JP4811066B2 - Chargeable powder for circuit formation, method for producing the same, and method for producing a glass substrate having a circuit pattern - Google Patents
Chargeable powder for circuit formation, method for producing the same, and method for producing a glass substrate having a circuit pattern Download PDFInfo
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- JP4811066B2 JP4811066B2 JP2006074772A JP2006074772A JP4811066B2 JP 4811066 B2 JP4811066 B2 JP 4811066B2 JP 2006074772 A JP2006074772 A JP 2006074772A JP 2006074772 A JP2006074772 A JP 2006074772A JP 4811066 B2 JP4811066 B2 JP 4811066B2
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- 239000011521 glass Substances 0.000 title claims description 160
- 239000000758 substrate Substances 0.000 title claims description 48
- 230000015572 biosynthetic process Effects 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000843 powder Substances 0.000 title description 31
- 239000002245 particle Substances 0.000 claims description 97
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 34
- 239000002923 metal particle Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 25
- 230000009477 glass transition Effects 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000011247 coating layer Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は、電子写真法によって被印刷物上に回路パターンを形成するにあたって用いられる回路形成用荷電性粉末およびその製造方法に関し、さらに電子写真法によって形成された回路パターンを有するガラス基板の製造方法に関する。 The present invention relates to a charged powder for circuit formation used for forming a circuit pattern on a printed material by electrophotography and a method for manufacturing the same, and further relates to a method for manufacturing a glass substrate having a circuit pattern formed by electrophotography. .
被印刷物上に導電性の回路パターンを形成する方法として電子写真法がある。電子写真法に用いられる回路パターン形成用の荷電性粒子には以下の特性が要求される。 There is an electrophotographic method as a method for forming a conductive circuit pattern on a substrate. The charged particles for forming circuit patterns used in electrophotography are required to have the following characteristics.
（１）導電性を有する必要がある一方、十分に帯電するためには、少なくとも外周が絶縁物で構成されている必要がある。 (1) While it is necessary to have electrical conductivity, at least the outer periphery needs to be comprised with an insulator in order to fully charge.
（２）回路パターンのはがれを防止するため、被印刷物に対して十分な固着強度を有していなければならない。 (2) In order to prevent peeling of the circuit pattern, it must have a sufficient fixing strength to the substrate.
かかる要求を満たそうとするものとして、特許文献１に記載された回路形成用荷電性粉末がある。この回路形成用荷電性粉末は、導電性金属粉末の表面に金属酸化物粒子を固着させ、その外周に樹脂を被覆したことを特徴とする。 There exists a chargeable powder for circuit formation described in patent document 1 as what is going to satisfy | fill this request | requirement. This charged powder for circuit formation is characterized in that metal oxide particles are fixed to the surface of a conductive metal powder and a resin is coated on the outer periphery thereof.
この発明は、導電性金属粉末の表面に金属酸化物粒子を固着させることにより、被印刷物であるセラミック基板と回路パターンとの接合強度を向上させている。また、外周を樹脂で被覆することにより帯電性を確保している。 According to the present invention, the bonding strength between a ceramic substrate as a printed material and a circuit pattern is improved by fixing metal oxide particles to the surface of the conductive metal powder. In addition, the charging property is secured by coating the outer periphery with a resin.
さらに別の先行技術として特許文献２には、導電性金属粉末とガラス粉末とを荷電制御剤を熱溶融性樹脂中に分散した構造を有する回路印刷用荷電性粒子が記載されている。この発明によれば、ガラス粉末を含むことにより、ガラス粉末が絶縁基板中のガラス成分と反応して回路パターンと絶縁基板の界面での密着性が向上する。また、熱溶融性樹脂によって帯電性を確保している。
特許文献１および２に記載された発明は、被印刷物としてセラミック基板やガラス成分を含む絶縁基板を用いているが、近年、電子写真法によってガラス基板上に回路を形成することが試みられている。 In the inventions described in Patent Documents 1 and 2, a ceramic substrate or an insulating substrate containing a glass component is used as a substrate to be printed. In recent years, attempts have been made to form a circuit on a glass substrate by electrophotography. .
特許文献１，２に記載された回路形成用荷電性粒子を用いてガラス基板上に回路パターンを形成する場合、回路パターンとガラス基板との間に十分な接着強度を得られない。これは、特許文献１，２は例えば１０００℃（特許文献1の［００２０］段落参照）や９００℃（特許文献２の［００１６］段落参照）といった高温での熱処理に耐えうるセラミック基板や絶縁基板を被印刷物としているため、荷電性粒子の印刷後に高温で熱処理することによって被印刷物との接着強度を高めることができるのに対して、ガラス基板はこのような高温での熱処理に耐えられないためである。 When a circuit pattern is formed on a glass substrate using the charged particles for circuit formation described in Patent Documents 1 and 2, sufficient adhesive strength cannot be obtained between the circuit pattern and the glass substrate. For example, Patent Documents 1 and 2 are ceramic substrates and insulating substrates that can withstand heat treatment at high temperatures such as 1000 ° C. (see paragraph [0020] in Patent Document 1) and 900 ° C. (see paragraph [0016] in Patent Document 2). Because the glass substrate cannot withstand the heat treatment at such a high temperature, the glass substrate cannot withstand the heat treatment at such a high temperature. It is.
また、特許文献２に記載された発明では、熱溶融性樹脂中に導電性金属粉末を分散させた構造であるため、荷電性粒子の表面に導電性金属粉末が露出することがある。荷電性粒子の表面に一部でも導体が存在する場合には帯電性が大きく低下するため、特許文献２に記載された発明では、十分な帯電性が得られないことがあった。 In the invention described in Patent Document 2, the conductive metal powder may be exposed on the surface of the charged particles because the conductive metal powder is dispersed in the heat-meltable resin. When even a portion of the conductor is present on the surface of the chargeable particles, the chargeability is greatly reduced. Therefore, in the invention described in Patent Document 2, sufficient chargeability may not be obtained.
本発明はこのような問題点を解決しようとするものであり、高温での熱処理に耐えられないガラス基板上に回路パターンを形成するのに好適な回路形成用荷電性粒子およびその製造方法を提供することを目的とする。また、電子写真法を用いた回路パターンを有するガラス基板の製造方法を提供することを目的とする。 The present invention is intended to solve such problems, and provides a charged particle for forming a circuit suitable for forming a circuit pattern on a glass substrate that cannot withstand heat treatment at a high temperature, and a method for manufacturing the same. The purpose is to do. It is another object of the present invention to provide a method for producing a glass substrate having a circuit pattern using electrophotography.
上記問題点を解決するため本願第１の発明に係る回路形成用荷電性粒子は、導電性金属粒子と、該導電性金属粒子の表面に固着されたガラス粒子と、該ガラス粒子よりも外周に形成された樹脂被覆層と、を有し、前記ガラス粒子はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする。 In order to solve the above-mentioned problems, the charged particles for circuit formation according to the first invention of the present application include conductive metal particles, glass particles fixed to the surface of the conductive metal particles, and outer periphery than the glass particles. The glass particles are made of glass having a glass transition point of 350 ° C. or higher and lower than 640 ° C.
ここでガラス粒子のガラス転移点が３５０℃以上とされている理由は、ガラス転移点がこれより低いとガラス転移点と樹脂の分解温度が近接しすぎて、印刷後の加熱時に溶融したガラスの内部に樹脂が閉じこめられて樹脂がガス化し印刷パターンに亀裂や剥がれが生じるおそれがあるからである。 The reason why the glass transition point of the glass particles is 350 ° C. or higher is that if the glass transition point is lower than this, the glass transition point is too close to the decomposition temperature of the resin, and the glass melted when heated after printing. This is because the resin is confined inside and the resin is gasified, and there is a possibility that the printed pattern may be cracked or peeled off.
また、ガラス粒子のガラス転移点が６４０℃未満とされている理由は、ガラス転移点がこれより高いと一般的にソーダガラスからなるガラス基板の軟化点に接近してしまうためである。印刷後の加熱工程では、ガラス基板の変形を防ぐためにガラス基板の軟化点以上に加熱することはできないので、ガラス粒子のガラス転移点がガラス基板の軟化点より十分低くされていないと、印刷後の加熱時にガラス粉末が十分に溶融せずに密着強度の不足や導電性金属粒子の焼結拡散不良が発生するからである。 Moreover, the reason why the glass transition point of the glass particles is lower than 640 ° C. is that if the glass transition point is higher than this, the glass particle generally approaches the softening point of a glass substrate made of soda glass. In the heating process after printing, since the glass substrate cannot be heated above the softening point of the glass substrate in order to prevent deformation of the glass substrate, the glass transition point of the glass particles is not sufficiently lower than the softening point of the glass substrate. This is because the glass powder is not sufficiently melted during heating, resulting in insufficient adhesion strength and poor sintering diffusion of the conductive metal particles.
本願第２の発明に係る回路形成用荷電性粒子は、導電性金属粒子と、該導電性金属粒子の表面に形成された膜状のガラス層と、該ガラス層よりも外周に形成された樹脂被覆層と、を有し、前記ガラス層はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする。 The charged particles for circuit formation according to the second invention of the present application are conductive metal particles, a film-like glass layer formed on the surface of the conductive metal particles, and a resin formed on the outer periphery of the glass layer. The glass layer is made of glass having a glass transition point of 350 ° C. or higher and lower than 640 ° C.
ガラス層を構成するガラスのガラス転移点が３５０℃以上６４０℃未満とされている理由は、本願第１発明においてガラス粒子のガラス転移点が３５０℃以上６４０℃未満とされている理由と同様である。 The reason why the glass transition point of the glass constituting the glass layer is 350 ° C. or more and less than 640 ° C. is the same as the reason why the glass transition point of the glass particles is 350 ° C. or more and less than 640 ° C. in the first invention of this application. is there.
また本願第３の発明に係る回路形成用荷電性粒子の製造方法は、導電性金属粒子とガラス粒子とを機械被覆装置に投入して該導電性金属粒子の表面に該ガラス粒子を固着させるガラス粒子固着工程と、前記ガラスが固着した導電性金属粒子と樹脂とを機械被覆装置に投入して前記ガラス粒子よりも外周に樹脂被覆層を形成する樹脂被覆工程と、を含み、前記ガラス粒子はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする。 Further, the method for producing charged particles for circuit formation according to the third invention of the present application is a glass in which conductive metal particles and glass particles are put into a machine coating apparatus and the glass particles are fixed to the surface of the conductive metal particles. Including a particle fixing step, and a resin coating step in which the conductive metal particles and the resin to which the glass is fixed are put into a machine coating apparatus to form a resin coating layer on the outer periphery of the glass particles. The glass transition point is made of glass having a temperature of 350 ° C. or higher and lower than 640 ° C.
本願第４の発明に係る回路形成用荷電性粒子の製造方法は、導電性金属粒子とガラス粒子とを機械被覆装置に投入して該導電性金属粒子の表面にガラスを固着させるガラス粒子固着工程と、前記ガラスが固着した導電性粒子を加熱して前記ガラス粒子を溶融させることにより前記導電性金属粒子の表面に膜状のガラス層を形成するガラス層形成工程と、前記ガラス層が形成された導電性金属粒子と樹脂とを機械被覆装置に投入して前記ガラス層よりも外周に樹脂被覆層を形成する樹脂被覆工程と、を含み、前記ガラス粒子はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする。 The method for producing charged particles for circuit formation according to the fourth invention of the present application is a glass particle fixing step in which conductive metal particles and glass particles are put into a machine coating apparatus and glass is fixed to the surface of the conductive metal particles. A glass layer forming step of forming a film-like glass layer on the surface of the conductive metal particles by heating the conductive particles to which the glass is fixed to melt the glass particles, and the glass layer is formed. A resin coating step in which the conductive metal particles and the resin are put into a machine coating apparatus to form a resin coating layer on the outer periphery of the glass layer, and the glass particles have a glass transition point of 350 ° C. or higher and 640 ° C. It consists of glass which is less than.
さらに本願第５の発明に係る回路パターンを有するガラス基板の製造方法は、第１または第２の発明に係る回路形成用荷電性粒子を電子写真法によってガラス基板上に印刷する工程と、前記ガラス基板および前記回路形成用荷電性粒子を加熱することにより前記樹脂被覆層を熱分解させるとともに前記ガラス粒子または前記ガラス層を溶融させ、前記ガラス基板上に回路パターンを形成する熱処理工程と、を有し、前記熱処理工程における最高温度は前記ガラス粒子または前記ガラス層のガラス転移点よりも高くかつ前記ガラス基板の軟化点よりも低いことを特徴とする。 Furthermore, the method for producing a glass substrate having a circuit pattern according to the fifth invention of the present application includes the step of printing the charged particles for circuit formation according to the first or second invention on a glass substrate by electrophotography, and the glass A heat treatment step of thermally decomposing the resin coating layer by heating the substrate and the charged particles for circuit formation and melting the glass particles or the glass layer to form a circuit pattern on the glass substrate. The maximum temperature in the heat treatment step is higher than the glass transition point of the glass particles or the glass layer and lower than the softening point of the glass substrate.
なお、ガラス軟化点はガラスの粘度が４．５×１０7Ｐ（＝４．５×１０6Ｐａ・ｓ）となる温度である。 The glass softening point is a temperature at which the viscosity of the glass is 4.5 × 10 7 P (= 4.5 × 10 6 Pa · s).
第１の発明によれば、導電性金属粒子の表面にガラス転移点が３５０℃〜６４０℃であるガラスからなるガラス粒子が固着されているため、ガラス基板に印刷後、低温の熱処理でもガラス粒子がガラス基板と反応して回路パターンとガラス基板との接着性を向上させることができる。また、ガラス粒子が導電性金属粒子の表面に固着しているため、例えばガラス粒子が樹脂被覆層中に分散されている場合と比較して、少ないガラスの量でも十分な接着強度を得ることができる。 According to the first invention, glass particles made of glass having a glass transition point of 350 ° C. to 640 ° C. are fixed to the surface of the conductive metal particles. Reacts with the glass substrate to improve the adhesion between the circuit pattern and the glass substrate. Further, since the glass particles are fixed to the surface of the conductive metal particles, sufficient adhesive strength can be obtained even with a small amount of glass compared to, for example, the case where the glass particles are dispersed in the resin coating layer. it can.
さらに、ガラス粒子よりも外周に樹脂被覆層を形成しているため、表面に導電性金属粒子が露出する可能性が低く、十分な帯電性を確保することができる。 Furthermore, since the resin coating layer is formed on the outer periphery rather than the glass particles, the possibility that the conductive metal particles are exposed on the surface is low, and sufficient chargeability can be secured.
第２の発明によれば、導電性金属粒子の表面にガラス転移点が３５０℃〜６４０℃であるガラスから膜状のガラス層が固着されているため、ガラス基板に印刷後、低温の熱処理でもガラス層がガラス基板と反応して回路パターンとガラス基板との接着性を向上させることができる。また、ガラス層が導電性金属粒子の表面に固着しているため、例えばガラス粒子が樹脂被覆層中に分散されている場合と比較して、少ないガラスの量でも十分な接着強度を得ることができる。 According to the second aspect of the invention, since the film-like glass layer is fixed from the glass having a glass transition point of 350 ° C. to 640 ° C. on the surface of the conductive metal particles, even after low temperature heat treatment after printing on the glass substrate. The glass layer can react with the glass substrate to improve the adhesion between the circuit pattern and the glass substrate. Further, since the glass layer is fixed to the surface of the conductive metal particles, sufficient adhesive strength can be obtained even with a small amount of glass compared to, for example, the case where the glass particles are dispersed in the resin coating layer. it can.
さらに、印刷時にはガラス層が絶縁層としても機能するため、第１の発明よりもより確実に帯電性を確保することができる。 Furthermore, since the glass layer also functions as an insulating layer during printing, the charging property can be ensured more reliably than in the first invention.
第３の発明によれば、第１の発明に係る回路形成用荷電性粒子を容易に製造することができる。より具体的には、ガラス粒子固着工程と樹脂被覆工程とをともに機械被覆装置を用いて行うので、工程が簡略化される。また設備投資を抑制することができる。 According to the third invention, the charged particles for circuit formation according to the first invention can be easily manufactured. More specifically, since both the glass particle fixing process and the resin coating process are performed using a machine coating apparatus, the process is simplified. Moreover, capital investment can be suppressed.
第４の発明によれば、第２の発明に係る回路形成用荷電性粒子を容易に製造することができる。より具体的には、ガラス粒子固着工程と樹脂被覆工程とをともに機械被覆装置を用いて行うので、工程が簡略化させる。また設備投資を抑制することができる。さらにまた、ガラス粒子が３５０℃〜６４０℃のガラス転移点を有するガラスからなるので、ガラスを流動化させることが容易であり、ガラス層形成工程において容易に膜状のガラス層を形成することができる。
According to the fourth invention, the charged particles for circuit formation according to the second invention can be easily manufactured. More specifically, since both the glass particle fixing step and the resin coating step are performed using a machine coating apparatus, the steps are simplified. Moreover, capital investment can be suppressed. Furthermore, since the glass particles are made of glass having a glass transition point of 350 ° C. to 640 ° C., it is easy to fluidize the glass, and a film-like glass layer can be easily formed in the glass layer forming step. it can.
第５の発明によれば、本願第１または第２の発明に係る回路形成用荷電性粒子を用いているので、ガラス基板の軟化点よりも低い熱処理によってガラス基板と回路パターンとの接着強度を高めることができる。 According to the fifth invention, since the circuit-forming charged particles according to the first or second invention of the present application are used, the adhesive strength between the glass substrate and the circuit pattern is increased by a heat treatment lower than the softening point of the glass substrate. Can be increased.
以下において添付図面を参照しつつ本発明を実施するための最良の形態について説明する。 The best mode for carrying out the present invention will be described below with reference to the accompanying drawings.
図１は本発明の第１の実施例に係る回路形成用荷電性粒子の製造工程を模式的に示す断面図である。 FIG. 1 is a cross-sectional view schematically showing a manufacturing process of charged particles for circuit formation according to a first embodiment of the present invention.
まず、平均粒径２０μｍの銀粉末と平均粒径１μｍのビスマス系ガラス粉末（ガラス転移点Ｔｇが４８０℃）を重量比で９５：５の割合で混合し、かさ体積で３００ｃｃを計量して機械被覆装置（ホソカワミクロン社製、ノビルタＮＯＢ−１３０）に投入した。この機械被覆装置を毎分３０００回転の回転速度で２０分間運転して、図１（ａ）に示すように銀粉末１１の表面にガラス粉末１２を固着させた。 First, a silver powder having an average particle diameter of 20 μm and a bismuth glass powder having an average particle diameter of 1 μm (glass transition point Tg of 480 ° C.) are mixed at a weight ratio of 95: 5, and a volume of 300 cc is measured by a bulk volume. It was put into a coating apparatus (Nobilta NOB-130 manufactured by Hosokawa Micron Corporation). This machine coating apparatus was operated for 20 minutes at a rotational speed of 3000 rpm, and the glass powder 12 was fixed to the surface of the silver powder 11 as shown in FIG.
次に、銀粉末１１およびガラス粉末１２の合計量に対して重量比で１／１０の固形状のアクリル樹脂（１次粒子径１μｍ、ガラス転移点Ｔｇが６０℃）を前記機械被覆装置に追加投入し、毎分３０００回転の回転速度で２０分間運転した。これにより、回転時の摩擦熱でアクリル樹脂が軟化して銀粉末１１の表面に付着し、図１（ｂ）に示すように、ガラス粉末１２よりも外周に樹脂被覆層１４が形成された。 Next, a solid acrylic resin (primary particle diameter of 1 μm, glass transition point Tg of 60 ° C.) with a weight ratio of 1/10 with respect to the total amount of silver powder 11 and glass powder 12 is added to the machine coating apparatus. It was put in and operated for 20 minutes at a rotational speed of 3000 revolutions per minute. As a result, the acrylic resin was softened by the frictional heat during rotation and adhered to the surface of the silver powder 11, and the resin coating layer 14 was formed on the outer periphery of the glass powder 12 as shown in FIG.
さらに荷電性粒子の流動性を高めるための外添剤として平均粒径７ｎｍのシリカ微粒子を、ガラス粉末および樹脂で被覆された銀粉末１００重量部に対して０．５重量部投入して図１（ｃ）に示すように樹脂被覆層１４にシリカ微粒子１５が付着した回路形成用荷電性粒子１０を作成した。 Further, 0.5 part by weight of silica fine particles having an average particle diameter of 7 nm as an external additive for enhancing the fluidity of the charged particles is added to 100 parts by weight of the silver powder coated with the glass powder and the resin. As shown in (c), the charged particles 10 for circuit formation were prepared in which the silica fine particles 15 were adhered to the resin coating layer 14.
この回路形成用荷電性粒子１０の帯電量分布をホソカワミクロン社製イースパートアナライザーで測定したところ、ゼロまたは正の帯電粒子の割合は０．５％であり、高い帯電性を確保できていることがわかった。 When the charge amount distribution of the circuit-forming charged particles 10 was measured by an espert analyzer manufactured by Hosokawa Micron, the ratio of zero or positive charged particles was 0.5%, and high chargeability was ensured. all right.
この回路形成用荷電性粒子１０と負帯電用のフェライト系キャリア（平均粒径５０μｍ）を重量比で１：５の割合で混合振とうして、電子写真用の現像剤を得た。 The electrophotographic developer was obtained by mixing and shaking the charged particles 10 for circuit formation and the ferrite carrier for negative charging (average particle size 50 μm) at a weight ratio of 1: 5.
コロナ帯電器によって感光体の表面を帯電させ、さらに感光体にレーザを照射して所望の潜像パターンを形成し、前記現像剤を該潜像パターンに静電力によって吸着させ、現像された回路形成用荷電性粒子を被印刷物であるソーダガラスからなるガラス基板に転写した。このガラス基板は、軟化点が６５０℃以上７００℃未満であることを事前に実験的に確認してある。 The surface of the photoconductor is charged by a corona charger, and further, a laser beam is irradiated on the photoconductor to form a desired latent image pattern, and the developer is adsorbed to the latent image pattern by an electrostatic force to form a developed circuit. The charged particles for use were transferred to a glass substrate made of soda glass, which is a substrate to be printed. This glass substrate has been experimentally confirmed in advance that the softening point is 650 ° C. or higher and lower than 700 ° C.
次いでガラス基板を６５０℃で３０分間熱処理し、樹脂被覆層を熱分解させるとともにガラス粒子を溶融させて、ガラス基板上に回路パターンを形成した。 Next, the glass substrate was heat-treated at 650 ° C. for 30 minutes to thermally decompose the resin coating layer and melt the glass particles, thereby forming a circuit pattern on the glass substrate.
ガラス基板上に形成された回路パターンのうち、幅３００μｍ、長さ１００ｍｍの測定用ラインの抵抗値を４端子法で測定したところ、抵抗値は３．０μΩｃｍであった。また、試料の測定用ラインに隣接する１ｍｍ×１ｍｍの領域を光学顕微鏡で観察したときに該領域内に存在する回路形成用荷電性粒子の数を「カブリ量」と定義してカブリを評価したところ、カブリ量は３粒であった。帯電性の良好な回路形成用荷電性粒子を用いたため、カブリ量を抑制することができた。 Among the circuit patterns formed on the glass substrate, when the resistance value of the measurement line having a width of 300 μm and a length of 100 mm was measured by the four-terminal method, the resistance value was 3.0 μΩcm. Further, when a 1 mm × 1 mm area adjacent to the measurement line of the sample was observed with an optical microscope, the number of circuit forming charged particles existing in the area was defined as “fogging amount” to evaluate the fog. However, the amount of fog was 3 grains. Since the chargeable particles for forming a circuit having good chargeability were used, the amount of fog could be suppressed.
使用する銀粉末とガラス粉末の粒径を変化させた以外は実施例１と同じ方法で回路形成用荷電性粒子を作製し、帯電量分布の測定、カブリ量の観察および抵抗値の測定を行った（試料Ａ〜Ｅ）。銀粉末とガラス粉末の粒径比（ガラス粉末の平均粒径／銀粉末の平均粒径）および測定結果を表１に示す。 The charged particles for circuit formation were prepared in the same manner as in Example 1 except that the particle sizes of the silver powder and glass powder used were changed, and the charge amount distribution was measured, the fog amount was observed, and the resistance value was measured. (Samples A to E). Table 1 shows the particle size ratio between silver powder and glass powder (average particle size of glass powder / average particle size of silver powder) and measurement results.
表１に示された結果から、銀粉末の平均粒径は１５μｍ以上であることが好ましいとともに、ガラス粉末の平均粒径は３．８μｍ以下が好ましいことがわかった。 From the results shown in Table 1, it was found that the average particle diameter of the silver powder is preferably 15 μm or more, and the average particle diameter of the glass powder is preferably 3.8 μm or less.
被覆用の樹脂としてアクリル樹脂の替わりにガラス転移点Ｔｇが５６℃のポリエステル樹脂またはＴｇが６０℃のスチレンアクリル樹脂を使用した以外は実施例１と同じ方法で回路形成用荷電性粒子を作製し、帯電量分布の測定、カブリ量の観察および抵抗値の測定を行った（試料Ｆ，Ｇ）。測定結果を表２に示す。 A charged particle for circuit formation was prepared in the same manner as in Example 1 except that a polyester resin having a glass transition point Tg of 56 ° C. or a styrene acrylic resin having a Tg of 60 ° C. was used instead of the acrylic resin as the coating resin. Then, measurement of charge amount distribution, observation of fog amount and measurement of resistance value were performed (samples F and G). The measurement results are shown in Table 2.
表２に示されるように、実施例１と同様の良好な特性を示す回路形成用荷電性粒子を得ることができた。 As shown in Table 2, charged particles for circuit formation showing good characteristics similar to those of Example 1 could be obtained.
図２は本発明の第４の実施例に係る回路形成用荷電性粒子の製造工程を模式的に示す断面図である。 FIG. 2 is a cross-sectional view schematically showing a process for producing charged particles for circuit formation according to the fourth embodiment of the present invention.
まず、平均粒径２０μｍの銀粉末と平均粒径１μｍのビスマス系ガラス粉末（Ｔｇが４８０℃）を重量比で９５：５の割合で混合し、かさ体積で３００ｃｃを計量して機械被覆装置（ホソカワミクロン社製、ＮＯＢ−１３０ノビルタ）に投入する。この機械被覆装置を毎分３０００回転の回転速度で２０分間運転して、図２（ａ）に示すように銀粉末１１の表面にガラス粉末１２を固着させる。 First, a silver powder having an average particle diameter of 20 μm and a bismuth glass powder having an average particle diameter of 1 μm (Tg is 480 ° C.) are mixed at a weight ratio of 95: 5, and 300 cc is measured by a bulk volume to measure a mechanical coating device ( Into Hosokawa Micron Corporation, NOB-130 Nobilta). The machine coating apparatus is operated at a rotational speed of 3000 rpm for 20 minutes to fix the glass powder 12 on the surface of the silver powder 11 as shown in FIG.
次に、表面にガラス粉末１２が固着した銀粉末を熱処理装置（日本ニューマチック社製、メテオレインボーＭＲ−３）によって５００℃で熱処理することによってガラス粉末１２を溶融させて層状とし、図２（ｂ）に示すように銀粉末１１の表面にガラス層１３を形成する。 Next, the silver powder having the glass powder 12 fixed on the surface thereof is heat-treated at 500 ° C. by a heat treatment apparatus (manufactured by Nippon Pneumatic Co., Ltd., Meteole Inbo MR-3), thereby melting the glass powder 12 into a layered form. A glass layer 13 is formed on the surface of the silver powder 11 as shown in b).
ガラス層１３を形成した銀粉末１１を再び機械被覆装置に投入し、銀粉末１１およびガラス粉末１２の合計量に対して重量比で１／１０の固形状のアクリル樹脂（１次粒子径１μｍ、ガラス転移点Ｔｇが６０℃）を前記機械被覆装置に投入し、毎分３０００回転の回転速度で２０分間運転する。これにより、回転時の摩擦熱でアクリル樹脂が軟化してガラス層１３の表面に付着し、図２（ｃ）に示すように、ガラス層１３の外周に樹脂被覆層１４が形成される。これにより、本発明に係る回路形成用荷電性粒子１０が作製される。 The silver powder 11 on which the glass layer 13 is formed is again put into the machine coating apparatus, and a solid acrylic resin (primary particle diameter of 1 μm, 1/10 in weight ratio) with respect to the total amount of the silver powder 11 and the glass powder 12. The glass transition point Tg is 60 ° C.) is put into the machine coating apparatus and is operated for 20 minutes at a rotational speed of 3000 revolutions per minute. As a result, the acrylic resin is softened by the frictional heat during rotation and adheres to the surface of the glass layer 13, and a resin coating layer 14 is formed on the outer periphery of the glass layer 13 as shown in FIG. Thereby, the charged particle 10 for circuit formation which concerns on this invention is produced.
本実施例によれば、ガラス粒子１２を溶融させてガラス層１３を形成しているので、樹脂を被覆する際にガラスが導電性金属粉末（銀粉末）１１の表面から脱落することを防止でき、また、導電性金属粉末１１の表面がほぼ隙間なくガラスで覆われることとなるのでガラス基板との接着強度が向上する。さらに、導電性金属粉末１１の表面をほぼ隙間なく覆うガラス層１３が絶縁層として機能し、帯電性が向上する。 According to the present embodiment, the glass particles 12 are melted to form the glass layer 13, so that the glass can be prevented from falling off from the surface of the conductive metal powder (silver powder) 11 when the resin is coated. Moreover, since the surface of the conductive metal powder 11 is covered with glass with almost no gap, the adhesive strength with the glass substrate is improved. Furthermore, the glass layer 13 covering the surface of the conductive metal powder 11 with almost no gap functions as an insulating layer, and the chargeability is improved.
１０ 回路形成用荷電性粒子
１１ 銀粉末（導電性金属粒子）
１２ ガラス粉末
１３ ガラス層
１４ 樹脂被覆層
10 Charged particles for circuit formation 11 Silver powder (conductive metal particles)
12 Glass powder 13 Glass layer 14 Resin coating layer
Claims (5)
前記ガラス粒子はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする回路形成用荷電性粒子。 Conductive metal particles, glass particles fixed to the surface of the conductive metal particles, and a resin coating layer formed on the outer periphery of the glass particles,
The charged particles for circuit formation, wherein the glass particles are made of glass having a glass transition point of 350 ° C. or higher and lower than 640 ° C.
前記ガラス層はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする回路形成用荷電性粒子。 Conductive metal particles, a film-like glass layer formed on the surface of the conductive metal particles, and a resin coating layer formed on the outer periphery of the glass layer,
The charged particle for circuit formation, wherein the glass layer is made of glass having a glass transition point of 350 ° C or higher and lower than 640 ° C.
前記ガラスが固着した導電性金属粒子と樹脂とを機械被覆装置に投入して前記ガラス粒子よりも外周に樹脂被覆層を形成する樹脂被覆工程と、を含み、
前記ガラス粒子はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする回路形成用荷電性粒子の製造方法。 A glass particle fixing step in which the conductive metal particles and the glass particles are put into a machine coating apparatus to fix the glass particles to the surface of the conductive metal particles;
A resin coating step in which the conductive metal particles and the resin to which the glass is fixed are put into a machine coating apparatus to form a resin coating layer on the outer periphery of the glass particles,
The method for producing charged particles for circuit formation, wherein the glass particles are made of glass having a glass transition point of 350 ° C or higher and lower than 640 ° C.
前記ガラスが固着した導電性粒子を加熱して前記ガラス粒子を溶融させることにより前記導電性金属粒子の表面に膜状のガラス層を形成するガラス層形成工程と、
前記ガラス層が形成された導電性金属粒子と樹脂とを機械被覆装置に投入して前記ガラス層よりも外周に樹脂被覆層を形成する樹脂被覆工程と、を含み、
前記ガラス粒子はガラス転移点が３５０℃以上６４０℃未満であるガラスからなることを特徴とする回路形成用荷電性粒子の製造方法。 A glass particle fixing step in which the conductive metal particles and the glass particles are put into a machine coating apparatus to fix the glass particles to the surface of the conductive metal particles;
A glass layer forming step of forming a film-like glass layer on the surface of the conductive metal particles by heating the conductive particles to which the glass is fixed to melt the glass particles;
A resin coating step in which the conductive metal particles and the resin on which the glass layer is formed are put into a machine coating apparatus to form a resin coating layer on the outer periphery of the glass layer,
The method for producing charged particles for circuit formation, wherein the glass particles are made of glass having a glass transition point of 350 ° C or higher and lower than 640 ° C.
前記ガラス基板および前記回路形成用荷電性粒子を加熱することにより前記樹脂被覆層を熱分解させるとともに前記ガラス粒子または前記ガラス層を溶融させ、前記ガラス基板上に回路パターンを形成する熱処理工程と、を有し、
前記熱処理工程における最高温度は前記ガラス粒子または前記ガラス層のガラス転移点よりも高くかつ前記ガラス基板の軟化点よりも低いことを特徴とする回路パターンを有するガラス基板の製造方法。 Printing the charged particles for circuit formation according to claim 1 or 2 on a glass substrate by electrophotography;
A heat treatment step of thermally decomposing the resin coating layer by heating the glass substrate and the charged particles for circuit formation and melting the glass particles or the glass layer to form a circuit pattern on the glass substrate; Have
The method for producing a glass substrate having a circuit pattern, wherein a maximum temperature in the heat treatment step is higher than a glass transition point of the glass particles or the glass layer and lower than a softening point of the glass substrate.
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