WO2014189024A1 - 銀粒子の製造方法 - Google Patents
銀粒子の製造方法 Download PDFInfo
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- WO2014189024A1 WO2014189024A1 PCT/JP2014/063280 JP2014063280W WO2014189024A1 WO 2014189024 A1 WO2014189024 A1 WO 2014189024A1 JP 2014063280 W JP2014063280 W JP 2014063280W WO 2014189024 A1 WO2014189024 A1 WO 2014189024A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/056—Particle size above 100 nm up to 300 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to a method for producing silver particles. Specifically, the present invention relates to a method for producing silver particles having a uniform particle size while controlling the size in producing silver particles having a particle size in the range of several tens of nm to several hundreds of nm.
- Silver (Ag) is a kind of noble metal that has long been known for use as a decorative product, but has excellent conductivity, light reflectivity, and unique properties such as catalytic action and antibacterial action. Therefore, the metal is expected to be used for various industrial applications such as electrodes / wiring materials, reflective film materials, catalysts, and antibacterial materials.
- As a utilization form of silver for these various uses there is one in which silver particles are dispersed and suspended in an appropriate solvent. For example, in forming electrodes / wirings of a wiring board mounted on an electronic component such as a semiconductor device, desired electrodes / wirings can be formed by pasting silver particles and applying and firing this metal paste.
- a generally known method for producing silver particles is a liquid phase reduction method.
- a silver compound as a precursor is dissolved in a solvent, and silver is precipitated by adding a reducing agent thereto.
- a compound called a protective agent it is usual to add a compound called a protective agent.
- the protective agent binds to the silver particles that have been reduced and deposited, and suppresses the silver particles from contacting each other, thereby preventing aggregation of the silver particles.
- the method for producing silver particles by the liquid phase reduction method can produce silver particles efficiently by adjusting the concentration of the silver compound in the solvent, the type and amount of the reducing agent, and further selecting an appropriate protective agent.
- silver particles produced by the liquid phase reduction method tend to have a relatively large particle size, and the particle size distribution tends to vary due to the concentration gradient of the reactants in the solvent.
- the thermal decomposition method of a silver complex is reported as a manufacturing method of the silver particle replaced with a liquid phase reduction method (patent document 1).
- This method basically utilizes the characteristics of a silver compound having thermal decomposability such as silver oxalate (Ag 2 C 2 0 4 ), and forms a complex between the silver compound and an organic compound serving as a protective agent. Then, this is a method of obtaining silver particles by heating as a precursor.
- an amine is added as a protective agent to silver oxalate to form a silver-amine complex, which is heated at a predetermined temperature and thermally decomposed to produce silver particles.
- this thermal decomposition method extremely fine silver fine particles of several nm to several tens of nm can be produced, and silver fine particles having a relatively uniform particle diameter can be obtained.
- the application field of silver particles tends to widen, and therefore, not only silver fine particles having a fine particle size of 10 nm or less, but also moderately small particle sizes of about several tens to several hundreds of nm depending on applications.
- silver particles In order to meet this requirement, a manufacturing method capable of controlling the particle diameter over a wide range is required for the silver particles to be manufactured.
- the conventional method for producing silver particles described above is insufficient from the viewpoint of particle size control, and only large (about several ⁇ m) silver particles can be produced by the liquid phase reduction method.
- the pyrolysis method is suitable for producing fine silver particles, but it is possible to produce silver particles with a medium size of about several tens of nanometers to several hundreds of nanometers with a targeted particle size. difficult.
- the silver particles obtained by the pyrolysis method have a uniform particle size to some extent because the particle size of the obtained particles depends on the type of the silver compound. It was difficult to adjust the particle size. For example, when a silver oxalate amine complex is used as the silver compound, although silver fine particles having a particle size of about several tens of nm are obtained, the silver particles having a larger particle size (average particle size of several tens of nm or more) Those having a uniform particle size could not be obtained.
- the present invention provides a method for producing silver particles having a uniform particle size while adjusting the particle size within a range of several tens to several hundreds of nm as a method for producing silver particles. .
- the inventors of the present invention as a method for solving the above-mentioned problems, first made a study based on a method for producing silver particles by a pyrolysis method.
- the pyrolysis method is capable of producing silver particles having a relatively uniform particle size, and is thought to be easier to adjust the particle size than the liquid phase reduction method.
- the present inventors considered the generation mechanism of silver particles by the thermal decomposition method as follows while referring to the general Lamer rule as the precipitation mechanism of monodisperse fine particles from the closed solution system.
- the silver oxalate complex coordinated with hexylamine is thermally decomposed to produce silver particles.
- silver “nucleation” begins to occur at temperatures slightly below the decomposition temperature of the complex (approximately 110 ° C.) (80-90 ° C.). .
- the complex is decomposed on the surface of the generated nucleus by the heating up to the vicinity of the decomposition temperature (90 ° C. to 110 ° C.), and “nuclear growth” occurs. At this time, “new nucleation” other than the previous nucleation also occurs. And silver particle produces
- the particle diameter of the generated silver particles varies depending on the heating rate. That is, it is considered that silver particles having a small particle size are generated by increasing the heating rate, and silver particles having a large particle size are generated when the heating rate is low.
- the heating rate is adjusted, the above-mentioned tendency is observed as a whole, but it is not easy to produce uniform silver particles having no variation in particle size distribution. This is because not only the growth of nuclei but also the generation of new nuclei occurs in the heating up to the vicinity of the decomposition temperature.
- the larger the particle size of the target silver particle the easier it is to generate new nuclei while the particle grows, and the variation in particle size distribution tends to increase, making it difficult to produce silver particles of uniform particle size. It is estimated to be.
- the present inventors considered that the deviation in the timing of the nucleation is derived from the heterogeneity in the decomposition characteristics (stability) of the complex. Then, the inventors have found that the precipitation of silver particles can be made uniform by adding a predetermined organic compound to the reaction system as an additive for promoting the homogenization of the stability of the complex.
- the present invention is a method comprising the following steps, wherein a silver-amine complex having thermal decomposability is used as a precursor, and silver particles are produced by heating a reaction system containing the precursor, Step (a): A step of producing a silver-amine complex as a precursor by mixing a thermally decomposable silver compound and an amine. (B) Step: A step of adding an organic compound represented by the following formula having an amide (carboxylic amide) as a skeleton to the reaction system. Step (c): Step of heating the reaction system Prior to the heating in step (c), the water content of the reaction system is 20 to 100 parts by weight relative to 100 parts by weight of the silver compound. .
- the present invention relates to a method for producing silver particles for heating a reaction system containing a precursor, a thermally decomposable silver-amine complex, and an organic compound having an amide (carboxylic amide) as a skeleton in the reaction system.
- the main feature is the addition.
- the silver particle manufacturing method according to the present invention including this feature will be described.
- a silver-amine complex which is a precursor of silver particles is generated.
- This silver-amine complex is thermally decomposable, and its raw material is a thermally decomposable silver compound.
- Silver cyanate, silver citrate, silver lactate and the like can be applied.
- silver oxalate (Ag 2 C 2 O 4 ) is particularly preferable.
- Silver oxalate can be decomposed at a relatively low temperature without a reducing agent to produce silver particles.
- oxalate ions released by the decomposition of silver oxalate are removed as carbon dioxide, no impurities remain in the solution.
- silver oxalate is an explosive powdery solid, water or an organic solvent (alcohol, alkane, alkene, alkyne, ketone, ether, ester, carboxylic acid, fatty acid, aromatic, amine, amide, It is preferable to use a mixture obtained by mixing a nitrile or the like as a dispersion solvent and making it wet.
- a mixture of 10 to 200 parts by weight of a dispersion solvent with respect to 100 parts by weight of silver oxalate is preferable.
- the amount of water in the reaction system is strictly defined, and when water is mixed, it is necessary to make the amount not exceed the specified amount of the present invention.
- (mono) amine having one amino group or diamine having two amino groups is applied.
- the number of alkyl groups replacing the hydrogen atom of the amino group is preferably one or two, that is, primary amine (RNH 2 ) or secondary amine (R 2 NH) is preferable.
- RNH 2 primary amine
- R 2 NH secondary amine
- at least one amino group is preferably a primary amine or a secondary amine.
- Tertiary amines tend not to form complexes with silver compounds.
- the alkyl group substituted for the amine a hydrocarbon chain is preferable, and a linear alkane (saturated hydrocarbon) is particularly preferable.
- an alkylamine having only a hydrocarbon hydrocarbon group is preferred, and a primary (mono) amine consisting of one amino group and one alkyl group is particularly preferred. .
- the total number of carbon atoms of the alkyl groups in the amine is preferably 5-10.
- the preferable range for the total number of carbon atoms of the alkyl group is defined by the amine coordinated to the silver compound, the stability of the silver-amine complex to be formed, and the decomposition temperature thereof. This is because the particle size is changed.
- the particle size variation of silver particles tends to be large when the particle size is several tens of nm to several ⁇ m.
- an amine having a total carbon number exceeding 10 is applied, the silver-amine complex is hardly thermally decomposed during synthesis, and a large amount of unreacted substances other than silver particles remain.
- preferred amines in the present invention include N, N-dimethyl-1,3-diaminopropane H 2 N (CH 2 ) 3 N (CH 3 ) 2 , 2,2-dimethylpropylamine, n-pentylamine, They are cyclohexylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine.
- the particle size of the silver particles can be controlled by selecting the type of amine. it can. According to the configuration of the present invention, for example, when hexylamine is applied, silver particles having a particle diameter of 20 to 200 nm can be produced. Further, when octylamine is applied, finer silver particles can be formed than when hexylamine is applied, and silver particles having a particle diameter of 10 to 150 nm can be produced. Moreover, the amine made to react with a silver compound in this invention can apply 2 or more types.
- intermediate stability complexes are formed for the respective amines, and silver particles having a particle size corresponding to the complex can be produced.
- silver particles having an intermediate particle size can be produced with respect to the particle size range in which both can be produced.
- the mixing ratio of the silver compound and the amine is the ratio of the number of moles of the amine compound (mol amine compound ) to the number of moles of silver ion (Ag + ) of the silver compound (mol Ag + ) (mol amine compound / mol Ag + ). It is preferable to set it to .6 or more. If the molar ratio is less than 1.6, unreacted silver compounds may remain, and sufficient silver particles cannot be produced, and the particle size distribution of the silver particles tends to vary. On the other hand, the upper limit value (the upper limit amount of amine) of the above molar ratio need not be specified, but is preferably 6 or less in consideration of the purity of silver particles.
- a silver-amine complex that is a precursor of silver particles is formed by the reaction of the silver compound and the amine.
- the organic compound represented by Chemical Formula 1 having an amide (carboxylic amide) as a skeleton is added to the reaction system thus formed (step (b)).
- this organic compound should be referred to as a homogenizing agent that homogenizes the stability of the silver-amine complex.
- the homogenizing agent is an additive that equalizes the particle size of silver particles by making the stability of the silver-amine complex in the reaction system uniform and by aligning the timing of nucleation and growth in the decomposition temperature range of the complex. . When such a homogenizing agent is added, it is possible to obtain particles having a uniform particle size even for silver particles having a large particle size (for example, 50 nm or more), which are likely to have large variations in particle size.
- the organic compound that functions as a homogenizing agent is required to have an amide (carboxylic amide) (NC—O) in its skeleton.
- R represents hydrogen, hydrocarbon, aminoalkyl or an amino group comprising a combination thereof
- R ′, R ′′ represents hydrogen or hydrocarbon.
- organic compound that is a homogenizing agent examples include urea, urea derivatives, N, N-dimethylformamide (DMF: (CH 3 ) 2 NCHO), N, N-diethylformamide (DEF: (C 2 H 5 ) 2 NCHO), N, N-dimethylacetamide (C 4 H 9 NO), N, N-dimethylpropionamide (C 5 H 11 NO), N, N-diethylacetamide (C 6 H 13 NO) Etc.
- urea derivatives include 1,3-dimethylurea (C 3 H 8 N 2 O), tetramethylurea (C 5 H 12 N 2 O), 1,3-diethylurea (C 5 H 12 N 2 O), and the like. Is mentioned.
- the addition amount of the homogenizing agent to the reaction system is the ratio of the number of moles of the homogenizing agent (mol homogenizing agent ) to the number of moles of silver ions (Ag + ) of the silver compound (mol Ag + ) (mol homogenizing agent / mol).
- Ag + is preferably 0.1 or more.
- the total addition amount is preferably 0.1 or more.
- the molar ratio is less than 0.1, it is difficult to obtain a uniform particle size of silver particles.
- the upper limit of the molar ratio (the upper limit of the homogenizing agent) is not particularly specified, but is preferably 4 or less with respect to silver of the silver compound in consideration of the purity of the silver particles.
- the homogenizing agent is preferably added as it is in the case of a liquid organic compound. Further, in the case of a solid compound such as urea, it may be added as a solid or may be added as an aqueous solution. However, when the aqueous solution is used, it is necessary to consider the water content of the reaction system.
- a predetermined range of moisture needs to be present in the reaction system in the heating step of step (c).
- the water in the reaction system acts as a buffering agent for adjusting the heating rate in the heating step for decomposing the complex.
- the complex can be decomposed to produce silver particles even if heating is performed as it is. However, if the heating at this time is not performed uniformly, there is a possibility that the particle size varies.
- water is positively interposed in the reaction system, and water is dispersed as a thermal buffer so that the temperature difference in the reaction system is mild and the particle diameters of the silver particles are uniform.
- the water content of the reaction system needs to be in the range of 20 to 100 parts by weight with respect to 100 parts by weight of the silver compound.
- the water content is less than 20 parts by weight, silver particles having a large variation in particle diameter are produced.
- the amount of water exceeds 100 parts by weight, the particle size of the silver particles tends to be coarsened, and it becomes difficult to obtain silver particles having a targeted particle size.
- the water content of this reaction system is the water content immediately before the heating process, and it is necessary to consider the amount of water added to the reaction system so far.
- the amount of water including the amount of water used at that time is taken. That is, when the water content is in the above range only by the amount originally contained in the silver compound or the homogenizing agent, it can be heated as it is without adjusting the water content of the reaction system.
- the water content is less than the lower limit (20 parts by weight), it is necessary to adjust the water content such as adding water separately.
- the reaction system in the present invention may be composed of a silver-amine complex, an organic compound serving as a homogenizing agent, and an appropriate range of moisture, and silver particles having a uniform particle size without any other additives. Can be manufactured. However, the addition of an additive that further stabilizes the complex is not excluded. Examples of the additive applicable in the present invention include oleic acid, myristic acid, palmitoleic acid, linoleic acid and the like. These additives have a ratio (mol additive / mol Ag + ) of the number of moles of additive (mol additive ) to the number of moles of silver ion (Ag + ) (mol Ag + ). It is preferable to do this.
- step (c) silver particles are precipitated by heating the reaction system (step (c)).
- the heating temperature at this time is preferably not less than the decomposition temperature of the silver-amine complex.
- the decomposition temperature of the silver-amine complex varies depending on the type of amine coordinated to the silver compound, but the specific decomposition temperature in the case of applying the above-mentioned preferred amine is 90 to 130 ° C.
- the heating rate affects the particle size of the silver particles that are precipitated. That is, in the present invention, the particle size of the silver particles can be controlled by adjusting the type of amine of the silver-amine complex as a precursor (the type of amine to be reacted with the silver compound) and the heating rate in the heating step. .
- the heating rate in the heating step is preferably adjusted in the range of 2.5 to 50 ° C./min up to the decomposition temperature.
- silver particles are deposited.
- silver particles can be taken out through appropriate washing and solid-liquid separation. In some cases, the silver particles may be fixed to each other, but this can be easily crushed and separated.
- the recovered silver particles can be stored and used in ink, paste, slurry, or dried powder dispersed in an appropriate solvent.
- the method for producing silver particles according to the present invention can easily control the particle size of the silver particles to be generated.
- the silver particles produced at this time are uniform in size.
- Test No. 1 of the first embodiment SEM photograph of 1-3 silver particles.
- Test No. 1 of the first embodiment. SEM photographs of silver particles 7 and 8.
- Test No. 1 of the first embodiment. SEM photograph of silver particles 9-13.
- Test No. 1 of the first embodiment. SEM photographs of 19 and 20 silver particles.
- Test No. 1 of the first embodiment. SEM photograph of 21 silver particles.
- Test No. 1 of the first embodiment. SEM photographs of 22 and 24 silver particles.
- Test No. 1 of the first embodiment. SEM photograph of silver particles such as 23.
- the particle size distribution map of silver particles such as test No. 2 of 1st Embodiment.
- the particle size distribution map of silver particles such as test No. 9 of 1st Embodiment.
- Test No. 2 of the second embodiment SEM photograph of 29 and 30 silver particles.
- silver particles were produced while changing various conditions along the process of FIG. 1, and their properties were evaluated.
- silver oxalate (Ag 2 C 2 O 4 ) (silver ion (Ag + ) 9.9 mmol) was used as the thermally decomposable silver compound.
- this silver oxalate there were prepared a case where it was used in a dry state and a wet state by adding 0.3 g of water (20 parts by weight with respect to 100 parts by weight of silver oxalate). Then, n-hexylamine, n-octylamine or a mixed amine of both was added as an amine to silver oxalate to produce a silver-amine complex. Silver oxalate and amine were mixed at room temperature and kneaded until a white cream was formed.
- urea, DMF, and DEF as a homogenizing agent were added singly or in combination to the produced silver-amine complex.
- either solid state or solution state added with 0.4 g of water 27 parts by weight with respect to 100 parts by weight of silver oxalate was added.
- oleic acid was added as an additive after the addition of the homogenizing agent.
- the amount of water varies depending on the raw materials used.
- the reaction system was heated from room temperature to decompose the silver-amine complex and precipitate silver particles.
- the heating temperature at this time assumed 110 degreeC as a decomposition temperature of a complex, and made this the ultimate temperature.
- the heating rate was 10 ° C./min.
- the present invention is based on a thermal decomposition method in which silver particles are produced by thermal decomposition of a silver-amine complex, and the reaction system is made of an organic compound having an amide (carboxylic amide) as a skeleton. It is essential to add an agent and to coexist with a predetermined amount of water. As for this point, no. In 21 (anhydrous state without additives), the silver particle size is limited to fine particles (average particle size of less than 10 nm) depending on the type of silver-amine complex, and is about several tens to several hundreds of nm.
- test no When a homogenizing agent is added such as 2 to 5 and the water content is appropriate, silver particles having an average particle diameter of 20 nm to 150 nm and uniform particle diameter are obtained (FIG. 9, Table 2). The effectiveness of can be confirmed.
- urea alone Test No. 10 to 12
- DMF alone Test No. 18
- DEF alone Test No. 19
- Test Nos. 6-8, 20 etc. are also effective.
- the magnitude relationship of the addition amount is not limited.
- the addition amount of the homogenizing agent was confirmed to have an effect of improving the particle size distribution when the total molar ratio was 0.1 or more (Test Nos. 4 to 8).
- the size of silver particles is limited to a minute one depending on the type of silver-amine complex.
- test no For the water content of the reaction system, test no. From the results of 9 to 17, it is as described above that water is necessary, but it can be confirmed that the upper limit exists. In addition to making the particle size of the silver particles coarse, the amount of water becomes a factor of variation in the particle size.
- the effectiveness of n-hexylamine, n-octylamine, and mixed amines thereof can be confirmed (Test Nos. 22 to 25). It can be seen that when octylamine is used, silver particles having a particle size finer than that of n-hexylamine are produced. Further, when a mixed amine of n-hexylamine and n-octylamine is used, silver particles having a larger particle diameter are produced as the mixing ratio of n-hexylamine is higher (Test Nos. 23 to 25). Thus, the silver particle of an intermediate particle diameter is manufactured by using mixed amine.
- the heating rate up to the decomposition temperature is common, it can be confirmed that the particle size can be adjusted by selecting an amine.
- the mixing amount of the amine for forming the silver-amine complex is preferably 1.6 or more (Test Nos. 1 to 3). No. At a molar ratio of 1.5, most of the silver compounds formed silver-amine complexes, but some unreacted products that did not form complexes were observed (FIG. 2).
- test no As to the necessity of oleic acid as an additive, test no. From 26 to 28, it can be confirmed that the addition of an additive such as oleic acid is not essential. Oleic acid is thought to be effective in maintaining a suitable particle size distribution, but suitable silver particles can be produced without the addition of oleic acid.
- the particle size of silver particles varies depending on the amine for forming a silver-amine complex.
- the heating rate of the reaction system it is possible to cope with the heating rate of the reaction system as a means for adjusting the particle size. is there. Therefore, next, the above test No. 2, no.
- the heating rate was changed about 22 and the silver particle was manufactured.
- the heating rate is 10 ° C./min.
- the heating rate was 6 ° C./min (Test No. 29).
- the heating rate was 1 ° C./min (Test No. 30).
- Table 3 The evaluation results for the silver particles produced here are shown in Table 3.
- Table 3 shows that the particle size can be adjusted by changing the heating rate. By reducing the heating rate, the particle size of the silver particles tends to increase (Test Nos. 29 and 30). As described above, in the present invention, it is possible to adjust the particle size of the silver particles to be manufactured from different approaches of selecting an amine and adjusting the heating rate. Even when the heating rate is adjusted in this way, a good particle size distribution will not be lost.
- uniform silver particles can be produced while controlling the particle size.
- the present invention can efficiently produce high quality silver particles used for various applications such as electrodes / wiring materials, reflective film materials, catalysts, antibacterial materials and the like.
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Abstract
Description
(a)工程:熱分解性を有する銀化合物とアミンとを混合して前駆体である銀-アミン錯体を製造する工程。
(b)工程:反応系に、アミド(カルボン酸アミド)を骨格として有する下記式で示される有機化合物を添加する工程。
前記(c)工程の加熱前、反応系の水分含有量は、前記銀化合物100重量部に対して20~100重量部である銀粒子の製造方法に関する。
変動係数(%)=(標準偏差/平均粒径)×100
Claims (6)
- (a)工程の熱分解性を有する銀化合物は、シュウ酸銀、硝酸銀、酢酸銀、炭酸銀、酸化銀、亜硝酸銀、安息香酸銀、シアン酸銀、クエン酸銀、乳酸銀のいずれか1種である請求項1記載の銀粒子の製造方法。
- (a)工程のアミンは、炭素数の総和が5~10である請求項1又は請求項2記載の銀粒子の製造方法。
- (b)工程の有機化合物として、尿素、尿素誘導体、N,N-ジメチルフォルムアミド、N,N-ジエチルフォルムアミドの少なくともいずれか1種を添加する請求項1~請求項3のいずれかに記載の銀粒子の製造方法。
- (b)工程の有機化合物は、銀化合物中の銀イオンに対してモル比で0.1倍以上添加する請求項1~請求項4のいずれかに記載の銀粒子の製造方法。
- (c)工程の加熱温度は、銀-アミン錯体の分解温度以上とする請求項1~請求項5のいずれかに記載の銀粒子の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/891,725 US9901985B2 (en) | 2013-05-24 | 2014-05-20 | Method for manufacturing silver particles |
DE112014002558.5T DE112014002558B4 (de) | 2013-05-24 | 2014-05-20 | Verfahren zum Herstellen von Silberteilchen |
KR1020157035094A KR20160006771A (ko) | 2013-05-24 | 2014-05-20 | 은 입자의 제조 방법 |
JP2015518247A JP6270831B2 (ja) | 2013-05-24 | 2014-05-20 | 銀粒子の製造方法 |
CN201480029930.8A CN105246622B (zh) | 2013-05-24 | 2014-05-20 | 银粒子的制造方法 |
Applications Claiming Priority (2)
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JP2013109523 | 2013-05-24 | ||
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JP (1) | JP6270831B2 (ja) |
KR (1) | KR20160006771A (ja) |
CN (1) | CN105246622B (ja) |
DE (1) | DE112014002558B4 (ja) |
MY (1) | MY176474A (ja) |
TW (1) | TWI490347B (ja) |
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Cited By (1)
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WO2015087967A1 (ja) * | 2013-12-11 | 2015-06-18 | 田中貴金属工業株式会社 | 銀粒子の製造方法及び当該方法により製造される銀粒子 |
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JP7320515B2 (ja) | 2018-08-30 | 2023-08-03 | 田中貴金属工業株式会社 | 低温焼成用の銀インク |
TWI774439B (zh) * | 2020-07-03 | 2022-08-11 | 日商田中貴金屬工業股份有限公司 | 耐彎折性優異之金屬配線及導電薄片以及為形成該金屬配線之金屬糊 |
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- 2014-05-20 KR KR1020157035094A patent/KR20160006771A/ko not_active Application Discontinuation
- 2014-05-20 DE DE112014002558.5T patent/DE112014002558B4/de active Active
- 2014-05-20 MY MYPI2015703967A patent/MY176474A/en unknown
- 2014-05-20 CN CN201480029930.8A patent/CN105246622B/zh active Active
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Also Published As
Publication number | Publication date |
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DE112014002558B4 (de) | 2020-06-18 |
DE112014002558T5 (de) | 2016-03-10 |
US20160121404A1 (en) | 2016-05-05 |
US9901985B2 (en) | 2018-02-27 |
KR20160006771A (ko) | 2016-01-19 |
JP6270831B2 (ja) | 2018-01-31 |
MY176474A (en) | 2020-08-11 |
TW201500564A (zh) | 2015-01-01 |
CN105246622B (zh) | 2017-03-15 |
CN105246622A (zh) | 2016-01-13 |
JPWO2014189024A1 (ja) | 2017-02-23 |
TWI490347B (zh) | 2015-07-01 |
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