JPS61286149A - Liquid jet recording head and liquid jet recorder - Google Patents

Abstract

PURPOSE:To enhance the heat response of a liquid jet recording head provided with a heating resistor, by a method wherein the heating resistor layer constitut ing an electrothermal conversion body consists of a specific amorphous material containing carbon atoms as the base. CONSTITUTION:A heating resistor layer 14, constituting an electrothermal conver sion body in the liquid jet recording head, consists of an amorphous material containing carbon atoms as the base, halogen atoms, hydrogen atoms, and a material controlling the electric conductivity. This construction allows the liquid jet recording head and the liquid jet recorder to have remarkably excel lent heat response and repeated use durability. Additionally, the variation in the contents of halogen atom, hydrogen atoms, and/or material controlling the electric conductivity in the film thickness direction in the heating resistor layer 14 is suitably chosen so as to easily obtain the desired characteristics in heat accumulation, heat radiation, adhesion between a substrate 12 and the resistor layer 14, resistance to chemical reaction to a recording liquid, and the like. Electrodes 16, 17 are protected by the heating resistor 14, eliminating the need for forming a protective layer thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid jet recording head and a liquid jet recording apparatus equipped with the recording head.

[Prior Art] Among the various recording methods currently known, the non-impact recording method generates almost no noise during recording, is capable of high-speed recording, and uses special fixing treatment on plain paper. The so-called inkjet recording method, which can perform recording without the need for a conventional inkjet recording method, is recognized as an extremely useful recording method. Regarding this inkjet recording method, various methods have been proposed so far, some of which have been improved and commercialized, and efforts are still being made to put some into practical use.

In the inkjet recording method, recording is performed by causing droplets of a recording liquid called ink to fly based on various working principles and making them adhere to a recording member such as paper.

The present applicant has also already proposed a new system related to such an inkjet recording method. This new method has been proposed in Japanese Patent Laid-Open No. 52-118798, and its basic principle is as outlined below.

In other words, in this inkjet recording method, a thermal pulse is applied as an information signal to the recording liquid introduced into an action chamber that can contain the recording liquid, whereby the recording liquid generates vapor bubbles and self-contracts. In this method, the recording liquid is ejected from an ejection port communicating with the action chamber according to the acting force generated in the process, and is caused to fly as small droplets, which are attached to a recording member to perform recording.

By the way, this method has a high-density multi-array configuration and is easily adapted to high-speed recording and color recording, and the configuration of the implementation device is simpler than conventional ones, so the overall recording head can be made more compact and mass-produced. to turn towards;
By making full use of the advantages of IC technology and micro-processing technology, which have seen remarkable technological progress and improved reliability in the semiconductor field, it has the advantage of being easy to lengthen, and is a method with a wide range of applications. be.

The characteristic recording head of the liquid jet recording apparatus described above is provided with an electrothermal transducer as a means for ejecting liquid from an ejection port to form flying droplets.

The electrothermal converter is used to efficiently apply the generated thermal energy to the liquid, increase the ON-OFF response speed of the thermal effect on the liquid, and so on.

It is said that it is desirable to have a structure in which the discharge port is provided in a heat acting part communicating with the liquid so as to be in direct contact with the liquid.

However, since the electrothermal converter basically consists of a heating resistor that generates heat when energized and a pair of electrodes for energizing the heating resistor,
If the heating resistor is in direct contact with the liquid, electricity may flow through the liquid depending on the electrical resistance of the recording liquid.

The liquid itself may be electrolyzed by the flow of electricity through the liquid, or the heating resistor and liquid may react when electricity is applied to the heating resistor, resulting in a change in resistance value or heat generation due to corrosion of the heating resistor itself. Damage or destruction of the resistor may occur, or furthermore, the heat generating resistor may be damaged or broken due to mechanical shock due to a change in state from the generation of liquid vapor bubbles to self-extinction due to the action of heat generated by the heat generating resistor. In some cases, the surface of the heating resistor may be damaged, or a portion of the heating resistor may crack and be destroyed.

For this reason, in the past, alloys such as NiCr and Zr
B2. The heating resistor is made of an inorganic material that has relatively excellent characteristics as a heating resistor material, such as metal boride such as HfB2, and 5i0 is applied on the heating resistor made of the material.
By providing a protective layer (upper layer) made of a material with excellent oxidation resistance such as No. It has been proposed to improve durability against repeated use.

However, a liquid jet recording device having a recording head equipped with an electrothermal converter having the above-mentioned configuration uses a liquid with relatively low electrical conductivity (for example, water or alcohol as a liquid medium) as a colored liquid for recording. When using a recording liquid with high content of Na ions and high electrical conductivity, it has excellent acid resistance and is satisfactory in terms of repeated use durability. When using electrolyte or electrolyte liquids, they were insufficient in terms of durability for repeated use and resistance to changes over time.Therefore, there were restrictions on the selection of recording liquids to be used, especially when using multi-colored liquids. In addition, it has been an obstacle when recording natural colors.

Furthermore, even when a protective layer is provided on the heating resistor as described above, it is possible to virtually completely prevent liquid from entering the heating resistor due to defects in the protective layer itself that occur during layer formation, for example. It is extremely difficult in terms of performance and mass production. Furthermore, a liquid flow path (nozzle) having a high density and a large number of heat acting parts as part of its structure is provided. In the case of so-called high-density multi-orifice technology, it is necessary to provide at least as many electrothermal converters as the number of liquid flow channels at once, so the impact of failure due to defects in the protective layer on the manufacturing yield of electrothermal converters is limited. This is a big problem, including in terms of manufacturing costs. Furthermore, there is also the problem that thermal responsiveness is sacrificed due to the presence of the protective layer. Furthermore, the presence of the protective layer sacrifices heat generation responsiveness to a given electrical signal. Therefore, even when there is no protective layer and the heating resistor is in direct contact with the recording liquid, it has excellent heat resistance, oxidation resistance, mechanical shock resistance, electrochemical reaction resistance, and thermal response. It is widely desired to develop a liquid jet recording device equipped with an electrothermal converter.

[Object of the invention] The present invention has been made in view of the above points, and
The main object of the present invention is to provide an excellent liquid jet recording head that solves the above-mentioned conventional problems and a liquid jet recording apparatus equipped with the recording head.

Another object of the present invention is to have particularly high chemical stability, excellent electrochemical reaction resistance, and oxidation resistance, as well as excellent mechanical impact resistance and heat resistance, and furthermore, by eliminating the protective layer, thermal response is improved. It is an object of the present invention to provide a liquid jet recording head equipped with a heating resistor capable of improving performance and a liquid jet recording apparatus equipped with the recording head.

[Summary of the Invention] According to the present invention, the above-mentioned object includes an ejection port provided for ejecting a liquid to form flying droplets, and a heat utilized for forming the flying droplets. In a liquid jet recording head equipped with an electrothermal transducer that generates energy, the heating resistance layer constituting the electrothermal transducer is composed of carbon atoms as a matrix, halogen atoms, hydrogen atoms, and a substance that controls electrical conductivity. The heating resistance layer is characterized in that halogen atoms, hydrogen atoms, and/or substances controlling electrical conductivity are distributed non-uniformly in the film thickness direction. This is achieved by a liquid jet recording head and a liquid jet recording apparatus equipped with the liquid jet recording head.

Hereinafter, the present invention will be specifically explained with reference to the drawings.

FIG. 1 is a partial plan view showing the structure of an embodiment of the liquid jet recording head of the present invention, and FIG. 2 is a cross-sectional view taken along the line 1--2.

In the figure, 12 is a support body on which an electrothermal converter is provided, 14 is a heating resistance layer constituting the electrothermal converter, and 16 and 17 are paired electrodes constituting the electrothermal converter. As shown in FIG. 1, a plurality of pairs of a heat generating resistor layer 14 and a pair of electrodes 16, 17 connected to the heat generating resistor layer 14 are provided side by side, thereby creating an effective heat generating section 18.
18".

18'',... fists are arranged at predetermined intervals. In this embodiment, one electrode 16 is a common electrode in which a plurality of electrodes are grouped together. 18.18”, 18”.

An electric signal is applied to the heat generating resistor layer 14 constituting the... through electrodes 16 and 17, and each heat generating portion generates heat based on this.

As shown in FIG. 2, a top plate 20 in which a groove is formed on the side of the heat generating portion of the support 12 is bonded to a substrate having the support 12, the heat generating resistance layer 14, and the electrodes 16,17. A sectional view taken along the line ■-■ in FIG. 2 is shown in FIG. 3. As shown in FIGS.
~． ■-■ in Figure 1 in the positions corresponding to e-kai and -, respectively.
Grooves 22, 22', 22'', . It has a heat acting part 24 that applies thermal energy.

On the left side in FIG. 2, the space opens to the outside, and this opening becomes a liquid discharge port 26. The space is connected to a recording liquid supply source on the right side in FIG. When thermal energy is generated from a heat generating part in the space based on the recording signal and acts on the recording liquid in the space, vapor bubbles are generated in the recording liquid, and the pressure at that time causes the recording liquid near the discharge port 26 to Discharge in the direction of.

Furthermore, as can be seen from the above explanation, in Fig. 1, the top plate 2
The illustration of 0 is omitted.

In the present invention, the material of the support 12 is not particularly limited, but in practice, the heating resistance layer 1 formed on the surface of the support 12 is not particularly limited.
4 and during use, the heat generating resistive layer 1
A material having good durability against the heat generated by No. 4 is preferably used. Further, it is preferable that the support 12 has a higher electrical resistance than the heat generating resistance layer 14 formed on the surface thereof, but in the case where an insulating layer is interposed between the support 12 and the heat generating resistance layer 14. Alternatively, the support 12 may be made of a material having a smaller electrical resistance than the heat generating resistance layer 14.Furthermore, in the present invention, depending on the usage conditions of the liquid jet recording head, the support 12 may be made of a material having a lower electrical resistance than the heat generating resistance layer 14. Small or large supports 12 can be used.

The support 12 used in the present invention is glass,
Examples include those made of inorganic materials such as ceramics, silicon, and metals, and those made of organic materials such as polyamide resin and polyimide resin.

In the present invention, one heating resistance layer 14 is made of an amorphous material having carbon atoms as its base material and containing halogen atoms, hydrogen atoms, and a substance controlling electrical conductivity. As the halogen atom, F, C1, Br, I, etc. can be used, and these may be used alone or in combination. As the halogen atom, F and CI are particularly preferable, and F is particularly preferable. As the substance that controls the conductivity, what is known as an impurity in the semiconductor field, that is, a p-type impurity that provides p'a conduction characteristics and an n-type impurity that provides n-type conduction characteristics can be used. As a p-type impurity, it is listed in the Periodic Table of Elements.
Atoms belonging to the group, such as B, A1. Ga, In, T.I.
etc., with B and Ga being particularly preferred.N-type impurities include atoms belonging to Group V of the periodic table of elements, such as P and As.
, Sb, Bi, etc., with P and As being particularly preferred.

These may be used alone or in combination.

The content of halogen atoms in the heating resistance layer 14 is appropriately selected depending on the purpose of use so as to obtain desired characteristics, and is preferably 0.0001 to 30 at.%, more preferably 0.0001 to 30 at.%. 0005 to 20 atomic %, preferably 0.001 to 10 atomic %.

The content of hydrogen atoms in the heat generating resistor layer 14 is appropriately selected so as to obtain desired characteristics depending on the purpose of use.
Preferably o,ooot to 30 atomic %, more preferably 0.0005 to 20 atomic %, preferably 0.0005 to 20 atomic %.
001 to 10 atomic %.

The sum of the halogen atom content and the hydrogen atom content in the heating resistance layer 14 is appropriately selected to obtain desired characteristics depending on the purpose of use, but is preferably 0.0001.
~40 at%, more preferably 0.0005~3
It is 0 atomic %, preferably 0.001 to 20 M %.

The content of the electrically conductive controlling substance in the heat generating resistance layer 14 is appropriately selected depending on the purpose of use so as to obtain desired characteristics, but is preferably 0.01 to 50,000 atomic ppm.
and more preferably 0.5 to 10,000 atomic ppm
and optimally from 1 to 5000 atomic ppm.

In the present invention, the distribution of halogen atoms, hydrogen atoms and/or electrically conductive substances in the heating resistance layer 14 is non-uniform in the thickness direction. The content of atoms, hydrogen atoms, and/or electrically conductive substances may be changed so that the content gradually increases from the support 12 side to the surface side, or vice versa. Furthermore, the change in the content of halogen atoms, hydrogen atoms, and/or electrically conductive substances may have a maximum value or a minimum value in the heating resistance layer 14.

Changes in the content of halogen atoms, hydrogen atoms, and/or electrically conductive substances in the thickness direction of the heating resistor layer 14 are appropriately selected so as to obtain desired characteristics.

4 to 9 show the heating resistance layer 14 of the recording head of the present invention.
In these figures, the vertical axis represents the change in the film thickness direction from the interface with the support 12. t represents the thickness of the heating resistance layer 14; the horizontal axis represents the content C of halogen atoms, hydrogen atoms, and/or electrically conductive substances; in each figure, the vertical axis The scales of T and the horizontal axis C are not necessarily uniform, but are varied to bring out the characteristics of each figure. Therefore, in actual applications, various distributions based on the differences in specific values are used for each figure.

Furthermore, there is no particular limit to the thickness of the heat generating resistor layer 14.

In the recording head of the present invention, an amorphous material (hereinafter referred to as ra-C: (X)) comprising carbon as a matrix and containing halogen atoms, hydrogen atoms, and an electrically conductive dominant substance.

H) (p, n) Sometimes abbreviated as J. Here, X represents a halogen atom, and p and n represent electrically conductive substances. It is formed.

For example, a-C: (X, H) (
In order to form the resistance layer 14 consisting of p, n), basically the support 12 is placed in a deposition chamber under reduced pressure, and a raw material for C supply that can supply carbon atoms (C) into the deposition chamber is used. A raw material gas for supplying X that can supply gas and halogen atoms (X), a raw material gas for supplying H that can supply hydrogen atoms (H), and a raw material gas for supplying an electrically conductive substance are introduced. Grow discharge is generated and supported in the deposition chamber using high frequency or microwave while changing the introduced amount of the raw material gas for supplying X, the raw material gas for supplying H, and/or the raw material gas for supplying electrically conductive substance. a-C:' on the surface of body 12 (F)
A layer consisting of (X, H) (p, n) may be formed.

In addition, a-C: (X,!()
In order to form the resistance layer 14 made of (p, n), basically the support 12 is placed in a deposition chamber under reduced pressure, and inert gas such as Ar, He, etc. When sputtering a target composed of C in a gas-based mixed gas atmosphere, X
A raw material gas for supply, a raw material gas for H supply, and a raw material gas for supplying an electrically conductive substance may be introduced, and the amounts introduced may be changed at this time.

In the above method, the raw material gas for C supply, the raw material gas for X supply, the raw material gas for H supply, and the raw material gas for supplying electrically conductive substance may be in a gas state at room temperature and normal pressure, or in a reduced pressure. Any substance that can be gasified can be used.

Examples of raw materials for supplying C include saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, aromatic hydrocarbon rings, A
Physically, saturated hydrocarbons include methane (CH4), ethane (C2Ha), propa7 (C3HB),
n-butane (n-C4H10), pentane (C5H1
2), x Tyrenic hydrocarbons include ethylene (C2
H4), propylene (C3Ha), butene-1 (
C4H8), butene-2 (C4H8), inbutylene (C4H8).

Pentene (C5Hlo), acetylene hydrocarbons and acetylene (C2B2), methylacetylene (C3H4)-butyne (C4Ha), and aromatic hydrocarbons include benzene (CeHa) and the like.

Examples of raw materials for supplying X include halogens, halides, interhalogen compounds, /\halogen-substituted hydrocarbon derivatives, etc. Specifically, the halogens include F2, C12,
Br2, I2, HF, HC as halides
l, HBr, HI, interhalogen compounds include BrF,
CIF, ClF3, BrF5, BrF3, IF3
, IF7, IC1, IBr, halogen-substituted hydrocarbon derivatives include CF4, CHF3, CH2F2,
CH3F, CCl4. CHCl3. CH2C12,CH
3Cl, CB r4 , CHB r3 , CH2B r
2, CH3Br, CI4, CHI3, CH2I2,
Examples include CH3I.

Examples of raw materials for supplying H include hydrogen gas and hydrocarbons such as saturated hydrocarbons, ethylene hydrocarbons, acetylene hydrocarbons, and aromatic hydrocarbons, which are also the raw materials for supplying C.

Examples of raw materials for supplying electrically conductive substances include the following.

Examples of raw materials for supplying group (III) atoms include B2 Ha, B4 Hlo, B5 B9, and B5 for supplying boron atoms.
H□□, BOH□. , B6H12, BGH14, etc., and boron halides such as BF3, BC13, BBr3, etc., and A for supplying other atoms.
lCl3, GaCl3, Ga(CH3)3. Inc.
l3. TlCl3 etc. are used.

As raw materials for supplying Group V atoms, for example, hydrogenated phosphorus such as PH3, F2 H4, PH41, P
F3, PF5, PC13, PCl5. PBr3. P
Br3. Phosphorus halides such as PI3 are used, and AsH3, AsF3, AsC1 are used to supply other atoms.
3, AsBr3, AsF5, SbH3, SbF3
, SbF5.5bC13, 5bC15, BiH3, Bi
Cl3. B1Br3 etc. are used.

These raw materials may be used alone or in combination.

In the heat generating resistance layer forming method as described above, the amount of I\rogen atoms contained in the formed resistance layer 14.

The amount of hydrogen atoms, the amount of electrically conductive substance, and the resistance layer 14
In order to control the characteristics, the support temperature, the supply amount of raw material gas, the discharge power, the pressure inside the deposition chamber, etc. are appropriately set.

In particular, in order to obtain the heating resistance layer 14 in which the distribution of halogen atoms, hydrogen atoms, and/or electrically conductive substances is non-uniform in the thickness direction of the present invention, halogen atoms,
It is preferable to change the amount of hydrogen atoms and/or the electrically conductive substance introduced over time, for example, by controlling a valve.

The support temperature is preferably selected from 20-1500°C, more preferably 30-1200°C, and optimally 50-1100°C.

The supply amount of the raw material gas is determined as appropriate depending on the intended heating resistance layer property and the targeted film formation rate.

The discharge power is preferably o, ooi to 20 W/cm'', more preferably 0.01 to 15 W/cm''.

Optimally, it is selected from 0.05 to IOW/crn.

The pressure inside the deposition chamber is preferably 10-4 to 1 OTorr.
, more preferably 10-2 to 5 Torr.

The resistive layer of the recording head of the present invention obtained using the heat generating resistive layer forming method as described above has characteristics close to those of diamond.

That is, for example, a material having a Vickers hardness of 1,800 to 5,000 can be obtained. In addition, since it contains halogen atoms, hydrogen atoms, and electrically conductive substances, it has particularly good controllability of resistance value.

The heating resistance layer in the present invention has high durability against mechanical impact and excellent chemical stability, and therefore does not require a special protective layer. Therefore, in the liquid jet recording using the heat generating resistive layer according to the present invention, the thermal energy generated in response to signal input is applied to the liquid extremely efficiently, resulting in good responsiveness. This means that
This also leads to improved ejection responsiveness of flying droplets that are formed in response to signals input to the liquid jet recording head.

However, as long as the desired responsiveness is exhibited, a protective layer may be formed on the yA heat resistance layer as described above.

Furthermore, when the recording liquid is conductive, a protective layer is necessary to prevent short circuits between electrodes.

In the above embodiment example, an example is shown in which the heat generating resistive layer and the electrode are provided on the support in this order, but in the recording head of the present invention, the electrode and the heat generating resistive layer may be provided in this order on the support. , FIG. 10 is a partial cross-sectional view of a substrate having an electrothermal transducer of such a recording head.

In the embodiments described above, the support 12 is assumed to be a single body, but the support 12 in the present invention may be a composite body. As shown in FIG. 11, the support 12 is composed of a composite of a base 12a and a surface layer 12b, and the base 12a can be made of the support materials described above with respect to FIGS. For the layer 12b, a material with better adhesion to the resistance layer 14 formed thereon can be used.The surface layer 12b may be made of, for example, an amorphous material containing carbon atoms as a matrix or a conventionally known material. It is composed of oxides etc. Such a surface layer 12b can be obtained by depositing an appropriate raw material on the base 12a by a method similar to the above-described method for forming the heating resistor layer. In addition, the surface layer 12
b may be a normal glassy glaze layer, or if the base 12a is metal, it may be an oxide layer formed by oxidizing its surface.

The electrodes 16 and 17 in the recording head of the present invention may be made of any material having a predetermined conductivity, such as Au or Cu.
, A1. Made of metal such as Ag and Ni.

Next, the outline of the method for manufacturing the recording head of the present invention will be explained.

FIG. 12 is a schematic explanatory diagram showing an example of a deposition apparatus used when forming a heat generating resistive layer on the surface of a support. 1
101 is a deposition chamber, 1102 to 1106 are gas cylinders, 1107 to 1111 are mass flow controllers, 1112 to 1116 are inflow valves;
117-1121 are outflow valves, 1122-11
26 is a gas cylinder valve, 1127 to 1131
is an outlet pressure gauge, 1132 is an auxiliary valve,
1133 is a lever, 1134 is a main valve, 1135 is a leak valve, 1136 is a vacuum gauge, 1137 is a support material for forming a substrate with an electrothermal converter to be manufactured, 1138 is a heater, 1139 is a support means, 1140
is a high voltage power supply, 1141 is an electrode, and 1142
is the shutter. Note that 1142-1 is a target attached to the electrode 1141 when performing the sputtering method.

For example, 1102 is sealed with CF4 gas (99.9% purity or higher) diluted with Ar gas, and 1103
PH3 gas diluted with Ar gas (99.9% purity)
1104 is sealed with B2 He gas (purity of 99.9% or more) diluted with Ar gas. Before the gas in these cylinders is allowed to flow into the deposition chamber 1101, it is confirmed that the valves 1122 to 1126 and the leak valve 1135 of each gas cylinder 1102 to 1106 are closed, and the inflow valves i and t are closed.
t 2 to 1116, confirm that the outflow valves 1117 to 1121 and the auxiliary valve 1132 are open, and first open the main valve 1134 to evacuate the deposition chamber ttot and gas piping C. Next, check the reading of the vacuum gauge 1136. is 1.
5X10-6T.

rr, the auxiliary valve 1132. Inflow valves 1112-1116 and outflow valves 1117-1121
Close. Thereafter, a valve of a gas pipe connected to a cylinder of gas to be introduced into the deposition chamber 1101 is opened to introduce a desired gas into the deposition chamber 1101.

Next, an example of the procedure for forming the resistance layer of the recording layer of the present invention by the glow discharge method using the above-mentioned apparatus will be described. Open the valve 1122 and turn on the gas pump 110
2, open the valve 1123 to let the PH3/Ar gas flow out from the gas pump 1103, and set the pressure on the outlet pressure gauges 1127 and 1128 to 1 kg.
/crn” and adjust the primary inflow valve 1112.111
3 gradually open the mass flow controller 1107.1.
108, and then the outflow valve 111.
7.1118, gradually open the auxiliary valve 1132 CF
4/ Ar gas and PH3/Ar gas in deposition chamber 1
101. At this time, adjust the mass flow controllers 1107 and 1108 so that the ratio of the flow rate of CF+/Ar gas and the flow rate of PH3/Ar gas becomes a desired value,
Further, the opening degree of the main valve 1134 is adjusted while checking the reading of the vacuum gauge 1136 so that the pressure in the deposition chamber 1101 reaches a desired value. Then, the support means 1 in the deposition chamber 1101
After the support 1137 supported by the support 1139 is heated by the heater 1138 to a desired temperature, the shutter 1142 is opened to generate glow discharge in the deposition chamber ttoi. Then, by manually or by an external drive motor or the like, the flow rate of the CF, /Ar gas and/or the flow rate of the PH3/Ar gas is adjusted over time according to a pre-designed rate of change curve. As a result, the content of F atoms, H atoms, and/or electrically conductive substances in the resistance layer 14 is changed in the film thickness direction.

Next, an example of the procedure for forming the resistive layer of the recording head of the present invention by sputtering using the above-described apparatus will be described. A high-purity graphite (11
42-. 1 as a target, and CF from the gas pump 1102 in the same way as in the glow discharge method.
4/Ar gas and PH3/Ar gas are introduced into the deposition chamber 1101 from the gas pump 1103 at desired flow rates. The target 1142-1 is sputtered by opening the shutter 1142 and turning on the high voltage power supply 1140. At this time, the support 1 is heated by the heater 1138.
137 to a desired temperature and adjusting the opening degree of the main valve 1134 to bring the inside of the deposition chamber 1101 to a desired pressure is similar to the glow discharge method. Then, as in the case of the glow discharge method described above, the outflow valve 11
17. Perform an operation to change the opening degree of 1118 to open CF.
, /Ar gas flow rate and/or PH3/Ar gas flow rate are changed over time according to a predesigned rate of change curve, thereby reducing F atoms, H atoms, and/or the electrically conductive dominant substance in the resistance layer 14. The content rate of the film is changed in the film thickness direction.

In the case of a substrate having an electrothermal transducer of a liquid jet recording head as shown in FIGS. 1 to 3, after forming a heat generating resistor layer on the support as described above, A conductive layer (for example, an Au layer or an A1 layer) for forming an electrode is formed, and then the conductive layer and the heat-generating resistive layer are patterned using photolithography technology. A protective layer may be laminated.

In addition, in the case of a substrate having an electrothermal converter of a liquid jet recording head as shown in FIG. After this, a heat generating resistor layer is formed by the glow discharge method or sputtering method as described above.

The grooved top plate may be made of the same material as the above-mentioned support, for example, by mechanical cutting with a microcutter, chemical etching, etc., or if the top plate is made of photosensitive glass, the desired shape can be formed. It is possible to use a material in which grooves are formed by pattern exposure and development.

The substrate having the electrothermal transducer and the top plate can be bonded after sufficient alignment, for example, by bonding with an adhesive or by thermal fusion depending on the material of the top plate.

In the above embodiment, a liquid jet recording head of the type shown in a partial perspective view in FIG. However, in the present invention, the fourteenth
As shown in the figure, the liquid discharge port 26 may be provided directly on the top plate 20. In the head of the type shown in FIG. The recording liquid is ejected from the ejection port 26 in the direction of arrow Y. Of course, one end of the groove 22 may be closed, and the recording liquid may be introduced from at least one opening.

Next, a modification of the liquid jet recording head of the present invention will be described.

FIG. 15 is a sectional view taken along line IX-IK in FIG. 14. In this case, the portion of the top plate 20 other than the groove 22 is in close contact with the substrate having the electrothermal converter.

Therefore, the respective heat-acting parts 24 formed corresponding to the six grooves 22 of the top plate 20 are isolated from each other by the barrier part 30 formed by the part in close contact with the support body 12.

In FIG. 15, each heat generating part 18 is provided corresponding to each discharge port 26.

16 to 18 are sectional views corresponding to FIG. 15 showing other examples.

In the case of FIG. 16, the barrier portion 30 is not in complete contact with the support 12, and the heat acting portions 24 corresponding to the respective heat generating portions 18 are in communication with each other.

In the case of FIG. 17, the barrier portion 30 is formed on the substrate instead of the top plate 20, and the heat acting portions 24 corresponding to the six heat generating portions 18 communicate with each other as in the case of FIG. 16.

In the case of FIG. 18, no barrier portion is formed as in the cases of FIGS. 15 to 17.

15 to 18 above relate to the liquid jet recording head of the type shown in FIG. 14, but the same applies to the type of liquid jet recording head shown in FIG. 13.

The barrier part (wall) 30 does not necessarily have to be provided as described above, and even if it affects the ejection direction, ejection speed, or ejection amount of the liquid ejected from the adjacent ejection ports, the flying droplets may be prevented. It is not necessary to provide a barrier section unless there is an error that exceeds an allowable range in the point of impact of the liquid on the recording material. In order to improve the performance, it is preferable to provide a barrier portion, and it goes without saying that the barrier portion may be formed integrally with the top plate, or only the barrier portion may be a separate member. The flat top plate may be made of the same material as the grooved top plate. Also.

Photosensitive resin can also be used for the barrier part and the top plate.

Specific examples of the liquid jet recording head of the present invention will be shown below.

[Example] First, a substrate having an electrothermal converter used in the following Examples and Comparative Examples was prepared in the following manner.

As a support, 97059 glass manufactured by Corning Co., Ltd.
A Si plate provided with a thermally oxidized 5i02 heat storage layer (thickness: 5 g, m) as a surface layer was used.

A heating resistance layer, an electrode, and optionally a protective layer are formed on the support. The layer configurations of the heating resistor layer, electrode, and protective layer were of the following three types: A, B, and C.

A heating resistor layer was formed on the Type A support using the deposition apparatus shown in FIG. The conditions during the deposition are as shown in Tables 1 and 2, respectively.

The Examples listed in Table 1 were carried out by the glow discharge method, and the Examples and Comparative Examples listed in Table 2 were carried out by the sputtering method. Graphite (99,99%) was used as a target during sputtering except for the comparative example, in which HfB2 was used.

During the deposition, the flow rate of each gas and other conditions were maintained as shown in Tables 1 and 2, respectively, and the heat generation resistance layer was formed with the thickness shown in Table 3. An A1 layer was formed on the resistance layer by an electron beam method, a resist pattern was formed by photolithography, and Alfi was etched into a desired shape to form a plurality of pairs of electrodes. Subsequently, a resist pattern was formed by photolithography, and predetermined portions of the heating resistor layer were removed using an HF-based etching solution. As an example, a heating resistor element was formed in which the above-mentioned electrodes were attached to a heating portion consisting of a heating resistor layer portion of 40 ILm x 200 JLm. The heat generating parts were arranged at a pitch of 8 pieces/mm.

Next, a photosensitive polyimide (trade name: Photonice) is spin-coded. Then, prebaked at 80℃ for 1 hour,
After exposure with an aligner, develop.

The heat generating part has a structure with a window opening. And 140
C. for 30 minutes and then post-baked at 400.degree. C. for 1 hour to complete a substrate having an electrothermal transducer.

The resistance of each heat generating part of the electrothermal converter thus obtained was as shown in Table 3.

Note that the photosensitive polyimide is used to prevent electrolysis in the ink of the A1 electrode.

19 is a schematic perspective view of a completed substrate having an electrothermal converter, and FIG. 20 is a schematic cross-sectional view thereof. In FIG. 0, 28 is a polyimide layer.

Type B A heating resistance layer was formed on the support in the same manner as in Type A. The deposition conditions are as shown in Tables 1 and 2, respectively. During the deposition, the flow rate of each gas and other conditions were maintained as shown in Tables 1 and 2, respectively, and the heating resistor layer with the thickness shown in Table 3 was formed. An Au layer was formed on the heating resistor layer by an electron beam method, a resist pattern was formed by photolithography, and the Au layer was etched into a desired shape to form a plurality of pairs of electrodes. Next, a resist pattern is formed using photolithography technology and HF is applied.
Predetermined portions of the heat generating resistor layer were removed using an etching solution. As an example, a heat generating resistor element was formed in which the above electrode was attached to a heat generating portion consisting of a portion of a heat generating resistor layer measuring 40 lm x 200 lm. The heat generating parts were arranged at a pitch of 8 pieces/mm. In this way, a substrate having an electrothermal transducer is completed.

The resistance of each heat generating part of the electrothermal converter thus obtained was as shown in Table 3.

A schematic perspective view of a completed substrate having an electrothermal converter is shown in FIG. 21, and a schematic cross-sectional view is shown in FIG. 22.

Type C: A1 layer is formed on the support by electron beam method, and a resist pattern is formed by photolithography.
After etching the layer into a desired shape to form a plurality of pairs of electrodes, a heating resistor layer was formed on the patterned A1 layer.

The heating resistance layer was formed in the same manner as in the case of type A.

The deposition conditions were maintained as shown in Tables 1 and 2, respectively, and heat generating resistive layers having the thicknesses shown in Table 3 were formed. Subsequently, a resist pattern was formed by photolithography, and predetermined portions of the heating resistor layer were removed using an HF-based etching solution. For example, 40J
A heat generating resistor element was formed in which the above electrode was attached to a heat generating portion consisting of a heat generating resistor layer of LmX200#Lm.

The heat generating parts were arranged at a pitch of 8 pieces/mm. Furthermore, A
Since one electrode is protected by this heating resistance layer, there is no need to form a protective film.

A substrate having an electrothermal transducer is completed.

The resistance of each heat generating part of the electrothermal converter thus obtained was as shown in Table 3.

A schematic perspective view of a completed substrate having an electrothermal converter is shown in FIG. 23, and a schematic cross-sectional view is shown in FIG. 24.

A liquid jet recording head is manufactured using the substrate having the electrothermal converter completed as described above.The heads to be created include the type shown in FIG. 13 (hereinafter referred to as type I) and the type 14 shown in There is a type shown in the figure (hereinafter referred to as type 2).

Type 1 was created using two methods, and Type 2 was created using one method. The method for creating them will be described below.

Type 1-1 First, as shown in the schematic perspective view of FIG.
A grooved top plate 20 is prepared by cutting a plurality of grooves 22 (width: 40 m, depth: 40 m) and a groove 42 serving as a common ink chamber using a micro cutter.

Next, the substrate completed above and the top plate 20 are connected to the heat generating part and the groove 2.
2 and then joined together, and furthermore, as shown in the schematic perspective view of FIG. 26, an ink introduction pipe 44 for introducing ink from an ink supply section (not shown) to the common ink chamber is connected. Record Rad 46 was completed in one piece.

Type 1-2 A photosensitive film 50 (trade name: Odile, Tokyo Ohka) is laminated on the substrate completed above. Then, a glass plate 54 laminated with a photosensitive resin film 52 (trade name Odile, Tokyo Ohka) is placed on top of the patterned film, which is exposed and developed using an aligner to create a desired pattern shape. Glue and join.

Then, this joined body is shaped by machining such as dicing to form the discharge port 26, and an ink introduction pipe 44 is connected from an ink supply section (not shown) to the common ink chamber, as shown in the schematic diagram of FIG. A recording head 56 as shown in the perspective view was integrally completed.

Type 2 First, the top plate 20 in which the discharge port 26 is formed is created. The top plate 20 is created by forming a pattern of photosensitive film (trade name: PHT-145FT-50, Hitachi Chemical) on a stainless steel plate with grooves formed by etching, etc., and then decorating the pattern with Ni plating. . The portion where the hole is formed as the discharge port 26 is where the pattern of the photosensitive film is located. The top plate 20 created in this way and the substrate completed above are aligned with the heat generating parts and the discharge ports 26 corresponding thereto, and then bonded with adhesive. The board is machined to make holes so that ink can be supplied into the top plate 20. Next, a hole is made by machining so that ink can be introduced into the common ink chamber from an ink supply section (not shown) on the back side of the joined board. The introduction pipe 60 of the second
A recording head 62 as shown in the schematic perspective view of FIG. 8 was integrally completed. Note that 64 is a recessed portion of the top plate 20 and constitutes a rebarrier portion.

Types A, B, and C of the layer structure of the substrate having an electrothermal converter, and types 1-1 and 1-2 of the head manufacturing method. Although there is a combination with Type 2, a combination of Type A and Type 1-1 was used in the following durability experiment.

Hereinafter, an experiment regarding the durability of the produced recording head will be described.

The recording head created in the above manner has a lead having electrode leads (individual electrode leads and common electrode leads: not shown) connected to individual electrodes 17 for each heat generating part and electrodes 16 common to each heat generating part. The board was attached and the recording head unit was completed.

Using these recording head units, a liquid jet recording apparatus as shown in a schematic perspective view in FIG. 29 was constructed.

In FIG. 29, 70 is a recording head unit;
72 is a carriage on which the recording head unit 70 is placed, and 74 is a guide member for reciprocating the carriage 72. Also, 76 is a platen,
Reference numeral 78 indicates a recording member, such as paper, held on the platen 76.

The recording liquid ejection ports of the recording head unit 70 are oriented in the direction of arrow Z, and the recording liquid is ejected in the form of droplets in the direction of the arrow, and is deposited in the form of dots on the recording member 78 on the platen 76. . Main scanning is performed by moving the recording head unit 70 along the guide member 74 by an appropriate driving means, and sub-scanning is performed by rotating the platen 76 around a rotation axis 77 by an appropriate driving means. As a result, recording is performed on the recording member 78.

The experimental conditions were as follows.

Pulse width of 1OILsec, 200ILsec in the heating part
A rectangular pulse with a voltage 1.2 times the minimum bubbling voltage (the voltage at which bubbling begins in the ink) (for example, 24 V if the minimum bubbling voltage is 20 V) was applied with a pulse input period of . The composition of the ink used was as follows.

Water: 68 parts by weight DEC: 30 parts by weight Black dye: 2 parts by weight When an ink droplet ejection experiment was conducted using the above experimental conditions and ink, durability evaluations as shown in Table 3 were obtained.

The durability of these Examples and Comparative Examples was evaluated based on the number of times electrical pulses could be repeatedly applied as follows. In other words, "
0'' and ``x'' indicate the number of times the electric pulse was applied in return as shown below.

From the results of 0 109 times or more x 10 6 times or more, it can be seen that in the example of the present invention, a recording head having significantly superior durability compared to the comparative example was obtained. Further, in the examples of the present invention, the recording properties were also excellent.

In the above durability experiment, the above type A and type 1-1 were used.
Similar results were obtained with other combinations.

Table 3 Next, FIG. 30 shows a partially cutaway perspective view of an embodiment of the liquid jet recording apparatus of the present invention.

In this embodiment, two recording head units 7
0 are held in parallel by the carriage 72 by the holding member 71.
It is fixed and placed on. Recording head unit 70
is a so-called disposable type, and contains recording liquid. The movement of the carriage 72 along the guide member 74 is achieved by fixing a part of the wire 82 wound between the pulleys 80 and 81 to the carriage 72, and moving the carriage 72 along the guide member 74 using the motor 84.
This is done by driving and rotating the pulley 81.

On the other hand, the rotating shaft 77 of the platen 76 is driven and rotated by a motor 86 and a gear mechanism 88, thereby feeding the recording member 78.

90 connects the recording head unit 70 via the gear ridge 72
This is a flexible wiring board connected to the carriage 72 in order to supply an electric signal for ejecting recording liquid in the Z direction.

[Effects of the Invention] According to the present invention as described above, an amorphous material containing carbon atoms as a matrix and containing halogen atoms, hydrogen atoms, and an electrically conductive dominant substance is used as the heating resistance layer. As a result, it has an electrothermal converter that has high chemical stability, excellent electrochemical reactivity resistance, and oxidation resistance, as well as excellent mechanical impact resistance and heat resistance. Therefore, it has excellent thermal response and repeated use durability. Provided are a liquid jet recording head and a liquid jet recording device that have extremely good performance. According to the present invention, the resistance value controllability of the heating resistance layer is particularly good.

Therefore, according to the present invention, it is possible to realize liquid jet recording with high frequency response and high reliability.

Furthermore, according to the present invention, the content of halogen atoms, hydrogen atoms, and/or electrically conductive substances in the heating resistance layer is distributed non-uniformly in the film thickness direction, which improves heat storage, heat dissipation, and support. Various properties such as adhesion between the body and the resistance layer and resistance to chemical reaction with the recording liquid can be easily achieved.

[Brief explanation of the drawing]

FIG. 1 is a partial plan view of the recording head of the present invention, FIG. 2 is a sectional view taken along line 1--2, and FIG. 3 is a sectional view taken along line mm in FIG. 4 to 9 are graphs showing the distribution of the content of I\rogen atoms, hydrogen atoms and/or electrical conductivity controlling substances in the heating resistor layer. 10 and 11 are partial cross-sectional views of a substrate having an electrothermal transducer of the recording head of the present invention. FIG. 12 is a schematic explanatory diagram of the deposition apparatus. 13 and 14 are partial perspective views of the recording head of the present invention. 15 to 18 are partial cross-sectional views of the recording head of the present invention. 19, 21 and 23 are perspective views of a substrate having an electrothermal converter of the recording head of the present invention, and FIGS.
FIG. 22 and FIG. 24 are sectional views thereof, respectively. FIG. 25 is a perspective view of the top plate of the recording head of the present invention. 26, 27, and 28 are perspective views of the recording head of the present invention. FIG. 29 is a perspective view of the recording apparatus of the present invention. FIG. 30 is a partially cutaway perspective view of the recording apparatus of the present invention. 12: Support 24: Heat generating resistive layer 16. 17: Electrode 18: Heat generating part 20: Top plate 24: Heat acting part 26: Discharge port agent Patent attorney Seki Yamashita Square 1 Figure 3 Dot+ 24 24 4th Figure 5 Figure 6 Figure 7 Figure 8 Figure 7 Figure C1
Figure 3 Figure 14 Figure 15 Figure 1G Flash Figure 17 Figure 20 Figure 2 Figure 22

Claims (2)

[Claims] (1) A liquid comprising an ejection port provided for ejecting a liquid to form flying droplets, and an electrothermal converter that generates thermal energy used to form the flying droplets. In the ejection recording head, the heating resistance layer constituting the electrothermal converter is made of an amorphous material containing carbon atoms as a matrix, halogen atoms, hydrogen atoms, and a substance controlling electrical conductivity, and A liquid jet recording head characterized in that a halogen atom, a hydrogen atom, and/or a substance controlling electrical conductivity are distributed nonuniformly in the film thickness direction in a resistive layer. (2) A liquid comprising an ejection port provided for ejecting liquid to form flying droplets, and an electrothermal converter that generates thermal energy used to form the flying droplets. In a liquid jet recording device equipped with a jet recording head, the heat generating resistive layer constituting the electrothermal converter has carbon atoms as a matrix and contains halogen atoms, hydrogen atoms, and a substance controlling electrical conductivity. A liquid jet recording device made of an amorphous material, characterized in that halogen atoms, hydrogen atoms, and/or a substance controlling electrical conductivity are unevenly distributed in the film thickness direction in the heating resistance layer.