JP6746409B2 - Dispersion solution of fine metal particles and sintered conductor - Google Patents
Dispersion solution of fine metal particles and sintered conductor Download PDFInfo
- Publication number
- JP6746409B2 JP6746409B2 JP2016136582A JP2016136582A JP6746409B2 JP 6746409 B2 JP6746409 B2 JP 6746409B2 JP 2016136582 A JP2016136582 A JP 2016136582A JP 2016136582 A JP2016136582 A JP 2016136582A JP 6746409 B2 JP6746409 B2 JP 6746409B2
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- Prior art keywords
- fine particles
- metal fine
- dispersion solution
- surfactant
- metal
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Description
本発明は、粘度の保存安定性に優れる金属微粒子の分散溶液、及び大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる焼結導電体に関する。 TECHNICAL FIELD The present invention relates to a dispersion solution of metal fine particles having excellent storage stability of viscosity, and a sintered conductor having a small frequency of occurrence of large voids (voids) in a sintered film, low electrical resistance, and excellent conductivity.
従来から、ナノメートルサイズ（１μｍ未満のサイズをいう。以下同じ。）の金属微粒子を含む分散溶液は、例えば、基板上に塗布し、焼結過程を経て焼結導電体を形成させる等して、その用途に応じて、プリント配線、および半導体の内部配線などの電子部品の導電性形成材料として広く利用されてきた。 Conventionally, a dispersion solution containing fine metal particles of a nanometer size (which means a size of less than 1 μm; the same applies hereinafter) is applied, for example, on a substrate, and a sintered conductor is formed through a sintering process. Depending on its application, it has been widely used as a conductive forming material for electronic parts such as printed wiring and semiconductor internal wiring.
また、ナノメートルサイズ（１μｍ未満のサイズをいう。以下同じ。）の金属微粒子を含む分散溶液は、例えば、電子部品の接合面に塗布し、当該塗布した接合面上に他の電子部品を積層配置し、焼結過程を経て電子部品同士を接合させる等して、その用途に応じて、電子部品間の導電性接合材料としても広く利用されてきた。 Further, a dispersion solution containing metal fine particles of nanometer size (meaning a size of less than 1 μm; the same applies hereinafter) is applied to, for example, a joint surface of an electronic component, and another electronic component is laminated on the applied joint surface. It has been widely used as a conductive bonding material between electronic components, depending on the application, such as by arranging them and joining electronic components through a sintering process.
例えば、特許文献１には、特定の分子量を有する有機分散剤（Ｏ）で被覆された金属微粒子（Ｐ１）と、Ｐ１と粒径範囲の異なる金属微粒子（Ｐ２）と、有機分散媒（Ｄ）とを含み、Ｐ１とＰ２の配合割合（Ｐ１／Ｐ２）、およびＰとＤの配合割合（Ｐ／Ｄ）を特定した導電性ペーストが開示されている。 For example, in Patent Document 1, metal fine particles (P1) coated with an organic dispersant (O) having a specific molecular weight, metal fine particles (P2) having a particle size range different from P1 and an organic dispersion medium (D). A conductive paste containing P and P2 and a mixture ratio of P1 and P2 (P1/P2) and a mixture ratio of P and D (P/D) is disclosed.
しかしながら、特許文献１に開示された導電性ペーストは、焼結体の割れを抑制し、接合部において良好なシェア強度（剥離強度）が得られる一方で、焼結過程で有機分散媒（Ｄ）から分解生成された水分子（Ｈ２Ｏ）が焼結膜内に残存し、焼結膜内に大きな空隙（ボイド）が発生すると考えられる。 However, the conductive paste disclosed in Patent Document 1 suppresses cracking of the sintered body, and good shear strength (peeling strength) is obtained at the joint, while the organic dispersion medium (D) is used in the sintering process. It is considered that the water molecules (H 2 O) decomposed and produced from the above remain in the sintered film, and large voids (voids) are generated in the sintered film.
本発明は、上述した事情に鑑みてなされたものであり、経時的な粘度の低下などによる変化が少なく、粘度の保存安定性に優れる、金属微粒子（Ｐ）の分散溶液を提供することを目的とするものである。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dispersion solution of metal fine particles (P), which has little change due to a decrease in viscosity over time, and has excellent storage stability of viscosity. It is what
また、本発明は、上記金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる、焼結導電体を提供することを目的とするものである。 Further, in the present invention, large voids (voids) are generated in the sintered film in the process of applying the dispersion solution of the metal fine particles (P) onto a substrate and performing sintering by heat treatment (sintering process). It is an object of the present invention to provide a sintered conductor having a reduced frequency, a low electric resistance, and excellent conductivity.
上記課題を解決するために、本発明の第１の実施形態に係る金属微粒子の分散溶液は、平均一次粒子径が５〜５００ｎｍの範囲にある、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）、および界面活性剤（Ｂ）を、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）に分散させてなる金属微粒子（Ｐ）の分散溶液中、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）が、界面活性剤（Ｂ）によって表面修飾されてなる。 In order to solve the above-mentioned problems, the dispersion solution of metal fine particles according to the first embodiment of the present invention has a metal having a mean primary particle diameter in the range of 5 to 500 nm and coated with a polymer dispersant (D). In a dispersion solution of metal fine particles (P) obtained by dispersing the fine particles (P) and the surfactant (B) in an organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol, a polymer dispersant ( The metal fine particles (P) coated with D) are surface-modified with a surfactant (B).
また、本発明の第１の実施形態に係る金属微粒子の分散溶液において、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の原料となる金属が、銅、銀、金、白金、およびパラジウムの中から選択される１種または２種以上であることが好ましい。 In the dispersion solution of metal fine particles according to the first embodiment of the present invention, the metal as a raw material of the metal fine particles (P) coated with the polymer dispersant (D) is copper, silver, gold, platinum, And at least one selected from the group consisting of palladium and palladium.
また、本発明の第１の実施形態に係る金属微粒子の分散溶液において、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）が、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−ブテン−１，４−ジオール、１，２−ペンタンジオール、１，５−ペンタンジオール、１，２−ヘキサンジオール、１，６−ヘキサンジオール、グリセロール、１，２，４−ブタントリオール、および１，２，６−ヘキサントリオールの中から選択されることが好ましい。 In the dispersion solution of metal fine particles according to the first embodiment of the present invention, the organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol is ethylene glycol, diethylene glycol, 1,2-propanediol, 1 ,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol , 1,2-hexanediol, 1,6-hexanediol, glycerol, 1,2,4-butanetriol, and 1,2,6-hexanetriol are preferred.
また、本発明の第１の実施形態に係る金属微粒子の分散溶液において、高分子分散剤（Ｄ）が、分子中に少なくとも１つのカルボニル基を有する化合物、又は分子中に少なくとも１つの窒素原子を有する化合物であることが好ましい。 Further, in the dispersion solution of metal fine particles according to the first embodiment of the present invention, the polymer dispersant (D) contains a compound having at least one carbonyl group in the molecule, or at least one nitrogen atom in the molecule. It is preferable that the compound has.
また、本発明の第１の実施形態に係る金属微粒子の分散溶液において、高分子分散剤（Ｄ）が、ポリビニルピロリドン、ポリエチレンイミン、ポリアクリル酸、カルボキシメチルセルロース、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキシド、デンプン、およびゼラチンの中から選択される１種または２種以上であることが好ましい。 In the dispersion solution of metal fine particles according to the first embodiment of the present invention, the polymer dispersant (D) is polyvinylpyrrolidone, polyethyleneimine, polyacrylic acid, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyethylene glycol, It is preferably one or more selected from polyethylene oxide, starch, and gelatin.
また、本発明の第１の実施形態に係る金属微粒子の分散溶液において、界面活性剤（Ｂ）が、糖アルコール脂肪酸エステル類の群から選択される少なくとも１種であることが好ましい。 Further, in the dispersion solution of metal fine particles according to the first embodiment of the present invention, it is preferable that the surfactant (B) is at least one selected from the group of sugar alcohol fatty acid esters.
また、本発明の第１の実施形態に係る金属微粒子の分散溶液において、界面活性剤（Ｂ）が、金属微粒子（Ｐ）の分散溶液を基板上に塗布し、加熱処理による焼結を行う際に、焼結膜を形成する加熱温度よりも低い融点を有し、界面活性剤（Ｂ）の融点が、５０〜１００℃の範囲にあることが好ましい。 Further, in the dispersion solution of metal fine particles according to the first embodiment of the present invention, when the surfactant (B) applies the dispersion solution of metal fine particles (P) on a substrate and performs sintering by heat treatment. Furthermore, it is preferable that the melting point of the surfactant (B) is lower than the heating temperature for forming the sintered film, and the melting point of the surfactant (B) is in the range of 50 to 100°C.
本発明によれば、経時的な粘度の低下などによる変化が少なく、粘度の保存安定性に優れる、金属微粒子（Ｐ）の分散溶液を得ることができる。 According to the present invention, it is possible to obtain a dispersion solution of metal fine particles (P) which is less likely to change due to a decrease in viscosity over time and has excellent storage stability of viscosity.
また、本発明によれば、上記金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる、焼結導電体を得ることができる。 Further, according to the present invention, in the process of applying the dispersion solution of the metal fine particles (P) onto the substrate and performing the sintering by the heat treatment (sintering process), large voids (voids) are formed in the sintered film. It is possible to obtain a sintered conductor that is suppressed in frequency of occurrence, has low electric resistance, and is excellent in conductivity.
（１）金属微粒子（Ｐ）の分散溶液（第１の実施形態）
第１の実施形態に係る金属微粒子（Ｐ）の分散溶液は、平均一次粒子径が５〜５００ｎｍの範囲にある、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）、および界面活性剤（Ｂ）を、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）に分散させてなる。
第１の実施形態に係る金属微粒子（Ｐ）の分散溶液中、本発明で用いる界面活性剤（Ｂ）は、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）に表面修飾される。
(1) Dispersion solution of metal fine particles (P) (first embodiment)
The dispersion solution of the metal fine particles (P) according to the first embodiment is a metal fine particles (P) coated with a polymer dispersant (D) having an average primary particle diameter in the range of 5 to 500 nm, and a surfactant. The agent (B) is dispersed in an organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol.
In the dispersion solution of the metal fine particles (P) according to the first embodiment, the surfactant (B) used in the present invention is surface-modified to the metal fine particles (P) coated with the polymer dispersant (D). ..
（１−１）高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）
本発明において、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の原料となる金属は、特に限定されないが、銅、銀、金、白金、およびパラジウムの中から選択される１種または２種以上であることが好ましい。
(1-1) Metal fine particles (P) coated with polymer dispersant (D)
In the present invention, the metal serving as a raw material for the metal fine particles (P) coated with the polymer dispersant (D) is not particularly limited, but is one selected from copper, silver, gold, platinum, and palladium. Alternatively, two or more kinds are preferable.
本発明で用いる、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の原料となる金属の形態は、単体金属、合成金属（合金）、および金属化合物の群から選択される少なくとも１種であることが好ましい。 The form of the metal used as the raw material of the metal fine particles (P) coated with the polymer dispersant (D) used in the present invention is at least one selected from the group consisting of a simple metal, a synthetic metal (alloy), and a metal compound. It is preferably a seed.
単体金属としては、例えば、銅、銀、金、白金、およびパラジウムの中から選択されることが好ましい。 The elemental metal is preferably selected from, for example, copper, silver, gold, platinum, and palladium.
合成金属（合金）としては、例えば、銅、銀、金、白金、およびパラジウムの中から選択される少なくとも２種以上から構成されることが好ましい。 The synthetic metal (alloy) is preferably composed of, for example, at least two kinds selected from copper, silver, gold, platinum, and palladium.
金属化合物としては、上記単体金属の酸化物、および上記合成金属（合金）の酸化物等であることが好ましい。 The metal compound is preferably an oxide of the elemental metal, an oxide of the synthetic metal (alloy), or the like.
本発明において、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の平均一次粒子径は、５〜５００ｎｍの範囲にある。好ましくは１０〜５０ｎｍの範囲にある。 In the present invention, the average primary particle size of the metal fine particles (P) coated with the polymer dispersant (D) is in the range of 5 to 500 nm. It is preferably in the range of 10 to 50 nm.
上記金属微粒子（Ｐ）の平均一次粒子径が、上記範囲（５〜５００ｎｍ）にある場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応において、金属微粒子（Ｐ）が触媒として作用し、加水分解反応の進行速度を向上させ、金属微粒子（Ｐ）の分散溶液の焼結を促進させる効果が期待できる。 When the average primary particle diameter of the metal fine particles (P) is in the above range (5 to 500 nm), a process of applying a dispersion solution of the metal fine particles (P) onto a substrate and performing sintering by heat treatment. In the hydrolysis reaction of water molecules (H 2 O) decomposed and produced in the (sintering process) and the surfactant (B), the metal fine particles (P) act as a catalyst, and the progress rate of the hydrolysis reaction And the effect of promoting the sintering of the dispersion solution of the metal fine particles (P) can be expected.
上記金属微粒子（Ｐ）の平均一次粒子径が、上記範囲未満（５ｎｍ未満）である場合には、金属微粒子（Ｐ）が酸化され易くなる他、凝集し易くなり、分散溶液中、均一分散され難く、粘度の保存安定性に劣るおそれがある。 When the average primary particle diameter of the metal fine particles (P) is less than the above range (less than 5 nm), the metal fine particles (P) are likely to be oxidized and easily aggregated to be uniformly dispersed in the dispersion solution. It may be difficult and the storage stability of the viscosity may be poor.
一方、上記金属微粒子（Ｐ）の平均一次粒子径が、上記範囲を超える（５００ｎｍを超える）場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う焼結温度を上げなければならず、緻密性の高い均質な焼結膜を形成することができないおそれがある。 On the other hand, when the average primary particle diameter of the metal fine particles (P) exceeds the above range (exceeds 500 nm), the dispersion solution of the metal fine particles (P) is applied onto the substrate and sintered by heat treatment. Since the sintering temperature to be performed must be raised, there is a possibility that a highly dense and homogeneous sintered film cannot be formed.
ここで「平均一次粒子径」とは、走査型電子顕微鏡（ＳＥＭ）を使用して、観察可能な任意に選択した粒子の一次粒径をそれぞれ測定し、特定の粒径分布範囲にある粒子を対象として、それぞれの一次粒径の測定値の平均を算出したものをいう。 Here, the "average primary particle size" means that the primary particle size of any observable particles is measured by using a scanning electron microscope (SEM), and particles in a specific particle size distribution range are measured. As an object, the average of the measured values of each primary particle size is calculated.
具体的には、走査型電子顕微鏡（ＳＥＭ）を使用して、観察可能な任意に選択した８０個の金属微粒子（Ｐ）の一次粒径を測定した。
測定した金属微粒子（Ｐ）全体（８０個）のうち、一次粒径が小さい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）と、一次粒径が大きい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）とを除き、残り金属微粒子（Ｐ）全体（８０個）の９０％に相当する金属微粒子（Ｐ）（７２個）を対象とし、７２個の金属微粒子（Ｐ）の一次粒径の測定値の平均を算出し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の平均一次粒径とした。
Specifically, a scanning electron microscope (SEM) was used to measure the primary particle diameter of 80 observable arbitrarily selected metal fine particles (P).
Of the measured total metal fine particles (P) (80 pieces), the metal primary particles (P) (4 pieces) corresponding to 5% of the whole metal fine particle (P) pieces (80 pieces) are counted in order from the smallest primary particle size. ) And metal fine particles (P) (4 pieces) corresponding to 5% of the whole metal fine particles (P) (80 pieces) counted in order from the largest primary particle diameter, the remaining metal fine particles (P) as a whole Targeting the fine metal particles (P) (72 pieces) corresponding to 90% of (80 pieces), the average of the measured primary particle diameters of the 72 fine metal particles (P) was calculated, and the polymer dispersant (D) The average primary particle diameter of the metal fine particles (P) coated with
本発明で用いる金属微粒子（Ｐ）の含有量は、金属微粒子（Ｐ）の分散溶液の全量１００重量％に対して、２０〜７０重量％であることが好ましい。 The content of the metal fine particles (P) used in the present invention is preferably 20 to 70% by weight based on 100% by weight of the total amount of the dispersion solution of the metal fine particles (P).
上記金属微粒子（Ｐ）の含有量が、上記範囲にある場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布するのに適した粘度が得られ、加熱処理による焼結を行う過程（焼結過程）で、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応において、金属微粒子（Ｐ）が触媒として作用し、加水分解反応の進行速度を向上させ、金属微粒子（Ｐ）の分散溶液の焼結を促進させる効果が期待できる。 When the content of the metal fine particles (P) is within the above range, a viscosity suitable for coating the dispersion solution of the metal fine particles (P) on the substrate is obtained, and sintering by heat treatment is performed. In the hydrolysis reaction of water molecules (H 2 O) generated by decomposition in the process (sintering process) and the surfactant (B), the metal fine particles (P) act as a catalyst to promote the hydrolysis reaction. The effect of improving the speed and promoting the sintering of the dispersion solution of the metal fine particles (P) can be expected.
上記金属微粒子（Ｐ）の含有量が、上記範囲未満である場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布するのに適した粘度よりも低く、液だれし易いおそれがある他に、加熱処理による焼結を行う過程（焼結過程）で、金属微粒子（Ｐ）が触媒として作用する効果が期待できないおそれがある。 When the content of the metal fine particles (P) is less than the above range, the dispersion solution of the metal fine particles (P) is lower than the viscosity suitable for coating on the substrate, and the liquid may easily drip. In addition, there is a possibility that the effect of the metal fine particles (P) acting as a catalyst cannot be expected in the process of performing heat treatment sintering (sintering process).
一方、上記金属微粒子（Ｐ）の含有量が、上記範囲を超える場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布するのに適した粘度よりも高く、塗布する方法が制限されるおそれがある他に、金属微粒子（Ｐ）が触媒として作用する割合が高くなるため、有機溶媒（Ｓ）の分解が早く進行し、焼結膜を形成する加熱温度（焼結温度）に達する前に有機溶媒（Ｓ）が枯渇してしまうおそれがある。 On the other hand, when the content of the metal fine particles (P) exceeds the above range, the dispersion solution of the metal fine particles (P) is higher than the viscosity suitable for coating on the substrate, and the coating method is limited. In addition to the possibility that the metal fine particles (P) act as a catalyst, the decomposition of the organic solvent (S) progresses quickly and reaches the heating temperature (sintering temperature) for forming a sintered film. The organic solvent (S) may be depleted before.
（１−２）高分子分散剤（Ｄ）
本発明で用いる高分子分散剤（Ｄ）は、金属微粒子（Ｐ）の原料となる金属の表面を被覆して、金属微粒子（Ｐ）を形成することができるものであれば、特に限定されるものではない。
(1-2) Polymer dispersant (D)
The polymer dispersant (D) used in the present invention is particularly limited as long as it can form the metal fine particles (P) by coating the surface of the metal as the raw material of the metal fine particles (P). Not a thing.
ここで「被覆」とは、金属微粒子（Ｐ）の原料となる金属の表面の少なくとも一部を覆うことを指していい、金属微粒子（Ｐ）の原料となる金属の表面の全体を覆うものであってもよい。 Here, “coating” refers to covering at least a part of the surface of the metal that is the raw material of the metal fine particles (P), and covers the entire surface of the metal that is the raw material of the metal fine particles (P). It may be.
本発明で用いる高分子分散剤（Ｄ）の数平均分子量は、特に限定されないが、３，０００〜５，０００であることが好ましい。 The number average molecular weight of the polymer dispersant (D) used in the present invention is not particularly limited, but is preferably 3,000 to 5,000.
上記高分子分散剤（Ｄ）の数平均分子量が、上記範囲未満である場合には、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させることができず、金属微粒子（Ｐ）と界面活性剤（Ｂ）との間で、分子間力が作用し難くなり、金属微粒子（Ｐ）の表面に界面活性剤（Ｂ）を好適に修飾させることができないおそれがある。 When the number average molecular weight of the polymer dispersant (D) is less than the above range, the surface of the metal that is the raw material of the metal fine particles (P) cannot be suitably covered, and the metal fine particles (P) The intermolecular force is less likely to act between the surfactant and the surfactant (B), and the surfactant (B) may not be appropriately modified on the surface of the metal fine particles (P).
一方、上記高分子分散剤（Ｄ）の数平均分子量が、上記範囲を超える場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、焼結膜内に高分子分散剤（Ｄ）が残留し、電気抵抗を高める原因となるおそれがある。 On the other hand, when the number average molecular weight of the polymer dispersant (D) exceeds the above range, a process of applying a dispersion solution of the metal fine particles (P) on a substrate and performing sintering by heat treatment (calcination) During the binding process), the polymer dispersant (D) may remain in the sintered film, which may increase the electric resistance.
本発明で用いる高分子分散剤（Ｄ）は、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させる観点から、分子中に少なくとも１つのカルボニル基を有する化合物、又は分子中に少なくとも１つの窒素原子を有する化合物であることが好ましい。 The polymer dispersant (D) used in the present invention is a compound having at least one carbonyl group in the molecule, or at least one in the molecule, from the viewpoint of suitably coating the surface of the metal as the raw material of the metal fine particles (P). It is preferable that the compound has one nitrogen atom.
本発明で用いる高分子分散剤（Ｄ）としては、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させることができるものであれば、特に限定されないが、例えば、ポリビニルピロリドン、ポリエチレンイミン、ポリアクリル酸、カルボキシメチルセルロース、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキシド、デンプン、およびゼラチン等が挙げられ、これらの中から選択される１種又は２種以上であることが好ましい。 The polymer dispersant (D) used in the present invention is not particularly limited as long as it can suitably coat the surface of the metal as the raw material of the metal fine particles (P), and examples thereof include polyvinylpyrrolidone and polyethylene. Examples thereof include imine, polyacrylic acid, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, starch, and gelatin, and one or more selected from these are preferable.
本発明で用いる、高分子分散剤（Ｄ）と高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）との重量比（Ｄ／Ｐ）は、特に限定されないが、０．２〜０．５の範囲にあることが好ましい。 The weight ratio (D/P) of the polymer dispersant (D) and the metal fine particles (P) coated with the polymer dispersant (D) used in the present invention is not particularly limited, but is 0.2 to 0. It is preferably in the range of 0.5.
上記高分子分散剤（Ｄ）と金属微粒子（Ｐ）との重量比（Ｄ／Ｐ）が、上記範囲未満である場合には、高分子分散剤（Ｄ）の割合が少な過ぎ、金属微粒子（Ｐ）の原料となる金属の表面を好適に被覆させることができず、金属微粒子（Ｐ）と界面活性剤（Ｂ）との間で、分子間力が作用し難くなり、金属微粒子（Ｐ）の表面に界面活性剤（Ｂ）を好適に修飾させることができないおそれがある。 When the weight ratio (D/P) of the polymer dispersant (D) and the metal fine particles (P) is less than the above range, the proportion of the polymer dispersant (D) is too small and the metal fine particles ( The surface of the metal which is the raw material of P) cannot be suitably coated, and it becomes difficult for an intermolecular force to act between the metal fine particles (P) and the surfactant (B). There is a possibility that the surfactant (B) cannot be suitably modified on the surface of the.
一方、上記高分子分散剤（Ｄ）の含有量が、上記範囲を超える場合には、高分子分散剤（Ｄ）の割合が多過ぎ、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、焼結膜内に高分子分散剤（Ｄ）が残留し、電気抵抗を高める原因となるおそれがある。 On the other hand, when the content of the polymer dispersant (D) exceeds the above range, the ratio of the polymer dispersant (D) is too high, and the dispersion solution of the metal fine particles (P) is applied onto the substrate. However, the polymer dispersant (D) may remain in the sintered film in the process of performing the sintering by the heat treatment (sintering process), which may increase the electric resistance.
本発明において、平均一次粒子径が５〜５００ｎｍの範囲にある、高分子分散剤（Ｄ）で被覆された表面を有する金属微粒子（Ｐ）を製造する方法は、特に限定されないが、液相還元法（電解法又は無電解法）を用いて製造することができる。 In the present invention, the method for producing the metal fine particles (P) having the average primary particle diameter in the range of 5 to 500 nm and having the surface coated with the polymer dispersant (D) is not particularly limited, but liquid phase reduction It can be manufactured using a method (electrolytic method or electroless method).
電解法による液相還元法としては、例えば、金属イオンを含む水溶液および高分子分散剤（Ｄ）を含む混合溶液を電解槽に入れ、電極（陽極：アノード、陰極：カソード）を配置し、アノードとカソード間で通電させることによってカソード付近に、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）が電析し、回収される。 As the liquid-phase reduction method by electrolysis, for example, a mixed solution containing an aqueous solution containing metal ions and a polymer dispersant (D) is placed in an electrolytic cell, electrodes (anode:anode, cathode:cathode) are arranged, and an anode is prepared. By supplying electricity between the cathode and the cathode, the metal fine particles (P) coated with the polymer dispersant (D) are electrodeposited near the cathode and collected.
これに対して、無電解法による液相還元法としては、例えば、還元剤を含む水溶液に、高分子分散剤（Ｄ）を添加して、攪拌溶解させ、金属イオンを含む水溶液を滴下し、金属微粒子の混合溶液を調製する。 On the other hand, as a liquid-phase reduction method by an electroless method, for example, a polymer dispersant (D) is added to an aqueous solution containing a reducing agent and dissolved by stirring, and an aqueous solution containing metal ions is dropped, A mixed solution of metal fine particles is prepared.
なお、金属微粒子の混合溶液は、金属イオンを含む水溶液に、高分子分散剤（Ｄ）を添加して、攪拌溶解させ、還元剤を含む水溶液を加えて調製されてもよい。 The mixed solution of metal fine particles may be prepared by adding the polymer dispersant (D) to an aqueous solution containing metal ions, stirring and dissolving the solution, and adding an aqueous solution containing a reducing agent.
ここで用いる還元剤としては、例えば、水素化ホウ素ナトリウム、ヒドラジン、ジメチルアミノボラン、およびトリメチルアミノボラン等が挙げられる。 Examples of the reducing agent used here include sodium borohydride, hydrazine, dimethylaminoborane, and trimethylaminoborane.
また、ここで用いる金属イオンを形成する金属塩としては、例えば、塩化物、硝酸塩、亜硝酸塩、硫酸塩、アンモニウム塩、および酢酸塩等の金属塩が挙げられる。 Examples of the metal salt forming a metal ion used here include metal salts such as chlorides, nitrates, nitrites, sulfates, ammonium salts, and acetates.
次に、上記のように調製した金属微粒子の混合溶液に、凝集促進剤などの添加剤を添加し、攪拌し静置した後、沈殿した固形分を含む混合溶液を遠心分離機に供給することによって、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）が分離・回収される。 Next, to the mixed solution of metal fine particles prepared as described above, add an additive such as an aggregation promoter, stir and leave still, and then supply the mixed solution containing the precipitated solid content to the centrifuge. Thus, the metal fine particles (P) coated with the polymer dispersant (D) are separated and collected.
ここで用いる凝集促進剤としては、ハロゲン系炭化水素が好ましく用いられ、例えば、塩化メチル、塩化メチレン、クロロホルム、および四塩化炭素等の炭素原子数１の塩素系化合物；塩化エチル、１,１−ジクロルエタン、１,２−ジクロルエタン、１,１−ジクロルエチレン、１,２−ジクロルエチレン、トリクロルエチレン、四塩化アセチレン、およびエチレンクロロヒドリン等の炭素原子数２の塩素系化合物；１,２−ジクロルプロパン、および塩化アリル、等の炭素原子数３の塩素系化合物；クロロプレン等の炭素原子数４の塩素系化合物；クロルベンゼン、塩化ベンジル、ｏ−ジクロルベンゼン、ｍ−ジクロルベンゼン、ｐ−ジクロルベンゼン、α−クロルナフタリン、およびβ−クロルナフタリン等の芳香族系塩素系化合物；ブロモホルム、およびブロムベンゾール等の臭素系化合物；等が挙げられる。 As the aggregation accelerator used here, a halogen-based hydrocarbon is preferably used, and examples thereof include a chlorine-based compound having 1 carbon atom such as methyl chloride, methylene chloride, chloroform, and carbon tetrachloride; ethyl chloride, 1,1- Chlorinated compounds having 2 carbon atoms such as dichloroethane, 1,2-dichloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, acetylene tetrachloride, and ethylenechlorohydrin; 1,2 A chlorine-containing compound having 3 carbon atoms such as dichloropropane and allyl chloride; a chlorine-containing compound having 4 carbon atoms such as chloroprene; chlorobenzene, benzyl chloride, o-dichlorobenzene, m-dichlorobenzene, Aromatic chlorine-based compounds such as p-dichlorobenzene, α-chlornaphthalene, and β-chlornaphthalene; bromine compounds such as bromoform and brombenzol; and the like.
（１−３）有機溶媒（Ｓ）
本発明で用いる有機溶媒は、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）である。
上記二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）を用いることで、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）が、ガス成分と水分子（Ｈ２Ｏ）とに好適に分解される。
(1-3) Organic solvent (S)
The organic solvent used in the present invention is an organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol.
A process of applying a dispersion solution of metal fine particles (P) onto a substrate and sintering by heat treatment by using the organic solvent (S) composed of the above dihydric alcohol and/or trihydric alcohol (sintering process ), the organic solvent (S) is suitably decomposed into gas components and water molecules (H 2 O).
本発明で用いる有機溶媒は、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）であれば、特に限定されない。
二価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、２−ブテン−１，４−ジオール、１，２−ペンタンジオール、１，５−ペンタンジオール、１，２−ヘキサンジオール、および１，６−ヘキサンジオール等が挙げられ、これらの中から選択される少なくとも１種であることが好ましい。
The organic solvent used in the present invention is not particularly limited as long as it is an organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol.
Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2- Butene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol and the like can be mentioned, and at least one selected from these It is preferably a seed.
また、三価アルコールとしては、例えば、グリセロール、１，２，４−ブタントリオール、および１，２，６−ヘキサントリオール等が挙げられ、これらの中から選択される少なくとも１種であることが好ましい。 Examples of the trihydric alcohol include glycerol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like, and at least one selected from these is preferable. ..
本発明で用いる、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）と有機溶媒（Ｓ）との重量比（Ｐ／Ｓ）は、特に限定されないが、３０／７０〜５５／４５の範囲にあることが好ましい。 The weight ratio (P/S) of the fine metal particles (P) coated with the polymer dispersant (D) and the organic solvent (S) used in the present invention is not particularly limited, but is 30/70 to 55/45. It is preferably in the range of.
上記金属微粒子（Ｐ）と有機溶媒（Ｓ）との重量比（Ｐ／Ｓ）が、上記範囲未満である場合には、有機溶媒（Ｓ）の割合が多過ぎ、金属微粒子（Ｐ）の分散溶液を、基板上に塗布するのに適した粘度よりも低く、液だれし易いおそれがある他に、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）が、ガス成分と水分子（Ｈ２Ｏ）とに好適に分解されないおそれがある。 When the weight ratio (P/S) of the metal fine particles (P) to the organic solvent (S) is less than the above range, the proportion of the organic solvent (S) is too large, and the metal fine particles (P) are dispersed. The solution has a viscosity lower than that suitable for coating on a substrate and may easily drip. In addition, a dispersion solution of metal fine particles (P) is coated on a substrate and sintered by heat treatment. In the process (sintering process), the organic solvent (S) may not be appropriately decomposed into gas components and water molecules (H 2 O).
一方、上記金属微粒子（Ｐ）と有機溶媒（Ｓ）との重量比（Ｐ／Ｓ）が、上記範囲を超える場合には、有機溶媒（Ｓ）の割合が少な過ぎ、金属微粒子（Ｐ）の分散溶液を、基板上に塗布するのに適した粘度よりも高く、塗布する方法が制限されるおそれがある他に、加熱処理による焼結を行う過程（焼結過程）で、焼結膜を形成する加熱温度（焼結温度）に達する前に有機溶媒（Ｓ）が枯渇してしまう（気化してしまう）おそれがある。 On the other hand, when the weight ratio (P/S) of the metal fine particles (P) to the organic solvent (S) exceeds the above range, the ratio of the organic solvent (S) is too small, and the metal fine particles (P) have The viscosity of the dispersion solution is higher than that suitable for coating on the substrate, the coating method may be limited, and a sintered film is formed in the process of sintering by heat treatment (sintering process). The organic solvent (S) may be depleted (vaporized) before reaching the heating temperature (sintering temperature).
本発明で用いる、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）は、緻密性の高い均質な焼結膜を形成する観点から、金属微粒子（Ｐ）の分散溶液を基板上に塗布し、加熱処理による焼結を行う際に、焼結膜を形成する加熱温度（焼結温度）よりも高い沸点を有するものが好ましく用いられる。 The organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol used in the present invention is a dispersion solution of metal fine particles (P) coated on a substrate from the viewpoint of forming a highly dense and homogeneous sintered film. However, when performing sintering by heat treatment, those having a boiling point higher than the heating temperature (sintering temperature) for forming the sintered film are preferably used.
すなわち、本発明で用いる、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）は、沸点が、焼結膜を形成する加熱温度（焼結温度）よりも高く、２５０℃以上の範囲にあるものが好ましく用いられる。 That is, the organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol used in the present invention has a boiling point higher than the heating temperature (sintering temperature) for forming a sintered film and is in the range of 250° C. or higher. Some are preferably used.
上記有機溶媒（Ｓ）の沸点が、上記範囲未満である場合には、金属微粒子（Ｐ）の分散溶液を基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、焼結膜を形成する加熱温度（焼結温度）に達する前に有機溶媒（Ｓ）が気化して枯渇してしまうおそれがある。 When the boiling point of the organic solvent (S) is less than the above range, the dispersion solution of the metal fine particles (P) is applied onto the substrate and sintered in a heating process (sintering process). The organic solvent (S) may be vaporized and exhausted before reaching the heating temperature (sintering temperature) for forming the conjunctiva.
本発明において、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）、および界面活性剤（Ｂ）を分散溶媒中に分散させる方法は、特に限定されず、公知の手法に従い、例えば、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）および界面活性剤（Ｂ）を、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）に添加し、３本ロールミル、遠心混練、および超音波発生機（超音波ホモジナイザー）などの分散機を用いて分散処理を行うことで、均一分散させる。 In the present invention, the method of dispersing the metal fine particles (P) coated with the polymer dispersant (D) and the surfactant (B) in the dispersion solvent is not particularly limited, and may be a known method, for example, The metal fine particles (P) coated with the polymer dispersant (D) and the surfactant (B) are added to an organic solvent (S) consisting of a dihydric alcohol and/or a trihydric alcohol, followed by three-roll milling and centrifugation. Kneading and dispersion treatment using a disperser such as an ultrasonic generator (ultrasonic homogenizer) are performed to achieve uniform dispersion.
（１−４）界面活性剤（Ｂ）
本発明で用いる界面活性剤（Ｂ）は、分散溶液中、高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）に表面修飾する性質を有するものであれば、特に限定されるものではない。
(1-4) Surfactant (B)
The surfactant (B) used in the present invention is not particularly limited as long as it has a property of surface-modifying the metal fine particles (P) coated with the polymer dispersant (D) in the dispersion solution. Absent.
ここで「表面修飾」とは、高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）と界面活性剤（Ｂ）との間で、静電力に起因する分子間力が作用し、金属微粒子（Ｐ）の表面に、界面活性剤（Ｂ）が引き付けられて修飾される（覆われる）ことを指していう。 Here, the term "surface modification" means that an intermolecular force due to electrostatic force acts between the metal fine particles (P) coated with the polymer dispersant (D) and the surfactant (B), and It means that the surface of the fine particles (P) is attracted and modified (covered) with the surfactant (B).
本発明においては、分散溶液中、高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）の表面が、界面活性剤（Ｂ）により修飾される（覆われる）ため、撥水効果が付与され、水分子（Ｈ２Ｏ）が高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）の内部に滲み入る（吸湿される）のを抑制することができる。 In the present invention, the surface of the metal fine particles (P) coated with the polymer dispersant (D) in the dispersion solution is modified (covered) with the surfactant (B), so that a water repellent effect is imparted. Thus, it is possible to prevent water molecules (H 2 O) from seeping into (absorbing) the metal fine particles (P) coated with the polymer dispersant (D).
このため、金属微粒子（Ｐ）の分散溶液は、分散溶液中、水分子（Ｈ２Ｏ）が金属微粒子（Ｐ）の内部に滲み入り難いため（吸湿され難いため）、ある程度長期保存した後であっても（例えば、１か月間保存した後であっても）、経時的な粘度の低下などによる変化が少なく、粘度の保存安定性に優れる。 Therefore, in the dispersion solution of the metal fine particles (P), water molecules (H 2 O) hardly penetrate into the inside of the metal fine particles (P) in the dispersion solution (because it is difficult to absorb moisture), and thus after being stored for a long time to some extent. Even if it exists (for example, even after storage for one month), there is little change due to a decrease in viscosity over time, and the storage stability of viscosity is excellent.
また、本発明において、金属微粒子（Ｐ）の分散溶液を用いて形成される焼結導電体は、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、分散溶液中の二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）が、ガス成分と水分子（Ｈ２Ｏ）とに分解される。 In the present invention, the sintered conductor formed by using the dispersion solution of the metal fine particles (P) is a process in which the dispersion solution of the metal fine particles (P) is applied on the substrate and sintered by heat treatment. In the (sintering process), the organic solvent (S) composed of the dihydric alcohol and/or the trihydric alcohol in the dispersion solution is decomposed into gas components and water molecules (H 2 O).
このとき、有機溶媒（Ｓ）の分解により生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）とが反応し、加水分解が進行し、水分子（Ｈ２Ｏ）がＨ（プロトン成分）とＯＨ（水酸化物成分）とに分離し、これらはそれぞれの反応生成物に取り込まれるため、基板上に形成される焼結膜内に水分子（Ｈ２Ｏ）が残存するのを抑制することができる。 At this time, the water molecule (H 2 O) generated by the decomposition of the organic solvent (S) and the surfactant (B) react with each other, the hydrolysis proceeds, and the water molecule (H 2 O) becomes H( Proton component) and OH (hydroxide component) are separated, and these are incorporated into the respective reaction products, so that water molecules (H 2 O) remain in the sintered film formed on the substrate. Can be suppressed.
このため、金属微粒子（Ｐ）の分散溶液を用いて形成される焼結導電体は、焼結過程で、有機溶媒（Ｓ）から分解生成される水分子（Ｈ２Ｏ）が焼結膜内に残存し難いため、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる。 Therefore, in the sintered conductor formed by using the dispersion solution of the metal fine particles (P), water molecules (H 2 O) decomposed and produced from the organic solvent (S) in the sintering process are present in the sintered film. Since it does not easily remain, the frequency with which large voids (voids) occur in the sintered film is suppressed, and the electrical resistance is low and the conductivity is excellent.
本発明で用いる界面活性剤（Ｂ）としては、高分子分散剤（Ｄ）に被覆された金属微粒子（Ｐ）の分散溶液中、金属微粒子（Ｐ）に表面修飾する性質を有するものであれば、特に限定されないが、例えば、「糖アルコール脂肪酸エステル」が好ましく用いられる。 As the surfactant (B) used in the present invention, as long as it has a property of surface-modifying the metal fine particles (P) in a dispersion solution of the metal fine particles (P) coated with the polymer dispersant (D). Although not particularly limited, for example, “sugar alcohol fatty acid ester” is preferably used.
ここで「糖アルコール脂肪酸エステル」とは、「糖アルコール」と「脂肪酸」との脱水縮合反応により生成されるエステル化合物のことを指していう。 Here, the "sugar alcohol fatty acid ester" refers to an ester compound produced by a dehydration condensation reaction between a "sugar alcohol" and a "fatty acid".
界面活性剤（Ｂ）として「糖アルコール脂肪酸エステル」を用いた場合、有機溶媒（Ｓ）の分解により生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）とが反応し、加水分解が進行し、水分子（Ｈ２Ｏ）がＨ（プロトン成分）とＯＨ（水酸化物成分）とに分離し、これらはそれぞれの反応生成物、すなわち「糖アルコール」および「脂肪酸」にそれぞれ取り込まれる。 When the “sugar alcohol fatty acid ester” is used as the surfactant (B), the water molecule (H 2 O) generated by the decomposition of the organic solvent (S) reacts with the surfactant (B) to give water. As the decomposition progresses, water molecules (H 2 O) are separated into H (proton component) and OH (hydroxide component), which are divided into respective reaction products, that is, “sugar alcohol” and “fatty acid”, respectively. It is captured.
有機溶媒（Ｓ）から分解生成する水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）として用いた「糖アルコール脂肪酸エステル」とが加水分解反応することによって、「脂肪酸」が生成される。当該「脂肪酸」の生成は、加熱処理による焼結を行う過程（焼結過程）で、金属微粒子（Ｐ）の分散溶液の焼結を促進させる効果が期待できる。 Water molecules (H 2 O) that are decomposed and produced from the organic solvent (S) and the “sugar alcohol fatty acid ester” used as the surfactant (B) undergo a hydrolysis reaction to produce “fatty acids”. The production of the "fatty acid" can be expected to have an effect of promoting the sintering of the dispersion solution of the metal fine particles (P) in the process of performing the heating treatment (the sintering process).
「糖アルコール脂肪酸エステル」を構成する「糖アルコール」としては、特に限定されないが、炭素原子数Ｃ３〜Ｃ６の糖アルコールが好ましく用いられる。 The "sugar alcohol" constituting the "sugar alcohol fatty acid ester" is not particularly limited, but a sugar alcohol having a carbon number of C3 to C6 is preferably used.
「糖アルコール」の具体例としては、例えば、プロピレングリコール（炭素原子数：３，ＯＨ基：２）、グリセロール（炭素原子数：３，ＯＨ基：３）、エリスリトール（炭素原子数：４，ＯＨ基：４）、キシリトール（炭素原子数：５，ＯＨ基：５）、アラビトール（炭素原子数：５，ＯＨ基：５）、ソルビトール（炭素原子数：６，ＯＨ：６）、およびマンニトール（炭素原子数：６，ＯＨ基：６）等が代表的に挙げられる。 Specific examples of the "sugar alcohol" include, for example, propylene glycol (carbon atom number: 3, OH group: 2), glycerol (carbon atom number: 3, OH group: 3), erythritol (carbon atom number: 4, OH). Group: 4), xylitol (number of carbon atoms: 5, OH group: 5), arabitol (number of carbon atoms: 5, OH group: 5), sorbitol (number of carbon atoms: 6, OH: 6), and mannitol (carbon) Typical examples are the number of atoms: 6, OH group: 6) and the like.
「糖アルコール脂肪酸エステル」を構成する「脂肪酸」としては、特に限定されないが、炭素原子数Ｃ１０〜Ｃ２２の飽和又は不飽和の脂肪酸が好ましく用いられる。 The "fatty acid" constituting the "sugar alcohol fatty acid ester" is not particularly limited, but a saturated or unsaturated fatty acid having 10 to 22 carbon atoms is preferably used.
「脂肪酸」の具体例としては、例えば、カプリン酸（炭素原子数：１０）、ラウリン酸（炭素原子数：１２）、ミリスチン酸（炭素原子数：１４）、パルミチン酸（炭素原子数：１６）、オレイン酸（炭素原子数：１８）、ステアリン酸（炭素原子数：１８）、およびベヘン酸（炭素原子数：２２）等が代表的に挙げられる。 Specific examples of the “fatty acid” include, for example, capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms). Representative examples thereof include oleic acid (carbon atom number: 18), stearic acid (carbon atom number: 18), and behenic acid (carbon atom number: 22).
本発明において、界面活性剤（Ｂ）として好ましく用いられる「糖アルコール脂肪酸エステル」としては、例えば、プロピレングリコールモノラウレート、プロピレングリコールモノパルミテート、プロピレングリコールモノオレート、プロピレングリコールモノステアレート、およびプロピレングリコールモノベヘネート等のプロピレングリコール脂肪酸エステル；グリセリンモノカプリレート、グリセリンモノラウレート、グリセリンモノオレート、グリセリンモノステアレート、およびグリセリンモノベヘネート等のグリセリン脂肪酸エステル；ソルビタンラウレート、ソルビタンミリステート、ソルビタンパルミテート、ソルビタンオレート、ソルビタントリオレート、ソルビタンステアレート、ソルビタントリステアレート、およびソルビタントリベヘネート等のソルビタン脂肪酸エステル；等が代表的に挙げられる。これらは、１種又は２種以上を組み合わせて用いることができる。 Examples of the “sugar alcohol fatty acid ester” preferably used as the surfactant (B) in the present invention include propylene glycol monolaurate, propylene glycol monopalmitate, propylene glycol monooleate, propylene glycol monostearate, and propylene. Propylene glycol fatty acid ester such as glycol monobehenate; glycerin monocaprylate, glycerin monolaurate, glycerin monooleate, glycerin monostearate, and glycerin fatty acid ester such as glycerin monobehenate; sorbitan laurate, sorbitan myristate, sorbitan Representative examples thereof include sorbitan fatty acid esters such as palmitate, sorbitan oleate, sorbitan trioleate, sorbitan stearate, sorbitan tristearate, and sorbitan tribehenate. These can be used alone or in combination of two or more.
本発明で用いる界面活性剤（Ｂ）の含有量は、金属微粒子（Ｐ）の分散溶液の全量１００重量％に対して、１．０〜５．０重量％であることが好ましい。 The content of the surfactant (B) used in the present invention is preferably 1.0 to 5.0% by weight based on 100% by weight of the total amount of the dispersion solution of the metal fine particles (P).
上記界面活性剤（Ｂ）の含有量が、上記範囲にある場合には、分散溶液中、水分子（Ｈ２Ｏ）が金属微粒子（Ｐ）の内部に滲み入り難いため（吸湿され難いため）、ある程度長期保存した後であっても経時的な粘度の低下などによる変化が少なく、粘度の保存安定性に優れる、金属微粒子（Ｐ）の分散溶液が得られる。 When the content of the surfactant (B) is within the above range, water molecules (H 2 O) are less likely to permeate into the metal fine particles (P) in the dispersion solution (because they are less likely to be absorbed). It is possible to obtain a dispersion solution of the metal fine particles (P), which has little change due to a decrease in viscosity over time even after being stored for a certain period of time, and has excellent viscosity storage stability.
また、上記界面活性剤（Ｂ）の含有量が、上記範囲にある場合には、金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）から分解生成される水分子（Ｈ２Ｏ）が焼結膜内に残存し難いため、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる、焼結導電体が得られる。 When the content of the surfactant (B) is in the above range, a process of applying a dispersion solution of the metal fine particles (P) on a substrate and performing sintering by heat treatment (sintering process ), it is difficult for water molecules (H 2 O) generated by decomposition from the organic solvent (S) to remain in the sintered film, so that the frequency of occurrence of large voids (voids) in the sintered film is suppressed, and the electrical resistance is A sintered conductor having a small amount and excellent conductivity can be obtained.
上記界面活性剤（Ｂ）の含有量が、上記範囲未満である場合には、界面活性剤（Ｂ）の含有量が少な過ぎ、金属微粒子（Ｐ）と界面活性剤（Ｂ）との間で、分子間力が作用し難くなり、金属微粒子（Ｐ）の表面に界面活性剤（Ｂ）を好適に修飾させることができず、水分子（Ｈ２Ｏ）が金属微粒子（Ｐ）の内部に滲み入り易いため（吸湿され易いため）、粘度の保存安定性に劣る、金属微粒子（Ｐ）の分散溶液しか得られないおそれがある。 When the content of the surfactant (B) is less than the above range, the content of the surfactant (B) is too small, and the content between the metal fine particles (P) and the surfactant (B) is small. However, the intermolecular force becomes difficult to act, the surface of the metal fine particles (P) cannot be suitably modified with the surfactant (B), and the water molecules (H 2 O) remain inside the metal fine particles (P). Since it easily penetrates (because it is easily absorbed), there is a possibility that only a dispersion solution of the metal fine particles (P) having poor storage stability of viscosity can be obtained.
また、上記界面活性剤（Ｂ）の含有量が、上記範囲未満である場合には、金属微粒子（Ｐ）の分散溶液の焼結過程で、水分子（Ｈ２Ｏ）が焼結膜内に残存し易く、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられず、電気抵抗が増大し導電性に劣る、焼結導電体しか得られないおそれがある。 When the content of the surfactant (B) is less than the above range, water molecules (H 2 O) remain in the sintered film during the sintering process of the dispersion solution of the metal fine particles (P). However, the frequency of occurrence of large voids (voids) in the sintered film cannot be suppressed, the electrical resistance increases, and the electrical conductivity is inferior.
一方、上記界面活性剤（Ｂ）の含有量が、上記範囲を超える場合には、界面活性剤（Ｂ）の含有量が多過ぎ、分散溶液中、水分子（Ｈ２Ｏ）が金属微粒子（Ｐ）の内部に滲み入り難いものの（吸湿され難いものの）、その一方で、金属微粒子（Ｐ）の表面に修飾された（覆われた）界面活性剤（Ｂ）が、時間の経過とともに剥がれ易く、粘度の保存安定性に劣る、金属微粒子（Ｐ）の分散溶液しか得られないおそれがある。 On the other hand, when the content of the surfactant (B) exceeds the above range, the content of the surfactant (B) is too large, and the water molecules (H 2 O) in the dispersion solution are metal fine particles ( P) does not easily penetrate into the interior of P) (although it is difficult to absorb moisture), on the other hand, the surface-modified surfactant (B) modified (covered) on the surface of the metal fine particles (P) easily peels off with the passage of time. However, there is a possibility that only a dispersion solution of the metal fine particles (P) having poor storage stability of viscosity can be obtained.
また、上記界面活性剤（Ｂ）の含有量が、上記範囲を超える場合には、金属微粒子（Ｐ）の分散溶液の焼結過程で、焼結膜内に水分子（Ｈ２Ｏ）が残存するのを抑制することはできるものの、その一方で、焼結膜内に界面活性剤（Ｂ）が残留し、電気抵抗を高める原因となるおそれがある。 If the content of the surfactant (B) exceeds the above range, water molecules (H 2 O) remain in the sintered film during the sintering process of the dispersion solution of the metal fine particles (P). However, on the other hand, the surfactant (B) may remain in the sintered film, which may increase the electric resistance.
本発明で用いる界面活性剤（Ｂ）は、金属微粒子（Ｐ）の分散溶液を基板上に塗布し、加熱処理による焼結を行う過程（焼結過程）で、有機溶媒（Ｓ）の分解により生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）とが反応し、加水分解を好適に進行させる観点から、水分子（Ｈ２Ｏ）が分解生成する温度範囲において、界面活性剤（Ｂ）が溶融状態にあるものが好ましく用いられる。 The surfactant (B) used in the present invention is obtained by applying a dispersion solution of the metal fine particles (P) onto a substrate and performing sintering by heat treatment (sintering process) by decomposing the organic solvent (S). and a water molecule (H 2 O) generated, in response surfactant and (B) is, from the viewpoint of suitably proceeds hydrolysis in the temperature range of a water molecule (H 2 O) is produced degradation, surfactant The agent (B) in a molten state is preferably used.
すなわち、本発明で用いる界面活性剤（Ｂ）は、金属微粒子（Ｐ）の分散溶液を基板上に塗布し、加熱処理による焼結を行う際に、焼結膜を形成する加熱温度（焼結温度）よりも低い融点を有するものが好ましく用いられる。 That is, the surfactant (B) used in the present invention is a heating temperature (sintering temperature) for forming a sintered film when a dispersion solution of metal fine particles (P) is applied onto a substrate and sintered by heat treatment. Those having a melting point lower than that of (1) are preferably used.
本発明で用いる界面活性剤（Ｂ）の融点は、５０〜１００℃の範囲にあることが好ましい。 The melting point of the surfactant (B) used in the present invention is preferably in the range of 50 to 100°C.
上記界面活性剤（Ｂ）の融点が、上記範囲にある場合には、金属微粒子（Ｐ）の分散溶液の焼結過程で、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応が好適に進行し、水分子（Ｈ２Ｏ）が焼結膜内に残存し難く、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる焼結導電体が得られる。 When the melting point of the surfactant (B) is within the above range, water molecules (H 2 O) decomposed and generated in the sintering process of the dispersion solution of the metal fine particles (P) and the surfactant ( The hydrolysis reaction with B) proceeds properly, water molecules (H 2 O) hardly remain in the sintered film, the frequency of large voids (voids) generated in the sintered film is suppressed, and the electrical resistance is low. A sintered conductor having excellent conductivity can be obtained.
本発明で用いる界面活性剤（Ｂ）の融点が、上記範囲未満である場合には、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応が好適に進行し難く、水分子（Ｈ２Ｏ）が焼結膜内に残存し易いおそれがある。 When the melting point of the surfactant (B) used in the present invention is less than the above range, the hydrolysis reaction between the water molecule (H 2 O) generated by decomposition and the surfactant (B) is suitable. It is difficult to proceed, and water molecules (H 2 O) may easily remain in the sintered film.
一方、本発明で用いる界面活性剤（Ｂ）の融点が、上記範囲を超える場合には、分解生成される水分子（Ｈ２Ｏ）が気化され易い環境におかれるため、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応が好適に進行し難くなるおそれがある。 On the other hand, when the melting point of the surfactant (B) used in the present invention exceeds the above range, water molecules (H 2 O) that are decomposed and formed are placed in an environment where they are easily vaporized, so that water that is decomposed and formed is generated. There is a possibility that the hydrolysis reaction between the molecule (H 2 O) and the surfactant (B) may be difficult to proceed suitably.
本発明で用いる界面活性剤（Ｂ）の沸点は、１００℃以下の範囲にあることが好ましく、３０〜７０℃の範囲にあることがより好ましい。 The boiling point of the surfactant (B) used in the present invention is preferably in the range of 100°C or lower, and more preferably in the range of 30 to 70°C.
上記界面活性剤（Ｂ）の沸点が、上記範囲にある場合には、金属微粒子（Ｐ）の分散溶液の焼結過程で、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応が好適に進行し、水分子（Ｈ２Ｏ）が焼結膜内に残存し難く、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる焼結導電体が得られる。 When the boiling point of the surfactant (B) is in the above range, water molecules (H 2 O) decomposed and generated in the sintering process of the dispersion solution of the metal fine particles (P) and the surfactant ( The hydrolysis reaction with B) proceeds properly, water molecules (H 2 O) hardly remain in the sintered film, the frequency of large voids (voids) generated in the sintered film is suppressed, and the electrical resistance is low. A sintered conductor having excellent conductivity can be obtained.
本発明で用いる界面活性剤（Ｂ）の沸点が、上記範囲を超える場合には、分解生成される水分子（Ｈ２Ｏ）が気化され易い環境におかれるため、分解生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解反応が好適に進行し難くなるおそれがある。 When the boiling point of the surfactant (B) used in the present invention exceeds the above range, the water molecules (H 2 O) that are decomposed and formed are placed in an environment where they are easily vaporized, and therefore the water molecules ( There is a possibility that the hydrolysis reaction between H 2 O) and the surfactant (B) may not proceed appropriately.
（１−５）その他の添加剤
上述したように、第１の実施形態に係る金属微粒子（Ｐ）の分散溶液は、平均一次粒子径が５〜５００ｎｍの範囲にある、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）、および界面活性剤（Ｂ）を、二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）に分散させてなる。
(1-5) Other Additives As described above, the dispersion solution of the metal fine particles (P) according to the first embodiment has a polymer dispersant (D) having an average primary particle diameter in the range of 5 to 500 nm. ) The fine metal particles (P) coated with (1) and the surfactant (B) are dispersed in an organic solvent (S) composed of a dihydric alcohol and/or a trihydric alcohol.
第１の実施形態に係る金属微粒子（Ｐ）の分散溶液は、平均一次粒子径が５〜５００ｎｍの範囲にある、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）、界面活性剤（Ｂ）、および二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）を必須の配合成分とする分散溶液であるが、用途に応じて、適宜その他の添加剤を配合させてもよい。 The dispersion solution of the metal fine particles (P) according to the first embodiment has a mean primary particle diameter in the range of 5 to 500 nm, the metal fine particles (P) coated with the polymer dispersant (D), and a surfactant. Although it is a dispersion solution containing (B) and an organic solvent (S) consisting of a dihydric alcohol and/or a trihydric alcohol as essential components, other additives may be appropriately blended depending on the application. ..
その他の添加剤としては、例えば、流動性向上剤、分散安定化剤、増粘剤、粘度調整剤、チクソトロピー調整剤、および消泡剤等が代表的に挙げられる。これらは、１種又は２種以上を組み合わせて用いることができる。 Representative examples of other additives include fluidity improvers, dispersion stabilizers, thickeners, viscosity modifiers, thixotropy modifiers, and defoamers. These can be used alone or in combination of two or more.
（２）焼結導電体（第２の実施形態）
第２の実施形態に係る焼結導電体は、上述した第１の実施形態に係る金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、大気雰囲気中又は不活性ガス雰囲気中、加熱処理による焼結を行う過程（焼結過程）で、焼結膜を形成する加熱温度（焼結温度）は、緻密性の高い均質な焼結膜を形成する観点から、２００〜２７０℃の温度範囲にあることが好ましい。
(2) Sintered conductor (second embodiment)
The sintered conductor according to the second embodiment is obtained by applying the dispersion solution of the metal fine particles (P) according to the above-described first embodiment onto a substrate and performing heat treatment in an air atmosphere or an inert gas atmosphere. The heating temperature (sintering temperature) for forming the sintered film in the process of performing the sintering (sintering process) is in the temperature range of 200 to 270° C. from the viewpoint of forming a highly dense and homogeneous sintered film. It is preferable.
上記焼結膜を形成する加熱温度（焼結温度）が、上記範囲未満である場合には、焼結温度が低過ぎ、金属微粒子（Ｐ）の分散溶液の焼結を好ましく進行させることができず、緻密性の高い均質な焼結膜が形成されず、電気抵抗が増大し導電性に劣る、焼結導電体しか得られないおそれがある。 When the heating temperature for forming the above-mentioned sintered film (sintering temperature) is less than the above range, the sintering temperature is too low, and the sintering of the dispersion solution of the metal fine particles (P) cannot proceed favorably. However, there is a possibility that only a sintered conductor may be obtained in which a highly dense and homogeneous sintered film is not formed, electric resistance increases, and conductivity is poor.
上述した第１の実施形態に係る金属微粒子（Ｐ）の分散溶液を用いれば、焼結膜を形成する焼結条件を、無加圧又は低加圧としたとしても、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れる焼結導電体が得られる。 If the dispersion solution of the metal fine particles (P) according to the first embodiment described above is used, large voids (voids) will be burned even if the sintering conditions for forming the sintered film are no pressure or low pressure. The frequency of occurrence in the conjunctiva is suppressed, and a sintered conductor having low electrical resistance and excellent conductivity can be obtained.
ここで「無加圧」とは、全く加圧をかけないことを指していい、「低加圧」とは、加圧力を最大でも１ＭＰａとしたものである。 Here, "no pressure" means that no pressure is applied at all, and "low pressure" means that the pressure is 1 MPa at the maximum.
上述した第１の実施形態に係る金属微粒子（Ｐ）の分散溶液によれば、焼結条件を、無加圧又は低加圧としたとしても、緻密性の高い均質な焼結膜を形成することができるが、必要に応じて適宜加圧してもよい。 According to the dispersion solution of the metal fine particles (P) according to the first embodiment described above, it is possible to form a highly dense and homogeneous sintered film even if the sintering condition is no pressure or low pressure. However, the pressure may be appropriately increased if necessary.
例えば、水分子（Ｈ２Ｏ）が焼結膜内に残存し、大きな空隙（ボイド）が焼結膜内に発生してしまった場合、適宜加圧を行うことで焼結膜に生じた不具合を改善することができることもある。 For example, when water molecules (H 2 O) remain in the sintered film and large voids (voids) are generated in the sintered film, the pressurization is appropriately performed to improve the problem caused in the sintered film. There are some things you can do.
金属微粒子（Ｐ）の分散溶液を、基板上に塗布し、加熱処理による焼結を行う前に、予め、加熱処理等による乾燥を行うことが、緻密性の高い均質な焼結膜を形成する観点から望ましい。
上記加熱処理等による乾燥条件は、使用する有機溶媒（Ｓ）にもよるが、望ましくは１００〜２００℃の温度で１５〜３０分間の乾燥条件を挙げることができる。
From the viewpoint of forming a highly dense and homogeneous sintered film, the dispersion solution of the metal fine particles (P) is applied onto the substrate and dried by heat treatment or the like before sintering by heat treatment. From desirable.
The drying conditions by the above heat treatment and the like depend on the organic solvent (S) used, but preferably, the drying conditions at a temperature of 100 to 200° C. for 15 to 30 minutes can be mentioned.
金属微粒子（Ｐ）の分散溶液を基板上に塗布する方法は、特に限定されないが、例えば、スキージ法、スクリーン印刷、マスク印刷、インクジェット印刷、ディスペンサ印刷、スプレーコート、バーコート、ナイフコート、およびスピンコート等が挙げられる。 The method of applying the dispersion solution of the metal fine particles (P) onto the substrate is not particularly limited, and examples thereof include squeegee method, screen printing, mask printing, inkjet printing, dispenser printing, spray coating, bar coating, knife coating, and spin. Examples include coats.
金属微粒子（Ｐ）の分散溶液を塗布する基板の種類は、特に限定されないが、例えば、ガラス基板、セラミック基板、銅基板、およびポリイミド基板等が挙げられる。 The type of substrate on which the dispersion solution of the metal fine particles (P) is applied is not particularly limited, and examples thereof include a glass substrate, a ceramic substrate, a copper substrate, and a polyimide substrate.
（３）導電接続部材（その他の実施形態）
その他の実施形態に係る導電接続部材は、上述した第１の実施形態に係る金属微粒子（Ｐ）の分散溶液を、電子部品における半導体素子、回路基板の電極端子、及び導電性基板のいずれかの一の接合面に塗布した後、当該塗布した一の接合面上に、更に接続する別の半導体素子、電極端子、及び導電性基板のいずれかの他の接合面を積層配置し、加熱処理又は加圧処理により上記一の接合面と上記他の接合面とを焼結して導電接続部材を形成するものである。
(3) Conductive connection member (other embodiments)
A conductive connecting member according to another embodiment is obtained by using the dispersion solution of the metal fine particles (P) according to the first embodiment described above in any one of a semiconductor element in an electronic component, an electrode terminal of a circuit board, and a conductive board. After applying to one bonding surface, another semiconductor element to be further connected, an electrode terminal, and any other bonding surface of the conductive substrate are laminated and arranged on the applied one bonding surface, and heat treatment or The conductive connection member is formed by sintering the one joint surface and the other joint surface by a pressure treatment.
導電接続部材としては、半導体素子と導電性基板間を接合するための導電性ダイボンド部等が挙げられるがこれらに限定されない。 Examples of the conductive connection member include, but are not limited to, a conductive die bond portion for joining a semiconductor element and a conductive substrate.
導電性ダイボンド部は、通常、金属微粒子（Ｐ）の分散溶液を電子部品における回路基板の接合面に載せ（塗布、印刷等も含まれる）、当該銅微粒子集合体の分散溶液上に更に接続する他方の電極端子の接合面を積層配置した後、加熱処理又は加圧処理により上記一の接合面と上記他の接合面とを焼結して形成される。 The conductive die bond portion is usually placed with a dispersion solution of metal fine particles (P) on a bonding surface of a circuit board in an electronic component (including coating and printing), and further connected to the dispersion solution of the copper fine particle aggregate. After the bonding surface of the other electrode terminal is laminated and arranged, it is formed by sintering the one bonding surface and the other bonding surface by heat treatment or pressure treatment.
加圧下の加熱処理は、両電極端子間、又は電極端子と基板間の加圧により導電接続部材前躯体と両電極端子接合面、又は電極端子と導電性基板間との接合を確実にするか、又は導電接続部材前躯体に適切な変形を生じさせて電極端子接合面との確実な接合を行うことができるとともに、導電接続部材前躯体と電極端子接合面との接合面積が大きくなり、接合信頼性を一層向上することができる。 Does the heat treatment under pressure ensure bonding between the electrode terminals or between the electrode terminals and the substrate by applying pressure between the conductive connecting member precursor and both electrode terminal joint surfaces or between the electrode terminals and the conductive substrate? , Or the conductive connection member precursor can be appropriately deformed to perform reliable bonding with the electrode terminal bonding surface, and the bonding area between the conductive connecting member precursor and the electrode terminal bonding surface increases, The reliability can be further improved.
また、半導体素子と導電接続部材前躯体間を加圧型ヒートツ−ル等を用いて加圧下で焼結を行うと、接合部での焼結性が向上してより良好な接合部が得られる。上記両電極端子間、又は電極端子と基板間の加圧は、０．５〜１５ＭＰａが好ましい。 When the semiconductor element and the conductive connecting member precursor are sintered under pressure using a pressure type heat tool or the like, the sinterability at the joint is improved and a better joint can be obtained. The pressure applied between the two electrode terminals or between the electrode terminals and the substrate is preferably 0.5 to 15 MPa.
以下に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、これらの実施例のみに限定されるものではない。
本実施例及び比較例において行った試験方法は、以下のとおりである。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The test methods used in the examples and comparative examples are as follows.
（１）金属微粒子（Ｐ）の評価（平均一次粒子径）
走査型電子顕微鏡（ＳＥＭ）を使用して、観察可能な任意に選択した８０個の金属微粒子（Ｐ）の一次粒径を測定した。
測定した金属微粒子（Ｐ）全体（８０個）のうち、一次粒径が小さい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）と、一次粒径が大きい方から順に数えて、金属微粒子（Ｐ）全体（８０個）の５％に相当する金属微粒子（Ｐ）（４個）とを除き、残り金属微粒子（Ｐ）全体（８０個）の９０％に相当する金属微粒子（Ｐ）（７２個）を対象とし、７２個の金属微粒子（Ｐ）の一次粒径の測定値の平均を算出し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の平均一次粒子径とした。
(1) Evaluation of metal fine particles (P) (average primary particle diameter)
A scanning electron microscope (SEM) was used to measure the primary particle size of 80 observable arbitrarily selected metal fine particles (P).
Of the measured total metal fine particles (P) (80 pieces), the metal primary particles (P) (4 pieces) corresponding to 5% of the whole metal fine particle (P) pieces (80 pieces) are counted in order from the smallest primary particle size. ) And metal fine particles (P) (4 pieces) corresponding to 5% of the whole metal fine particles (P) (80 pieces) counted in order from the largest primary particle diameter, the remaining metal fine particles (P) as a whole Targeting the fine metal particles (P) (72 pieces) corresponding to 90% of (80 pieces), the average of the measured primary particle diameters of the 72 fine metal particles (P) was calculated, and the polymer dispersant (D) The average primary particle diameter of the metal fine particles (P) coated with
（２）金属微粒子（Ｐ）の分散溶液の評価（保存安定性）
金属微粒子（Ｐ）の分散溶液を得る工程において得られた、金属微粒子（Ｐ）の分散溶液に対し、回転式せん断粘度計（英弘精機社製、製品名；回転粘度計（ブルックフィールド））を用い、２５℃、せん断速度４．０Ｓ−１の条件下で、保存前の粘度の測定をした。
一方、金属微粒子（Ｐ）の分散溶液を得る工程において得られた、金属微粒子（Ｐ）の分散溶液を、ガラス製のサンプル瓶に入れ、密栓をして室温で１か月間保存し、上記保存前の粘度測定と同様の条件下で、保存後の粘度の測定をした。
保存前と保存後の粘度測定の結果をそれぞれ比較し、粘度の変化量を以下のように評価した。
Ａ：粘度の変化量が、±１０Ｐａ・ｓ未満のもの
Ｂ：粘度の変化量が、±１０Ｐａ・ｓ以上、且つ、±３０Ｐａ・ｓ以上未満のもの
Ｃ：粘度の変化量が、±３０Ｐａ・ｓ以上のもの
(2) Evaluation of dispersion solution of metal fine particles (P) (storage stability)
A rotary shear viscometer (manufactured by Eiko Seiki Co., Ltd., product name; rotational viscometer (Brookfield)) was used for the dispersion solution of the metal fine particles (P) obtained in the step of obtaining the dispersion solution of the metal fine particles (P). The viscosity before storage was measured under conditions of 25° C. and a shear rate of 4.0 S −1 .
On the other hand, the dispersion solution of the metal fine particles (P) obtained in the step of obtaining the dispersion solution of the metal fine particles (P) was put in a glass sample bottle, and the bottle was tightly stoppered and stored at room temperature for 1 month. The viscosity after storage was measured under the same conditions as the previous viscosity measurement.
The results of viscosity measurement before storage and after storage were compared, and the amount of change in viscosity was evaluated as follows.
A: Viscosity change amount is less than ±10 Pa·s B: Viscosity change amount is ±10 Pa·s or more, and less than ±30 Pa·s C: Viscosity change amount is ±30 Pa·s more than s
（３）焼結膜の評価
（３−１）ボイドの含有率(%)
金属微粒子（Ｐ）の分散溶液の焼結工程において得られた、ガラス基板上に形成された焼結膜に対し、走査型電子顕微鏡（ＳＥＭ）を用い、５００倍率で観察した。
焼結膜に発生した空隙の大きさを、画像処理ソフトで２値化し、所定の単位面積当たり５０％以上の空隙を有する部分をボイドとし、焼結膜に発生したボイドの含有率（％）を算出した。
(3) Evaluation of sintered film (3-1) Void content (%)
The sintered film formed on the glass substrate and obtained in the sintering step of the dispersion solution of the metal fine particles (P) was observed with a scanning electron microscope (SEM) at a magnification of 500.
The size of voids generated in the sintered film is binarized with image processing software, and the content of voids generated in the sintered film (%) is calculated by defining voids that have 50% or more voids per given unit area as voids. did.
（３−２）電気抵抗率（Ω・ｃｍ）
金属微粒子（Ｐ）の分散溶液の焼結工程において得られた、ガラス基板上に形成された焼結膜に対し、抵抗率計（三菱化学社製、製品名；ロレスターＧＰ）を用い、直流四端子法で、焼結膜の電気抵抗率（Ω・ｃｍ）を測定した。
(3-2) Electric resistivity (Ω·cm)
Using a resistivity meter (Mitsubishi Chemical Co., Ltd., product name: Lorester GP) for the sintered film formed on the glass substrate obtained in the sintering step of the dispersion solution of the metal fine particles (P), DC four terminals Method, the electrical resistivity (Ω·cm) of the sintered film was measured.
（４）接合部の評価（ダイシェア強度）
金属微粒子（Ｐ）の分散溶液を得る工程において得られた、金属微粒子（Ｐ）の分散溶液を、ガラス基板（基板サイズ；１５ｍｍ×１５ｍｍ）の接合面に塗布した後、当該塗布した接合面上にシリコンチップの接合面を積層配置した。
(4) Evaluation of joint (die shear strength)
The dispersion solution of the metal fine particles (P) obtained in the step of obtaining the dispersion solution of the metal fine particles (P) is applied to the bonding surface of the glass substrate (substrate size; 15 mm×15 mm), and then on the applied bonding surface. The bonding surfaces of the silicon chips were stacked and arranged.
続いて、窒素ガス雰囲気中、２５０℃の温度で５分間、無加圧下で、加熱処理による焼結を行い、ガラス基板とシリコンチップとを接合させ、室温まで炉冷し、ダイシェア強度測定用のサンプルを作製した。 Then, in a nitrogen gas atmosphere, at a temperature of 250° C. for 5 minutes, without pressure, sintering by heat treatment is performed to bond the glass substrate and the silicon chip, and the furnace is cooled to room temperature to measure the die shear strength. A sample was prepared.
上記作製したサンプルに対して、ダイシェア強度測定機（テイジ・ジャパン（株）社製、製品名；万能型ボンドテスター、型式；シリーズ４０００）を用い、米国ＭＩＬ‐ＳＴＤ‐８８３に準拠し、２５℃の条件下で、ガラス基板とシリコンチップとの接合部のダイシェア強度（剥離強度）を測定した。 Using a die shear strength measuring machine (manufactured by Tage Japan Co., Ltd., product name; universal bond tester, model: series 4000) for the sample prepared above, in accordance with US MIL-STD-883, at 25°C. Under the conditions, the die shear strength (peel strength) of the joint between the glass substrate and the silicon chip was measured.
（実施例１）
（金属微粒子（Ｐ）の分離・回収工程）
金属微粒子（Ｐ）の原料として酢酸第二銅（（ＣＨ３ＣＯＯ）２Ｃｕ・１Ｈ２Ｏ）０．２ｇを蒸留水１０ｍｌに溶解させ、酢酸第二銅水溶液１０ｍｌを調製した。
一方、金属イオン還元剤として水素化ホウ素ナトリウム（ＮａＢＨ４）を、濃度が５．０ｍoｌ/ｌとなるように蒸留水に混合し、水素化ホウ素ナトリウム水溶液１００ｍｌを調製した。
(Example 1)
(Separation/collection process of fine metal particles (P))
As a raw material for the metal fine particles (P), 0.2 g of cupric acetate ((CH 3 COO) 2 Cu·1H 2 O) was dissolved in 10 ml of distilled water to prepare 10 ml of an aqueous cupric acetate solution.
On the other hand, sodium borohydride (NaBH 4 ) as a metal ion reducing agent was mixed with distilled water to a concentration of 5.0 mol/l to prepare 100 ml of an aqueous sodium borohydride solution.
次に、上記調製した水素化ホウ素ナトリウム水溶液１００ｍｌに、高分子分散剤（Ｄ）としてポリビニルピロリドン（ＰＶＰ、数平均分子量；約３，５００）０．１ｇ（金属微粒子（Ｐ）の全量に対して０．５重量％）を添加して攪拌溶解させ、続いて、窒素ガス雰囲気中で、上記調製した酢酸第二銅水溶液１０ｍｌを滴下し、金属微粒子の混合溶液を調製した。 Next, to 100 ml of the above-prepared aqueous sodium borohydride solution, 0.1 g of polyvinylpyrrolidone (PVP, number average molecular weight; about 3,500) as a polymer dispersant (D) (based on the total amount of metal fine particles (P)) 0.5% by weight) was added and dissolved by stirring, and then 10 ml of the above prepared cupric acetate aqueous solution was added dropwise in a nitrogen gas atmosphere to prepare a mixed solution of metal fine particles.
次に、上記調製した金属微粒子の混合溶液に、凝集促進剤としてクロロホルム（ＣＨＣｌ３）５ｍｌを添加して数分間攪拌し、更に数分間静置した後、沈殿した固形分を含む混合溶液を遠心分離機に供給し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）を分離、回収した。 Next, 5 ml of chloroform (CHCl 3 ) as an aggregating promoter was added to the prepared mixed solution of metal fine particles, stirred for several minutes, and allowed to stand for several minutes, and then the mixed solution containing the precipitated solid content was centrifuged. The fine metal particles (P) coated with the polymer dispersant (D) were separated and collected by supplying to a separator.
ここで、上記分離・回収した金属微粒子（Ｐ）の一部を採取し、高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の一次粒径を測定し、平均一次粒子径を算出したところ１２ｎｍであった。 Here, a part of the separated and collected metal fine particles (P) is collected, the primary particle diameter of the metal fine particles (P) coated with the polymer dispersant (D) is measured, and the average primary particle diameter is calculated. The result was 12 nm.
（金属微粒子（Ｐ）の分散溶液を得る工程）
上記金属微粒子（Ｐ）の分離・回収工程で回収された、金属微粒子（Ｐ）５５重量％（金属微粒子の分散溶液の全量に対する含有量）、および界面活性剤（Ｂ）としてグリセリンモノカプリレート（融点；３１℃）１重量％（金属微粒子の分散溶液の全量に対する含有量）を、三価アルコールからなる有機溶媒（Ｓ）としてグリセロール（示性式；Ｃ３Ｈ５（ＯＨ）３，沸点；２９０℃）４４重量％（金属微粒子の分散溶液の全量対する含有量）に添加して、超音波発生機（超音波ホモジナイザー）による分散処理を３０分間行い、金属微粒子の分散溶液を得た。
(Step of Obtaining Dispersion Solution of Metal Fine Particles (P))
55% by weight of the metal fine particles (P) (content relative to the total amount of the dispersion solution of the metal fine particles) recovered in the separation/collection step of the metal fine particles (P), and glycerin monocaprylate (as the surfactant (B)). Melting point: 31° C.) 1% by weight (content relative to the total amount of the fine metal particle dispersion solution) is used as an organic solvent (S) consisting of a trihydric alcohol, glycerol (rational formula: C 3 H 5 (OH) 3 , boiling point; 290° C.) 44% by weight (content relative to the total amount of the fine metal particle dispersion solution), and the dispersion treatment was performed for 30 minutes by an ultrasonic generator (ultrasonic homogenizer) to obtain a fine metal particle dispersion solution.
（金属微粒子（Ｐ）の分散溶液の塗布・焼結工程）
上記得られた金属微粒子（Ｐ）の分散溶液を、スキージ法でガラス基板（基板サイズ；１５ｍｍ×１５ｍｍ）上に塗布した（塗布サイズ；１０ｍｍ×１０ｍｍ）。
(Coating/sintering process of dispersion solution of fine metal particles (P))
The dispersion solution of the obtained metal fine particles (P) was applied onto a glass substrate (substrate size; 15 mm×15 mm) by a squeegee method (application size; 10 mm×10 mm).
窒素ガス雰囲気中、２５０℃の温度で５分間、無加圧下で、加熱処理による焼結を行い、室温まで炉冷し、ガラス基板上に焼結膜が形成された実施例１の焼結導電体を得た。 Sintered conductor of Example 1 in which a sintered film was formed on a glass substrate by sintering in a nitrogen gas atmosphere at a temperature of 250° C. for 5 minutes under no pressure and by heat treatment, followed by furnace cooling to room temperature. Got
（実施例２）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの銅微粒子（Ｐ）から平均一次粒径が１５ｎｍの金属微粒子（Ｐ）に変更し、当該金属微粒子（Ｐ）の含有量を５５重量％から６９重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の種類を三価アルコールのグリセロールから二価アルコールのエチレングリコール（示性式；Ｃ２Ｈ５（ＯＨ）２，沸点；１９７．３℃）に変更し、当該有機溶媒（Ｓ）の含有量を４４重量％から３０重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 2)
In the separation/collection step of the metal fine particles (P) of Example 1, the copper fine particles (P) having an average primary particle diameter of 12 nm were changed to the metal fine particles (P) having an average primary particle diameter of 15 nm, and the metal fine particles (P) ) Content was changed from 55% by weight to 69% by weight, and in the step of obtaining a dispersion solution of the metal fine particles (P) in Example 1, the organic solvent (S) was changed from trihydric alcohol glycerol to dicarboxylic acid. The content of the organic solvent (S) was changed from 44% by weight to 30% by weight by changing the ethylene glycol of the hydric alcohol (ratiomatic formula; C 2 H 5 (OH) 2 , boiling point; 197.3° C.). A sintered conductor was obtained in the same manner as in Example 1 except for the above.
（実施例３）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が１５ｎｍの金属微粒子（Ｐ）に変更し、当該金属微粒子（Ｐ）の含有量を５５重量％から２１重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の含有量を４４重量％から７８重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 3)
In the separation and recovery step of the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle diameter of 12 nm were changed to the metal fine particles (P) having an average primary particle diameter of 15 nm, and the metal fine particles (P ) Content from 55% by weight to 21% by weight, and in the step of obtaining the dispersion solution of the metal fine particles (P) in Example 1, the content of the organic solvent (S) is changed from 44% by weight to 78% by weight. A sintered conductor was obtained in the same manner as in Example 1 except that the content was changed to %.
（実施例４）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が１８ｎｍの金属微粒子（Ｐ）に変更し、当該金属微粒子（Ｐ）の含有量を５５重量％から５０重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の種類を三価アルコールのグリセロールから二価アルコールのジエチレングリコール（示性式；Ｏ（ＣＨ２ＣＨ２ＯＨ）２，沸点；２４４．３℃）に変更し、当該有機溶媒（Ｓ）の含有量を４４重量％から４９重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 4)
In the step of separating and recovering the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle diameter of 12 nm were changed to the metal fine particles (P) having an average primary particle diameter of 18 nm, and the metal fine particles (P) ) Content is changed from 55% by weight to 50% by weight, and in the step of obtaining the dispersion solution of the metal fine particles (P) in Example 1, the organic solvent (S) is changed from trihydric alcohol glycerol to dicarboxylic acid. The content of the organic solvent (S) was changed from 44 wt% to 49 wt% by changing the dihydric alcohol to diethylene glycol (ratiomatic formula; O(CH 2 CH 2 OH) 2 , boiling point; 244.3° C.). A sintered conductor was obtained in the same manner as in Example 1 except for the above.
（実施例５）
実施例４の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の種類を二価アルコールのジエチレングリコールから三価アルコールのグリセロールに変更し、界面活性剤（Ｂ）の種類をグリセリンカプリレートからソルビタンステアレート（融点；５３℃）に変更したこと以外は、実施例４と同様にして焼結導電体を得た。
(Example 5)
In the step of obtaining the dispersion solution of the metal fine particles (P) of Example 4, the kind of the organic solvent (S) was changed from diethylene glycol which is a dihydric alcohol to glycerol which was a trihydric alcohol, and the kind of the surfactant (B) was glycerin. A sintered conductor was obtained in the same manner as in Example 4 except that caprylate was changed to sorbitan stearate (melting point; 53°C).
（実施例６）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が１５ｎｍの金属微粒子（Ｐ）に変更し、実施例１の金属微粒子（Ｐ）の分散溶液の塗布・焼結工程において、焼結過程の加圧条件を、無加圧下から１ＭＰａの加圧下に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 6)
In the step of separating and recovering the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle size of 12 nm was changed to the metal fine particles (P) having an average primary particle size of 15 nm to obtain the metal of Example 1. In the coating/sintering step of the dispersion solution of fine particles (P), the sintered conductor was carried out in the same manner as in Example 1 except that the pressure condition in the sintering process was changed from no pressure to 1 MPa. Got
（実施例７）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が１５ｎｍの金属微粒子（Ｐ）に変更し、実施例１の金属微粒子（Ｐ）の分散溶液の塗布・焼結工程において、焼結過程の加圧条件を、無加圧下から２５ＭＰａの加圧下に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 7)
In the step of separating and recovering the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle size of 12 nm was changed to the metal fine particles (P) having an average primary particle size of 15 nm to obtain the metal of Example 1. In the coating/sintering step of the dispersion solution of the fine particles (P), the sintering conductor was carried out in the same manner as in Example 1 except that the pressure condition in the sintering process was changed from no pressure to 25 MPa. Got
（実施例８）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、金属微粒子（Ｐ）の含有量を５５重量％から５０重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の含有量を４４重量％から４９．９重量％に変更し、界面活性剤（Ｂ）の含有量を１重量％から０．１重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 8)
In the step of separating and recovering the metal fine particles (P) of Example 1, the content of the metal fine particles (P) was changed from 55% by weight to 50% by weight, and further, the dispersion solution of the metal fine particles (P) of Example 1 In the step of obtaining, the content of the organic solvent (S) was changed from 44% by weight to 49.9% by weight, and the content of the surfactant (B) was changed from 1% by weight to 0.1% by weight. A sintered conductor was obtained in the same manner as in Example 1 except for the above.
（実施例９）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、銅微粒子（Ｐ）の含有量を５５重量％から５０重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の含有量を４４重量％から４９．５重量％に変更し、界面活性剤（Ｂ）の含有量を１重量％から０．５重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 9)
In the step of separating and collecting the metal fine particles (P) of Example 1, the content of the copper fine particles (P) was changed from 55% by weight to 50% by weight, and further, the dispersion solution of the metal fine particles (P) of Example 1 was used. In the step of obtaining, the content of the organic solvent (S) was changed from 44% by weight to 49.5% by weight, and the content of the surfactant (B) was changed from 1% by weight to 0.5% by weight. A sintered conductor was obtained in the same manner as in Example 1 except for the above.
（実施例１０）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が１３ｎｍの金属微粒子（Ｐ）に変更し、当該金属微粒子（Ｐ）の含有量を５５重量％から５０重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の含有量を４４重量％から３０重量％に変更し、界面活性剤（Ｂ）の含有量を１重量％から２０重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 10)
In the separation and recovery step of the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle diameter of 12 nm were changed to the metal fine particles (P) having an average primary particle diameter of 13 nm, and the metal fine particles (P ) Content from 55% by weight to 50% by weight, and further, in the step of obtaining the dispersion solution of the metal fine particles (P) of Example 1, the content of the organic solvent (S) is changed from 44% by weight to 30% by weight. %, and the content of the surfactant (B) was changed from 1% by weight to 20% by weight, and a sintered conductor was obtained in the same manner as in Example 1.
（実施例１１）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が１８ｎｍの金属微粒子（Ｐ）に変更し、当該金属微粒子（Ｐ）の含有量を５５重量％から４９重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の種類と含有量を三価アルコールのグリセロール４４重量％から三価アルコールのグリセロール２０重量％と二価アルコールのジエチレングリコール３０重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Example 11)
In the step of separating and recovering the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle diameter of 12 nm were changed to the metal fine particles (P) having an average primary particle diameter of 18 nm, and the metal fine particles (P) ) Content is changed from 55% by weight to 49% by weight, and in the step of obtaining the dispersion solution of the metal fine particles (P) in Example 1, the type and content of the organic solvent (S) are changed to trihydric alcohol. A sintered conductor was obtained in the same manner as in Example 1 except that 44% by weight of glycerol was changed to 20% by weight of glycerol as a trihydric alcohol and 30% by weight of diethylene glycol as a dihydric alcohol.
（比較例１）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、金属微粒子（Ｐ）の含有量を５５重量％から５０重量％に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の含有量を４４重量％から５０重量％に変更し、界面活性剤（Ｂ）を添加しなかったこと以外は、実施例１と同様にして焼結導電体を得た。
(Comparative Example 1)
In the step of separating and recovering the metal fine particles (P) of Example 1, the content of the metal fine particles (P) was changed from 55% by weight to 50% by weight, and further, the dispersion solution of the metal fine particles (P) of Example 1 In the step of obtaining S., the same procedure as in Example 1 was conducted except that the content of the organic solvent (S) was changed from 44% by weight to 50% by weight and the surfactant (B) was not added. Got the body
（比較例２）
実施例１の金属微粒子（Ｐ）の分離・回収工程において、平均一次粒径が１２ｎｍの金属微粒子（Ｐ）から平均一次粒径が５μｍの金属微粒子（Ｐ）に変更し、更に、実施例１の金属微粒子（Ｐ）の分散溶液を得る工程において、有機溶媒（Ｓ）の含有量を４４重量％から４３重量％に変更し、界面活性剤（Ｂ）の含有量を１重量％から２重量％に変更したこと以外は、実施例１と同様にして焼結導電体を得た。
(Comparative example 2)
In the step of separating and collecting the metal fine particles (P) of Example 1, the metal fine particles (P) having an average primary particle size of 12 nm was changed to the metal fine particles (P) having an average primary particle size of 5 μm, and further, Example 1 In the step of obtaining the dispersion solution of the metal fine particles (P), the content of the organic solvent (S) is changed from 44% by weight to 43% by weight, and the content of the surfactant (B) is changed from 1% by weight to 2% by weight. A sintered conductor was obtained in the same manner as in Example 1 except that the content was changed to %.
（結果）
表１には、各実施例および各比較例において行われた、（１）金属微粒子（Ｐ）の評価結果（平均一次粒子径）、（２）金属微粒子（Ｐ）の分散溶液の評価結果（保存安定性）、（３）焼結膜の評価結果（（３−１）ボイドの含有率，（３−２）電気抵抗率）、および（４）接合部の評価結果（ダイシェア強度）を示す。
(result)
In Table 1, (1) evaluation results of metal fine particles (P) (average primary particle diameter), and (2) evaluation results of dispersion solutions of metal fine particles (P) performed in Examples and Comparative Examples ( The storage stability), (3) evaluation results of the sintered film ((3-1) void content, (3-2) electrical resistivity), and (4) evaluation results of joint (die shear strength) are shown.
（結果のまとめ）
表１に記載されている評価結果から、以下のことが分かる。
(Summary of results)
The following can be seen from the evaluation results shown in Table 1.
比較例１の金属微粒子（Ｐ）の分散溶液では、界面活性剤（Ｂ）を添加しなかったことに起因し、以下のことが示された。
比較例１で得られた金属微粒子（Ｐ）の分散溶液は、経時的な粘度の低下による変化が大きく、粘度の保存安定性に劣ることが分かった。
また、比較例１で得られた焼結導電体は、焼結過程で、大きな空隙（ボイド）が焼結膜内に多く発生し、電気抵抗率が高く導電性に劣ることが分かった。
更に、比較例１の金属微粒子（Ｐ）の分散溶液を用いて形成された接合部は、ダイシェア強度が低いことが分かった。
In the dispersion solution of the metal fine particles (P) of Comparative Example 1, the following was shown due to the fact that the surfactant (B) was not added.
It was found that the dispersion solution of the metal fine particles (P) obtained in Comparative Example 1 had a large change due to a decrease in viscosity over time and was inferior in storage stability of viscosity.
It was also found that the sintered conductor obtained in Comparative Example 1 had a large number of large voids (voids) in the sintered film during the sintering process and had a high electrical resistivity and poor conductivity.
Further, it was found that the joint portion formed using the dispersion solution of the metal fine particles (P) of Comparative Example 1 had a low die shear strength.
比較例２の金属微粒子（Ｐ）の分散溶液では、本発明で規定する平均一次粒子径の範囲を超える金属微粒子（Ｐ）を用いたことに起因し、以下のことが示された。
比較例２で得られた金属微粒子（Ｐ）の分散溶液は、経時的な粘度の低下による変化が大きく、粘度の保存安定性に劣ることが分かった。
また、比較例２で得られた焼結導電体は、金属微粒子（Ｐ）が触媒として作用せず、焼結過程で、有機溶媒（Ｓ）の分解により生成される水分子（Ｈ２Ｏ）と、界面活性剤（Ｂ）との加水分解の反応が好適に進行することができず、大きな空隙（ボイド）が焼結膜内に多く発生し、電気抵抗率が高く導電性に劣ることが分かった。
更に、比較例２の金属微粒子（Ｐ）の分散溶液を用いて形成された接合部は、ダイシェア強度が低いことが分かった。
In the dispersion solution of the metal fine particles (P) of Comparative Example 2, the following facts were shown due to the use of the metal fine particles (P) exceeding the range of the average primary particle diameter specified in the present invention.
It was found that the dispersion solution of the metal fine particles (P) obtained in Comparative Example 2 had a large change due to a decrease in viscosity with time and was inferior in storage stability of viscosity.
Further, in the sintered conductor obtained in Comparative Example 2, the metal fine particles (P) did not act as a catalyst, and water molecules (H 2 O) generated by decomposition of the organic solvent (S) in the sintering process. It was found that the hydrolysis reaction with the surfactant (B) could not proceed favorably, large voids were generated in the sintered film, and the electrical resistivity was high and the conductivity was poor. It was
Furthermore, it was found that the joint portion formed using the dispersion solution of the metal fine particles (P) of Comparative Example 2 had a low die shear strength.
これに対して、実施例１〜１１の金属微粒子（Ｐ）の分散溶液では、本発明で規定する平均一次粒子径の範囲の金属微粒子（Ｐ）を用い、本発明で規定する金属微粒子（Ｐ）に表面修飾する界面活性剤（Ｂ）を用い、本発明で規定する二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）を用いたことに起因し、以下のことが示された。 On the other hand, in the dispersion solution of the metal fine particles (P) of Examples 1 to 11, the metal fine particles (P) within the range of the average primary particle diameter defined by the present invention are used, and the metal fine particles (P) defined by the present invention are used. The following was shown due to the fact that the surfactant (B) for surface modification was used for the above) and the organic solvent (S) consisting of the dihydric alcohol and/or the trihydric alcohol defined in the present invention was used. ..
実施例１〜７で得られた金属微粒子（Ｐ）の分散溶液は、経時的な粘度の低下による変化が少なく、粘度の保存安定性に優れることが分かった。
更に、実施例１〜７の金属微粒子（Ｐ）の分散溶液を用いて形成された接合部は、ダイシェア強度が高いことが分かった。
これらの中でも、実施例１〜５の焼結導電体は、焼結の加圧条件を無加圧としたとしても、焼結過程で、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れることが分かった。
It was found that the dispersion solutions of the metal fine particles (P) obtained in Examples 1 to 7 showed little change due to the decrease in viscosity with time and were excellent in storage stability of viscosity.
Further, it was found that the joints formed using the dispersion solutions of the metal fine particles (P) of Examples 1 to 7 had high die shear strength.
Among them, in the sintered conductors of Examples 1 to 5, even if the pressure condition for sintering was set to no pressure, the frequency of occurrence of large voids (voids) in the sintered film during the sintering process was high. It was found that it was suppressed, the electric resistance was small, and the conductivity was excellent.
実施例６の焼結導電体は、焼結の加圧条件を１ＭＰａとして得られたものであるが、実施例１の焼結導電体と同程度に、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少なく導電性に優れることが分かった。 The sintered conductor of Example 6 was obtained by setting the sintering pressurizing condition to 1 MPa, but large voids (voids) were formed in the sintered film to the same extent as the sintered conductor of Example 1. It was found that the occurrence frequency was suppressed, the electrical resistance was low, and the conductivity was excellent.
実施例７の焼結導電体は、焼結の加圧条件を２５ＭＰａとして得られたものであったため、実施例１〜６よりも大きな空隙（ボイド）が焼結膜内に発生する頻度が更に抑えられ、電気抵抗がより少なく導電性に優れることが分かった。
また、実施例７の金属微粒子（Ｐ）の分散溶液を用いて形成された接合部は、実施例１〜６よりもダイシェア強度が高いことが分かった。
The sintered conductor of Example 7 was obtained under the sintering pressurizing condition of 25 MPa, so that the frequency of generation of voids larger than those in Examples 1 to 6 in the sintered film is further suppressed. It was found that the electrical resistance was smaller and the conductivity was excellent.
It was also found that the joint portion formed using the dispersion solution of the metal fine particles (P) of Example 7 had a higher die shear strength than Examples 1 to 6.
実施例８、９で得られた金属微粒子（Ｐ）の分散溶液は、界面活性剤（Ｂ）の含有量が少なかったため、経時的な粘度の低下による変化がみられた。また、実施例８、９の焼結導電体は、実施例１〜７よりも大きな空隙（ボイド）が焼結膜内に発生する頻度が増し、電気抵抗が高くなる傾向がみられた。
更に、実施例８、９の金属微粒子（Ｐ）の分散溶液を用いて形成された接合部は、実施例１〜７よりもダイシェア強度が低くなる傾向がみられた。
Since the dispersion solutions of the metal fine particles (P) obtained in Examples 8 and 9 contained a small amount of the surfactant (B), changes due to a decrease in viscosity with time were observed. In addition, in the sintered conductors of Examples 8 and 9, the voids larger than those in Examples 1 to 7 were more frequently generated in the sintered film, and the electric resistance tended to increase.
Furthermore, the joints formed using the dispersion solutions of the metal fine particles (P) of Examples 8 and 9 tended to have lower die shear strength than Examples 1 to 7.
実施例１０で得られた金属微粒子（Ｐ）の分散溶液は、界面活性剤（Ｂ）の含有量が多かったため、経時的な粘度の低下による変化がみられた。また、実施例１０の焼結導電体は、実施例８、９よりも大きな空隙（ボイド）が焼結膜内に発生する頻度は少なくなる傾向がみられ、電気抵抗は高くなる傾向がみられた。
更に、実施例１０の金属微粒子（Ｐ）の分散溶液を用いて形成された接合部は、実施例８、９よりもダイシェア強度が低くなる傾向がみられた。
The dispersion solution of the metal fine particles (P) obtained in Example 10 contained a large amount of the surfactant (B), so that the change due to the decrease in viscosity with time was observed. Further, in the sintered conductor of Example 10, the frequency with which voids (voids) larger than those in Examples 8 and 9 tend to occur in the sintered film was observed to be low, and the electric resistance was likely to be increased. ..
Furthermore, the bonded portion formed using the dispersion solution of the metal fine particles (P) of Example 10 tended to have lower die shear strength than Examples 8 and 9.
実施例１１の金属微粒子（Ｐ）の分散溶液では、二価アルコール及び三価アルコール両方からなる有機溶媒（Ｓ）を用いたことに起因し、以下のことが示された。
実施例１１で得られた金属微粒子（Ｐ）の分散溶液は、経時的な粘度の低下による変化が少ないことが分かった。
また、実施例２で得られた焼結導電体は、焼結過程で、大きな空隙（ボイド）が焼結膜内に発生する頻度が抑えられ、電気抵抗が少ないことが分かった。
In the dispersion solution of the metal fine particles (P) of Example 11, due to the use of the organic solvent (S) consisting of both dihydric alcohol and trihydric alcohol, the following was shown.
It was found that the dispersion solution of the metal fine particles (P) obtained in Example 11 had little change due to the decrease in viscosity with time.
It was also found that the sintered conductor obtained in Example 2 had a low frequency of occurrence of large voids (voids) in the sintered film during the sintering process, and had a low electric resistance.
Claims (4)
前記高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）が、前記界面活性剤（Ｂ）によって表面修飾されてなり、
前記高分子分散剤（Ｄ）で被覆された金属微粒子（Ｐ）の原料となる金属が、銅であり、
前記高分子分散剤（Ｄ）が、分子中に少なくとも１つのカルボニル基を有する化合物、又は分子中に少なくとも１つの窒素原子を有する化合物であり、前記高分子分散剤（Ｄ）の数平均分子量が、３０００〜５０００であり、
前記界面活性剤（Ｂ）が、糖アルコール脂肪酸エステル類の群から選択される少なくとも１種であり、前記界面活性剤（Ｂ）の含有量が、金属微粒子（Ｐ）の分散溶液の全量１００重量％に対して、１．０〜５．０重量％であり、
前記二価アルコール及び／又は三価アルコールからなる有機溶媒（Ｓ）の沸点が１９７．３℃以上の範囲にある、金属微粒子の分散溶液。 The metal fine particles (P) coated with the polymer dispersant (D) and the surfactant (B) having an average primary particle diameter of 5 to 500 nm are composed of a dihydric alcohol and/or a trihydric alcohol. In a dispersion solution of metal fine particles (P) dispersed in an organic solvent (S),
The coated metal particles with a polymer dispersant (D) (P) is, Ri Na been surface modified by the surfactant (B),
The metal as a raw material of the metal fine particles (P) coated with the polymer dispersant (D) is copper,
The polymer dispersant (D) is a compound having at least one carbonyl group in the molecule, or a compound having at least one nitrogen atom in the molecule, and the number average molecular weight of the polymer dispersant (D) is , 3000-5000,
The surfactant (B) is at least one selected from the group of sugar alcohol fatty acid esters, and the content of the surfactant (B) is 100 weight% of the total amount of the dispersion solution of the metal fine particles (P). % To 1.0 to 5.0% by weight,
It said divalent boiling alcohols and / or organic solvents consisting of trihydric alcohols (S) is area by the near above 197.3 ° C., the dispersion solution of metal fine particles.
前記界面活性剤（Ｂ）の融点が、５０〜１００℃の範囲にあることを特徴とする、請求項１から３のいずれか１項に記載の金属微粒子の分散溶液。 The surfactant (B) has a melting point lower than the heating temperature for forming a sintered film when the dispersion solution of the metal fine particles (P) is applied onto a substrate and sintered by heat treatment,
The melting point of the surfactant (B), characterized in that in the range of 50 to 100 ° C., the dispersion solution of metal fine particles according to any one of claims 1 to 3.
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