JP5657860B2 - Glazed insulating substrate, collective insulating substrate, manufacturing method thereof, and fuse resistor - Google Patents
Glazed insulating substrate, collective insulating substrate, manufacturing method thereof, and fuse resistor Download PDFInfo
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- JP5657860B2 JP5657860B2 JP2008324293A JP2008324293A JP5657860B2 JP 5657860 B2 JP5657860 B2 JP 5657860B2 JP 2008324293 A JP2008324293 A JP 2008324293A JP 2008324293 A JP2008324293 A JP 2008324293A JP 5657860 B2 JP5657860 B2 JP 5657860B2
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- 239000000758 substrate Substances 0.000 title claims description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000011521 glass Substances 0.000 claims description 36
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 31
- 239000001023 inorganic pigment Substances 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 14
- 229910052596 spinel Inorganic materials 0.000 claims description 9
- 239000011029 spinel Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
Landscapes
- Glass Compositions (AREA)
- Inorganic Insulating Materials (AREA)
- Fuses (AREA)
Description
本発明は、ヒューズ抵抗器、センサー、薄膜抵抗器等の小型のチップ型電子部品等に使用され、グレーズ層における平滑性、熱的特性を確保し、製造時における基板分割の際にバリやクラックの発生が抑制されたグレーズド絶縁基板、該グレーズド絶縁基板を製造するためのレーザー光照射による基板の分割溝刻設を設けた集合絶縁基板、その製造方法及び該グレーズド絶縁基板を備えたヒューズ抵抗器に関する。 The present invention is used for small chip-type electronic components such as fuse resistors, sensors, thin film resistors, etc., ensuring smoothness and thermal characteristics in the glaze layer, and burrs and cracks when dividing the substrate during manufacturing. Glazed insulating substrate with suppressed generation, collective insulating substrate provided with dividing grooves of substrate by laser beam irradiation for manufacturing the glazed insulating substrate, manufacturing method thereof, and fuse resistor including the glazed insulating substrate About.
従来、チップ型ヒューズ又はヒューズ抵抗器等の表面実装型の電子部品においては、ヒューズ膜やヒューズ抵抗膜等の機能を十分確保するために、絶縁基板の表面上に特定な物性値を有するガラスペーストを印刷・乾燥及び焼成した透明なグレーズ層を形成することが提案され、実施されている(特許文献１)。
このグレーズ層は、絶縁基板の表面の粗さを平滑にし、ヒューズ膜やヒューズ抵抗膜の形成厚さを均一化することを容易にすると共に、使用時におけるこれらの膜に対する熱等による影響を抑制し、電気的信頼性を確保するため等に作用する。
電子部品に使用される上記絶縁基板は、通常、多数の絶縁基板の単位を有する一枚の絶縁板に、個々の基板単位に分割するための縦横分割溝を形成する工程が行なわれる。
このような分割溝は、レーザー光照射により形成することが提案されている(特許文献２)。また、レーザー光照射適性を確保し、且つグレーズ層の平滑性を充分に確保した、特定の黒色無機顔料を用いたグレーズド絶縁基板も提案されている(特許文献３)。
一方、グレーズ層に用いられるガラス成分としては、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＳｉＯ2を基本として、ＣａＯ、ＳｒＯ、ＢａＯ、Ｌａ2Ｏ3、ＺｒＯ2、Ｙ2Ｏ3等を適宜配合した組成が種々提案されている。例えば、特許文献４には、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＳｉＯ2、ＣａＯ、ＳｒＯ、ＢａＯを主成分とし、ＺｒＯ2を１０質量％以下配合したグレーズ組成物が提案されている。しかし、上記レーザー光照射適正と、分割溝の分割適正との両者を考慮したガラス成分の提案はなされていない。
This glaze layer smoothes the surface roughness of the insulating substrate, makes it easy to uniformize the thickness of the fuse film and fuse resistance film, and suppresses the effects of heat on these films during use. And acts to ensure electrical reliability.
The insulating substrate used for the electronic component is usually subjected to a process of forming vertical and horizontal dividing grooves for dividing each substrate into a single insulating plate having a number of insulating substrate units.
It has been proposed to form such dividing grooves by laser light irradiation (Patent Document 2). Also, a glazed insulating substrate using a specific black inorganic pigment that has ensured laser beam irradiation suitability and sufficiently smoothed the glaze layer has been proposed (Patent Document 3).
On the other hand, the glass component used in the glaze layer, suitably blended B 2 O 3, Al 2 O 3, SiO 2 as the basic, CaO, SrO, BaO, La 2 O 3, a ZrO 2, Y 2 O 3, etc. Various compositions have been proposed. For example, Patent Document 4 proposes a glaze composition containing B 2 O 3 , Al 2 O 3 , SiO 2 , CaO, SrO, BaO as main components and containing 10% by mass or less of ZrO 2 . However, there has been no proposal of a glass component that takes into consideration both the above-mentioned laser beam irradiation appropriateness and the appropriateness of dividing grooves.
ところで、近年、電子部品の短期間における大量生産を実現するために、上記レーザー光の走査速度を上げる試みが検討されている。
しかし、従来提案されているグレーズ層が形成された絶縁板に分割溝を形成するにあたり、上記レーザー光の走査速度をある程度以上に上げると、分割時にバリやクラックが発生する割合が高くなり、グレーズド絶縁基板の製造における歩留りが低下するという問題が生じ易いことが分かってきた。また、この傾向は、絶縁基板の厚さが薄いほど顕著である。
Incidentally, in recent years, attempts have been made to increase the scanning speed of the laser beam in order to realize mass production of electronic components in a short period of time.
However, if the laser beam scanning speed is increased to a certain degree when forming the dividing grooves in the conventionally proposed insulating plate on which the glaze layer is formed, the rate of occurrence of burrs and cracks at the time of division increases, and the It has been found that the problem of a decrease in yield in the production of an insulating substrate is likely to occur. Moreover, this tendency becomes more conspicuous as the insulating substrate is thinner.
本発明の課題は、分割溝の分割時におけるバリやクラックの発生を抑制し、かつグレーズ層としての平滑性を確保した、分割溝を有する集合絶縁基板、これを分割したグレーズド絶縁基板及び該グレーズド絶縁基板を用いたヒューズ抵抗器を提供することにある。
本発明の別の課題は、分割溝を有する集合絶縁基板を製造するにあたり、分割溝形成時のレーザー光照射におけるレーザー光の走査速度を上げた場合にも、また、絶縁板の厚さが薄い場合にも、分割時のバリやクラックの発生を抑制しうる、レーザー光照射による分割溝の形成を容易にし、グレーズ層としての平滑性も確保した集合絶縁基板を歩留り良く製造することが可能な分割溝を有する集合絶縁基板の製造方法を提供することにある。
An object of the present invention is to suppress the generation of burrs and cracks at the time of dividing the dividing groove, and to ensure smoothness as a glaze layer, a collective insulating substrate having divided grooves, a glazed insulating substrate obtained by dividing the same, and the glazed It is an object of the present invention to provide a fuse resistor using an insulating substrate.
Another problem of the present invention is that the thickness of the insulating plate is thin even when the scanning speed of the laser beam in the laser beam irradiation at the time of forming the dividing groove is increased in manufacturing the collective insulating substrate having the dividing groove. Even in this case, it is possible to easily form a dividing groove by laser light irradiation, which can suppress the generation of burrs and cracks at the time of division, and it is possible to manufacture a collective insulating substrate that ensures smoothness as a glaze layer with a high yield. An object of the present invention is to provide a method for manufacturing a collective insulating substrate having divided grooves.
本発明によれば、絶縁基板と、該絶縁基板表面に形成されるグレーズ層とを備え、該グレーズ層が、SiO2、BaO、CaO、Al2O3及びZrO2を含むガラスと、スピネル構造を有するFe2O3、Cr2O3及びCoOから実質的になる黒色無機顔料とを含み、該黒色無機顔料の含有割合が、ガラス１００質量部に対して７．０〜１２．０質量部の割合であり、かつガラス中のZrO2の含有割合が１５〜２０質量％であることを特徴とするグレーズド絶縁基板が提供される。
また本発明によれば、絶縁基板と、該絶縁基板表面に形成されるグレーズ層とを備えるグレーズド絶縁基板からなり、該グレーズド絶縁基板のグレーズ層が設けられた面上に、縦横分割溝を形成した集合絶縁基板であって、該グレーズ層が、SiO2、BaO、CaO、Al2O3及びZrO2を含むガラスと、スピネル構造を有するFe2O3、Cr2O3及びCoOから実質的になる黒色無機顔料とを含み、該黒色無機顔料の含有割合が、ガラス１００質量部に対して７．０〜１２．０質量部の割合であり、ガラス中のZrO2の含有割合が１５〜２０質量％であり、且つ前記分割溝が、前記グレーズ層から前記絶縁基板にまで達していることを特徴とする集合絶縁基板が提供される。
更に本発明によれば、グレーズド集合絶縁基板を得るために、SiO2、BaO、CaO、Al2O3及びZrO2を含むガラスと、スピネル構造を有するFe2O3、Cr2O3及びCoOから実質的になる黒色無機顔料とを含み、該黒色無機顔料の含有割合が、ガラス１００質量部に対して７．０〜１２．０質量部の割合であり、ガラス中のZrO2の含有割合が１５〜２０質量％であるグレーズ用ペーストを、絶縁板の表面に印刷し、グレーズ層を形成する工程(a)と、グレーズ層が形成されたグレーズド絶縁板を、９０ｍｍ／秒以上の速度でレーザー光を走査して、縦横分割溝を形成する工程(b)と、を含むことを特徴とする集合絶縁基板の製造方法が提供される。
前記ガラス中の各ガラス質成分の含有割合は、SiO 2 が４１〜４３質量％、BaOが２５．５〜２７．５質量％、CaOが１０〜１１質量％、Al 2 O 3 が１〜１１質量％、及びZrO 2 が１５〜２０質量％であることが好ましい。
更にまた本発明によれば、上記グレーズド絶縁基板を備えたヒューズ抵抗器が提供される。
According to the present invention, an insulating substrate and a glaze layer formed on the surface of the insulating substrate are provided, and the glaze layer includes glass containing SiO 2 , BaO, CaO, Al 2 O 3 and ZrO 2 , and a spinel structure. A black inorganic pigment substantially composed of Fe 2 O 3 , Cr 2 O 3 and CoO having a content of 7.0 to 12.0 parts by mass with respect to 100 parts by mass of the glass And a content ratio of ZrO 2 in the glass is 15 to 20% by mass.
Further, according to the present invention, the insulating substrate and a glaze insulating substrate comprising a glaze layer formed on the surface of the insulating substrate are formed, and vertical and horizontal dividing grooves are formed on the surface of the glaze insulating substrate provided with the glaze layer. The glaze layer is substantially composed of glass containing SiO 2 , BaO, CaO, Al 2 O 3 and ZrO 2 and Fe 2 O 3 , Cr 2 O 3 and CoO having a spinel structure. The black inorganic pigment content is 7.0 to 12.0 parts by mass with respect to 100 parts by mass of the glass, and the ZrO 2 content in the glass is 15 to There is provided a collective insulating substrate characterized in that it is 20% by mass and the dividing grooves reach from the glaze layer to the insulating substrate.
Further according to the present invention, in order to obtain a glazed collective insulating substrate, SiO 2, BaO, CaO, and the glass comprising Al 2 O 3 and ZrO 2, Fe 2 O 3 having a spinel structure, Cr 2 O 3 and CoO And the black inorganic pigment content is 7.0 to 12.0 parts by mass with respect to 100 parts by mass of the glass, and the content of ZrO 2 in the glass A paste for glaze having an amount of 15 to 20% by mass is printed on the surface of the insulating plate to form a glaze layer (a), and the glazed insulating plate on which the glaze layer is formed at a speed of 90 mm / second or more. And a step (b) of forming vertical and horizontal dividing grooves by scanning with a laser beam.
The content ratio of each glassy component in the glass is as follows: SiO 2 is 41 to 43% by mass, BaO is 25.5 to 27.5% by mass, CaO is 10 to 11% by mass, and Al 2 O 3 is 1 to 11%. mass%, and is preferably ZrO 2 is 15 to 20 mass%.
Furthermore, according to this invention, the fuse resistor provided with the said glazed insulation board | substrate is provided.
本発明の集合絶縁基板は、グレーズ層中に特定な組合せの黒色無機材料とZrO2を含有するガラス成分とを特定量含むので、レーザー光を縦横に走査してなる分割溝の分割時におけるバリやクラックの発生を抑制し、かつグレーズ層としての平滑性も確保される。従って、寸法精度が良い、グレーズド絶縁基板を提供することができる。
本発明の集合絶縁基板の製造方法では、特定の組合せの黒色無機材料とZrO2を含有するガラス成分とを特定量含むグレーズ層を形成する工程を含むので、分割溝形成時のレーザー光照射におけるレーザー光の走査速度を上げた場合にも、また、絶縁板の厚さが薄い場合にも、分割時のバリやクラックの発生を抑制しうる、レーザー光照射による分割溝の形成が容易であり、且つグレーズ層としての平滑性も確保することができる。従って、このようなグレーズ層を有する集合絶縁基板を、歩留り良く製造することができる。また、本発明の製造方法では、上述の集合絶縁基板を、短期間で大量に製造することが可能である。
本発明のグレーズド絶縁基板は、上記グレーズ層を備えるので、チップ型ヒューズやヒューズ抵抗器、センサー、薄膜抵抗器等の電子部品に有用である。更にこの基板を用いた本発明のヒューズ抵抗器は、所望のヒューズ抵抗膜の特性を十分引出すことができる。
The collective insulating substrate of the present invention includes a specific amount of a specific combination of black inorganic material and a glass component containing ZrO 2 in the glaze layer. Generation of cracks and cracks and smoothness as a glaze layer are ensured. Therefore, a glazed insulating substrate with good dimensional accuracy can be provided.
The method for manufacturing a collective insulating substrate according to the present invention includes a step of forming a glaze layer containing a specific amount of a specific combination of black inorganic material and a glass component containing ZrO 2 . Even when the scanning speed of the laser beam is increased and the insulating plate is thin, it is easy to form a dividing groove by laser beam irradiation that can suppress the generation of burrs and cracks during the division. In addition, smoothness as a glaze layer can be ensured. Therefore, a collective insulating substrate having such a glaze layer can be manufactured with high yield. In the manufacturing method of the present invention, the above-described collective insulating substrate can be manufactured in large quantities in a short period of time.
Since the glazed insulating substrate of the present invention includes the glazed layer, it is useful for electronic components such as chip-type fuses, fuse resistors, sensors, and thin film resistors. Furthermore, the fuse resistor of the present invention using this substrate can sufficiently bring out the desired characteristics of the fuse resistance film.
以下本発明を更に詳細に説明する。
本発明のグレーズド絶縁基板は、絶縁基板と、該絶縁基板表面に形成されるグレーズ層とを備える。
前記絶縁基板としては、例えば、純度約９６％等のアルミナセラミック基板、窒化アルミナ基板、ＭｇＯ・ＳｉＯ2を主成分とするステアタイトセラミック基板、２ＭｇＯ・ＳｉＯ2を主成分とするフォルステライトセラミック基板が挙げられるが、本発明の効果をより発揮することが可能なアルミナセラミック基板の使用が好ましい。
絶縁基板の厚さは、薄い方が、本発明の所望の効果が発揮され易いため好ましく、通常、０．５ｍｍ以下、特に、０．３ｍｍ以下であることが好ましい。
The present invention will be described in detail below.
The glazed insulating substrate of the present invention includes an insulating substrate and a glaze layer formed on the surface of the insulating substrate.
Wherein the insulating substrate is, for example, alumina ceramic substrate having a purity of about 96%, etc., alumina nitride substrates, steatite ceramic substrate composed mainly of MgO · SiO 2, the forsterite ceramic substrate composed mainly of 2MgO · SiO 2 Although mentioned, use of the alumina ceramic substrate which can exhibit the effect of the present invention more is preferred.
A thinner insulating substrate is preferable because the desired effect of the present invention is easily exhibited, and is usually 0.5 mm or less, and particularly preferably 0.3 mm or less.
前記グレーズ層は、特定のガラス質成分を含むガラス及びスピネル構造を有する特定の黒色無機顔料を含むが、本発明の目的が達成されるものであれば、他の成分が含まれていても良い。
前記ガラスは、SiO2、BaO、CaO、Al2O3及びZrO2をガラス質成分として含む。該ガラスは、グレーズ層に用いることにより、例えば、ヒューズ抵抗器を目的とする場合において、ヒューズ機能として安定な溶断特性や他の電気的特性における信頼性を向上させ、過負荷通電時における熱放散及び蓄熱バランスを好適なものとするために、後述する黒色無機顔料との組合せにおいて得られるグレーズ層の物性値、例えば、ガラス軟化点が９３６〜９５６℃、ガラス転移点が７９０〜８１０℃、熱膨張係数が７．３×１０-6〜７．９×１０-6となることが好ましい。
The glaze layer contains a glass containing a specific glassy component and a specific black inorganic pigment having a spinel structure, but may contain other components as long as the object of the present invention is achieved. .
The glass contains SiO 2 , BaO, CaO, Al 2 O 3 and ZrO 2 as vitreous components. The glass is used for the glaze layer, for example, in the case of a fuse resistor, to improve the reliability of the fusing function as a fuse function and reliability in other electrical characteristics, and to dissipate heat during overload energization. In order to make the heat storage balance suitable, the physical properties of the glaze layer obtained in combination with the black inorganic pigment described later, for example, a glass softening point of 936 to 956 ° C., a glass transition point of 790 to 810 ° C., heat The expansion coefficient is preferably 7.3 × 10 −6 to 7.9 × 10 −6 .
前記ガラス中の各ガラス質成分の含有割合は、SiO2が通常、４１〜４３質量％、BaOが通常、２５．５〜２７．５質量％、CaOが通常、１０〜１１質量％、Al2O3が通常、１〜１１質量％、好ましくは１〜６質量％、ZrO2が１５〜２０質量％である。
ZrO2が１５質量％未満の場合には、分割溝を有する集合絶縁基板を製造する際のグレーズ層に使用した場合に、分割によりバリやクラックが生じ易くなり、また、後述する黒色無機顔料の割合によって、形成するグレーズ層の表面平滑性が得られないおそれや分割溝の深さが充分でないおそれがある。
一方、ZrO2が２０質量％を超える場合には、グレーズ層の表面平滑性が得られないおそれやグレーズ層にうねりが生じるおそれがあり、また、後述する黒色無機顔料の割合によって、前記クラックが生じるおそれがある。
従って、特に、ガラス中のZrO2の含有割合が上記範囲外では、本発明の所望の効果が得られないおそれがある。
As for the content ratio of each glassy component in the glass, SiO 2 is usually 41 to 43% by mass, BaO is usually 25.5 to 27.5% by mass, CaO is usually 10 to 11% by mass, Al 2 O 3 is usually 1 to 11% by mass, preferably 1 to 6% by mass, and ZrO 2 is 15 to 20% by mass.
When ZrO 2 is less than 15% by mass, burrs and cracks are likely to occur due to the splitting when used in a glaze layer in the production of an aggregate insulating substrate having split grooves. Depending on the ratio, the surface smoothness of the glaze layer to be formed may not be obtained, and the depth of the dividing groove may not be sufficient.
On the other hand, when ZrO 2 exceeds 20% by mass, the surface smoothness of the glaze layer may not be obtained or the glaze layer may be swelled, and the crack may be caused by the proportion of the black inorganic pigment described later. May occur.
Therefore, in particular, if the content ratio of ZrO 2 in the glass is out of the above range, the desired effect of the present invention may not be obtained.
前記スピネル構造を有する黒色無機顔料は、Fe2O3、Cr2O3及びCoOから実質的になり、また、所望に応じてNiO等を含んでいても良い。前記必須３成分のうち１成分が含有されない場合は、レーザー光照射適性と、グレーズ層としての平滑特性とがバランス良く得られず、本発明の目的が達成できないおそれがある。これら３成分の好ましい配合割合は、黒色無機顔料中のFe2O3が４３〜４８質量％、Cr2O3が２６〜３０質量％及びCoOが２４〜２８質量％である。
これら黒色無機顔料のグレーズ層中の含有割合は、ガラス１００質量部に対して７．０〜１２．０質量部の割合とする必要がある。
黒色無機顔料の前記割合が７．０質量部未満では、所望のレーザー光照射適性が得られず、分割溝の深さが充分でないおそれがあり、また、前記ガラス中のZrO2の含有割合を適正範囲にした場合であっても、前記分割時にクラックが生じるおそれがある。
一方、黒色無機顔料の前記割合が１２．０質量部を超える場合には、グレーズ層の表面平滑性が得られないおそれやグレーズ層にうねりが生じるおそれがある。
従って、グレーズ層中の上記黒色無機顔料の含有割合が上記範囲外では、本発明の所望の効果が得られないおそれがある。
The black inorganic pigment having a spinel structure is substantially composed of Fe 2 O 3 , Cr 2 O 3 and CoO, and may contain NiO or the like as desired. When one of the essential three components is not contained, the suitability for laser beam irradiation and the smoothness characteristics as the glaze layer cannot be obtained in a good balance, and the object of the present invention may not be achieved. The preferable blending ratio of these three components is 43 to 48% by mass of Fe 2 O 3 in the black inorganic pigment, 26 to 30% by mass of Cr 2 O 3 and 24 to 28% by mass of CoO.
The content of these black inorganic pigments in the glaze layer needs to be 7.0 to 12.0 parts by mass with respect to 100 parts by mass of the glass.
If the ratio of the black inorganic pigment is less than 7.0 parts by mass, desired laser light irradiation suitability may not be obtained, and the depth of the dividing groove may not be sufficient, and the content ratio of ZrO 2 in the glass may be Even in the proper range, cracks may occur during the division.
On the other hand, when the said ratio of a black inorganic pigment exceeds 12.0 mass parts, there exists a possibility that the surface smoothness of a glaze layer may not be acquired or a waviness may arise in a glaze layer.
Therefore, if the content ratio of the black inorganic pigment in the glaze layer is out of the above range, the desired effect of the present invention may not be obtained.
本発明の集合絶縁基板は、グレーズド絶縁基板に分割溝が縦横に多数一体的に形成された、上記グレーズド絶縁基板を製造するためのものであって、上記絶縁基板と同様な材質の絶縁板上に少なくとも上記本発明のグレーズド絶縁基板において説明したグレーズ層を有する。そして、各々のグレーズド絶縁基板を分割するための分割溝が、グレーズ層が設けられた面上に縦横に、且つ前記グレーズ層から前記絶縁板に溝が達するように備えられている。
この集合絶縁基板は、分割溝に沿って分割することにより、上述の本発明のグレーズド絶縁基板とすることができる。
The collective insulating substrate of the present invention is for manufacturing the above-mentioned glazed insulating substrate, in which a large number of dividing grooves are integrally formed in the glazed insulating substrate vertically and horizontally, on an insulating plate made of the same material as that of the above insulating substrate. At least the glaze layer described in the above-described glazed insulating substrate of the present invention. Dividing grooves for dividing each of the glazed insulating substrates are provided vertically and horizontally on the surface on which the glazed layer is provided, and from the glazed layer to the insulating plate.
This collective insulating substrate can be made the above-described glazed insulating substrate of the present invention by dividing along the dividing groove.
本発明の集合絶縁基板の製造方法では、上述のガラス質成分を含むガラスと、特定の黒色無機顔料とを特定割合で含むグレーズ層を形成するためのグレーズ用ペーストを、絶縁板の表面に印刷し、グレーズ層を形成する工程(a)を含む。
工程(a)において、グレーズ用ペーストは、上述のガラス質成分を含むガラスと、特定の黒色無機顔料とを特定割合で含み、常法により溶剤及び有機質ビヒクルを用いてペースト状にすることによって得ることができる。
工程(a)において用いる絶縁板の材料としては、前述の絶縁基板において例示した基板の材料等が挙げられる。絶縁板の厚さは、薄い方が、本発明の所望の効果が発揮され易いため好ましく、通常、０．５ｍｍ以下、特に、０．３ｍｍ以下であることが好ましい。
工程(a)においてグレーズ用ペーストの絶縁板表面への印刷は、スクリーン印刷等により行うことができ、グレーズ層の形成は、該印刷したペーストを、乾燥、焼成することにより行うことができる。この際、印刷、乾燥及び焼成は、得られるグレーズ層の膜厚が、５０〜８０μｍになるように行なうことが望ましい。また、焼成は、絶縁板の変形等が生じないように、通常１０００℃以上、好ましくは１２００〜１３００℃で約３０分間程度の条件で行うことが好ましい。
更に、このグレーズ層の形成前においては分割溝が形成されていないので、昇温及び降温時間等を適宜設定することにより容易に絶縁板の変形等を抑制することができる。例えば、グレーズ層を焼成するために、まず１０００℃まで毎分２０℃の割合で温度上昇させ、次いで、１３００℃に達するまで毎分５℃の割合で温度上昇させ、１３００℃で３０分間程度焼成した後、常温まで毎分２０℃程度で降温させる条件が挙げられる。
In the method for producing a collective insulating substrate of the present invention, a paste for glaze for forming a glaze layer containing a glass containing the above-mentioned vitreous component and a specific black inorganic pigment in a specific ratio is printed on the surface of the insulating plate. And a step (a) of forming a glaze layer.
In the step (a), the paste for glaze contains a glass containing the above-mentioned glassy component and a specific black inorganic pigment in a specific ratio, and is obtained by making a paste using a solvent and an organic vehicle by a conventional method. be able to.
Examples of the material of the insulating plate used in the step (a) include the substrate materials exemplified in the above-described insulating substrate. A thinner insulating plate is preferable because the desired effect of the present invention is easily exhibited, and is usually 0.5 mm or less, and particularly preferably 0.3 mm or less.
In step (a), the glaze paste can be printed on the surface of the insulating plate by screen printing or the like, and the glaze layer can be formed by drying and baking the printed paste. At this time, it is desirable to perform printing, drying and baking so that the thickness of the resulting glaze layer is 50 to 80 μm. The firing is preferably performed at a temperature of usually 1000 ° C. or higher, preferably 1200 to 1300 ° C. for about 30 minutes so that the insulating plate is not deformed.
Further, since the dividing groove is not formed before the formation of the glaze layer, it is possible to easily suppress deformation of the insulating plate and the like by appropriately setting the temperature rising and cooling time. For example, in order to fire the glaze layer, the temperature is first increased to 1000 ° C. at a rate of 20 ° C. per minute, then the temperature is increased at a rate of 5 ° C. per minute until reaching 1300 ° C., and the firing is performed at 1300 ° C. for about 30 minutes. After that, the temperature can be lowered to about 20 ° C. per minute to room temperature.
本発明の集合絶縁基板の製造方法では、工程(a)で調製したグレーズド絶縁板を、特定速度以上でレーザー光を走査して、縦横分割溝を形成する工程(b)を含む。
工程(b)に用いるレーザー光のパワーとしては、好ましくはパワー１０〜１２Ｗの出力を有するＹＡＧレーザー光等が使用できる。
レーザー光を走査する速度は、本発明の所望の効果である短期間における大量生産を可能にするために、９０ｍｍ／秒以上とする必要があり、その上限は特に限定されないが、通常１００〜１１０ｍｍ／秒である。前述のとおり、レーザー光を照射するグレーズ層は、レーザー光照射適性を有するように形成されているので、分割溝を形成する他の条件は、走査速度が本願発明のように速い場合であっても、グレーズ層及び絶縁板の厚さに応じて容易に設定することができる。
本発明の集合絶縁基板の製造方法では、上記工程が含まれておれば、通常、目的とする基板の種類等に応じて行なう他の工程を含んでいても良い。また、得られた集合絶縁基板は、常法により分割して本発明のグレーズド絶縁基板とすることができる。
The method for manufacturing a collective insulating substrate of the present invention includes the step (b) of forming vertical and horizontal dividing grooves by scanning the glazed insulating plate prepared in the step (a) with a laser beam at a specific speed or higher.
As the power of the laser beam used in the step (b), YAG laser beam having a power of 10 to 12 W is preferably used.
The speed of scanning with laser light needs to be 90 mm / second or more in order to enable mass production in a short period, which is a desired effect of the present invention, and the upper limit is not particularly limited, but is usually 100 to 110 mm. / Sec. As described above, since the glaze layer that irradiates laser light is formed so as to have laser beam irradiation suitability, another condition for forming the division grooves is that the scanning speed is high as in the present invention. Also, it can be easily set according to the thickness of the glaze layer and the insulating plate.
In the method for manufacturing a collective insulating substrate of the present invention, as long as the above-described steps are included, other steps usually performed according to the type of the target substrate may be included. Further, the obtained collective insulating substrate can be divided by a conventional method to obtain the glazed insulating substrate of the present invention.
本発明のヒューズ抵抗器は、本発明のグレーズド絶縁基板に、ヒューズ抵抗膜が形成されたものであれば良く、電極、保護コート膜等の他の構成要件における、材料の種類、形態等は特に限定されず、所望の性能を得るために適宜選択することができる。
本発明のヒューズ抵抗器は、良好な平滑性及び熱安定性等を有するグレーズ層が形成された基板を用いているので、各膜の特性を十分発揮させることができる。
The fuse resistor of the present invention only needs to have a fuse resistance film formed on the glazed insulating substrate of the present invention. It is not limited but can be selected as appropriate in order to obtain desired performance.
Since the fuse resistor of the present invention uses a substrate on which a glaze layer having good smoothness and thermal stability is formed, the characteristics of each film can be sufficiently exhibited.
以下本発明を実施例及び比較例により更に詳細に説明するが、本発明はこれらに限定されない。
製造例
（グレーズ用ペーストの製造）
表１に示す組成の8種のガラス質成分(1)〜(8)に、Fe2O3４５質量％、Cr2O3２８質量％及びCoO２７質量％からなる黒色無機顔料をガラス質成分１００質量部に対して表２〜７に示す割合で配合し、常法により溶剤及び有機質ビヒクルを添加混合してそれぞれグレーズ用ペーストを調製した。尚、ガラス質成分(1)はZrO2が０質量％、ガラス質成分(2)はZrO2が１０質量％、ガラス質成分(3)はZrO2が１３質量％、ガラス質成分(4)はZrO2が１５質量％、ガラス質成分(5)はZrO2が１７．５質量％、ガラス質成分(6)はZrO2が２０質量％、ガラス質成分(7)はZrO2が２２質量％、ガラス質成分(8)はZrO2が３０質量％の例である。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.
Production example (production of glaze paste)
In eight of the vitreous component of the compositions shown in Table 1 (1) ~ (8) , Fe 2 O 3 45 wt%, Cr 2 O 3 28% by weight and vitreous components 100 a black inorganic pigment consisting CoO27 wt% It mix | blended in the ratio shown to Tables 2-7 with respect to a mass part, and the paste for glazes was prepared by adding and mixing a solvent and an organic vehicle by a conventional method, respectively. The vitreous component (1) is 0% by mass of ZrO 2 , the vitreous component (2) is 10% by mass of ZrO 2 , the vitreous component (3) is 13% by mass of ZrO 2 , and the vitreous component (4) Is 15% by weight of ZrO 2 , glassy component (5) is 17.5% by weight of ZrO 2 , glassy component (6) is 20% by weight of ZrO 2 , and glassy component (7) is 22% by weight of ZrO 2 The glassy component (8) is an example in which ZrO 2 is 30% by mass.
実施例１〜７、９〜１３、比較例１〜２４
製造例で調製した各々のグレーズ用ペーストを、厚さ０．３２ｍｍ、純度約９６％のアルミナセラミック基板上に、常法によりスクリーン印刷し、乾燥し、１３００℃で３０分間焼成することによって、膜厚約７０μｍのグレーズ層を有する集合絶縁基板を作製した。なお、それぞれのグレーズ層は、焼成により、ガラス質と黒色無機材料とが略原料の配合割合で含まれるものであった。更に、得られたそれぞれのグレーズ層のガラス軟化点は９３６〜９５６℃、ガラス転移点は７９０〜８１０℃、熱膨張係数は７．３×１０-6〜７．９×１０-6の範囲のものであった。
次いで、日本電気社製ＹＡＧレーザー発振器ＳＬ１１６Ｅを備えたＳＬ４１１Ｂのレーザースクライパー装置を用いて、出力１１．５Ｗ、周波数２０ＫＨｚ、スピード１００ｍｍ／秒で、それぞれの集合絶縁基板に対し、グレーズ層上に同一条件で３回スキャンを行ない格子状の縦横分割溝を形成した。
Examples 1-7 , 9-13 , Comparative Examples 1-24
Each glaze paste prepared in the production example was screen-printed by a conventional method on an alumina ceramic substrate having a thickness of 0.32 mm and a purity of about 96%, dried and fired at 1300 ° C. for 30 minutes to form a film. A collective insulating substrate having a glaze layer having a thickness of about 70 μm was produced. Each glaze layer contained a vitreous material and a black inorganic material in an approximately raw material mixing ratio by firing. Furthermore, each obtained glaze layer has a glass softening point of 936 to 956 ° C., a glass transition point of 790 to 810 ° C., and a thermal expansion coefficient of 7.3 × 10 −6 to 7.9 × 10 −6 . It was a thing.
Next, using a SL411B laser scraper device equipped with a YAG laser oscillator SL116E manufactured by NEC Corporation, an output of 11.5 W, a frequency of 20 KHz, a speed of 100 mm / sec. Scanning was performed three times under the same conditions to form grid-like vertical and horizontal dividing grooves.
得られた分割溝を有する集合絶縁基板に対して以下に示す評価を行なった。結果を表２〜７に示す。
＜分割溝周辺におけるバリ、クラックの発生評価＞
分割溝に沿って分割した後に生じる、微小な凸状突起をバリ、グレーズ層の微小なヒビをクラックと言い、それぞれの未発生率が９０％以上を○、９０％未満７０％以上を△、７０％未満を×とした。
＜グレーズ層の表面粗さ及びうねり評価＞
(株)東京精密製の表面粗さ計(サーフコム２０２Ｂ)を用いて測定した。表面粗さの評価は、グレーズ層の表面粗さが０．０２μｍ未満を◎、０．０３μｍ未満であったものを○、０．０３μｍ以上１μｍ未満であったものを△、１μｍ以上のものを×とした。
うねり評価は、グレーズ層表面うねりが、０．２ｍｍ／４５ｍｍ以下のものを○、０．２ｍｍ／４５ｍｍ以上０．３ｍｍ／４５ｍｍ未満のものを△、０．３ｍｍ／４５ｍｍ以上のものを×とした。
＜分割溝評価＞
分割溝評価は、グレーズ層面に形成された分割溝の平均深さが０．１ｍｍ以上０．２ｍｍ未満に達したものを○、０．０５ｍｍ以上０．１ｍｍ未満、０．２ｍｍ以上０．２５ｍｍ未満を△、０．０５ｍｍ未満と０．２５ｍｍ以上のものを×とした。尚、○のうち０．１ｍｍ以上０．１５ｍｍ未満のものを◎とした。
The following evaluation was performed with respect to the collective insulating substrate having the obtained divided grooves. The results are shown in Tables 2-7.
<Evaluation of occurrence of burrs and cracks around the dividing groove>
Minute convex protrusions generated after dividing along the dividing grooves are called burrs, and minute cracks in the glaze layer are called cracks, and each non-occurrence rate is 90% or more, ◯, less than 90% 70% or more, △, Less than 70% was set as x.
<Evaluation of surface roughness and waviness of glaze layer>
It was measured using a surface roughness meter (Surfcom 202B) manufactured by Tokyo Seimitsu Co., Ltd. The evaluation of the surface roughness is ◎ if the surface roughness of the glaze layer is less than 0.02 μm, ○ if it is less than 0.03 μm, △ if it is 0.03 μm or more and less than 1 μm, △ 1 μm or more. X.
As for the waviness evaluation, when the glaze layer surface waviness is 0.2 mm / 45 mm or less, ○, 0.2 mm / 45 mm or more and less than 0.3 mm / 45 mm is Δ, and 0.3 mm / 45 mm or more is ×. .
<Division groove evaluation>
In the evaluation of the dividing groove, the average depth of the dividing groove formed on the glaze layer surface is 0.1 mm or more and less than 0.2 mm, ○, 0.05 mm or more and less than 0.1 mm, 0.2 mm or more and less than 0.25 mm △, less than 0.05 mm and 0.25 mm or more were marked with ×. Of the circles, those with a diameter of 0.1 mm or more and less than 0.15 mm were marked with.
Claims (8)
かつ前記ガラス中の各ガラス質成分の含有割合は、SiO 2 が４１〜４３質量％、BaOが２５．５〜２７．５質量％、CaOが１０〜１１質量％、Al 2 O 3 が１〜１１質量％、及びZrO2が１５〜２０質量％であることを特徴とするグレーズド絶縁基板。 An insulating substrate; and a glaze layer formed on the surface of the insulating substrate, wherein the glaze layer includes glass containing SiO 2 , BaO, CaO, Al 2 O 3 and ZrO 2 , and Fe 2 O 3 having a spinel structure. , and a black inorganic pigment consisting essentially of Cr 2 O 3 and CoO, the content of said black inorganic pigment, a ratio of the 7.0 to 12.0 parts by weight with respect to the glass 100 parts by weight,
And the content of the vitreous component in the glass, SiO 2 is 41 to 43 mass%, BaO is 25.5 to 27.5 wt%, CaO is 10 to 11 wt%, Al 2 O 3 is 1 A glazed insulating substrate comprising 11% by mass and 15-20% by mass of ZrO 2 .
該グレーズ層が、SiO2、BaO、CaO、Al2O3及びZrO2を含むガラスと、スピネル構造を有するFe2O3、Cr2O3及びCoOから実質的になる黒色無機顔料とを含み、該黒色無機顔料の含有割合が、前記ガラス１００質量部に対して７．０〜１２．０質量部の割合であり、
前記ガラス中の各ガラス質成分の含有割合は、SiO 2 が４１〜４３質量％、BaOが２５．５〜２７．５質量％、CaOが１０〜１１質量％、Al 2 O 3 が１〜１１質量％、及びZrO2が１５〜２０質量％であり、且つ前記分割溝が、前記グレーズ層から前記絶縁基板にまで達していることを特徴とする集合絶縁基板。 A collective insulating substrate comprising a glazed insulating substrate comprising an insulating substrate and a glazed layer formed on the surface of the insulating substrate, wherein the glazed insulating substrate has a glaze layer provided on the surface provided with vertical and horizontal dividing grooves. ,
The glaze layer includes glass containing SiO 2 , BaO, CaO, Al 2 O 3 and ZrO 2 and a black inorganic pigment substantially composed of Fe 2 O 3 , Cr 2 O 3 and CoO having a spinel structure. , the content of said black inorganic pigment, a ratio of the 7.0 to 12.0 parts by weight with respect to the glass 100 parts by weight,
Content of the vitreous component in the glass, SiO 2 is 41 to 43 mass%, BaO is 25.5 to 27.5 wt%, CaO is 10 to 11 wt%, Al 2 O 3 is 1 to 11 The collective insulating substrate, wherein the mass% and ZrO 2 are 15 to 20 mass%, and the dividing groove reaches from the glaze layer to the insulating substrate.
前記ガラス中の各ガラス質成分の含有割合は、SiO 2 が４１〜４３質量％、BaOが２５．５〜２７．５質量％、CaOが１０〜１１質量％、Al 2 O 3 が１〜１１質量％、及びZrO2が１５〜２０質量％であるグレーズ用ペーストを、絶縁板の表面に印刷し、グレーズ層を形成する工程(a)と、該グレーズ層が形成されたグレーズド絶縁板を、９０ｍｍ／秒以上の速度でレーザー光を走査して、縦横分割溝を形成する工程(b)と、を含むことを特徴とする集合絶縁基板の製造方法。 To obtain a glazed collective insulating substrate, SiO 2, BaO, CaO, Al 2 O 3 and a glass containing ZrO 2, black inorganic consisting essentially of Fe 2 O 3, Cr 2 O 3 and CoO having a spinel structure and a pigment, the content of said black inorganic pigment, a ratio of the 7.0 to 12.0 parts by weight with respect to the glass 100 parts by weight,
Content of the vitreous component in the glass, SiO 2 is 41 to 43 mass%, BaO is 25.5 to 27.5 wt%, CaO is 10 to 11 wt%, Al 2 O 3 is 1 to 11 mass%, and ZrO 2 is a glaze paste is 15 to 20 wt%, and printed on the surface of the insulating plate, (a) forming a glaze layer, the glazed insulating plate to which the glaze layer is formed, And (b) forming a vertical and horizontal dividing groove by scanning a laser beam at a speed of 90 mm / second or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3891452A (en) * | 1973-04-11 | 1975-06-24 | Nasa | Refractory porcelain enamel passive control coating for high temperature alloys |
| JPS60176943A (en) * | 1982-06-28 | 1985-09-11 | オ−エンス−イリノイ・インコ−ポレ−テツド | Lead-free and cadmium-free glass frit composition for glazing, enameling and decorating treatment |
| JPS63162545A (en) * | 1986-12-26 | 1988-07-06 | Central Glass Co Ltd | Translucent crystalline glass |
| JPH0643258B2 (en) * | 1987-11-27 | 1994-06-08 | 昭栄化学工業株式会社 | Dielectric material for circuit boards |
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