4H, polyether compound side S adjacent methylene group, etc.).

Synthesis Example 5 Thioether-containing organic compound (A-3)
Ethylene bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylpropionate)
(Ring-opening addition compound of polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400) with ethylene glycol bis (mercaptopropionic acid))

  Instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, ethylene glycol = bis (mercaptopropionate) (1.41 g, 5.61 mmol) was used, and the others were synthesis examples. In the same manner as in No. 4, 5.44 g of the title thioether-containing organic compound (A-3) was obtained (yield: about 87%).

¹ H-NMR (deuterated chloroform): δ = 4.27 (t, 4H, ester adjacent ethylene group), 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.35 (s, 6H, PEG Terminal methoxy group), 2.81 (m, 4H, thiol compound side S adjacent methylene group), 2.63 (m, 8H, polyether compound side S adjacent methylene group, ester carbonyl group α-position methylene group, etc.).

Synthesis Example 6 Thioether-containing organic compound (A-4)
Tetramethylene bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl acetate)
(Ring-opening addition compound of 1,4-butanediol = bis (mercaptoacetate) of polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400))

  Instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, 1,4-butanediol bis (mercaptotate) (1.32 g, 5.41 mmol) was used, and the others were synthesized. When carried out in the same manner as in Example 4, 5.56 g of the title thioether-containing organic compound (A-4) was obtained (yield: about 89%).

¹ H-NMR (deuterated chloroform): δ = 4.14 (t, 4H, ester adjacent methylene group), 4.0-3.5 (m, polyethylene glycol chain, etc.), 3.36 (s, 6H, PEG Terminal methoxy group), 3.29 (s, 4H, thiol compound side S adjacent methylene group), 2.73 (m, 4H, polyether compound side S adjacent methylene group), 1.72 (m, 4H, ester oxygen) β-position methylene group).

Synthesis Example 7 Thioether-containing organic compound (A-5)
Tetramethylene bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylpropionate)
(Ring-opening addition compound of 1,4-butanediol = bis (mercaptopropionate) of polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400))

  1,4-butanediol = bis (mercaptopropionic acid) ester (1.51 g, 5.38 mmol) instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, and others Was carried out in the same manner as in Synthesis Example 4, and 5.81 g of the title thioether-containing organic compound (A-5) was obtained (yield: about 90%).

¹ H-NMR (deuterated chloroform): δ = 4.11 (t, 4H, ester adjacent methylene group), 3.7-3.5 (m, polyethylene glycol chain, etc.), 3.35 (s, 6H, PEG Terminal methoxy group), 2.81 (m, 4H, thiol compound side S adjacent methylene group), 2.62 (m, 8H, polyether compound side S adjacent methylene group, ester carbonyl group α-position methylene group), 1. 69 (m, 4H, ester oxygen β-position methylene group).

Synthesis Example 8 Thioether-containing organic compound (A-6)
2-ethyl-2- (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylacetoxymethyl) propane-1,3-diyl bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl Acetate)
(Ring-opening addition compound of polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400) with trimethylolpropane = tris (mercaptoacetate))

  Instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, trimethylolpropane = tris (mercaptoacetate) (1.12 g, 2.95 mmol) was used. When conducted in the same manner as in No. 4, 5.33 g of the title thioether-containing organic compound (A-6) was obtained (yield: about 85%).

¹ H-NMR (deuterated chloroform): δ = 4.10 (s, 6H, ester adjacent methylene group), 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.37 (s, 9H, PEG Terminal methoxy group), 3.33 (s, 6H, thiol compound side S adjacent methylene group), 2.75 (m, 6H, polyether compound side S adjacent methylene group), 1.51 (q, 2H, terminal ethyl) Methylene group), 0.91 (t, 3H, terminal ethylmethyl group).

Synthesis Example 9 Thioether-containing organic compound (A-7)
2-ethyl-2- (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylpropanoyloxymethyl) propane-1,3-diyl-bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxy Propylsulfanylpropionate)
(Ring-Opening Addition Compound of Polyethylene Glycol Methyl Glycidyl Ether (Polyethylene Glycol Chain Molecular Weight 400) with Trimethylolpropane = Tris (Mercaptopropionate))

  Instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, trimethylolpropane = tris (mercaptopropionate) (1.66 g, 4.03 mmol) was used. When carried out in the same manner as in Example 4, 5.88 g of the title thioether-containing organic compound (A-7) was obtained (yield: about 92%).

¹ H-NMR (deuterated chloroform): δ = 4.06 (s, 4H, ester adjacent ethylene group), 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.37 (s, 9H, PEG Terminal methoxy group), 2.82 (t, 6H, thiol compound side S adjacent methylene group), 2.66 (m, 12H, polyether compound side S adjacent methylene group, ester carbonyl group α-position methylene group), 1. 49 (q, 2H, terminal ethylmethylene group), 0.89 (t, 3H, terminal ethylmethyl group).

Synthesis Example 10 Thioether-containing organic compound (A-8)
2,2-bis ((3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylacetoxymethyl) propane-1,3-diyl bis ((3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropyl Sulfanyl acetate)
(Ring-opening addition compound of polyethylene glycol methylglycidyl ether (molecular weight of polyethylene glycol chain 400) with pentaerythritol = tetrakis (mercaptoacetate))

  Instead of ethylene glycol = bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, pentaerythritol = tetrakis (mercaptoacetate) (1.21 g, 2.79 mmol) was used. In the same manner as above, 5.33 g of the title thioether-containing organic compound (A-8) was obtained (yield: about 86%).

¹ H-NMR (deuterated chloroform): δ = 4.21 (s, 8H, ester adjacent methylene group), 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.36 (s, 12H, PEG Terminal methoxy group), 3.35 (s, 8H, thiol compound side S adjacent methylene group), 2.73 (m, 8H, polyether compound side S adjacent methylene group).

Synthesis Example 11 Thioether-containing organic compound (A-9)
2,2-bis ((3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylpropanoyloxymethyl) propane-1,3-diyl bis ((3- (methoxy (polyethoxy) ethoxy) -2- Hydroxypropylsulfanylpropionate)
Ring Opening Addition Compound of Polyethylene Glycol Methyl Glycidyl Ether (Molecular Weight of Polyethylene Glycol Chain 400) with Pentaerythritol = Tetrakis (Mercaptopropionate)

  Instead of ethylene glycol = bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, pentaerythritol = tetrakis (mercaptopropionate) (1.37 g, 2.68 mmol) was used. In the same manner as in Example 4, 5.61 g of the title thioether-containing organic compound (A-9) was obtained (yield: about 89%).

¹ H-NMR (deuterated chloroform): δ = 4.17 (s, 4H, ester adjacent ethylene group), 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.35 (s, 12H, PEG Terminal methoxy group), 2.82 (t, 8H, thiol compound side S adjacent methylene group), 2.66 (m, 16H, polyether compound side S adjacent methylene group, ester carbonyl group α-position methylene group).

Synthesis Example 12 Thioether-containing organic compound (A-10)
1,2-bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl) ethane (polyethylene glycol methylglycidyl ether (polyethylene glycol chain molecular weight 400) ring-opening addition compound with 1,2-ethanedithiol)

  Instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, 1,2-ethanedithiol (0.488 g, 5.18 mmol) was used, and the others were the same as in Synthesis Example 4. Then, 4.80 g of the title thioether-containing organic compound (A-10) was obtained (yield: about 87%).

¹ H-NMR (deuterated chloroform): δ = 3.9-3.4 (m, polyethylene glycol chain, etc.), 3.35 (s, 6H, PEG terminal methoxy group), 2.78 (t, 4H, thiol) Compound side S adjacent methylene group), 2.66 (m, 4H, polyether compound side S adjacent methylene group).

Synthesis Example 13 Thioether-containing organic compound (A-11)
1,9-bis (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl) -3,7-dithianonane (polyethylene glycol methyl glycidyl ether (polyethylene glycol chain molecular weight 400) 3,7-dithia-1 , 9-nonanedithiol ring-opening addition compound)

  3,7-dithia-1,9-nonanedithiol (1.39 g, 5.90 mmol) instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, When carried out in the same manner as in Synthesis Example 4, 4.58 g of the title thioether-containing organic compound (A-11) was obtained (yield: about 92%).

¹ H-NMR (deuterated chloroform): δ = 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.36 (s, 6H, PEG terminal methoxy group), 2.76-2.59 (m , 12H, thiol compound side S adjacent methylene group), 1.82 (m, 2H, thiol compound Sβ methylene group).

Synthesis Example 14 Thioether-containing organic compound (A-12)
Tris ((3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanylpropanoyloxy) ethyl) = isocyanurate

  Polyethylene glycol methyl glycidyl ether (polyethylene glycol chain molecular weight 400) (2.4 g, 5 mmol), tris ((3-mercaptopropionyloxy) ethyl) isocyanurate (0.8 g, 1.5 moml) obtained in Synthesis Example 2 And 1 mol / L tetrabutylammonium fluoride / tetrahydrofuran solution (500 μL, 0.5 mmol) were mixed and stirred at 70 to 75 ° C. for 5 hours. The post-treatment was carried out in the same manner as in Example 3. 50 mL of heptane was added to the resulting concentrated dry solid and mixed well, and the remaining oil was recovered by decantation. This operation was repeated two more times, and the residue was dried under reduced pressure to give the title thioether-containing organic compound (A-12) (1.3 g, yield 58%).

¹ H-NMR (deuterated chloroform): δ = 3.9-3.5 (m, polyethylene glycol chain, N-ethylene group), 3.54 (t, 6H, O-ethylene group), 3.38 (terminal) Methoxy group), 2.8-2.6 (m, thiol compound side S adjacent methylene group and thiol compound Sβ methylene group).

Comparative Synthesis Example 1 Thioether-containing organic compound (A-13)
Methyl = 3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl) propionate (ring-opening addition compound of polyethylene glycol methyl glycidyl ether (molecular weight of polyethylene glycol chain 400) with methyl 3-mercaptopropionate)

  Instead of ethylene glycol bis (mercaptoacetate) (1.11 g, 5.30 mmol) in Synthesis Example 4, 3-mercaptopropion was used with respect to polyethylene glycol methyl glycidyl ether (molecular weight of methoxypolyethylene glycol 400, 97.2 g). 115.0 g of the title thioether-containing organic compound (A-13) was obtained in the same manner as in Synthesis Example 4 except that methyl acid (22.5 ml, 207.5 mmol) was used (yield: about 94%). .

¹ H-NMR (deuterated chloroform): δ = 3.9-3.5 (m, polyethylene glycol chain, etc.), 3.70 (s, 3H, ester methyl group), 3.36 (s, 3H, PEG end Methoxy group), 2.84 (t, 2H, J = 7.2 Hz, thiol compound side S adjacent methylene group), 2.76-2.59 (m, 4H, polyether compound side S adjacent methylene group, ester carbonyl Group α-position methylene group).

Comparative Synthesis Example 2 Comparative methacrylate copolymer 70 parts of methyl ethyl ketone (hereinafter referred to as MEK) is kept at 80 ° C. in a nitrogen stream, and while stirring, 10 parts of methacrylic acid, 5 parts of benzyl methacrylate, methoxypolyethylene glycol methacrylate; 85 parts of molecular weight 1000, thioglycol A mixture comprising 2 parts of acid, 80 parts of MEK, and 4 parts of a polymerization initiator (“Perbutyl (registered trademark) O” manufactured by NOF Corporation) was added dropwise over 2 hours. After completion of the dropwise addition, 2 parts of “Perbutyl (registered trademark) O” was added and stirred at 80 ° C. for 22 hours. Water was added to the resulting reaction mixture and the solvent was removed under reduced pressure, and the nonvolatile content was adjusted with water (41% nonvolatile content). The obtained copolymer had a weight average molecular weight of 9800 (gel permeation chromatography) and an acid value of 76.5 mgKOH / g.

Example 1. Synthesis of complex of organic compound and nano copper particles (Preparation of complex of organic compound and nano copper particles)
To a mixture of copper (II) acetate monohydrate (3.00 g, 15.0 mmol), the thioether-containing organic compound (A-1) (0.454 g) obtained in Synthesis Example 3 and ethylene glycol (10 mL). The mixture was heated while blowing nitrogen at a flow rate of 200 mL / min, and deaerated by aeration and stirring at 125 ° C. for 2 hours. The mixture was returned to room temperature, and a solution of hydrazine hydrate (1.50 g, 30.0 mmol) diluted with 7 mL of water was slowly added dropwise using a syringe pump. At this time, caution was required because foaming was vigorously caused by the generation of nitrogen accompanying the initial reduction reaction. About 1/4 amount was dripped slowly over 2 hours, and the dripping of one end was stopped here. After stirring for 2 hours and confirming that foaming subsided, the remaining amount was further dropped over 1 hour. The resulting brown solution was heated to 60 ° C. and further stirred for 2 hours to complete the reduction reaction. At this time, a small amount of the black reaction solution was collected over time, diluted with degassed purified water added with 0.1% hydrazine hydrate, and an ultraviolet-visible absorption spectrum was immediately obtained. A peak was observed at 570 to 580 nm. Observed. This is an absorption derived from the plasmon resonance absorption exhibited by nano-sized reduced copper, and this confirmed the formation of nano-copper particles (FIG. 1).

(Preparation of aqueous dispersion)
Subsequently, this reaction mixture is circulated in a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm ² , molecular weight cut off 150,000) manufactured by Daisen Membrane Systems Co., Ltd. While adding 0.1% hydrazine hydrate aqueous solution, it was circulated until the filtrate from the ultrafiltration module was about 500 mL and purified. When the supply of the 0.1% hydrazine hydrate aqueous solution was stopped and concentrated as it was by an ultrafiltration method, an aqueous dispersion of a composite of 2.85 g of an organic compound and nano copper particles was obtained. The non-volatile content in the dispersion was 18% and the metal content in the non-volatile was 86%. Wide-angle X-ray diffraction of the dispersion confirmed that it was reduced copper (FIG. 2).

Examples 2-12 (Aqueous dispersion of complex of organic compound and nano copper particles)
It carried out similarly about the other thioether containing organic compound A-2-12, and the composite_body | complex of an organic compound and nano copper particle was prepared. When a part of the reaction mixture was taken and the UV-visible absorption spectrum was measured, it was confirmed that the absorption maximum derived from the surface plasmon resonance of the nanocopper particles was observed between 570 and 600 nm when any compound was used. did.

(Measurement of particle size of dispersion)
When the copper particles obtained in Example 3 (when the compound A-3 obtained in Synthesis Example 3 was used) were observed with an electron microscope, they were found to be fine particles having an average particle diameter of 7 nm (FIG. 3). Moreover, the average particle diameter measured by the dynamic light scattering method at this time was 106 nm. Other examples are summarized in Table 1 below.

Example 13 Synthesis of Complex of Organic Compound and Nano Copper (I) Oxide Particles Copper (II) acetate monohydrate (2.00 g, 10.0 mmol), thioether-containing organic compound A-1 obtained in Synthesis Example 3 above ( 0.30 g) and ethylene glycol (6.6 mL) was added a solution of N, N-diethylhydroxylamine (85%, 1.15 g, 11.0 mmol) diluted with 4.6 mL of water. After stirring at room temperature for 30 minutes, it was transferred to a centrifuge tube made of polypropylene, and an acceleration of 13000 G was applied for 20 minutes with a centrifuge to cause centrifugal sedimentation. The supernatant was discarded, and water degassed by bubbling with argon gas for 30 minutes was added to the sediment to adjust the nonvolatile content to 30%. The content of nano copper (I) oxide in the nonvolatile material was 85%. When the sediment was observed with an electron microscope, it was an aggregate of fine particles having an average particle diameter of about 5 nm (FIG. 5).

Examples 14 to 24 (Aqueous dispersions of composites of organic compounds and nano copper (I) oxide particles)
In place of the thioether-containing organic compound A-1 in Example 13, the thioether-containing organic compounds A-2 to A-12 were similarly processed to prepare an aqueous dispersion of nano copper (I) oxide. The particle diameter of the obtained copper (I) oxide is summarized in Table 2.

Comparative Example 1
In Example 1, a reduction reaction was performed in the same manner as in Example 1 except that the thioether-containing organic compound A-13 synthesized in Comparative Synthesis Example 1 was used instead of the thioether-containing organic compound A-1. When a part of the reaction mixture at the time of partial reduction was taken and the primary particle diameter of copper (I) oxide was measured by TEM, the average particle diameter was 8 nm.

  When a part of the reaction mixture was taken and the ultraviolet-visible absorption spectrum was measured, it was confirmed that the absorption maximum derived from the surface plasmon resonance of the nanocopper particles was observed between 570 and 590 nm. Further, when the obtained copper particles were observed with an electron microscope, there were fine particles having a particle diameter of 5 nm, but particles of about 20 nm were also mixed, the average was 15 nm, and the shape was irregular (FIG. 4).

Comparative Example 2
In Example 1, a reduction reaction was performed in the same manner as in Example 1 except that the comparative methacrylate copolymer synthesized in the comparative synthesis example was used instead of the thioether-containing organic compound A-1. A part of the mixture after the reaction was taken in the same manner as in Example 1, and the ultraviolet-visible absorption spectrum was measured. As a result, it was confirmed that there was no peak observed between 570 and 600 nm.

Application example 1. Preparation of copper thin film and measurement of specific resistance of thin film In an argon-filled glove bag, the aqueous dispersion of the composite obtained in Example 5 was roughly removed from one end of a clean glass slide of 7.6 × 2.6 cm. About 0.2 mL was dropped in the vicinity of 0.5 cm, developed using a bar coater (No. 8) to form a thin film, and dried as it was under an argon atmosphere. When the dried glass slide was confirmed by wide-angle X-ray diffraction, only copper was detected even after 6 days from drying (FIG. 6). 3% hydrogen-containing argon gas was flowed through this copper film at a flow rate of 0.5 L / min. And heated at 250 ° C. for 30 minutes. After standing to cool, the electrical resistivity was measured and found to be 1.9 × 10 ⁻⁴ Ω · cm.

Comparative application example 1
The composite dispersion obtained in Comparative Example 1 was also similarly applied on a slide glass and dried with nitrogen gas. However, copper (I) oxide was slightly detected the next day after drying, and the thioether-containing organic compound was detected. It was confirmed that the ability as a colloidal copper protective agent was increased by using polythioether (FIG. 7). Moreover, when this dry glass slide was placed on a hot plate and heated at 250 ° C. for 30 minutes in an atmosphere in which 3% hydrogen-containing argon gas was flowed at a flow rate of 0.5 L / min, 2.4 × 10 ⁻⁴ Ω -It was cm.

Application Example 2 Preparation of copper thin film using copper (I) oxide nanoparticle composite and measurement of specific resistance of thin film The aqueous dispersion of nano copper oxide composite obtained in Example 13 above was cleaned at 7.6 × 2.6 cm. In an atmosphere where about 0.2 mL was dropped from one end of a simple slide glass to about 0.5 cm and developed into a thin film using a bar coater (No. 8), and nitrogen gas was flowed at a flow rate of 0.2 L / min. Dried. When the dried slide glass was confirmed by the wide-angle X-ray diffraction method, only copper (I) oxide was detected (FIG. 8).

  A copper (I) oxide thin film was prepared on a slide glass by the same method as described above, using the aqueous dispersion of the nano copper (I) complex obtained in the above example. The dried glass slide was placed in a furnace substituted with nitrogen gas, and heated at 300 ° C. for 30 minutes in an atmosphere in which 3% hydrogen-containing argon gas was flowed at a flow rate of 3 L / min. After standing to cool, the electrical resistivity was measured, and the results are summarized in a table. Moreover, after carrying out a specific resistance measurement, the production | generation of copper has been confirmed with the wide-angle X-ray-diffraction method by baking the slide glass (FIG. 9).

  The dispersion liquid of the composite of nano copper particles obtained in Example 3 was stored in a refrigerator in a polypropylene sealed container, and the appearance, ultraviolet-visible absorption spectrum, dynamic light scattering method and electron microscope particle after 3 months passed When the diameter distribution was measured, there was no change over March (Table 3).

Claims (10)

The following general formula (1) or general formula (2)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—] _m Y (1)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—R′—] _l Z (2)
[X in the formula (1) and (2) is an alkyl group of _C 1 -C _8, R is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, R May be the same or different for each repeating unit, and Y is a divalent to tetravalent group in which a carbon atom is directly bonded to a sulfur atom, and is a C ₁ -C ₄ saturated carbonization Two or three hydrogen groups or C ₁ -C ₄ saturated hydrocarbon groups are connected by —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). It is a group. M in Formula (1) is an integer of 2-4. R ′ in the formula (2) is a C _{2 to} C ₅ alkylcarbonyloxy group, Z is a divalent to hexavalent group in which a carbon atom is directly bonded to a sulfur atom, and C _{2 to} C ₆ saturated hydrocarbon groups and C ₂ -C ₆ saturated hydrocarbon groups are —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). ~ 3 linked groups, or isocyanuric acid-N, N ', N "-triethylene group, and l is an integer of 2-6.]
The composite of the organic compound and nano copper particle characterized by containing the thioether containing organic compound (A) represented by these, and a nano copper particle. The following general formula (1) or general formula (2)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—] _m Y (1)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—R′—] _l Z (2)
[X in the formula (1) and (2) is an alkyl group of _C 1 -C _8, R is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, R May be the same or different for each repeating unit, and Y is a divalent to tetravalent group in which a carbon atom is directly bonded to a sulfur atom, and is a C ₁ -C ₄ saturated carbonization Two or three hydrogen groups or C ₁ -C ₄ saturated hydrocarbon groups are connected by —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). It is a group. M in Formula (1) is an integer of 2-4. R ′ in the formula (2) is a C _{2 to} C ₅ alkylcarbonyloxy group, Z is a divalent to hexavalent group in which a carbon atom is directly bonded to a sulfur atom, and C _{2 to} C ₆ saturated hydrocarbon groups and C ₂ -C ₆ saturated hydrocarbon groups are —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). ~ 3 linked groups, or isocyanuric acid-N, N ', N "-triethylene group, and l is an integer of 2-6.]
A composite of an organic compound and nano-copper oxide (I) particles, characterized in that it comprises a thioether-containing organic compound (A) represented by formula (1) and nano-copper oxide (I) particles. The complex according to claim 1 or 2, wherein the thioether-containing organic compound (A) is obtained by reacting a glycidyl group-terminated polyether compound (a1) and a thiol compound (a2). The content rate of the thioether containing organic compound (A) in the said composite_body | complex is 2-15 mass%, The composite body in any one of Claims 1-3. The composite according to any one of claims 1 to 4, wherein the composite is in the form of particles, and an average particle diameter of 100 particles observed in a transmission electron microscope image is in the range of 2 to 20 nm. The following general formula (1) or general formula (2)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—] _m Y (1)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—R′—] _l Z (2)
[X in the formula (1) and (2) is an alkyl group of _C 1 -C _8, R is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, R May be the same or different for each repeating unit, and Y is a divalent to tetravalent group in which a carbon atom is directly bonded to a sulfur atom, and is a C ₁ -C ₄ saturated carbonization Two or three hydrogen groups or C ₁ -C ₄ saturated hydrocarbon groups are connected by —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). It is a group. M in Formula (1) is an integer of 2-4. R ′ in the formula (2) is a C _{2 to} C ₅ alkylcarbonyloxy group, Z is a divalent to hexavalent group in which a carbon atom is directly bonded to a sulfur atom, and C _{2 to} C ₆ saturated hydrocarbon groups and C ₂ -C ₆ saturated hydrocarbon groups are —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). ~ 3 linked groups, or isocyanuric acid-N, N ', N "-triethylene group, and l is an integer of 2-6.]
In the presence of a thioether-containing organic compound (A) represented by
(I) mixing a divalent copper ion compound with a solvent;
(Ii) a step of reducing copper ions to zero-valent nano copper particles (B);
The manufacturing method of the composite_body | complex of the organic compound and nano copper particle | grains characterized by having. The method for producing a complex according to claim 6, wherein the reduction reaction in the step (ii) is performed using hydrazine hydrate, asymmetric dimethylhydrazine, an aqueous hydroxylamine solution or sodium borohydride. The following general formula (1) or general formula (2)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—] _m Y (1)
[X— (OCH ₂ CHR) _n —O—CH ₂ —CH (OH) —CH ₂ —S—R′—] _l Z (2)
[X in the formula (1) and (2) is an alkyl group of _C 1 -C _8, R is a hydrogen atom or a methyl radical, n is an integer indicating the number of repetitions of 2 to 100, R May be the same or different for each repeating unit, and Y is a divalent to tetravalent group in which a carbon atom is directly bonded to a sulfur atom, and is a C ₁ -C ₄ saturated carbonization Two or three hydrogen groups or C ₁ -C ₄ saturated hydrocarbon groups are connected by —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). It is a group. M in Formula (1) is an integer of 2-4. R ′ in the formula (2) is a C _{2 to} C ₅ alkylcarbonyloxy group, Z is a divalent to hexavalent group in which a carbon atom is directly bonded to a sulfur atom, and C _{2 to} C ₆ saturated hydrocarbon groups and C ₂ -C ₆ saturated hydrocarbon groups are —O—, —S— or —NHR ″ — (R ″ is a C _{1 to} C ₄ saturated hydrocarbon group). ~ 3 linked groups, or isocyanuric acid-N, N ', N "-triethylene group, and l is an integer of 2-6.]
In the presence of a thioether-containing organic compound (A) represented by
(I) mixing a divalent copper ion compound with a solvent;
(Ii ′) a step of reducing copper ions to monovalent nano-copper oxide (I) particles (C);
The manufacturing method of the composite_body | complex of the organic compound and nano copper (I) particle | grains characterized by having. The reduction reaction in the step (II ') is carried out using hydrazine hydrate, asymmetric dimethylhydrazine, aqueous hydroxylamine solution, ascorbic acid, acetaldehyde, hydroxyacetone or N, N-diethylhydroxylamine. A method for producing the composite according to 8. The said thioether containing organic compound (A) is a thing obtained by making the polyether compound (a1) and thiol compound (a2) which have a glycidyl group in the terminal react, The any one of Claims 6-9 Production method.