JP5002290B2 - Method for manufacturing liquid discharge head substrate - Google Patents

Description

  The present invention relates to a liquid discharge head base for discharging liquid, a liquid discharge head using the base, and methods for manufacturing the same.

  A liquid discharge head that discharges liquid from a liquid discharge port is particularly widely used as an ink jet head used in an ink jet recording apparatus (ink jet printer). A method of manufacturing this ink jet head is disclosed in, for example, Japanese Patent Laid-Open No. 6-286149.

In recent years, an ink jet head as an example of the liquid discharge head is required to have higher recording resolution, higher image quality, and higher speed. Among these, as one solution to the demand for higher resolution and higher image quality, the amount of ink ejected per dot is made smaller (when ink is ejected as a droplet, the diameter of the ink droplet is reduced). Can be mentioned. In an inkjet head that ejects ink using thermal energy as disclosed in the above publication, the area of the heat generating portion is reduced and the shape of the nozzle is changed in order to achieve a smaller ink droplet. This has been dealt with by reducing the area of the ink discharge port.
JP-A-6-286149

  In order to realize such a small droplet discharge amount, it is necessary to form the ink discharge port with high accuracy. However, as disclosed in JP-A-6-286149, when a flow path forming member that constitutes an ink flow path wall or an ink discharge port is formed of a resin material, the resin material swells due to ink or the like, and the ink discharges. The shape of the outlet may be deformed. So far, these deformations have been minor and have not been a problem. However, in order to obtain a higher quality image at a higher speed, an ink jet head substrate in which a large number of ejection ports without such deformation is formed is required.

  Furthermore, the resin material and the substrate may be easily peeled at the interface of the substrate due to deformation due to the swelling of the resin material due to the ink described above or alteration due to a chemical reaction with the ink component itself.

  In addition, since the flow path forming member is made of a photosensitive resin material, sagging occurs in the shape of the discharge port due to uneven exposure or reflection from the ground, and the formation of a discharge port with a small area corresponding to small droplets May not be formed with high accuracy. In this case, a so-called dry etching technique such as reactive etching or plasma etching is used instead of a photolithography technique in which a photosensitive resin is exposed and developed to form discharge ports corresponding to small droplets and ink mist reduction. It is being considered. Specifically, the dry etching is performed using an inorganic film such as a SiOC film, which is a material having a larger selection ratio at the time of etching compared to the flow path forming member, as a mask. However, in the conventional film formation method (for example, plasma CVD method), the substrate temperature becomes high temperature of 200 ° C. to 300 ° C. or higher during film formation, so that the flow path forming member formed of resin is deformed. Therefore, it is necessary to use a material that can be formed at a low temperature that does not cause deformation of the flow path forming member for the mask when performing etching for forming the discharge port on the upper surface of the flow path forming member.

  On the other hand, in order to obtain ejection characteristics that achieve further improvement in recording quality, the inner wall (inner surface) of the ink flow path is substantially hydrophilic, and the outside of the flow path forming member including the opening of the ink ejection port More preferably, the surface region has water repellency. In particular, in order to suppress deformation of the ink discharge port, it is preferable to avoid swelling due to ink on the surface where the ink discharge port is open (the discharge port opening surface of the ink jet head that faces the recording medium when recording is performed).

  In order to solve the above-described problems, an object of the present invention is to use a liquid discharge head substrate in which swelling by a liquid is suppressed and a liquid path inner surface and a discharge port are formed with high accuracy and reliability. It is an object of the present invention to provide a liquid discharge head and a manufacturing method thereof.

In order to achieve the above object, a method of manufacturing a liquid discharge head substrate according to the present invention includes:
A substrate including an energy generating element that generates energy for discharging liquid from a liquid discharge port;
Anda portion constituting the inner surface of the liquid path for supplying liquid to the liquid discharge port and the liquid discharge port, the liquid path portion constituting the inner surface and the inside of the substrate said energy generating element is provided, et al are that the side provided with a method for manufacturing a liquid discharge head substrate having a resin structure constituting the liquid passage,
Forming a mold material in a region to be the liquid path on the substrate;
Hydrophilic primary formation protection having a portion to be a flow path inner surface protective layer provided on the inner surface of the liquid passage and a portion to be an interface protective layer for protecting the interface between the substrate and the resin structure on the substrate. Forming a layer so as to cover the mold material by catalytic chemical vapor deposition;
Providing a member to be the resin structure on the primary protective layer;
Forming an opening for forming the liquid discharge port at a position of the member facing the energy generating element;
A hydrophilic secondary forming protective layer having a protective layer covering the opening surface of the liquid discharge port and the inner surface of the liquid discharge port of the resin structure is formed by opening the opening of the member by catalytic chemical vapor deposition. Forming an opening surface that is a surface on the side and an inner surface of the opening; and
A portion of the secondary protection layer that covers the opening surface on the side where the opening of the member is open is subjected to water repellent treatment, and the opening of the member of the secondary protection layer is opened. Water repellent part covering the opening surface that is the surface on the side, hydrophilic to the part covering the inner surface of the opening;
Etching the inside of the opening to form the liquid discharge port;
Removing the mold material and forming the liquid path;
The a, the opening surface of the liquid discharge port of the resin structure is water-repellent, the inner surface of the liquid discharge ports manufacturing method of a liquid discharge head substrate, wherein the hydrophilic der Rukoto.

  According to the present invention, there is provided a liquid discharge head substrate in which swelling by a liquid is suppressed and a liquid path inner surface and a discharge port are formed with high accuracy and high reliability, a liquid discharge head using the substrate, and a manufacturing method thereof. Obtainable.

  Hereinafter, an embodiment of the present invention will be described using an inkjet head substrate as an embodiment of a liquid ejection head substrate and an inkjet head as an embodiment of a liquid ejection head, respectively.

  FIG. 1 is a schematic perspective view with a part cut away for explaining one ink jet head substrate 1. Here, 2 is a silicon substrate, and 3 is a heat generating portion that generates thermal energy (discharge energy) for discharging from an ink discharge port 6 as a liquid discharge port for discharging a liquid. Reference numeral 7 denotes an ink supply port that penetrates the silicon substrate 2 and opens on the surface thereof. Reference numeral 5 denotes a discharge port opening surface in which a plurality of ink discharge ports 6 are opened, and faces a recording medium such as a recording sheet when used as an inkjet head. 4 is provided on the surface of the silicon substrate 2 in which an ink flow path 8 (see FIG. 2B) from the ink supply port 7 to the ink discharge port 6 through a portion where the heat generating portion 3 is provided is formed. It is the flow-path formation member as a formed resin structure.

  2A is a diagram schematically illustrating a cross section taken along line XX in FIG. 1, and FIG. 2B is an enlarged view of the vicinity of the portion indicated by a circle in FIG. 2A. It is a schematic diagram. Here, 9 is an adhesion layer for joining the silicon substrate 2 and the flow path forming member 4 together. Reference numeral 10 denotes a flow path through which ink is supplied in the ink discharge direction during ink discharge, and is referred to as a discharge unit. The discharge unit 10 is a part of the ink flow path 8 and has a discharge port 6 at one end. The ejection unit 10 is located at a position where the heat generation unit 3 and the ink ejection port 6 facing each other communicate with each other. The discharge port opening surface 5 is the surface of the flow path forming member 4 where the discharge port 6 is open. This surface is usually subjected to water repellent treatment in order to prevent adhesion of ink that is liquid.

In order to suppress swelling of the resin structure (for example, the flow path forming member 4) that forms a liquid path (for example, the ink flow path 8) by the liquid (for example, ink) , the inkjet head substrate 1 includes at least one of the following parts: One or more sites have a protective layer. This protective layer is formed using a catalytic chemical vapor deposition (hereinafter referred to as Cat-CVD method).
(1) Discharge port opening surface 5
(2) Interface (bonding surface or bonding site) between silicon substrate 2 and flow path forming member 4
(3) Inner surface of the ink flow path 8 formed in the flow path forming member 4 (part excluding the inner surface of the ink flow path of the ejection unit 10)
(4) Inner surface of ink flow path of discharge section 10 (5) Outer surface of flow path forming member 4 When all of the above-mentioned (1) to (5) are provided with a silicon-based protective layer by Cat-CVD method In other words, at least a portion of the flow path forming member 4 that comes into contact with the ink is covered with a protective layer obtained by the Cat-CVD method. As a result, the flow path forming member 4 does not come into contact with ink. However, even when a protective layer is formed only in a part of (1) to (5) by the Cat-CVD method, it has the following effects.

  First, the above-mentioned (1) is a part that greatly affects ink ejection characteristics (for example, ink droplet ejection direction).

  Usually, the discharge port opening surface 5 preferably has water repellency. Further, the inner surface forming the ink flow path 8 inside the flow path forming member 4 is preferably hydrophilic in order to make the ink flow smooth. In the conventional ink jet head, the water repellent treatment is performed on the discharge port opening surface 5, but the hydrophilic treatment is not performed on the inner surface of the ink flow path 8 formed in the flow path forming member 4. The layer (film) formed by the Cat-CVD method has a characteristic that each part of the inkjet head requires a water-repellent layer (film) and a hydrophilic layer (film) by selecting a material to be a layer. Can be formed accordingly.

  Further, the shape of the ink ejection port 6 has a great influence on the ink ejection characteristics (ink droplet ejection direction, etc.). However, if wet etching is used when forming the ink discharge ports 6, an unintended shape may occur due to unnecessary etching such as over-etching. Therefore, a discharge port is formed by using a so-called dry etching technique in which a silicon-based protective layer is formed on the discharge port opening surface 5 by a Cat-CVD method and reactive etching or plasma etching is performed using the silicon-based protective layer as a mask. It is preferable.

  However, when a silicon-based insulating layer is formed on the surface of a structure of an organic resin that is a material of the flow path forming member 4 by a normal plasma CVD method or the like, the temperature is 200 ° C., which is higher than the temperature at which the organic resin is deformed. It is necessary to form at a substrate temperature of ˜300 ° C.

  On the other hand, when the Cat-CVD method is used, a film can be formed even if the substrate temperature is at room temperature without controlling the heating of the substrate holder. Accordingly, even when the substrate temperature is lower than the temperature at which the organic resin is deformed, the film can be formed on the structure of the organic resin. For this reason, according to the Cat-CVD method, a silicon-based protective layer can be formed on an organic resin structure without deformation of the structure.

  According to the Cat-CVD method, a silicon-based protective layer (protective film) can be formed on the flow path forming member 4 or the silicon substrate 2. The silicon protective layer includes a silicon oxide (SiO) layer, a silicon nitride (SiN) layer, a silicon oxynitride (SiON) layer, a silicon oxycarbide (SiOC) layer, a silicon carbonitride (SiCN) layer, or silicon carbide ( SiC) layer and the like.

  Here, the surface of the protective layer composed of the SiC layer and the SiOC layer is a surface (water film) having a water contact angle of 80 ° or more. By providing the protective layer made of these materials by the Cat-CVD method, the water-repellent protective layer can be directly formed on a predetermined surface (for example, the discharge port opening surface 5).

  In addition, the surface of the protective layer made of the SiN layer and the SiON layer is a surface (water) having a water contact angle of 40 ° or less and having hydrophilicity. When such a hydrophilic protective layer is formed by Cat-CVD and it is necessary to impart water repellency to the obtained hydrophilic protective layer, for example, a method of laminating a water-repellent dry film or water repellency This is achieved by performing a water repellent treatment by a method of forming a resin coating layer or the like.

  Next, as described in (2) above, by providing a silicon-based protective layer by a Cat-CVD method at the interface (bonding surface) between the silicon substrate 2 and the flow path forming member 4, the flow path forming member 4 and The adhesion between the two at the interface with the silicon substrate 2 can be improved by this protective layer. The bonding surface between the silicon substrate 2 and the flow path forming member may be provided with an adhesion layer 9 and a protective layer formed by Cat-CVD. Thereby, peeling with the flow path formation member 4 and the silicon substrate 2 resulting from an ink can be suppressed. Further, the protective layer at this site does not directly contact the ink, but is preferably hydrophilic from the viewpoint of improving the adhesion between the flow path forming member 4 and the silicon substrate 2.

  Further, in the above (3), the contact of the flow path forming member 4 with the ink is provided by providing a silicon-based protective layer by a Cat-CVD method on the inner surface forming the ink flow path 8 inside the flow path forming member 4. It is possible to suppress a decrease in reliability caused by alteration or deformation due to the above.

  Further, in the above (4), by providing a silicon-based protective layer by Cat-CVD method on the inner surface of the flow path forming member 4 that forms the discharge section 10, ink discharge due to alteration or deformation of the flow path forming member 4 is performed. Deformation of the outlet 6 can be suppressed.

  Further, the above (5) is less in contact with the ink than the other (1) to (4), and is not particularly discussed here. In many cases, the water repellent treatment is performed at the same time when the water repellent treatment (1) is performed on the discharge port opening surface 5. In fact, also in each of the embodiments described below, when the protective layer is formed on the discharge port opening surface 5 by the Cat-CVD method, the outer surface 4a (the above-described (5)) of the flow path forming member 4 is simultaneously protected. A layer is formed.

  By manufacturing an inkjet head including an inkjet substrate having a protective layer by the above-described Cat-CVD method and mounting the inkjet head on an inkjet recording apparatus (inkjet printer) as a liquid ejection apparatus, higher-quality inkjet recording can be performed. it can.

  Next, a Cat-CVD apparatus and a protective layer forming method using the apparatus will be described.

  The Cat-CVD apparatus shown in FIG. 3 introduces a source gas into the film forming chamber 301 so as to come into contact with the substrate holder 302, a heater 304 serving as a catalyst body for catalytic decomposition reaction of the gas, and the heater 304. A gas introduction part 303 is formed. Further, an exhaust pump 305 is provided for depressurizing the film formation chamber 301. A temperature control device (not shown) for controlling the substrate temperature is also provided.

  In the Cat-CVD method, a catalyst body (heater 304) made of tungsten (W) or the like is heated, and the gas species molecules / atoms decomposed by catalytic reaction of the source gas with the catalyst body are placed on the substrate holder 302. In this method, a layer (film) is formed by being deposited on the surface of a silicon substrate or the like. Since such a principle is used, a deposited layer can be formed on the surface of the object without particularly heating the substrate. That is, the Cat-CVD method can form a film even when the substrate temperature is about room temperature or about 20 ° C.

The film formation by the Cat-CVD method using the apparatus of FIG. 3 will be described by taking the SiOC layer as an example. First, the film formation chamber 301 is exhausted using the exhaust pump 305. Next, a mixture of silane (SiH ₄ ) gas, ammonia (NH ₃ ) gas, dinitrogen monoxide (N ₂ O) gas, methane (CH ₄ ) gas, and hydrogen (H ₂ ) in a predetermined ratio is used as a gas. The film is introduced into the film formation chamber 301 from the introduction port 303. In addition, after adjusting the substrate temperature, the heater 304 as a catalyst body is heated to 1700 ° C. A SiOC layer is formed by a catalytic decomposition reaction between the catalyst body and various gases. Further, by changing the composition of the introduced gas continuously or stepwise, it is possible to form a water repellent layer in which the atomic composition is changed in the layer thickness direction. For example, a water repellent layer in which the atomic composition of the SiOC layer is changed can be formed by changing the gas flow rate. Moreover, a SiC layer can also be produced by changing the kind of gas in source gas, and those mixing ratios.

On the other hand, when the SiN layer is formed, monosilane (SiH ₄ ), disilane (Si ₂ H ₆ ), or the like can be used as a silicon source gas, and ammonia (NH ₃ ) can be used as a nitrogen source gas. Further, hydrogen (H ₂ ) may be added to improve the coverage. Furthermore, a SiON layer can be formed by adding a trace amount of oxygen (O ₂ ).

Moreover, a SiC layer can be formed from dimethylsilane (DMS), tetraethoxysilane (TEOS), or dimethylsiloxane (DMDMOS) as a source gas. Furthermore, an SiOC layer can be formed by adding oxygen (O ₂ ) to the source gas.

  When forming a SiN layer, a SiON layer, a SiOC layer, a SiCN layer, or a SiC layer, these layers can be formed using, for example, a plasma CVD method. However, in the film formation method using the plasma CVD method, the substrate temperature needs to be 200 ° C. to 300 ° C. or higher during the film formation, so that the flow path forming member 4 formed of resin is deformed. End up. However, in the Cat-CVD method according to the present embodiment, the substrate temperature during film formation can be formed at a low temperature of about 20 ° C. For this reason, even when a protective layer is formed on the surface of the flow path forming member 4, a dense protective layer with few defects can be formed without deforming the flow path forming member 4.

  Next, an ink jet head cartridge using the ink jet head described above and an ink jet recording apparatus equipped with the ink jet head cartridge will be described.

  The ink jet head according to this embodiment can be mounted on an apparatus such as a printer, a copying machine, a facsimile having a communication system, a word processor having a printer unit, or an industrial recording apparatus combined with various processing apparatuses. By using this inkjet head, recording can be performed on various recording media such as paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, and ceramics.

  In this specification, “recording” means not only giving an image having a meaning such as a character or a figure to a recording medium but also giving an image having no meaning such as a pattern. .

  Next, an ink jet cartridge in the form of a cartridge in which an ink jet head is integrated with an ink tank and an ink jet recording apparatus (ink jet printer) using the same will be described.

  FIG. 4 is a diagram illustrating a configuration example of an ink jet cartridge 110 having a cartridge form that can be attached to the ink jet recording apparatus.

  The inkjet cartridge 110 includes an ink tank unit 104 and an inkjet head unit 105. A TAB (Tape Automated Bonding) tape member 102 having a terminal 103 for supplying power to the inkjet cartridge 110 from the outside is disposed on the surface of the casing of the inkjet cartridge 110. The electrical connection portion of the inkjet head portion 105 is connected to a wiring (not shown) extending from the external connection terminal 103 of the TAB tape member 102.

  FIG. 5 shows a schematic configuration example of an ink jet recording apparatus that performs recording using the ink jet cartridge 110 of FIG.

  In the ink jet recording apparatus, a carriage 200 fixed to an endless belt 201 is provided, and main scanning is performed along a guide shaft 202 in a reciprocating direction (A direction in the drawing).

  An ink jet cartridge 110 in the form of a cartridge is mounted on the carriage 200. In the ink jet cartridge 110, the ink discharge ports 6 face the paper P as a recording medium, and the arrangement direction of the ink discharge ports 6 is different from the scanning direction of the carriage 200 (for example, the transport direction of the paper P). Mounted on the carriage 200. The number of combinations of the ink jet head unit 105 and the ink tank unit 104 can be set to correspond to the ink color to be used. In the example shown in the figure, four corresponding to four colors (for example, black, yellow, magenta, and cyan) are provided. A set is provided.

  The recording paper P as a recording medium is intermittently conveyed in the direction of arrow B orthogonal to the moving direction of the carriage 200.

  With the configuration as described above, the recording paper is recorded while the recording of the width corresponding to the column length of the ink discharge ports 6 of the ink jet cartridge 110 and the conveyance of the recording paper P are alternately repeated as the carriage 200 moves. Recording is performed on the entire P.

  The carriage 200 stops at a fixed position at the end of the carriage movement area, which is called a home position as necessary when recording starts or during recording. At this home position, a cap member 203 for capping the surface (discharge port opening surface 5) provided with the ink discharge port 6 of each ink jet cartridge 110 and rubber for scraping off ink remaining on the discharge port opening surface 5 of the ink jet head. A blade is provided. The cap member 203 is connected to a suction device (not shown) for forcibly sucking ink from the ink discharge port 6 to prevent the ink discharge port 6 from being clogged. A configuration that cleans the discharge port opening surface 5 and the ink discharge port 6 including the rubber blade, the cap member, the suction device, and the like is referred to as a recovery means for recovering and maintaining the ink discharge performance.

Hereinafter, a structure and a manufacturing method of a silicon substrate 2 to be an inkjet head substrate 1 according to an embodiment of the present invention will be described in detail with reference to the drawings. The first and third embodiments are reference embodiments.

(First embodiment)
The discharge port opening surface 5 of the ink jet head is preferably subjected to water repellent treatment, and in fact, conventionally has been subjected to water repellent treatment. In the following embodiments, the effect of forming the protective layer by the Cat-CVD method is most effective, and the formation of the protective layer by the Cat-CVD method on the discharge port opening surface 5 corresponding to the above (1). Will be described.

The manufacturing method described here has the following steps.
A step of forming a mold material in a region on the substrate where the liquid path is formed in a later step.
A process of covering the mold material and forming a resin structure.
A step of forming a discharge port opening surface protective layer, which will be described later, on the surface of the resin structure on which the liquid discharge port is formed by a Cat-CVD method.
A step of forming an opening from the portion serving as the liquid discharge port to the mold material in the discharge port opening surface protective layer and the resin structure.
A process of removing the mold material and forming a liquid path inside the resin structure.

  As described above, the shape of the ink discharge port 6 greatly affects the ink discharge characteristics (for example, the ink droplet discharge direction). However, according to the present embodiment, the ink discharge port 6 can be formed on the discharge port opening surface 5 by using a dry etching method. Further, direct contact between the flow path forming member 4 and the ink (droplet) can be avoided, and swelling of the flow path forming member 4 due to ink can be suppressed. Further, the protective layer can be formed at a temperature lower than the deformation temperature of the material constituting the flow path forming member 4. Thereby, it is possible to manufacture the ink discharge port 6 having an accurate shape, and it is possible to manufacture an ink jet head capable of suppressing the deformation of the flow path forming member 4 and the ink discharge port 6 and performing higher quality recording. .

  A method for manufacturing the inkjet head substrate 1 of FIG. 1 will be described with reference to schematic sectional views for each step of FIG.

A SiO ₂ layer having a layer thickness of 0.7 μm is formed on the front side surface and the back side surface of the silicon (Si) substrate 2 having a plane orientation <100> by using a thermal oxidation method. The SiO ₂ layer formed on one (front side) surface of the silicon substrate 2 separates each semiconductor element of a drive circuit (not shown) that drives the heat generating portion 3 that becomes an ejection energy generating element for ejecting ink. Is a layer. The SiO ₂ layer 12 formed on the other surface (back side surface) of the silicon substrate 2 is used as an etching mask when the ink supply port 7 is opened in a later step.

  Thereafter, the heat generating portion 3 and a drive circuit (not shown) made of a semiconductor element for driving the heat generating portion 3 are formed on the front side surface of the silicon substrate 2 using a normal semiconductor manufacturing technique. Since a signal for driving the drive circuit is supplied to the drive circuit from the outside, an input electrode (not shown) for receiving a signal for driving the drive circuit from the outside is provided. Thereafter, the heat generating portion 3 is formed on the front surface of the silicon substrate 2 by using a manufacturing method such as that disclosed in Japanese Patent Application Laid-Open No. 8-112902 (FIG. 6A).

  Further, a protective layer (not shown) for protecting the heat generating portion 3 and the wiring from ink is provided at a predetermined portion of the silicon substrate 2 as necessary. An ink jet head can be obtained by forming the flow path forming member 4 and the like on the protective layer.

A patterning mask 13 serving as a mask for forming the ink supply port 7 is formed on the SiO ₂ layer 12 on the back side surface of the silicon substrate 2. In this forming method, first, a mask agent is applied and cured on the entire back surface of the silicon substrate 2 by spin coating or the like, and then a positive resist is applied and dried thereon by spin coating or the like. Next, the positive resist is patterned by a photolithography technique, and the exposed portion of the mask agent that becomes the patterning mask 13 is removed by dry etching using the positive resist as a mask. Finally, the positive resist is peeled off to obtain a patterning mask 13 having a desired pattern (FIG. 6B).

  Next, a positive photoresist is formed on the front side surface of the silicon substrate 2 by spin coating or the like so as to be a layer having a predetermined thickness. Next, a mold material 14 having a desired thickness and a planar pattern is formed on a portion of the silicon substrate 2 where the heat generating portion 3 is formed by using a photolithography technique in which exposure and development are performed using ultraviolet rays, Deep-UV light, or the like. Is done. The mold material 14 is dissolved in a later step, and a space formed by dissolution and removal becomes an ink flow path. The mold member 14 is formed to have a corresponding layer thickness and planar pattern in order to form an ink flow path having a desired height and planar pattern (FIG. 6C).

  Next, a material for forming the flow path forming member 4 is applied on the front side surface of the silicon substrate 2 by spin coating or the like. Then, the area | region removed by a post process is exposed using a mask.

  As a material of the flow path forming member 4, a known photosensitive resin (composition) such as a positive photosensitive epoxy resin or a photosensitive acrylic resin can be appropriately selected and used. The flow path forming member 4 is a member in which an ink flow path is formed, and always comes into contact with ink when the ink jet head is used. Therefore, a photocurable epoxy resin is particularly suitable as the material. In addition, as the material of the flow path forming member 4, durability and the like greatly depend on the type and characteristics of the ink to be used, so a compound other than the above materials may be selected depending on the ink to be used.

Next, a silicon-based protective layer 11 is formed on the front side surface of the flow path forming member 4 using a Cat-CVD method. (FIG. 6 (d)). At this time, the outer surface of the flow path forming member 4 is substantially covered with the protective layer 11 at the same time (not shown). This protective layer 11 becomes a discharge port opening surface protective layer to be described later.

  Thereafter, a positive type photoresist layer 15 is formed, and this positive type photoresist layer 15 is patterned using a photolithography technique. Next, using the patterned photoresist layer 15 as a mask, the exposed portion of the protective layer 11 is removed by dry etching or the like (FIG. 6E).

  Thereafter, the flow path forming member 4 is removed by etching using a dry etching method to form an ink discharge port 6 (FIG. 6F). As a result, an opening extending from the ink discharge port 6 to the mold member 14 is formed in the discharge port opening surface protective layer and the flow path forming member 4.

Here, the opening process of the ink discharge port 6 is performed using a dry etching technique. This dry etching has the following advantages compared to the wet etching formed by exposing and developing a photosensitive resin.
(1) The ink discharge port 6 having a small area opening or a fine shape can be formed with high accuracy.
(2) Since the material for the flow path forming member 4 does not have to be particularly photosensitive, the degree of freedom in material selection is increased.

  Note that the dry etching mask of the flow path forming member 4 may use the patterned photoresist layer 15 as a mask or the patterned protective layer 11 as a hard mask.

Next, using the patterning mask 13 as a mask, the SiO ₂ layer 12 is patterned by wet etching or the like, and a part of the SiO ₂ layer 12 is removed. At the removed portion, the back side surface of the silicon substrate 2 is exposed and becomes an etching start opening for forming the ink supply port 6.

Next, the ink supply port 7 serving as a through-hole penetrating the silicon substrate 2 is formed by anisotropic etching using the SiO ₂ layer 12 as a mask (FIG. 6G).

  At this time, a protective material (so that the etchant does not touch the front side surface of the silicon substrate 2 on which the functional elements of the inkjet head (such as the heat generating portion 3 and the drive circuit) and the flow path forming member 4 are formed) (Not shown).

  Finally, the patterning mask 13 and the protective material (not shown) are removed. Thereafter, the mold member 14 is eluted and removed from the ink discharge port 6 and the ink supply port 7 (FIG. 6 (h)).

  After the mold material 14 is removed, the inkjet head substrate 1 is dried, and the manufacturing process of the ink discharge port 6 and the ink supply port 7 is completed. Thereafter, an electric connection part for driving the heat generating part 3 and for exchanging electric power and signals from the outside is provided to complete the ink jet head.

Figure 6 also shows the schematic view enlarging a portion near indicated by a circle in FIG. 6 (h).

  FIG. 7A is a schematic enlarged cross-sectional view of the vicinity of the ink discharge port 6 on which the protective layer 11 formed using the Cat-CVD method is formed. The protective layer 11 formed using the Cat-CVD method is preferably composed of a SiO layer, a SiN layer, a SiON layer, a SiOC layer, a SiCN layer, or a SiC layer. Among these, since the protective layer composed of the SiC layer, the SiOC layer, and the SiCN layer has water repellency, the protective layer having water repellency can be directly formed by forming a protective layer made of these materials by the Cat-CVD method. It can be formed on a predetermined surface that requires water repellency (discharge port opening surface 5 in this embodiment).

  The layer thickness of the protective layer 11 formed on the flow path forming member 4 is a layer formed on the discharge port opening surface 5 rubbed by the rubber blade that scrapes the ink, and is preferably 0.5 μm or more. . The upper limit of the layer thickness is not particularly limited, but when the layer thickness is increased, the time required for film formation or dry etching becomes longer and the productivity is deteriorated. Therefore, it is generally considered that the upper limit is about 3 μm to 5 μm.

  When the protective layer 11 is used as a hard mask for forming the ink discharge ports 6 in the flow path forming member 4, the protective layer 11 has an SiN layer having a large etching selectivity with respect to the organic resin during anisotropic dry etching. It is preferable to use a SiON layer, a SiCN layer, or a SiC layer.

  When a positive photosensitive epoxy resin is used as the material of the flow path forming member 4, the deformation temperature at which the photosensitive epoxy resin starts to be softened and deformed is approximately 200 ° C. Therefore, during the film formation by the Cat-CVD method, It is necessary to form the film at a substrate temperature lower than 200 ° C. In addition, when a photosensitive acrylic resin is used as the material of the flow path forming member 4, the deformation temperature of the photosensitive acrylic resin is about 150 ° C., so the substrate temperature during film formation by the Cat-CVD method is higher than 150 ° C. It is necessary to form a film at a low temperature. For this reason, it is preferable that the substrate temperature during the film formation by the Cat-CVD method is equal to or lower than the deformation temperature of the material of the flow path forming member 4.

When the protective layer 11 is hydrophilic, ink remains on the discharge port opening surface 5, which causes clogging of the ink discharge port 6. Therefore, it is necessary to modify the discharge port opening surface 5 to be water repellent. In order to impart water repellency (water contact angle of 80 ° or more) to the protective layer 11 made of a hydrophilic SiO layer, SiN layer, or SiON layer, there are the following water repellent treatment methods.
(1) Fluorine ions are implanted into the surface of the protective layer 11 using an ion implantation method, and the surface modification of the protective layer 11 is performed. Thereby, it is possible to impart water repellency to the ink on the surface of the protective layer 11.

By performing ion implantation, as shown in FIG. 7B, the protective layer 11 has an upper layer modified to a water-repellent protective layer 11a, and a lower layer remains an unmodified hydrophilic protective layer 11b. ing. Depending on the layer thickness of the protective layer 11 and ion implantation conditions, the entire protective layer 11 may be modified to become a water-repellent protective layer 11a.
(2) As shown in FIG. 7C, a protective layer in which another water-repellent layer 11c is newly formed on the protective layer 11 (the surface of the protective layer 11). In this case, after forming the protective layer 11 shown in FIG. 6D, the water-repellent layer 11c is applied and formed, and the two layers of the water-repellent layer 11c and the protective layer 11 are dry-etched using a photoresist as a mask. In the same step using the method. For such a water repellent layer 11c, a known organic resin containing fluorine or silicon can be used.

  In the conventional method in which the above-described SiO layer, SiN layer, SiON layer, SiOC layer, SiCN layer, or SiC layer is formed on the protective layer 11 by the plasma CVD method, a high-quality layer (film) is obtained at the time of film formation. The substrate temperature needs to be 200 to 300 ° C. or higher. Therefore, when the film is formed on the flow path forming member 4 made of resin by the plasma CVD method, the flow path forming member 4 is deformed. However, the Cat-CVD method described in this embodiment can be formed even when the substrate temperature during film formation is room temperature or a low temperature of about 20 ° C. For this reason, even in the process after the flow path forming member 4 is formed on the silicon substrate 2, a dense protective layer with few defects can be formed without deforming the flow path forming member 4.

  Thus, the main manufacturing process of the inkjet head substrate 1 is completed. The ink-jet head substrate 1 formed in this way is attached with an electrical connecting portion for driving the heat generating portion 3 and an ink tank for supplying ink as required. Needless to say, the inkjet head substrate 1 can use a so-called multi-cavity technique used as a general semiconductor manufacturing technique. In this multi-cavity method, elements (here, inkjet heads) having the same configuration are formed on a single substrate in a grid pattern. A large number of elements formed on the substrate are then separated into chips one by one by die cutting or the like.

(Second Embodiment)
In the following embodiment, a manufacturing method for forming a protective layer by the Cat-CVD method at the above-described sites (1) to (4) will be described using the schematic cross-sectional views for each step of FIG.

The manufacturing method described here has the following steps.
A step of forming a mold material in a region on the substrate where a liquid path is formed in a later step.
-A flow path inner surface protective layer (details will be described later) which covers the mold material and protects the inner surface of the liquid channel on the base, and an interface protective layer (details) which protects the interface between the base and the resin structure Are described later) by a Cat-CVD method .
A step of forming a resin structure on the inner surface protective layer and the interface protective layer so as to cover the energy generating element.
A step of forming an opening from a portion serving as a liquid discharge port to a mold material on a surface where the liquid discharge port of the resin structure is formed.
A step of removing the mold material and forming the liquid path inside the resin structure.

Further, a discharge port that protects the surface on the surface where the liquid discharge port of the resin structure is formed between the step of forming the above-described opening and the step of forming the liquid passage inside the resin structure. It has the process of forming an opening surface protective layer (it mentions later for details) by Cat-CVD method.
As described above, the portion corresponding to (2) to (4) is preferably hydrophilic, whereas (1) is required to be water repellent. In the manufacturing method of the present embodiment, a hydrophilic protective layer is formed on the parts (1) to (4) by the Cat-CVD method, and then the first part is formed on the part (1) (discharge port opening surface 5). The water repellent treatment method described in the embodiment is applied. Thereby, the inner surface (inner wall) that forms the ink flow path 8 inside the flow path forming member 4 can be covered with the hydrophilic protective layer including the ejection portion 10. Furthermore, the interface (entirely or partially) between the flow path forming member 4 and the silicon substrate 2 can be covered with a protective layer.
Hereinafter, the manufacturing method of this embodiment will be described. First, the SiO ₂ layer 12 is formed on the front side surface and the back side surface of the silicon substrate 2, and the heat generating portion 3 is formed on the front side surface (FIG. 8A). The detailed description of this process is the same as the description of FIG. 6A of the first embodiment.
Next, a patterning mask 13 is formed on the SiO ₂ layer 12 on the back side surface of the silicon substrate 2 (FIG. 8B). The detailed description of this process is the same as the description of FIG. 6B of the first embodiment.
Next, a mold member 14 is formed on the front side surface of the silicon substrate 2 so as to cover the heat generating portion 3 (FIG. 8C). The detailed description of this process is the same as the description of FIG. 6C of the first embodiment.

  Subsequently, the first protective layer is formed on the front side surface of the silicon substrate 2 by Cat-CVD so as to cover the front side surface of the silicon substrate 2 on which the mold material 14 and the mold material 14 are not provided. The protective layer formed by the first Cat-CVD film formation thus formed is used as a primary protective layer 16 (FIG. 8D). Here, the primary protective layer 16 covering the mold member 14 becomes a part of the flow channel inner surface protective layer 19 of the ink flow channel 8 after the head is completed. A part of the primary protective layer 16 covering the front side surface of the silicon substrate 2 on which the mold member 14 is not provided becomes an interface protective layer 20 between the flow path forming member 4 and the silicon substrate 2 after the head is completed. Such a primary protection layer 16 is preferably formed with a hydrophilic layer such as a SiN layer or a SiON layer. Further, the substrate temperature of the Cat-CVD apparatus at this time is such that the mold material 14 formed of a positive photoresist material is not deformed by heat. In this embodiment, it is 150 ° C. or lower, more preferably 200 ° C. or lower.

  Next, a photosensitive resin material is applied by spin coating or the like so as to cover the mold material 14 and the primary formation protective layer 16 to form the flow path forming member 4 (FIG. 8E). The material selection and the specific formation method of the flow path forming member 4 are the same as those described in FIG. 6D of the first embodiment.

  Next, the photosensitive resin material forming the flow path forming member 4 is patterned by a photolithography technique, formed by removing the portions that become the ink discharge ports 6 and the discharge portions 10, and then cured (FIG. 8). (F)).

  Next, a protective layer that covers the surface of the flow path forming member 4 (discharge port opening surface 5) and the inner surface (the flow channel inner surface of the discharge unit 10) from the ink discharge port 6 is formed using the Cat-CVD method. To do. The protective layer formed by the second Cat-CVD method is used as the secondary protective layer 17 (FIG. 8G). Here, since the inner surface of the flow path of the ejection unit 10 is a part of the ink flow path 8, it is preferable to have hydrophilicity with respect to the ink. Therefore, it is preferable that the secondary protective layer 17 is formed with a hydrophilic layer such as a SiN layer or a SiON layer. Further, the substrate temperature of the Cat-CVD apparatus at this time is the temperature at which the mold material 14 formed of the positive photoresist material is not deformed by heat, as in the first embodiment.

  Next, a positive resist (not shown) is applied to the upper surface of the secondary protective layer 17 formed on the discharge port opening surface 5 by spin coating or the like, and then dried. Then, this positive resist is patterned using a photolithography technique to form a mask, and the secondary formation protective layer 17 exposed at the bottom of the opening to be the ink discharge port 6 and the primary formation protection layer below the secondary formation protection layer 17. 16 is removed by dry etching or the like. Thereby, the discharge part 10 by which the hydrophilic protective layer was formed in the flow path inner surface is completed. Finally, the positive resist is peeled off (FIG. 8H). As a result, an opening from the ink discharge port 6 to the mold member 14 is formed in the discharge port opening surface protective layer and the flow path forming member 4 described later.

  The secondary protective layer 17 may cover the entire surface of the discharge port opening surface 5, but is patterned so as to partially cover the discharge port opening surface 5 within a range in which the intended effect can be obtained. It may be. The same applies to a third embodiment described later.

  Here, since the secondary formation protective layer 17 formed on the discharge port opening surface 5 has hydrophilicity with respect to the ink as described above, at least the surface thereof is formed by the method described in the first embodiment, for example. It is preferable to modify the water repellency. Specifically, a water-repellent dry film is laminated on the surface of the secondary protective layer 17 formed on the discharge opening 5 or the surface is coated with a water-repellent resin. A water layer is formed. In addition, after forming the secondary protective layer 17, fluorine ions are implanted into a region from the surface of the secondary protective layer 17 to a certain depth using an ion implantation method, and the surface portion of the secondary protective layer 17 is formed. Modification may be performed. At this time, fluorine ion implantation is performed so that, for example, fluorine ions are not implanted into the secondary protective layer 17 covering the inner surface of the ink flow path 8 of the ejection unit 10 that is a portion that does not need to be subjected to water repellent treatment. Do. Specifically, the ion implantation is preferably performed perpendicular to the substrate surface or perpendicular to the opening surface of the ink discharge port 6.

  By such a process, the surface of the secondary formation protective layer 17 on the discharge port opening surface 5 has a water repellent effect on the ink. On the other hand, the secondary formation protective layer 17 which covers the flow path inner surface of the discharge part 10 is a layer which maintained hydrophilicity.

  In the inkjet head substrate 1 obtained by the above configuration, the above-described (3) and (4) are protected by the hydrophilic primary-forming protective layer 16, and the above-mentioned (2) is the hydrophilic secondary-forming protective layer. 17 is protected. The above (1) is protected by the hydrophilic secondary formation protective layer 17 whose surface is modified to be water repellent. The above-described (5) (outer surface 4a of the flow path forming member 4) is substantially simultaneously protected by the secondary protective layer 17 when the secondary protective layer 17 is formed in FIG. Is done.

Next, the ink supply port 7 serving as a through-hole penetrating the silicon substrate 2 is formed by anisotropic etching using the SiO ₂ layer 12 as a mask (FIG. 8I). At this time, a protective material (so that the etchant does not touch the front side surface of the silicon substrate 2 on which the functional elements of the inkjet head (such as the heat generating portion 3 and the drive circuit) and the flow path forming member 4 are formed and the side surface of the substrate). (Not shown). This is the same as FIG. 6G of the first embodiment.

  Finally, the patterning mask 13 and the protective material (not shown) are removed. Thereafter, the mold member 14 is eluted and removed from the ink discharge port 6 and the ink supply port 7 (FIG. 8 (j)). This is the same as FIG. 6H of the first embodiment.

  After the mold material 14 is removed, the inkjet head substrate 1 is dried, and the manufacturing process of the ink discharge port 6 and the ink supply port 7 is completed. Thereafter, an electric connection part for driving the heat generating part 3 and for exchanging electric power and signals from the outside is provided to complete the ink jet head.

  FIG. 8K is a schematic diagram enlarging the part indicated by the circle in FIG.

  The layer thickness of the secondary protective layer 17 formed on the flow path forming member 4 is preferably 0.5 μm or more because it is formed on the discharge port opening surface 5 on which the rubber blade that scrapes off the ink rubs. . The upper limit of the layer thickness is not particularly limited, but when the layer thickness is increased, the time required for film formation or dry etching becomes longer and the productivity is deteriorated. Therefore, it is generally considered that the upper limit is about 3 to 5 μm.

  When a positive photosensitive epoxy resin is used as the material of the flow path forming member 4, the deformation temperature at which the photosensitive epoxy resin starts to be softened and deformed is approximately 200 ° C. Therefore, during the film formation by the Cat-CVD method, It is necessary to form the film at a substrate temperature lower than 200 ° C. In addition, when a photosensitive acrylic resin is used as the material of the flow path forming member 4, the deformation temperature of the photosensitive acrylic resin is about 150 ° C., so the substrate temperature during film formation by the Cat-CVD method is higher than 150 ° C. It is necessary to form a film at a low temperature. For this reason, it is preferable that the substrate temperature during the film formation by the Cat-CVD method is equal to or lower than the deformation temperature of the material of the flow path forming member 4. For the same reason, the primary protective layer 16 is preferably formed at a substrate temperature equal to or lower than the temperature at which the mold 14 made of resin is deformed by heat.

  The inkjet head substrate 1 manufactured by the above steps has the following configuration.

It has a SiO ₂ layer that covers the heat generating portion 3 provided on the surface of the silicon substrate 2 that hits the lowermost surface of the ink flow path, its driving element, wiring, etc., and protects it from ink.

  Moreover, the discharge port opening surface 5 is formed with a protective layer (discharge port opening surface protective layer) formed by the Cat-CVD method. Further, the interface between the silicon substrate 2 and the flow path forming member 4 is covered with an interface protective layer 20 formed by a Cat-CVD method. The interface protective layer 20 is a part of the primary formation protective layer 16. In addition, the adhesion layer 9 and the protective layer formed by the Cat-CVD method may be provided on the bonding surface (bonding portion) between the silicon substrate 2 and the flow path forming member. Further, the inner surface (inner wall) of the ink flow path 8 inside the flow path forming member 4 and the flow path inner surface of the ejection unit 10 that is a part of the ink flow path 8 are formed by the Cat-CVD method. The inner surface protective layer 19 is covered. The flow path inner surface protective layer 19 is formed of a primary formed protective layer 16 and a secondary formed protective layer 17.

  Accordingly, the surface of the protective layer (discharge port opening surface protective layer) of the discharge port opening surface 5 is subjected to water repellent treatment, thereby suppressing ink accumulation on the surface and enabling recording with high recording quality. . Furthermore, since the surface of the protective layer (flow channel inner surface protective layer 19) formed by the Cat-CVD method formed on the inner surface of the ink flow path 8 has hydrophilicity, a smooth ink flow can be formed, and stable ink can be formed. Foaming and ink ejection are possible. By having the interface protective layer 20 formed by the Cat-CVD method at the interface between the silicon substrate 2 and the flow path forming member 4, contact with and penetration of the ink is suppressed, and the adhesion between the two is improved. .

(Third embodiment)
In the following embodiments, a manufacturing method for forming a protective layer by the Cat-CVD method at the above-described sites (1) to (4) will be described using the schematic cross-sectional views for each step of FIG. The difference between this embodiment and the second embodiment described above is that a hydrophilic protective layer is formed at least on the above-described parts (3) and (4) by the Cat-CVD method. ) Is formed by a Cat-CVD method with a water-repellent protective layer. FIGS. 9A to 9E are the same manufacturing steps as FIGS. 8A to 8E, respectively. In particular, the primary protective layer 16 is the same as the protective layer of the second embodiment. 9 (i) and FIG. 9 (j) are the same manufacturing steps as FIG. 8 (i) and FIG. 8 (j), respectively. Therefore, the substrate temperature at the time of forming each protective layer is also set to a temperature that does not cause thermal deformation of the material on which the protective layer is formed, and the film forming conditions are the same as those in the above-described embodiment.

  First, a protective layer that covers the surface (discharge port opening surface 5) of the flow path forming member 4 made of a photosensitive resin material is formed using the Cat-CVD method (FIG. 9F). The protective layer is a water-repellent SiC layer, SiOC layer, or SiCN layer. Therefore, in this embodiment, it is a protective layer formed by the second Cat-CVD method film formation, but has a water repellency unlike the hydrophilic secondary protective layer 17 described above, and therefore the secondary protective layer 17R To do.

  Next, a positive resist 15 is applied on the upper surface of the secondary protective layer 17R by spin coating or the like, and then dried. Next, this positive resist 15 is patterned using a photolithography technique to form a mask, and the secondary protective layer 17R is patterned using this mask. In this way, a two-layer mask is obtained on the surface of the discharge port opening surface 5 (FIG. 9G).

  Next, dry etching or the like is performed using this two-layer mask. By this processing step, the photosensitive resin material and the primary formation protective layer 16 that are not protected by the mask are removed (FIG. 9H). The removed photosensitive resin material forms a discharge portion 10 that is a part of the ink flow path 8. Further, the removed primary formation protective layer 16 is a portion that faces the ink discharge port 6 and covers the mold member 14.

  Next, the positive resist 15 formed on the upper surface of the secondary protective layer 17R is peeled off to obtain an ink discharge port 6 having a desired pattern, and an ink supply port 7 is formed (FIG. 9 (i)). . In this step, an opening from the ink discharge port 6 to the mold member 14 is formed in the secondary formation protective layer 17R (discharge port opening surface protective layer described later) and the flow path forming member 4.

  Finally, the patterning mask 13 and the protective material (not shown) are removed. Thereafter, the mold member 14 is eluted and removed from the ink discharge port 6 and the ink supply port 7 (FIG. 9 (j)).

  After the mold material 14 is removed, the inkjet head substrate 1 is dried, and the manufacturing process of the ink discharge port 6 and the ink supply port 7 is completed. Thereafter, the ink jet head substrate 1 is provided with an electrical connection part for driving the heat generating part 3 and for exchanging electric power and signals from the outside, and is completed as an ink jet head.

  In the inkjet head substrate 1 manufactured by the above steps, since the secondary formation protective layer 17R itself has water repellency, further water repellency treatment (for example, implantation of fluorine ions) is performed on the secondary formation protection layer 17R. The configuration that does not need to be applied is different from the above-described second embodiment.

The ink jet head substrate 1 of the present embodiment has a SiO ₂ layer that covers the heat generating portion 3 provided on the surface of the silicon substrate 2 corresponding to the lowermost surface of the ink flow path, its driving element, wiring, etc., and protects from ink. Furthermore, the interface between the silicon substrate 2 and the flow path forming member 4 is covered with an interface protective layer 20 formed by a Cat-CVD method. The interface protective layer 20 is a part of the primary formation protective layer 16. In addition, the adhesion layer 9 and the protective layer formed by the Cat-CVD method may be provided on the bonding surface (bonding portion) between the silicon substrate 2 and the flow path forming member. Further, the inner surface (inner wall) of the ink flow path 8 inside the flow path forming member 4 is covered with a flow path inner surface protective layer 19 formed by Cat-CVD. The flow path inner surface protective layer 19 is formed of the primary formation protective layer 16. Further, the protective layer (discharge port opening surface protective layer) of the discharge port opening surface 5 is formed of a secondary formed protective layer 17R having water repellency.

  As a result, the protective layer on the discharge port opening surface 5 has water repellency, so that ink accumulation on the surface of the protective layer is suppressed, and recording with high recording quality is possible. Furthermore, since the surface of the protective layer formed by Cat-CVD provided on the inner surface of the ink flow path 8 has hydrophilicity, it is possible to form a smooth ink flow, and stable ink foaming and ink ejection are possible. . By having the protective layer formed by the Cat-CVD method at the interface between the silicon substrate 2 and the flow path forming member 4, contact with and penetration of the ink is suppressed, contributing to improvement in adhesion between the two.

  In the above-described embodiment described with reference to FIG. 9, no protective layer is formed on the inner surface of the ink flow path of the ejection unit 10 (part corresponding to the above-described (2)). Therefore, another manufacturing method will be described in which a hydrophilic protective layer is formed also on this part by the Cat-CVD method.

  Since the steps shown in FIGS. 9A to 9H are the same, the subsequent steps will be described. First, a silicon substrate on which a hydrophilic primary-forming protective layer 16, a water-repellent secondary-forming protective layer 17R, and a positive resist 15 are formed through the steps of FIGS. 9A to 9H described above. 2 is prepared.

  Next, a hydrophilic protective layer is formed by Cat-CVD on the mask formed by the secondary protective layer 17R and the positive resist 15 formed on the discharge port opening surface 5, the inner surface of the discharge unit 10, and the discharge unit 10 And is formed on the primary protective layer 16 on the mold 14 (FIG. 10A). The hydrophilic protective layer formed by the third Cat-CVD film formation in this embodiment is referred to as a tertiary protective layer 18. The hydrophilic tertiary protective layer 18 is a SiO layer, SiN layer, SiON layer or the like as described above.

  Next, the tertiary protection layer 18 on the positive resist 15 and the primary protection layer 16 and the tertiary protection layer 18 on the mold 14 at the bottom of the discharge unit 10 are removed by dry etching or the like. . At this time, dry etching is performed so as to be perpendicular to the opening surface of the ink discharge port 6 so that the tertiary protection layer 18 formed on the inner surface of the discharge unit 10 is not removed. Thereafter, the positive resist 15 formed on the upper surface of the secondary protective layer 17R is peeled off to obtain an ink discharge port 6 having a desired pattern, and an ink supply port 7 is formed (FIG. 10B).

  The subsequent steps are as described in the above embodiments.

  According to this manufacturing method, a water-repellent protective layer is formed on the discharge port opening surface 5 and the inner surface of the discharge unit 10 as compared with the inkjet head substrate 1 described with reference to each step diagram of FIG. A hydrophilic protective layer can be formed. The inkjet head substrate 1 manufactured in this way includes a discharge portion as a part of the flow path inner surface protective layer 19 in addition to the protective layers of the inkjet head substrate 1 obtained by the manufacturing method described with reference to FIG. The tertiary formation protective layer 18 is provided on the inner surface of the ten channels.

  Thereby, compared with the inkjet head substrate 1 described with reference to FIG. 9, the protection of the hydrophilic protective layer on the inner surface of the ink flow path 8 can be enhanced although the number of manufacturing steps is increased.

It is a typical perspective view which cuts and shows a part of ink jet recording head board of an embodiment concerning the present invention. FIG. 2 is a diagram schematically illustrating a cross section taken along line XX in FIG. 1, and FIG. 2B is an enlarged schematic view of the vicinity of a portion indicated by a circle in FIG. It is a schematic diagram of the Cat-CVD apparatus for forming a protective layer. It is a perspective view showing an ink jet cartridge constituted using an ink jet head of an embodiment concerning the present invention. It is a typical perspective view which shows the schematic structural example of the inkjet recording device using the inkjet cartridge shown in FIG. FIGS. 6A to 6H are schematic cross-sectional views illustrating a method for manufacturing the inkjet head substrate according to the first embodiment of the present invention, and FIGS. 6A to 6H are schematic cross-sectional views illustrating each process, and FIG. ) Is a schematic diagram enlarging the vicinity of the part indicated by a circle in FIG. FIG. 7 is a schematic cross-sectional enlarged view of the vicinity of the ink discharge port according to the first embodiment of the present invention, and FIG. 7A is a schematic cross-sectional enlarged view of the vicinity of the ink discharge port on which the protective layer is formed. FIG. 7B is a schematic cross-sectional view in the vicinity of an ink discharge port showing a modified layer formed by fluorine ion implantation in the protective layer of FIG. 7A, and FIG. FIG. 3 is a schematic enlarged cross-sectional view in the vicinity of an ink discharge port in which a water repellent layer is formed on a protective layer. FIGS. 8A to 8J are schematic cross-sectional views illustrating a method for manufacturing an inkjet head substrate according to a second embodiment of the present invention, and FIGS. ) Is a schematic diagram enlarging the vicinity of the part indicated by a circle in FIG. FIGS. 9A to 9J are schematic cross-sectional views illustrating a method for manufacturing an ink jet head substrate according to a third embodiment of the present invention, and FIGS. 9A to 9J are schematic cross-sectional views illustrating each process. ) Is a schematic diagram enlarging the vicinity of the part indicated by a circle in FIG. It is typical sectional drawing which shows the manufacturing method of the inkjet head board | substrate of the further another form of 3rd Embodiment based on this invention, Fig.10 (a), (b) is typical sectional drawing which shows each process. .

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Inkjet head substrate 2 Silicon substrate 3 Heat generating part 4 Flow path forming member 5 Discharge port opening surface 6 Ink discharge port 7 Ink supply port 8 Ink flow channel 9 Adhesion layer 10 Discharge part 11 Protective layer 14 Mold material 16 Primary forming protective layer 17 Second Secondary protection layer 17R Secondary protection layer 18 Tertiary protection layer 19 Flow path inner surface protection layer 20 Interface protection layer

Claims (3)

A substrate including an energy generating element that generates energy for discharging liquid from a liquid discharge port;
The liquid discharge port, and a portion constituting an inner surface of a liquid path for supplying a liquid to the liquid discharge port, and the portion constituting the inner surface of the liquid passage is set on the inside of the substrate. And a resin structure that constitutes the liquid path by being provided on the side provided with the energy generating element,
Forming a mold material in a region to be the liquid path on the substrate;
On the substrate, a portion serving as a flow path inner surface protective layer provided on the inner surface of the fluid passage, the primary form protective hydrophilic and a portion serving as an interface protective layer for protecting the interface between the substrate and the resin structure Forming a layer so as to cover the mold material by catalytic chemical vapor deposition;
Said primary forming protective layer, and the step of providing a member serving as the resin structure,
Forming an opening for forming the liquid discharge port at a position of the member facing the energy generating element;
A hydrophilic secondary forming protective layer having a protective layer covering the opening surface of the liquid discharge port and the inner surface of the liquid discharge port of the resin structure is formed by opening the opening of the member by catalytic chemical vapor deposition. Forming an opening surface that is a surface on the side and an inner surface of the opening; and
A portion of the secondary protection layer that covers the opening surface on the side where the opening of the member is open is subjected to water repellent treatment, and the opening of the member of the secondary protection layer is opened. Water repellent part covering the opening surface that is the surface on the side, hydrophilic to the part covering the inner surface of the opening;
Etching the inside of the opening to form the liquid discharge port;
Removing the mold material and forming the liquid path;
The a, the opening surface of the liquid discharge port of the resin structure is water-repellent, the inner surface of the liquid discharge ports manufacturing method of a liquid discharge head substrate, wherein the hydrophilic der Rukoto. The substrate temperature when forming the secondary form protective layer by a catalytic chemical vapor deposition method, the production of a liquid discharge head substrate according to claim 1, wherein the resin structure is a temperature lower than the temperature at which deformation Method. Substrate temperature in the primary forming protective layer is formed by a catalytic chemical vapor deposition method for manufacturing a liquid discharge head substrate according to claim 1 or 2, wherein the mold material is a temperature lower than the temperature at which deformation .

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