Ink jet head manufacturing method using ion machining and ink jet head manufactured thereby

Abstract: An ink jet recording head (201) manufacturing method for manufacturing ink jet recording head (201) having an ink passage (109), wherein a droplet of ink is ejected through the passage from an ink ejection outlet (106) at an end of a passage (109) onto a recording material, the improvement comprising: ions are injected into a surface (120) having the ink ejection outlet (106) to change a surface property of the surface (120).

Description: FIELD OF THE INVENTION AND RELATED ART The present invention relates to an ink jet head and a manufacturing method of the ink jet head, the ink jet head ejecting droplets of ink onto a recording material to effect recording images, characters or the like, more particularly to an ink jet head manufacturing method using ion machining method or ion injecting method, and an ink jet head manufactured thereby. It is desired that an ink jet printer can print fine and clear images, characters or the like. Therefore, a micro-lithographic technique has been used to manufacture a great number of fine ejection outlets at high density so as to permit a high speed and high density printing. Figure 1 is a perspective view of an example of an ink jet recording head having been manufactured through such a method. It comprises a base plate 1 having a silicone wafer plate or the like, a heat accumulation layer, a heater an electrode and a protection layer thereon. It also comprises an orifice plate having election outlets of 50 microns diameter manufactured through electrocasting or laser machining. It further comprises ejection outlet 3 and ink supply pipe 4. However, in the ink jet recording system, a further high density ejection outlets are required, more particularly the ejection outlets having a diameter of as small as 20 microns diameter. On the other hand, in the recording head having the conventional ejection outlet density, the accuracy of the ejection outlets are desired to improve the printing performance to meet the demands in the graphic printing field. Figure 2 is a cross-sectional view of the ink jet recording bead of Figure 1 adjacent the ejection outlets. There are shown two examples in which ink droplets 8 are ejected through the ink passages. In Figure 2, (A), the ink droplet is ejected in a proper direction wherein the ejection side surface 9 is not wetted by the ink; whereas in Figure 2, (B), a part of the ejection side surface 9 is wetted by the ink before the ink election, therefore, the ink droplet is ejected in an incorrect direction. The wetting of the election side surface 9 occurs in the following cases. First the ink spreads upon the ink ejection. In the case of an ink jet recording head carried on a carriage, the mechanical vibration or the like during movement in the scanning printing or upon the reversing of the carriage, the inside ink adjacent the nozzle flows out to wet the ejection side surface. When the ink wetting the ejection side surface 9 returns into the passage through the ejection outlet, or when the periphery of the ejection outlet is uniformly wetted, the ink droplet ejecting direction is correct, as shown in Figure 2, (A), and therefore, the ink ejection and therefore the recording operation are stabilized. However, in the prior art ink jet recording head, the ejection side surface 9 is wetted non-uniformly, or the ink remains non-uniformly once it wets the ejection side surface 9, with the result of instable ejection, as shown in Figure 2, (B). There is a significant interrelationship between the wetting of the ejection outlet side surface and the surface condition thereof. If the surface condition of the ejection side surface is not proper, the instable ejection, improper recording and therefore deteriorated record quality, result. This problems arise not only in the ink jet recording head shown in Figure 1 but also in another type ink jet recording head. In the case where the ink ejection outlets are closely disposed with each other as in the case of Figure 1, the peripheral wetting of the ejection outlets may result in wetting which connects the adjacent ejection outlets with the result of more significant influence. As a result, the recorded character may be deformed, or the recorded image may be disturbed, thus remarkably deteriorating the print quality or image quality. Therefore, it is required to strictly control the ejection side surface. In order to accomplish this, it would be considered that the ejection side surface is treated for a water repelling nature, thus preventing the wetting thereof. Many proposals have been made as to the provision of a water repelling material on the ink ejection side surface. For example, water repelling fluorine resin or the like; an organic polymer or the like having a water repelling property is applied by evaporation or sputtering. However, the coating thus produced does not have sufficient adhesion relative to the ejection side surface with the result of possibility of removal thereof from the ejection side surface. Therefore, the durability is a problem. As for the demand far recent ink jet recording apparatus, there is a larger choice of the recording materials, in other words, the printing is possible on any kind of sheets. However, some sheets easily produce paper dust or the like, which may be deposited on the ejection side surface of the ink jet recording head. If this occurs, the ink ejected is influenced by the paper dust or the like with the result of deteriorated printing. Therefore, it is desired that the paper dust or the like is removed. At present, a blade is periodically used to scrape the ejection side surface to remove the paper dust or the like containing the ink droplets. The water repelling material adhered through the above-described conventional process, does not have the sufficient adhesion, and therefore, the usable material for the blade is limited. Therefore, it is desirable to reduce the limitation for the blade material from the standpoint of increasing the design latitude and low cost. It is desirable, therefore, that a durable water-repelling nature is provided on the ejection side surface. The paper dust is more easily deposited on the ejection side surface when the ejection side surface is of electrically insulative nature. This is because the ejection side surface is easily charged electrically, upon which the paper dust is electrostatically attracted. Therefore, the ejection side surface is preferably of electroconductive nature. In an ink jet recording head, the ink liquid ejection responsivity, ejection efficiency or the ejection stability or the like are deteriorated in some cases if a high speed or long term recording is carried out. The reason for this is production of bubbles from the ink in a liquid chamber of the recording head. If they are produced, the motion of the ink is obstructed adjacent fine ejection outlets. In addition, the ink ejecting force provided by ejection energy generating means such as a piezoelectric element or heat generating resistor or the like is absorbed by the bubbles with the result of degraded responsivity. Therefore, the liquid droplets are not stably ejected in response to signals. In a recording head using piezoelectric elements, the abrupt pressure change in the ink by the piezoelectric element may produce cavitation in the ink. In the case of the recording head in which the ink is ejected by thermal energy, the change of state of the ink (production of a bubble by thermal energy) is used for the ejection force of the ink. Therefore, unnecessary bubbles tend to be produced, which significantly influence the ejection responsivity, ejection efficiency and ejection stability or the like. The unnecessary bubbles once produced hardly disappear in the liquid chamber, and the production of the unnecessary bubbles is promoted by the dissolved gasses in the ink. Various methods have been proposed to remove the unnecessary bubbles in the ink. As a method for reducing the content of the dissolved gasses, a hermetically sealed container is used, or an oxygen absorbing material is added in the ink. In another method, a passage for removing the bubbles is used which is in fluid communication with the liquid chamber, at an upper position of the liquid chamber of the recording head, by which the buoyancy of the bubbles is used to trap the bubbles in the upper passage. However, these methods are not satisfactory, as the case may be. For example, even if the ink is contained in a container made of sealing material, the gasses (air) penetrate through the material for a long term to the extent of substantially saturation amount. Addition of the oxygen absorbing material in the ink may result in adverse influence to the natures of the ink. In the case of the recording head in which the ink is ejected by thermal energy, an abrupt state change is advantageous from the standpoint of improving the responsivity and ejection efficiency or the like. From this, the gasses may be positively dissolved in the ink. Therefore, the elimination of the dissolved gasses can not always be the best way. In the case of the provision of the passage for trapping the air bubbles at an upper position of a liquid chamber of the recording head, the bubble motion is dependent solely on the buoyancy. Since the trapping passage is so small that the elimination of the bubble is small. As for the method of eliminating unnecessary bubbles in the liquid chamber, Japanese Laid-Open Patent Application No. 12074/1980 proposes a mechanism for flowing the ink in the liquid chamber. In this method, large bubbles may be easily removed however, the significant cost is imposed on the mechanism to completely remove the fine bubbles, and the size of the apparatus is increased. For the purpose of uniform material around the ejection outlets, provision of the water repelling nature with the ejection side surface and the uniform shapes of the ejection outlets for the stabilization of the ink ejection in the correct direction, there is proposed an ink jet recording head having an orifice plate made of water repelling material. In this head, the back side of the ejection side surface also exhibits the water repelling nature with the result of easy stagnation of the bubbles. If the unnecessary bubbles stagnate, the ejection state becomes instable. Therefore, proper recording state is not maintained, but the record quality is deteriorated. The shape of the ejection outlet is influential to the ink ejection property. In the prior art, the ejection outlet is formed by etching technique. However, this method involves a problem that a straight opening can not be formed, and as a result, the resultant ejection outlet is tapered. Therefore, it is difficult to accurately manufacture the fine ejection outlets. It would be considered to use a thin material in an attempt to improve the accuracy of the ejection outlet, but it would result in impractically insufficient mechanical strength of the orifice plate. In another method, a laser machining is used. However, the shavings produced by the laser machining are deposited around the ejection outlets with the result of degraded print quality. This problem is more remarkable in a high density ink jet recording head. SUMMARY OF THE INVENTION Accordingly, it is the object of the present invention to provide an ink jet recording head and a method for its manufacturing in which substantially constant volumes of droplets can be ejected in a predetermined direction in high speed recording, and the durability is high. It is another goal of the present invention to provide an ink jet recording head which can eject the ink stably with large choice of recording materials. It is a further goal of the present invention to provide an ink jet recording head in which the surface treated for the water repelling property is provided with wear-resistance, thus permitting a larger choice of the blade material. It is a further goal of the present invention to provide an ink jet recording head in which stagnation of a bubble at a portion in contact with the ink is avoided, thus avoiding the reduction of the record quality, thus permitting a stabilized and high speed recording. It is a further goal of the present invention to provide a method of forming ejection outlets with high precision and at high density. With respect to the method, the object is achieved with a method having the features of claims 1 and 12, and with respect to the recording head, it is solved with the features of claims 2 and 11. These and other objects, features and advantages of the present invention will become more apparent upon a consideration of the following description of the preferred embodiments of the present invention taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic perspective view of an example of a conventional recording head. Figure 2 illustrates ink ejection. Figure 3 is a schematic view of a converging ion beam apparatus. Figure 4 is a schematic illustration of ion injector. Figure 5 is a schematic illustration of a DC plasma CVD apparatus. Figure 6 is a perspective view of an example of a recording apparatus to which the present invention is applicable. Figure 7 is a perspective view of an example of a recording head according to an embodiment of the present invention. Figure 8 is a perspective view of a recording head of Figure 7 in which the ejection side surface of the recording head has been machined. Figure 9 is a perspective view of another example of the recording head. Figure 10 shows a blank of the recording head. Figure 11 is a recording head at a step of the manufacturing process thereof. Figure 12 is a recording head at a step of manufacturing the same. Above Figures 10, 11 and 12 illustrate the manufacturing steps. Figures 13A, 13B, 13C, 13D and 13E illustrate manufacturing process of a recording head according to an embodiment of the present invention. Figures 14A, 14B, 14C and 14D illustrate manufacturing steps of a recording head according to another embodiment. Figures 15A and 15B illustrate a recording head according to a further embodiment of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS The description will first be made as to the ion machining method for machining the ejection outlets and an ion injecting method for improving a surface property of an ink ejection side surface and a part of the inside surfaces of the recording head. Ion Machining According to an aspect of the present invention, the ejection outlets are formed in an orifice plate through an ion machining method in which particular ion machining conditions are used in combination. As for an ion machining apparatus, a high intensity converging ion beam apparatus (FIB) is used. Referring to Figure 3, there is shown a basic structure of FIB. As shown in this Figure, the FIB comprises, in the vacuum, an ion source 11, a mass spectrograph 12, an objective lens 15, a beam scanning system constituted by elements 16, 17, 18 and 20, and a secondary electron detector 21. The secondary electron detector 21 functions to detect the secondary electrons emitted by FIB irradiation to permit observation and machining position detection of the material to be machined. In order to apply the FIB for formation of ink jet recording head, novel machining conditions are selected according to the present invention. The conditions will be described. As for the machining ion source, high intensity liquid metal is used, examples of which include Ga, Al, Si-Au, Ge-Au or another low melting point metal, or alloy thereof. When the alloy is used, the vapor pressure and the melting point are substantially equivalent to those of the non-alloy metal. As for the ions provided by the ion source, Ga + , Al + , Au + and Ge + or the like. The ion accelerating voltage is 100 - 300 keV, preferably 150 - 200 keV. The 300 keV limit is determined from the performance limit of the FIB, and if the accelerating voltage is larger than that, the substrate will be overheated. The 100 keV limit is determined from the machinability. Larger ion beam diameter is preferable from the standpoint of larger beam current and therefore higher etching speed, but correspondingly, the accuracy decreases. Therefore, the beam diameter is determined on the basis of the required accuracy. Here, the ion beam diameter is 0.5 - 50 microns, preferably 1 - 5 microns. If it is smaller than 0.5 micron, the sufficient etching speed is not provided, and on the contrary, if it is smaller than 50 microns, the machining of fine ejection outlets with the sufficient accuracy becomes difficult. The ion current 100 - 10,000 pA, preferably 100 - 5,000 pA. If it is smaller than 10 pA, the sufficient etching speed is not provided. If it is larger than 10,000 pA, the ion stability is deteriorated. The material in which the ejection outlets are formed through the ion machining, may be any if it it a structural member. Among metals, Ni or SUS is preferable. Among inorganic material, Si glass is preferable. Among resin materials, polysulfone or the like is preferable. The present invention using the FIB is advantageous in: (1) that the ion etching is possible without registration; (2) that the linearity of the ion beam is so good that the cross-sectional shape of the machined part is perpendicular. In an aspect of the present invention, the orifice plate having the ejection outlets formed by the ion machining or the orifice plate before the ion machining process, is given the water repelling nature by ion injection process. In this invention, the order of formation of ejection outlets of ion machining process and the water repelling treatment by the ion injection, is not limited. Ion Injection In an aspect of the present invention, a surface layer is formed on the ejection side surface, and thereafter, the ions are implanted into the surface layer, thus providing the water repelling property. This is advantageous in that: (1) It is not necessary that the surface layer is of a water repelling material, and therefore, the material of the surface layer can be selected from various materials irrespective of the water repelling nature: (2) Since the material may not exhibit the water repelling nature, the material may be selected from the material exhibiting high adhesion to the ejection side surface: (3) Since the ions are implanted into the surface layer, the adhesion between the surface layer and the ejection side surface can be further improved: (4) The surface property of the surface can be improved by the ion injection: (5) The surface layer may be given electro-conductivity by the ion injection, so that the paper dust or the like is prevented from being deposited on the ejection side surface: and (6) Since the ions are injected after formation of the surface layer, the smoothness and the water repelling nature of the ejection side surface is uniform, and therefore, the proper ink ejection is possible, even if the ejection side surface is of a plurality of materials. According to an aspect of the present invention, the combination of the surface layer and the injected ions, the adhesion, surface hardness and the conductivity can be properly provided. The material constituting the surface layer is selected from the material which is durable against the high temperature during the ion injection and which is securedly adhered to the ejection side surface after the ion injection. Particularly, the usable metals include Au, Ni, Cr, Ti, Al, Ta, W, V or the like. The usable inorganic materials include SiO 2 , Ta 2 O 5 , Ta 2 n, BN or the like. These materials or organic materials are preferable because they exhibit high adhesion property relative to an organic or inorganic compound of the ejection side surface, such as semiconductor (Si or the like), glass, ceramic material, oxide of semiconductor material, organic polymer or organic resin. The preferable surface layer forming methods include evaporation method, sputtering method, CVD method or other vacuum film forming method. Among them, sputtering method is preferable from the standpoint of the adhesion property. The surface layer may be formed by painting or spray method. In this case, if the heating operation is carried out after the painting, the adhesion is improved. The film thickness of the surface layer is 0.05 - 5 microns, preferably 0.1 - 3 microns, because if it is larger than 5 microns, the remaining stress is large with the result of easy removal of the film, and if it is smaller than 0.05 micron, the desired nature of the film is not provided. In this invention, the water repelling property is given by the ion injection into the surface layer thus formed. The ion injection method will be described. In the ion injection method, ions accelerated to 10 - several hundreds keV, are applied to the surface of a solid material to control the nature of the surface. This ion injection method is used for the purpose of formation of diffused layer by impurity doping for a semiconductor device or for the purpose of adjustment of carrier density. In addition, in an attempt to improve the surface nature of metal (for example, hardness or wear resistance improvement in a drill), the investigations are carried out. Figure 4 shows a typical structure of an ion injector. The ions are produced in an ion source 11. The ions are extracted from plasma provided by DC or RF discharge in the gas of approx. 10 -3 Torr. The extracted ion beam contains atom ions, molecule ions, residual gas ions and others, and therefore, only the required ions are extracted by means of mass spectrograph 12. The spectrograph 12 is not necessarily required. In the case of improvement of the surface nature of the metal, it is hardly used. On the other hand, in the case of semiconductor device manufacturing, they are usually employed. The required ions selected by the mass spectrograph 12 are passed through a beam slit 13, an accelerator 14, a lens 15, a neutral beam trap, and a gate 16. Thereafter, the ion beam is scanningly deflected relative to X axis and Y axis by a Y scanner 17 or X scanner 18 to uniformly scan the substrate 19 such as wafer. Designated by reference numeral 20 is a beam trap. In another ion injector, the material supporting table is rotated to effect the uniform injection. Since the water repelling property treatment using the ion injection, improves the nature of the surface, and therefore, the adhesion is satisfactory as compared with the method in which a coating layer is formed on the surface. In addition, since the injecting ions can be selected, the hardness and the electroconductivity as well as the water repelling property can be provided. The ion source for giving the water repelling property is in the form of a gas under the normal or reduced pressure. The usable ones include: (1) Gasses containing at least C and F such as CF 4 , C 2 F 6 , CHF 3 or the like: (2) A combination of gas containing F and gas containing C, as represented by a combination of F gas and methane gas: (3) F gas only, when the material in which the ions are injected contains C. The usable ions extracted from the ion source include: (1) Ions containing C and F, as represented by CF 3 + , C 2 F 6 + , C 2 F 3 + or the like: (2) A combination of F + and C + : and (3) F + only, when the material into which the ions are injected contains C. As for the ion source for increasing the surface hardness of the ejection side surface, contains N gas, Si containing gas such as SiF 4 , SiCl 4 or the like, a combination of BCl 3 gas and NH 3 gas, or the like. They are in the form of a gas under the normal or reduced pressure. The usable ions extracted from the ion source include N + , Si containing ion such as Si + or SiCl 3 + or the like, a combination of B + and N + . The usable ion source for giving the electroconductivity contains metal compound which is in the form of a gas under the normal or reduced pressure such as (C 2 H 5 ) 3 Al, WF 6 , MoCl 5 or the like. The usable ions extracted from the ion source include metal ions such as Al + , N + Mo + , W + or the like. The ion accelerating voltage is 5 - 100 keV, preferably 10 - 60 keV. The distribution of the injected ions in the material is in the form of a Gaussian distribution, and therefore, there is an optimum value of the ion accelerating voltage in the above mentioned range. If it is smaller than 5 keV, the stability of ion acceleration is lost. If it is larger than 100 eV, the ions go into too deeply, and therefore, the efficient surface improvement is deteriorated, and the surface may be overheated. The dose amount is 1x10 14 - 1x10 8 cm -2 , preferably 1x10 15 - 1x10 17 cm -2 . If it is smaller than 1x10 14 cm -2 , the water repelling property is not sufficient. If it is larger than 1x10 18 cm -2 , the material will be overheated. The water repelling property by the ion injection can be effected to any material constituting the ink jet recording head, such as organic compound or inorganic compound such as semiconductor (Si or the like), glass, ceramic material, oxide of semiconductor, organic polymer or organic resin material. After the ion injection process, a heating process may be carried out for the purpose of enhancing the water repelling nature. The ion injection method for the surface property improvement is not limited to the type described above. For example, a DC plasma CVD method or the like is usable. Figure 5 shows an example of the DC plasma CVD apparatus. In a chamber 31, there are provided an anode 32 and a cathode 33, with which a DC voltage source 34 is connected. A gas is supplied to them through a mass flow 36 from a gas container. An exhaust system comprises a gate valve 37, a turbo molecular pump 38 and a rotary pump 39. On the cathode 33, the recording head 40 is placed with the ejection side surface facing up. The gasses usable for the purpose of the surface property improvement, include any gasses that contain C and F such as CF 4 , C 2 F 6 , CHF 3 or the like, which is in the form of a gas under the normal or reduced pressure. The operating conditions are 0.1 - 5 Torr gas pressure, 0.05 - 10 mA/cm 2 current, preferably. The water repelling property by the ion injection according to the present invention provides the following advantages: (1) The surface hardness of the ejection side surface of the orifice plate can be increased: and (2) The ejection side surface of the orifice plate can be given the electric conductivity. The ion machining apparatus of Figure 3 and the ion injector apparatus of Figure 4 are both operated under high vacuum, a converging ion beam function may be added to the ion injector, thus permitting continuous processing operations. More particularly, if the performance of the beam scanning system and the objective lens in the ion injector is improved, and if the secondary electron detecting system is added, both of the ion machining and the ion injection can be carried out by a single apparatus although ion source is to be exchanged. In this case, the ejection side surface formation and the water repelling treatment can be contemporaneously carried out. In the foregoing the description has been made as to the water repelling property given by the ion injection method. However, if the ions to be injected are changed, the hydrophilic nature can be easily given. In this case, the ions may be any if they give the hydrophilic property. They include O + , H + , Au + or the like. They may be used alone or in combination. The operating conditions in the ion injection, are the same as have been described in connection with the water repelling property treatment. Referring to Figure 6, there is shown an example of an ink jet recording apparatus IJRA loaded with an ink jet head cartridge IJC having a recording head according to an embodiment of the present invention. The ink jet head cartridge is indicated by a reference numeral 1120 and is provided with a plurality of nozzles for ejecting the ink onto a recording surface of a fed recording material. It is supported on a carriage 1116, which is connected with a part of a driving belt 1118 for transmitting the driving force from a driving motor 1117. The carriage 1116 is slidably supported on two guiding shafts 1119A and 1119B extended in parallel with each other, so that reciprocating movement is possible to cover the entire width of the recording sheet. A recording head recovery device 1126 is disposed at an end of a reciprocation path of the ink jet cartridge 1120, for example a home position. By the driving force of the motor 1122, the head recovery device 1126 is operated through a transmission mechanism 1123, and the ink jet cartridge 1120 is capped. In interrelation with the capping action, the ink is sucked by sucking means in the head recovery device 1126, or the ink is pressure-fed by suitable pressure means disposed in the ink supply passage to the ink jet cartridge 1120, so that the ink is forcedly discharged through the ejection outlets, by which the viscosity increased ink is removed from the nozzle. Upon the completion of the recording operation, the head is capped to protect the ink jet recording head. A wiping member in the form of a blade 1130 is disposed at a side of the head recovery device 1126 and is made of silicone rubber. The blade 1130 is supported in a canti-lever supporting manner on a blade supporting member 1130A. Similarly to the head recovery device 1126, it is operated by the motor 1122 and through the transmission mechanism 1123 to permit engagement with the ejection side surface of the ink jet head cartridge 1120. Thus, at proper timing in a recording operation of the ink jet cartridge 1120, or after the ejection recovery process operation using the head recovery device 1126, the blade 1130 is projected into the moving path of the ink jet cartridge 1120, so that the dew water, the ink, the dust or the like is removed from the ejection side surface of the ink jet cartridge 1120 during the movement thereof. The embodiments of the present invention will be described. First, an embodiment in which the ions are injected into the ejection side surface to provide the water repelling property. Referring to Figure 7, a line recording head is treated for the water repelling property. The recording head is manufactured in the following manner. A lower SiO 2 layer is formed on a first substrate in the form of a silicon wafer 51, and a heat generating element 52 (ejection pressure generating element) is formed thereon. Further thereon, nozzle walls 53 are formed of photosensitive acrylic resin material through photolithography. An acrylic resin material is applied as a bonding layer 55 on a second substrate 54 of glass, and it is bonded on the nozzle walls 53. Finally, the first substrate 51, the nozzle walls 53 and the second substrate 54 are simultaneously cut, thus forming the ejection outlets 56. At the ejection side surface 59, there are four materials, namely, silicon, SiO 2 , acrylic resin material and glass. Such an ejection side surface 59 is treated for the surface property improvement under the following conditions. Embodiment 1 The ejection side surface 59 of the head shown in Figure 7 was coated with Ni with the thickness of 0.2 micron through evaporation method. For the purpose of water repelling property, C 2 F 4 + ions are injected into the ejection side surface 59 in a direction perpendicular thereto with the acceleration energy of 20 keV and with dose of 1x10 16 cm -2 . In this manner, a recording head having been treated for the water repelling property at the ejection side surface thereof, has been manufactured as shown in Figure 8. Embodiment 2 Similarly to Embodiment 1, the Ni layer is formed on the ejection side surface 59 of the recording head. Subsequently, C 2 F 4 + ions for providing the water repelling nature were injected into the ejection side surface 59 in a direction perpendicular thereto with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 . Then, in order to enhance the surface hardness, N + ions are injected under the same conditions with the acceleration energy of 20 keV but with the dose of 2x10 16 cm -2 . Embodiment 3 Similarly to Embodiment 1, the Ni layer is formed on the ejection side surface 59 of the recording head, and then, C 2 F 4 + ions are injected into the ejection side surface 59 with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 in the direction perpendicular to the ejection side surface to provide the ejection side surface 59 with the water repelling property. Subsequently, in order to provide the surface with the electroconductivity, Al + ions are similarly injected with the acceleration energy of 20 keV and the dose of 1x10 15 cm -2 . Embodiment 4 Similarly to Embodiment 1, the Ni layer is formed on the ejection side surface of the recording head, and then, C 2 F 4 + ions are injected in the direction perpendicular to the ejection side surface 59 with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 to provide the surface with the water repelling property. Subsequently, in order to enhance the surface hardness of the ejection side surface, N + ions are injected in the similar direction with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 . Additionally, in order to provide the ejection side surface with the electroconductivity, the Al + ions are injected in the same conditions with the acceleration energy of 20 keV and the dose of 1x10 15 cm -2 . Embodiment 5 The ejection side surface of a recording head having the heat generating elements as shown in Figure 7 is coated with carbon through a sputtering method up to 0.2 micron. Subsequently, in order to provide the surface with the water repelling property, F + ions are similarly injected with the acceleration energy of 40 keV and the dose of 5x10 16 cm -2 . Embodiment 6 Ejection outlets are formed through photolithographic in an orifice plate 2 of stainless steel having the structure shown in Figure 1. It is coated with carbon through sputtering method up to 0.2 micron. Subsequently, the orifice plate surface is injected with F + ions with the acceleration energy of 40 keV and the dose of 5x10 16 cm -2 to give the water repelling property. The orifice plate is bonded to the ink jet recording head substrate having the nozzle walls or the like formed therein. Figure 9 shows the thus manufactured recording head. Comparison Example 1 A recording head as shown in Figure 8 has been manufactured through a process similar to that of Embodiment 1 except that fluorine resin material (DEFEN7710, trade name available from DIK) has been transferred onto the ejection side surface by rubber elastic material transfer method. The ink ejecting operations were carried out with the above-described recording heads under the following conditions: Signal pulses: Pulse width: 10 µsec Pulse frequency: 3 kHz Applied energy: 0.02 mJ/pulse (per heat generating element) Ink: Water: 70 % Diethylene glycol: 26 % Direct Black: 4 % Under these conditions, stabilized ejection and accurate record positions could be maintained over more than 10 9 pulses. In the ink jet recording head having the ejection side surface treated in accordance with the above-described embodiments, the ejection side surface is not non-uniformly wetted, and therefore, the ink droplet ejecting direction is stabilized, so that the high quality prints and images can be produced. The ink jet recording head of the foregoing embodiments are loaded in a printer, and the ejection side surface is wiped a plurality of times by urethane rubber blade, silicone rubber blade, and butyl rubber blade, and the printing performance is evaluated thereafter. Table 1 shows the results when the urethane rubber blade is used. Results of Wiping Test Level 1 Level 2 Level 3 Embodiments 1, 3, 5 & 6 G G N Embodiments 2 & 4 G G G Comp. Example N N N Level 1: 2000 wiping operations Level 2: 10000 wiping operations Level 3: 30000 wiping operations Evaluation G: Good Evaluation N: Improper print (shot position deviation is remarkable) The above results are same-with the other blade materials. This is because of the increase of the strength of the ejection side surface and the increase of the wear-resistance thereof. For this reason, the design latitude is enhanced, and the cost reduction is possible. The recovery operation of rubbing the ejection side surface of the recording head loaded in the recording apparatus by rubbing with sponge, was carried out a plurality of times, and the print performance is evaluated. Table 2 shows the results. Level 1 Level 2 Level 3 Embodiments 1, 3, 5 & 6 G G N Embodiments 2 & 4 G G G Comp. Example G N N Level 1: 100 recovery operations Level 2: 500 recovery operations Level 3: 1000 recovery operations Evaluation G: Good Evaluation N: No good (remarkable shot position deviation) As will be understood from Table 2, the water repelling property is not deteriorated in the tests in which contact type recovery means is used. Therefore, the contact type recovery system is usable. Therefore, the recovery operation is assured. Even when the ejection side surface is made of a plurality of materials, the smoothness and the water repelling property of the ejection side surface is uniform because the ions are injected after the ejection side surface is constituted. Therefore, very good ejection is possible. By ion injection of F + ions after the formation of the carbon coating on the ejection side surface as in Embodiments 5 and 6, the sufficient water repelling nature could be given even with the material exhibiting difficulty in providing the water repelling nature only by the ion injection. In Embodiments 2 - 4, the properties other than the water repelling property are provided to the ejection side surface. In the recording head of Embodiment 2, the water repelling property is given by C 2 F 4 + ions. In addition, by the injection of N + ions, the mechanical strength of the nozzle walls of the resin material at the ejection side surface, the bonding layer and the orifice plate, is enhanced. Accordingly, the durability has been improved more than in Embodiment 1. Furthermore, the resistances of the ejection side surfaces of the recording heads manufactured in accordance with the Embodiments and Comparison Example, were measured. In the recording heads of Embodiments 1, 2 and 5 and the Comparison Example, the resistances are in the range of 10 13 - 10 14 ohm/□. On the other hand, in the recording heads of Embodiments 3 and 4, they are within the range of 10 8 - 10 10 ohm/□. With the recording head of Embodiment 3, the water repelling property is given by C 2 F 4 + ions. In addition, the Al + ions are injected, by which the electroconductivity is given to the ejection side surface. By doing so, the ejection side surface is not easily electrostatically charged with the result that the paper dust or the like are not easily deposited. Therefore, the improper printing due to the paper dust or the like has been reduced. As regards the recording head of Embodiment 4, the further advantageous effects are provided by the combinations of Embodiments 2 and 3. As described in the foregoing, the ink jet recording head provided with the water repelling property at the ejection side surface by the ion injection method, is capable of stably ejecting the ink in a predetermined direction at all times with substantially uniform volumes of the liquid, and therefore, the high speed recording is possible. By injecting the ions after formation of the surface layer, the choice of the materials of the surface layer and the choice of the ions are large. Therefore, a high hardness ejection side surface can be provided, so that the choice of the material of the blade for removing the paper dust or the like becomes larger. Additionally, a contact type recovery system for removing the foreign matter or ink which can not be removed by the blade, is usable. By the electroconductivity of the ejection side surface provided by the ion injection, the paper dust or the like is not easily deposited thereon, so that the number of removing operations can he reduced, thus permitting high speed long term printing. As a result, the durability of the ink jet recording head is improved, and the choice of the printing or recording materials becomes larger. Embodiment 7 Similarly to Embodiment 1, C + ions are injected into the ejection side surface of the recording head in a direction perpendicular thereto with accelerating energy of 20 keV and the dose of 1x10 16 cm -2 . Subsequently, in order to provide the water repelling property, F + ions are similarly injected with the acceleration energy of 20 keV and the dose of 2x10 16 cm -2 . Embodiment 8 The water repelling treatment has been effected to the ejection side surface of the orifice plate 2 of the recording head used in Embodiment 6, under the same conditions as in Embodiment 1, with the exception that Ni layer is not formed. Embodiment 9 The water repelling property treatment has been effected to the ejection side surface of the orifice plate 2 of the head used in Embodiment 6, under the same conditions as in Embodiment 7. Embodiments 10 - 12 The water repelling property treatment has been effected to the ejection side surface of the orifice plate used in Embodiment 6 under the same conditions as in Embodiments 2 - 4, with the exception that the Ni layer is not formed. The ink ejection tests are carried out with the above-described recording heads under the following conditions: Signal pulses: Pulse width: 10 µsec Pulse frequency: 3 kHz Applied energy: 0.02 mJ/pulse (per heat generating element) Ink: Water: 70 % Diethylene glycol: 26 % Direct Black: 4 % It has been confirmed that the stabilized ejection with high shot position accuracy could be maintained over more than 10 9 pulses. The ejection side surface of the recording head which has been treated according to each of the above-described embodiments, is not non-uniformly wetted, and therefore, the ejection direction thereof is stabilized, so that the high print quality can be provided. The ink jet recording head of these embodiments are loaded in a printer, and the printing operations are carried out. As a result, the strength of the water repelling surface against the blade for removing the paper dust or the like, has been improved, and the wear-resistance is improved, and therefore, various materials are usable for the blade. Thus, the latitude of the design is increased, and the cost can be reduced. In addition, when the contact type recovery system is used, the water repelling property does not decrease, and therefore, the contact type recovery system is usable. Thus, the recovery operation is assured. In the case that N + ions are injected, the mechanical strength of the ejection side surface has been improved. When the Al + ions are injected, the electroconductivity is given to the ejection side surface, so that the triboelectric charge can be suppressed with the result that the paper dust is not easily deposited. Embodiment 13 The ion injection is possible using a CVD apparatus shown in Figure 5 in place of the apparatus shown in Figure 4. In the embodiment, the initial vacuum is 7.10 -7 (7E - 7) Torr and the distance between the electrodes was 60 mm with the diameter of the electrodes being 30 cm. The discharge was carried out under the conditions shown in Table 3. The recording head used was the same as in Embodiment 1. As a result of electric discharge under these conditions, the recording head was not etched or charged, and therefore, the surface property improvement and the water repelling property were confirmed. Using such a recording head, the ink ejection tests were carried out with the following signal pulse conditions: Printing pulse: 10 µsec Pulse frequency: 3 kHz Print energy: 0.02 mJ/pulse (per heat generating element) As a result, the stabilized ejections with correct ink shot positions can be maintained over more than 10 9 ejections. Experimental Conditions Gas C 2 F 6 Volt. source 400 mA Const. Gas pressure 0.7 Torr Gas flow 70 sccm Discharge time 30 min. The ink ejection outlets of the ink jet recording head having the ejection side surface treated in accordance with this embodiment, is not wetted non-uniformly, and therefore, the ink droplet ejection direction is stabilized, and the print and image qualities were good. Embodiment 14 The experiment conditions were as follows: Experimental Conditions Gas CF 4 /H 2 (80 %) Volt. source 400 mA Const. Gas pressure 0.5 Torr Gas flow 50 sccm Discharge time 30 min. At shown in Table 4, a mixture gas of CF 4 and H22 was used, and the similar experiments as in Embodiment 13 were carried out. Under these conditions, satisfactory water repelling property, durability of the property and the print durability were satisfactory. Embodiment 15 Experiment conditions were as follows: Experimental Conditions Gas CHF 3 Volt. source 400 mA Const. Gas pressure 0.9 Torr Gas flow 50 sccm Discharge time 40 min. The sufficient water repelling properties, and the durabilities of the properties, and the print durabilities were satisfactory with these conditions. Embodiment 16 Experimental Conditions Gas CHF 3 , H 2 Volt. source 400 mA Const. Gas pressure 0.4 Torr Gas flow CHF 3 : 10 sccm H 2 : 40 sccm Discharge time 60 min. Two gas containers for CHF 3 and H 2 were used as shown in Table 6, and the experiments have been carried out as in Embodiment 13. The sufficient water repelling property, the durability of the property, and the print durability were satisfactory with these conditions. With respect to these recording heads, the following evaluations were made. (1) Blade Wiping Test The ejection side surface was wiped a plurality of times by urethane blade, and the printing operations were carried out thereafter. The results are shown in Table 7. Level 1 Level 2 Level 3 Embodiments 7, 8, 9, 11, 13 14, 15 & 16 G G N Embodiments 10 & 12 G G G Level 1: number of wiping operations: 2000 Level 2: number of wiping operations: 10000 Level 3: number of wiping operations: 30000 Evaluation G: Good printing Evaluation N: Improper printing (remarkable deflection) (2) Recovery Test Rubbing recording operation was carried out a plurality of times by sponge (trade name: Belclean), and thereafter, the printing operations were carried out, and the prints were evaluated. The results are shown in Table 8. Level 1 Level 2 Level 3 Comp. Example G N N Embodiments 7, 8, 9, 11, 13 14, 15 & 16 G G N Embodiments 10 & 12 G G G Level 1: number of wiping operations: 100 Level 2: number of wiping operations: 500 Level 3: number of wiping operations: 1000 Evaluation G: Good printing Evaluation N: Improper printing (remarkable deflection) (3) Electric Conductivity The electroconductivity of the part for which the surface property is improved by ion injection, was measured. The results are shown in Table 9. Conductivity Embodiments 7, 8, 9, 11, 13 14, 15 & 16 10 13 - 10 14 Ω/□ Embodiments 10 & 12 10 8 - 10 10 Ω/□ As described in the foregoing, according to the present invention, the ions are injected into the ejection side surface of an ink jet recording head to improve the surface property. With this ion injection method, the material of the ejection side surface is improved, and therefore, the adhesion is maintained satisfactory. By properly selecting the ions to be injected, the hardness as well as the water repelling property is improved, and an electroconductivity can be given. In addition, the property of the surface can be improved in any material, the improvement can be effectively made even when the ejection side surface is made of different materials. The recording head manufactured through the above-described process can stably eject a substantially constant volume in a predetermined direction at all times, and the high speed recording is sufficiently carried out with satisfactory durability. In addition, such an ink jet recording head does not choose the recording material. More particularly, the following advantages can be provided by the provision of the ejection side surface having the water repelling property by the surface property improvement: 1. Print durability. 2. Durability against blade for removing the paper dust or the like. 3. A contacting recovery system is usable. By increasing the hardness of the surface by the surface improvement, the above-described advantages can be enhanced. By providing the ejection side surface with the electroconductivity, the paper dust or the like is not hardly deposited on the ejection side surface. When the surface improvement is made by using CVD, the recording head having excellent durability of the water repelling property can be manufactured by less expensive apparatus. When Rf P-CVD apparatus is used for forming film on the recording head, what is required is to exchange the voltage source only. In addition, the simultaneous processing is possible for the part corresponding to the area of the cathode, is possible, and therefore, the productivity is high. The description will be made as to embodiments in which the ejection side surface is provided with the water repelling property by ion injection, and the ejection outlets are formed by ion machining. Embodiment 17 As shown in Figure 10, C 2 F 4 + ions injected for providing the water repelling nature were injected into an orifice plate 62 surface 69 made polysulfone resin with an acceleration energy of 20 keV, and the dose of 1x10 16 cm -2 in a direction perpendicular to the surface. By doing so, the orifice plate shown in Figure 11 is provided with the surface treated for the water repelling property. Subsequently, using FIB shown in Figure 3, the etching operation is carried out by etching ions Ga + with the acceleration energy of 200 keV, the beam diameter of 1 micron and beam current of 500 pA. The ejection outlets 63 of 15 microns diameter were formed at 30 microns pitch, as shown in Figure 12. In this embodiment, the ion injection and the ion machining were carried out by different. apparatuses. However, as described in the foregoing, both apparatuses may be combined into one apparatus, and it is advantageous in the mass-production. The orifice plate was bonded to an ink jet recording head having nozzle walls or the like therein to provide the ink jet recording head shown in Figure 1. Embodiment 18 The C + ions are injected into the orifice plate surface 69 with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 in the direction perpendicular to the surface of the orifice plate. Subsequently, the F + ions are injected with the acceleration energy of 20 keV and the dose of 2x10 16 cm -2 to provide the ejection side surface with the water repelling property. In the ink jet recording head was thus produced with the other conditions being the same as in Embodiment 16. Embodiment 19 The water repelling property providing C 2 F 4 + ions are injected into the orifice plate surface with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 in the direction perpendicular to the surface of the orifice plate. In order to improve the surface hardness, N + ions are injected in the similar condition with the acceleration energy of 20 keV and the dose of 2x10 16 cm -2 . The ink jet recording head was produced in the similar manner as in Embodiment 1 in the other respects. Embodiment 20 To provide the orifice plate surface 59 with the water repelling property, C 2 F 4 + ions are injected perpendicularly into the orifice plate surface with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 . In order to provide it with the electroconductivity, Al + ions are similarly injected with the acceleration energy of 20 keV and the dose of 1x10 15 cm -2 . The ink jet recording head was produced in the similar manner as in Embodiment 16 in the other respect. Embodiment 21 In order to provide the orifice plate surface 59 with the water repelling property, C 2 F 4 + ions are injected into the orifice plate in the direction perpendicular thereto with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 . Subsequently, in order to improve the surface hardness, N + ions are injected similarly with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 . Furthermore, in order to provide it with the electroconductivity, Al + ions are similarly injected with the acceleration energy of 20 keV and the dose of 1x10 15 cm -2 . The ink jet recording head was produced in the similar manner as in Embodiment 16 in the other respects. Those recording heads were operated with the following conditions: Signal pulses: Applied pulse width: 10 µsec Pulse frequency: 3 kHz Applied energy: 0.01 mJ/pulse (per heat generating element) Ink: Water: 70 % Diethylene glycol: 26 % Direct Black: 4 % It has been confirmed that the ejection outlets are arranged at such a high density as 30 microns pitch, the stabilized ejection with accurate shot position can be obtained over more than 10 9 pulses. In the ink jet recording head having the ejection side surface treated in the manners described in the foregoing embodiments, the ejection side surface is not wetted non-uniformly, and therefore, the ink droplet ejection direction is stabilized, so that high print and image quality can be provided. The highly accurate machining by the ion machining for the ejection outlets and the perpendicular shape in the cross-section, can provide proper ejection, and therefore, high printing and image qualities. The ink jet recording heads according to Embodiments 17 - 21, are loaded in a printer, and the ejection side surface was wiped a plurality of times by a blade of urethane rubber, silicone rubber and butyl rubber. Then, the printing performance was evaluated (blade wiping test). Table 10 shows the results of test. Level 1 Level 2 Level 3 Embodiments 17, 18 & 20 G G N Embodiments 19 & 21 G G G Level 1: number of wipings: 2000 Level 2: number of wipings: 10000 Level 3: number of wipings: 30000 Evaluation G: Good printing Evaluation N: Improper printing (remarkable deflection) The results are the same as with the other blade. This is because the strength of the water repelling surface of the recording head is improved, and the durability is improved. Therefore, the latitude of the design is increased, and the cost can be reduced. Furthermore, sponge is contacted to the ejection side surface of the recording head in a recording apparatus, and the ejection side surface was subjected to the recovery operation using the sponge a plurality of time, and the evaluation was made. The results are shown in Table 11. Level 1 Level 2 Level 3 Embodiments 17, 18 & 20 G G N Embodiments 19 & 21 G G G Level 1: number of recovery operations: 100 Level 2: number of recovery operations: 500 Level 3: number of recovery operations: 1000 Evaluation G: Good printing Evaluation N: Improper printing (remarkable deflection) As will be understood from Table 11, the water repelling property is not deteriorated in the contact type recovery system using tests. Therefore, the contact type recovery system is usable. Thus, the recovery operation is assured. According to Embodiments 19 - 21, the surface hardness is improved, and the conductivity is given, in addition to the water repelling property of the ejection side surface. The description will be made in this respect further. In the recording head of Embodiment 19, the water repelling property is given by C 2 F 4 + ions. In addition, by the injection of N + ions, the mechanical strength of the nozzle walls of the resin material at the ejection side surface, the bonding layer and the orifice plate, is enhanced. Accordingly, the durability has been improved more than in Embodiments 17 and 18. Furthermore, the resistances of the ejection side surfaces of the recording heads manufactured in accordance with the Embodiments 17 - 21, were measured. In the recording heads of Embodiments 17, 18 and 19, the resistances are in the range of 10 13 -10 14 ohm/□. On the other hand, in the recording heads of Embodiments 20 and 21, they are within the range of 10 8 - 10 10 ohm/□. With the recording head of Embodiment 20, the water repelling property is given by C 2 F 4 + ions. In addition, the Al + ions are injected, by which the electroconductivity is given to the ejection side surface. By doing so, the ejection side surface is not easily electrostatically charged with the result that the paper dust or the like are not easily deposited. Therefore, the proper printing could be maintained for a long term. As regards the recording head of Embodiment 20, the further advantageous effects of printing performance and durability are provided by the combinations of Embodiments 17, 19 and 20. As described, the high density and high accuracy and fine ejection outlets can be formed by the ion machining. By adjusting the ion beam diameter, the ejection outlets without taper can be formed, and therefore, a high quality printing is possible with a high density of dots. As described in the foregoing, the ink jet recording head provided with the water repelling property at the ejection side surface by the ion injection method, is capable of stably ejecting the ink in a predetermined direction at all times with substantially uniform volumes of the liquid, and therefore, the high speed recording is possible. By injecting the ions which provides high ejection side surface, the choice of the materials of the surface layer and the choice of the ions are large. Therefore, a high hardness ejection side surface can be provided, so that the choice of the material of the blade for removing the paper dust or the like becomes larger. Additionally, a contact type recovery system for removing the foreign matter or ink which can not be removed by the blade, is usable. By the electroconductivity of the ejection side surface provided by the ion injection, the paper dust or the like is not easily deposited thereon, so that the number of removing operations can be reduced, thus permitting high speed long term printing. As a result, the durability of the ink jet recording head is improved, and the choice of the printing or recording materials becomes larger. The description will be made as to Embodiments in which at least a part of ink contacting portion of the inside of the recording head is treated for hydrophilic property to prevent the bubble or bubbles stagnating inside the recording head so as to improve the ejection performance. Figure 13A is a perspective view of an ink jet recording head which has been treated for the hydrophilic property. In Figure 13A, the ink jet recording head comprises a substrate 102, ejection outlet 106, and an ink supply port 107. Figure 13B is a sectional view taken along a line A-A in Figure 13A. In Figure 13B, reference numeral 103 is a heater for ejection energy generation: 104 is a liquid chamber; and 109 is ink passages. In this invention, at least part of the ink jet recording head which is in contact with liquid. i.e., liquid chamber portion 104 of the top plate 105, the ink passage 109 or the like, is given the hydrophilic property by ion injection method. In this case, the material constituting the liquid contact portion may be a semiconductor (Si or the like), glass, ceramic material, oxide, nitride, carbide of semiconductor or organic compound such as organic polymer, or inorganic compound. Figure 14A shows an example of the recording head having an orifice plate 108 having ejection outlet 106 at an end of passages 109. The orifice plate 108 is of water repelling material. The backside 120 of the ejection outlets 106 of the plate 108 has been treated for the hydrophilic property, and therefore, the bubble does not stagnate at the joint portion 121 between the top plate 105, the substrate 102 and the orifice plate 108. The hydrophilic material is preferably eutectic plating of Teflon (trademark) fine particles and metal, such as Kaniflon (available from Japan Kanigen, Japan), or fluorine resin material such as Teflon, Cytop (available from Asahi Glassu Kabushiki Kaisha, Japan) or Defensa (Dainippon Ink Kogyo Kabushiki Kaisha, Japan). Embodiment 22 As shown in Figure 13A and 13B, a lower layer in the form of SiO 2 layer (not shown) is formed on a silicon wafer substrate 102. On the lower layer, ejection energy generating elements 103 are formed. Subsequently, nozzle walls 111 are formed with photosensitive acrylic resin material through photolithographic system on the lower layer (Figure 13E). As shown in Figure 13C, a top glass plate 105 is formed with the ink supply port 107 and with the recess 104' for providing the liquid chamber 104. Subsequently, O + ions are injected into the recess surface 104' with the acceleration voltage of 30 keV and the dose of 5x10 16 cm -2 . Then, a plate 105 of glass is bonded on the nozzle walls 111. Finally, the substrate 102, the nozzle walls 111 and the glass top plate 105 are simultaneously cut to form the ejection outlet 106. The recording head thus manufactured exhibit the hydrophilic property in the liquid chamber, and therefore, the bubble formation is less, and the bubble does not stagnate in the liquid chamber. Therefore, the bubble is not deposited in the liquid chamber. When the ink ejection was observed, the stabilized ejections are confirmed. Embodiment 23 The recording head was manufactured in the same conditions as with Embodiment 22 except that in order to provide the hydrophilic nature H + ions are injected with the acceleration energy of 20 keV and the dose of 1x10 16 cm -2 . Embodiment 24 First of all, an orifice plate was manufactured. As shown in Figure 14B, a pattern 211 corresponding to ejection outlets was formed by plating resist on a stainless plate 210. Thereafter, electroless Ni plating for providing the water repelling property was carried out to provide the plating layer 208'. This Ni electroless plating is called Kaniflon (available from Japan Kanigen, Japan) plating which is eutectic plating of Teflon (trademark) fine particles and Ni. Subsequently, the plated resist 211 is solved by a solvent so that the plated layer 208' is removed from the stainless steel 210, so that the orifice plate 208 shown in Figure 14C was provided. As shown in figure 14D, O + ions are injected through ion injection method into a surface opposite from the front surface 213 having the ejection outlets 206, with the acceleration voltage of 30 keV and the dose of 5x10 16 cm -2 , thus providing the hydrophilic portion 212. The orifice plate 208 thus treated for the hydrophilic property is secured to an end 122 by a spring (not shown) in much a manner that as shown in Figure 14A the ion injected surface (hydrophilic portion 212) is faced to the end 122 of the ink passage 109 of the recording head 201 and that the ink passages are aligned with the ejection outlets. If desired, the orifice plate may he secured by bonding. To the recess surface or the top plate, O + ions are injected to provide the hydrophilic property as in Embodiment 22. The face surface of such an ink jet recording head is of water repelling material, and therefore it exhibits the water repelling nature. However, the inside is treated for the hydrophilic nature by the ion injection method. Embodiment 25 An ink jet recording head was produced in the same manner as in Embodiment 24 except that the ions to be injected are H + . Embodiment 26 The ink jet recording head has the structure shown in Figure 15A. Figure 15B is a sectional view taken along a line A-A in Figure 15. In the ink jet recording heads of these embodiments, the ink flowing through the ink passages 309 is heated by ejection energy generating elements 303 (heater), by which the ink droplets are ejected upwardly from ink ejection outlet 306. The orifice plate 308 was manufactured in the same manner as in Embodiment 24. The used ions are O + ions, and the hydrophilic treatment was effected with the same condition as with Embodiment 24. The orifice plate was bonded and secured to the liquid passage wall in such a manner that the ion injected surface is inside and that the ink ejection outlets 306 are aligned with the ink ejection energy generating elements 303. Embodiment 27 An ink jet recording head was manufactured in the same manner as with Embodiment 26 except that the injected ions are H + . Comparison Example 2 An ink jet recording head was manufactured in the same manner as with Embodiment 22 except for the ion injections are not effected. Comparison Example 3 An ink jet recording head was manufactured in the same manner as with Embodiment 24 with the exception that the ion injection was not effected. Comparison Example 4 An ink jet recording head was manufactured in the same manner as with Embodiment 26 except that the ion injection was not effected. Ink ejecting tests were performed by the thus manufactured recording heads under the following conditions: Signal pulses: Applied pulse width: 10 µsec Pulse frequency: 10 kHz Ink: Water: 70 parts by weight Diethylene glycol: 26 parts by weight Direct Black 154: 4 parts by weight All of the ink jet recording heads according to the embodiments were stably operated to eject the ink with high accuracy of ink droplet shot position over more than 10 9 pulses. A test was carried out in which the ink supplied from the ink supply port deliberately contains fine bubbles. However, the ink could be ejected without problem. With the ink jet recording heads of Comparison Examples, improper ejections were frequently observed. Deposition of fine bubbles on the top wall in the liquid chamber was observed in the case of the recording head of Comparison Example 2. With the recording head of Comparison Example 3, fine bubbles were deposited to the inside of the orifice plate and the inside of the top wall. In Comparison Example 4, fine bubbles are observed as being deposited on the inside of the orifice plate. As described in the foregoing, at least a part of ink contacting portion of the ink jet recording head is treated for hydrophilic property by ion injection through ion injection method, and the back side of the orifice plate made of water repelling material is injected by ions through ion injection method to obtain the hydrophilic property, and therefore: 1) Stable ejections are possible over a long period of time of ink ejections: 2) Unnecessary bubbles do not stagnate in the ink jet recording head, and therefore there is no need of special means for removing the bubbles. Therefore, it is possible to provide low cost ink jet recording apparatus: 3) These advantageous effects are particularly remarkable when a high speed frequency printing is carried out. This invention includes any combination of the foregoing embodiments. Therefore, it is possible to combine the ejection outlet formation in the orifice plate by ion machining, the surface treatment of the orifice plate, and the ion injection water repelling treatment, can be combined. In addition, the hydrophilic treatment by ion injection to the ink contacting portion of the inside wall of the recording head, may be combined with the water repelling property treatment by ion injection into the ejection side surface. The surface treatment of the ejection side surface may he combined with the ejection outlet formation by ion machining. For example, the ink contact portion of the inside wall of the recording head is treated for the hydrophilic property to prevent the bubble stagnation, and in addition, the ejection side surface may be treated for the water repelling property. Then, the ejection energy loss is low, and the ink ejection direction is stabilized, so that very stable recording is possible. While the invention has been described with reference to the structures disclosed herein, it is not confined to the details set forth and this application is intended to cover such modifications or changes as may come within the scope of the following claims.]

Claims: A method for manufacturing an ink jet recording head having an ink passage, wherein a droplet of ink is ejected through the passage from an ink ejecting outlet (56) at an end of said passage onto a recording material, the method comprising ion injection into a surface (59) having the ink ejection outlet (56) to change a surface property of the surface (59). An ink jet recording head comprising an ink passage, an ink ejection outlet (56) at an end of said passage, wherein a droplet of ink is ejectable through the passage from the ejection outlet (56) onto a recording material, wherein a surface property of the surface (59) having the ink ejection outlet (56) is changed by injecting ions into said surface (59). An ink jet recording head according to claim 2, wherein the ink is ejected by an electrothermal transducer (52) for generating thermal energy upon electric energy supply thereto. An ink jet recording head according to claim 2, wherein a plurality of ejection outlets is provided over an entire recording width of the recording material. An ink jet recording head according claim 2, wherein said ink passage comprises a an ink ejection energy generating element (52) which causes a state change of the ink, and ejects a droplet of ink upon the state change of the ink, and wherein said surface (59) having said ejection outlets (56) comprises a surface layer on the ink ejection side thereof, a surface property of said surface being changed by injecting ions into said surface layer after it has been formed. An ink jet recording head according to claim 5, wherein said ink ejection energy generating element (52) is a heat generating resistor. A method according to claim 1, comprising the steps of: preparing an ink passage having an ink ejection energy generating element (52) which causes a state change of the ink in said passage, forming an ink ejection outlet (56) in communication with said ink passage, forming a surface layer on an ink ejection side surface (59) having the ink ejection outlet, and injecting ions into said surface layer to change a surface property of said surface (59). A method according to claim 1, comprising the steps of: preparing an ink passage having an ink ejection energy generating element for causing a state change of ink in said passage, preparing an orifice plate (62), forming an ink ejection outlet (63) in communication with said passage, through which a droplet of ink is ejected onto a recording material upon a state change of the ink, wherein said ejection outlet (63) is formed by ion machining in said orifice plate (62). A method according to claim 8, wherein ions are injected into a surface (69) of said orifice plate (62) to change a surface property of the surface (69) having the ejection outlet (63). A method according to claim 8, wherein an ion accelerating voltage is 100 to 300 keV, an ion beam diameter is 0.5 to 50 µm (microns), and an ion current is 10 to 10 000 pA. An ink jet recording head comprising an ink passage (109) having an ink ejection energy generating element (103) in said ink passage, an ink ejection outlet (106) in communication with said ink passage (109) through which a droplet of ink is ejected onto a recording material upon actuation of the ink ejection energy generating element (103), an ink chamber (104) in communication with said ink ejection outlet (106) through said ink passage (109), wherein a part of an inside surface (104, 109) of said ink jet recording head, which is in contact with the ink is provided with a hydrophilic property generated by ejecting ions into said part of an inside surface (104, 109). A method for manufacturing an ink jet recording head, comprising the steps of preparing an ink passage (109) having an ink ejection energy generating element (103) in said ink passage, forming an ink ejection outlet (106) in communication with said ink passage (109) through which a droplet of ink is ejected onto a recording material upon actuation of the ink ejection energy generating element (103), preparing an ink chamber (104) in communication with said ink ejection outlet (106) through said ink passage (109), and injecting ions into a part of an inside surface (104, 109) of said ink jet recording head which is in contact with the ink to provide the part (104, 109) with a hydrophilic property. An ink jet recording head according to claim 11, further comprising an orifice plate (108) arranged at an end of said ink passage (109) and provided with said ejection outlets (106), wherein said orifice plate (108) is made from a water repelling material, and wherein a surface (120) of said orifice plate (108) inside the recording head is provided with a hydrophilic property by injecting ions into the plate (108). A method according to claim 12, further comprising the steps of providing an orifice plate (108) having said ejection outlets (106) at an end of said ink passage (109), wherein said orifice plate (108) is made from a water repelling material, and injecting ions into a surface (120) of said orifice plate (108) inside said recording head to provide the inside surface (120) with a hydrophilic property. An ink jet recording head according to claim 11, wherein the ink is ejected by a state change thereof caused by an electrothermal transducer (103) for generating thermal energy upon electric energy supply thereto.

Inventors: INAMOTO TADAYOSHI, KOMURO HIROKAZU, MASHIO HIDEAKI, MURAKAMI KEIICHI, SUZUKI TOSHIO, INAMOTO, TADAYOSHI, KOMURO, HIROKAZU, MASHIO, HIDEAKI, MURAKAMI, KEIICHI, SUZUKI, TOSHIO
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1993
Main classification: B41J2
IPC codes: B41J2