JP3204640B2 - Heater and thermal head - Google Patents
Heater and thermal headInfo
- Publication number
- JP3204640B2 JP3204640B2 JP10891098A JP10891098A JP3204640B2 JP 3204640 B2 JP3204640 B2 JP 3204640B2 JP 10891098 A JP10891098 A JP 10891098A JP 10891098 A JP10891098 A JP 10891098A JP 3204640 B2 JP3204640 B2 JP 3204640B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- grain boundary
- heating resistor
- boundary phase
- thermal conductivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01012—Magnesium [Mg]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/01019—Potassium [K]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/01—Chemical elements
- H01L2924/0102—Calcium [Ca]
Landscapes
- Electronic Switches (AREA)
- Non-Adjustable Resistors (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明はセラミックス基板表面に
発熱抵抗体を配設したヒーターおよびサーマルヘッドに
係り、特に発熱抵抗体への印加電圧のON−OFF制御
に対する熱応答性に優れたヒーターおよび高速印字化,
高精細化が可能なサーマルヘッドに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heater and a thermal head having a heating resistor disposed on the surface of a ceramic substrate, and more particularly to a heater and a heater having excellent thermal response to ON-OFF control of a voltage applied to the heating resistor. High-speed printing,
The present invention relates to a thermal head capable of high definition.
【0002】[0002]
【従来の技術】一般にセラミックスヒーターは、任意の
幅および長さを有する線状の発熱抵抗体をセラミックス
基板上にパターン印刷して形成され、例えば、ディーゼ
ルエンジン用グロープラグ,サーマルヘッドの構造部品
として広く利用されている。2. Description of the Related Art In general, a ceramic heater is formed by pattern-printing a linear heating resistor having an arbitrary width and length on a ceramic substrate, for example, as a structural component of a glow plug for a diesel engine or a thermal head. Widely used.
【0003】ここでサーマルヘッドの基本構成は、セラ
ミックス基板に発熱抵抗体を形成し、さらに電気導線や
耐摩耗層を形成したもので各種印字機器に使用されてい
る。例えば計測記録計、各種プリンタやファクシミリな
どの感熱記録デバイスに電気信号として送信される情報
を感熱記録紙上に文字、記号または図形画像に変換する
ために各種のサーマルヘッドが使用されている。サーマ
ルヘッドは加熱によって発色する化学材料を塗布した感
熱記録紙面に文字、画像を形成するために電流加熱され
る発熱抵抗体を有している。[0003] Here, the basic structure of a thermal head is one in which a heating resistor is formed on a ceramic substrate, and further, an electric conductive wire and a wear-resistant layer are formed, and is used for various printing devices. For example, various thermal heads are used to convert information transmitted as an electrical signal to a thermal recording device such as a measurement recorder, various printers and facsimile devices into a character, symbol or graphic image on thermal recording paper. The thermal head has a heating resistor which is heated by current to form a character and an image on a heat-sensitive recording paper surface coated with a chemical material which develops a color by heating.
【0004】すなわち、従来の厚膜式サーマルプリンタ
の記録部となるサーマルヘッドの基本構成は、一般に図
10に示すように、アルミナ(Al2 O3 )から成るセ
ラミックス基板1と、この基板1上に形成され、電圧印
加によって発熱する発熱抵抗体2と、発熱抵抗体2の端
部に対向するように接続された電気導線(電極)3と、
感熱記録紙4の接触摩耗から上記発熱抵抗体2および電
気導線3を保護するための耐摩耗層5とから構成されて
いる。That is, as shown in FIG. 10, a basic structure of a thermal head which is a recording unit of a conventional thick film type thermal printer generally includes a ceramic substrate 1 made of alumina (Al 2 O 3 ) and a ceramic substrate 1 on the substrate 1. A heating resistor 2 that is formed on the substrate and generates heat when a voltage is applied thereto; and an electrical conductor (electrode) 3 that is connected to an end of the heating resistor 2 so as to face the heating resistor 2.
The heat-resistant resistor 2 and the abrasion-resistant layer 5 for protecting the electric conductive wire 3 from the contact abrasion of the thermal recording paper 4.
【0005】この厚膜形サーマルヘッドに送りローラ6
を介して感熱記録紙4が圧着され、この状態で発熱抵抗
体2にパルス電圧が印加されると、感熱記録紙4に塗布
されていた発色剤が化学反応を起こし、発熱抵抗体2部
分に接触している発色層が点(ドット)状に発色する。
送りローラによって記録紙4を順次、矢印方向に移動さ
せながら、パルス状加熱を繰り返すことにより、多数の
発色ドットが得られ、この発色ドットの配列の仕方によ
り、文字、記号または画像の記録がなされる。A feed roller 6 is attached to the thick film type thermal head.
When a pulse voltage is applied to the heat-generating resistor 2 in this state, the coloring agent applied to the heat-sensitive recording paper 4 undergoes a chemical reaction, and is applied to the heat-generating resistor 2 portion. The color-forming layer that is in contact develops a dot (dot) shape.
By repeating the pulsed heating while sequentially moving the recording paper 4 in the direction of the arrow by the feed roller, a number of coloring dots are obtained, and characters, symbols or images are recorded according to the arrangement of the coloring dots. You.
【0006】[0006]
【発明が解決しようとする課題】しかしながら、前記従
来のヒーターにおけるセラミックス基板は、熱伝導率が
小さいアルミナ(Al2 O3 )を主たる構成材料として
形成されているため、熱応答特性が低い問題点がある。
すなわち発熱抵抗体への通電のON−OFF操作に伴う
ヒーターの表面温度が所定値になるまでの時間の遅れが
大きいという問題点があった。However, since the ceramic substrate of the conventional heater is formed mainly of alumina (Al 2 O 3 ) having a low thermal conductivity, the ceramic substrate has a low thermal response characteristic. There is.
In other words, there is a problem that the time delay until the surface temperature of the heater reaches a predetermined value due to the ON-OFF operation of energizing the heating resistor is large.
【0007】一方、上記従来のサーマルヘッドのセラミ
ックス基板も、熱伝導率が小さいアルミナ(Al
2 O3 )を主たる構成材料として形成されているため、
熱応答特性が低く、一旦加熱されたヘッドが感熱紙の発
色温度以下の温度までに冷却されるまでの放熱時間が長
くなり、その結果、記録紙の地汚れや印字の尾引きが発
生し易くなり、高速記録プリンタ用のヘッドとしては不
適な場合が多かった。近年印字速度の高速化が求められ
ており、より印字の高速化に充分な対応ができ、熱応答
特性および信頼性が高いサーマルヘッドが希求されてい
る。On the other hand, the ceramic substrate of the above-described conventional thermal head is also made of alumina (Al) having a low thermal conductivity.
2 O 3 ) as the main constituent material,
Thermal response characteristics are low, and the heat radiation time until the heated head cools down to the temperature below the color development temperature of the thermal paper becomes longer, and as a result, the recording paper becomes liable to be stained and the print trailed. In many cases, the head is not suitable for a head for a high-speed recording printer. In recent years, there has been a demand for a higher printing speed, and there is a need for a thermal head which can sufficiently respond to a higher printing speed and has high thermal response characteristics and high reliability.
【0008】一方窒化アルミニウム製基板は他のセラミ
ックス基板と比較して高い熱伝導率と低熱膨張係数の特
徴を有するため、高速化、高出力化、多機能化、大型化
が進展する半導体チップの回路部品やパッケージ材料と
して普及しているが、ヒーターやサーマルヘッドに必要
な機械的強度,高温強度の点で充分に満足できるものは
得られていない。また高温時に酸素,水分と反応し易
く、特性上不安定な面も有する。On the other hand, aluminum nitride substrates have characteristics of high thermal conductivity and low coefficient of thermal expansion as compared with other ceramic substrates, so that high-speed, high-power, multi-functional, and large-sized semiconductor chips have been developed. Although it is widely used as a circuit component or package material, there has not been obtained a material which is sufficiently satisfactory in mechanical strength and high-temperature strength required for a heater and a thermal head. In addition, it easily reacts with oxygen and moisture at high temperatures, and has a characteristically unstable surface.
【0009】さらに上記セラミックス構造部材を主たる
構成材とするヒーターやサーマルヘッドを固定部に固定
した場合、印字動作時の押圧力や衝撃力によってヒータ
ーやサーマルヘッドが破損し、適用製品の信頼性を大幅
に低減させることとなる。したがって、ヒーターやサー
マルヘッドにおいても、外力に耐える高強度特性と、高
出力化,高速化に対応できる優れた熱応答特性を兼ね備
えたものが要請されている。特に感熱記録デバイスに使
用されるサーマルヘッドには高精細化,高速化などの高
機能化が要求されている。Further, when a heater or a thermal head mainly composed of the above-mentioned ceramic structural member is fixed to a fixed portion, the heater or the thermal head is damaged by a pressing force or an impact force during a printing operation, and the reliability of the applied product is reduced. It will be greatly reduced. Therefore, there is a demand for a heater or a thermal head that has both high strength characteristics that can withstand external force and excellent thermal response characteristics that can cope with high output and high speed. In particular, a thermal head used for a thermal recording device is required to have higher functions such as higher definition and higher speed.
【0010】本発明は上記のような課題要請に対処する
ためになされたものであり、窒化けい素焼結体が本来備
える高強度特性に加えて、熱伝導率が高く熱応答性に優
れた窒化けい素焼結体を開発し、これをヒーターやサー
マルヘッド用の基板材料に適用することにより、高強度
特性に加えて、熱伝導率が高く熱応答性に優れたヒータ
ーと、同じく高強度特性および熱応答性を兼ね備え、よ
り高速度の印字記録を可能とするサーマルヘッドとを提
供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in order to address the above-mentioned demands. In addition to the high strength characteristics inherent to a silicon nitride sintered body, a nitride having a high thermal conductivity and excellent thermal responsiveness is provided. By developing a silicon sintered body and applying it to substrate materials for heaters and thermal heads, in addition to high strength characteristics, a heater with high thermal conductivity and excellent thermal responsiveness, as well as high strength characteristics and It is an object of the present invention to provide a thermal head having thermal responsiveness and capable of printing at a higher speed.
【0011】[0011]
【課題を解決するための手段】本発明者は上記目的を達
成するため、特に優れた靭性値,曲げ強度などの機械的
強度を有する窒化けい素焼結体に着目し、この機械的強
度を損うことなく、熱伝導性を高める方策を種々検討
し、ヒーターおよびサーマルヘッド用の基板材料への適
用性について研究した。すなわち従来の窒化けい素焼結
体に対して窒化けい素粉末の種類、焼結助剤や添加物の
種類および添加量、焼結体中に不純物として含有し熱伝
導率を低下させる元素およびその含有量、焼結条件等を
種々検討を加えた結果、従来の窒化けい素焼結体の有す
る熱伝導率の2倍以上の高い熱伝導性を有する窒化けい
素焼結体を開発し、さらにこの窒化けい素焼結体をヒー
ターやサーマルヘッド用の基板材料として使用する際に
効果が大きいことを初めて確認した。Means for Solving the Problems In order to achieve the above-mentioned object, the present inventor pays particular attention to a silicon nitride sintered body having excellent mechanical strength such as excellent toughness and bending strength. Various measures were taken to increase the thermal conductivity without any problems, and the applicability to substrate materials for heaters and thermal heads was studied. That is, the type of silicon nitride powder, the type and amount of sintering aids and additives, and the elements contained as impurities in the sintered body and lowering the thermal conductivity with respect to the conventional silicon nitride sintered body and the content thereof As a result of various studies on the amount, sintering conditions, etc., a silicon nitride sintered body having high thermal conductivity twice or more the thermal conductivity of the conventional silicon nitride sintered body was developed. For the first time, it was confirmed that the effect was great when the sintered body was used as a substrate material for a heater or a thermal head.
【0012】具体的には、微細で高純度を有する窒化け
い素粉末に希土類元素、必要に応じ窒化アルミニウム、
アルミナなどのアルミニウム成分を所定量添加した原料
混合体を成形脱脂し、得られた成形体を所定温度で一定
時間加熱保持して緻密化焼結を実施した後、従来製法と
比較して低い所定以下の冷却速度で徐冷したときに熱伝
導率が従来の窒化けい素焼結体の2倍以上、具体的には
60W/m・Kを超えるほど大きく向上し、かつ高強度
を併有する窒化けい素焼結体が得られることが判明し、
放熱特性および強度特性を共に満足する新規な窒化けい
素材料を開発した。そして、この窒化けい素材料を、ヒ
ーターおよびサーマルヘッドを構成するセラミックス基
板に適用したときに、優れた熱応答特性と耐久性とを同
時に達成できることが判明した。Specifically, a rare earth element and, if necessary, aluminum nitride are added to fine and high-purity silicon nitride powder.
A raw material mixture to which a predetermined amount of an aluminum component such as alumina is added is molded and degreased, and the obtained molded body is heated and held at a predetermined temperature for a certain period of time to perform densification sintering. When gradually cooled at the following cooling rate, the thermal conductivity is more than twice as large as that of the conventional silicon nitride sintered body, more specifically, more than 60 W / m · K, and the silicon nitride has both high strength and high strength. It was found that an elementary sintered body was obtained,
A new silicon nitride material that satisfies both heat dissipation and strength characteristics has been developed. It has been found that when this silicon nitride material is applied to a ceramic substrate constituting a heater and a thermal head, excellent thermal response characteristics and durability can be achieved at the same time.
【0013】また上記セラミックス基板の構成原料とし
て、酸素や不純物陽イオン元素含有量を低減した高純度
の窒化けい素原料粉末を使用し、上記条件にて焼結する
ことにより、粒界相におけるガラス相(非晶質相)の生
成を効果的に抑制でき、粒界相における結晶化合物相を
20体積%以上(粒界相全体に対し)、好ましくは50
体積%以上とすることにより希土類元素酸化物のみを原
料粉末に添加した場合においても60W/m・Kを超え
る値の高熱伝導率を有する窒化けい素基板が得られると
いう知見を得た。Further, as a constituent material of the ceramic substrate, a high-purity silicon nitride raw material powder having a reduced content of oxygen and impurity cation elements is used and sintered under the above conditions to obtain a glass in the grain boundary phase. Phase (amorphous phase) can be effectively suppressed, and the amount of the crystalline compound phase in the grain boundary phase is 20% by volume or more (based on the whole grain boundary phase), preferably 50%.
It has been found that by setting the volume% or more, even when only a rare earth element oxide is added to the raw material powder, a silicon nitride substrate having a high thermal conductivity of a value exceeding 60 W / m · K can be obtained.
【0014】特に、従来、焼結操作終了後に焼成炉の加
熱用電源をOFFとして焼結体を炉冷していた場合に
は、冷却速度が毎時400〜800℃と急速であった
が、本発明者の実験によれば、冷却速度を毎時100℃
以下に緩速に制御することにより、窒化けい素焼結体中
の粒界相を、少なくとも20体積%以上、好ましくは5
0体積%以上(粒界相全体に対し)の結晶相を含む相に
し、高強度特性と高伝熱特性とが同時に達成され、この
窒化けい素焼結体をヒーターおよびサーマルヘッドのセ
ラミックス基板として使用した際に、優れた耐久性およ
び熱応答特性が得られることが判明した。In particular, conventionally, when the sintered body was cooled with the heating power supply turned off after the sintering operation was completed, the cooling rate was rapidly as high as 400 to 800 ° C. per hour. According to the experiment of the inventor, the cooling rate was set to 100 ° C./hour.
By controlling it slowly below, the grain boundary phase in the silicon nitride sintered body is reduced to at least 20% by volume or more, preferably 5% by volume or more.
A phase containing a crystal phase of 0% by volume or more (based on the whole grain boundary phase), high strength characteristics and high heat transfer characteristics are simultaneously achieved, and this silicon nitride sintered body is used as a ceramic substrate for a heater and a thermal head. Then, it was found that excellent durability and thermal response characteristics were obtained.
【0015】本発明は上記知見に基づいて完成されたも
のである。すなわち本発明に係るヒーターは、窒化けい
素粒子および粒界相により構成され、粒界相中における
結晶化合物相が粒界相全体に対して体積比で20体積%
以上、好ましくは50体積%以上を占め、前記気孔率が
1.5vol.%以下,三点曲げ強度が80kg/mm2 以上で
熱伝導率が60W/m・Kを超える値、好ましくは80
W/m・K以上である高熱伝導性窒化けい素基板に発熱
抵抗体を一体に配置したことを特徴とする。The present invention has been completed based on the above findings. That is, the heater according to the present invention is composed of silicon nitride particles and a grain boundary phase, and the crystal compound phase in the grain boundary phase is 20% by volume with respect to the whole grain boundary phase.
Above, preferably 50% by volume or more, the porosity is 1.5 vol.% Or less, the three-point bending strength is 80 kg / mm 2 or more, and the thermal conductivity exceeds 60 W / m · K, preferably 80%.
A heating resistor is integrally disposed on a silicon nitride substrate having a high thermal conductivity of not less than W / m · K.
【0016】さらに本発明で使用する高熱伝導性窒化け
い素基板は、不純物イオン元素量,陽イオン元素量
(0.3重量%以下),焼結体中の粒界相における結晶
化合物相の割合(50体積%以上),気孔率(0.3体
積%以下),その他製造に使用する窒化けい素粉末の粒
径および含有酸素量などを適正に制御することにより、
その熱伝導率を100W/m・Kとすることができる。Further, the high thermal conductive silicon nitride substrate used in the present invention has an impurity ion element amount, a cation element amount (0.3% by weight or less), and a ratio of a crystalline compound phase in a grain boundary phase in a sintered body. (50% by volume or more), porosity (0.3% by volume or less), and other parameters by properly controlling the particle size and oxygen content of the silicon nitride powder used for production.
Its thermal conductivity can be 100 W / m · K.
【0017】発熱抵抗体はTi,Zr,Hf,V,C
r,Mo,W,NiCr,ネサ膜,Ta−Si,Ta2
N,Ta−SiO2 およびNb−SiO2 から選択され
る少なくとも1種の元素または化合物から形成するとよ
い。The heating resistors are Ti, Zr, Hf, V, C
r, Mo, W, NiCr, Nesa film, Ta-Si, Ta 2
N, may be formed from at least one element or compound selected from Ta-SiO 2 and Nb-SiO 2.
【0018】ここで上記高融点金属(タングステン系,
モリブデン系)合金を主成分とする発熱抵抗体は窒化け
い素基板との密着性に優れており、耐久性の良いヒータ
ーが得られる。特にタングステンにTi,Zr,Hfの
少なくとも1種を含有した発熱抵抗体は、さらに窒化け
い素基板の密着性(密着強度)に優れている。また、タ
ングステン−白金合金で形成した発熱抵抗体は、耐酸化
性に優れているため、長寿命のヒーターが得られる。な
お、発熱抵抗体は、メタライズ法により形成してもよい
が、電気抵抗線を配設して形成することもできる。Here, the refractory metal (tungsten,
A heating resistor mainly composed of a (molybdenum) alloy has excellent adhesion to a silicon nitride substrate, and a heater with good durability can be obtained. In particular, a heat generating resistor containing at least one of Ti, Zr, and Hf in tungsten is further excellent in adhesion (adhesion strength) of a silicon nitride substrate. Further, since the heating resistor formed of the tungsten-platinum alloy has excellent oxidation resistance, a long-life heater can be obtained. The heating resistor may be formed by a metallizing method, but may be formed by disposing an electric resistance wire.
【0019】また上記発熱抵抗体を覆うように窒化けい
素基板上に絶縁体層を形成して構成することもできる。
この絶縁体層を形成することにより、導電性を有する発
熱抵抗体が周辺の構成部品と電気的に接触して、誤動作
等を引き起こすことが効果的に防止できる。この絶縁体
層を構成する材料としては、汎用のアルミナ,ムライ
ト,Si3 N4 などが使用できる。特にこの絶縁体層の
構成材料として窒化けい素基板と同一の材料を使用する
ことによって、絶縁体層および窒化けい素基板の熱膨張
率を等しくすることができ、両者の熱膨張差による剥離
を防止することができ、耐久性が優れたヒーターを形成
することができる。Further, an insulating layer may be formed on a silicon nitride substrate so as to cover the heating resistor.
By forming the insulating layer, it is possible to effectively prevent the heat generating resistor having conductivity from coming into electrical contact with surrounding components and causing a malfunction or the like. As a material constituting the insulator layer, general-purpose alumina, mullite, Si 3 N 4 and the like can be used. In particular, by using the same material as the silicon nitride substrate as a constituent material of the insulator layer, the thermal expansion coefficients of the insulator layer and the silicon nitride substrate can be made equal, and separation due to the difference in thermal expansion between the two can be achieved. Thus, a heater having excellent durability can be formed.
【0020】また本発明に係るサーマルヘッドは、窒化
けい素粒子および粒界相により構成され、粒界相中にお
ける結晶化合物相が粒界相全体に対して体積比で20%
以上、好ましくは50体積%以上を占め、気孔率が1.
5vol.%以下,三点曲げ強度が80kg/mm2 以上で熱伝
導率が60W/m・Kを超える値、好ましくは80W/
m・K以上である高熱伝導性窒化けい素基板表面に、発
熱抵抗体および耐摩耗層を一体に積層して構成してもよ
い。この場合、特に結晶化合物相を粒界相全体に対して
体積比で50%以上とし、さらに前記不純物陽イオン元
素含有量や焼結後の冷却速度等を制御することにより、
熱伝導率が、80W/m・K以上、さらには100W/
m・K以上の高熱伝導性窒化けい素基板を得ることがで
きる。The thermal head according to the present invention is composed of silicon nitride particles and a grain boundary phase, and the crystalline compound phase in the grain boundary phase is 20% by volume relative to the whole grain boundary phase.
Occupies 50% by volume or more, and preferably has a porosity of 1.
5 vol.% Or less, a three-point bending strength of 80 kg / mm 2 or more, and a thermal conductivity of more than 60 W / m · K, preferably 80 W / m · K.
A heating resistor and a wear-resistant layer may be integrally laminated on the surface of a silicon nitride substrate having a high thermal conductivity of at least m · K. In this case, in particular, by controlling the volume of the crystalline compound phase to 50% or more with respect to the whole grain boundary phase, and further controlling the content of the impurity cation element, the cooling rate after sintering, and the like,
The thermal conductivity is 80 W / m · K or more, further 100 W / m
It is possible to obtain a silicon nitride substrate having a high thermal conductivity of at least m · K.
【0021】なお、本発明のヒーターおよびサーマルヘ
ッドは以上のような構成,組成,組織を有する窒化けい
素基板を有するものであるが、この窒化けい素基板を主
体とし、さらにSiC等の添加物を加えた複合材料基板
を使用することも可能であり、これらの態様も本発明の
範囲に含まれる。The heater and the thermal head of the present invention have a silicon nitride substrate having the above-described structure, composition, and structure. The silicon nitride substrate is mainly used, and an additive such as SiC is used. It is also possible to use a composite material substrate to which is added, and these embodiments are also included in the scope of the present invention.
【0022】上記ヒーターおよびサーマルヘッドに使用
される高熱伝導性窒化けい素基板は、例えば以下の方法
で製造される。すなわち、酸素を1.7重量%以下、不
純物陽イオン元素としてのLi,Na,K,Fe,C
a,Mg,Sr,Ba,Mn,Bを0.3重量%以下、
α相型窒化けい素を90重量%以上含有し、平均粒径
0.8μm以下の窒化けい素粉末に、希土類元素を酸化
物に換算して1.0〜7.5重量%を添加した原料混合
体をドクターブレード法等によって成形して成形体を調
製し、得られた成形体を脱脂後、温度1800〜200
0℃で雰囲気加圧焼結し、上記焼結温度から、上記希土
類元素により焼結時に形成された液相が凝固する温度ま
でに至る焼結体の冷却速度を毎時100℃以下に設定
し、得られた焼結体を研削研摩加工して製造される。The silicon nitride substrate having high thermal conductivity used for the heater and the thermal head is manufactured, for example, by the following method. That is, oxygen is 1.7% by weight or less, and Li, Na, K, Fe, C as impurity cation elements are used.
a, Mg, Sr, Ba, Mn, B in an amount of 0.3% by weight or less;
Raw material containing 90% by weight or more of α-phase type silicon nitride and adding 1.0 to 7.5% by weight of a rare earth element converted to oxide to silicon nitride powder having an average particle size of 0.8 μm or less. The mixture was molded by a doctor blade method or the like to prepare a molded body, and the obtained molded body was degreased.
Atmospheric pressure sintering at 0 ° C., the cooling rate of the sintered body from the sintering temperature to a temperature at which a liquid phase formed during sintering by the rare earth element solidifies is set to 100 ° C. or less per hour, It is manufactured by grinding and polishing the obtained sintered body.
【0023】また上記製造方法において、上記原料混合
体に、さらにTi,Zr,Hf,V,Nb,Ta,C
r,Mo,Wの酸化物,炭化物、窒化物、けい化物、硼
化物からなる群より選択される少なくとも1種を0.2
〜3.0重量%と、必要に応じてアルミナおよび窒化ア
ルミニウムの少なくとも一方を0.1〜2.0重量%と
を添加してもよい。In the above-mentioned production method, Ti, Zr, Hf, V, Nb, Ta, C
0.2, at least one selected from the group consisting of oxides, carbides, nitrides, silicides, and borides of r, Mo, W
To 3.0% by weight, and if necessary, 0.1 to 2.0% by weight of at least one of alumina and aluminum nitride.
【0024】上記製造方法によれば、窒化けい素結晶組
織中に希土類元素等を含む粒界相が形成され、気孔率が
1.5%以下、熱伝導率が60W/m・Kより大きく、
三点曲げ強度が室温で80kg/mm2 以上の機械的特性お
よび熱伝導特性が共に優れた高熱伝導性窒化けい素基板
が得られる。According to the above manufacturing method, a grain boundary phase containing a rare earth element or the like is formed in the silicon nitride crystal structure, the porosity is 1.5% or less, the thermal conductivity is larger than 60 W / m · K,
A high thermal conductive silicon nitride substrate having a three-point bending strength of 80 kg / mm 2 or more at room temperature and excellent in both mechanical properties and thermal conductivity properties can be obtained.
【0025】上記高熱伝導性窒化けい素基板の主原料と
なる窒化けい素粉末としては、例えば焼結性、強度およ
び熱伝導率を考慮して、酸素含有量が1.7重量%以
下、好ましくは0.5〜1.5重量%、Li,Na,
K,Fe,Mg,Ca,Sr,Ba,Mn,Bなどの不
純物陽イオン元素の含有量が0.3重量%以下、好まし
くは0.2重量%以下で、焼結性が優れたα相型窒化け
い素を90重量%以上、好ましくは93重量%以上含有
し、平均粒径が0.8μm以下、好ましくは0.4〜
0.6μm程度の微細な窒化けい素粉末を使用する。The silicon nitride powder used as the main raw material of the silicon nitride substrate having a high thermal conductivity has an oxygen content of 1.7% by weight or less in consideration of, for example, sinterability, strength and thermal conductivity. Is 0.5-1.5% by weight, Li, Na,
Α phase having excellent sinterability with a content of impurity cation elements such as K, Fe, Mg, Ca, Sr, Ba, Mn, and B being 0.3% by weight or less, preferably 0.2% by weight or less. Containing at least 90% by weight, preferably at least 93% by weight, of silicon nitride having an average particle diameter of 0.8 μm or less, preferably 0.4 to
A fine silicon nitride powder of about 0.6 μm is used.
【0026】平均粒径が0.8μm以下の微細な原料粉
末を使用することにより、少量の焼結助剤であっても気
孔率が1.5%以下の緻密な焼結体を形成することが可
能であり、また焼結助剤が熱伝導特性を阻害するおそれ
も減少する。By using a fine raw material powder having an average particle diameter of 0.8 μm or less, it is possible to form a dense sintered body having a porosity of 1.5% or less even with a small amount of a sintering aid. Is also possible, and the possibility that the sintering aid impairs the heat transfer properties is reduced.
【0027】また前記窒化けい素原料粉末に焼結助剤と
して添加する希土類元素としてはY,La,Sc,P
r,Ce,Nd,Dy,Ho,Gdなどの酸化物もしく
は焼結操作により、これらの酸化物となる物質が単独
で、または2種以上の酸化物を組み合せたものを含んで
もよいが、特に酸化イットリウム(Y2 O3 )が好まし
い。これらの焼結助剤は、窒化けい素原料粉末と反応し
て液相を生成し、焼結促進剤として機能する。The rare earth elements to be added as a sintering aid to the silicon nitride raw material powder are Y, La, Sc, P
Oxides such as r, Ce, Nd, Dy, Ho, and Gd, or substances that become these oxides by a sintering operation may be used alone or in combination of two or more oxides. Yttrium oxide (Y 2 O 3 ) is preferred. These sintering aids react with the silicon nitride raw material powder to generate a liquid phase and function as sintering accelerators.
【0028】さらに、他の添加成分としてのアルミナ
(Al2 O3 )は、上記希土類元素の焼結促進剤の機能
を助長する役目を果すものであり、特に加圧焼結を行な
う場合に著しい効果を発揮するものである。Al2 O3
の添加量が0.1重量%未満の場合においては緻密化が
不充分である一方、2.0重量%を超える過量となる場
合には過量の粒界相を生成したり、または窒化けい素に
固溶し始め、熱伝導の低下が起こるため、添加量は2.
0重量%以下、好ましくは0.1〜2.0重量%の範囲
とする。特に強度、熱伝導率共に良好な性能を確保する
ためには添加量を0.2〜1.5重量%の範囲とするこ
とが望ましい。Further, alumina (Al 2 O 3 ) as another additive component plays a role of promoting the function of the rare earth element sintering accelerator, and is particularly remarkable in pressure sintering. It is effective. Al 2 O 3
If the addition amount of the element is less than 0.1% by weight, the densification is insufficient. On the other hand, if the addition amount exceeds 2.0% by weight, an excessive amount of the grain boundary phase is generated, or silicon nitride is added. To form a solid solution and decrease in heat conduction.
0% by weight or less, preferably in the range of 0.1 to 2.0% by weight. In particular, in order to ensure good performance in both strength and thermal conductivity, it is desirable that the amount added is in the range of 0.2 to 1.5% by weight.
【0029】また、後述するAlNと併用する場合に
は、その合計添加量は2.0重量%以下とすることが望
ましい。When used in combination with AlN, which will be described later, the total amount thereof is desirably 2.0% by weight or less.
【0030】さらに他の添加成分としての窒化アルミニ
ウム(AlN)は焼結過程における窒化けい素の蒸発な
どを抑制するとともに、上記希土類元素の焼結促進剤と
しての機能をさらに助長する役目を果すものである。Aluminum nitride (AlN) as another additive component serves to suppress the evaporation of silicon nitride during the sintering process and to further promote the function of the rare earth element as a sintering accelerator. It is.
【0031】AlNの添加量が0.3重量%未満(アル
ミナと併用する場合では0.1重量%未満)の場合にお
いては緻密化が不充分である一方、2.0重量%を超え
る過量となる場合には過量の粒界相を生成したり、また
は窒化けい素に固溶し始め、熱伝導率の低下が起こるた
め、添加量は2.0重量%以下、好ましくは0.3〜
2.0重量%の範囲とする。特に強度、熱伝導率共に良
好な性能を確保するためには添加量を0.5〜1.5重
量%の範囲とすることが望ましい。なお前記Al2 O3
と併用する場合には、AlNの添加量は0.1〜2.0
重量%の範囲が好ましい。When the addition amount of AlN is less than 0.3% by weight (less than 0.1% by weight when used in combination with alumina), the densification is insufficient, while the excess amount exceeding 2.0% by weight In some cases, an excessive amount of the grain boundary phase is generated, or solid solution starts to be formed in silicon nitride, resulting in a decrease in thermal conductivity. Therefore, the addition amount is 2.0% by weight or less, preferably 0.3 to 0.3% by weight.
The range is 2.0% by weight. In particular, in order to ensure good performance in both strength and thermal conductivity, it is desirable that the amount added is in the range of 0.5 to 1.5% by weight. The above Al 2 O 3
When used together, the addition amount of AlN is 0.1 to 2.0.
A range of weight% is preferred.
【0032】また他の添加成分として使用するTi,Z
r,Hf,V,Nb,Ta,Cr,Mo,Wの酸化物,
炭化物、窒化物、けい化物、硼化物は、上記希土類元素
の焼結促進剤の機能を促進すると共に、窒化けい素結晶
組織において分散強化の機能を果しSi3 N4 基板の機
械的強度を向上させるものである。これらの化合物の添
加量が0.2重量%未満の場合においてはSi3 N4 基
板の緻密化が不充分である一方、3.0重量%を超える
過量となる場合には熱伝導率および機械的強度や電気絶
縁破壊強度の低下が起こるため、添加量は0.2〜3.
0重量%の範囲とする。特に好ましくは0.3〜2.0
重量%とすることが望ましい。Ti, Z used as other additive components
oxides of r, Hf, V, Nb, Ta, Cr, Mo, W;
Carbides, nitrides, silicides, and borides promote the function of the rare earth element sintering accelerator and also function to enhance dispersion in the silicon nitride crystal structure, thereby increasing the mechanical strength of the Si 3 N 4 substrate. It is to improve. When the addition amount of these compounds is less than 0.2% by weight, the densification of the Si 3 N 4 substrate is insufficient, while when the addition amount exceeds 3.0% by weight, the thermal conductivity and mechanical Since the mechanical strength and the electrical breakdown strength decrease, the amount of addition is 0.2 to 3.0.
The range is 0% by weight. Particularly preferably 0.3 to 2.0
% By weight.
【0033】また窒化アルミニウム(AlN)は焼結過
程における窒化けい素の蒸発などを抑制する一方、上記
焼結促進剤の機能をさらに助長し、アルミナと同様に上
記Ti,Zr,Hf,V,Nb,Ta,Cr,Mo,W
などの酸化物の添加量を相対的に軽減する役目を果す。
これらアルミナや窒化アルミニウムなどのアルミニウム
化合物の添加量はTi,Zr,Hf,V,Nb,Ta,
Cr,Mo,Wの酸化物などの添加量と密接な関係があ
る。すなわち上記Ti化合物等の添加量が0.2重量%
未満であり、かつAl2 O3 およびAlN等のアルミニ
ウム化合物が単独または併用して添加され、その添加量
が0.1重量%未満の場合においては緻密化が不充分で
ある一方、アルミニウム化合物の添加量が2.0重量%
を超える過量となる場合には過量の粒界相を生成した
り、または窒化けい素に固溶し始め、熱伝導率の低下が
起こるため、添加量は0.1〜2.0重量%の範囲とす
る。特に強度、熱伝導率共に良好な性能を確保するため
には添加量を0.2〜1.5重量%の範囲とすることが
望ましい。While aluminum nitride (AlN) suppresses evaporation of silicon nitride during the sintering process, it further promotes the function of the sintering accelerator and, like alumina, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W
It serves to relatively reduce the amount of oxides added.
The addition amounts of these aluminum compounds such as alumina and aluminum nitride are Ti, Zr, Hf, V, Nb, Ta,
There is a close relationship with the amount of Cr, Mo, W oxides and the like added. That is, the amount of the Ti compound or the like is 0.2% by weight.
And aluminum compounds such as Al 2 O 3 and AlN are added alone or in combination, and when the addition amount is less than 0.1% by weight, the densification is insufficient, while the aluminum compound 2.0% by weight
When the excess amount exceeds 0.1%, an excessive amount of the grain boundary phase is generated, or the solid solution starts to be dissolved in silicon nitride, and the thermal conductivity decreases. Range. In particular, in order to ensure good performance in both strength and thermal conductivity, it is desirable that the amount added is in the range of 0.2 to 1.5% by weight.
【0034】また窒化けい素基板の気孔率は、その熱伝
導率および強度に大きく影響するため1.5%以下、望
ましくは0.5%以下に設定される。気孔率が1.5%
を超えると熱伝導の妨げとなり、基板の熱伝導率が低下
するとともに、基板の強度低下が起こる。The porosity of the silicon nitride substrate is set to 1.5% or less, preferably 0.5% or less, since it greatly affects the thermal conductivity and strength. 1.5% porosity
If it exceeds, the heat conduction is hindered, the thermal conductivity of the substrate decreases, and the strength of the substrate decreases.
【0035】また、窒化けい素結晶組織に形成される粒
界相は基板の熱伝導率に大きく影響するため、本発明に
係るヒーターおよびサーマルヘッドに使用する窒化けい
素基板においては、体積比で粒界相の20体積%以上、
好ましくは50体積%以上が結晶相で占めるように設定
される。結晶相が20%未満では熱伝導率が60W/m
・Kを超えるような放熱特性に優れ、かつ高温強度に優
れた高熱伝導性窒化けい素基板が得られないからであ
る。Since the grain boundary phase formed in the silicon nitride crystal structure greatly affects the thermal conductivity of the substrate, the silicon nitride substrate used in the heater and thermal head according to the present invention has a volume ratio of 20% by volume or more of the grain boundary phase,
Preferably, it is set so that 50% by volume or more is occupied by the crystal phase. When the crystal phase is less than 20%, the thermal conductivity is 60 W / m.
-It is because it is not possible to obtain a high thermal conductive silicon nitride substrate having excellent heat dissipation characteristics exceeding K and high temperature strength.
【0036】さらに上記のように窒化けい素基板の気孔
率を1.5%以下にし、また窒化けい素結晶組織に形成
される粒界相の20体積%以上、好ましくは50体積%
以上が結晶相で占めるようにするためには、窒化けい素
成形体を温度1800〜2000℃で0.5〜10時間
程度、加圧焼結し、かつ焼結操作完了直後における焼結
体の冷却速度を毎時100℃以下に調整制御することが
必要である。Further, as described above, the porosity of the silicon nitride substrate is set to 1.5% or less, and at least 20% by volume, preferably 50% by volume of the grain boundary phase formed in the silicon nitride crystal structure.
In order for the above to be occupied by the crystal phase, the silicon nitride molded body is pressure-sintered at a temperature of 1800 to 2000 ° C. for about 0.5 to 10 hours, and It is necessary to adjust and control the cooling rate to 100 ° C. or less per hour.
【0037】焼結温度を1800℃未満に設定した場合
には、窒化けい素基板の緻密化が不充分で気孔率が1.
5vol%以上になり機械的強度および熱伝導性が共に低下
してしまう。一方焼結温度が2000℃を超えると窒化
けい素成分自体が蒸発分解し易くなる。特に加圧焼結で
はなく、常圧焼結を実施した場合には、1800℃付近
より窒化けい素の分解蒸発が始まる。When the sintering temperature is set to less than 1800 ° C., the densification of the silicon nitride substrate is insufficient, and the porosity is 1.
When the content becomes 5 vol% or more, both the mechanical strength and the thermal conductivity decrease. On the other hand, when the sintering temperature exceeds 2000 ° C., the silicon nitride component itself is liable to be vaporized and decomposed. In particular, when normal pressure sintering is performed instead of pressure sintering, decomposition and evaporation of silicon nitride starts at about 1800 ° C.
【0038】上記焼結操作完了直後における窒化けい素
焼結体の冷却速度は粒界相を結晶化させるために重要な
制御因子であり、冷却速度が毎時100℃を超えるよう
な急速冷却を実施した場合には、焼結体組織の粒界相が
非結晶質(ガラス相)となり、焼結体に生成した液相が
結晶相として粒界相に占める体積割合が20%未満とな
り、強度および熱伝導性は低い。The cooling rate of the silicon nitride sintered body immediately after the completion of the sintering operation is an important control factor for crystallizing the grain boundary phase, and rapid cooling was performed so that the cooling rate exceeded 100 ° C./hour. In this case, the grain boundary phase in the structure of the sintered body becomes amorphous (glass phase), the volume ratio of the liquid phase formed in the sintered body as a crystalline phase to the grain boundary phase is less than 20%, and the strength and heat are reduced. Conductivity is low.
【0039】上記冷却速度を厳密に調整すべき温度範囲
は、所定の焼結温度(1800〜2000℃)から、前
記の焼結助剤の反応によって生成する液相が凝固するま
での温度範囲で充分である。ちなみに前記のような焼結
助剤を使用した場合の液相凝固点は概略1600〜15
00℃である。そして少なくとも焼結温度から上記液相
凝固温度に至るまでの焼結体の冷却速度を毎時100℃
以下、好ましくは50℃以下に制御することにより、体
積比で粒界相の20%以上、望ましくは50%以上が結
晶相になり、熱伝導率および機械的強度が共に優れた高
熱伝導性窒化けい素基板が得られる。The temperature range in which the cooling rate should be strictly adjusted is a temperature range from a predetermined sintering temperature (1800 to 2000 ° C.) to a temperature at which a liquid phase produced by the reaction of the sintering aid solidifies. Is enough. Incidentally, the liquidus freezing point when using the sintering aid as described above is approximately 1600 to 15
00 ° C. Then, at least the cooling rate of the sintered body from the sintering temperature to the liquid phase solidification temperature is set to 100 ° C./hour.
By controlling the temperature to preferably 50 ° C. or less, a high thermal conductive nitride having a volume ratio of 20% or more, preferably 50% or more of the grain boundary phase becomes a crystalline phase, and excellent in both thermal conductivity and mechanical strength. A silicon substrate is obtained.
【0040】本発明に係るヒーターおよびサーマルヘッ
ドは、例えば以下のようなプロセスを経て製造される。
すなわち前記所定の微細粒径を有し、また不純物含有量
が少ない微細な窒化けい素粉末に対して所定量の焼結助
剤、有機バインダ等の添加剤および必要に応じAl2 O
3 やAlNまたはTi,Zr,Hf等の化合物を加えて
原料混合体を調整し、次に得られた原料混合体を成形し
て所定形状の成形体を得る。原料混合体の成形法として
は、汎用の金型プレス法、あるいはドクターブレード法
のようなシート成形法なども適用できる。上記成形操作
に引き続いて、成形体を非酸化性雰囲気中で温度600
〜800℃で1〜2時間加熱して、予め添加していた有
機バインダ成分を充分に除去し、脱脂する。次に脱脂処
理された成形体を窒素ガス、水素ガスやアルゴンガスな
どの不活性ガス雰囲気中で1800〜2000℃の温度
で所定時間雰囲気加圧焼結を行い、さらに得られた焼結
体を研削研摩加工して所定形状の高熱伝導性窒化けい素
基板が得られる。この製法によって製造された窒化けい
素基板は気孔率が1.5%以下、60W/m・K(25
℃)を超える高熱伝導率を有し、また三点曲げ強度が常
温で80kg/mm2 以上と機械的特性にも優れている。The heater and the thermal head according to the present invention are manufactured through, for example, the following process.
That is, a predetermined amount of a sintering aid, an additive such as an organic binder, and, if necessary, Al 2 O are added to the fine silicon nitride powder having the predetermined fine particle size and a small impurity content.
3 or AlN or a compound such as Ti, Zr, or Hf is added to prepare a raw material mixture, and then the obtained raw material mixture is molded to obtain a molded body having a predetermined shape. As a forming method of the raw material mixture, a general-purpose mold pressing method, a sheet forming method such as a doctor blade method, or the like can be applied. Subsequent to the above molding operation, the molded body was heated at a temperature of 600 in a non-oxidizing atmosphere.
The mixture is heated at 800800 ° C. for 1 to 2 hours to sufficiently remove the organic binder component added in advance and degrease. Next, the degreased molded body is subjected to atmospheric pressure sintering at a temperature of 1800 to 2000 ° C. for a predetermined time in an inert gas atmosphere such as nitrogen gas, hydrogen gas or argon gas, and further, the obtained sintered body is By grinding and polishing, a high thermal conductive silicon nitride substrate having a predetermined shape is obtained. The silicon nitride substrate manufactured by this method has a porosity of 1.5% or less and 60 W / m · K (25%).
° C), and has excellent three-point bending strength of 80 kg / mm 2 or more at room temperature.
【0041】そして得られた高熱伝導性窒化けい素基板
に発熱抵抗体および必要に応じて絶縁体層を一体に形成
することにより、本発明に係るヒーターが得られる。な
お上記ヒーターの窒化けい素基板,発熱抵抗体および絶
縁体層を同時焼成によって一体に形成することもでき
る。すなわち、まず前記低酸素で不純物が少ない微細な
窒化けい素原料粉末に焼結助剤を添加し、有機バインダ
および溶剤等を添加して均一な混合体を調製し、得られ
た混合体をドクターブレード法等により板状に射出して
グリーンシートを成形し、得られたグリーンシート上
に、タングステンまたはモリブデン粉末を主成分とする
導体(発熱抵抗体)ペーストを用い、スクリーン印刷法
などによって配線パターンを印刷し、発熱抵抗体を形成
する。The heater according to the present invention is obtained by integrally forming the heating resistor and, if necessary, the insulator layer on the obtained high thermal conductive silicon nitride substrate. In addition, the silicon nitride substrate, the heating resistor, and the insulator layer of the heater may be integrally formed by simultaneous firing. That is, first, a sintering aid is added to the fine silicon nitride raw material powder having a low oxygen content and few impurities, and an organic binder and a solvent are added to prepare a uniform mixture. A green sheet is formed by injecting into a plate shape by a blade method or the like, and a wiring pattern is formed on the obtained green sheet using a conductor (heating resistor) paste containing tungsten or molybdenum powder as a main component by a screen printing method or the like. Is printed to form a heating resistor.
【0042】さらに発熱抵抗体の上面に重なるように、
アルミナ,ムライト,窒化けい素などの絶縁体を主成分
とする絶縁ペーストをスクリーン印刷により基板全面に
印刷して絶縁体層を形成する。なお絶縁体層は、発熱抵
抗体の端部を絶縁体層の外部に導出するためのスルーホ
ールを設け、各スルーホール内を導体ペーストで充填し
てリードパッドを形成する。そして得られたヒーター積
層体をN2 などの不活性雰囲気中で脱脂,焼成して一体
化し、所定形状のヒーターを得ることもできる。このよ
うに窒化けい素基板、発熱抵抗体および絶縁体層を同時
焼成によって一体に形成することにより、各構成材間の
密着性が向上し、特に発熱抵抗体の電気抵抗の経時変化
が効果的に防止される。Further, so as to overlap the upper surface of the heating resistor,
An insulating paste mainly composed of an insulator such as alumina, mullite or silicon nitride is printed on the entire surface of the substrate by screen printing to form an insulator layer. The insulator layer is provided with through holes for leading the ends of the heating resistor to the outside of the insulator layer, and filling each through hole with a conductive paste to form a lead pad. Then, the obtained heater laminate is degreased and fired in an inert atmosphere such as N 2 to be integrated to obtain a heater having a predetermined shape. By thus integrally forming the silicon nitride substrate, the heating resistor and the insulator layer by simultaneous firing, the adhesion between the constituent materials is improved, and particularly, the electric resistance of the heating resistor is effectively changed with time. Is prevented.
【0043】一方、前記得られた高熱伝導性窒化けい素
基板に発熱抵抗体および耐摩耗層を一体に形成して、本
発明に係るサーマルヘッドが製造される。このサーマル
ヘッドの発熱抵抗体は、印加されたパルス電圧によって
発熱し、感熱記録をドット状に発色させるものであり、
例えばTa2 N,NiCr合金,ネサ膜,Ta−SiO2 ,T
a−Siなどの原料をペースト状にした後に、スクリー
ン印刷法などの製膜技術を利用して形成される。On the other hand, a thermal head according to the present invention is manufactured by integrally forming a heating resistor and a wear-resistant layer on the obtained high thermal conductive silicon nitride substrate. The heating resistor of the thermal head generates heat by the applied pulse voltage, and causes the thermal recording to be colored in a dot shape.
For example Ta 2 N, NiCr alloy, Nesa film, Ta-SiO 2, T
After a raw material such as a-Si is made into a paste, it is formed using a film forming technique such as a screen printing method.
【0044】[0044]
【作用】上記構成に係るヒーターおよびサーマルヘッド
によれば、その強度特性および熱応答特性を支配するセ
ラミックス基板として、窒化けい素焼結体が本来的に備
える高強度特性に加えて、60W・m・Kより大きな高
い熱伝導率を併有する新規な高熱伝導性窒化けい素基板
を使用しているため、発熱抵抗体に印加する電圧のON
−OFF動作に対して優れた熱応答特性を発揮できると
ともに優れた耐久性を示すことができる。特に上記サー
マルヘッドにおいては、従来のアルミナと比較して熱伝
導率が少なくとも2〜5倍も高い高熱伝導性窒化けい素
基板を使用しているため、一旦印字温度まで立上げて発
熱した抵抗体を所定温度まで冷却するまでの立下げ時間
が大幅に短縮される。したがって発熱抵抗体の温度の立
上り時間と立下げ時間との和である印字の繰返し時間が
極めて短かくなる結果、サーマルヘッドの熱応答性が大
幅に改善され、記録速度を大幅に上昇させることが可能
となる。According to the heater and the thermal head having the above-described structure, the ceramic substrate governing the strength characteristics and the thermal response characteristics is 60 W · m · m in addition to the high strength characteristics inherently provided by the silicon nitride sintered body. Since a new high thermal conductivity silicon nitride substrate having a high thermal conductivity larger than K is used, the voltage applied to the heating resistor is turned on.
-It can exhibit excellent thermal response characteristics to the OFF operation and exhibit excellent durability. In particular, the thermal head uses a high thermal conductivity silicon nitride substrate having a thermal conductivity that is at least 2 to 5 times higher than that of conventional alumina. The cooling down time until cooling to a predetermined temperature is greatly reduced. Therefore, the repetition time of printing, which is the sum of the rise time and the fall time of the temperature of the heating resistor, becomes extremely short. As a result, the thermal responsiveness of the thermal head is greatly improved, and the recording speed can be greatly increased. It becomes possible.
【0045】[0045]
【実施例】次に本発明を以下に示す実施例を参照して具
体的に説明する。まず本発明に係るヒーターおよびサー
マルヘッドの強度特性および熱応答特性を支配する高熱
伝導性窒化けい素基板について以下の実施例に基づき説
明し、しかる後にヒーターおよびサーマルヘッドに適用
した事例を順次説明する。Next, the present invention will be specifically described with reference to the following examples. First, a high thermal conductive silicon nitride substrate that governs the strength characteristics and thermal response characteristics of the heater and the thermal head according to the present invention will be described based on the following examples, and then examples of application to the heater and the thermal head will be sequentially described. .
【0046】実施例1〜3 酸素を1.3重量%、不純物陽イオン元素としてのL
i,Na,K,Fe,Ca,Mg,Sr,Ba,Mn,
Bを合計で0.15重量%含有し、α相型窒化けい素9
7%を含む平均粒径0.55μmの窒化けい素原料粉末
に対して、焼結助剤として平均粒径0.7μmのY2 O
3 (酸化イットリウム)粉末5重量%、平均粒径0.5
μmのAl2 O3 (アルミナ)粉末1.5重量%を添加
し、エチルアルコール中で24時間湿式混合した後に乾
燥して原料粉末混合体を調整した。次に得られた原料粉
末混合体に有機バインダを所定量添加して均一に混合し
た後に、1000kg/cm2 の成形圧力でプレス成形し、
長さ50mm×幅50mm×厚さ5mmの成形体を多数製作し
た。次に得られた成形体を700℃の雰囲気ガス中にお
いて2時間脱脂した後に、この脱脂体を窒素ガス雰囲気
中7.5気圧にて1900℃で6時間保持し、緻密化焼
結を実施した後に、焼結炉に付設した加熱装置への通電
量を制御して焼結炉内温度が1500℃まで降下するま
での間における焼結体の冷却速度がそれぞれ100℃/
hr(実施例1)、50℃/hr(実施例2)、25℃/hr
(実施例3)となるように調整して焼結体を冷却し、さ
らに得られた各焼結体を研摩加工してそれぞれ実施例1
〜3に係る窒化けい素基板を調製した。 Examples 1 to 3 1.3% by weight of oxygen, L as impurity cation element
i, Na, K, Fe, Ca, Mg, Sr, Ba, Mn,
B containing 0.15% by weight in total, and α-phase silicon nitride 9
With respect to the average particle size silicon nitride material powder of 0.55μm containing 7%, an average particle size of 0.7μm as a sintering aid Y 2 O
3 (yttrium oxide) powder 5% by weight, average particle size 0.5
1.5 wt% of Al 2 O 3 (alumina) powder of μm was added, wet-mixed in ethyl alcohol for 24 hours, and dried to prepare a raw material powder mixture. Next, a predetermined amount of an organic binder is added to the obtained raw material powder mixture, and the mixture is uniformly mixed, and then press-molded at a molding pressure of 1000 kg / cm 2 ,
A number of molded bodies having a length of 50 mm, a width of 50 mm and a thickness of 5 mm were produced. Next, after the obtained molded body was degreased in an atmosphere gas at 700 ° C. for 2 hours, the degreased body was held in a nitrogen gas atmosphere at 7.5 atm at 1900 ° C. for 6 hours to carry out densification sintering. Thereafter, the cooling rate of the sintered body until the temperature in the sintering furnace falls to 1500 ° C. is controlled by controlling the amount of electricity to a heating device attached to the sintering furnace, respectively, to 100 ° C. /
hr (Example 1), 50 ° C./hr (Example 2), 25 ° C./hr
(Example 3) The sintered body was cooled by adjusting so as to become (Example 3), and each of the obtained sintered bodies was polished to obtain Example 1, respectively.
To 3 were prepared.
【0047】比較例1 一方、緻密化焼結完了直後に、加熱装置電源をOFFに
し、従来の炉冷による冷却速度(約500℃/hr)で焼
結体を冷却した点以外は実施例1と同一条件で焼結処理
して比較例1に係る窒化けい素基板を調製した。 Comparative Example 1 On the other hand, immediately after the completion of the densification sintering, the power of the heating device was turned off and the sintered body was cooled at the conventional cooling rate by furnace cooling (about 500 ° C./hr). By performing sintering treatment under the same conditions as in the above, a silicon nitride substrate according to Comparative Example 1 was prepared.
【0048】比較例2 酸素を1.5重量%、不純物陽イオン元素を0.6重量
%含有し、α相型窒化けい素93%を含む平均粒径0.
60μmの窒化けい素原料粉末を用いた点以外は実施例
1と同一条件で処理し、比較例2に係る窒化けい素基板
を調製した。COMPARATIVE EXAMPLE 2 1.5% by weight of oxygen, 0.6% by weight of an impurity cation element, and 93% of α-phase type silicon nitride have an average particle diameter of 0.1%.
Processing was performed under the same conditions as in Example 1 except that a silicon nitride raw material powder of 60 μm was used, and a silicon nitride substrate according to Comparative Example 2 was prepared.
【0049】比較例3 酸素を1.7重量%、不純物陽イオン元素を0.7重量
%含有し、α相型窒化けい素91%を含む平均粒径1.
1μmの窒化けい素原料粉末を用いた点以外は実施例1
と同一条件で処理し、比較例3に係る窒化けい素基板を
調製した。 Comparative Example 3 An average particle diameter of 1.7% by weight of oxygen, 0.7% by weight of an impurity cation element, and 91% of α-phase silicon nitride.
Example 1 except that 1 μm silicon nitride raw material powder was used.
The same treatment as in Example 1 was performed to prepare a silicon nitride substrate according to Comparative Example 3.
【0050】こうして得た実施例1〜3および比較例1
〜3に係る窒化けい素基板について気孔率、熱伝導率
(25℃)、室温での三点曲げ強度の平均値を測定し
た。さらに、各基板をX線回折法によって粒界相に占め
る結晶相の割合(体積比)を測定し、下記表1に示す結
果を得た。Examples 1 to 3 and Comparative Example 1 thus obtained
The average values of the porosity, the thermal conductivity (25 ° C.), and the three-point bending strength at room temperature of the silicon nitride substrates according to Nos. 1 to 3 were measured. Further, the ratio (volume ratio) of the crystal phase to the grain boundary phase of each substrate was measured by X-ray diffraction, and the results shown in Table 1 below were obtained.
【0051】[0051]
【表1】 [Table 1]
【0052】表1に示す結果から明らかなように実施例
1〜3に係る窒化けい素基板においては、比較例1と比
較して緻密化焼結完了直後における焼結体の冷却速度を
従来より小さく設定しているため、粒界相に結晶相を含
み、結晶相の占める割合が高い程、高熱伝導率を有する
放熱性の高い高強度かつ高熱伝導性窒化けい素基板が得
られた。As is clear from the results shown in Table 1, in the silicon nitride substrates according to Examples 1 to 3, the cooling rate of the sintered body immediately after the completion of the densification sintering was lower than that of Comparative Example 1. Since the grain boundary phase is set to be small, a silicon nitride substrate having a high thermal conductivity, a high strength and a high thermal conductivity having a high thermal conductivity is obtained as the ratio of the crystal phase to the crystal phase increases.
【0053】一方、比較例1のように焼結体の冷却速度
を大きく設定し、急激に冷却した場合は粒界相が全て非
結晶質で形成され熱伝導率が低下した。また、比較例2
のように前記不純物陽イオン元素を0.6重量%と多く
含有した窒化けい素粉末を用いた場合は焼結体の冷却速
度を実施例1と同一にしても粒界相が全て非結晶質で形
成され熱伝導率が低いものであった。On the other hand, when the cooling rate of the sintered body was set to a high value as in Comparative Example 1, and the material was rapidly cooled, all the grain boundary phases were formed in an amorphous state, and the thermal conductivity was lowered. Comparative Example 2
When silicon nitride powder containing as much as 0.6% by weight of the above-mentioned impurity cation element is used, even if the cooling rate of the sintered body is the same as in Example 1, all the grain boundary phases are non-crystalline. And low thermal conductivity.
【0054】さらに比較例3のように平均粒径が1.1
μmと粗い窒化けい素粉末を用いた場合は、焼結におい
て緻密化が不充分で強度、熱伝導率とも低下いものであ
った。Further, as in Comparative Example 3, the average particle size was 1.1.
In the case of using silicon nitride powder as coarse as μm, densification was insufficient in sintering, and both strength and thermal conductivity were low.
【0055】なお本実施例において調製した各高熱伝導
性窒化けい素基板の強度は、室温を基準として評価して
いるが、各実施例の窒化けい素基板は、室温のみなら
ず、窒化けい素焼結体の特徴である1000〜1200
℃以上の高温における強度についても優れていることが
確認された。The strength of each of the silicon nitride substrates having high thermal conductivity prepared in this example was evaluated with reference to room temperature. 1000-1200 which is a characteristic of the union
It was also confirmed that the strength at a high temperature of not less than ℃ was excellent.
【0056】実施例4〜12および比較例4〜7 実施例4〜12として実施例1において使用した窒化け
い素粉末とY2 O3粉末とAl2 O3 粉末とを表2に示
す組成比となるように調合して原料混合体をそれぞれ調
製した。 Examples 4 to 12 and Comparative Examples 4 to 7 The composition ratios of the silicon nitride powder, Y 2 O 3 powder and Al 2 O 3 powder used in Example 1 as Examples 4 to 12 are shown in Table 2. And the raw material mixtures were prepared respectively.
【0057】次に得られた各原料混合体を実施例1と同
一条件で成形脱脂処理した後、表2に示す条件で焼結処
理し、さらに研摩加工してそれぞれ実施例4〜12に係
る窒化けい素基板を製造した。Next, each of the obtained raw material mixtures was subjected to molding and degreasing under the same conditions as in Example 1, and then subjected to sintering under the conditions shown in Table 2 and further subjected to polishing to obtain the mixtures according to Examples 4 to 12, respectively. A silicon nitride substrate was manufactured.
【0058】一方比較例4〜7として表2に示すように
Al2 O3 を過少量に添加したもの(比較例4)、Y2
O3 を過少量に添加したもの(比較例5)、Al2 O3
を過量に添加したもの(比較例6)、Y2 O3 を過量に
添加したもの(比較例7)の原料混合体をそれぞれ調製
し、実施例1と同一条件で原料混合から焼結操作を実施
してそれぞれ比較例4〜7に係る窒化けい素基板を製造
した。On the other hand, as shown in Table 2, Comparative Examples 4 to 7 in which Al 2 O 3 was added in an excessively small amount (Comparative Example 4), Y 2
O 3 added in an excessively small amount (Comparative Example 5), Al 2 O 3
Those added to an excessive amount (Comparative Example 6), Y a 2 O 3 was prepared which was added to excess the raw material mixture (Comparative Example 7), respectively, the sintering operation from the raw material mixed under the same conditions as in Example 1 Then, silicon nitride substrates according to Comparative Examples 4 to 7 were manufactured.
【0059】こうして製造した実施例4〜12および比
較例4〜7に係る各窒化けい素基板について実施例1と
同一条件で気孔率、熱伝導率(25℃)、室温での三点
曲げ強度の平均値、X線回折法による粒界相に占める結
晶相の割合を測定し、下記表2に示す結果を得た。The porosity, the thermal conductivity (25 ° C.), and the three-point bending strength at room temperature of the silicon nitride substrates according to Examples 4 to 12 and Comparative Examples 4 to 7 manufactured in the same manner as in Example 1 were obtained. And the ratio of the crystal phase to the grain boundary phase by X-ray diffraction was measured, and the results shown in Table 2 below were obtained.
【0060】[0060]
【表2】 [Table 2]
【0061】表2に示す結果から明らかなように、Y2
O3 ,Al2 O3 を所定量含有し、焼結後の冷却速度を
所定に設定した実施例4〜12に係る窒化けい素基板
は、いずれも高熱伝導率で高強度値を有している。一
方、比較例4〜7に示すように、Y2 O3 ,Al2 O3
の少なくとも1種の成分が過少量、あるいは過量添加さ
れた場合は、緻密化が不充分であったり、粒界相が過量
あるいは粒界相に占める結晶相の割合が低過ぎるため
に、曲げ強度が低下、または熱伝導率が劣ることが確認
された。As is apparent from the results shown in Table 2, Y 2
The silicon nitride substrates according to Examples 4 to 12 containing predetermined amounts of O 3 and Al 2 O 3 and having a predetermined cooling rate after sintering had high thermal conductivity and high strength values. I have. On the other hand, as shown in Comparative Examples 4 to 7, Y 2 O 3 and Al 2 O 3
If at least one of the components is too small or too large, the flexural strength is insufficient due to insufficient densification or an excessive amount of the grain boundary phase or an excessively low proportion of the crystal phase in the grain boundary phase. Was confirmed to be low or the thermal conductivity was inferior.
【0062】実施例13〜16 実施例13〜16として実施例1において使用したY2
O3 粉末に置き換えて表3に示す希土類酸化物を使用し
た以外は実施例1と同一条件で処理して実施例13〜1
6に係る窒化けい素基板を製造した。 Examples 13 to 16 Y 2 used in Example 1 as Examples 13 to 16
Examples 13 to 1 were treated under the same conditions as in Example 1 except that the rare earth oxides shown in Table 3 were used instead of O 3 powder.
6 was manufactured.
【0063】こうして得た実施例13〜16に係る窒化
けい素基板について実施例1と同一条件で気孔率、熱伝
導率(25℃)、室温での三点曲げ強度の平均値、X線
回折による粒界相に占める結晶相の割合を測定し下記表
3に示す結果を得た。The silicon nitride substrates according to Examples 13 to 16 thus obtained were subjected to the same conditions as in Example 1 under the same conditions as those of Example 1; porosity, thermal conductivity (25 ° C.), average value of three-point bending strength at room temperature, and X-ray diffraction. The ratio of the crystal phase occupying the grain boundary phase was measured, and the results shown in Table 3 below were obtained.
【0064】[0064]
【表3】 [Table 3]
【0065】表3に示す結果から明らかなようにY2 O
3 に置き換えて他の希土類元素を使用した実施例13〜
16に係る窒化けい素基板はY2 O3 添加のものと同等
の性能を有することが確認された。As is apparent from the results shown in Table 3, Y 2 O
Examples 13 to 13 using other rare earth elements instead of 3
It was confirmed that the silicon nitride substrate according to No. 16 had the same performance as that of the substrate having Y 2 O 3 added.
【0066】次に上記高熱伝導性窒化けい素基板を、ヒ
ーターに適用した例について、以下の実施例を参照して
説明する。Next, an example in which the high thermal conductive silicon nitride substrate is applied to a heater will be described with reference to the following examples.
【0067】実施例17 図1および図2は、本発明に係るヒーターの一実施例の
構成を示す平面図および断面図である。本実施例17に
示すヒーター10は、実施例3において調製したところ
の熱伝導率が115W/m・Kで三点曲げ強度が98kg
/mm2 である高熱伝導性窒化けい素基板をセラミックス
基板11として使用し、その表面に窒化タンタル(Ta
2 N)から成る発熱抵抗体12を形成し、さらに発熱抵
抗体12を覆うようにセラミックス基板11表面に絶縁
体層13を一体に形成して構成される。上記高熱伝導性
窒化けい素から成るセラミックス基板11の寸法は20
×10×1.0mmであり、発熱抵抗体12の蛇行幅Wは
3mm,蛇行間隔Lは0.2mmとした。上記絶縁体層13
およびセラミックス基板11は共に実施例3において、
調製した高熱伝導性窒化けい素焼結体から形成されてい
る。 Embodiment 17 FIGS. 1 and 2 are a plan view and a sectional view showing the structure of an embodiment of the heater according to the present invention. The heater 10 shown in Example 17 had a thermal conductivity of 115 W / m · K and a three-point bending strength of 98 kg prepared in Example 3.
/ Mm 2 , a high thermal conductive silicon nitride substrate was used as the ceramic substrate 11 and the surface thereof was tantalum nitride (Ta).
Forming a heating resistor 12 consisting of 2 N), configured to form an insulator layer 13 integrally with the ceramic substrate 11 surface so as to cover the heating resistor 12. The size of the ceramic substrate 11 made of high thermal conductive silicon nitride is 20
The heating resistor 12 had a meandering width W of 3 mm and a meandering interval L of 0.2 mm. The insulator layer 13
And the ceramic substrate 11 in Example 3
It is formed from the prepared high thermal conductive silicon nitride sintered body.
【0068】上記実施例17に係るヒーターによれば、
発熱抵抗体12を担持するセラミックス基板11および
絶縁体層13が共に高強度および高熱伝導性を有する窒
化けい素焼結体で形成されているため、発熱抵抗体12
に印加する電圧のON−OFF動作に対応して優れた熱応
答性および耐久性が同時に発揮される。According to the heater of the seventeenth embodiment,
Since the ceramic substrate 11 supporting the heating resistor 12 and the insulator layer 13 are both formed of a silicon nitride sintered body having high strength and high thermal conductivity, the heating resistor 12
Excellent thermal responsiveness and durability are simultaneously exhibited in response to the ON-OFF operation of the voltage applied to the substrate.
【0069】さらにセラミックス基板11と絶縁体層1
3とを共に同一材質で構成しているため、両者の熱膨脹
差による剥離や割れの発生が効果的に防止でき、優れた
耐久性を発揮する。Further, the ceramic substrate 11 and the insulator layer 1
Since both of them are made of the same material, the occurrence of peeling or cracking due to the difference in thermal expansion between them can be effectively prevented, and excellent durability is exhibited.
【0070】実施例18 図3は本発明に係るヒーターの他の実施例を示す断面図
である。すなわち図3に示す実施例18に係るヒーター
10aは、図2に示す高熱伝導性窒化けい素で形成した
絶縁体層13に代えて、通常のSi3 N4 焼結体,Al
2 O3 ,ムライトなどの絶縁材で絶縁体層13aを形成
した以外は実施例17のヒーター10と同一である。 Embodiment 18 FIG. 3 is a sectional view showing another embodiment of the heater according to the present invention. That heater 10a according to the embodiment 18 shown in Figure 3, instead of the insulating layer 13 formed in the high thermal conductivity silicon nitride as shown in FIG. 2, usually the Si 3 N 4 sintered body, Al
This is the same as the heater 10 of the seventeenth embodiment except that the insulator layer 13a is formed of an insulating material such as 2 O 3 or mullite.
【0071】本実施例のヒーター10aによれば、発熱
抵抗体12を担持するセラミックス基板11として、高
熱伝導性窒化けい素基板を使用しているため、図におい
て下方向に対する熱伝導性が優れており、同様に高い熱
応答特性を発揮することができる。According to the heater 10a of this embodiment, since the silicon nitride substrate having high thermal conductivity is used as the ceramic substrate 11 supporting the heating resistor 12, the thermal conductivity in the downward direction in the figure is excellent. As a result, similarly high thermal response characteristics can be exhibited.
【0072】実施例19 図4は本発明に係るヒーターの他の実施例を示す断面図
である。すなわち図4に示す実施例19に係るヒーター
10bは、図2〜3に示すヒーター10,10aにおい
て、絶縁体層を被着しない以外は実施例17〜18のヒ
ーター10a,10bと同一である。 Embodiment 19 FIG. 4 is a sectional view showing another embodiment of the heater according to the present invention. That is, the heater 10b according to Example 19 shown in FIG. 4 is the same as the heaters 10a and 10b of Examples 17 and 18 except that the insulator layer is not attached to the heaters 10 and 10a shown in FIGS.
【0073】本実施例のヒーター10bにおいて、絶縁
体層がなく発熱抵抗体12が表面に露出した簡素な構造
を採用している。したがってヒーター10bの周囲に、
発熱抵抗体12と接触して短絡等を生じる他の導電体等
が配設されない場合については、本実施例のヒーター1
0bで充分である。In the heater 10b of this embodiment, a simple structure is employed in which the heating resistor 12 is exposed on the surface without the insulator layer. Therefore, around the heater 10b,
In the case where no other conductor or the like that causes a short circuit or the like due to contact with the heating resistor 12 is provided, the heater 1 of the present embodiment is used.
0b is sufficient.
【0074】実施例20 図5は本発明に係るヒーターの他の実施例を示す断面図
である。すなわち図5に示す実施例20に係るヒーター
10cは、図2に示す高熱伝導性窒化けい素で形成した
セラミックス基板11に代えて、通常のSi3 N4 焼結
体,Al2 O3 ,ムライトなどの絶縁材でセラミックス
基板11aを形成した以外は実施例17のヒーター10
と同一である。 Embodiment 20 FIG. 5 is a sectional view showing another embodiment of the heater according to the present invention. That is, the heater 10c according to Example 20 shown in FIG. 5 is different from the ceramic substrate 11 formed of high thermal conductive silicon nitride shown in FIG. 2 in that a normal Si 3 N 4 sintered body, Al 2 O 3 , mullite is used. Except that the ceramic substrate 11a was formed of an insulating material such as
Is the same as
【0075】本実施例のヒーター10cによれば、絶縁
体層13の構成材料として、高熱伝導性窒化けい素基板
を使用しているため、図において上方向に対する熱伝導
性が優れており、同様に高い熱応答特性を発揮すること
ができる。According to the heater 10c of the present embodiment, since the silicon nitride substrate having high thermal conductivity is used as the constituent material of the insulator layer 13, the thermal conductivity in the upward direction in the drawing is excellent. High thermal response characteristics can be exhibited.
【0076】比較例8 一方、図2で示す実施例17のヒーター10に使用した
セラミックス基板11および絶縁体層13に代えて、熱
伝導率が25W/m・Kで三点曲げ強度が31kg/mm2
のAl2 O3 焼結体でセラミックス基板および絶縁体層
を形成した以外は実施例17と同様に処理して、比較例
8に係るAl2 O3 ヒーターを作成した。 Comparative Example 8 On the other hand, the ceramic substrate 11 and the insulator layer 13 used in the heater 10 of Example 17 shown in FIG. 2 were replaced with a thermal conductivity of 25 W / m · K and a three-point bending strength of 31 kg /. mm 2
Except that in the Al 2 O 3 sintered body to form a ceramic substrate and the insulating layer was treated in the same manner as in Example 17, was prepared the Al 2 O 3 heaters of Comparative Example 8.
【0077】比較例9 また、図2で示す実施例17のヒーター10に使用した
セラミックス基板11および絶縁体層13に代えて、熱
伝導率が140W/m・Kで三点曲げ強度が32kg/mm
2 のAlN焼結体でセラミックス基板および絶縁体層を
形成した以外は実施例17と同様に処理して、比較例9
に係るAlNヒーターを作成した。 Comparative Example 9 In place of the ceramic substrate 11 and the insulator layer 13 used for the heater 10 of Example 17 shown in FIG. 2, the thermal conductivity was 140 W / m · K and the three-point bending strength was 32 kg / mm
Comparative Example 9 was treated in the same manner as in Example 17 except that the ceramic substrate and the insulator layer were formed of the AlN sintered body of No. 2.
Was produced.
【0078】こうして調製した実施例17および比較例
8〜9に係る各ヒーターについて、その昇温特性(熱応
答性)を評価するために、各ヒーターの発熱抵抗体12
への通電量を15Wに設定し、無負荷状態においてヒー
ターの表面温度の経時変化を測定し、図6に示す結果を
得た。また各ヒーターの加熱能力の指標として、昇温速
度および電力密度を測定し、下記表4に示す結果を得
た。For the heaters according to Example 17 and Comparative Examples 8 to 9 thus prepared, the heating resistor 12 of each heater was evaluated in order to evaluate the temperature rise characteristics (thermal response).
The amount of electricity supplied to the heater was set to 15 W, and the change over time in the surface temperature of the heater in a no-load state was measured, and the results shown in FIG. 6 were obtained. The heating rate and the power density were measured as indices of the heating capacity of each heater, and the results shown in Table 4 below were obtained.
【0079】[0079]
【表4】 [Table 4]
【0080】図6および表4に示す結果から明らかなよ
うに、高強度かつ高熱伝導性窒化けい素基板によりセラ
ミックス基板および絶縁体層を形成した実施例17のヒ
ーターによれば、Al2 O3 焼結体で形成した比較例8
のヒーターと比較して、表面温度が通電開始直後から急
激に上昇し、優れた熱応答特性を有することが確認でき
た。また図6において、実施例17のヒーターとAlN
焼結体で形成した比較例9のヒーターとは双方とも高い
熱伝導率を有するため、ほぼ同等の昇温特性を示してい
る。しかしながら、表4から明らかなように、比較例9
に係るヒーターの三点曲げ強度は、実施例17のヒータ
ーと比較して1/3程度であり、耐久性が極めて劣って
いることがわかる。As is clear from the results shown in FIG. 6 and Table 4, according to the heater of Example 17 in which the ceramic substrate and the insulator layer were formed by the high-strength and high-thermal-conductivity silicon nitride substrate, Al 2 O 3 Comparative Example 8 formed of a sintered body
As compared with the heater of No. 5, the surface temperature increased rapidly immediately after the start of energization, and it was confirmed that the heater had excellent thermal response characteristics. In FIG. 6, the heater of Example 17 and AlN
Since both the heater of Comparative Example 9 formed of a sintered body has high thermal conductivity, it shows almost the same temperature rise characteristics. However, as apparent from Table 4, Comparative Example 9
The three-point bending strength of the heater according to Example 1 is about 1/3 of that of the heater of Example 17, which indicates that the durability is extremely poor.
【0081】なお以上説明した実施例においては、平板
形状を有するヒーターを例にとって説明したが、ヒータ
ーの形状は上記に限定されるものではなく、加熱対象物
の形状等に対応して、適宜、管状,円環状等の形状に製
作することも可能である。In the embodiment described above, the heater having a flat plate shape has been described as an example. However, the shape of the heater is not limited to the above, and may be appropriately adjusted according to the shape of the object to be heated. It can also be manufactured in a tubular or annular shape.
【0082】次に前記実施例にて調製した高熱伝導性窒
化けい素基板をサーマルヘッドに適用した例について、
以下の実施例を参照して説明する。Next, an example in which the high thermal conductive silicon nitride substrate prepared in the above embodiment is applied to a thermal head will be described.
This will be described with reference to the following examples.
【0083】実施例21 図7は本発明に係る厚膜形サーマルヘッドの一実施例を
示す断面図である。なお図10に示す従来例と同一要素
には同一符号を付してその重複する説明を省略する。 Embodiment 21 FIG. 7 is a sectional view showing an embodiment of a thick film type thermal head according to the present invention. The same elements as those in the conventional example shown in FIG. 10 are denoted by the same reference numerals, and the description thereof will not be repeated.
【0084】すなわち本実施例に係る厚膜形サーマルヘ
ッドは、表面粗さRaが1μm以下であり、実施例3に
おいて調製した熱伝導率が115W/m・K,三点曲げ
強度が98kg/mm2 の高熱伝導性窒化けい素基板7表面
に、発熱抵抗体2および耐摩耗層5を積層して構成され
る。また発熱抵抗体2の両端部にはAu,Ag,Pd−
Ag,Pt−Au等の導体ペーストを転写焼成して形成
された電気導線(電極)3が接合されている。That is, the thick film type thermal head according to this embodiment has a surface roughness Ra of 1 μm or less, a thermal conductivity of 115 W / m · K prepared in Example 3, and a three-point bending strength of 98 kg / mm. the second high thermal conductivity silicon nitride substrate 7 surface, formed by stacking the heating resistor 2 and the abrasion layer 5. Au, Ag, Pd-
An electric conductor (electrode) 3 formed by transferring and baking a conductive paste such as Ag, Pt-Au or the like is joined.
【0085】本実施例に係るサーマルヘッドはセラミッ
クス基板として、従来のアルミナ基板と比較して4〜5
倍の熱伝導率を有する高熱伝導性窒化けい素基板7を使
用することを大きな特徴としている。The thermal head according to the present embodiment is 4 to 5 times smaller than a conventional alumina substrate as a ceramic substrate.
The use of a highly thermally conductive silicon nitride substrate 7 having twice the thermal conductivity is a major feature.
【0086】また上記高熱伝導性窒化けい素基板7の表
面粗さRa(JIS B0601に規定する中心線平均
粗さ)の大小は、基板7と基板上に配設される発熱抵抗
体2との密着性および化学的接合強度に大きく影響する
ため、1μm以下に設定するとよい。表面粗さRaが1
μmを超えると、基板7と発熱抵抗体2や電気導線3と
の密着性および接合強度が低下してサーマルヘッドの信
頼性および耐久性が低下するからである。The surface roughness Ra (center line average roughness specified in JIS B0601) of the high thermal conductivity silicon nitride substrate 7 is larger than that of the substrate 7 and the heat generating resistor 2 disposed on the substrate. Since it greatly affects the adhesion and the chemical bonding strength, the thickness is preferably set to 1 μm or less. Surface roughness Ra is 1
If the thickness exceeds μm, the adhesion and the bonding strength between the substrate 7 and the heating resistor 2 or the electric conductor 3 are reduced, and the reliability and durability of the thermal head are reduced.
【0087】このような表面粗さRaが1μm以下の高
熱伝導性窒化けい素基板7は、焼結体表面を通常の鏡面
研摩加工すること等によって調製することができる。Such a highly thermally conductive silicon nitride substrate 7 having a surface roughness Ra of 1 μm or less can be prepared by subjecting the surface of the sintered body to ordinary mirror polishing.
【0088】また発熱抵抗体2は、電気導線(電極)
3,3に印加されたパルス電圧によって発熱し、感熱記
録紙の発色剤をドット状に発色させるものであり、例え
ばTa2 N,NiCr,ネサ膜,SiO2 −Ta,Si
−Taなどの原料をペースト状にした後に、スクリーン
印刷などの膜製造技術を利用して形成される。The heating resistor 2 is formed of an electric wire (electrode).
And heating the applied pulse voltage to 3,3, which is color thermosensitive recording paper of the color agent in a dot pattern, for example, Ta 2 N, NiCr, Nesa film, SiO 2 -Ta, Si
After forming a raw material such as -Ta into a paste, the film is formed using a film manufacturing technique such as screen printing.
【0089】また耐摩耗層5は感熱記録紙の接触摩耗か
ら発熱抵抗体2を保護するために設けられ、例えばSi
O2 −Ta2 O3 ,SiC,Al2 O3 ,SiO2 など
の材料から構成される。The wear-resistant layer 5 is provided to protect the heating resistor 2 from contact abrasion of the thermal recording paper.
It is made of a material such as O 2 -Ta 2 O 3 , SiC, Al 2 O 3 , and SiO 2 .
【0090】電極3,3を経由して発熱抵抗体2にパル
ス電圧を印加すると、サーマルヘッドの発熱抵抗体2が
発熱し、耐摩耗層5を介して送りローラ6によって抵抗
体2に押圧されている感熱記録紙4に塗布された発色剤
がドット状に発色する。パルス電圧の印加時間は通常1
〜10ms程度である。When a pulse voltage is applied to the heating resistor 2 via the electrodes 3, 3, the heating resistor 2 of the thermal head generates heat and is pressed by the feed roller 6 by the feed roller 6 via the wear-resistant layer 5. The coloring agent applied to the heat-sensitive recording paper 4 forms a dot. The application time of the pulse voltage is usually 1
About 10 ms.
【0091】そしてパルス電圧の消失によって発熱抵抗
体2の熱は高熱伝導性窒化けい素基板7を経て系外に放
出され、発熱抵抗体2は所定の印字下限温度まで冷却さ
れる。そして次のパルス電圧の印加によって同様に発熱
と冷却とを繰り返し、移動する感熱記録紙上に多数のド
ットを発色させ、各ドットの配列によって所定の文字、
記号または画像等が記録される。Then, due to the disappearance of the pulse voltage, the heat of the heating resistor 2 is released out of the system through the high thermal conductive silicon nitride substrate 7, and the heating resistor 2 is cooled to a predetermined minimum printing temperature. Heating and cooling are repeated in the same manner by applying the next pulse voltage, and a number of dots are colored on the moving thermosensitive recording paper.
Symbols or images are recorded.
【0092】次に本実施例に係るサーマルヘッドの優位
性を従来例と比較して述べる。図8は図7に示す高熱伝
導性窒化けい素基板7を使用した実施例21の厚膜形サ
ーマルヘッドと、図10に示すAl2 O3 セラミックス
基板1を使用した従来例の厚膜形サーマルヘッドとをそ
れぞれプリンタに装着して印字試験を行なった場合にお
ける各発熱抵抗体温度の経時変化を示すグラフである。Next, the superiority of the thermal head according to the present embodiment will be described in comparison with the conventional example. FIG. 8 shows a thick film type thermal head of Example 21 using the high thermal conductive silicon nitride substrate 7 shown in FIG. 7 and a conventional thick film type thermal head using the Al 2 O 3 ceramic substrate 1 shown in FIG. 6 is a graph showing the change over time in the temperature of each heating resistor when a print test is performed with the heads mounted on a printer.
【0093】図8において実線で示すように、本実施例
においては高熱伝導性窒化けい素基板7をセラミックス
基板として使用しているため、パルス電圧消失後におけ
る放熱特性が優れており、発熱抵抗体が所定の印字下限
温度までに冷却されるまでの放熱時間t1 が、Al2 O
3 製のセラミックス基板1で構成した従来例の場合に必
要な放熱時間t0 と比較して大幅に短縮することが可能
となった。As shown by the solid line in FIG. 8, in this embodiment, since the high thermal conductive silicon nitride substrate 7 is used as the ceramic substrate, the heat radiation characteristics after the pulse voltage disappears are excellent, The heat radiation time t 1 until the substrate is cooled to the predetermined lower limit printing temperature is Al 2 O
The heat radiation time t 0 required in the case of the conventional example composed of three ceramic substrates 1 can be greatly reduced.
【0094】このことは、加熱昇温時間と放熱時間との
合計時間で表わされる印字の繰り返し時間が低減される
ことを意味し、プリンタなどの記録機器の高速化を図る
ことができる。This means that the printing repetition time represented by the total time of the heating time and the heat release time is reduced, and the speed of a recording device such as a printer can be increased.
【0095】次に本発明に係るサーマルヘッドの発熱抵
抗体の形状例について説明する。従来、一対の電気導線
間に配設される発熱抵抗体は各軸方向位置における断面
が等しくなるように帯状に形成されていた。Next, an example of the shape of the heating resistor of the thermal head according to the present invention will be described. Conventionally, a heating resistor disposed between a pair of electric wires has been formed in a band shape so that the cross sections at respective axial positions are equal.
【0096】しかしながら、図9に示すようにサーマル
ヘッドの発熱抵抗体2aの電極3,3と接続する部分を
帯状に形成する一方、中央部の幅Wを端部より小さく設
定し、中央部がくびれた形状に形成してもよい。この場
合、発熱抵抗体2aの中央部が最も高い抵抗値を有する
こととなる。この発熱抵抗体2aに電極3,3を介して
電圧を印加し電流を流すと、まず中央部のみが発熱して
温度が上昇し、感熱記録紙に塗布されたインクを溶解さ
せる温度に達し、小さなドットが紙上に転写される。こ
の状態で、発熱抵抗体2aに電圧印加を継続すると、イ
ンク溶解温度に達する領域が徐々に拡大していく。この
ように発熱抵抗体2a毎に印加するエネルギを電圧印加
パルス幅によって可変に調整することによって、転写さ
れる各ドットのサイズを、画像の濃淡に対応して可変と
することができる。すなわち各ドット毎に階調を有する
こととなり、解像度の低下を招くことなく、階調性に優
れた印字記録が可能となる。However, as shown in FIG. 9, the portion of the heat generating resistor 2a of the thermal head connected to the electrodes 3, 3 is formed in a strip shape, while the width W of the central portion is set smaller than the end portion, and It may be formed in a constricted shape. In this case, the central portion of the heating resistor 2a has the highest resistance value. When a voltage is applied to the heating resistor 2a through the electrodes 3 and 3 to cause a current to flow, first, only the central portion generates heat and the temperature rises to reach a temperature at which the ink applied to the thermal recording paper is dissolved, Small dots are transferred on the paper. In this state, when the voltage is continuously applied to the heating resistor 2a, a region where the temperature reaches the ink melting temperature gradually increases. As described above, by variably adjusting the energy applied to each heating resistor 2a according to the voltage application pulse width, the size of each transferred dot can be made variable in accordance with the density of the image. That is, each dot has a gradation, and print recording with excellent gradation can be performed without lowering the resolution.
【0097】なお以上の各実施例では、室温から数百度
の温度範囲で使用されるヒーターやサーマルヘッドで例
示しているが、各実施例において使用した高熱伝導性窒
化けい素基板は、窒化けい素焼結体としての高温強度
(1000〜1200℃以上における強度)と高放熱性
とを併せ持っており、高温下で使用される高強度部材と
しても有効であることは言うまでもない。In each of the embodiments described above, the heater and the thermal head used in a temperature range from room temperature to several hundred degrees are exemplified. However, the silicon nitride substrate having high thermal conductivity used in each of the embodiments is a silicon nitride substrate. Needless to say, it has both high-temperature strength (strength at 1000 to 1200 ° C. or higher) as a sintered element and high heat dissipation, and is also effective as a high-strength member used at high temperatures.
【0098】[0098]
【発明の効果】以上説明の通り、本発明に係るヒーター
およびサーマルヘッドによれば、その強度特性および熱
応答特性を支配するセラミックス基板として、窒化けい
素焼結体が本来的に備える高強度特性に加えて、60W
・m・Kより大きい熱伝導率を併有する新規な高熱伝導
性窒化けい素基板を使用しているため、発熱抵抗体に印
加する電圧のON−OFF動作に対して優れた熱応答特
性を発揮できるとともに優れた耐久性を示すことができ
る。特に上記サーマルヘッドにおいては、従来のアルミ
ナと比較して熱伝導率が少なくとも2〜5倍も高い高熱
伝導性窒化けい素基板を使用しているため、一旦印字温
度まで立上げて発熱した抵抗体を所定温度まで冷却する
までの立下げ時間が大幅に短縮される。したがって発熱
抵抗体の温度の立上り時間と立下げ時間との和である印
字の繰返し時間が極めて短かくなる結果、サーマルヘッ
ドの熱応答性が大幅に改善され、記録速度を大幅に上昇
させることが可能となる。As described above, according to the heater and the thermal head according to the present invention, the ceramic substrate, which governs the strength characteristics and the thermal response characteristics, has the high strength characteristics inherently provided by the silicon nitride sintered body. In addition, 60W
・ Excellent thermal response characteristics to ON-OFF operation of the voltage applied to the heating resistor because a new high thermal conductivity silicon nitride substrate with thermal conductivity greater than m · K is used. As well as excellent durability. In particular, since the thermal head uses a high thermal conductivity silicon nitride substrate having a thermal conductivity at least 2 to 5 times higher than that of conventional alumina, the resistor which once rises to the printing temperature and generates heat is used. The cooling down time until cooling to a predetermined temperature is greatly reduced. Therefore, the repetition time of printing, which is the sum of the rise time and the fall time of the temperature of the heating resistor, becomes extremely short. As a result, the thermal responsiveness of the thermal head is greatly improved, and the recording speed can be greatly increased. It becomes possible.
【図1】本発明に係るヒーターの一実施例の構成を示す
断面図。FIG. 1 is a sectional view showing a configuration of an embodiment of a heater according to the present invention.
【図2】図1に示すヒーターの断面図。FIG. 2 is a sectional view of the heater shown in FIG.
【図3】本発明に係るヒーターの他の実施例を示す断面
図。FIG. 3 is a sectional view showing another embodiment of the heater according to the present invention.
【図4】本発明に係るヒーターの他の実施例を示す断面
図。FIG. 4 is a sectional view showing another embodiment of the heater according to the present invention.
【図5】本発明に係るヒーターの他の実施例を示す断面
図。FIG. 5 is a sectional view showing another embodiment of the heater according to the present invention.
【図6】実施例および比較例に係るヒーターの表面温度
の経時変化を示すグラフ。FIG. 6 is a graph showing the change over time of the surface temperature of the heater according to the example and the comparative example.
【図7】本発明に係る厚膜型サーマルヘッドの一実施例
を示す断面図。FIG. 7 is a cross-sectional view showing one embodiment of a thick film type thermal head according to the present invention.
【図8】本発明に係る厚膜型サーマルヘッドの熱応答特
性を従来例と比較して示すグラフ。FIG. 8 is a graph showing the thermal response characteristics of the thick-film type thermal head according to the present invention in comparison with a conventional example.
【図9】発熱抵抗体の形状例を示す平面図。FIG. 9 is a plan view showing a shape example of a heating resistor.
【図10】従来の厚膜型サーマルヘッドの構成例を示す
断面図。FIG. 10 is a sectional view showing a configuration example of a conventional thick film type thermal head.
1 セラミックス基板(Al2 O3 ) 2,2a 発熱抵抗体 3 電気導線(電極) 4 感熱記録紙 5 耐摩耗層 6 送りローラ 7 高熱伝導性窒化けい素基板 10,10a,10b,10c ヒーター 11,11a セラミックス基板 12 発熱抵抗体 13,13a 絶縁体層1 ceramic substrate (Al 2 O 3) 2, 2a heating resistor 3 electrical conductors (electrodes) 4 thermosensitive recording paper 5 wear layer 6 feed roller 7 high thermal conductivity silicon nitride substrate 10, 10a, 10b, 10c heaters 11, 11a Ceramic substrate 12 Heating resistor 13, 13a Insulator layer
フロントページの続き (56)参考文献 特開 昭61−237919(JP,A) 特開 平4−77361(JP,A) 特開 昭62−95241(JP,A) (58)調査した分野(Int.Cl.7,DB名) H01C 7/00 B41J 2/335 Continuation of the front page (56) References JP-A-61-237919 (JP, A) JP-A-4-77361 (JP, A) JP-A-62-95241 (JP, A) (58) Fields investigated (Int .Cl. 7 , DB name) H01C 7/00 B41J 2/335
Claims (13)
され、粒界相中における結晶化合物相が粒界相全体に対
して体積比で20%以上を占め、気孔率が1.5vo
l.%以下,三点曲げ強度が80kg/mm2以上で熱
伝導率が60W/m・Kより大きく、アルミナを0.1
〜2.0重量%含有している高熱伝導性窒化けい素基板
に、発熱抵抗体を一体に配置したことを特徴とするヒー
ター。The present invention comprises a silicon nitride particle and a grain boundary phase, wherein a crystalline compound phase in the grain boundary phase occupies at least 20% by volume of the whole grain boundary phase, and a porosity of 1.5 vol.
l. %, A three-point bending strength of 80 kg / mm 2 or more, a thermal conductivity of more than 60 W / m · K,
A heater characterized in that a heating resistor is integrally disposed on a high thermal conductive silicon nitride substrate containing up to 2.0% by weight.
80W/m・K以上であることを特徴とする請求項1記
載のヒーター。2. The heater according to claim 1, wherein the thermal conductivity of the silicon nitride substrate having a high thermal conductivity is 80 W / m · K or more.
全体に対し体積比で50体積%以上を占めることを特徴
とする請求項1記載のヒーター。3. The heater according to claim 1, wherein the crystalline compound phase in the grain boundary phase occupies 50% by volume or more with respect to the whole grain boundary phase.
r,Mo,W,NiCr,ネサ膜,Ta−Si,Ta2
N,Ta−SiO2およびNb−SiO2から選択され
る少なくとも1種の元素または化合物から成ることを特
徴とする請求項1記載のヒーター。4. The heating resistor is made of Ti, Zr, Hf, V, C
r, Mo, W, NiCr, Nesa film, Ta-Si, Ta 2
N, heater according to claim 1, characterized in that it consists of at least one element or compound selected from Ta-SiO 2 and Nb-SiO 2.
基板に配置された発熱抵抗体と、この発熱抵抗体を覆う
ようにセラミックス基板上に設けられた絶縁体層とから
成るヒーターにおいて、上記絶縁体層が、窒化けい素粒
子および粒界相により構成され、粒界相中における結晶
化合物相が粒界相全体に対して体積比で20%以上を占
め、気孔率が1.5vol.%以下,三点曲げ強度が8
0kg/mm2以上で熱伝導率が60W/m・Kより大
きく、アルミナを0.1〜2.0重量%含有している高
熱伝導性窒化けい素で構成されていることを特徴とする
ヒーター。5. A heater comprising: a ceramic substrate; a heating resistor disposed on the ceramic substrate; and an insulator layer provided on the ceramic substrate so as to cover the heating resistor. , Silicon nitride particles and a grain boundary phase, and the crystalline compound phase in the grain boundary phase occupies at least 20% by volume of the whole grain boundary phase, and has a porosity of 1.5 vol. % Or less, and the three-point bending strength is 8
A heater characterized in that the heat conductivity is greater than 60 W / m · K at 0 kg / mm 2 or more, and is made of high heat conductive silicon nitride containing 0.1 to 2.0% by weight of alumina. .
80W/m・K以上であることを特徴とする請求項5記
載のヒーター。6. The heater according to claim 5, wherein the high thermal conductivity silicon nitride substrate has a thermal conductivity of 80 W / m · K or more.
全体に対し体積比で50体積%以上を占めることを特徴
とする請求項5記載のヒーター。7. The heater according to claim 5, wherein the crystalline compound phase in the grain boundary phase accounts for 50% by volume or more with respect to the whole grain boundary phase.
r,Mo,W,NiCr,ネサ膜,Ta−Si,Ta2
N,Ta−SiO2およびNb−SiO2から選択され
る少なくとも1種の元素または化合物から成ることを特
徴とする請求項5記載のヒーター。8. The heating resistor is made of Ti, Zr, Hf, V, C
r, Mo, W, NiCr, Nesa film, Ta-Si, Ta 2
N, at least one element or a heater according to claim 5, wherein the a compound selected from Ta-SiO 2 and Nb-SiO 2.
され、粒界相中における結晶化合物相が粒界相全体に対
して体積比で20%以上を占め、気孔率が1.5vo
l.%以下,三点曲げ強度が80kg/mm2以上で熱
伝導率が60W/m・Kより大きく、アルミナを0.1
〜2.0重量%含有している高熱伝導性窒化けい素基板
表面に、発熱抵抗体および耐摩耗層を一体に積層したこ
とを特徴とするサーマルヘッド。9. A composition comprising silicon nitride particles and a grain boundary phase, wherein the crystalline compound phase in the grain boundary phase occupies at least 20% by volume relative to the whole grain boundary phase, and the porosity is 1.5 vol.
l. %, A three-point bending strength of 80 kg / mm 2 or more, a thermal conductivity of more than 60 W / m · K,
A thermal head characterized in that a heating resistor and a wear-resistant layer are integrally laminated on the surface of a highly thermally conductive silicon nitride substrate containing up to 2.0% by weight.
が80W/m・K以上であることを特徴とする請求項9
記載のサーマルヘッド。10. The high thermal conductivity silicon nitride substrate has a thermal conductivity of 80 W / m · K or more.
The described thermal head.
相全体に対し体積比で50体積%以上を占めることを特
徴とする請求項9記載のサーマルヘッド。11. The thermal head according to claim 9, wherein the crystalline compound phase in the grain boundary phase accounts for 50% by volume or more of the whole grain boundary phase.
Cr,Mo,W,NiCr,ネサ膜,Ta−Si,Ta
2N,Ta−SiO2およびNb−SiO2から選択さ
れる少なくとも1種の元素または化合物から成ることを
特徴とする請求項9記載のサーマルヘッド。12. The heating resistor of Ti, Zr, Hf, V,
Cr, Mo, W, NiCr, Nesa film, Ta-Si, Ta
2 N, at least one element or a thermal head according to claim 9, wherein the a compound selected from Ta-SiO 2 and Nb-SiO 2.
接続され、電極と接続する発熱抵抗体の端部を帯状に形
成する一方、中央部の幅を端部の幅より小さく設定した
ことを特徴とする請求項9記載のサーマルヘッド。13. A heating resistor, wherein both ends are respectively connected to electrodes, and an end of the heating resistor connected to the electrode is formed in a strip shape, while a width of a central portion is set to be smaller than a width of the end. The thermal head according to claim 9, wherein:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10891098A JP3204640B2 (en) | 1998-04-20 | 1998-04-20 | Heater and thermal head |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10891098A JP3204640B2 (en) | 1998-04-20 | 1998-04-20 | Heater and thermal head |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP05333596A Division JP3089926B2 (en) | 1993-12-27 | 1993-12-27 | Heater and thermal head |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH1174102A JPH1174102A (en) | 1999-03-16 |
JP3204640B2 true JP3204640B2 (en) | 2001-09-04 |
Family
ID=14496745
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10891098A Expired - Lifetime JP3204640B2 (en) | 1998-04-20 | 1998-04-20 | Heater and thermal head |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3204640B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6494923B2 (en) | 1998-05-16 | 2002-12-17 | Wella Aktiengesellschaft | Agents and method for producing temporary colorations of keratin fibers |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4978042B2 (en) * | 2006-04-04 | 2012-07-18 | Tdk株式会社 | Thermal head and printing device |
-
1998
- 1998-04-20 JP JP10891098A patent/JP3204640B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6494923B2 (en) | 1998-05-16 | 2002-12-17 | Wella Aktiengesellschaft | Agents and method for producing temporary colorations of keratin fibers |
Also Published As
Publication number | Publication date |
---|---|
JPH1174102A (en) | 1999-03-16 |
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