WO2023176705A1 - インクジェットヘッド用部材、インクジェットヘッド用部材の製造方法及びインクジェットヘッド - Google Patents

インクジェットヘッド用部材、インクジェットヘッド用部材の製造方法及びインクジェットヘッド Download PDF

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Publication number
WO2023176705A1
WO2023176705A1 PCT/JP2023/009193 JP2023009193W WO2023176705A1 WO 2023176705 A1 WO2023176705 A1 WO 2023176705A1 JP 2023009193 W JP2023009193 W JP 2023009193W WO 2023176705 A1 WO2023176705 A1 WO 2023176705A1
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Prior art keywords
layer
base material
inkjet head
adhesion layer
material adhesion
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Ceased
Application number
PCT/JP2023/009193
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English (en)
French (fr)
Japanese (ja)
Inventor
晃久 山田
勇作 田中
弘典 ▲高▼橋
明久 下村
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Konica Minolta Inc
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Konica Minolta Inc
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Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to EP23770660.1A priority Critical patent/EP4494882A4/en
Priority to JP2024508114A priority patent/JPWO2023176705A1/ja
Priority to US18/843,721 priority patent/US20250214339A1/en
Priority to CN202380026545.7A priority patent/CN118871296A/zh
Publication of WO2023176705A1 publication Critical patent/WO2023176705A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1606—Coating the nozzle area or the ink chamber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/14—Structure thereof only for on-demand ink jet heads
    • B41J2/1433—Structure of nozzle plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/162—Manufacturing of the nozzle plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1626—Manufacturing processes etching
    • B41J2/1628—Manufacturing processes etching dry etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/1632—Manufacturing processes machining
    • B41J2/1634—Manufacturing processes machining laser machining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/164—Manufacturing processes thin film formation
    • B41J2/1642—Manufacturing processes thin film formation thin film formation by CVD [chemical vapor deposition]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/164—Manufacturing processes thin film formation
    • B41J2/1645—Manufacturing processes thin film formation thin film formation by spincoating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/135—Nozzles
    • B41J2/16—Production of nozzles
    • B41J2/1621—Manufacturing processes
    • B41J2/164—Manufacturing processes thin film formation
    • B41J2/1646—Manufacturing processes thin film formation thin film formation by sputtering

Definitions

  • the present invention relates to an inkjet head member, a method for manufacturing an inkjet head member, and an inkjet head, and in particular, it is possible to achieve both durability in the manufacturing process and adhesion between a base material and a functional layer.
  • the present invention relates to a member for an inkjet head that can ensure long-term durability against ink and scratch resistance, and has excellent continuous ejection properties.
  • Inkjet recording devices which are currently widely used, hold an inkjet head equipped with a nozzle plate in which a plurality of nozzle holes are arranged in a row, and hold the inkjet head by attaching it to a frame or the like.
  • An image is formed on a recording medium by ejecting ink of each color in the form of minute droplets.
  • Typical ink ejection methods for inkjet heads include a method in which water in the ink is vaporized and expanded by the heat generated by passing an electric current through an electric resistor placed in a pressurizing chamber, and pressure is applied to the ink to eject it.
  • a piezoelectric material for a part of the flow channel member constituting the pressurizing chamber, or by installing a piezoelectric material in the flow channel member and selectively driving the piezoelectric material corresponding to a plurality of nozzle holes, each piezoelectric material can be There is a method of deforming a pressurizing chamber based on the dynamic pressure of the body and ejecting liquid from a nozzle.
  • the surface characteristics of the surface on which the nozzle is provided are extremely important in achieving good ejection performance of ink droplets.
  • a silicone-based compound or a fluorine-containing organic compound such as a silane coupling agent
  • a silane coupling agent to form a liquid-repellent layer in this way, a liquid-repellent layer with excellent adhesion can be formed.
  • Patent Document 2 metal is used in the base layer that is the base of the liquid-repellent layer of the nozzle plate, and in Patent Document 3, metal is used in the intermediate layer to increase the bonding force between the nozzle plate and the bonding film containing organosiloxane. It is disclosed that the adhesion of a liquid repellent layer and a bonding film can be improved by using a nitride film. However, in the case of a metal nitride film that does not contain oxygen atoms, it is known that adhesion with the liquid repellent layer and the bonding film cannot be ensured.
  • the base material of the nozzle plate, etc. may be provided with a protective layer to protect the base material from corrosion, or an adhesive for bonding the base material with another base material. It is known to provide layers. There is a need to improve the adhesion between functional layers such as a liquid repellent layer, a base layer, a protective layer, and an adhesive layer and a base material.
  • Patent No. 6217170 European Patent No. 2484526 Patent No. 4900457
  • the present invention was made in view of the above-mentioned problems and circumstances, and the object to be solved is to achieve both durability in the manufacturing process and adhesion between the base material and the functional layer. As a result, it is an object of the present invention to provide an inkjet head member, a method for manufacturing an inkjet head member, and an inkjet head that can ensure long-term durability and scratch resistance against ink and have excellent continuous ejection properties.
  • the inventors of the present invention in the process of studying the causes of the above problems, discovered that group 4 or group 5 elements, nitrogen elements, and oxygen elements were added to the base material adhesion layer between the base material and the functional layer.
  • group 4 or group 5 elements, nitrogen elements, and oxygen elements were added to the base material adhesion layer between the base material and the functional layer.
  • the atomic concentration (atm%) of oxygen element on the surface of the functional layer side of the base material adhesion layer higher than the inside of the base material adhesion layer, durability in the manufacturing process and
  • the inventors have discovered that it is possible to achieve both adhesion with the functional layer, ensure long-term durability against ink and abrasion resistance, and have excellent continuous ejection properties, leading to the present invention. That is, the above-mentioned problems related to the present invention are solved by the following means.
  • An inkjet head member comprising at least a base material, a base material adhesion layer, and a functional layer in this order,
  • the base material adhesion layer contains a group 4 or group 5 element, a nitrogen element and an oxygen element
  • An inkjet head member wherein the atomic concentration (atm %) of oxygen element on the surface of the base adhesive layer on the functional layer side is higher than the inside of the base adhesive layer.
  • the base layer is a layer containing at least an inorganic oxide or an oxide containing carbon (C).
  • the base layer is a layer made of a silane coupling agent containing at least carbon (C) and oxygen (O).
  • silane coupling agent contained in the underlayer has a reactive functional group at both ends and a molecular structure containing a hydrocarbon chain and a benzene ring in the middle. Element.
  • An inkjet head comprising the inkjet head member according to any one of Items 1 to 12.
  • the means of the present invention it is possible to achieve both durability in the manufacturing process and adhesion between the base material and the functional layer, and as a result, long-term durability against ink and scratch resistance can be ensured.
  • the base material adhesion layer contains a group 4 or 5 element, a nitrogen element, and an oxygen element
  • heat resistance is improved by using a nitride film of a group 4 or 5 element with a high melting point. Adhesion can be improved. As a result, it is possible to improve the heat resistance in the manufacturing process of the inkjet head member and the adhesion durability of the interface between the base material and the functional film.
  • the atomic concentration (atm%) of the oxygen element on the surface of the functional layer side of the base material adhesion layer higher than the inside of the base material adhesion layer covalent bonds exhibiting larger bond energy and hydrogen Chemical bonds such as bonds are more likely to occur, and the adhesion between the base material and the functional film can be improved.
  • the base material adhesion layer contains a group 4 or group 5 element and imparts conductivity, it is possible to prevent mist adhesion during ink ejection and improve continuous ejection properties.
  • Schematic sectional view showing an example of a nozzle plate A schematic sectional view showing another example of the configuration of the nozzle plate.
  • Graph showing an example of each element concentration distribution curve (depth profile) in the thickness direction of the base material and base material adhesion layer Graph showing an example of the results of XRD diffraction measurement of the base material adhesion layer
  • Schematic diagram showing an example of an RIE mode high frequency plasma device used for forming a base material adhesion layer A schematic perspective view showing an example of the structure of an inkjet head to which the nozzle plate of the present invention can be applied.
  • the inkjet head member of the present invention is an inkjet head member having at least a base material, a base material adhesion layer, and a functional layer in this order, wherein the base material adhesion layer contains a group 4 or group 5 element, nitrogen element, and oxygen.
  • the atomic concentration (atm %) of the oxygen element on the surface of the base material adhesion layer on the functional layer side is higher than the inside of the base material adhesion layer.
  • the Group 5 element contained in the base material adhesion layer is tantalum (Ta), since it can impart conductivity and improve ink ejectability.
  • the value of the ratio of the atomic concentration (atm%) of the nitrogen element and the Group 4 or Group 5 element in the base material adhesion layer is expressed by the formula (I) (0.3 ⁇ atomic concentration of the nitrogen element/4 It is preferable that the atomic concentration of the Group or Group 5 element satisfies 1) from the viewpoint of imparting conductivity and preventing mist adhesion during ink ejection.
  • the base material adhesion layer has a peak derived from Ta 2 N in X-ray diffraction (XRD) measurement from the viewpoint of imparting electrical conductivity and preventing mist adhesion during ink ejection.
  • the thickness of the base material adhesion layer is preferably within the range of 1 to 1500 nm from the viewpoint of uniformity of nozzle shape by nozzle processing and deposition distribution of the base material adhesion layer.
  • the functional layer includes a liquid-repellent layer containing a coupling agent containing fluorine (F) in terms of improved adhesion with the base material adhesion layer and scratch resistance against ink.
  • F fluorine
  • the functional layer includes a liquid-repellent layer containing a coupling agent containing fluorine (F) and a base layer serving as a base for the liquid-repellent layer, since this can improve the adhesion of the liquid-repellent layer.
  • a liquid-repellent layer containing a coupling agent containing fluorine (F) and a base layer serving as a base for the liquid-repellent layer, since this can improve the adhesion of the liquid-repellent layer.
  • the base layer is a layer containing at least an inorganic oxide or an oxide containing carbon (C), preferably, the base layer contains at least carbon (C) as the oxide containing carbon (C). , silicon (Si), and oxygen (O), the liquid repellent layer has the effect of retaining the coupling agent containing fluorine (F) contained in the upper liquid repellent layer. This is preferable in that the adhesion between the layer and the base material adhesion layer is further improved.
  • the base layer is a layer made of a silane coupling agent containing at least carbon (C) and oxygen (O), and further, the silane coupling agent has reactive functional groups at both ends.
  • a molecular structure containing a hydrocarbon chain and a benzene ring in the middle allows for high-density polymerization and mutual stacking interaction, which makes the base material particularly susceptible to stress in the thickness direction.
  • the base material is a nozzle plate, the surface is subjected to stress in the width direction due to wipes used during maintenance. This is preferable in that it can also improve resistance when exposed to water.
  • the base material is made of stainless steel because it can exhibit better durability.
  • the base material adhesion layer is formed on the base material
  • the functional layer is formed on the base material adhesion layer
  • a nozzle is formed by laser processing.
  • the base material adhesion layer is formed by a reactive sputtering method using a dry process. Further, as the surface treatment of the base material adhesion layer, it is preferable to perform oxygen plasma treatment in that the atomic concentration of oxygen element on the surface of the base material adhesion layer on the functional layer side can be easily increased.
  • the inkjet head member of the present invention is suitably used in inkjet heads.
  • ⁇ is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • the inkjet head member of the present invention is an inkjet head member having at least a base material, a base material adhesion layer, and a functional layer in this order, wherein the base material adhesion layer contains a group 4 or group 5 element, nitrogen element, and oxygen.
  • the atomic concentration (atm %) of the oxygen element on the surface of the base material adhesion layer on the functional layer side is higher than the inside of the base material adhesion layer.
  • the inkjet head member of the present invention is a member constituting an inkjet head, and includes, for example, a nozzle plate, a nozzle substrate, an ink flow path, an ink chamber, or a member constituting an exterior part.
  • FIG. 1 is a schematic cross-sectional view showing an example of a nozzle plate.
  • the basic structure of the nozzle plate 1 is to form a base material adhesion layer 3 containing a group 4 or 5 element, a nitrogen element, and an oxygen element on a base material 2; , a functional layer 4.
  • the atomic concentration (atm %) of the oxygen element on the surface of the base material adhesion layer 3 on the functional layer 4 side is higher than the inside of the base material adhesion layer 3 .
  • the functional layer 4 may be, for example, a single layer of a liquid repellent layer, a base layer and a liquid repellent layer underlying the liquid repellent layer, or a protective layer that protects the base material. Alternatively, it may be an adhesive layer for bonding the base material of the nozzle plate and another base material.
  • the other base materials include base materials for pressure chambers, flow path boards, wiring boards, common flow paths, cap holders, exterior packaging, and the like. Materials include stainless steel, metals such as nickel (Ni), gold (Au), aluminum (Al), copper (Cu), silicon, metal oxides, metal nitrides, polyimide, liquid crystal polymers, PPS, Examples include resins such as epoxy.
  • FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the nozzle plate.
  • the base layer has a two-layer structure of a second base layer 41b and a second base layer 41b.
  • the first base layer 41a has a reactive functional group at both ends and a silane coupling agent containing a hydrocarbon chain and a benzene ring in the middle
  • the second base layer 41b has a structure in which carbon ( C), silicon (Si), and oxygen (O) as main components, such as a low molecular weight silane compound or a silane compound.
  • FIG. 3 is a schematic cross-sectional view showing an example of a partial configuration in which nozzle holes are formed in the nozzle plate described above.
  • a base material adhesion layer 3 containing a group 4 or 5 element, nitrogen element, and oxygen element is provided between the base material 2 and the functional layer 4 (base layer 41 and liquid repellent layer 42).
  • the adhesion between the base material 2 and the functional film 4 can be improved by providing a higher atomic concentration of the oxygen element on the surface of the base material adhesion layer 3 on the functional layer 4 side than in the inside. .
  • each constituent material of a nozzle plate composed of a base material, a base material adhesion layer, a base layer, and a liquid repellent layer
  • the base material adhesion layer contains a group 4 or 5 element, a nitrogen element, and an oxygen element, and the atomic concentration (atm%) of the oxygen element on the surface of the base material adhesion layer on the functional layer side is lower than the base material adhesion layer. Higher than the inside of the material adhesion layer.
  • the surface of the base material adhesion layer on the functional layer side refers to a region within a depth of 5 nm from the outermost surface on the surface side of the base material adhesion layer that is in contact with the functional layer.
  • inside the base material adhesion layer refers to the area excluding the surface of the base material adhesion layer on the functional layer side and the surface on the base material side, that is, the surface side of the base material adhesion layer that is in contact with the functional layer and the area on the base material side. This refers to a region deeper than 5 nm from the outermost surface of the surface in contact with the base material.
  • the atomic concentration (atm%) of the oxygen element on the functional layer side surface of the base material adhesion layer is preferably within the range of 20 to 75 atm%, more preferably within the range of 25 to 65 atm%. . Further, the atomic concentration (atm%) of the oxygen element inside the base material adhesion layer is preferably within the range of 0 to 50 atm%, and preferably within the range of 0 to 35 atm%.
  • the base material constituting the nozzle plate can be selected from materials that have high mechanical strength, ink resistance, and excellent dimensional stability, such as inorganic materials, metal materials, resin films, etc.
  • inorganic materials and metal materials are preferable, and metal materials such as silicon wafers, iron (e.g., stainless steel (SUS)), aluminum, nickel, and stainless steel are more preferable.
  • SUS stainless steel
  • the thickness of the base material constituting the nozzle plate is not particularly limited, and is within the range of 10 to 500 ⁇ m, preferably within the range of 30 to 150 ⁇ m.
  • the base material adhesion layer according to the present invention contains a group 4 or 5 element, nitrogen element, and oxygen element, and the atomic concentration (atm%) of the oxygen element on the surface of the base material adhesion layer on the functional layer side is higher than inside the adhesive layer.
  • the surface of the base material adhesion layer on the functional layer side is the surface on the functional layer side that comes into contact with the base material, and generally, the surface of the base material adhesion layer is a surface of up to 5 nm in depth in the direction of the base material from the outermost surface of the base material adhesion layer. Refers to an area.
  • Examples of the Group 4 elements include titanium (Ti), zirconium (Zr), hafnium (Hf), etc.
  • examples of the Group 5 elements include vanadium (V), niobium (Nb), tantalum (Ta), etc.
  • tantalum (Ta), titanium (Ti), and zirconium (Zr) are preferred, and tantalum (Ta) is particularly preferred.
  • the method of measuring the composition ratio of the elements constituting the base material adhesion layer is not particularly limited, but in the present invention, for example, using a glass knife for trimming, etc., 10 nm from the surface of the base material adhesion layer is measured.
  • IR infrared spectroscopy
  • the base material adhesion layer is an extremely thin film of 10 nm or less, it can be quantified by XPS (X-ray Photoelectron Spectroscopy) analysis method.
  • XPS X-ray Photoelectron Spectroscopy
  • using the XPS analysis method is advantageous because it allows elemental analysis even for extremely thin films, and from the viewpoint of being able to measure the composition distribution profile in the layer thickness direction of the entire base material adhesion layer by depth profile measurement, which will be described later. , is the preferred method.
  • X-ray photoelectron spectroscopy is a type of photoelectron spectroscopy called XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis). exists on the surface This method analyzes the constituent elements and their electronic states.
  • the atomic concentration (atm%) of oxygen element on the surface on the functional layer side is preferably within the range of 20 to 75 atm%, and the base material adhesion layer is The internal atomic concentration (atm%) of oxygen element is preferably within the range of 25 to 65 atm%.
  • the value of the ratio (S/I) of the atomic concentration (S) of the oxygen element on the surface of the base material adhesion layer on the functional layer side and the atomic concentration (I) of the oxygen element inside the base material adhesion layer is 1. It is preferable to set it to 01 or more.
  • the ratio of the atomic concentration (atm %) of the nitrogen element and the Group 4 or Group 5 element in the base material adhesion layer satisfies the following formula (I).
  • the atomic concentration distribution curve (hereinafter referred to as "depth profile") from the base material adhesion layer to the thickness direction of the base material according to the present invention is the concentration of metal oxide or nitride (atm%), Concentrations of silicon oxides or nitrides (atm%), concentrations of carbon (C), nitrogen (N), oxygen (O), group 4 or group 5 elements (atm%), etc., were measured using X-ray photoelectron spectroscopy. By using a combination of measurement of It can be measured by analyzing the surface composition of the material side.
  • a distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis representing the concentration of each element (unit: atm %) and the horizontal axis representing the etching time (sputtering time).
  • the etching time roughly correlates with the distance from the surface of the base material adhesion layer in the layer thickness direction. The distance from the surface of the base material adhesion layer in the direction can be adopted as the distance from the surface of the base material adhesion layer calculated from the relationship between the etching rate and etching time adopted during XPS depth profile measurement. .
  • a rare gas ion sputtering method using argon (Ar) as an etching ion species can be employed as a sputtering method employed in such XPS depth profile measurement.
  • the etching rate can be measured using a SiO 2 thermal oxide film whose thickness is known in advance, and the etching depth is often expressed as an SiO 2 thermal oxide film conversion value.
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI ⁇ X-ray source: Monochromatic Al-K ⁇ 15kV 25W ⁇ Sputter ion: Ar (1keV) - Depth profile: Measurements are repeated at predetermined thickness intervals using the SiO 2 equivalent sputtering thickness to determine the depth profile in the depth direction. This thickness interval was set to 2.6 nm (data can be obtained every 2.6 nm in the depth direction) - Quantification: Background was determined using the Shirley method, and quantification was performed using the relative sensitivity coefficient method from the obtained peak area. MultiPak manufactured by ULVAC-PHI is used for data processing.
  • Figure 4 shows a structure composed of a base material (SUS)/base material adhesion layer (TaN)/first base layer (SiOC)/second base layer (SiOC)/liquid repellent layer (coupling agent containing fluorine).
  • SUS base material
  • TiN base material adhesion layer
  • SiOC first base layer
  • SiOC second base layer
  • liquid repellent layer coupling agent containing fluorine
  • the atomic concentration distribution curve (death profile) shown in Figure 4 shows an example in which a base material adhesion layer is formed on the surface of an SUS base material by sputtering film formation, and shows the oxygen (O) concentration inside the base material adhesion layer. , indicating that the oxygen concentration on the surface of the base material adhesion layer is high.
  • the point where the concentration of carbon (C) derived from the base layer among the constituent atoms of the base material from the liquid repellent layer is 1/2 of the peak concentration is located on the surface of the base material adhesive layer (the interface between the first base layer and the base material adhesive layer). ) can be understood as In other words, a location approximately 94 nm from the surface of the liquid-repellent layer when the etching time is 60 (min) can be considered to be the interface between the first underlayer and the base material adhesion layer.
  • the point where the oxygen concentration levels off can be understood as being inside the base material adhesion layer. That is, here, the etching time is 74 (min) and the location approximately 116 nm from the surface of the liquid repellent layer can be considered as the interface between the base material adhesion layer and the base material. It can be seen that there is a layer in which the oxygen concentration at the surface of the base material adhesion layer is higher than the oxygen concentration inside the base material.
  • the base material adhesion layer according to the present invention has a peak derived from Ta 2 N in X-ray diffraction (XRD) measurement from the viewpoint of imparting conductivity and preventing mist adhesion during ink ejection.
  • XRD X-ray diffraction
  • X-ray diffraction measurement of the base material adhesion layer can be performed by the following procedure. Using a 6-inch silicon wafer as a base material, sputtering was performed on the base material using a Ta target in an atmosphere of argon gas and nitrogen gas to form a base material adhesion layer. Specifically, under vacuum conditions, sputtering was performed using a Ta target that had been set in advance on the electrode of a DC sputtering film forming apparatus under the following conditions. ⁇ Sputtering conditions Target: Ta DC power density: 1.1W/ cm2 Power: 200W Temperature: 25°C Pressure: 0.3Pa Introduced gas: Argon gas + Nitrogen gas Film forming time: 10 min
  • the base material adhesion layer formed on the silicon wafer described above was measured using an X-ray diffraction device (Rigaku Corporation's multipurpose X-ray diffraction device Ultima III) under the following conditions to obtain an X-ray diffraction pattern.
  • Scan speed 10°/min
  • FIG. 5 is an example showing the results of XRD diffraction measurement of the base material adhesive layer. As shown in FIG. 5, in the measured X-ray diffraction spectrum, a peak at 2 ⁇ of 32.6° was attributed to Ta 2 N.
  • the resistivity of the base material adhesion layer according to the present invention is preferably a low value within the range of 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 16 ⁇ cm.
  • the resistivity of TaN contained in the base material adhesion layer according to the present invention is low in the range of 100 to 350 ⁇ cm; , Ta 2 O 5 exhibits high insulating properties and high resistivity.
  • Known methods for measuring the resistivity include the two-probe method, the four-probe method, and the four-probe method.
  • Method for forming base material adhesion layer Although there are no particular limitations on the method for forming the base material adhesion layer according to the present invention, the following method can be applied.
  • Film forming methods for the base material adhesion layer that can be applied to the present invention include dry film forming methods such as physical vapor deposition method (PVD method) and chemical vapor deposition method (CVD method), electrolytic plating, etc. Examples include wet film forming methods such as electroless plating, but in the present invention, dry film forming methods are preferred in that a thin and dense film can be formed.
  • PVD method physical vapor deposition method
  • CVD method chemical vapor deposition method
  • electrolytic plating etc.
  • wet film forming methods such as electroless plating
  • dry film forming methods are preferred in that a thin and dense film can be formed.
  • the dry film forming method includes a sputtering method, a vacuum evaporation method, a laser ablation method, an ion plating method, an electron beam epitaxy method (MBE method), a metal organic chemical vapor deposition method (MOCVD method), and a plasma CVD method.
  • a plasma etching mode method using oxygen gas (O 2 PE mode) oxygen gas
  • O 2 RIE mode reactive ion etching method using oxygen gas
  • a method in which a film is formed by a sputtering method and then a surface treatment is performed by a plasma treatment is preferable in that a desired base material adhesion layer can be formed.
  • Typical methods for forming the base material adhesion layer include the following methods. 1. Film formation method: After forming a metal layer (content 30 to 70 atm%) consisting of a group 4 or 5 element on a base material by a sputtering method that targets a group 4 or 5 element, the metal layer is coated with the metal layer as described below. A base material adhesion layer is formed by plasma treatment. Note that Ta (tantalum) will be explained below as an example of a metal consisting of a Group 4 or Group 5 element.
  • a metal of group 4 or group 5 element for example, Ta
  • a metal of group 4 or group 5 element for example, Ta
  • a sputtering method reactive Sputtering
  • a method of forming a film by sputtering in an argon gas atmosphere using a nitride target of a group 4 or group 5 metal can be used. It is preferable to use the former (reactive sputtering) because it is easier to control the optimal film composition.
  • Sputtering was performed under vacuum conditions using a Ta target that had been set in advance on the electrode of a DC sputtering film forming apparatus under the following conditions. At this time, other plasma sources may be used instead of DC sputtering.
  • Plasma treatment after sputtering Plasma etching modes applicable to the present invention include RIE mode and PE mode.
  • the "RIE" (Reactive Ion Etching) mode referred to in the present invention refers to a pair of flat plate electrodes facing each other, in which a base material constituting a nozzle plate, such as SUS304, is placed on the power supply electrode side as an object to be plasma treated, and the object to be plasma treated is This method performs plasma treatment on the surface.
  • the "PE” (Plasma Etching) mode is a method in which an object to be plasma treated is placed on the ground electrode side of a pair of opposing flat electrodes, and plasma processing is performed on the surface of the object to be plasma treated.
  • FIG. 6 is a schematic diagram showing an example of a high frequency plasma apparatus in RIE mode (reactive ion etching mode) used for forming the base material adhesion layer.
  • RIE mode reactive ion etching mode
  • FIG. 6 is a schematic diagram showing an example of a high frequency plasma apparatus in RIE mode (reactive ion etching mode) used for forming the base material adhesion layer.
  • RIE mode is suitable for physical and high-speed surface treatment by ion bombardment.
  • a high-frequency plasma apparatus 20A in RIE mode includes a reaction chamber 21, a high-frequency power source 22 (RF (Radio Frequency) power source), a capacitor 23, a flat electrode 24 (cathode, ), a counter electrode 25 (anode, also referred to as a "ground electrode”), a grounding part 26, and the like.
  • the reaction chamber 21 has a gas inlet 27 and an outlet 28 . Planar electrode 24 and counter electrode 25 are arranged within reaction chamber 21 .
  • a pair of electrodes consisting of a planar electrode 24 connected to a high frequency power source 22 via a capacitor 23 and a counter electrode 25 that faces the planar electrode 24 and is grounded by a grounding section 26 are placed inside the reaction chamber 21 which can be sealed. It is located. Further, a nozzle plate base material 30 as an object to be subjected to plasma treatment is placed on the planar electrode 24 .
  • the high frequency power supply 22 is started, and the high frequency power supply 22 is supplied with a high frequency of 3 MHz or more and 100 MHz or less. (usually 13.56 MHz), a discharge D is generated between the plane electrode 24 and the counter electrode 25, and a discharge space where low-temperature plasma (cations and electrons) of the reaction gas G and radical species are generated.
  • the high frequency power density is preferably set within the range of 0.01 to 3 W/cm.
  • Examples of the reactive gas G used for etching include rare gases (for example, helium gas, neon gas, argon gas, krypton gas, xenon gas), oxygen gas, and hydrogen gas.
  • rare gases for example, helium gas, neon gas, argon gas, krypton gas, xenon gas
  • oxygen gas oxygen gas
  • hydrogen gas hydrogen gas
  • argon gas is used as the reactive gas G.
  • the RIE mode plasma processing method used is called "Ar-RIE mode plasma processing"
  • the RIE mode plasma processing method using oxygen gas as a reactive gas is called "O 2 -RIE mode plasma processing”.
  • the layer thickness of the base material adhesion layer is generally within the range of 1 to 20,000 nm, but from the viewpoint of uniformity of the nozzle shape by nozzle processing and deposition distribution of the base material adhesion layer, the layer thickness is 1 to 5,000 nm. It is preferably within the range, and from the viewpoint of productivity, it is even more preferably within the range of 1 to 1500 nm.
  • the base layer according to the present invention is formed between the base material adhesion layer and the liquid repellent layer according to the present invention, and is preferably a layer containing at least an inorganic oxide or an oxide containing carbon (C). preferable.
  • the inorganic oxides that can be applied to the formation of the underlayer according to the present invention are not particularly limited, and include, for example, oxides of metals including transition metals, noble metals, alkali metals, alkaline earth metals, etc. Examples include composite oxides. More specifically, the inorganic oxide fine particles are oxides or composite oxides containing one or more metal elements selected from silicon, aluminum, titanium, magnesium, zirconium, antimony, iron, and tungsten. It is preferable that there be.
  • the oxide or composite oxide may further contain one or more selected from phosphorus, boron, cerium, alkali metals, and alkaline earth metals.
  • Common inorganic oxides include, for example, aluminum oxide, silica (silicon dioxide), magnesium oxide, zinc oxide, lead oxide, tin oxide, tantalum oxide, indium oxide, bismuth oxide, yttrium oxide, cobalt oxide, copper oxide, Examples include manganese oxide, selenium oxide, iron oxide, zirconium oxide, germanium oxide, tin oxide, titanium oxide, niobium oxide, molybdenum oxide, and vanadium oxide.
  • the inorganic oxide contained in the underlayer is a layer composed of silicon dioxide as a main component.
  • the inorganic oxide may contain an organic substance such as an organic group or a resin as a subcomponent.
  • the underlayer is an organic oxide containing at least carbon (C).
  • organic oxides containing carbon (C) include, for example, silicon compounds such as silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxy.
  • silicon compounds such as silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxy.
  • zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bis-acetylacetonate, and zirconium acetylacetonate. nate, zirconium acetate, zirconium hexafluoropentanedionate, and the like.
  • aluminum compounds include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, triethyldialuminum tri-s -butoxide, etc.
  • the layer containing carbon (C), silicon (Si), and oxygen (O) as main components be made of a silane compound with a molecular weight of 300 or less (for example, an alkoxy silane, silazane, etc.) or a silane coupling agent.
  • the base layer according to the present invention is preferably a layer formed using a silane coupling agent, and further, the silane coupling agent contained in the base layer has reactive functional groups at both terminals.
  • the intermediate portion contains a hydrocarbon chain and a benzene ring.
  • the base layer has a reactive functional group at both ends and a carbonized base layer in the middle part.
  • first base layer a high-density polymer film is formed by a dehydration condensation reaction of silane coupling agent A containing a hydrogen chain and a benzene ring, and the base layer is made of an inorganic oxide or at least Si.
  • second base layer is that the second base layer is composed of an oxide mainly composed of an organic oxide containing.
  • silane coupling agent A having reactive functional groups at both terminals and containing a hydrocarbon chain and a benzene ring in the middle is used as a silane coupling agent used to form the base layer by a dehydration condensation reaction. It is preferable to apply.
  • the silane coupling agent A that can be applied to the underlayer is not particularly limited, and conventionally known compounds that meet the above requirements can be appropriately selected and used; From the viewpoint of making it possible, it has an alkoxy group, chlorine, acyloxy group, or amino group as a reactive functional group at both terminals represented by the following general formula (1), and a hydrocarbon chain and a benzene ring (phenylene group) in the middle part. ) is preferable.
  • alkoxy group examples include an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, ethoxy group, propoxy group, butoxy group, preferably an alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 8 carbon atoms. 6 alkoxy group, etc.
  • acyloxy group examples include linear or branched acyloxy groups having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, carbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy, etc.).
  • an amino group an amino group (-NH 2 ) and a substituted amino group having 1 to 15 carbon atoms (for example, methylamino, dimethylamino, ethylamino, methylethylamino, diethylamino, n-propylamino, methyl- n-propylamino, ethyl-n-propylamino, n-propylamino, isopropylamino, isopropylmethylamino, isopropylethylamino, diisopropylamino, phenylamino, diphenylamino, methylphenylamino, ethylphenylamino, n-propylphenylamino , and isopropylphenylamino).
  • a substituted amino group having 1 to 15 carbon atoms for example, methylamino, dimethylamino, ethylamino, methylethylamino
  • the base layer according to the present invention is prepared by using the silane coupling agent A according to the present invention, which has reactive functional groups at both terminals and contains a hydrocarbon chain and a benzene ring in the middle part, in an organic solvent such as ethanol, propanol, etc. , butanol, 2,2,2-trifluoroethanol, etc. to a desired concentration to prepare a coating solution for forming the base layer, and then coated on a substrate by a wet coating method and dried to form the base layer.
  • an organic solvent such as ethanol, propanol, etc. , butanol, 2,2,2-trifluoroethanol, etc.
  • the concentration of silane coupling agent A in the coating solution for forming the base layer is not particularly limited, but is generally in the range of 0.5 to 50% by mass, preferably in the range of 1.0 to 30% by mass. be.
  • the thickness of the first underlayer according to the present invention is not particularly limited, but it is preferably within the range of approximately 1 to 500 nm, and more preferably within the range of 5 to 200 nm.
  • the second base layer is made of an oxide mainly composed of an organic oxide containing Si.
  • the base layer 41 is composed of two layers, a first base layer 41a and a second base layer 41b, and the first base layer 41a has reactive functional groups at both terminals as described above.
  • the second base layer 41b is made of an organic oxide containing Si as described below.
  • the second underlayer is made up of the following.
  • alkoxysilanes, silazane, or silane coupling agents having a molecular weight of 300 or less that can be applied to the present invention are shown below, but the present invention is not limited to these exemplified compounds.
  • the numerical value in parentheses after each compound is the molecular weight (Mw).
  • alkoxysilane examples include tetraethoxysilane (Si(OC 2 H 5 ) 4 , Mw: 208.3), methyltriethoxysilane (CH 3 Si(OC 2 H 5 ) 3 , Mw: 178.3), Methyltrimethoxysilane (CH 3 Si(OCH 3 ) 3 , Mw: 136.2), Dimethyldiethoxysilane ((CH 3 ) 2 Si(OC 2 H 5 ) 2 , Mw: 148.3), Dimethyldimethoxysilane ((CH 3 ) 2 Si(OCH 3 ) 2 , Mw: 120.2) and the like.
  • silazane examples include 1,1,1,3,3,3-hexamethyldisilazane ((CH 3 ) 3 SiNHSi(CH 3 ) 3 , 161.4), 1,1,1,3, 3,3-hexaethyldisilazane ((C 2 H 5 ) 3 SiNHSi(C 2 H 5 ) 3 , 245.4), others include 1,3-bis(chloromethyl)tetramethyldisilazane, 1, Examples include 3-divinyl-1,1,3,3-tetramethyldisilazane.
  • Amino-based silane coupling agent 3-aminopropyltrimethoxysilane (H 2 NCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , mW: 179.3), 3-(2-aminoethylamino)propyl trimethoxysilane Methoxysilane (H 2 NCH 2 CH 2 NHCH 2 CH 2 CH 2 Si(OCH 3 ) 3 , Mw: 222.4), 3-(2-aminoethylamino)propylmethyldimethoxysilane (H 2 NCH 2 CH 2 NHCH 2CH2CH2Si ( CH3 )( OCH3 ) 2 , Mw : 206.4) and the like.
  • Epoxy-based silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane (Mw: 236.3) and 3-glycidoxypropyltriethoxysilane (Mw: 278.4).
  • the second base layer according to the present invention comprises a silane compound according to the present invention having a molecular weight of 300 or less, such as a conventionally known alkoxysilane, silazane, or a silane coupling agent, and an organic solvent such as ethanol, propanol, butanol.
  • a coating solution for forming an intermediate layer by dissolving it in 2,2,2-trifluoroethanol or the like to a desired concentration, it is coated on the base layer by a wet coating method and dried to form the intermediate layer.
  • the concentration of the inorganic oxide forming material in the second base layer forming coating liquid is not particularly limited, but is generally in the range of 0.5 to 50% by mass, preferably 1.0 to 30% by mass. is within the range of
  • the layer thickness of the second base according to the present invention is within the range of 0.5 to 500 nm, preferably within the range of 1 to 300 nm, and more preferably within the range of 5 to 100 nm.
  • liquid-repellent layer also referred to as “water-repellent layer” contains a coupling agent containing fluorine (F) (hereinafter also referred to as coupling agent B).
  • F fluorine
  • the coupling agent B containing fluorine (F) that can be applied to the liquid-repellent layer according to the present invention is not particularly limited; (2) a compound having a perfluoroalkyl group containing a phosphonic acid group or a hydroxy group; A mixture containing a compound having a group or a mixture containing a compound having a perfluoropolyether group is preferable.
  • a specific compound of the coupling agent B containing fluorine (F) that can be applied to the liquid repellent layer according to the present invention is chlorodimethyl[3-(2,3,4,5,6-pentafluorophenyl)] propyl]silane, pentafluorophenyldimethylchlorosilane, pentafluorophenylethoxydimethylsilane, pentafluorophenylethoxydimethylsilane, trichloro(1H,1H,2H,2H-tridecafluoro-n-octyl)silane, trichloro(1H,1H, 2H,2H-heptadecafluorodecyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, triethoxy-1H,
  • silane coupling agents containing fluorine (F) are available as commercial products, such as those manufactured by Toray-Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., Daikin Industries, Ltd. (e.g. , Optool DSX), Asahi Glass Co., Ltd. (eg, Cytop), Seco Co., Ltd. (eg, TopCleanSafe (registered trademark)), Fluoro Technology Co., Ltd. (eg, Fluorosurf), Gelest Inc. It is marketed by Solvay Solexis Co., Ltd. (for example, Fluorolink S10) and is easily available. Fluorine Chem. , 79(1).
  • a compound having a silane group-terminated perfluoropolyether group for example, "Optool DSX” manufactured by Daikin Industries, Ltd. shown above
  • a compound having a silane group-terminated fluoroalkyl group for example, examples of polymers having perfluoroalkyl groups include "FG-5010Z130-0.2” manufactured by Fluorosurf Co., Ltd., and "S F Coat Series” manufactured by AGC Seimi Chemical Co., Ltd., which has a fluorine-containing heterocyclic structure in the main chain.
  • the polymer include the above-mentioned "CYTOP” manufactured by Asahi Glass Co., Ltd.
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • a coupling agent having a fluorine (F) other than the silane group terminal a phosphonic acid derivative having a fluorinated alkyl chain (for example, FOPA) manufactured by Dojindo Kagaku Kenkyusho Co., Ltd. can also be used.
  • FOPA fluorinated alkyl chain
  • Evaporation substances WR1 and WR4 manufactured by Merck Japan Co., Ltd. which are fluoroalkylsilane mixed oxides, are used as the fluorine-based compound, and, for example, a liquid repellent layer is formed using WR1 on a silicon substrate. It is preferable to form a silicon oxide layer in advance as a base layer in this case.
  • the liquid-repellent layer formed by WR1 and WR4 exhibits liquid-repellent properties not only to water but also to organic solvents such as alcohols such as ethanol, ethylene glycol (including polyethylene glycol), thinners, and paints.
  • the thickness of the liquid-repellent layer according to the present invention is approximately within the range of 1 to 500 nm, preferably within the range of 1 to 400 nm, and more preferably within the range of 2 to 200 nm.
  • the base material adhesion layer is formed on the base material, the functional layer is formed on the base material adhesion layer, and then a nozzle is formed by laser processing.
  • the base material adhesion layer be formed by a reactive sputtering method using a dry process, and oxygen plasma treatment is preferably performed as the surface treatment of the base material adhesion layer.
  • a method for manufacturing a nozzle plate in which the above-mentioned base layer and liquid-repellent layer are used as functional layers will be described below.
  • the method for manufacturing the nozzle plate is described in detail above, 1) forming a base material adhesion layer on the base material, 2) The atomic concentration of oxygen element on the functional layer side surface of the base material adhesion layer is configured to be higher than the inside of the base material adhesion layer, 3) Next, on the base material adhesion layer, a base layer is formed of an inorganic oxide or an oxide containing carbon (C), 4) Next, a liquid-repellent layer is formed on the base layer using a coupling agent containing fluorine (F). 5) Next, a nozzle is formed on the base material, base material adhesion layer, base layer, and liquid repellent layer by laser processing.
  • FIG. 2 is a schematic cross-sectional view showing an example of the configuration of the nozzle hole portion of the nozzle plate according to the present invention.
  • a nozzle portion N having a desired shape as an ink ejection portion is formed on the base material 2, the base material adhesion layer 3, the base layer 41, and the liquid repellent layer 42.
  • Japanese Patent Publication No. 005-533662 Japanese Patent Application Publication No. 2007-152871, Japanese Patent Application Publication No. 2007-313701, Japanese Patent Application Publication No. 2009-255341, and Japanese Patent Application Publication No. 2009-255341. 2009-274415, 2009-286036, 2010-023446, 2011-011425, 2013-202886, 2014-144485, 2018-
  • JP 083316, JP 2018-111208, and the like can be referred to, and detailed description thereof will be omitted here.
  • the nozzle plate manufactured as described above can achieve both durability in the manufacturing process and adhesion between the base material and the base layer and liquid repellent layer, and also has long-term durability against ink and scratch resistance. It is possible to ensure sex.
  • the nozzle holes are preferably formed by laser processing.
  • the nozzle plate according to the present invention in the manufacturing method thereof, it is preferable to use a laser in processing the external shape of the nozzle holes, and it is further preferable that the laser is a pulsed laser or a CW laser.
  • CW laser beam continuous wave laser beam
  • pulsed laser beam pulsed laser beam
  • Laser beams that can be used here include gas lasers such as Ar laser, Kr laser, and excimer laser, single crystal YAG, YVO 4 , forsterite (Mg 2 SiO 4 ), YAlO 3 , GdVO 4 , YLF, and One or more of Nd, Yb, Cr, Ti, Ho, Er, Tm, and Ta are added to crystalline (ceramic) YAG, Y 2 O 3 , YVO 4 , YAlO 3 , and GdVO 4 as dopants.
  • Gas lasers such as Ar laser, Kr laser, and excimer laser
  • the laser used is preferably YAG-UV (yttrium aluminum garnet crystal: wavelength 266 nm), which emits ultraviolet laser light with a wavelength of about 266 nm, or YVO 4 (wavelength: 355 nm).
  • a laser with a wavelength of about 266 nm can dissociate molecular bonds such as C--H bonds and C--C bonds by thermal action.
  • the pulse width is 12 ns and the output is 1.6 W
  • YVO4 wavelength: 355 nm
  • the pulse width is 18 ns and the output is 2. It is 4W.
  • ultrafast lasers that produce intense laser pulses with durations of approximately 10 -11 seconds (10 psec) to 10 -14 seconds (10 fsec) and durations of approximately 10 -10 seconds (100 psec) to 10 -11 seconds
  • Short pulse lasers that produce intense laser pulses (10 psec) can also be used. These pulsed lasers are also useful for cutting or drilling a wide variety of materials.
  • FIG. 7 is a schematic external view showing an example of the structure of an inkjet head to which the nozzle plate according to the present invention can be applied.
  • FIG. 8 is a bottom view of an inkjet head equipped with a nozzle plate according to the present invention.
  • an inkjet head 100 equipped with a nozzle plate according to the present invention is installed in an inkjet printer (not shown), and includes a head chip that ejects ink from a nozzle, and a head chip that is arranged to eject ink from a nozzle.
  • a third joint 82 attached to the third ink port of the manifold, and a cover member 59 attached to the housing 56.
  • mounting holes 68 are formed for mounting the housing 56 on the printer main body side.
  • the cap receiving plate 57 shown in FIG. 8 is formed as a substantially rectangular plate whose outer shape is elongated in the left-right direction in accordance with the shape of the cap receiving plate attachment portion 62, and a plurality of nozzles N are formed approximately in the center of the cap receiving plate 57.
  • a nozzle opening 71 that is elongated in the left-right direction is provided.
  • inkjet heads are shown in FIGS. 7 and 8, there are other examples as well, such as JP-A No. 2012-140017, JP-A No. 2013-010227, JP-A No. 2014-058171, and JP-A No. 2014. -097644, 2015-142979, 2015-142980, 2016-002675, 2016-002682, 2016-107401, 2017-109476
  • An inkjet head having a configuration described in Japanese Patent Publication No. 2017-177626, etc. can be appropriately selected and applied.
  • Inkjet ink There are no particular restrictions on the inkjet ink that can be applied to the inkjet recording method using the inkjet head of the present invention.
  • oil-based inkjet ink that does not contain water
  • organic solvent-based inkjet ink that contains a solvent that evaporates at room temperature and does not substantially contain water
  • hot-melt ink that prints by heating and melting ink that is solid at room temperature
  • inkjet inks such as active energy ray-curable inkjet inks that are cured by active rays such as ultraviolet rays, but in the present invention, alkaline inks are applied from the viewpoint of being able to exhibit the effects of the present invention. This is a preferred embodiment.
  • Ink includes, for example, alkaline ink and acidic ink.
  • alkaline ink may cause chemical deterioration of the base material, liquid repellent layer, and nozzle forming surface. It is particularly effective to apply the inkjet head equipped with the nozzle plate of the present invention to the inkjet recording method that has been used.
  • the ink applicable to the present invention includes coloring materials such as dyes and pigments, water, water-soluble organic solvents, pH adjusters, and the like.
  • water-soluble organic solvents examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, triethylene glycol, ethanol, and propanol.
  • the pH adjuster for example, sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium bicarbonate, alkanolamine, hydrochloric acid, acetic acid, etc. can be used.
  • the alkaline ink has a pH of 8.0 or higher.
  • the liquid-repellent layer is formed from a fluorine-containing silane coupling agent or the like.
  • the liquid-repellent layer has a structure in which a silicon-containing partial structure and a fluorine-containing partial structure are bonded by a substituent such as a methylene group (CH 2 ).
  • the bond energy between carbon (C) and carbon (C) is smaller than the bond energy between silicon (Si) and oxygen (O) and the bond energy between carbon (C) and fluorine (F), so carbon
  • the part where (C) and carbon (C) are bonded is more bonded than the part where silicon (Si) and oxygen (O) are bonded, and the part where carbon (C) and fluorine (F) are bonded. weak and susceptible to mechanical and chemical damage.
  • a nozzle plate having the configuration defined in the present invention is effective in increasing durability.
  • nozzle plate 1 A nozzle plate 1 composed of the base material 2/base material adhesion layer 3/first base layer 41a/second base layer 41b/liquid repellent layer 42 shown in FIG. 2 was produced according to the following method.
  • base material As a base material, a stainless steel base material (SUS304) with a length of 3 cm, a width of 8 cm, and a thickness of 50 ⁇ m without surface treatment was used.
  • SUS304 stainless steel base material
  • sputtering was performed using a Ta target that had been set in advance on the electrode of a DC sputtering film forming apparatus under the following conditions.
  • A-1 was prepared by mixing the following constituent materials.
  • Silane coupling agent a 1,4-bis(trimethoxysilylethyl)benzene ((CH 3 O) 3 Si(CH 2 ) 2 (C 6 H 4 )(CH 2 ) 2 Si(OCH 3 ) 3 )( refer to the following) 2mL
  • Preparation of A-2 liquid> Mixed solution of ethanol and 2,2,2-trifluoroethanol (8:2 by volume) 19.5mL Pure water 30mL Hydrochloric acid (36% by volume) 0.5mL
  • Second base layer (preparation of coating liquid for forming second base layer)
  • a second base layer forming coating liquid was prepared by mixing the following constituent materials.
  • Silane coupling agent c 3-aminopropyltriethoxysilane ((C 2 H 5 O) 3 SiC 3 H 6 NH 2 ), Shin-Etsu Chemical Co., Ltd. KBE-903) (see below) 1mL
  • the coating solution for forming the second base layer prepared above (KBE-903 concentration: 1.0% by volume) is applied onto the first base layer of the base material by a spin coating method so that the layer thickness of the second base layer after drying is Coating was carried out under conditions such that the thickness was 20 nm.
  • the spin coating conditions were 3000 rpm and 20 seconds. Thereafter, the base material was dried at room temperature for 1 hour, and then heat-treated at 90° C. and 80% RH for 1 hour.
  • a coating solution for forming a liquid-repellent layer was prepared by mixing the following constituent materials.
  • Fluorine-containing coupling agent b (2-perfluorooctyl)ethyltrimethoxysilane (CF 3 (CF 2 ) 7 C 2 H 4 Si(OCH 3 ) 3 ) 0.2mL
  • the coating liquid for forming a liquid repellent layer containing 0.2% by volume of the coupling agent b containing a fluorine atom (see below) prepared above was applied onto the second base layer formed above by a spin coating method, after drying. Coating was carried out under conditions such that the thickness of the liquid-repellent layer was 10 nm. The spin coating conditions were 1000 rpm and 20 seconds. Thereafter, the base material was dried at room temperature for 1 hour, and then heat-treated at 90° C. and 80% RH for 1 hour to produce nozzle plate 1.
  • a nozzle plate 2 was produced in the same manner as the above nozzle plate 1, except that after forming the base material adhesion layer, treatment was performed in O 2 -RIE plasma mode using a high frequency plasma apparatus in the following manner.
  • Plasma treatment conditions are as follows.
  • Plasma processing device RIE mode high frequency plasma device Reactive gas G: Oxygen gas Gas flow rate: 30 sccm Gas pressure: 10Pa High frequency power: 13.56MHz High frequency power density: 0.10W/ cm2 Interelectrode voltage: 450W Processing time: 5min
  • a nozzle plate 3 was produced in the same manner as in the production of the nozzle plate 1, except that after forming the base material adhesion layer, processing was performed in the Ar-RIE plasma mode using a high frequency plasma apparatus in the following manner.
  • Plasma treatment conditions are as follows.
  • Plasma processing device RIE mode high frequency plasma device Reaction gas G: Argon gas Gas flow rate: 50 sccm Gas pressure: 10Pa High frequency power: 13.56MHz High frequency power density: 0.10W/ cm2 Interelectrode voltage: 450W Processing time: 5min
  • a nozzle plate 4 was produced in the same manner as in the production of the nozzle plate 1, except that a Ti target was used to form a film by the method described below when forming the base material adhesion layer.
  • a nozzle plate 5 was produced in the same manner as in the production of the nozzle plate 1, except that a Ta target was used to form a film by the method described below when forming the base material adhesion layer.
  • a nozzle plate 5 was produced in the same manner as in the production of the nozzle plate 1, except that a Ti target was used to form a film by the method described below when forming the base material adhesion layer.
  • a composition analysis in the thickness direction of the base material adhesion layer was performed by the above-mentioned XPS analysis, and the elemental compositions on the surface and inside of the base material adhesion layer are shown in the table below.
  • the specific conditions are as follows.
  • ⁇ Analyzer QUANTERA SXM manufactured by ULVAC-PHI
  • ⁇ X-ray source Monochromatic Al-K ⁇ 15kV 25W
  • ⁇ Sputter ion Ar (1keV)
  • Depth profile Measurements are repeated at predetermined thickness intervals using the SiO 2 equivalent sputtering thickness to determine the depth profile in the depth direction.
  • This thickness interval was set to 2.6 nm (data can be obtained every 2.6 nm in the depth direction) - Quantification: Background was determined using the Shirley method, and quantification was performed using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used.
  • Disperse dye C. I. Disperse Yellow 160 24.0% by mass Diethylene glycol 30.6% by mass Styrene-maleic anhydride copolymer (dispersant) 12.0% by mass Water 33.4% by mass
  • Disperse dye C. I. Disperse Yellow 160 24.0% by mass Diethylene glycol 30.6% by mass Styrene-maleic anhydride copolymer (dispersant) 12.0% by mass Water 33.4% by mass
  • the above mixture was dispersed using ceramic beads having a diameter of 0.5 mm using a sand grinder manufactured by Imex Corporation at a rotation speed of 2500 rpm for 5 hours.
  • Dispersion liquid 1 20.0% by mass Ethylene glycol 10.0% by mass Glycerin 8.0% by mass Emulgen 911 (manufactured by Kao Corporation) 0.05% by mass Ion-exchanged water was added to make it 100% by mass.
  • Emulgen 911 manufactured by Kao Corporation
  • the liquid properties of the prepared ink were investigated, and it was confirmed that it was alkaline (pH 8.0 or higher).
  • Ink consisting of a black pigment dispersion and triethylene glycol monomethyl ether acetate is introduced into an inkjet head in which nozzles made from Example nozzle plates 1 to 4 and Comparative example nozzle plates 5 and 6 are joined.
  • Continuous injection was performed from all nozzles with a gap to the media of about 6 mm, and the ejection after continuous injection for 30 minutes (continuous injection performance) was evaluated according to the following criteria.
  • B After 30 minutes of continuous injection, clear droplets were observed on the nozzle surface and some ejection failures were confirmed. was done
  • the nozzle plate having the configuration defined in the present invention is able to withstand nitrogen in the base material adhesion layer and oxygen on the surface, even in an environment where it is exposed to ink components for a long time. It can be seen that since the concentration is higher than the inside, the bond between the base material adhesion layer and the underlayer is high, and the ink resistance is excellent. Furthermore, evaluation of continuous injection properties showed that there was little adhesion of droplets to the nozzle surface having the nitrogen-containing base material adhesion layer. This phenomenon is caused by the low surface resistance of the adhesion layer of the base material containing nitrogen. Therefore, we consider this to be a result of the nozzle surface not being charged and the adhesion of mist caused by injection being suppressed.
  • Example 2 In the production of nozzle plates 1 to 4 of Example 1, a liquid repellent layer (fluorine-containing coupling agent) was directly formed on the base material adhesion layer without providing the first and second base layers. Nozzle plates 7 to 10 were prepared. At this time, Optool DSX (manufactured by Daikin Industries, Ltd.) was used as the fluorine-containing coupling agent in place of the fluorine-containing coupling agent b.
  • nozzle plates 1 to 4 in Example 1 After forming nozzle holes in a stainless steel base material (SUS304) by laser processing, a base material adhesion layer was formed by sputtering, and a liquid repellent layer (fluorine The nozzle plates 11 to 14 were prepared by forming a coupling agent containing the above-mentioned coupling agent. At this time, Optool DSX (manufactured by Daikin Industries, Ltd.) was used as the fluorine-containing coupling agent in place of the fluorine-containing coupling agent b. Furthermore, nozzle plates 15 and 16 were produced in the same manner as in the production of plate 12, except that the thickness of the base material adhesion layer was changed as shown in Table III below by changing the film formation time. Note that the conditions for forming the nozzle plates 15 and 16 are shown below.
  • Example 3 A base material adhesion layer is formed in the same manner as nozzle plate 1 of Example 1 on a plate in which nozzle holes are formed in a silicon wafer by the Deep-RIE method, and a hydrogen repellent (fluorine-containing coupling agent) is directly applied thereon.
  • a nozzle plate 17 was manufactured by forming a nozzle plate 17.
  • Optool DSX manufactured by Daikin Industries, Ltd.
  • This nozzle plate 17 was evaluated for ink durability, scratch durability, and continuous ejection evaluation in the same manner as in Example 1. The results are shown in Table III below. Similar to the results of Example 1, excellent effects in ink resistance, scratch durability, and continuous injection stability were confirmed.
  • nozzle plates 1 to 17 were measured using an X-ray diffraction device (Rigaku Corporation's multipurpose X-ray diffraction device Ultima III) under the following conditions to obtain an X-ray diffraction pattern of the base material adhesion layer.
  • Scan speed 10°/min
  • the present invention can be used for an inkjet head member, a method for manufacturing an inkjet head member, and an inkjet head that can ensure long-term durability and scratch resistance against ink and have excellent continuous ejection properties.
  • Nozzle plate 2 Base material 3
  • Base material adhesion layer 4 Functional layer 41
  • Liquid repellent layer 20A RIE plasma processing apparatus 21
  • Reaction chamber 22 High frequency power source 23
  • Capacitor 24 Planar electrode (power supply electrode) )
  • Counter electrode (ground electrode) 26
  • Ground 27 Gas inlet 28
  • Nozzle plate base material 31
  • Power supply line 56 Housing 57
  • Cap receiving plate 59 Cover member 61
  • Nozzle plate 62 Cap receiving plate attachment part 68 Attachment hole 71
  • Inkjet head D
  • D Discharge G
  • Reactive gas N
  • N Nozzle P Pump In Ink

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Particle Formation And Scattering Control In Inkjet Printers (AREA)
PCT/JP2023/009193 2022-03-17 2023-03-10 インクジェットヘッド用部材、インクジェットヘッド用部材の製造方法及びインクジェットヘッド Ceased WO2023176705A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP23770660.1A EP4494882A4 (en) 2022-03-17 2023-03-10 INKJET HEAD ELEMENT, METHOD FOR MANUFACTURING INKJET HEAD ELEMENT, AND INKJET HEAD
JP2024508114A JPWO2023176705A1 (https=) 2022-03-17 2023-03-10
US18/843,721 US20250214339A1 (en) 2022-03-17 2023-03-10 Member for inkjet head, method for manufacturing member for inkjet head, and inkjet head
CN202380026545.7A CN118871296A (zh) 2022-03-17 2023-03-10 喷墨头用构件、喷墨头用构件的制造方法及喷墨头

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Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3668233A (en) 1962-10-30 1972-06-06 Minnesota Mining & Mfg Esters of perfluoro-tertiaryalkyl alcohols and hydrocarbyl or holo-hydrocarbyl carboxylic acids
JPS5035698A (https=) 1973-08-04 1975-04-04
JPS58122979A (ja) 1982-01-19 1983-07-21 Asahi Glass Co Ltd ガラス表面の撥水撥油剤
JPH07242675A (ja) 1994-03-04 1995-09-19 Agency Of Ind Science & Technol 含フッ素ケイ素化合物の製造法
JPH0961605A (ja) 1995-06-15 1997-03-07 Sumitomo Chem Co Ltd 反射防止フィルター
JP2000064348A (ja) 1998-08-26 2000-02-29 Hitachi Constr Mach Co Ltd 建設機械
JP2000144097A (ja) 1998-01-31 2000-05-26 Toppan Printing Co Ltd 防汚剤、防汚層の形成方法、光学部材、反射防止光学部材、光学機能性部材及び表示装置
JP2007152871A (ja) 2005-12-08 2007-06-21 Konica Minolta Holdings Inc ノズルプレート、ノズルプレートの製造方法及び液体吐出ヘッド
JP2007313701A (ja) 2006-05-24 2007-12-06 Konica Minolta Holdings Inc ノズルプレートの製造方法
US20080225088A1 (en) * 2007-03-16 2008-09-18 Qisda Corporation Fluid jet device and method for manufacturing the same
JP2009255341A (ja) 2008-04-15 2009-11-05 Konica Minolta Holdings Inc ノズルプレートの製造方法
JP2009274415A (ja) 2008-05-19 2009-11-26 Konica Minolta Holdings Inc ノズルプレート及び液体吐出ヘッド
JP2009286036A (ja) 2008-05-30 2009-12-10 Konica Minolta Holdings Inc 撥液膜の成膜方法、液体吐出ヘッド用ノズルプレートの製造方法及び撥液膜の製造装置
JP2010023446A (ja) 2008-07-24 2010-02-04 Konica Minolta Holdings Inc ノズルプレート及びその製造方法
JP2011000893A (ja) * 2010-10-05 2011-01-06 Seiko Epson Corp シリコン製ノズル基板、シリコン製ノズル基板を備えた液滴吐出ヘッド、液滴吐出ヘッドを搭載した液滴吐出装置、及びシリコン製ノズル基板の製造方法
JP2011011425A (ja) 2009-07-01 2011-01-20 Konica Minolta Holdings Inc 液体吐出ヘッド用ノズルプレートの製造方法
JP4900457B2 (ja) 2007-11-05 2012-03-21 セイコーエプソン株式会社 液滴吐出ヘッドおよび液滴吐出装置
JP2012140017A (ja) 2012-04-26 2012-07-26 Konica Minolta Holdings Inc インクジェットヘッド
EP2484526A1 (en) 2011-02-08 2012-08-08 Fujifilm Corporation Inkjet recording method and printed material
JP2013010227A (ja) 2011-06-29 2013-01-17 Konica Minolta Ij Technologies Inc インクジェットヘッドの駆動回路及びインクジェットヘッド
JP2013202886A (ja) 2012-03-28 2013-10-07 Konica Minolta Inc ノズルプレートの製造方法
JP2014058171A (ja) 2014-01-06 2014-04-03 Konica Minolta Inc 画像形成装置
JP2014097644A (ja) 2012-11-16 2014-05-29 Konica Minolta Inc インクジェットヘッド
JP2014144485A (ja) 2009-06-05 2014-08-14 Panasonic Corp レーザ加工方法、およびノズルの製造方法
JP2014157850A (ja) * 2013-02-14 2014-08-28 Ricoh Co Ltd 電気機械変換素子、液滴吐出ヘッド及び画像形成装置
JP2015142980A (ja) 2014-01-31 2015-08-06 コニカミノルタ株式会社 インクジェットヘッド、インクジェット記録装置及びインクジェットヘッドの位置調整方法
JP2015142979A (ja) 2014-01-31 2015-08-06 コニカミノルタ株式会社 インクジェットヘッド及びインクジェット記録装置
JP2016002682A (ja) 2014-06-16 2016-01-12 コニカミノルタ株式会社 インクジェットヘッド及びインクジェット記録装置
JP2016002675A (ja) 2014-06-16 2016-01-12 コニカミノルタ株式会社 ヘッドユニット及び液体吐出装置
JP2016107401A (ja) 2014-12-02 2016-06-20 コニカミノルタ株式会社 ヘッドモジュール、インクジェット記録装置及びヘッドモジュールの組み立て方法
JP2017109476A (ja) 2015-12-11 2017-06-22 コニカミノルタ株式会社 インクジェットヘッド及びインクジェット記録装置
JP2017177626A (ja) 2016-03-31 2017-10-05 コニカミノルタ株式会社 ヘッドユニットの製造方法
JP6217170B2 (ja) 2013-06-23 2017-10-25 株式会社リコー 液体吐出ヘッド及び画像形成装置
JP2018083316A (ja) 2016-11-22 2018-05-31 コニカミノルタ株式会社 ノズルプレートの製造方法およびインクジェットヘッドの製造方法
JP2018111208A (ja) 2016-12-26 2018-07-19 コニカミノルタ株式会社 ノズルプレートの製造方法
WO2019180882A1 (ja) * 2018-03-22 2019-09-26 コニカミノルタ株式会社 インクジェットヘッド及びその製造方法
WO2019215851A1 (ja) * 2018-05-09 2019-11-14 コニカミノルタ株式会社 インクジェットヘッド及び画像形成方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7605469B2 (en) * 2004-06-30 2009-10-20 Intel Corporation Atomic layer deposited tantalum containing adhesion layer
JP2011155077A (ja) * 2010-01-26 2011-08-11 Renesas Electronics Corp 半導体装置の製造方法
JPWO2017164031A1 (ja) * 2016-03-23 2019-02-14 富士フイルム株式会社 印刷版、印刷版の製造方法および印刷方法
JP7088188B2 (ja) * 2017-07-10 2022-06-21 コニカミノルタ株式会社 インクジェットヘッド、インクジェット記録装置及びインクジェットヘッドの製造方法
JP7020543B2 (ja) * 2018-04-20 2022-02-16 コニカミノルタ株式会社 ノズルプレートの製造方法及びインクジェットヘッド
US11845277B2 (en) * 2019-01-11 2023-12-19 Konica Minolta, Inc. Inkjet head, method of manufacturing inkjet head, and inkjet recording method

Patent Citations (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3668233A (en) 1962-10-30 1972-06-06 Minnesota Mining & Mfg Esters of perfluoro-tertiaryalkyl alcohols and hydrocarbyl or holo-hydrocarbyl carboxylic acids
JPS5035698A (https=) 1973-08-04 1975-04-04
JPS58122979A (ja) 1982-01-19 1983-07-21 Asahi Glass Co Ltd ガラス表面の撥水撥油剤
JPH07242675A (ja) 1994-03-04 1995-09-19 Agency Of Ind Science & Technol 含フッ素ケイ素化合物の製造法
JPH0961605A (ja) 1995-06-15 1997-03-07 Sumitomo Chem Co Ltd 反射防止フィルター
JP2000144097A (ja) 1998-01-31 2000-05-26 Toppan Printing Co Ltd 防汚剤、防汚層の形成方法、光学部材、反射防止光学部材、光学機能性部材及び表示装置
JP2000064348A (ja) 1998-08-26 2000-02-29 Hitachi Constr Mach Co Ltd 建設機械
JP2007152871A (ja) 2005-12-08 2007-06-21 Konica Minolta Holdings Inc ノズルプレート、ノズルプレートの製造方法及び液体吐出ヘッド
JP2007313701A (ja) 2006-05-24 2007-12-06 Konica Minolta Holdings Inc ノズルプレートの製造方法
US20080225088A1 (en) * 2007-03-16 2008-09-18 Qisda Corporation Fluid jet device and method for manufacturing the same
JP4900457B2 (ja) 2007-11-05 2012-03-21 セイコーエプソン株式会社 液滴吐出ヘッドおよび液滴吐出装置
JP2009255341A (ja) 2008-04-15 2009-11-05 Konica Minolta Holdings Inc ノズルプレートの製造方法
JP2009274415A (ja) 2008-05-19 2009-11-26 Konica Minolta Holdings Inc ノズルプレート及び液体吐出ヘッド
JP2009286036A (ja) 2008-05-30 2009-12-10 Konica Minolta Holdings Inc 撥液膜の成膜方法、液体吐出ヘッド用ノズルプレートの製造方法及び撥液膜の製造装置
JP2010023446A (ja) 2008-07-24 2010-02-04 Konica Minolta Holdings Inc ノズルプレート及びその製造方法
JP2014144485A (ja) 2009-06-05 2014-08-14 Panasonic Corp レーザ加工方法、およびノズルの製造方法
JP2011011425A (ja) 2009-07-01 2011-01-20 Konica Minolta Holdings Inc 液体吐出ヘッド用ノズルプレートの製造方法
JP2011000893A (ja) * 2010-10-05 2011-01-06 Seiko Epson Corp シリコン製ノズル基板、シリコン製ノズル基板を備えた液滴吐出ヘッド、液滴吐出ヘッドを搭載した液滴吐出装置、及びシリコン製ノズル基板の製造方法
EP2484526A1 (en) 2011-02-08 2012-08-08 Fujifilm Corporation Inkjet recording method and printed material
JP2013010227A (ja) 2011-06-29 2013-01-17 Konica Minolta Ij Technologies Inc インクジェットヘッドの駆動回路及びインクジェットヘッド
JP2013202886A (ja) 2012-03-28 2013-10-07 Konica Minolta Inc ノズルプレートの製造方法
JP2012140017A (ja) 2012-04-26 2012-07-26 Konica Minolta Holdings Inc インクジェットヘッド
JP2014097644A (ja) 2012-11-16 2014-05-29 Konica Minolta Inc インクジェットヘッド
JP2014157850A (ja) * 2013-02-14 2014-08-28 Ricoh Co Ltd 電気機械変換素子、液滴吐出ヘッド及び画像形成装置
JP6217170B2 (ja) 2013-06-23 2017-10-25 株式会社リコー 液体吐出ヘッド及び画像形成装置
JP2014058171A (ja) 2014-01-06 2014-04-03 Konica Minolta Inc 画像形成装置
JP2015142980A (ja) 2014-01-31 2015-08-06 コニカミノルタ株式会社 インクジェットヘッド、インクジェット記録装置及びインクジェットヘッドの位置調整方法
JP2015142979A (ja) 2014-01-31 2015-08-06 コニカミノルタ株式会社 インクジェットヘッド及びインクジェット記録装置
JP2016002682A (ja) 2014-06-16 2016-01-12 コニカミノルタ株式会社 インクジェットヘッド及びインクジェット記録装置
JP2016002675A (ja) 2014-06-16 2016-01-12 コニカミノルタ株式会社 ヘッドユニット及び液体吐出装置
JP2016107401A (ja) 2014-12-02 2016-06-20 コニカミノルタ株式会社 ヘッドモジュール、インクジェット記録装置及びヘッドモジュールの組み立て方法
JP2017109476A (ja) 2015-12-11 2017-06-22 コニカミノルタ株式会社 インクジェットヘッド及びインクジェット記録装置
JP2017177626A (ja) 2016-03-31 2017-10-05 コニカミノルタ株式会社 ヘッドユニットの製造方法
JP2018083316A (ja) 2016-11-22 2018-05-31 コニカミノルタ株式会社 ノズルプレートの製造方法およびインクジェットヘッドの製造方法
JP2018111208A (ja) 2016-12-26 2018-07-19 コニカミノルタ株式会社 ノズルプレートの製造方法
WO2019180882A1 (ja) * 2018-03-22 2019-09-26 コニカミノルタ株式会社 インクジェットヘッド及びその製造方法
WO2019215851A1 (ja) * 2018-05-09 2019-11-14 コニカミノルタ株式会社 インクジェットヘッド及び画像形成方法

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
COLLECT. CZECH. CHEM. COMMUN., vol. 44, pages 750 - 755
INORG. CHEM., vol. 10, 1971, pages 889 - 892
J. AMER. CHEM. SOC., vol. 112, 1990, pages 2341 - 2348
J. FLUORINE CHEM., vol. 79, no. 1, 1996, pages 87
MATERIAL TECHNOLOGY, vol. 16, no. 5, 1998, pages 209
See also references of EP4494882A4

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CN118871296A (zh) 2024-10-29

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