CN116096578A - Ink jet head - Google Patents

Ink jet head Download PDF

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Publication number
CN116096578A
CN116096578A CN202080103509.2A CN202080103509A CN116096578A CN 116096578 A CN116096578 A CN 116096578A CN 202080103509 A CN202080103509 A CN 202080103509A CN 116096578 A CN116096578 A CN 116096578A
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CN
China
Prior art keywords
layer
ink
stainless steel
steel substrate
inkjet head
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CN202080103509.2A
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Chinese (zh)
Inventor
山田晃久
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of CN116096578A publication Critical patent/CN116096578A/en
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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
    • B41J2/14—Structure thereof only for on-demand ink jet heads

Abstract

The invention provides an ink jet head which has excellent adhesion, ink resistance and adhesion durability among structural components. The ink jet head of the present invention is characterized by comprising a member having a stainless steel substrate, wherein the stainless steel substrate has a resin layer thereon, the surface or side surface portion of the resin layer is in contact with ink, and the ratio (Ar/Cr) of Ar to Cr concentration (atm%) in the surface portion of the stainless steel substrate has a value of 0.01 or more.

Description

Ink jet head
Technical Field
The present invention relates to an inkjet head. More specifically, the present invention relates to an inkjet head excellent in adhesion between members, ink resistance, and adhesion durability.
Background
An inkjet recording apparatus, which is widely used at present, is configured to form an image on a recording medium by attaching an inkjet head having a nozzle plate formed by arranging a plurality of nozzle holes in an array to a frame or the like, and then ejecting ink of each color in a state of fine droplets from the plurality of nozzles toward the recording medium.
As a typical ink ejection method of an inkjet head, there are the following methods: a method in which a current is passed through a resistor disposed in a pressurizing chamber to generate heat, and water in the ink is expanded by the heat to apply pressure to the ink and discharge the ink; and a method in which a part of the flow path member constituting the pressurizing chamber is made into a piezoelectric body or the flow path member is provided with a piezoelectric body, and the piezoelectric bodies corresponding to the plurality of nozzle holes are selectively driven, whereby the pressurizing chamber is deformed based on dynamic pressure of each piezoelectric body, and the liquid is ejected from the nozzles.
In an inkjet head, in order to achieve good ejection performance of ink droplets, the surface characteristics of the surface on which nozzles are provided are very important.
If ink or garbage adheres to the vicinity of the nozzle hole of the inkjet head, there is a problem that the ejection direction of the ejected ink droplet is curved or the ejection angle of the ink droplet on the nozzle hole is widened, resulting in satellite droplets.
In order to stably eject ink droplets, a method of optimizing the design in the ink flow path and applying pressure to the ink is required, but this is not sufficient, and it is also required to continuously maintain the surroundings of the nozzle hole ejecting the ink in a stable surface state. Therefore, a method of providing a lyophobic layer having lyophobicity to the peripheral portion of the nozzle hole on the ink ejection face of the nozzle plate so as not to adhere or leave unnecessary ink has been studied.
In general, for a lyophobic film formed on a nozzle surface of a nozzle plate provided in an ink jet head, an organosilicon compound and a fluorine-containing organic compound are used, and for example, a silane coupling agent or the like is used.
It is known that a lyophobic layer having excellent adhesion can be formed by using a silane coupling agent when forming the lyophobic layer. However, when the density of hydroxyl groups in the base material and the underlayer constituting the nozzle plate is low, the alkali component constituting the ink breaks the hydrogen bond and the hydroxyl bond existing therein, and breaks the bond, which causes a problem of becoming a lyophobic layer with low alkali resistance.
In order to solve the above-described problems, patent document 1 discloses an inkjet printer, which is characterized in that, as a head member surface treatment method capable of contributing to improvement of corrosion resistance of a liquid contact portion of an inkjet head in contact with ink, a CrNx compound layer composed of nitrogen and chromium is formed on a wall surface of a member that supplies liquid (ink) to the inkjet head, whereby corrosion of the inner wall of the inkjet head or the inner side of an ink supply pipe or the like of the member in contact with ink can be prevented, and durability can be improved.
However, the method proposed in patent document 1 has a problem that the adhesion between the CrN layer and the base layer is insufficient, and durability (durability due to scratch durability, thermal stress, and the like) cannot be ensured.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2004-66510.
Disclosure of Invention
The present invention has been made in view of the above-described problems and conditions, and an object of the present invention is to provide an inkjet head excellent in adhesion between members, ink resistance, and adhesion durability.
As a result of intensive studies in view of the above problems, the present inventors have found that an ink jet head having the following structure can achieve an ink jet head excellent in adhesion between members, ink resistance and adhesion durability, and have completed the present invention: the ink jet head is composed of a member having a stainless steel substrate, wherein the stainless steel substrate has a resin layer thereon, the surface or side surface portion of the resin layer is in contact with ink, the surface of the stainless steel substrate has a Cr-containing layer, and the Cr-containing layer contains Ar element in a specific ratio or more with respect to Cr element.
That is, the above-described problems of the present invention can be solved by the following method.
1. An ink jet head comprising a member having a stainless steel base material, characterized in that,
the stainless steel substrate has a resin layer thereon, and the surface or side surface of the resin layer is in contact with ink, wherein the ratio (Ar/Cr) of Ar to Cr concentration (atm%) in the surface of the stainless steel substrate is 0.01 or more.
2. The ink jet head according to claim 1, wherein the content of Cr having a valence of 3 in the surface portion of the stainless steel substrate is 50atm% or more relative to the total Cr content.
3. The inkjet head according to claim 1 or 2, wherein the ratio of the concentration of the constituent elements on the surface portion of the stainless steel substrate to the concentration of Cr (atm%) of Fe (Cr/Fe) is 0.8 or more.
4. The inkjet head according to any one of items 1 to 3, wherein the stainless steel substrate has a Cr-containing layer on a surface thereof, and the layer thickness of the Cr-containing layer is in a range of 5 to 50 nm.
5. The inkjet head according to any one of items 1 to 4, wherein the member having the stainless steel substrate is a member constituting a nozzle plate, an ink flow path, an ink chamber, or an exterior portion that contacts the ink.
6. The inkjet head according to any one of items 1 to 5, wherein the resin layer is composed of at least a polymerizable polymer.
7. The inkjet head according to claim 5, wherein the resin layer is a base layer and a lyophobic layer constituting the nozzle plate.
8. The inkjet head according to claim 7, wherein the base layer is a layer containing a silane coupling agent.
9. The inkjet head according to claim 8, wherein the silane coupling agent contained in the underlayer has reactive functional groups at both ends and contains a hydrocarbon chain and a benzene ring in an intermediate portion.
10. The inkjet head according to any one of claims 7 to 9, wherein the lyophobic layer is a layer formed using a coupling agent having fluorine (F).
11. The inkjet head according to any one of items 1 to 10, wherein the ink contains at least 1 mass% or more of a coloring material and water.
12. The inkjet head according to any one of claims 1 to 11, wherein the ink is a base ink.
Effects of the invention
According to the present invention, an inkjet head excellent in adhesion between members, ink resistance, and adhesion durability can be provided.
The working mechanism or action mechanism of the present invention is presumed as follows.
In the ink jet head of the present invention, which is composed of a member having a stainless steel substrate, a resin layer is provided on the stainless steel substrate, and ink is brought into contact with the surface or side surface portion of the resin layer, and the ratio (Ar/Cr) of Ar to Cr concentration (atm%) on the surface portion of the stainless steel substrate is 0.01 or more.
Conventionally, there are the following phenomena of a hydrophobic film provided on a structural member of an inkjet head, for example, a nozzle plate surface of the inkjet head: when applied to an ink having high interfacial permeability (for example, an alkali ink) and contacted with the ink for a long period of time, peeling occurs at the interface between the stainless steel substrate and a functional layer formed thereon, for example, a base layer, and this phenomenon becomes an important factor for reducing adhesion durability.
The present inventors have conducted intensive studies on the solution of the above problems and have further sought a technique for performing plasma treatment on the surface of a stainless steel substrate, and as a result, have found that O is not performed as a method for forming a functional layer on the surface of a stainless steel substrate 2 The above object can be achieved by performing the plasma treatment, but performing the Ar plasma treatment to form an inert film on the stainless steel substrate and to provide the structure of Cr oxide with Ar element. When Cr present on the surface of the stainless steel substrate is in a crystalline state of 3 valence, the Cr exhibits higher resistance to water-based ink than when it is in a crystalline state of 6 valence. In the case of such a liquid contact portion, adhesion between the stainless steel substrate and the adjacent layer can be improved not only for a hydrophobic resin film but also for an organic film such as an adhesive and a protective layer.
Further, by setting the content of Cr of 3 valence in the surface portion of the stainless steel base material to 50atm% or more relative to the total Cr content, the adhesion durability can be significantly improved.
It was additionally found that: the alkali ink resistance can be improved by setting the ratio of Cr to Fe concentration (atm%) to a value of 0.8 or more as the concentration ratio of the structural elements on the surface portion of the stainless steel substrate.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of the structure of a nozzle plate as an example of a structural member of an ink jet head of the present invention.
Fig. 2 is a schematic cross-sectional view showing another example of the structure of a nozzle plate as an example of a structural member of the ink jet head of the present invention.
Fig. 3 is a schematic cross-sectional view showing an example of the structure of a nozzle hole portion of a nozzle plate.
Fig. 4 is a schematic cross-sectional view showing an example of the structure of the ink jet head of the present invention.
Fig. 5 is a schematic diagram showing an example of a high-frequency plasma apparatus in RIE mode.
Fig. 6 is a schematic diagram showing an example of a high-frequency plasma device in PE mode.
Fig. 7 is a diagram showing an example of the distribution of Cr in different valence numbers on the surface portion of the stainless steel base material.
Fig. 8 is 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.
Fig. 9 is a bottom view showing an example of a nozzle plate constituting the ink jet head shown in fig. 8.
Detailed Description
The ink jet head of the present invention is characterized by comprising a member having a stainless steel substrate, wherein the stainless steel substrate has a resin layer thereon, and wherein the surface or side surface portion of the resin layer is in contact with ink, and wherein the ratio (Ar/Cr) of Ar to Cr concentration (atm%) on the surface portion of the stainless steel substrate has a value of 0.01 or more. This feature is common to the inventions of the following embodiments.
In the embodiment of the present invention, from the viewpoint of further showing the effect of the object of the present invention, it is preferable that the content (atm%) of 3-valent Cr in the surface portion of the stainless steel substrate is 50atm% or more with respect to the total Cr content (atm%), and in this case, the adhesion to the stainless steel substrate can be further improved, and further excellent adhesion durability can be exhibited.
In addition, in the ratio of the concentration (atm%) of the constituent elements on the surface portion of the stainless steel substrate, when the value of the ratio (Cr/Fe) of Cr to the concentration (atm%) of Fe is 0.8 or more, it is preferable from the viewpoint that penetration of ink into the interface between the stainless steel substrate and the base layer can be prevented even if printing is performed with alkaline ink or the like for a long period of time, and separation between the stainless steel substrate and the base layer can be further prevented.
In addition, the stainless steel substrate has a Cr-containing layer on the surface thereof, and when the layer thickness of the Cr-containing layer is in the range of 1 to 50nm, it is preferable from the viewpoint of further improving the alkali ink resistance in the nozzle hole surface portion of the nozzle plate which is the object effect of the present invention.
In addition, when the member having the stainless steel base material is a member constituting a nozzle plate, an ink flow path, an ink chamber, or an exterior portion which is in contact with ink, it is preferable from the viewpoint of further showing the object and effect of the present invention.
In addition, when the resin layer is composed of at least a polymerizable polymer, it is preferable from the viewpoint of obtaining excellent adhesion to the adjacent layer.
In addition, when the resin layer is a base layer and a lyophobic layer constituting the nozzle plate, it is preferable from the viewpoint of further showing the effect of the present invention.
In the case where the underlayer is a layer having a silane coupling agent, it is preferable from the viewpoint of improving adhesion to the stainless steel substrate, improving adhesion between the stainless steel substrate of the nozzle plate and the constituent layers provided thereon when stress is applied to the nozzle plate, particularly stress in the thickness direction, improving adhesion, and improving adhesion durability when stress is applied to the wiping material or the like used for maintaining the surface of the nozzle plate in the thickness direction.
The ink may further exhibit the effect of the present invention when an alkali ink is used, and the ink contains at least a coloring material and at least 1 mass% of water.
The present invention and its constituent elements and modes for carrying out the present invention will be described in detail below. In the present application, "to" indicating a numerical range means that the numerical values described before and after are included as the lower limit value and the upper limit value.
Ink jet head
The ink jet head of the present invention is characterized by comprising a member having a stainless steel substrate, wherein the stainless steel substrate has a resin layer thereon, the surface or side surface portion of the resin layer is in contact with ink, and the ratio (Ar/Cr) of Ar to Cr concentration (atm%) on the surface portion of the stainless steel substrate has a value of 0.01 or more.
The member to be brought into contact with the ink constituting the ink jet head of the present invention is not particularly limited if it is constituted by a member having a stainless steel substrate and has a resin layer on the stainless steel substrate, and examples thereof include a member constituting a nozzle plate, a nozzle substrate, an ink flow path, an ink chamber, or an exterior.
Hereinafter, an example of a nozzle plate having a stainless steel base material and a resin layer on the stainless steel base material will be described as an example of a member that constitutes an ink jet head and is in contact with ink.
Fig. 1 is a schematic cross-sectional view showing an example of a structure of a nozzle plate, which is an example of a structural member of an ink jet head of the present invention.
As shown in fig. 1, the nozzle plate 1 has a basic structure in which an Ar element is contained in an amount of 0.01% by atm% or more relative to a Cr element on the surface of a stainless steel substrate 2, and a resin layer 4 is provided thereon. Here, the resin layer 4 is preferably composed of at least a polymerizable polymer.
Fig. 2 is a schematic cross-sectional view showing another example of the structure of a nozzle plate which is an example of a structural member of the ink jet head of the present invention.
With respect to the structure of the nozzle plate shown in fig. 1, the nozzle plate 1 shown in fig. 2 is a structure in which the resin layer 4 formed on the surface portion 3 of the stainless steel base material is composed of a base layer 5 and a lyophobic layer 6, and the base layer is a base layer 5 composed of a two-layer structure of a first base layer 5A and a second base layer 5B. For example, the first underlayer 5A may be configured to contain a silane coupling agent (hereinafter, also simply referred to as a silane coupling agent a) having a reactive functional group at both ends and containing a hydrocarbon chain and a benzene ring in the middle, and the second underlayer 5B may be configured to contain an oxide containing carbon (C), silicon (Si), and oxygen (O) as main components, for example, a low-molecular-weight silane compound or a silane coupling agent.
Fig. 3 is a schematic cross-sectional view showing an example of a partial structure in which nozzle holes are formed in a nozzle plate having the structure defined in the present invention described above.
As shown In fig. 3, when the surface portion 3 containing 0.01 or more of Ar element In terms of atm% of Cr element is provided between the stainless steel substrate 2 and the underlayer 5, it was found that penetration of the ink In into the interface between the stainless steel substrate 2 and the underlayer 5 can be prevented even if printing is performed with the ink In such as alkali ink for a long period of time, and peeling between the stainless steel substrate 2 and the underlayer 5 can be prevented. Further, the sealing durability can be remarkably improved by setting the content of Cr of valence 3 in the surface layer portion of the Cr-containing layer to 50atm% or more relative to the total Cr content.
It was found that the alkali ink resistance can be improved by setting the ratio of Cr to Fe concentration (atm%) to the concentration ratio of Cr/Fe (Cr/Fe) to 0.8 or more as the concentration ratio of the structural elements in the surface portion 3.
Structure of ink-jet head
Next, a typical configuration of the inkjet head of the present invention will be described with reference to the drawings.
Fig. 4 is a schematic cross-sectional view showing an example of the structure of the ink jet head of the present invention.
The inkjet head 10 includes a head chip 12, a holding portion 13, a common ink chamber 15, and the like.
The head chip 12 is configured by stacking and integrating a nozzle plate 21 (hereinafter also referred to as a nozzle substrate), an intermediate substrate 22, an actuator substrate 23, and a protective substrate 24 in this order from the lower side.
The nozzle substrate 21 has a nozzle hole N for ejecting a droplet of ink, a large diameter portion 212 communicating with the nozzle hole N, and an independent circulation flow path 213 for circulating the ink.
The intermediate substrate 22 is formed with a communication hole 221 that penetrates the intermediate substrate 22 in the vertical direction and communicates with the large diameter portion 212, and a common circulation channel 222 that can join the inks flowing through the plurality of independent circulation channels 213.
In the actuation substrate 23, a pressure chamber 231 that communicates with the through hole 221 and stores ink is formed.
The protective substrate 24 is formed with a supply channel 241 penetrating in the vertical direction, and communicates the common supply liquid chamber 51 with the pressure chamber 231.
The common ink chamber 15 has a common supply liquid chamber 51 filled with ink.
A connection portion 11 is provided at an upper portion of the common ink chamber 15, and ink supplied from the connection portion 11 to the head chip 2 is supplied.
Next, a circulation path of ink inside the inkjet head 10 will be described. Ink is supplied from the connection portion 11, flows in the order of the common supply liquid chamber 51, the supply flow path 241, the pressure chamber 231, the communication hole 221, the large diameter portion 212, the independent circulation flow path 213, the common circulation flow path 222, and the connection portion 12 of the common ink chamber 15, and is discharged to the outside of the inkjet head 10.
The arrows in fig. 4 indicate the flow direction of the ink.
Accordingly, the connection portion 11, the common supply liquid chamber 51, the supply channel 241, the pressure chamber 231, the communication hole 221, the large-diameter portion 212, the independent circulation channel 213, the common circulation channel 222, and the connection portion 12 of the common ink chamber 5 constitute a channel 200.
In the ink jet head having such a typical structure, the member having the stainless steel base material is preferably a member constituting a nozzle plate, a nozzle substrate, an ink flow path, an ink chamber, or an exterior.
As shown in fig. 4, a is the nozzle plate 21 having the structure described in fig. 1 and 2, b is the nozzle hole N described in fig. 3, C is a joint portion for forming an ink flow path between the nozzle plate 21 and the intermediate substrate 21, D1 and D2 are members for forming an ink flow path by joining the intermediate substrate 22 and the actuator substrate, and E is a member for forming a common flow path 241 of ink formed by the protective substrate 24 and the protective portion. Further, F is an outer part of the nozzle plate 21, and is a part that may be in contact with ink by maintenance or the like. By applying the member defined in the present invention to the portions which are formed of SUS substrates and are in contact with ink, an inkjet head excellent in adhesion between members, ink resistance, and adhesion durability can be provided.
[ materials of construction of nozzle plate ]
Next, the stainless steel substrate 2, the surface portion 3, the underlayer 5, the lyophobic layer 6, and the like, which are representative parts constituting the print head of the present invention, that is, the nozzle plate, will be described in detail.
[ stainless steel substrate ]
As the stainless steel base material 2 constituting the nozzle plate, stainless steel (SUS) is used, which is a material having high mechanical strength, ink resistance, and excellent dimensional stability. As a typical stainless steel, SUS304, the average composition in the state before the following treatment was performed was 71atm% of Fe, 18atm% of Cr, 8.5atm% of Ni, and the balance of other elements.
The thickness of the stainless steel substrate constituting the nozzle plate is in the range of 10 to 500. Mu.m, preferably 30 to 150. Mu.m.
The present invention is characterized in that the ratio (Ar/Cr) of Ar to Cr concentration (atm%) in the surface portion of the stainless steel substrate defined in the present invention is 0.01 or more. The surface portion of the stainless steel substrate in the present invention means a region ranging from the outermost surface of the substrate to a depth of 5 nm.
In addition, preferred modes are: the content of Cr of valence 3 in the surface portion 3 of the stainless steel substrate is 50atm% or more relative to the total Cr content; the ratio of Cr to Fe concentration (atm%) in the concentration ratio of the constituent elements in the surface layer portion of the Cr-containing layer is 0.8 or more; the surface of the stainless steel substrate contains a Cr-containing layer, and the layer thickness of the Cr-containing layer is in the range of 1 to 50 nm.
The surface portion 3 of the present invention may be obtained by a method (film forming method 1) of performing a surface treatment on the surface of a stainless steel substrate by an argon gas-based sputtering method, or may be obtained by a method (film forming method 2) of forming a Cr-containing layer on a stainless steel substrate by a sputtering method using Cr as a target material, and then performing a surface treatment on the Cr-containing layer by an argon gas-based sputtering method.
Characterized in that the ratio (Ar/Cr) of Ar to Cr concentration (atm%) in the surface portion of the stainless steel substrate of the present invention formed between the stainless steel substrate and a base layer described later is 0.01 or more.
(method for Forming Cr-containing layer)
In the present invention, the Cr-containing layer may be provided on the surface of the substrate, and the formation method thereof is not particularly limited, but is preferably formed by the following method.
Examples of the Cr-containing layer film forming method that can be used in the present invention include a dry film forming method such as a physical vapor phase growth method (PVD method) or a chemical vapor phase growth method (CVD method), a wet film forming method such as electroplating or electroless plating, and the dry film forming method is preferable in the present invention because a dense film can be formed from a thin film.
Examples of the dry film forming method include a sputtering method, a vacuum deposition method, a laser ablation method, an ion deposition method, an electron beam delay method (MBE method), an organometallic vapor phase growth method (MOCVD method), a plasma CVD method, a plasma etching mode method using argon gas (Ar-PE mode), a reactive ion etching method using argon gas (Ar-RIE mode), and the like, but from the viewpoint that a dense film having a high Cr concentration can be formed from a thin film, a sputtering method, a reactive ion etching method using argon gas (Ar-RIE mode), and a method combining these methods are preferable.
In the present invention, from the viewpoint of forming a desired Cr-containing layer, it is preferable that the method described above is a method in which film formation is performed by a sputtering method and then surface treatment is performed by a plasma treatment.
(specific method 1 for Forming a stainless Steel substrate surface)
The film formation on the surface portion of a typical stainless steel substrate (film formation method 1) will be described below.
As a plasma etching mode applicable to the present invention, RIE mode and PE mode are exemplified. The "RIE" (Reactive Ion Etching) mode described in the present invention is a method of disposing a stainless steel substrate such as SUS304 constituting a nozzle plate as a plasma processing target on the power supply electrode side in a pair of opposing flat plate electrodes and performing plasma processing on the surface of the plasma processing target. On the other hand, the "PE" (Plasma Etching) mode is a method of disposing a Plasma treatment object on the ground electrode side in a pair of opposed flat electrodes and performing Plasma treatment on the surface of the Plasma treatment object.
Further, details concerning each plasma etching mode will be described with reference to the drawings.
< 1: ar-RIE mode plasma processing apparatus
Fig. 5 is a schematic diagram showing an example of a high-frequency plasma apparatus in RIE mode (reactive ion etching mode) used for forming a Cr-containing layer. RIE mode is suitable for physically high-speed surface treatment based on ion bombardment.
In fig. 5, a high-frequency plasma apparatus 20A in RIE mode (hereinafter, also referred to as "plasma processing apparatus 20A") includes a reaction chamber 21, a high-frequency power supply 22 (RF (Radio Frequency) power supply), a capacitor 23, a planar electrode 24 (also referred to as a cathode, "power supply electrode"), a counter electrode 25 (also referred to as an anode, "ground electrode"), a ground portion 26, and the like. The reaction chamber 21 has an inflow port 27 and an outflow port 28 for gas. The planar electrode 24 and the counter electrode 25 are disposed in the reaction chamber 21.
A pair of electrodes including a planar electrode 24 connected to the high-frequency power supply 22 via a capacitor 23 and a grounded counter electrode 25 opposed to the planar electrode 24 and connected to a ground portion 26 are disposed in the closable reaction chamber 21. The nozzle plate substrate 30, which is the target of plasma treatment, is disposed on the planar electrode 24.
First, air is sufficiently removed from the reaction chamber 21 via the gas outflow port 28. In this state, the high-frequency power supply 22 is started while Ar gas is supplied as the reaction gas G into the reaction chamber 21 through the gas inlet 27, and electric power is supplied to the high-frequency power supply 22 at a high frequency of 3MHz to 100MHz (typically 13.56 MHz), whereby a discharge D is generated between the planar electrode 24 and the counter electrode 25, and a discharge space 31 for generating low-temperature plasma (cations and electrons) of the reaction gas G and radical species is formed. In this case, the high-frequency power density is preferably set in the range of 0.01 to 3W/cm.
In the above configuration, electrons are trapped by the planar electrode 24 due to the difference in mobility between ions and electrons, and the planar electrode 24 is relatively negatively charged (self-biased). Electrons of the planar electrode 24 are stopped at the capacitor 23 via the power supply line 33. The electrons of the counter electrode 25 flow into the ground 26 through the power supply line 32.
On the other hand, radical species and cations are not easily trapped by the electrode and move in the plasma. If the nozzle plate substrate 30 as the object to be processed in the plasma is disposed on the planar electrode 24, an ion sheath that causes a strong electric field is generated on the counter electrode 25 side of the nozzle plate substrate 30, and an electric field of 400 to 1000V is generated due to the cathode falling, cations moving in the nozzle plate substrate 30 collide or contact with the surface portion of the nozzle plate substrate 30. The surface treatment (etching in this case) of the object to be treated is performed in this manner.
2: ar-PE mode plasma processing apparatus
Fig. 6 is a schematic diagram showing an example of a high-frequency plasma apparatus in a PE mode (plasma etching mode) used for forming a Cr-containing layer. The PE mode can realize mild processing with little ion collision effect.
The high-frequency plasma apparatus 20B in PE mode (hereinafter also referred to as "plasma processing apparatus 20B") shown in fig. 6 is basically similar to the high-frequency plasma apparatus 20A in Ar-RIE mode described in fig. 5, but is a method of performing plasma processing on the surface of a plasma processing object by disposing a nozzle plate substrate 30 as the plasma processing object on the ground electrode 25 side in a pair of opposed plate electrodes.
In the present invention, this method using argon as a reaction gas is referred to as "Ar-PE mode plasma processing".
(specific method for Forming Cr-containing layer 2)
Hereinafter, a film formation of a representative Cr-containing layer (film formation method 2) will be described.
Formation of Cr-containing layer by sputtering (film Forming method 2)
In the sputtering method, a Cr layer is formed by performing sputtering film formation under an atmosphere of argon, oxygen, methane, or the like, with Cr as a target. The Cr content in the Cr layer formed by this sputtering method was approximately 100atm%.
An example of a film formation method obtained by a specific sputtering method is as follows.
The preset Cr target was sputtered on the electrode of the DC sputtering film forming apparatus under vacuum conditions under the following conditions. At this time, not limited to DC sputtering, other plasma sources may be used.
And (3) target: cr (Cr)
DC power density: 1.1W/cm 2
Electric power: RF power (13.56 MHz), 200W
Temperature: 25 DEG C
Pressure: 0.3Pa
Introducing gas: argon gas
Film formation time: 30 seconds
The layer thickness of the Cr-containing layer formed by the sputtering method was 20nm. The layer thickness of the Cr-containing layer of the present invention is generally in the range of 1 to 5000nm, and is preferably in the range of 5 to 50nm from the viewpoints of alkali resistance of the nozzle plate and workability at the time of forming the nozzle hole.
Next, the Ar plasma treatment described in the film formation method 1 was performed on the Cr layer of approximately 100atm% formed by the sputtering method, to form a Cr-containing layer having a desired atomic composition.
(method for measuring characteristic value of surface portion 3 of stainless Steel substrate)
The surface portion 3 of the stainless steel substrate of the present invention is characterized in that the ratio (Ar/Cr) of Ar to Cr concentration (atm%) is 0.01 or more. The content of Cr of valence 3 in the surface portion 3 of the stainless steel substrate is preferably 50atm% or more relative to the total Cr content, and the ratio of Cr to Fe concentration (Cr/Fe) is preferably 0.8 or more relative to the concentration ratio of the constituent elements in the surface portion 3 of the stainless steel substrate.
Hereinafter, the specific values of the characteristics of the surface portion 3 of the stainless steel substrate and the specific measurement method thereof will be described in detail.
Determination of the composition ratio of structural elements of surface portion 3 of stainless Steel substrate
In the present invention, the method of measuring the composition ratio of the elements constituting the surface portion 3 of the stainless steel substrate is not particularly limited, and in the present invention, for example, a method of quantitatively analyzing the composition of the material constituting the sliced portion by cutting off a region of 10nm from the surface of the Cr-containing layer using a glass cutter or the like for trimming with respect to the sample in which the surface portion 3 is formed on the stainless steel substrate; the quantification method such as the method of scanning the mass of a compound in the thickness direction of a Cr-containing layer by infrared spectroscopy (IR), atomic absorption or the like, and the quantification method of an extremely thin film having a Cr-containing layer of 10nm or less can be performed by XPS (X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy) analysis, wherein elemental analysis can be performed for an extremely thin film by XPS analysis, and the composition distribution state in the layer thickness direction of the entire Cr-containing layer can be measured by depth profile measurement described later.
Analytical method 1: measurement of the content of Cr 3 in surface portion 3 of stainless Steel substrate
The method of measuring the content of Cr of valence 3 in the surface portion 3 of the stainless steel substrate according to the present invention will be described.
In the surface portion 3 of the stainless steel substrate of the present invention, the content of Cr of valence 3 is preferably 50atm% or more relative to the total Cr content, and the content of Cr of valence 3 can be obtained by the method described below.
In the present invention, cr 0 (metallic monomer, cr (0)), cr 3 (Cr (III), e.g., cr) of the surface portion 3 of the stainless steel substrate is measured 2 O 3 ) And 6 valences (Cr (VI), e.g. CrO 3 ) In the case of the content of each valence of (3), an X-ray photoelectron spectroscopy is preferably used.
The X-ray photoelectron spectroscopy is a method of analyzing 1 of photoelectron spectroscopy called XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis, chemical analysis photoelectron spectroscopy) for constituent atoms and the state of electrons existing in a surface region of a sample having a depth of 10nm from the surface of a sample on which a surface portion 3 of a stainless steel substrate is formed.
Hereinafter, an example of specific conditions of XPS analysis that can be applied is shown.
Analysis device: quantura SXM manufactured by ULVAC-PHI Co
X-ray source: monochromatization of Al-K alpha 15kV 25W
·Pass energy：55eV
Data processing: using MultiPak manufactured by ULVAC-PHI Co
Atomic composition analysis: background treatment was performed using Shirley method, and atomic composition was quantified from the resulting peak areas using relative sensitivity coefficients.
Cr valence state analysis: the peak separation was performed on the Cr2p3/2 peak and the 0-, 3-, and 6-valent peaks of chromium on the basis of the correction of the charge-based peak shift according to the binding energy of the carbon 1s peak. The binding energy of each state was found to be 574.3eV, 576.0eV, 578.9eV, and the ratio of 0, 3, and 6 of chromium was obtained from the area ratio of each peak by fitting the values as peaks under conditions that the FWHM of the peak was 1.2 to 2.8.
The above-mentioned method is a method of obtaining the content of Cr of 3 valence in the surface portion (depth 5 nm) of a sample without the underlayer and lyophobic layer, but the content of Cr of 3 valence in the surface portion 3 of the stainless steel substrate can be obtained by the above-mentioned measurement using GCIB (gas cluster ion beam) to remove the underlayer and lyophobic layer in the sample with the underlayer and lyophobic layer.
By using the above-described X-ray photoelectron spectroscopy, for example, the content (atm%) of each valence of Cr in the nozzle plate forming the surface portion 3 of the stainless steel substrate by performing Cr sputtering and plasma treatment on the stainless steel substrate can be measured, and the content (atm%) of Cr of valence 3 relative to the total Cr content can be obtained.
Fig. 7 shows an example of the distribution of the valence numbers of Cr in the Cr-containing layer measured by the above method.
Analytical method 2: determination of the average composition ratio of the elements in the Cr-containing layer
In the present invention, the average composition ratio (atm%) of each element (for example, cr, fe, ar, N, etc.) on the surface portion 3 of the stainless steel substrate is calculated from the content (atm%) of Cr of 3 relative to the total Cr content (atm%) on the sample formed on the surface portion 3 of the stainless steel substrate. The average composition ratio was obtained by measuring 10 points at random for the sample, and using the average value, the ratio (Ar/Cr) of Ar to Cr concentration (atm%) and the ratio (Cr/Fe) of Cr to Fe concentration (atm%) on the surface portion 3 of the stainless steel substrate were calculated.
The analysis method 2 of the present invention is similar to the elemental composition analysis described in the above analysis method 1, but does not require valence state analysis, and thus is not particularly limited to "Pass energy". The above measurement can be performed on a sample having a underlayer and a lyophobic layer, by removing the underlayer and lyophobic layer using GCIB (gas cluster ion beam) in the same manner as in the analysis method 1.
[ resin layer ]
The ink jet head of the present invention is characterized by having a resin layer on a stainless steel substrate on which a Cr-containing layer is formed.
The resin layer of the present invention is further preferably composed of at least a polymerizable polymer.
(polymerizable Polymer)
The polymerizable polymer of the present invention is not particularly limited, and general polymerizable polymers can be used, and for example, unsaturated polyester resins, epoxy resins, silicone resins, phenolic resins, polyimide resins, polyurethane resins, diallyl phthalate resins, and the like can be used.
In the above-mentioned polymerizable polymer, for example, when applied to a nozzle plate, the base layer is a layer formed using a silane coupling agent as a structural material of the base layer and the lyophobic layer, the silane coupling agent contained in the base layer has a reactive functional group at both ends and contains a hydrocarbon chain and a benzene ring in the middle, and the lyophobic layer is preferably a layer formed using a coupling agent having fluorine (F).
(representative construction example of resin layer)
Hereinafter, details of the underlayer and the lyophobic layer constituting the nozzle plate as a representative example of the resin layer will be described.
Basal layer
As a more preferable embodiment, the underlayer of the present invention is formed between the Cr-containing layer and the lyophobic layer of the present invention, and as illustrated in fig. 2, the underlayer 5 is formed of a two-layer structure of a first underlayer 5A and a second underlayer 5B. For example, the first underlayer 5A is formed to have reactive functional groups at both ends and to contain a silane coupling agent (hereinafter, also referred to as a silane coupling agent a) including a hydrocarbon chain and a benzene ring in the middle, and the second underlayer 5B may be formed of an oxide containing an organic oxide including Si as a main component, for example, a low-molecular-weight silane compound or a silane coupling agent.
Forming a base layer based on a silane coupling agent a: first substrate layer
In the present invention, as the silane coupling agent for forming a base layer by a dehydration condensation reaction, a silane coupling agent a having reactive functional groups at both ends and containing a hydrocarbon chain and a benzene ring in the middle is preferably used.
The silane coupling agent a that can be applied to the underlayer is not particularly limited, and the conventionally known one can be appropriately selected and used, but from the viewpoint of effectively exhibiting the objective effect of the present invention, a compound having an alkoxy group, chlorine, acyloxy group, or amino group as a reactive functional group at both ends and a structure including a hydrocarbon chain and a benzene ring (phenylene) in the middle is preferable.
Compounds having a Structure represented by the general formula (1)
General formula (1)
X s Q 3-s Si(CH 2 ) t C 6 H 4 (CH 2 ) u SiR 3-m X m
In the above general formula (1), Q and R each represent a methyl group or an ethyl group. t and u each represent a natural number of 1 to 10. s and m each represent a natural number of 1 to 3. When s is 1 and m is 1, two Q and R are present, and the two Q and R may have the same structure or different structures. C (C) 6 H 4 Is phenylene. X represents an alkoxy group, chlorine, acyloxy group, or amino group.
Examples of the alkoxy group include an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, an alkoxy group having 1 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable.
Examples of the acyloxy group include a linear or branched acyloxy group having 2 to 19 carbon atoms (such as an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an octylcarbonyloxy group, a tetradecylcarbonyloxy group, and an octadecylcarbonyloxy group).
In addition, examples of the amino group include amino group (-NH) 2 ) And a substituted amino group having 1 to 15 carbon atoms (for example, methylamino group, dimethylamino group, ethylamino group, methylethylamino group, diethylamino group, n-propylamino group, methyl-n-propylamino group, ethyl-n-propylamino group, isopropylamino group, isopropylmethylamino group, isopropylethylamino group, diisopropylamino group, phenylamino group, diphenylamino group, methylphenylamino group, ethylphenylamino group, n-propylphenylamino group, isopropylphenylamino group and the like).
Hereinafter, the exemplified compounds having the structure represented by the general formula (1) of the present invention are exemplified, but the present invention is not limited to these exemplified compounds.
1) 1, 4-bis (trimethoxysilylethyl) benzene
2) 1, 4-bis (triethoxysilylethyl) benzene
3) 1, 4-bis (trimethoxysilylbutyl) benzene
4) 1, 4-bis (triethoxysilylbutyl) benzene
5) 1, 4-bis (trimethylsilylethyl) benzene
6) 1, 4-bis (triethylamino silylethyl) benzene
7) 1, 4-bis (trimethylsilylbutyl) benzene
7) 1, 4-bis (triacetoxysilylethyl) benzene
8) 1, 4-bis (trichloromethyl silyl ethyl) benzene
9) 1, 4-bis (trichloroethyl silylethyl) benzene
The compound having the structure represented by the general formula (1) of the present invention can be synthesized by a conventionally known synthesis method. Further, it can be obtained as a commercial product.
Method for Forming a base layer Using silane coupling agent A
The underlayer of the present invention is formed by dissolving a silane coupling agent a having a hydrocarbon chain and a benzene ring at the intermediate portion thereof in an organic solvent such as ethanol, propanol, butanol, 2-trifluoroethanol, etc. to obtain a desired concentration, preparing a coating liquid for underlayer formation, and then coating and drying the coating liquid on a stainless steel substrate having a Cr-containing layer by a wet coating method.
The concentration of the silane coupling agent a in the coating liquid for forming a base layer is not particularly limited, but is approximately in the range of 0.5 to 50 mass%, preferably in the range of 1.0 to 30 mass%.
The layer thickness of the first underlayer of the present invention is not particularly limited, but is preferably in the range of about 1 to 500nm, and more preferably in the range of 5 to 150 nm.
Formation of a underlayer made of an oxide containing an organic oxide containing Si as a main component: second substrate layer
In the underlayer of the present invention, a second underlayer containing an organic oxide containing Si as a main component is also preferable.
The preferred manner, as shown in fig. 2, is preferably: the base layer is composed of a base layer unit 4U based on two layers of the first base layer 6 and the second base layer 7, the first base layer 6 is composed of a first base layer having reactive functional groups at both ends described above and containing a silane coupling agent a including a hydrocarbon chain and a benzene ring in the middle, and the second base layer 7 is formed as a second base layer composed of an organic oxide including Si described below.
In the underlayer of the present invention, the compound constituting the layer containing the organic oxide containing Si as a main component may be the silane coupling agent a applied to the underlayer.
An example of an alkoxysilane, silazane or silane coupling agent having a molecular weight of 300 or less that can be used in the present invention is shown, but the present invention is not limited to these exemplified compounds. The values described in parentheses after each compound were molecular weights (Mw).
Examples of the alkoxysilane include silicon oxynitride film (Si (OC) 2 H 5 ) 4 Mw:208.3 Methyl triethoxysilane (CH) 3 Si(OC 2 H 5 ) 3 Mw:178.3 Methyltrimethoxysilane (CH) 3 Si(OCH 3 ) 3 Mw:136.2 Dimethyl diethoxy silane ((CH) 3 ) 2 Si(OC 2 H 5 ) 2 Mw:148.3 Dimethyl dimethoxy silane ((CH) 3 ) 2 Si(OCH 3 ) 2 Mw:120.2 And the like.
Examples of silazanes include 1, 3-hexamethyldisilazane ((CH) 3 ) 3 SiNHSi(CH 3 ) 3 161.4), 1, 3-hexaethyldisilazane ((C) 2 H 5 ) 3 SiNHSi(C 2 H 5 ) 3 245.4), and 1, 3-bis (chloromethyl) tetramethyldisilazane, 1, 3-divinyl-1, 3-tetramethyldisilazane, and the like are exemplified.
Further, as the silane coupling agent, 1) a vinyl silane coupling agent: vinyltrimethoxysilane (CH) 2 ＝CHSi(OCH 3 ) 3 Mw:148.2 Vinyl triethoxysilane (CH) 2 ＝CHSi(OC 2 H 5 ) 3 Mw:190.3 Further, CH can be mentioned 2 ＝CHSi(CH 3 )(OCH 3 ) 2 、CH 2 ＝CHCOO(CH 2 ) 2 Si(OCH 3 ) 3 、CH 2 ＝CHCOO(CH 2 ) 2 Si(CH 3 )Cl 2 、CH 2 ＝CHCOO(CH 2 ) 3 SiCl 3 、CH 2 ＝C(CH 3 )Si(OC 2 H 5 ) 3 Etc.
Examples of the silane coupling agent include 2) amino silane coupling agents: 3-aminopropyl trimethoxysilane (H) 2 NCH 2 CH 2 CH 2 Si(OCH 3 ) 3 mW:179.3 3- (2-aminoethylamino) propyl trimethoxysilane (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 2 CH 2 CH 2 Si(CH 3 )(OCH 3 ) 2 Mw:206.4 And the like.
Examples of the epoxy silane coupling agent include 3) an epoxy silane coupling agent: 3-glyceroxypropyl trimethoxysilane (Mw: 236.3), 3-glyceroxypropyl triethoxysilane (Mw: 278.4), and the like.
Method for forming second substrate layer
The second underlayer of the present invention can be formed by dissolving the silane compound having a molecular weight of 300 or less, for example, alkoxysilane, silazane, or silane coupling agent C of the present invention in an organic solvent such as ethanol, propanol, butanol, 2-trifluoroethanol, or the like to obtain a desired concentration, preparing a coating liquid for forming an intermediate layer, and then coating and drying the resultant layer on the underlayer by a wet coating method.
The concentration of the inorganic oxide forming material in the second underlayer forming coating liquid is not particularly limited, but is in the range of approximately 0.5 to 50 mass%, preferably 1.0 to 30 mass%.
The layer thickness of the second substrate of the present invention is in the range of 0.5 to 500nm, preferably in the range of 1 to 300nm, more preferably in the range of 5 to 100 nm.
(lyophobic layer)
In the present invention, the lyophobic layer preferably contains a coupling agent having fluorine (F) (hereinafter, also referred to as a coupling agent B).
The coupling agent B having fluorine (F) that can be used in the lyophobic layer of the present invention is not particularly limited, and preferably contains a fluorine-based compound that preferably contains (1) a compound having a perfluoroalkyl group containing at least an alkoxysilyl group, a phosphonic acid group, or a hydroxyl group, or a compound having a perfluoropolyether group containing an alkoxysilyl group, a phosphonic acid group, or a hydroxyl group, or (2) a mixture containing a compound having a perfluoroalkyl group, or a mixture containing a compound having a perfluoropolyether group.
As specific compounds of the coupling agent B having fluorine (F) which can be used in the lyophobic layer of the present invention, examples thereof include chlorodimethyl [3- (2, 3,4,5, 6-pentafluorophenyl) propyl ] silane, pentafluorophenyl dimethylchlorosilane, pentafluorophenyl ethoxydimethylsilane, trichloro (1H, 2H-tridecafluoro-n-octyl) silane trichloro (1H, 2H-heptadecafluorodecyl) silane, trimethoxy (3, 3-trifluoropropyl) silane, triethoxy (1H, 2H-nonafluorohexyl) silane, triethoxy-1H, 2H-heptadecafluorodecyl silane trichloro (1H, 2H-heptadecafluorodecyl) silane, trimethoxy (3, 3-trifluoropropyl) silane triethoxy (1H, 2H-nonafluorohexyl) silane, triethoxy-1H, 2H-heptadecafluorodecyl silane.
Further, silane coupling agents having fluorine (F) are commercially available, and are easily available, for example, from such products as Dow Corning silicone organosilicon (strain), xinyue chemical industry (strain), dain industry (strain) (for example, OPTOOL DSX), asahi Glass company (for example, CYTOP), or SECO (for example, top CleanSafe (registered trademark)), fluotech (strain), gelest Inc. Solvay solvent (strain) (for example, fluorink S10), and examples thereof include J.Fluorink chem.,79 (1). 87 (1996), materials technology 16 (5), 209 (1998), colllect Czem. Commun, volume 44, pages 750 to 755, J.Amer chem. Soc.1990, volume 112, pages 2341 to 2348, inorg.88m, pages 2, and so forth in 1971 to 35. Further, the composition can be produced by or based on the synthetic methods described in Japanese patent application laid-open No. 58-122979, japanese patent application laid-open No. 7-242675, japanese patent application laid-open No. 9-61605, japanese patent application laid-open No. 11-29585, japanese patent application laid-open No. 2000-64148, japanese patent application laid-open No. 2000-144097, and the like.
Specifically, examples of the compound having a silyl-terminated perfluoropolyether group include "OPTOOL DSX" manufactured by Dain Kagaku Kogyo Co., ltd., as described above, examples of the compound having a silyl-terminated fluoroalkyl group include "FG-5010Z130-0.2" manufactured by Fluosurf corporation, examples of the polymer having a perfluoroalkyl group include "SF-COAT series" manufactured by AGCSEIMI CHEMICAL corporation, examples of the polymer having a fluorine-containing heterocyclic structure in the main chain include "CYTOP" manufactured by Asahi Glass corporation, and examples of the polymer include. Further, a mixture of an FEP (ethylene tetrafluoride-propylene hexafluoride copolymer) dispersion and a polyamide imide resin may be mentioned.
The layer thickness of the lyophobic layer of the present invention is approximately in the range of 1 to 500nm, preferably in the range of 1 to 400nm, more preferably in the range of 2 to 200 nm.
[ processing of nozzle plate ]
As a method of manufacturing a nozzle plate of the present invention,
the details are as described above: examples are:
1) The nozzle plate is formed with a resin layer on a stainless steel substrate,
2) Forming a Cr-containing layer having a ratio (Ar/Cr) of Ar to Cr concentration (atm%) of 0.01 or more on the surface of the stainless steel substrate,
4) Forming a base layer on the Cr-containing layer by dehydration condensation reaction of a silane coupling agent, and
5) A method of forming the above lyophobic layer using a coupling agent having fluorine (F).
The nozzle plate 1 described above with reference to fig. 3 is a schematic cross-sectional view showing an example of the structure of a nozzle hole portion of the nozzle plate of the present invention.
As shown in fig. 2, a nozzle portion N having a desired shape as an ink discharge portion is formed in the nozzle plate 1.
Specific methods for forming nozzle holes and the like in the nozzle plate of the present invention can be described, for example, in JP-A2005-533662, JP-A2007-152871, JP-A2007-313701, JP-A2009-255341, JP-A2009-274415, JP-A2009-286036, JP-A2010-023446, JP-A2011-01425, JP-A2013-202886, JP-A2014-144485, JP-A2018-083316, JP-A2018-111208 and the like, and detailed descriptions thereof are omitted here.
Fig. 2 shows a structure of a nozzle plate according to the present invention, in which a surface portion 3 having a ratio (Ar/Cr) of Ar to Cr concentration (atm%) of 0.01 or more is formed on the surface of a stainless steel substrate 2, whereby interface destruction due to ink In can be prevented, and a nozzle plate having high durability can be obtained.
In the nozzle plate of the present invention, the nozzle holes are preferably formed by laser processing.
In the nozzle plate of the present invention, as the manufacturing method, a laser is preferably used for machining the outer shape of the nozzle hole, and more preferably, the laser is a pulse laser or a CW laser.
As a laser that can be used in the production of the nozzle plate of the present invention, a continuous oscillation type laser beam (CW laser beam) or a pulse oscillation type laser beam (pulse laser beam) is preferably used.
Examples of the laser beam that can be used here include gas lasers such as Ar laser, kr laser, and excimer laser, single-crystal YAG, and YVO 4 Forsterite (Mg) 2 SiO 4 )、YAlO 3 、GdVO 4 YAG, Y, YLF, or polycrystalline (ceramic) 2 O 3 、YVO 4 、YAlO 3 、GdVO 4 Examples of the dopant include a laser or glass laser in which 1 or more substances in Nd, yb, cr, ti, ho, er, tm, ta are added as a mediumRuby laser, alexandrite laser, ti: a laser oscillated from one or more of a sapphire laser, a copper vapor laser, or a gold vapor laser.
Among these, the laser used preferably emits ultraviolet laser light having a wavelength of about 266nm, for example, YAG-UV (yttrium aluminum garnet crystal: wavelength of 266 nm), YVO 4 (wavelength: 355 nm). In particular, when the object to be processed is an organic material, molecular bonds such as C-H bonds and C-C bonds can be dissociated by a thermal action in a laser beam having a wavelength of about 266 nm.
As an example of the irradiation conditions, for example, in YAG-UV (wavelength 266 nm), the pulse width is 12nsec, the output is 1.6W, YVO 4 (wavelength: 355 nm), the pulse width was 18nsec, and the output was 2.4W.
In addition, a generation duration of approximately from 10 may also be used -11 Second (10 picoseconds) to 10 -14 Super-high-speed laser with strong laser pulse of second (10 femtoseconds) and generation duration of about 10 -10 Second (100 picoseconds) to 10 -11 A short pulse laser of intense laser pulse of seconds (10 picoseconds). These pulsed lasers are also useful for cutting or perforating a wide range of materials.
Ink jet head
Fig. 8 is a schematic external view showing an example of the structure of an inkjet head in which the nozzle plate of the present invention can be used. Fig. 9 is a bottom view of the inkjet head including the nozzle plate of the present invention.
As shown in fig. 8, an inkjet head 100 provided with a nozzle plate according to the present invention is mounted on an inkjet printer (not shown), and includes a head chip for ejecting ink from nozzles; a wiring substrate provided with the head chip; a driving circuit substrate connected via the wiring substrate and the flexible substrate; a manifold for introducing ink through a filter in a channel of the head chip; a housing 56 in which a manifold is housed; a cover receiving plate mounted so as to close the bottom opening of the housing 56; first and second joints 81a and 81b mounted to the first and second ink ports of the manifold; a third fitting 82 mounted to a third ink port of the manifold; and a cover member 59 attached to the housing 56. Further, mounting holes 68 for mounting the housing 56 to the printer main body side are formed, respectively.
The cap receiving plate 57 shown in fig. 9 is formed in a substantially rectangular plate shape elongated in the lateral direction corresponding to the shape of the cap receiving plate mounting portion 62, and the nozzle plate 61 having the plurality of nozzles N disposed in the substantially central portion thereof is exposed, so that the elongated nozzle opening 71 is provided in the lateral direction. In addition, as for a specific structure of the inside of the inkjet head shown in fig. 8, for example, reference may be made to fig. 2 and the like described in japanese patent application laid-open No. 2012-140017.
While representative examples of the ink jet head are shown in fig. 8 and 9, in addition to these, for example, an ink jet head having a structure described in japanese patent application laid-open publication nos. 2012-140017, 2013-010227, 2014-058171, 2014-097644, 2015-142979, 2015-142980, 2016-002675, 2016-002682, 2016-107401, 2017-109476, and 177626 may be appropriately selected and used.
Ink-jet ink
The ink jet ink that can be used in the ink jet recording method using the ink jet head of the present invention is not particularly limited, and examples thereof include aqueous ink jet inks mainly containing water, oily ink jet inks mainly containing no volatile solvent at room temperature and containing substantially no water, organic solvent ink jet inks mainly containing a volatile solvent at room temperature, hot melt inks that are obtained by heating and melting solid ink at room temperature and printing, and active energy ray-curable ink jet inks that are cured by active light such as ultraviolet rays after printing.
The ink may be an alkali ink or an acid ink, and particularly an alkali ink may deteriorate the chemical properties of the substrate, the lyophobic layer, and the nozzle forming surface, and the ink jet head having the nozzle plate of the present invention is particularly effective for use in an ink jet recording method using such an alkali ink.
Specifically, the ink to which the present invention can be applied includes coloring materials such as dyes and pigments, water-soluble organic solvents, pH adjusters, and the like. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, triethylene glycol, ethanol, and propanol. Examples of the pH adjuster include sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydrogencarbonate, alkanolamine, hydrochloric acid, and acetic acid.
When sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydrogencarbonate, alkanolamine, or the like is used as the pH adjuster, the ink becomes alkaline, and there is a possibility that chemical damage (chemical deterioration) of the lyophobic layer and the nozzle formation surface may occur. The pH of the alkaline ink is 8.0 or more.
As described above, the lyophobic layer is formed of a fluorine-containing silane coupling agent or the like. The partial structure containing silicon and the partial structure containing fluorine in the lyophobic layer have a structure composed of methylene (CH 2 ) Such a substituent is bonded to the structure. Since the binding energy between carbon (C) and carbon (C) is smaller than the binding energy between silicon (Si) and oxygen (O) and the binding energy between carbon (C) and fluorine (F), the binding between the portion of carbon (C) and the portion of silicon (Si) and oxygen (O) and the portion of carbon (C) and fluorine (F) is weaker than the binding between the portions, and is susceptible to mechanical damage and chemical damage.
In an inkjet recording method using an alkali ink which is liable to cause such a phenomenon, the application of the nozzle plate having the constitution specified in the present invention is effective in terms of improvement of durability.
Examples
Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto. In the examples, the expression "part" or "%" is used, and unless otherwise specified, the expression "part by mass" or "% by mass" is used. Unless otherwise specified, each operation was carried out at room temperature (25 ℃).
Example 1
Manufacture of nozzle plate
[ production of nozzle plate 1 ]
The nozzle plate 1 composed of the stainless steel substrate 2, the surface portion 3, the first base layer 5A, the second base layer 5B, and the lyophobic layer 6 shown in fig. 2 was produced by the following method.
(1) Preparation of stainless steel substrate
As a substrate, a stainless steel substrate (SUS 304) was used which was not subjected to surface treatment of 3cm in the longitudinal direction, 8cm in the transverse direction and 50. Mu.m in thickness.
(2) Formation of first layer (Cr-containing layer)
Step 1: formation of Cr layer by sputtering
As a sputtering method, cr was used as a target, and a Cr-only metal layer was formed by sputtering a stainless steel substrate under an argon atmosphere. The content of Cr in the Cr layer formed by this sputtering method was approximately 100atm%.
Specifically, the Cr target placed on the electrode of the DC sputtering film forming apparatus was sputtered in advance under the vacuum condition under the following conditions.
And (3) target: cr (Cr)
DC power density: 1.1W/cm 2
Electric power: RF power (13.56 MHz), 200W
Temperature: 25 DEG C
Pressure: 0.3Pa
Introducing gas: argon gas
Film formation time: 30 seconds
Layer thickness: 20nm of
Step 2: etching using Ar-RIE plasma mode
Next, the stainless steel substrate having the Cr layer formed in step 1 was subjected to an etching treatment in an Ar-RIE plasma mode by the following method to form a Cr-containing layer.
The Cr layer was subjected to Ar plasma treatment using a high-frequency plasma apparatus in RIE mode having the structure shown in fig. 5, to form a Cr-containing layer having a layer thickness of 20 nm.
The plasma treatment conditions are shown below.
Plasma processing apparatus: RIE mode high frequency plasma device
Reaction gas G: argon gas
Gas flow rate: 50sccm
Gas pressure: 10Pa
High-frequency power: 13.56MHz
High frequency power density: 0.10W/cm 2
Voltage between electrodes: 450W
The treatment time is as follows: 3 minutes
Substrate treatment temperature: at a temperature below 80 DEG C
(3) Formation of layer 2 (first substrate layer)
(preparation of coating liquid for Forming first underlayer)
Preparation of A-1 liquid
The following constituent materials were mixed to prepare a-1 liquid.
30mL of a mixed solution of ethanol and 2, 2-trifluoroethanol (8:2 by volume ratio)
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 ) 2mL
Preparation of A-2 liquid
19.5mL of a mixed solution (8:2 by volume) of ethanol and 2, 2-trifluoroethanol
Pure water 30mL
Hydrochloric acid (36 vol%) 0.5mL
(formation of first base layer)
While stirring the above-prepared A-1 liquid with a stirring bar, 5mL of A-2 liquid was dropped. After stirring for about 1 hour after dripping, the mixture was applied to the Cr-containing layer by spin coating under conditions such that the layer thickness of the dried first underlayer became 100 nm. The spin coating conditions were 5000rpm for 20 seconds. Then, after drying the substrate at room temperature for 1 hour, firing was performed at 200℃for 30 minutes.
(4) Formation of third layer (second base layer)
(preparation of coating liquid for Forming second substrate layer)
The following constituent materials were mixed to prepare a second base layer-forming coating liquid.
69mL of a mixed solution (volume ratio of 8:2) of ethanol and 2, 2-trifluoroethanol
Pure water 30mL
Silane coupling agent c: 3-aminopropyl triethoxysilane ((C) 2 H 5 O) 3 SiC 3 H 6 NH 2 )
KBE-903 from Xinyue chemical Co., ltd.) 1mL
(formation of the second base layer)
The second base layer forming coating liquid prepared above was coated on the first base layer of the stainless steel substrate by spin coating under the condition that the layer thickness of the dried second base layer was 20nm (KBE-903 concentration: 1.0 vol%). The spin-coating conditions were 20 seconds at 3000 rpm. Then, the stainless steel substrate was dried at room temperature for 1 hour, and then subjected to heat treatment at 90℃and 80% RH for 1 hour.
(5) Formation of a fourth layer (lyophobic layer)
(preparation of coating liquid for lyophobic layer formation)
The following constituent materials were mixed to prepare a coating liquid for forming a lyophobic layer.
69.8mL of a mixed solution (volume ratio of 8:2) of ethanol and 2, 2-trifluoroethanol
Pure water 30mL
Fluorine-containing coupling agent b: (2-perfluorooctyl) ethyltrimethoxysilane (CF) 3 (CF 2 ) 7 C 2 H 4 Si(OCH 3 ) 3 ) 0.2mL
(formation of lyophobic layer)
The coating liquid for forming a lyophobic layer containing 0.2% by volume of the fluorine atom-containing coupling agent b prepared above was coated on the second underlayer formed as described above by spin coating under the condition that the layer thickness of the dried lyophobic layer became 10 nm. The spin-coating conditions were 20 seconds at 1000 rpm. Then, the stainless steel substrate was dried at room temperature for 1 hour, and then subjected to heat treatment at 90 ℃ and 80% rh for 1 hour, to prepare a nozzle plate 1.
[ chemical formula 1]
Silane coupling agent a
Figure BDA0004094999580000251
Fluorine-containing coupling agent b
Figure BDA0004094999580000261
Silane coupling agent c
(C 2 H 5 O) 3 SiC 3 H 6 NH 2
(6) Determination of Ar/Cr, cr/Fe of Cr-containing layer
The stainless steel substrate of the nozzle plate 1 was subjected to Cr sputtering and plasma treatment using XPS (X-ray Photoelectron Spectroscopy), and the surface of the sample formed to the Cr-containing layer was irradiated with X-rays to measure the energy of photoelectrons generated, thereby analyzing the concentrations (atm%) of the metal (Cr, fe), argon (Ar), oxygen (O), nitrogen (N), and carbon (C) as structural elements of the sample.
The measurement conditions are as follows.
Analysis device: quantura SXM manufactured by ULVAC-PHI Co
X-ray source: monochromatization of Al-K alpha
The Ar/Cr in the Cr-containing layer constituting the nozzle plate 1 measured by the above method was 0.02, and for Cr/Fe, cr was approximately 100atm%, and almost no Fe was detected, so that "+_infinity" was shown in Table 1.
(7) Determination of the content (atm%) of Cr 3 in the Cr-containing layer relative to the total Cr content
The content (atm%) of Cr of 3 valence relative to the total Cr content illustrated in fig. 7 was determined for a sample having a Cr-containing layer formed by Cr sputtering and plasma treatment on a substrate by an X-ray photoelectron spectroscopy method.
As a specific measuring apparatus, QUANTERASXM manufactured by ULVAC-PHI was used. The measurement sequence was that the X-ray anode used a monochromatized Al-K alpha to output a 25W measurement. The detailed analysis method of the measurement data is as described above, and description thereof is omitted.
The content of Cr of valence 3 constituting the Cr-containing layer of the nozzle plate 1 measured in the above method was 90atm%.
[ production of nozzle plate 2 ]
In the above-described production of the nozzle plate 1, the nozzle plate 2 was produced in the same manner as in the production of the Cr-containing layer except that only the "etching by ar—rie plasma mode" in step 2 was performed, and the "formation of the Cr layer by sputtering" in step 1 was not performed. Ar/Cr of the Cr-containing layer of the nozzle plate 2 was 0.03, cr/Fe was 1.2,3% Cr and the content of Cr relative to the total Cr content was 94atm%.
[ production of nozzle plate 3 ]
In the production of the nozzle plate 2, the process of "etching in ar—rie plasma mode" in step 2 of the Cr-containing layer formation process was changed to a process of degreasing the surface with acetone, and performing a treatment at 650 ℃ for 30 minutes in a nitrogen atmosphere, thereby producing the nozzle plate 3. The Cr-containing layer of the nozzle plate 3 has an N/Cr of 0.2 or more, and Cr/Fe and Cr having a valence of 3 cannot be measured.
[ production of nozzle plate 4 ]
In the production of the nozzle plate 2, instead of "etching in ar—rie plasma mode" in step 2 of the Cr-containing layer formation step, O is used instead 2 Gas was used as the reactant gas, using the "O-based" of PE plasma mode as described in FIG. 6 2 The nozzle plate 4 is made in the same way, except for the etching of the PE plasma mode ". Ar/Cr of the Cr-containing layer of the nozzle plate 4 was 0, cr/Fe was 1.0,3% Cr content relative to the total Cr content was 35atm%.
Evaluation of nozzle plate
The ink resistance and the adhesion durability of each of the nozzle plates produced as described above were evaluated by the following methods.
[ evaluation of ink resistance ]
(formation of nozzle hole)
The nozzle plates 1 to 6 thus produced were formed into a plurality of nozzle holes having a diameter of 25 μm by using a laser beam machine, the structure of which is shown in fig. 1 or 2.
(preparation of actual ink for evaluation: disperse dye ink)
Preparation of Dispersion
Figure BDA0004094999580000271
Ceramic beads having a diameter of 0.5mm were used for the above mixture, and the mixture was dispersed for 5 hours at a rotational speed of 2500rpm using a sander manufactured by AIMEX Co. The dispersion was treated with water/diethylene glycol=1 at a dye concentration of 5%: 4 was diluted to prepare a dispersion 1.
Preparation of actual ink
The respective compositions were added to the dispersion 1 and stirred to prepare an actual ink for evaluation (disperse dye ink).
Figure BDA0004094999580000281
Ion-exchanged water was added to prepare 100 mass%.
(evaluation of nozzle plate)
The nozzle plate on which each nozzle hole was formed was immersed in the actual ink at 60 c for a period of 30 days.
After the dipping treatment, the inside of the nozzle hole shown in fig. 1 and 2 was observed with a 100-fold magnifying glass for the presence or absence of peeling between the stainless steel substrate and the Cr-containing layer after washing with pure water and drying, and the adhesion resistance of the nozzle hole to the actual ink was evaluated based on the following criteria.
And (3) the following materials: no peeling was observed in all nozzles
And (2) the following steps: a nozzle of less than 5% showed very weak peeling, but there was no problem in practical use
Delta: at least 5% but less than 10% of the nozzles showed very weak peeling, but there was no problem in practical use
X: there are nozzles with significant peeling, which is practically problematic
[ evaluation of adhesion durability (wiping resistance) ]
(preparation of black ink)
The following black ink for structural evaluation was prepared.
Preparation of Black pigment Dispersion
Figure BDA0004094999580000282
/>
The above components were mixed and dispersed by a horizontal bead mill filled with 60% of zirconia beads of 0.3mm in volume ratio to obtain a black pigment dispersion. The average particle diameter was 125nm.
Preparation of Black ink
Figure BDA0004094999580000291
(wiping test)
In a container containing the black ink prepared as described above at 25 ℃, each nozzle plate having a plurality of nozzle holes formed by the above method was fixed with a fixing tool to a lyophobic layer on top, and the lyophobic layer surface of the nozzle plate was subjected to a plurality of wiping (wiping) operations using a doctor blade made of ethylene propylene diene rubber, and the adhesion durability was evaluated based on the following criteria.
And (3) the following materials: even with more than 5000 wiping operations, no peeling of lyophobic layer near the nozzles was observed in all the nozzles
O: in the wiping operation of less than 5000 times, the peeling of the lyophobic layer near the nozzles was not observed in all the nozzles, but extremely weak peeling occurred in less than 5% of the nozzles in the wiping operation of 5000 times or more
Delta: in less than 1000 wiping operations, no peeling of the lyophobic layer was observed in the vicinity of the nozzles, but very weak peeling was observed in less than 5% of the nozzles in the wiping in the range of 1000 to 5000 times
X: nozzle with peeling of the practically problematic obvious lyophobic layer occurring in 1000 wipes
The evaluation results obtained in the above are shown in table 1.
Figure BDA0004094999580000301
As shown in table 1, it is clear that: the nozzle plate having the structure defined in the present invention functions as a stress relaxation layer even when exposed to an environment of an alkali ink component or a surface is subjected to stress for a long period of time, and has high bonding properties between the constituent layers and excellent ink resistance and adhesion durability, compared with the comparative example. It is also clear that the nozzle plate of the present invention has excellent adhesion between the stainless steel substrate and the Cr-containing layer inside the nozzle hole even after being immersed in the alkaline ink for a long period of time.
Example 2
As a result of producing and applying the components 1 to 3 by forming a stainless steel base material/surface portion/base layer (second layer/third layer) structure and using the base layer having the resin layer as the adhesive layer at the respective positions of the components C, D, D2, and E having the stainless steel base material shown in fig. 4, the components 1 to 3 were confirmed to have an effect of excellent adhesion between the components, ink resistance, and adhesion durability, relative to the component 3 as a comparative example.
Industrial applicability
The ink jet head of the present invention has members excellent in adhesion between members, ink resistance and adhesion durability, and can be suitably used for ink jet printers using inks in various fields.
Symbol description
1,210 nozzle plate
2. Stainless steel base material
3. Surface portion
4. Resin layer
5. Lyophobic layer
5A first substrate layer
5B second substrate layer
6. Lyophobic layer
10 100 ink jet head
11. Connecting part
12. Nozzle chip
13. Holding part
15. Common ink chamber
21. Reaction chamber
22. High frequency power supply
23. Capacitor with a capacitor body
24. Plane electrode (Power supply electrode)
25. Counter electrode (grounding electrode)
26. Grounded (earth)
27. Gas inflow port
28. Gas outflow port
30. Nozzle plate substrate
31. Discharge space
32 33 power supply line
56. Basket body
57. Cover receiving plate
59. Cover member
61. Nozzle plate
62. Cover receiving plate mounting part
68. Mounting hole
71. Opening for nozzle
81a first joint
81b second joint
82. Third joint
220. Intermediate substrate
230. Actuation substrate
240. Protective substrate
221. Communication hole
20A RIE plasma processing apparatus
20B PE plasma processing device
In ink
D discharge
G reaction gas
N nozzle
P pump

Claims (12)

1. An ink jet head is characterized by comprising a member having a stainless steel base material,
a resin layer is provided on the stainless steel substrate,
the surface or side portion of the resin layer is in contact with the ink,
the ratio of Ar to Cr concentration in the surface portion of the stainless steel substrate, that is, the Ar/Cr value is 0.01 or more, and the concentration unit is atm%.
2. The inkjet head according to claim 1, wherein the stainless steel substrate has a Cr content of at least 50atm% at a valence 3 relative to the total Cr content in the surface portion.
3. The inkjet head according to claim 1 or claim 2, wherein the concentration ratio of constituent elements in the surface portion of the stainless steel substrate, the ratio of Cr to Fe concentration, i.e., the value of Cr/Fe, is 0.8 or more, and the concentration unit is atm%.
4. The inkjet head according to any one of claims 1 to 3, wherein a Cr-containing layer is provided on a surface portion of the stainless steel substrate, and a layer thickness of the Cr-containing layer is in a range of 5 to 50 nm.
5. The inkjet head according to any one of claims 1 to 4, wherein the member having the stainless steel substrate is a member constituting a nozzle plate, an ink flow path, an ink chamber, or an exterior portion that contacts ink.
6. The inkjet head according to any one of claims 1 to 5, wherein the resin layer is composed of at least a polymerizable polymer.
7. The inkjet head of claim 5, wherein the resin layer is a base layer and a lyophobic layer constituting the nozzle plate.
8. The inkjet head of claim 7, wherein the base layer is a layer containing a silane coupling agent.
9. The inkjet head of claim 8, wherein the silane coupling agent contained in the base layer has reactive functional groups at both ends and contains a hydrocarbon chain and a benzene ring in a middle portion.
10. The inkjet head according to any one of claims 7 to 9, wherein the lyophobic layer is a layer formed using a coupling agent having fluorine F.
11. The inkjet head according to any one of claims 1 to 10, wherein the ink contains at least a coloring material and 1 mass% or more of water.
12. The inkjet head according to any one of claims 1 to 11, wherein the ink is a base ink.
CN202080103509.2A 2020-08-28 2020-08-28 Ink jet head Pending CN116096578A (en)

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JPH0924337A (en) * 1995-07-10 1997-01-28 Matsushita Electric Ind Co Ltd Water-repellent stainless steel and its production
JP3553556B2 (en) * 2002-06-24 2004-08-11 オリヱント化学工業株式会社 Aqueous pigment ink and method for producing the same
JP2008105231A (en) * 2006-10-24 2008-05-08 Seiko Epson Corp Method for forming liquid repellent film, method for manufacturing inkjet head, inkjet head, and electronic device
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