JPH0655508B2 - Liquid jet recording apparatus equipped with liquid jet recording head - Google Patents

Description

The present invention relates to a liquid jet recording apparatus equipped with a liquid jet recording head.

[Prior Art] Among various currently known recording methods, it is a non-impact recording method that generates almost no noise during recording, high-speed recording is possible, and a special fixing process is performed on plain paper. The so-called ink jet recording method, which enables recording without need, is recognized as an extremely useful recording method. Regarding this ink jet recording method, various methods have been proposed and improved so far, and some have been commercialized, while others are still being put into practical use.

The ink jet recording method is one in which recording liquid droplets called ink are ejected by various principles of operation and are attached to a recording member such as paper for recording.

The applicant of the present application has already proposed a new method related to the inkjet recording method. This new method is proposed in Japanese Patent Laid-Open No. 52-118798, and its basic principle is as outlined below.
In other words, in this ink jet recording method, a thermal pulse is applied as an information signal to the recording liquid introduced into the working chamber capable of containing the recording liquid, whereby the recording liquid generates vapor bubbles and self-contracts. According to the acting force generated in the process, the recording liquid is discharged from a discharge port that communicates with the working chamber and is made to fly as small liquid droplets, and the liquid droplets are attached to a recording member to perform recording.

By the way, since this system has a high-density multi-array structure and is easily adapted to high-speed recording and color recording, and the structure of the embodying device is simpler than that of the conventional structure, the recording head can be made compact as a whole and mass-produced. Towards
In the field of semiconductors, the advantages of IC technology and microfabrication technology, which have been remarkably improved in technology and reliability, are fully utilized. is there.

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

The electrothermal converter has discharge ports communicating with each other so as to be in direct contact with the liquid in order to efficiently apply the generated heat energy to the liquid and to increase the ON-OFF response speed of the heat action on the liquid. It is said that it is desirable that the structure is provided in the heat acting part.

However, since the electrothermal converter is basically composed of a heating resistor that generates heat when energized and a pair of electrodes for energizing the heating resistor,
When the heating resistor is in direct contact with the liquid, electricity may flow through the liquid depending on the electric resistance value of the recording liquid, or the liquid itself may be electrolyzed by the flow of electricity through the liquid, or When the heating resistor is energized, the heating resistor reacts with the liquid to change the resistance value due to corrosion of the heating resistor itself, or damage or destruction of the heating resistor occurs. The surface of the heat-generating resistor is damaged or a part of the heat-generating resistor is cracked by the mechanical shock that accompanies the change in state from the generation of vapor bubbles of the liquid to the self-annihilation due to the action of the generated heat. Occasionally, it was destroyed and so on.

Therefore, conventionally, alloys such as NiCr and Zr have been used.
The heating resistor is made of an inorganic material such as a metal boride such as B ₂ or HfB _{2 which} is relatively excellent in characteristics as a heating resistor material, and SiO is formed on the heating resistor made of the material.
By providing a protective layer (upper layer) composed of a material having excellent oxidation resistance such as _{2 and the} like, it is possible to prevent the heating resistor from directly contacting the liquid, solve the above-mentioned problems, and improve reliability. It has been proposed to try to improve the durability against repeated use.

However, the liquid jet recording apparatus having the recording head provided with the electrothermal converter having the above-described configuration has a relatively low electric conductivity as a colored liquid for recording (for example, water or alcohol as the liquid medium). Is satisfactory in terms of oxidation resistance and durability against repeated use, but a recording liquid having a high content of Na ions and the like and a large electric conductivity is used. In the case of using the liquid electrolyte, it was insufficient in terms of durability against repeated use and resistance to change over time. Therefore, there is a limitation in selection of the recording liquid to be used, which is an obstacle in performing multicolor or natural color recording.

Further, even when the protective layer is provided on the heating resistor as described above, it is possible to substantially completely prevent liquid from entering the heating resistor side due to a defect of the protective layer itself which occurs during layer formation. It is very difficult in terms of productivity and mass productivity. Furthermore, in the case of so-called high-density multi-orifice in which a liquid flow path (nozzle) having a large number of heat acting parts as a part of its configuration is provided at high density, at least the number of liquid flow paths should be converted into electrothermal converters once. Since it is necessary to provide the protective layer, the influence of the defect due to the defect of the protective layer on the manufacturing yield of the electrothermal converter is a serious problem including the manufacturing cost. There is also a problem that the thermal response is sacrificed due to the presence of the protective layer. Furthermore, the presence of the protective layer sacrifices heat generation response to a predetermined electric signal. Therefore, even if 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 apparatus including the electrothermal converter.

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

Another object of the present invention is particularly high in chemical stability, excellent in electrochemical reaction resistance and oxidation resistance, and also in mechanical shock resistance and heat resistance. Furthermore, by eliminating the protective layer, thermal response is improved. It is an object of the present invention to provide a liquid jet recording apparatus equipped with a liquid jet recording head including a heating resistor capable of improving the property.

[Summary of the Invention] According to the present invention, the above object is to discharge a liquid to form flying droplets, and to store the liquid to form the flying droplets. A liquid jet recording head comprising: a heat acting portion for causing heat energy used for the purpose to act on the liquid; and an electrothermal converter provided in the heat acting portion for generating the heat energy, and the flying liquid. In a liquid jet recording apparatus equipped with a transporting means for transporting a recording medium to which droplets are attached, the heating resistance layer constituting the electrothermal converter includes silicon atoms, halogen atoms and hydrogen atoms with carbon atoms as a base material. Achieved by a liquid jet recording apparatus characterized by comprising an amorphous material contained therein, wherein the content ratio of silicon atoms, halogen atoms and / or hydrogen atoms in the heating resistance layer changes in the film thickness direction. To be done.

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

FIG. 1 is a partial plan view showing the configuration of an embodiment of the liquid jet recording head of the present invention, and FIG. 2 is a II-II sectional view thereof.

In the figure, 12 is a support on which an electrothermal converter is provided, 14 is a heat generating resistance layer that constitutes the electrothermal converter, and 16 and 17 are electrodes that form a pair that constitute the electrothermal converter. As shown in FIG. 1, a plurality of sets of the heating resistance layer 14 and a pair of electrodes 16 and 17 connected to the heating resistance layer 14 are provided side by side.
, 18 ', 18 ", ... Are arranged at a predetermined interval. In this embodiment, one electrode 16 is a common electrode in which a plurality of electrodes are grouped together. The electrodes 16 and 17 are respectively provided for the heating resistance layer 14 that constitutes each heating portion 18, 18 ', 18 ", ....
An electric signal is applied through the heat generating portions, and each heat generating portion generates heat based on the electric signal.

As shown in FIG. 2, a top plate 20 having a groove formed on the heat generating portion side of the support 12 is bonded to the substrate having the support 12, the heat generation resistance layer 14, and the electrodes 16 and 17. A sectional view taken along line III-III in FIG. 2 is shown in FIG. As shown in FIGS. 2 and 3, the heating elements 18, 18 ′, 1 are attached to the top plate 20.
8 ″, ... at positions corresponding to II- of FIG. 1, respectively.
Grooves 22, 22 ', 22 ", ... Are formed along the II direction. These grooves form a space for accommodating the recording liquid with the support 12. These spaces are the recording liquid. It has a heat acting portion 24 that acts on the heat energy.

On the left side in FIG. 2, the space is open to the outside, and the opening serves as a liquid discharge port 26. The space is connected to the recording liquid supply source on the right side in FIG. Then, when heat energy is generated from the heat generating portion based on the recording signal in the space 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 ejection port 26 to move toward the arrow X. Discharge in the direction of.

As can be seen from the above description, in FIG.
The illustration of 0 is omitted.

In the present invention, the material of the support 12 is not particularly limited, but in practice, the heat generating resistance layer 1 formed on the surface thereof.
The heat generating resistance layer 1 when used and when forming
Those having good durability against the heat generated by No. 4 are preferably used. Further, it is preferable that the support 12 has a larger electric resistance than the heat generating resistance layer 14 formed on the surface thereof, but when 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 an electric resistance smaller than that of the heat generating resistance layer 14. Further, in the present invention, the support 12 having a small or large thermal conductivity can be used depending on the usage of the liquid jet recording head.

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

In the present invention, the heating resistance layer 14 is made of an amorphous material containing carbon atoms as a matrix and containing silicon atoms, halogen atoms and hydrogen atoms. F and C as halogen atoms
l, Br, I and the like can be used, and these may be used alone or in combination. The halogen atom is preferably F or Cl. Among them, F is preferable because it is easy to handle.

The content ratio of silicon atoms in the heating resistance layer 14 is appropriately selected so as to obtain desired characteristics according to the purpose of use, but is preferably 0.0001 to 40 atom%, more preferably 0.0005 to 5 It is 20 atomic%, and preferably 0.001 to 10 atomic%.

The content of halogen atoms in the heat generation resistance layer 14 is appropriately selected so as to obtain desired characteristics depending on the purpose of use, but is preferably 0.0001 to 30 atom%, and more preferably 0.0005 to 5 atom%. It is 20 atomic%, and preferably 0.001 to 10 atomic%.

The content ratio of hydrogen atoms in the heating resistance layer 14 is appropriately selected so that desired characteristics can be obtained according to the purpose of use.
It is preferably 0.0001 to 30 atomic%, more preferably 0.0005 to 20 atomic%, and preferably 0.1.
It is 001 to 10 atomic%.

The sum of the content rate of silicon atoms, the content rate of halogen atoms, and the content rate of hydrogen atoms in the heating resistance layer 14 is appropriately selected so that desired characteristics can be obtained according to the purpose of use.
It is preferably 0.0001 to 40 atomic%, more preferably 0.0005 to 30 atomic%, and preferably 0.1.
It is 001 to 20 atomic%.

In the present invention, the content ratio of silicon atoms, halogen atoms and / or hydrogen atoms in the heating resistance layer 14 changes in the film thickness direction. The change in the content ratio of silicon atoms, halogen atoms and / or hydrogen atoms in the film thickness direction in the heat generation resistance layer 14 may be such that the content ratio gradually increases from the support 12 side to the surface side, or conversely. The content may be reduced. Further, the content change of the silicon atom, the halogen atom and / or the hydrogen atom may have the maximum value or the minimum value in the heating resistance layer 14. The change in the content ratio of silicon atoms, halogen atoms and / or hydrogen atoms in the film thickness direction in the heating resistance layer 14 is appropriately selected so that desired characteristics can be obtained.

4 to 9 show a heating resistance layer 14 of the recording head of the present invention.
Specific examples of changes in the content of silicon atoms, halogen atoms and / or hydrogen atoms in the film thickness direction are shown below. In these figures, the vertical axis represents the distance T in the film thickness direction from the interface with the support 12, and t represents the film thickness of the heating resistance layer 14. The horizontal axis represents the content ratio C of silicon atoms, halogen atoms and / or hydrogen atoms. In each figure, the scales of the vertical axis T and the horizontal axis C are not necessarily uniform, and are changed so that the characteristics of each figure are exhibited. Therefore, in actual application, various distributions based on the difference in specific numerical values are used for each figure.

For example, in these specific examples, as shown in FIGS. 4, 6 and 9, when the content change of the halogen atom in the film thickness direction in the heating resistance layer gradually increases from the support side to the surface side, Since silicon improves the mechanical strength of the surface portion, cavitation resistance can be enhanced. When the content of silicon atoms changes so as to gradually decrease from the support side to the surface side as shown in FIGS. 5 and 7, the mechanical strength of the entire film is improved while maintaining the chemical stability of the surface. Therefore, the ink resistance and the cavitation resistance can be improved. Then, as shown in FIG. 8, when the content of silicon atoms has a maximum value near the center of the heating resistance layer, the chemical stability of the surface was maintained without increasing the hardness of the contact surface of the support. Since the mechanical strength of the film can be improved as it is, it becomes possible to improve the adhesion as well as the ink resistance and the cavitation resistance.

In addition, as shown in FIGS. 4, 6 and 9, when the change in the content ratio of halogen atoms in the film thickness direction in the heating resistance layer is gradually increased from the support side to the surface side, the halogen-based surface Since the chemical stability is increased, the ink resistance can be improved. Also, when the content of halogen atoms changes so as to gradually decrease from the support side to the surface side as shown in FIGS. 5 and 7, the halogen lowers the thermal conductivity of the lower part, and therefore the heat storage property is enhanced. Is possible. When the content of halogen atoms has a maximum value near the center of the heating resistance layer as shown in FIG.
Since the number of unbonded covalent bonds of the lower carbon is increased, it is possible to improve the adhesion to the support.

Further, as shown in FIGS. 4, 6 and 9, when the change in the content ratio of hydrogen atoms in the film thickness direction in the heat generating resistance layer gradually increases from the support side to the surface side, Ink resistance can be improved because the number of unbonded covalent bonds increases. Further, when the content of hydrogen atoms changes so as to gradually decrease from the support side to the surface side as shown in FIGS. 5 and 7, hydrogen lowers the thermal conductivity of the lower part, so that the heat storage property can be improved. It will be possible. And
As shown in Fig. 8, when the hydrogen atom content has a maximum value near the center of the heating resistance layer, the number of unbonded covalent bonds in the lower carbon increases, and therefore the adhesion to the support is increased. It becomes possible to raise.

Further, the thickness of the heating resistance layer 14 is not particularly limited.

The recording head of the present invention may be abbreviated as an amorphous material (hereinafter, referred to as "aC: Si: (X, H)") containing silicon atoms, halogen atoms, and hydrogen atoms as a matrix of carbon. The heating resistance layer 14 made of X represents a halogen atom is formed by a vacuum deposition method such as a plasma CVD method such as a glow discharge method or a sputtering method.

For example, by a glow discharge method, aC: Si: (X,
In order to form the resistance layer 14 made of H), basically, the support 12 is placed in a deposition chamber under reduced pressure, and a source gas for C supply capable of supplying carbon atoms (C) is supplied into the deposition chamber. Introducing a source gas for supplying Si that can supply silicon atoms (Si), a source gas for supplying X that can supply halogen atoms (X) and a source gas for supplying H that can supply hydrogen atoms (H). At this time, while changing the introduction amount of the Si supply source gas, the X supply source gas, and / or the H supply source gas, a glow discharge is generated in the deposition chamber by using high frequency or microwave to generate the support 12. On the surface of a-C: Si:
A layer made of (X, H) may be formed.

Moreover, a-C: Si: (X,
In order to form the resistance layer 14 made of H), the support 12 is basically placed in a deposition chamber under reduced pressure, and an inert gas such as Ar or He or a base gas of these gases is used in the deposition chamber. When the target composed of C is sputtered in the mixed gas atmosphere described above, a source gas for supplying Si, a source gas for supplying X and / or a source gas for supplying H are introduced into the deposition chamber. The introduction amount may be changed.

In the above method, the raw material gas for supplying C, the raw material gas for supplying Si, the raw material gas for supplying X and the raw material gas for supplying H are not only those in a gas state at room temperature and normal pressure, but also substances that can be gasified under reduced pressure. Can be used.

As the raw material for supplying C, for example, a saturated hydrocarbon having 1 to 5 carbon atoms, an ethylene hydrocarbon having 2 to 5 carbon atoms, an acetylene hydrocarbon having 2 to 4 carbon atoms, an aromatic hydrocarbon and the like, specifically, the methane as a saturated hydrocarbon _(CH 4), ethane _{(C 2 H} 6), propane _{(C 3} H 8), n- butane _{(n-C 4 H 10)} , pentane _{(C 5 H 12),} ethylene Examples of hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene-1 (C ₄ H ₈ ), butene-2.
(C ₄ H ₈ ), isobutylene (C ₄ H ₈ ), pentene (C ₅ H ₁₀ ), acetylene hydrocarbons such as acetylene (C ₂ H ₂ ), methylacetylene (C ₃ H ₄ ), butyne (C ₄ ). H ₆ ), and aromatic hydrocarbons include benzene (C ₆ H ₆ ).

Examples of raw materials for supplying Si include SiH ₄ and Si ₂
Silicon hydrides (silanes) such as H ₆ , Si ₃ H ₈ and Si ₄ H ₁₀ , SiF ₄ , (SiF ₂ ) ₅ and (SiF ₂ )
₆ , (SiF ₂ ) ₄ , Si ₂ F ₆ , Si ₃ F ₈ , SiH
F ₃ , SiH ₂ F ₂ , SiCl ₄ (SiCl ₂ ) ₅ , S
iBr ₄ , (SiBr ₂ ) ₅ , Si ₂ Cl ₆ , Si ₂ C
l ₃ F ₃ and halogenated silicon (silane derivatives substituted with halogen atoms) and the like.

Examples of the raw material for supplying X include halogens, halides, interhalogen compounds, halogen-substituted hydrocarbon derivatives, and the like. Specifically, halogens include F ₂ , Cl ₂ , and B.
r ₂ , I ₂ , and halides such as HF, HCl, and HB
r, HI, as the interhalogen compound, BrF, ClF,
ClF ₃ , BrF ₅ , BrF ₃ , IF ₃ , IF ₇ , IC
l, IBr, CF as the halogen-substituted hydrocarbon derivative
₄ , CHF ₃ , CH ₂ F ₂ , CH ₃ F, CCl ₄ , CH
Cl ₃ , CH ₂ Cl ₂ , CH ₃ Cl, CBr ₄ , CHB
r ₃ , CH ₂ Br ₂ , CH ₃ Br, CI ₄ , CHI ₃ ,
CH ₂ I _2, CH ₃ I, and the like.

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

These raw materials may be used alone or in combination of two or more.

In the method for forming a heating resistance layer as described above, in order to control the amount of silicon atoms, the amount of halogen atoms and the amount of hydrogen atoms contained in the resistance layer 14 to be formed, and the characteristics of the resistance layer 14, the support temperature should be adjusted. The supply amount of the source gas, the discharge power, the pressure in the deposition chamber, etc. are set appropriately.

In particular, a heating resistance layer having a non-uniform distribution of silicon atoms, halogen atoms and / or hydrogen atoms in the film thickness direction of the present invention is used.
In order to obtain 4, it is preferable to change the introduced amount of silicon atoms, halogen atoms and / or hydrogen atoms into the deposition chamber with time by, for example, valve control.

The support temperature is preferably 20 to 1500 ° C, more preferably 30 to 1200 ° C, and most preferably 50 to 1100 ° C.

The supply amount of the raw material gas is appropriately determined according to the desired heating resistance layer performance and the target film formation rate.

Discharge power is preferably 0.001~20W / cm ^2, more preferably 0.01~15W / cm ^2, and optimally 0.05
It is selected from the range of 10 W / cm ² .

The pressure in the deposition chamber is preferably 10 ⁻⁴ to 10 Torr, more preferably 10 ^{−2 to 5} Torr.

The resistance layer of the recording head of the present invention obtained by using the heating resistance layer forming method as described above has characteristics close to those of diamond.
That is, for example, a Vickers hardness of 1800 to 5000 is obtained. Further, since it contains a silicon atom, a halogen atom and a hydrogen atom, the mechanical strength is particularly excellent.

The heat generating resistance layer in the present invention has high durability against mechanical shock and excellent chemical stability, and thus does not require a special protective layer. Therefore, in the liquid jet recording head using the heating resistance layer according to the present invention, the thermal energy generated by the signal input is applied to the liquid very efficiently, and the thermal response becomes good. This also improves the ejection response of the flying droplets formed in response to the signal input to the liquid jet recording head.

However, if the desired responsiveness is exhibited, it does not matter if the protective layer is formed on the heating resistance layer as described above.

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

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

In addition, although the support 12 is said to be a single support in the above-described embodiments, the support 12 in the present invention may be a composite. The structure of such an embodiment is shown in FIG. That is, the support 12 is composed of a composite of a base portion 12a and a surface layer 12b, and the support material described in connection with FIGS. 1 to 3 can be used as the base portion 12a, and the surface layer 12b can be formed thereon. It is possible to use a material having a better adhesiveness with the resistance layer 14 formed in the above. The surface layer 12b is made of, for example, an amorphous material having carbon atoms as a base material, a conventionally known oxide, or the like. Such a surface layer 12b is obtained by depositing on the base portion 12a by using a suitable raw material by a method similar to the above-mentioned heating resistance layer forming method. In addition, the surface layer 12
b may be an ordinary glassy glaze layer, or may be an oxide layer formed by oxidizing the surface of the base 12a if the base 12a is a metal.

The electrodes 16 and 17 in the recording head of the present invention may be those having a predetermined conductivity, such as Au and C.
It is made of a metal such as u, Al, Ag, and Ni.

Next, an outline of a method of manufacturing the recording head of the present invention will be described.

FIG. 12 is a schematic explanatory view showing an example of a deposition apparatus used when forming a heating resistance 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, 1
117 to 1121 are outflow valves, and 1122 to 11
Numeral 26 is a gas cylinder valve, and 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 having an electrothermal converter to be manufactured, 1138 is a heater, 1139 is a support member supporting means, 1140
Is a high voltage power supply, 1141 is an electrode, 1142
Is a shutter. Reference numeral 1142-1 is a target attached to the electrode 1141 when performing the sputtering method.

For example, in 1102, CF ₄ gas (purity 99.9% or more) diluted with Ar gas is sealed.
C ₂ F ₆ gas diluted with Ar gas (purity 99.9)
% Or more), 1104 is sealed with SiH ₄ gas diluted with Ar gas (purity is 99.9% or more), and 1105 is Si ₂ H diluted with Ar gas.
₆ gases (purity 99.9% or more) are sealed. Prior to injecting the gas in these cylinders into the deposition chamber 1101, the valves 1122 of the gas cylinders 1102 to 1106 are arranged.
~ 1126 and the leak valve 1135 are closed, and the inflow valves 1112 to 1116, the outflow valves 1117 to 1121 and the auxiliary valve 1132 are opened, the main valve 113 first.
4 is opened to exhaust the inside of the deposition chamber 1101 and the gas pipe.
Next, when the reading of the vacuum gauge 1136 reaches 1.5 × 10 ⁻⁶ Torr, the auxiliary valve 1132 and the inflow valve 1112.
~ 1116 and outflow valves 1117 to 1121 are closed. Then, the valve of the gas pipe connected to the cylinder of the gas to be introduced into the deposition chamber 1101 is opened to introduce the desired gas into the deposition chamber 1101.

Next, an example of a procedure for forming the resistance layer of the recording head of the present invention by the glow discharge method using the above apparatus will be described. Open the valve 1122 to open the gas cylinder 110.
2, CF ₄ / Ar gas is flown out, the valve 1124 is opened, SiH ₄ / Ar gas is flown out from the gas cylinder 1104, and the pressure of the outlet pressure gauges 1127 and 1129 is set to 1 kg.
/ cm ² and then gradually open the inflow valves 1112, 1114 to mass flow controllers 1107, 1109.
Let it flow in. Then, the outflow valves 1117, 1
119, gradually opening the auxiliary valve 1132 to CF ₄ / A
The r gas and the SiH ₄ / Ar gas are introduced into the deposition chamber 1101. At this time, the flow rate of CF ₄ / Ar gas and SiH ₄ /
The mass flow controllers 1107 and 1109 are adjusted so that the ratio with the flow rate of Ar gas becomes a desired value, and the vacuum gauge 1136 is adjusted so that the pressure in the deposition chamber 1101 becomes a desired value.
The opening of the main valve 1134 is adjusted while watching the reading. Then, after heating by the heater 1138 so that the temperature of the support body 1137 supported by the supporting means 1139 in the deposition chamber 1101 becomes a desired temperature, the shutter 1142 is opened and a glow discharge is generated in the deposition chamber 1101. Let Then, the opening degree of the outflow valves 1117 and 1119 is changed manually or by an external drive motor to change the flow rate of CF ₄ / Ar gas and / or SiH ₄ gas.
/ Ar gas flow rate is changed over time according to a previously designed rate-of-change curve, whereby S in the resistance layer 14 is changed.
The content of i atoms, F atoms and / or H atoms is changed in the film thickness direction.

Next, an example of the procedure for forming the resistance layer of the recording head of the present invention by the sputtering method using the above apparatus will be described. The high-purity graphite 11 is previously formed on the electrode 1141 to which a high voltage is applied by the high-voltage power supply 1140.
42-1 is installed as a target. From the gas cylinder 1102 to CF _{4 in the same} manner as in the glow discharge method.
/ Ar gas is introduced into the deposition chamber 1101 from the gas cylinder 1104 at a desired flow rate of SiH ₄ / Ar gas. The target 1142-1 is sputtered by opening the shutter 1142 and turning on the high voltage power supply 1140. At this time, the heater 1138 causes the support 1
Heating the 137 to a desired temperature and adjusting the opening of the main valve 1134 to bring the inside of the deposition chamber 1101 to a desired pressure is the same as in the glow discharge method. Then, as in the case of the glow discharge method, the outflow valve 111
7 and 1119 are operated to change the opening, and CF ₄
/ Ar gas flow rate and / or SiH ₄ / Ar gas flow rate is changed over time according to a previously designed change rate curve, whereby the content of Si atoms, F atoms and / or H atoms in the resistance layer 14 is increased. In the film thickness direction.

In the case of the substrate having the electrothermal converter of the liquid jet recording head as shown in FIGS. 1 to 3, after the heating resistance layer is formed on the support as described above, the heating resistance layer is formed on the heating resistance layer. A conductive layer (for example, Au layer, Al layer) for forming electrodes is formed, and then the conductive layer and the heating resistance layer are patterned by using a photolithography technique. If necessary, a protective layer made of an insulating material or the like may be laminated.

Further, in the case of a substrate having an electrothermal converter of a liquid jet recording head as shown in FIG. 10, a conductive layer is previously formed on a support, and the conductive layer is patterned by using a photolithography technique. After that, the heating resistance layer is formed by the glow discharge method or the sputtering method as described above.

The grooved top plate is made of, for example, a material similar to that of the above-mentioned support, and is formed by an appropriate means such as mechanical cutting with a microcutter or chemical etching, or when the top plate is a photosensitive glass or the like. It is possible to use a pattern in which grooves are formed by exposure and development.

The substrate having the electrothermal converter and the top plate can be joined by sufficiently aligning them, and then, for example, bonding with an adhesive or heat fusion depending on the material of the top plate.

In the embodiment described above, a liquid jet recording head of the type shown in the partial perspective view in FIG. 13, that is, a head in which the recording liquid discharge port 26 is opened in the direction of the groove 22 formed in the top plate 20. As described above, in the present invention, the 14th
As shown in the drawing, the liquid discharge port 26 may be directly provided on the top plate 20. In the head of the type shown in FIG. 14, the opening at the end of the groove 22 formed in the top plate 20 is used as a recording liquid introduction port, and 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 through at least one opening.

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

FIG. 15 is a sectional view taken along the line IX-IX in FIG.
In this case, the portion other than the groove 22 of the top plate 20 is in close contact with the substrate having the electrothermal converter. Therefore, each heat-acting part 24 formed corresponding to each groove 22 of the top plate 20 has the support 1
They are blocked from each other by a barrier portion 30 composed of a portion in close contact with 2. In addition, in FIG. 15, each heat generating portion 18 is provided corresponding to each discharge port 26.

16 to 18 are sectional views corresponding to FIG. 15 showing another example.

In the case of FIG. 16, the barrier portion 30 is not completely in close 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 respective heat generating portions 18 communicate with each other as in the case of FIG.

In the case of FIG. 18, the barrier portion as in the case of FIGS. 15 to 17 is not formed.

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

The barrier portion (wall) 30 is not necessarily provided as described above. Even if the ejection direction, the ejection speed, or the ejection amount of the liquid ejected from the adjacent ejection port is affected, there is no error beyond the allowable range at the landing point of the flying droplet on the recording member. It does not necessarily have to be provided. However, it is preferable to provide the barrier portion in order to further reduce the mutual influence between the ejection ports and to improve the energy efficiency (liquid ejection efficiency). Further, the barrier portion may be formed integrally with the top plate or only the barrier portion may be a separate member. As the flat top plate, the same material as that of the grooved top plate can be used. A photosensitive resin can also be used as the barrier portion and the top plate.

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

Example First, a substrate having an electrothermal converter used in the following examples and comparative examples was prepared in the following manner.

As the support, # 7059 glass manufactured by Corning,
A Si plate provided with a thermally oxidized SiO ₂ heat storage layer (thickness 5 μm) was used as the surface layer.

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

A heating resistance layer was formed on the type A support using the deposition apparatus shown in FIG. The conditions for the deposition are as shown in Table 1 and Table 2, respectively. The examples shown in Table 1 were performed by the glow discharge method, and the examples and comparative examples shown in Table 2 were performed by the sputtering method. Graphite (99.99%) was used as the target during sputtering except for the comparative example, and the comparative example was HfB.
₂ 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 heating resistance layer having the thickness shown in Table 3 was formed. Next, an Al layer was formed on the heating resistance layer by an electron beam method, a resist pattern was formed by a photolithography technique, and the Al layer was etched into a desired shape to form a plurality of pairs of electrodes. Subsequently, a resist pattern was formed by a photolithography technique, and the heating resistance layer in a predetermined portion was removed using an HF-based etching solution. As an example thereof, a heat generating resistance element having the above electrode attached to a heat generating portion formed of a heat generating resistance layer of 40 μm × 200 μm was formed. The heat generating parts were arranged at a pitch of 8 pieces / mm.

Next, photosensitive polyimide (trade name: Photo Nice) is spin-coated. Then, pre-bake at 80 ° C for 1 hour,
After exposure with an aligner, development is performed to form a heating portion with a window opening structure. Then, at 140 ° C for 30 minutes, 400 ° C
Then, post-baking is performed for 1 hour to complete the substrate having the electrothermal converter.

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

The photosensitive polyimide is for preventing electrolysis of the Al electrode in the ink.

A schematic perspective view of the substrate having the completed electrothermal converter is shown in FIG. 19 and a schematic sectional view thereof is shown in FIG. In the figure, 28 is a polyimide layer.

Type B A heating resistance layer was formed on the support in the same manner as in the case of type A. The deposition conditions are as shown in Table 1 and Table 2, respectively. During the deposition, the flow rate of each gas and other conditions were maintained as shown in Table 1 and Table 2, respectively, and the heating resistance layer having the thickness shown in Table 3 was formed. Next, an Au layer was formed on the heating resistance layer by an electron beam method, a resist pattern was formed by a photolithography technique, and the Au layer was etched into a desired shape to form a plurality of pairs of electrodes. Then, a resist pattern is formed by photolithography technique to form HF.
The heating resistance layer in a predetermined portion was removed by using a system etching solution. As an example thereof, a heating resistor element having the above-mentioned electrode attached to a heating portion formed of a 40 μm × 200 μm heating resistor layer was formed. The heat generating parts were arranged at a pitch of 8 pieces / mm. Thus, the substrate having the electrothermal converter is completed.

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

A schematic perspective view of the substrate having the completed electrothermal converter is shown in FIG. 21, and a schematic sectional view thereof is shown in FIG.

An Al layer is formed on the type C support by an electron beam method, and a resist pattern is formed by a photolithography technique.
The layers were etched into the desired shape to form pairs of electrodes. Next, a heating resistance layer was formed on the patterned Al layer.

The heating resistance layer was formed in the same manner as in the case of type A.
The deposition conditions were kept as shown in Tables 1 and 2, respectively, and the heating resistance layer having the thickness shown in Table 3 was formed. Subsequently, a resist pattern was formed by a photolithography technique, and the heating resistance layer in a predetermined portion was removed using an HF-based etching solution. As an example, 40μ
A heating resistor element was formed in which the above electrodes were attached to the heating portion consisting of the heating resistor layer of m × 200 μm. The heat generating parts were arranged at a pitch of 8 pieces / mm. Since the Al electrode is protected by this heating resistance layer, it is not necessary to form a protective film. Thus, the substrate having the electrothermal converter is completed.

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

A schematic perspective view of the substrate having the completed electrothermal converter is shown in FIG. 23, and a schematic sectional view thereof is shown in FIG.

A liquid jet recording head is produced 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 1) and the type shown in FIG. 14 (hereinafter referred to as type 2).

Type 1 was prepared by two kinds of preparation methods, and type 2 was prepared by one kind of preparation methods. The method of creating them will be described below.

Type 1-1 First, as shown in the schematic perspective view of FIG.
A plurality of grooves 22 (width 40 μm, depth 40 μm) and a groove 42 serving as a common ink chamber are formed by cutting with a micro-cutter at 0 to form a grooved top plate 20.

Next, the substrate and the top plate 20 completed as described above are combined with the heating portion and the groove 2.
2 and are joined together, and as shown in a schematic perspective view of FIG. 26, an ink introducing pipe 44 for introducing ink from an ink supply unit (not shown) into the common ink chamber is connected. The recording head 46 is integrally completed.

Type 1-2 A photosensitive film 50 (trade name: O'Deil, Tokyo Ohka) is laminated on the substrate completed above. Then, it is exposed with an aligner and developed to form a desired pattern shape. Next, a glass plate 54 laminated with a photosensitive resin film 52 (trade name: Audeil, Tokyo Ohka) is laminated and bonded on the above-mentioned patterned film.
The joined body is shaped by, for example, mechanical processing such as dicing to form the ejection port 26, and the ink supply tube (not shown) is connected to the common ink chamber to connect the ink introducing tube 44 to the pattern shown in FIG. The recording head 56 as shown in the schematic perspective view is integrally completed.

Type 2 First, the top plate 20 on which the discharge ports 26 are formed is created. The top plate 20 is formed by forming a pattern of a photosensitive film (trade name: PHT-145FT-50, Hitachi Chemical Co., Ltd.) on a stainless plate having a groove formed by etching, etc., and electroforming with Ni plating thereon. . The portion where the ejection port 26 has a hole is where the pattern of the photosensitive film exists. The top plate 20 thus formed and the substrate completed as described above are aligned with the heat generating portion and the discharge port 26 corresponding thereto, and are joined with an adhesive. The substrate is machined so that ink can be supplied to the top plate 20. Next, an introduction pipe 60 for introducing ink from an ink supply unit (not shown) to the common ink chamber is joined to the back surface of the joined substrate to form a second
A recording head 62 as shown in the schematic perspective view of FIG. 8 was integrally completed. Incidentally, reference numeral 64 is a concave portion of the top plate 20 and constitutes a barrier portion.

There are combinations of type A, type B, and type C of the layer structure of the substrate having the electrothermal converter and type 1-1, type 1-2, and type 2 of the head manufacturing method. A combination of type A and type 1-1 was used.

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

A lead having an electrode lead (individual electrode lead and common electrode lead: not shown) respectively connected to the individual electrode 17 relating to each heat generating portion and the electrode 16 common to each heat generating portion is provided in the recording head created as described above. The substrate was attached and the recording head unit was completed.

Using these recording head units, a liquid jet recording apparatus having a schematic perspective view shown 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 mounted, and 74 is a guide member for reciprocating the carriage 72. 76 is a platen,
Reference numeral 78 denotes a recording member, such as paper, held on the platen 76.

The recording liquid ejection port of the recording head unit 70 is directed in the direction of arrow Z, and the recording liquid is ejected as droplets in the direction of the arrow and adheres in a dot shape onto the recording target member 78 on the platen 76. . Main scanning is performed by moving the recording head unit 70 along the guide member 74 by appropriate driving means, while sub-scanning is performed by rotating the platen 76 around the rotation axis 77 by appropriate driving means. Thus, recording is performed on the recording member 78.

The experimental conditions were as follows.

With a pulse width of 10 μsec and a pulse input period of 200 μsec to the heat generating portion, a voltage 1.2 times the minimum foaming voltage (voltage at which foaming starts in ink) (for example, the minimum foaming voltage is 2).
If it is 0 V, a rectangular pulse of 24 V) was applied. The composition of the ink used was as follows.

Water 68 parts by weight DEG 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 evaluation as shown in Table 3 was obtained.

The durability of these examples and comparative examples was evaluated by the number of times the electric pulse could be repeatedly applied as follows. That is, “◯” and “×” shown in the column of durability in Table 3 indicate how many times the electric pulse was repeatedly applied.

○ 10 ¹⁰ times or more × 10 ⁶ times or less Here, when the number of repeated application of the electric pulse is 10 ⁹ times or more, the durability is remarkably superior to that of the conventional recording head. The product has a sufficiently long life. And, when it is 10 ⁶ times or less, the printing durability required for use by the user is insufficient.

Further, regarding the layer thickness and the resistance value, each numerical value of the heating resistance layer was appropriately adjusted so that the durability could be evaluated under substantially the same conditions.

From the above results, it can be seen that in the example of the present invention, the recording head having significantly superior durability as compared with the comparative example was obtained. Further, in the examples of the present invention, the recording property was also excellent.

In the durability test, the type A and the type 1-1 were used.
Was used, but similar results were obtained with other combinations.

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 carriages 72 by pressing members 71.
It is fixed and placed on. Recording head unit 70
Is a so-called disposable type and contains a recording liquid. To move the carriage 72 along the guide member 74, a part of the wire 82 wound between the pulleys 80 and 81 is fixed to the carriage 72, and the motor 84 is moved.
Is performed by drivingly rotating the pulley 81.

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

Reference numeral 90 denotes the recording head unit 70 via the carriage 72.
Is a flexible wiring board connected to the carriage 72 for supplying an electric signal for discharging the recording liquid in the Z direction.

[Advantages of the Invention] According to the present invention as described above, the use of an amorphous material containing a carbon atom as a base material, a silicon atom, a halogen atom, and a hydrogen atom as the heating resistance layer provides High stability, excellent electrochemical reaction resistance, oxidation resistance,
Further, there is provided a liquid jet recording head and a liquid jet recording apparatus which have an electrothermal converter excellent in mechanical shock resistance and heat resistance, and therefore have extremely excellent thermal response and durability against repeated use. According to the present invention, an electrothermal converter having excellent mechanical strength can be obtained.

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

Further, according to the present invention, since the content ratio of silicon atoms, halogen atoms and / or hydrogen atoms in the heat generating resistance layer is changed in the film thickness direction, heat storage properties, heat dissipation properties, support and resistance layer It is possible to easily realize various characteristics such as adhesion and chemical reaction resistance with the recording liquid.

[Brief description of drawings]

1 is a partial plan view of the recording head of the present invention, FIG. 2 is a sectional view taken along the line II-II, and FIG. 3 is a line III-III in FIG.
FIG. 4 to 9 are graphs showing distributions of the content rates of silicon atoms, halogen atoms and / or hydrogen atoms in the heating resistance layer. 10 and 11 are partial cross-sectional views of the substrate having the electrothermal converter of the recording head of the present invention. FIG. 12 is a schematic explanatory view of a deposition apparatus. 13 and 14 are partial perspective views of the recording head of the present invention. 15 to 18 are partial sectional views of the recording head of the present invention. FIG. 19, FIG. 21 and FIG. 23 are perspective views of the substrate having the electrothermal converter of the recording head of the present invention, and FIG.
22 and 24 are cross-sectional views thereof. 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 body, 24: heat generation resistance layer 16, 17: electrode, 18: heat generation part 20: top plate, 24: heat acting part 26: discharge port

 -------------------------------------------------------------------------------------------------------------- ─── Continued Front Page (72) Inventor Hirokazu Komuro 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yasuhiro Yano 3-30-2 Shimomaruko, Ota-ku, Tokyo Kya Non non corporation

Claims (1)

[Claims] 1. An ejection port provided for ejecting a liquid to form flying droplets, and thermal energy used for accommodating the liquid and forming the flying droplets to the liquid. A liquid jet recording head including a heat acting portion for acting and an electrothermal converter provided in the heat acting portion for generating the thermal energy, and a conveyance for conveying a recording medium to which the flying droplets adhere. In the liquid jet recording apparatus having means, the heating resistance layer constituting the electrothermal converter is made of an amorphous material containing carbon atoms as a matrix and containing silicon atoms, halogen atoms and hydrogen atoms, A liquid jet recording apparatus, wherein the content ratio of silicon atoms, halogen atoms and / or hydrogen atoms in the heating resistance layer changes in the film thickness direction.