WO2015087967A1 - 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 - Google Patents
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 Download PDFInfo
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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 medium average particle diameter of 20 nm to 200 nm, and producing silver particles having a uniform particle diameter while controlling the size.
- Silver (Ag) has excellent electrical conductivity and light reflectivity, and also has unique properties such as catalytic action and antibacterial action. Therefore, electrode / wiring material, adhesive / bonding material, heat conduction material, conductivity It is a metal that is expected to be used for various industrial applications such as adhesives, conductive bonding materials, reflective film materials, catalysts, and antibacterial materials.
- As an application mode of silver for these various uses there is one in which silver particles are dispersed and suspended in an appropriate solvent. For example, this metal paste is formed by pasting silver particles into electrodes / wiring formation, adhesives / bonding materials, conductive adhesives / conductive bonding materials, and heat conductive materials of wiring boards mounted on electronic components such as semiconductor devices.
- the desired electrode, wiring, joint, and pattern can be formed by applying and baking.
- 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 widen due to the concentration gradient of the reactant in the solvent.
- Such silver particles having a large particle size cannot form electrodes or wirings on the order of several microns, and cannot cope with the recent miniaturization of semiconductor devices and the like.
- unevenness in the film thickness tends to occur, and thus it can be said that application to applications requiring smoothness is difficult.
- the thermal decomposition method which makes a silver complex a precursor as a manufacturing method of the silver particle replaced with a liquid phase reduction method is reported (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. This is a method of heating this as a precursor to obtain silver particles.
- 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.
- the above thermal decomposition method of silver complex extremely fine silver fine particles of several nanometers can be produced, and the particle diameter can be made relatively uniform.
- the silver particles obtained by this method are conversely too small in particle size and may be difficult to apply depending on the application.
- an adhesive / bonding material, a conductive adhesive / conductive bonding material, or a heat conductive material cracks are likely to occur due to volume shrinkage during firing, and there is a concern about disconnection or peeling. .
- the present invention provides a method for producing silver particles, which can control the particle size within a range of an average particle size of 20 nm to 200 nm and can produce silver particles having a uniform particle size. To do.
- the inventors of the present invention as a silver particle production method for solving the above-mentioned problems, first studied based on a silver particle production method using a pyrolysis method. This is because, as described above, it is considered that the thermal decomposition method can adjust the particle size more than the liquid phase reduction method, and can produce silver particles having a relatively uniform particle size. Then, the present inventors considered that in the thermal decomposition method, the thermal decomposition characteristics of the silver compound used as a raw material affect the silver particles having a particle diameter to be generated.
- the thermal decomposition method in the said patent document 1 the manufacture example of the silver particle using silver oxalate as a silver compound is reported.
- the complex formed from silver oxalate is due to the fact that it easily decomposes to form metallic silver and, after decomposition, has the advantage of releasing carbon dioxide and leaving no impurities.
- the amine complex produced from silver oxalate is easily pyrolyzed, which means that the nucleation rate during silver particle precipitation is relatively high.
- the precipitation of silver particles proceeds by a combination of nucleation and nucleation by complex decomposition at the periphery of the nucleus, but when the nucleation rate is high, the particle size of the silver particles tends to be small.
- the silver particles produced by the conventional method are very small depending on the silver compound (silver oxalate) that is the raw material. It is considered that a silver compound having a characteristic may be applied.
- silver carbonate (Ag 2 CO 3 ) can be used in place of silver oxalate as a raw silver compound for the thermal decomposition method. This is because silver carbonate has a decomposition temperature slightly higher than that of silver oxalate, which makes it possible to produce silver particles having a relatively large particle size.
- silver carbonate when silver carbonate is applied as a silver compound as a raw material, silver particles are not always deposited smoothly from here. This is based on the decomposition characteristics of silver carbonate.
- silver in the decomposition process of silver carbonate, silver is not immediately generated from silver carbonate, but first silver oxide (AgO) is generated, and then silver is passed through. The two-stage decomposition phenomenon of generating lucidly appears (see FIG. 6 described later).
- an amine complex produced from a silver compound is used as a precursor.
- the present inventors have studied a method for forming an amine complex that can rapidly generate silver particles by heating while using silver carbonate as a raw material compound. As a result, the inventors have found that silver particles having a target particle size range can be produced by utilizing an amine complex obtained by reacting a limited range of amine compounds with silver carbonate, and have arrived at the present invention.
- the present invention comprises a step of producing a silver-amine complex as a precursor by mixing a thermally decomposable silver compound and an amine compound, and a step of depositing silver particles by heating the silver-amine complex.
- a silver-amine complex as a precursor by mixing a thermally decomposable silver compound and an amine compound
- a step of depositing silver particles by heating the silver-amine complex silver carbonate is used as the silver compound, and the silver compound is mixed with an amine compound represented by the following formula, wherein the amine compound is a primary amino group.
- R is a substituent satisfying the condition (1) or (2).
- (1) A hydrocarbon group having a straight chain structure or a branched or cyclic structure having 5 to 10 carbon atoms. However, R may partially contain oxygen. R may partially contain a primary amino group, a secondary amino group, or a tertiary amino group.
- (2) A hydrocarbon group having a straight chain structure having 4 carbon atoms. However, R may partially contain oxygen. R may partially contain a primary amino group or a secondary amino group.
- the present invention is a method for producing silver particles using silver carbonate as a heat decomposable silver compound as a raw material, producing an amine complex reacted with a specific amine, and using this as a precursor.
- the present invention comprises a step of producing a silver-amine complex by reacting silver carbonate and an amine, and a step of depositing silver particles by heating the silver-amine complex.
- the raw material silver carbonate may be a commercial product, it may be produced for carrying out the present invention.
- This silver carbonate is preferably in a dry state (water content of 1% by mass or less).
- silver carbonate has a property of being decomposed by light and may partially contain silver oxide unless stored in a light-shielded state. When such low-purity silver carbonate is used, the yield of silver particles may be deteriorated. Therefore, the silver carbonate used in the present invention preferably has a silver oxide content of 3% by mass or less.
- the amine to be reacted with silver carbonate is an amine compound (H 2 N—R) whose terminal is a primary amino group, and the substituent R is a hydrocarbon group having 5 or more carbon atoms or a straight chain having 4 carbon atoms. It is an amine compound that is a hydrocarbon group of a chain. Thus based on the number of carbons.
- the amine to be reacted with silver carbonate is limited to an amine having 3 or less carbon atoms, or when a branched amine having 4 carbon atoms is applied, the reaction with silver carbonate is too fast, This is because complex formation is localized and a uniform complex cannot be obtained, and suitable silver particles cannot be produced.
- the type of amine is limited to those whose terminal amino group is a primary amino group. Even if an amine compound composed only of a secondary amine or a tertiary amine is reacted, the complex formation reaction proceeds. This is because an unreacted portion remains difficult and silver particles are not precipitated even when heated.
- a preferred example is an amine having a primary amino group as a terminal and a hydrocarbon group having 5 or more carbon atoms bonded thereto.
- this amine compound is preferable is that the reactivity with silver carbonate is within an appropriate range and uniform complex formation is observed.
- the reason why the upper limit of the carbon number is 10 is that when amines having a large number of carbon atoms are used, the formation of a silver carbonate-amine complex hardly occurs and silver particles are not generated.
- the substituent of the amine compound having 5 or more carbon atoms is a hydrocarbon group having a linear structure, a branched structure or a cyclic structure, and examples thereof include an alkyl group having 5 or more carbon atoms and an aryl group.
- this substituent may contain oxygen in the skeleton of the hydrocarbon group.
- a part of the structural formula may contain a hydroxyl group, a methoxy group, an ethoxy group, or the like. Specific examples include 3-ethoxypropylamine, hexylamine, benzylamine, octylamine, 2-ethylhexylamine, phenethylamine, 6-amino-1-hexanol and the like.
- the amino group contained in the hydrocarbon group may be a primary amino group, a secondary amino group, or a tertiary amino group.
- Specific examples of such amine compounds containing primary to tertiary amino groups in addition to the terminal primary amino group include 3-dimethylaminopropylamine, 3-diethylaminopropylamine, methyliminobispropylamine, 3 -(2-hydroxyethylamino) propylamine, 2-aminomethylpiperidine, iminobispropylamine and the like.
- the substituent is a hydrocarbon group having a linear structure of 4 carbon atoms
- a hydrocarbon group having a branched structure is not applicable.
- An amine compound having a branched structure is difficult to undergo a complex formation reaction, and silver particles cannot be obtained.
- the amine compound having 4 carbon atoms may contain oxygen in the skeleton of the hydrocarbon group, and may contain, for example, a hydroxyl group, a methoxy group, an ethoxy group, or the like. Further, it may contain an amino group (primary amino group, secondary amino group). Specific examples of such an amine compound having 4 carbon atoms include butylamine, 3-methoxypropylamine, 1,4-diaminobutane, 4-aminobutanol, 3-methylaminopropylamine and the like.
- the range of amine compounds that can form an amine complex suitable for silver particle precipitation by reacting with silver carbonate is clarified.
- Each of the above amine compounds can form a complex alone with silver carbonate, and it is not necessary to mix a plurality of amine compounds.
- the mixing ratio of silver carbonate and amine compound is preferably 1.5 times the molar amount of the amine compound with respect to the number of moles of silver in the silver carbonate. If this molar ratio is less than 1.5, unreacted silver compounds may remain, sufficient silver particles cannot be produced, and the particle size distribution of the silver particles tends to vary.
- the upper limit (the upper limit amount of amine) of the above molar ratio is not particularly required to be specified. However, since excessive amine may affect the purity of silver particles, it is preferably 10 times the molar amount or less.
- a solvent may be used, but an amine complex can be formed without a solvent.
- the complex formation can be performed at normal temperature and pressure. After mixing the silver carbonate and the amine compound, it is preferable to stir so that a uniform reaction occurs.
- silver particles are precipitated by heating the reaction system.
- this heating step it is preferable to heat at a heating rate of 2.5 to 50 ° C./min until the reaction system reaches the set heating temperature. If the temperature rise is too slow, nucleation is prioritized over nucleation and coarse silver particles may be produced.
- complex formation can be performed at normal temperature and it is preferable to heat up from the state after complex formation.
- the heating temperature in the heating process is set to be equal to or higher 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 heating temperature is determined in consideration of the decomposition temperature of the amine complex generated by the amine compound applied in the present invention.
- the temperature is preferably from 65 to 160 ° C. Particularly preferred is 100 ° C. to 160 ° C.
- the reaction system is heated and held for 10 minutes to 2 hours to precipitate silver particles.
- the present invention is useful in that silver particles having a medium particle size of 20 nm to 200 nm, which cannot be produced by conventional methods, can be produced by using silver carbonate as a raw material. It is also useful in that silver particles having a uniform particle size can be produced while performing. The particle size can be adjusted by adjusting the temperature increase rate until the heating temperature is reached. Silver particles having a smaller particle size can be produced as the heating rate is increased.
- the silver particles having the target particle size range of the present application preferably have a heating rate of 2.5 to 50 ° C./min as described above.
- the amine carbonate used as an impurity may remain slightly.
- This amine carbonate is considered to be produced by the reaction of carbonic acid and amine generated when the silver-amine complex is decomposed.
- the amine carbonate may be included, when the silver particles are applied as paste or the like and applied and fired, the amine carbonate may be decomposed and the volume of the fired body may vary. Therefore, it is preferable that the amine carbonate is excluded, and specifically, the amine carbonate is preferably 5% by mass or less.
- the amine carbonate can be easily removed by washing the produced silver particles. This washing is preferably performed by dissolving and removing the amine carbonate with an alcohol such as methanol. The amine carbonate content can be reduced by repeating the washing.
- the silver particles produced by the above steps can be stored and used in the form of 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.
- the amine compounds used for forming the silver-amine complex in this embodiment are as follows.
- the amine compound was added in an amount of 10 mmol, 12 mmol, 15 mmol, 20 mmol, 30 mmol, that is, a 1-fold, 1.2-fold, 1.5-fold, 2-fold, 3-fold molar amount relative to silver in silver carbonate. Addition of the amine compound was carried out at room temperature, whereby a creamy silver-amine complex was formed.
- the amine complex was stirred for 10 to 30 minutes and then heated to precipitate silver particles.
- the temperature is increased from room temperature to 130 ° C. at a rate of temperature increase of 2, 5, 10, 20, 30, 40 ° C./min.
- methanol was added to the reaction solution for washing, and this was centrifuged. This washing and centrifugation were performed twice. Silver particles were obtained by the above operation.
- the collected silver particles were examined for their particle size (average particle size) and particle size distribution.
- the silver particles were observed by SEM and photographed, the particle size of the silver particles in the image was measured (about 100 to 200 particles), and the average value was calculated.
- Table 1 shows the evaluation results of the silver particles produced in this embodiment.
- silver particles having a medium particle size of 20 nm to 200 nm can be produced by using silver carbonate as a raw material (No. 3 to No. 5, No. 7 to No. 12, No. 14, No. 17 to No. 21).
- silver carbonate As a raw material
- the amine compound suitable for the present invention in which the substituent R is a hydrocarbon group having 5 to 10 carbon atoms is applied, silver particles having a target particle size and particle size distribution can be produced. (No. 3 to No. 5, No. 7 to No. 12, No. 14, No. 17 to No. 21).
- the amine compound (No. 1) having 3 carbon atoms and the amine compound (No. 13) having 12 carbon atoms generate coarse silver particles due to the excess or deficiency of the carbon number, or the complex formation reaction proceeds. This is not possible because silver particles cannot be obtained.
- the availability of silver particles depends on the structure of the amine compound.
- a silver compound having a suitable particle size and particle size distribution can be produced with an amine compound having a linear substituent (No. 3, No. 4), but a suitable silver particle is produced with a branched amine compound. It cannot be done (No. 22, No. 23).
- isobutylamine, etc. the reactivity is high, and since the formation and decomposition reaction of silver amine complex occur simultaneously at the moment of addition, the reaction cannot be controlled, and the particle size distribution of silver particles is very wide including large particles of several microns. turn into. This does not correspond to the targeted medium particle size range of 20 nm to 200 nm.
- the hydroxyl group and the methoxy group may be included in the substituent (No. 5, No. 14).
- the cyclic hydrocarbon may be included (No. 8).
- an amino group may be included in the structural formula of the substituent, and the amino group in the substituent may be a secondary or tertiary amino group (No. 14 to No. 21). .
- the amount of amine compound to be reacted with silver carbonate is preferably 1.5 times the molar amount or more of silver in silver carbonate (No. 6, No. 15). .
- the silver particle becomes coarse at about 2 ° C./min for the rate of temperature rise in the heating step, it is preferable to exceed this (No. 2).
- the particle size adjustment of a silver particle for example, it is No. 9 and no. From the comparison with 10, it can be seen that the temperature can be adjusted by the heating rate.
- FIG. 2 shows the No. in this embodiment. 9, no. 10, no. 19, no. 20 is an SEM photograph of silver particles produced in No. 20.
- FIG. 1, no. 15, no. 22, no. 2 is an SEM photograph of silver particles produced in 24.
- FIG. 9, no. 10, no. 20 shows the particle size distribution of 20 silver particles. The particle size distribution of 22 silver particles is shown.
- No. Silver particles produced using a suitable amine compound such as No. 9 have a uniform particle size. In No. 22, coarse silver particles of 300 nm or more are generated, and it can be confirmed that the particle diameters are not uniform.
- TG-DTA analysis mass-differential thermal analysis
- FIG. 6 shows the results of TG-DTA analysis of silver carbonate, silver-amine complex (No. 19), and silver particles. From FIG. 6, the mass loss near 200 ° C. and the mass loss near 400 ° C. are observed for the silver carbonate as the raw material. These mass reductions indicate a change from silver carbonate to silver oxide in the former and a change from silver carbonate to silver in the latter. As described above, silver carbonate exhibits a two-stage decomposition behavior. On the other hand, the amine complex starts to decompose at around 110 ° C. and changes to silver without exhibiting a two-stage decomposition behavior like silver carbonate. It can be said that the decomposition behavior was improved by complex formation with an appropriate amine compound.
- uniform silver particles can be produced while controlling the particle size.
- the present invention relates to silver particles used in various applications such as electrodes / wiring materials, adhesives / bonding materials, conductive adhesives / conductive bonding materials, thermal conductive materials, reflective film materials, catalysts, antibacterial materials, etc. High quality products can be manufactured.
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Abstract
Description
(1)炭素数5以上10以下の直鎖構造又は分枝構造若しくは環状構造を有する炭化水素基。但し、Rは、その一部において酸素を含んでいても良い。また、Rは、その一部において1級アミノ基又は2級アミノ基若しくは3級アミノ基を含んでいても良い。
(2)炭素数4の直鎖構造の炭化水素基。但し、Rは、その一部において酸素を含んでいても良い。また、Rは、その一部において1級アミノ基又は2級アミノ基を含んでいても良い。
Claims (5)
- 熱分解性を有する銀化合物とアミン化合物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と、前記銀-アミン錯体をその分解温度以上の加熱温度で加熱して銀粒子を析出させる工程と、を含む銀粒子の製造方法において、
前記銀化合物として炭酸銀を用い、
前記アミン化合物として、少なくとも一方の末端が1級アミノ基である下記式で示されるアミン化合物を混合して銀-アミン錯体を製造する銀粒子の製造方法。
(1)炭素数5以上10以下の直鎖構造又は分枝構造若しくは環状構造を有する炭化水素基。但し、Rは、その一部において酸素を含んでいても良い。また、Rは、その一部において1級アミノ基又は2級アミノ基若しくは3級アミノ基を含んでいても良い。
(2)炭素数4の直鎖構造の炭化水素基。但し、Rは、その一部において酸素を含んでいても良い。また、Rは、その一部において1級アミノ基又は2級アミノ基を含んでいても良い。 - 炭酸銀へのアミン化合物の混合量は、炭酸銀中の銀のモル量に対して、1.5~10倍モル量である請求項1記載の銀粒子の製造方法。
- 銀-アミン錯体を加熱する工程の加熱温度は、65~160℃である請求項1又は請求項2に記載の銀粒子の製造方法。
- 銀-アミン錯体を加熱する工程は、銀-アミン錯体を加熱温度に達するまで2.5~50℃/分の昇温速度で加熱するものである請求項1~請求項3のいずれかに記載の銀粒子の製造方法。
- 請求項1~請求項4のいずれかに記載の方法により製造される銀粒子であって、
平均粒径20~200nmであり、アミン炭酸塩の含有量が5質量%以下である銀粒子。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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KR1020187009848A KR20180038078A (ko) | 2013-12-11 | 2014-12-11 | 은 입자의 제조 방법 및 당해 방법에 의해 제조되는 은 입자 |
CN201480067173.3A CN105813782B (zh) | 2013-12-11 | 2014-12-11 | 银粒子的制造方法及通过该方法制造的银粒子 |
DE112014005640.5T DE112014005640B4 (de) | 2013-12-11 | 2014-12-11 | Verfahren zur Herstellung von Silberteilchen und Silberteilchen, die durch das Verfahren hergestellt werden |
KR1020167016391A KR102085744B1 (ko) | 2013-12-11 | 2014-12-11 | 은 입자의 제조 방법 |
US15/101,859 US10486235B2 (en) | 2013-12-11 | 2014-12-11 | Method for producing silver particles, and silver particles produced by the method |
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WO2018198810A1 (ja) * | 2017-04-27 | 2018-11-01 | 御国色素株式会社 | 広分布な粒度分布を持つ銀ナノ粒子の製造方法及び銀ナノ粒子 |
WO2019035246A1 (ja) * | 2017-08-18 | 2019-02-21 | 御国色素株式会社 | 広分布な粒度分布を持つ銀ナノ粒子の製造方法及び銀ナノ粒子 |
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CN108102579B (zh) * | 2017-12-26 | 2020-04-21 | 昆明贵金属研究所 | 一种高导热导电胶的制备方法及应用 |
JP7190449B2 (ja) * | 2018-01-09 | 2022-12-15 | 株式会社ノリタケカンパニーリミテド | 銀ナノ微粒子の製造方法および銀ナノ微粒子を含む銀ペースト |
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KR102085744B1 (ko) | 2020-03-06 |
JP5732520B1 (ja) | 2015-06-10 |
US20160303659A1 (en) | 2016-10-20 |
DE112014005640B4 (de) | 2021-10-07 |
US10486235B2 (en) | 2019-11-26 |
JP2015113488A (ja) | 2015-06-22 |
CN105813782A (zh) | 2016-07-27 |
KR20160088919A (ko) | 2016-07-26 |
TW201527556A (zh) | 2015-07-16 |
DE112014005640T5 (de) | 2016-09-01 |
CN105813782B (zh) | 2017-08-29 |
KR20180038078A (ko) | 2018-04-13 |
TWI638056B (zh) | 2018-10-11 |
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