JP2006256096A - Ink-wetted member, its manufacturing method, and inkjet head using ink-wetted member - Google Patents

Ink-wetted member, its manufacturing method, and inkjet head using ink-wetted member Download PDF

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JP2006256096A
JP2006256096A JP2005076586A JP2005076586A JP2006256096A JP 2006256096 A JP2006256096 A JP 2006256096A JP 2005076586 A JP2005076586 A JP 2005076586A JP 2005076586 A JP2005076586 A JP 2005076586A JP 2006256096 A JP2006256096 A JP 2006256096A
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ink
melting point
wetted member
cordierite
feldspar
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JP4576266B2 (en
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Shinichiro Hida
真一郎 肥田
Junji Suzuki
淳史 鈴木
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Toshiba TEC Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To suppress the generation of very fine particles from an ink-wetted member to the utmost. <P>SOLUTION: Feldspar is added to zircon and cordierite and mixed into them, molded in a plate shape of a predetermined size, and burnt at a high temperature set in accordance with the melting point of a main component. Subsequently, machining such as double-sided polishing is performed, and reburning is performed at a low temperature set in accordance with the melting point of feldspar, so that a top plate lid for closing a common liquid chamber as the ink-wetted member can be manufactured. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、インクに接触する部材であるインク接液部材およびこのインク接液部材の製造方法並びにこのインク接液部材を使用したインクジェットヘッドに関する。   The present invention relates to an ink contact member that is a member that contacts ink, a method for manufacturing the ink contact member, and an ink jet head that uses the ink contact member.

従来、チタン酸ジルコン酸鉛(商品名PZT)からなる基板に多数の長溝を所定の間隔で平行に形成し、この基板の上にカバー基板を接合するとともに各長溝の先端にインク吐出ノズルを形成したノズルプレートを配置して多数のインク室を形成したインクジェットヘッドにおいて、カバー基板に焼結アルミナ、石英ガラス類、焼結コージライト、焼結ムライト等のいずれかを使用することで圧電素子よりも弾性率を高くしたものが知られている(例えば、特許文献1、段落「0056」、「0132」等)
特開2000−177129号公報
Conventionally, a large number of long grooves are formed in parallel at a predetermined interval on a substrate made of lead zirconate titanate (trade name PZT), a cover substrate is bonded on the substrate, and an ink discharge nozzle is formed at the tip of each long groove. In an inkjet head in which a large number of ink chambers are formed by disposing a nozzle plate, the use of sintered alumina, quartz glass, sintered cordierite, sintered mullite, etc. for the cover substrate is more effective than piezoelectric elements. Those having a high elastic modulus are known (for example, Patent Document 1, paragraphs “0056”, “0132”, etc.)
JP 2000-177129 A

ところで、この種のインクジェットヘッドにおいてノズルにゴミなどの異物が詰まるとインクが吐出されない状態、すなわち、不吐出状態となる。このような不吐出はヘッド構成上再生ができなくなり、廃却品となってしまう。ノズルに詰まる異物について調べると、セラミックのゴミが一番多く、続いて環境ゴミとなっている。   By the way, in this type of ink jet head, when foreign matter such as dust is clogged in the nozzle, the ink is not ejected, that is, a non-ejection state. Such a non-ejection cannot be regenerated due to the head configuration and becomes a discarded product. When examining the foreign matter clogged in the nozzle, ceramic waste is the most, followed by environmental waste.

通常、インクジェットヘッドの製造工程においては、部品単体で洗浄し、組み立て後さらに洗浄するなど製品が製造されるまでには数回の洗浄が行われる。洗浄としては流水洗浄や超音波洗浄が実行される。部品によっては超音波洗浄時に高出力で洗浄すると、部品をミクロ的に破壊してしまい、インクが接液する壁などからパーティクルと呼ばれる微細なゴミが発生し、これがノズルを詰まらせる要因となる。   Usually, in an inkjet head manufacturing process, cleaning is performed several times before a product is manufactured, such as cleaning parts alone and further cleaning after assembly. As cleaning, running water cleaning or ultrasonic cleaning is performed. When cleaning with high output during ultrasonic cleaning, depending on the part, the part is microscopically destroyed, and fine dust called particles are generated from the wall where the ink comes into contact with liquid, which causes clogging of the nozzle.

上述したカバー基板はインク室に収容されているインクに接する部品の一つであるが、焼結アルミナ、石英ガラス類、焼結コージライト、焼結ムライト等使用して構成されるが、何ら加工が施されないので、インクジェットヘッドの製造工程で何回か洗浄されたとしても、微細なパーティクルが発生する可能性が高く、ノズルを不吐出にする要因になっていた。   The cover substrate mentioned above is one of the parts that come into contact with the ink contained in the ink chamber, but it is composed of sintered alumina, quartz glass, sintered cordierite, sintered mullite, etc. Therefore, even if the ink jet head is washed several times in the manufacturing process of the ink jet head, there is a high possibility that fine particles are generated, which causes the nozzle to fail to discharge.

本発明は、微細なパーティクルの発生を極力抑えることができるインク接液部材およびその製造方法を提供する。
また、本発明は、ノズルを詰まらせる要因となる微細なパーティクルの発生を極力抑えることができるインク接液部材を使用することで、パーティクルによってノズルがインク不吐出になるのを極力防止できるインクジェットヘッドを提供する。
The present invention provides an ink wetted member capable of suppressing generation of fine particles as much as possible and a method for manufacturing the ink wetted member.
In addition, the present invention uses an ink wetted member that can suppress the generation of fine particles that cause nozzle clogging as much as possible, thereby preventing ink from being ejected from the nozzles by particles as much as possible. I will provide a.

本発明は、ジルコンとコージライトを主成分とし、これに主成分の融点よりも低い融点の添加物を加えた材料からなり、この材料を所定の形状に成形し、さらに、焼成して研磨等機械加工を行った後、再焼成して構成されるインク接液部材にある。   The present invention consists of a material mainly composed of zircon and cordierite and added with an additive having a melting point lower than the melting point of the main component. The material is molded into a predetermined shape, and further fired and polished. After the mechanical processing, the ink wetted member is constituted by refiring.

また、本発明は、基板の先端部に多数の長溝を所定の間隔で平行に形成し、基板の上に四角形状で中空の天板枠をその一部が各長溝の先端部上を閉塞するように配置するとともに各長溝の先端にインク吐出ノズルを形成したノズルプレートを配置して多数のインク室を形成し、天板枠の上を天板蓋で閉塞して共通インク室を形成したインクジェットヘッドにおいて、少なくとも天板蓋をインク接液部材とし、このインク接液部材は、ジルコンとコージライトを主成分とし、これに主成分の融点よりも低い融点の添加物を加えた材料からなり、この材料を所定の形状に成形し、さらに、焼成して研磨等機械加工を行った後、再焼成して構成したインクジェットヘッドにある。   In the present invention, a large number of long grooves are formed in parallel at predetermined intervals at the front end of the substrate, and a rectangular and hollow top plate frame is partially blocked on the front end of each long groove on the substrate. Ink jets that are arranged in such a way that a nozzle plate having an ink discharge nozzle formed at the end of each long groove is formed to form a large number of ink chambers, and the top plate frame is closed with a top plate lid to form a common ink chamber In the head, at least the top cover is an ink wetted member, and the ink wetted member is mainly composed of zircon and cordierite, and is made of a material in which an additive having a melting point lower than the melting point of the main component is added. This material is formed into a predetermined shape, further fired and subjected to mechanical processing such as polishing, and then refired to provide an inkjet head.

本発明によれば、微細なパーティクルの発生を極力抑えることができるインク接液部材およびその製造方法を提供できる。
また、本発明によれば、ノズルを詰まらせる要因となる微細なパーティクルの発生を極力抑えることができるインク接液部材を使用することで、パーティクルによってノズルがインク不吐出になるのを極力防止できるインクジェットヘッドを提供できる。
ADVANTAGE OF THE INVENTION According to this invention, the ink wetted member which can suppress generation | occurrence | production of a fine particle as much as possible, and its manufacturing method can be provided.
In addition, according to the present invention, it is possible to prevent the nozzles from ejecting ink by particles as much as possible by using the ink wetted member that can suppress the generation of fine particles that cause the nozzles to be clogged as much as possible. An ink jet head can be provided.

以下、本発明の一実施の形態を、図面を参照して説明する。
図1はインクジェットヘッドの全体構成を示す分解斜視図であり、図2はインクジェットヘッドの構成を部分的に拡大して示す斜視断面図である。
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is an exploded perspective view showing the overall configuration of the inkjet head, and FIG. 2 is a perspective sectional view showing a partially enlarged configuration of the inkjet head.

低誘電率の基板1の先端部に、互いの分極の方向が向き合うようにして貼り合わせた、例えば、チタン酸ジルコン酸鉛(商品名PZT)からなる圧電部材2,3を埋設している。そして、前記圧電部材2、3及びその後方にある基板1の部分には、例えばダイヤモンドカッタによる切削加工により、一定の間隔で複数の長溝4を互いに平行に形成している。   Piezoelectric members 2 and 3 made of, for example, lead zirconate titanate (trade name PZT), which are bonded to each other so that their polarization directions face each other, are embedded in the front end portion of the low dielectric constant substrate 1. A plurality of long grooves 4 are formed in parallel to each other at regular intervals in the piezoelectric members 2 and 3 and the portion of the substrate 1 behind the piezoelectric members 2 and 3 by, for example, cutting with a diamond cutter.

前記基板1の上には、四角形状で中空の天板枠5を、その一部5aが各長溝4の先端部上を閉塞するように配置している。また、前記長溝4の先端には、各長溝4に位置してそれぞれインク吐出ノズル6を形成したノズルプレート7を配置している。そして、各長溝4を天板枠5の一部5aとノズルプレート7で閉塞することで多数のインク室を形成している。   On the substrate 1, a rectangular and hollow top plate frame 5 is arranged such that a part 5 a closes the tip of each long groove 4. Further, at the tip of the long groove 4, a nozzle plate 7, which is located in each long groove 4 and in which an ink discharge nozzle 6 is formed, is disposed. A large number of ink chambers are formed by closing each long groove 4 with a part 5 a of the top plate frame 5 and the nozzle plate 7.

前記天板枠5の上には、インク供給口8を有する天板蓋9を接着により固定し、これに各インク室にインクを供給する共通液室10を形成している。前記インク供給口8にはフィルタを備えたインク供給部材11を取り付け、外部に設けたインクタンクからこのインク供給部材11を経由して共通液室10にインクを供給するようになっている。   A top lid 9 having an ink supply port 8 is fixed on the top plate frame 5 by bonding, and a common liquid chamber 10 for supplying ink to each ink chamber is formed on the top lid 9. An ink supply member 11 having a filter is attached to the ink supply port 8, and ink is supplied from an ink tank provided outside to the common liquid chamber 10 via the ink supply member 11.

前記天板蓋9は、インク接液部材を構成し、ジルコンとコージライトを主成分とし、これに主成分の融点よりも低い融点の添加物として長石、例えばカリ長石を加えた材料で構成されている。前記天板蓋9は、図3に示すステップに沿って製造される。先ず、S1にて、ジルコンとコージライトに長石とバインダーを加えて混錬し樹脂化させる。続いて、S2にて、樹脂化されたセラミックを型に流し込んで所定のサイズの板形状に成形する。その後、S3にて、仮焼きを行い、樹脂分を飛ばしてセラミックのみにする脱脂を行う。   The top cover 9 constitutes an ink contact member, and is composed of a material in which zircon and cordierite are the main components and feldspar, for example, potassium feldspar, is added as an additive having a melting point lower than the melting point of the main components. ing. The top cover 9 is manufactured according to the steps shown in FIG. First, in S1, feldspar and binder are added to zircon and cordierite and kneaded to make a resin. Subsequently, in S2, the resinized ceramic is poured into a mold and formed into a plate shape of a predetermined size. Thereafter, in S3, calcination is performed, and degreasing is performed by skipping the resin component to make only ceramic.

続いて、S4にて、主成分の融点に合わせた高い温度、例えば、1300℃位で焼成する。続いて、S5にて、両面を研磨する等、機械加工を行い、さらに、S6にて、長石の融点に合わせた低い温度、例えば、1100度位で再焼成して製造される。なお、S4における焼成温度やS6における再焼成温度はこれに限定するものではなく、添付物の材質および組成比率に応じて設定される。   Subsequently, in S4, firing is performed at a high temperature that matches the melting point of the main component, for example, about 1300 ° C. Subsequently, in S5, machining is performed such as polishing of both surfaces, and in S6, re-firing is performed at a low temperature matching the melting point of feldspar, for example, about 1100 degrees. The firing temperature in S4 and the re-baking temperature in S6 are not limited to this, and are set according to the material and composition ratio of the attachment.

ジルコン、コージライト、長石の配合率は、天板枠5など接着する他の部品の線膨張係数によって決まる。すなわち、接着後のそり等を考えると、接着する他の部品の線膨張係数と同じ線膨張係数になるように配合率を決めるのが望ましい。例えば、接着する他の部品の線膨張係数が、5×10−6であれば、ジルコン60%、コージライト20%、長石20%の配合率にする。これにより、天板蓋9の線膨張係数も略5×10−6になる。 The mixing ratio of zircon, cordierite, and feldspar is determined by the linear expansion coefficient of other parts to be bonded such as the top frame 5. That is, in consideration of warpage after bonding, it is desirable to determine the blending ratio so as to have the same linear expansion coefficient as that of other parts to be bonded. For example, if the linear expansion coefficient of other parts to be bonded is 5 × 10 −6 , the blending ratio is set to 60% zircon, 20% cordierite, and 20% feldspar. Thereby, the linear expansion coefficient of the top cover 9 is also about 5 × 10 −6 .

ジルコン、コージライト、長石の配合率を、製造される製品の線膨張係数が、この製品が接着する他の部品の線膨張係数に合うようにする必要はあるが、長石は融点が低いので、長石の配合率を高くすると再焼成時に炉台に融着するなど不具合が発生する。例えば、長石の配合率を30%よりも高くすると、再焼成時に炉台に融着する問題が発生する。このため、長石の配合率は30%以下にする必要がある。   The blending ratio of zircon, cordierite, and feldspar needs to match the linear expansion coefficient of the manufactured product with that of the other parts to which this product adheres, but feldspar has a low melting point, If the blending ratio of feldspar is increased, problems such as fusing to the furnace bed during refiring occur. For example, when the blending ratio of feldspar is higher than 30%, there is a problem that the feldspar is fused to the furnace bed at the time of refiring. For this reason, the blending ratio of feldspar needs to be 30% or less.

このように、常にインクに接するインク接液部材である天板蓋9を、ジルコンとコージライトに長石を加えて混錬し、これを所定のサイズの板形状に成形した後、主成分の融点に合わせた高い温度で焼成し、続いて、両面を研磨する等の機械加工を行ってから、長石の融点に合わせた低い温度で再焼成して製造している。これにより、天板蓋9に対して表面の応力緩和、平滑化、再結合化を図ることができる。   In this way, the top plate lid 9 which is an ink contact member that is always in contact with ink is kneaded by adding feldspar to zircon and cordierite, and after forming this into a plate shape of a predetermined size, the melting point of the main component The material is baked at a high temperature according to the above, followed by machining such as polishing both surfaces, and then refired at a low temperature according to the melting point of feldspar. Thereby, surface stress relaxation, smoothing, and recombination can be achieved with respect to the top cover 9.

例えば、図4に示すように、セラミック製品21の表面を、研磨機22を使用して研磨加工すると、表面層が破壊されてクラックaやチッピングbを作ることになる。表面にはその他砥粒cなどが残るが、砥粒cなどは洗浄によって洗い流されるので問題にはならない。しかし、チッピングbは洗浄によって洗い流されない場合があり、インクジェットヘッドが製造された後に剥がれ落ちてパーティクルとなり、ノズルを詰まらせる要因となる。また、クラックaからもインクジェットヘッドが製造された後にパーティクルが発生する可能性が高く、このパーティクルもノズルを詰まらせる要因となる。   For example, as shown in FIG. 4, when the surface of the ceramic product 21 is polished using a polishing machine 22, the surface layer is destroyed and cracks a and chipping b are created. Other abrasive grains c and the like remain on the surface, but the abrasive grains c are not a problem because they are washed away by washing. However, the chipping b may not be washed away by washing, and after the ink jet head is manufactured, the chipping b peels off and becomes particles, which causes clogging of the nozzle. Further, there is a high possibility that particles are generated from the crack a after the ink jet head is manufactured, and these particles also cause clogging of the nozzle.

同様に、天板蓋9を製造する工程において、ステップS5の機械加工が終了した時点では、図5の(a)に示すように、加工された両面が粗くなっており、破壊層が形成される。従って、このまま使用したのではインクジェットヘッドが製造された後に剥がれ落ちてパーティクルとなり、ノズルを詰まらせる要因となる。   Similarly, in the process of manufacturing the top cover 9, when the machining in step S5 is completed, as shown in FIG. 5 (a), both processed surfaces are rough and a destructive layer is formed. The Therefore, if it is used as it is, it is peeled off after the ink jet head is manufactured and becomes particles, which causes clogging of the nozzle.

しかし、続く、ステップS6において、長石の融点に合わせた低い温度で再焼成するので、長石が再度溶融して加工された両面を、図5の(b)に示すように滑らかにし、機械加工で形成された破壊層を緩和させる。このように表面を長石の溶融によって滑らかにした天板蓋9を使用すればインクジェットヘッドが製造された後に天板蓋9からパーティクルが発生するのを防止できる。従って、この天板蓋9を使用することで、セラミックのパーティクルでノズルが詰まる要因を減らすことができ、インク吐出不能のなるのを極力防止できる。   However, in the subsequent step S6, since the calcite is refired at a low temperature according to the melting point of the feldspar, both sides processed by melting the feldspar again are made smooth as shown in FIG. Relax the formed destructive layer. If the top cover 9 whose surface is smoothed by melting feldspar in this way is used, particles can be prevented from being generated from the top cover 9 after the inkjet head is manufactured. Accordingly, the use of the top cover 9 can reduce the cause of clogging of the nozzles with ceramic particles, and can prevent ink discharge from being disabled as much as possible.

図6は、様々な部材からなる単品部品を製造した後、これを洗浄し、その後に発生したパーティクルの数を数えた結果を示している。図中、サンプルAはムライト系の部材であり、サンプルBはジルコン30%、コージライト50%、長石20%の配合率で再焼成した部材であり、サンプルCはジルコン60%、コージライト20%、長石20%の配合率であるが再焼成しない部材である。   FIG. 6 shows a result of manufacturing a single part made of various members, cleaning it, and counting the number of particles generated thereafter. In the figure, sample A is a mullite-based member, sample B is a member fired at a blending ratio of zircon 30%, cordierite 50%, feldspar 20%, and sample C is zircon 60%, cordierite 20%. It is a member that has a feldspar content of 20% but does not refire.

また、サンプルDは本実施の形態の部材であり、ジルコン60%、コージライト20%、長石20%の配合率で再焼成した、すなわち、図3の工程により製造した部材である。また、サンプルEはチタン酸ジルコン酸鉛(商品名PZT)からなる部材である。このように、洗浄後においてサンプルDに示す本実施の形態の部材からはパーティクルの発生が全く無かった。また、サンプルBのように長石が20%であってもコージライトの配合率が多いと再焼成してもパーティクルの発生を無くすことはできなかった。   Sample D is a member of the present embodiment, which is a member re-fired at a blending ratio of 60% zircon, 20% cordierite, and 20% feldspar, that is, a member manufactured by the process of FIG. Sample E is a member made of lead zirconate titanate (trade name PZT). Thus, no particles were generated from the member of the present embodiment shown in Sample D after cleaning. Further, even if the feldspar was 20% as in Sample B, the generation of particles could not be eliminated even if re-firing if the cordierite content was high.

なお、この実施の形態は、インクに接するインク接液部材として天板蓋9を対象にしたものについて述べたがこれに限定するものではなく、天板枠5もインク接液部材として含めても良い。このようにすれば、さらに、セラミックのパーティクルでノズルが詰まる要因を減らすことができる。また、この実施の形態は、低い融点の添加物として長石を使用したがこれに限定するものではないのは勿論である。   In this embodiment, the ink contact member that contacts the ink has been described for the top cover 9, but the present invention is not limited to this, and the top frame 5 may be included as the ink contact member. good. In this way, the cause of clogging the nozzle with ceramic particles can be further reduced. In this embodiment, feldspar is used as an additive having a low melting point, but the present invention is not limited to this.

本発明の一実施の形態に係るインクジェットヘッドの全体構成を示す分解斜視図。1 is an exploded perspective view showing an overall configuration of an inkjet head according to an embodiment of the present invention. 同実施の形態に係るインクジェットヘッドの部分斜視断面図。The fragmentary perspective sectional view of the ink-jet head concerning the embodiment. 同実施の形態に係るインクジェットヘッドの天板蓋を製造する工程を示す流れ図。The flowchart which shows the process of manufacturing the top-plate cover of the inkjet head which concerns on the embodiment. セラミック製品を研磨したときの表面層の状態を示す図。The figure which shows the state of the surface layer when grind | polishing a ceramic product. 同実施の形態に係るインクジェットヘッドの天板蓋を製造する工程における、機械加工終了後と再焼成終了後の表面状態を示す部分拡大図。The elements on larger scale which show the surface state after completion | finish of machining in the process of manufacturing the top-plate cover of the inkjet head which concerns on the embodiment, and completion | finish of rebaking. 本実施の形態の部材を含む各種部材のパーティクル発生状態を示すグラフ。The graph which shows the particle generation state of the various members containing the member of this Embodiment.

符号の説明Explanation of symbols

1…基板、2,3…圧電部材、4…長溝、5…天板枠、6…インク吐出ノズル、7…ノズルプレート、9…天板蓋。   DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2, 3 ... Piezoelectric member, 4 ... Long groove, 5 ... Top plate frame, 6 ... Ink discharge nozzle, 7 ... Nozzle plate, 9 ... Top plate cover.

Claims (4)

ジルコンとコージライトを主成分とし、これに主成分の融点よりも低い融点の添加物を加えた材料からなり、この材料を所定の形状に成形し、さらに、焼成して研磨等機械加工を行った後、再焼成して構成されることを特徴とするインク接液部材。   Consists of zircon and cordierite as main components, and an additive with a melting point lower than the melting point of the main components. This material is molded into a predetermined shape, and then fired and machined such as polishing. And an ink-wetted member characterized by being fired again. 添加物として長石を使用したことを特徴とする請求項1記載のインク接液部材。   2. The ink contact member according to claim 1, wherein feldspar is used as an additive. ジルコンとコージライトを主成分とし、これに主成分の融点よりも低い融点の添加物を加えて混錬し、続いて、所定の形状に成形してから焼成し、さらに、研磨等機械加工を行った後、再焼成して製造することを特徴とするインク接液部材の製造方法。   The main components are zircon and cordierite, and kneaded with additives having a melting point lower than the melting point of the main components, followed by molding into a predetermined shape and firing, and further machining such as polishing. A method for producing an ink wetted member, wherein the ink wetted member is refired and then produced. 基板の先端部に多数の長溝を所定の間隔で平行に形成し、前記基板の上に四角形状で中空の天板枠をその一部が前記各長溝の先端部上を閉塞するように配置するとともに各長溝の先端にインク吐出ノズルを形成したノズルプレートを配置して多数のインク室を形成し、前記天板枠の上を天板蓋で閉塞して共通インク室を形成したインクジェットヘッドにおいて、
少なくとも前記天板蓋をインク接液部材とし、このインク接液部材は、ジルコンとコージライトを主成分とし、これに主成分の融点よりも低い融点の添加物を加えた材料からなり、この材料を所定の形状に成形し、さらに、焼成して研磨等機械加工を行った後、再焼成して構成したことを特徴とするインクジェットヘッド。
A large number of long grooves are formed in parallel at a predetermined interval at the front end portion of the substrate, and a rectangular and hollow top plate frame is disposed on the substrate so that a part thereof closes the front end portion of each long groove. In addition, an inkjet head in which a nozzle plate having an ink discharge nozzle formed at the tip of each long groove is arranged to form a large number of ink chambers, and the top plate frame is closed with a top plate lid to form a common ink chamber.
At least the top cover is an ink wetted member, and the ink wetted member is made of a material mainly composed of zircon and cordierite, and an additive having a melting point lower than the melting point of the main component. An ink-jet head characterized in that it is formed into a predetermined shape, fired and subjected to mechanical processing such as polishing, and then refired.
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JP2019199402A (en) * 2014-06-30 2019-11-21 三星電子株式会社Samsung Electronics Co.,Ltd. Coating solution for silica layer formation and method for forming silica layer

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JP2019199402A (en) * 2014-06-30 2019-11-21 三星電子株式会社Samsung Electronics Co.,Ltd. Coating solution for silica layer formation and method for forming silica layer

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