Inkjet device

Abstract

The inkjet device of the present application is provided with a substrate, a resin layer laminated in contact with the substrate with at least one main surface, and an ink flow path provided in contact with a part of the resin layer with ink flowing therethrough, wherein the resin layer contains carbon, oxygen, nitrogen, and silicon, and at least one of the main surfaces satisfies the following (1) and (2) requirements. (1) The main surface is in contact with the substrate. (2) The relationship between the atomic concentrations (atm%) of nitrogen, oxygen, and silicon in the main surface and the inside of the resin layer measured by X-ray photoelectron spectroscopy is: main surface O > inside O and main surface N > 0, and main surface Si / inside Si is 5 or more.

Description

Technical Field

[0001] This invention relates to inkjet apparatuses. More specifically, this invention relates to inkjet apparatuses that provide long-term reliability through the excellent ink resistance of the interface between the resin layer disposed between or on the substrate and the substrate. Background Technology

[0002] Recently, inks with compositions that incorporate solvents that suppress moisture have been developed to suppress curling of printed materials when printing on paper media. Furthermore, inks containing water-soluble solvents such as methylpyrrolidone and γ-butyrolactone, which are highly soluble in resins, have been developed to improve printing characteristics on non-absorbent film media. These inks are water-based inks containing water and possess strong organic solvent properties, thus increasing their permeability to resin layers such as adhesive and protective layers in inkjet printers.

[0003] Therefore, when using the aforementioned ink in inkjet devices employing conventional water-based inks, the ink readily penetrates the resin layer and also readily penetrates the interface between the substrate and the resin layer. In particular, when a resin layer is formed between or on a substrate composed of hydrophilic materials such as metals or metal oxides, the ink penetrates even more easily to the interface between the substrate and the resin layer, resulting in a significant reduction in the adhesive strength between the substrate and the resin layer.

[0004] To address the aforementioned problems, for example, Patent Document 1 describes a liquid jet head having a flow path comprising a first component, a resin layer, and a second component, wherein the resin layer comprises a cured resin composition containing an epoxy compound, a polythiol compound having two or more thiol groups in its molecule, and an imidazole compound. Patent Document 1 describes that the resin layer exhibits high resistance to organic solvents and can cure at low temperatures, resulting in a liquid jet head possessing this resin layer exhibiting excellent initial adhesion and adhesion reliability.

[0005] Furthermore, in Patent Document 2, in a liquid ejector having flow path forming components arranged with pressure generating chambers, a formulation is described for the resin layer that joins the vibration mechanism that applies pressure to the pressure generating chambers with the flow path forming components, exhibiting high adhesion while curing at low temperatures (60°C, 80°C). Specifically, a resin layer formed from a curable resin composition comprising epoxy resin, polythiol compound, specific tackifying compound, and curing accelerator is described.

[0006] However, in the resin layer of the liquid ejector described in these patent documents, the adhesion at the interface between the substrate such as the flow path forming component and the resin layer may be insufficient, depending on the type of ink used.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2015-221541

[0010] Patent Document 2: Japanese Patent Application Publication No. 2019-155792 Summary of the Invention

[0011] The technical problem that the invention aims to solve

[0012] The present invention was made in view of the aforementioned problems and conditions, and the technical problem it solves is to provide an inkjet device that provides long-term reliability through the excellent ink resistance of the interface between the resin layer disposed between or on the substrate and the substrate.

[0013] means of solving technical problems

[0014] In order to solve the aforementioned technical problem, the inventors, during their research into the causes of the problem, discovered that by configuring the resin layer in an inkjet apparatus—which includes a substrate, a resin layer laminated with at least one main surface in contact with the substrate, and an ink flow path arranged such that ink flows through a portion of the resin layer—in a specific configuration, excellent ink resistance can be obtained at the interface between the resin layer disposed between or on the substrate and the substrate. This provides an inkjet apparatus with long-term reliability, thus completing the present invention. In other words, the technical problem of the present invention is solved by the following means.

[0015] 1. An inkjet apparatus comprising: a substrate, resin layers laminated thereon with at least one main surface in contact with the substrate, and an ink flow path disposed such that ink flows through and contacts a portion of the resin layer, wherein,

[0016] The resin layer contains carbon, oxygen, nitrogen, and silicon, and

[0017] At least one face of the main face satisfies the following requirements (1) and (2).

[0018] (1) The main surface is in contact with the substrate.

[0019] (2) When the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the main surface of the resin layer as determined by X-ray photoelectron spectroscopy are expressed by main surface N, main surface O and main surface Si respectively, and the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the interior of the resin layer are expressed by interior N, interior O and interior Si respectively, the main surface O > interior O and the main surface N > 0, and the ratio of main surface Si to interior Si expressed by main surface Si / interior Si is 5 or more.

[0020] 2. The inkjet apparatus according to the first item, wherein, in the main surface that satisfies the requirements of (1) and (2), the requirement of (3) is also satisfied.

[0021] (3) The ratio of the main face N to the interior N, expressed as main face N / interior N, is 1.5 or more.

[0022] 3. The inkjet apparatus according to the first or second claim, wherein, for the main surface satisfying the requirements of (1) and (2), the spectrum obtained by analyzing the bonding state of nitrogen atoms based on X-ray photoelectron spectroscopy has -NH2 or -NH3. + The peak.

[0023] 4. The inkjet apparatus according to any one of claims 1 to 3, wherein the resin layer comprises an epoxy compound and H at 25°C. + Cured products of resin compositions of curing agents and amino silane coupling agents with a pKa of 3 or higher for the adduct.

[0024] 5. The inkjet apparatus according to the fourth item, wherein the curing agent is a nitrogen-containing catalyst type curing agent.

[0025] 6. The inkjet apparatus according to claim 4 or 5, wherein the content of the curing agent is in the range of 3 to 15% by mass relative to the total amount of the resin composition.

[0026] 7. The inkjet apparatus according to any one of items four to six, wherein the molecular weight of a single nitrogen atom in the aminosilane coupling agent is 250 or less.

[0027] 8. The inkjet apparatus according to any one of claims 4 to 7, wherein the amino-based silane coupling agent has two or more alkoxy groups bonded to silicon atoms.

[0028] 9. The inkjet apparatus according to any one of claims 1 to 8, wherein the material of the substrate in contact with the main surface constituting the requirements of (1) and (2) comprises metal, metal oxide or glass.

[0029] 10. The inkjet apparatus according to any one of claims 1 to 9, wherein the ink comprises a compound having at least one group selected from carboxylic acid group, sulfonic acid group and phosphonic acid group, or selected from SO4. 2- PO4 3- B(C6F5)4 - SbF6 - PF6 - BF4 - CF3SO3 - and C4F9SO3 - At least one anion.

[0030] Invention Effects

[0031] Through the means described in this invention, an inkjet device with excellent ink resistance at the interface between the resin layer disposed between or on a substrate and the substrate can be provided, thereby granting it long-term reliability. The mechanism of action or effect of this invention is speculated as follows.

[0032] The inkjet apparatus of the present invention comprises a substrate, a resin layer laminated in such a way that at least one main surface contacts the substrate, and an ink flow path disposed in such a way that ink flows in contact with a portion of the resin layer, the resin layer having the following characteristics.

[0033] The resin layer contains carbon, oxygen, nitrogen, and silicon. Furthermore, at least one surface of the main surface satisfies the requirements of (1) and (2).

[0034] The resin layer in the inkjet apparatus of the present invention may, for example, be configured such that only one main surface of the resin layer contacts the substrate (hereinafter also referred to as "configuration having a resin layer on a substrate"), or may be configured such that the resin layer is sandwiched between two substrates, with both main surfaces of the resin layer contacting each substrate (hereinafter also referred to as "configuration having a resin layer between substrates"). In the case of the resin layer being on the substrate, the resin layer may, for example, have its main surface opposite to the surface contacting the substrate in contact with the ink flow path. In the case of the resin layer being between substrates, the resin layer may, for example, have its side surface in contact with the ink flow path.

[0035] In the inkjet apparatus of the present invention, when the structure has a resin layer on the substrate, the requirement (2) is satisfied in the main surface on the substrate side; when the structure has a resin layer between the substrates, the requirement (2) is satisfied in at least one main surface in contact with the substrate. The requirement (2) is composed of three requirements: (2-1) main surface O > interior O, (2-2) main surface N > 0, and (2-3) main surface Si / interior Si ≥ 5. In the present invention, the indicators used in (2-1) to (2-3) are used as indicators to indicate the presence of chemical bonds, groups that capture ink components, etc., at the interface between the substrate and the resin layer.

[0036] Specifically, when a resin layer is formed on a substrate as a cured resin composition, chemical bonding occurs between the substrate and the resin layer by reacting reactive groups on the substrate surface with components in the resin composition, thereby imparting strong adhesion. When the resin layer is formed by sandwiching it between substrates, the ink resistance of the resin layer, which serves as the adhesive bond between the substrates, is improved by generating the chemical bonds on the surfaces of at least one or both of the two substrates in contact with the resin layer.

[0037] In this invention, the "substrate-O-Si" bond (covalent bond) is envisioned as an indicator of the amount of chemical bonding, and requirements (2-1) and (2-3) are set. When the reactive group on the substrate surface is an OH group, and the resin composition contains a compound having a hydrolyzable silane, firstly, a silanol group (Si-OH) is formed through a hydrolysis reaction of the hydrolyzable silane. This silanol group undergoes a dehydration condensation reaction with the OH group (substrate-OH) on the substrate surface to form a chemical bond (substrate-O-Si). Therefore, given that: if requirements (2-1) and (2-3) are satisfied, when a resin layer is formed on the substrate, a sufficient amount of "-O-Si" bonds bonded to the substrate exist on the substrate-side main surface to improve the adhesion between the substrate and the resin layer; when a resin layer is formed between substrates, a sufficient amount of "-O-Si" bonds bonded to the substrate exist on at least one main surface in contact with the substrate to improve the adhesion between the substrate and the resin layer.

[0038] In this invention, when a resin layer is formed on a substrate, and nitrogen atoms are further present on the main surface of the substrate, ink components can be captured at the interface between the main surface of the resin layer and the substrate, thus setting the requirement (2-2). When a resin layer is formed between substrates, and nitrogen atoms are further present on at least one main surface in contact with the substrate, ink components can be captured at the interface between the main surface of the resin layer and the substrate, thus setting the requirement (2-2).

[0039] If nitrogen atoms exist on the main surface, for example as a primary amino group (-NH2), they can trap ink components such as water and acids by virtue of their charged nature, preventing ink from penetrating to the interface between the resin layer and the substrate, thus improving the ink resistance of the material. When nitrogen atoms exist as a primary amino group (-NH2), they sometimes hydrogen-bond with OH groups on the substrate surface, becoming substrate-O groups. - -NH3 + The base. In the hydrogen bonding with the substrate surface, -NH3... + In the case of the radical, it is impossible to capture water and acid, but the hydrogen bonds can be easily broken, thus becoming -NH2, which can help capture water and acid that invade from the outside.

[0040] In this invention, as described above, by using the aforementioned index to specify the relationship between the content of specific atomic types on the main surface and inside of the resin layer in contact with the substrate, the ink resistance of the interface between the resin layer disposed between or on the substrate and the substrate is improved. According to this invention, an inkjet apparatus with long-term reliability can be provided. Attached Figure Description

[0041] Figure 1 It is a schematic cross-sectional view of the peripheral portion of the resin layer when only one main surface of the resin layer is in contact with the substrate.

[0042] Figure 2 It is a schematic cross-sectional view of the peripheral portion of the resin layer when the two main surfaces of the resin layer are in contact with the substrate.

[0043] Figure 3 This is a perspective view illustrating an example of an embodiment of the inkjet device of the present invention.

[0044] Figure 4 yes Figure 3 The image shows a bottom view of the inkjet device.

[0045] Figure 5 It is Figure 3 The image shows a cross-sectional view of the lower part of the inkjet device cut along the left-right direction.

[0046] Figure 6 yes Figure 3 An exploded perspective view of the head chip of the inkjet device shown.

[0047] Figure 7 It is along Figure 6 A cross-sectional view of line VII-VII.

[0048] Figure 8 yes Figure 7 An enlarged view of the portion surrounded by dashed lines.

[0049] Figure 9 This is a partial cross-sectional view of another embodiment of the inkjet device of the present invention.

[0050] Figure 10 yes Figure 9 An enlarged view of the portion of the inkjet unit shown, enclosed by the dashed line.

[0051] Figure 11A This is a graph representing the XPS-based depth profile of Example 1.

[0052] Figure 11B This is a graph showing the XPS-based depth distribution of Example 2.

[0053] Figure 11C This is a graph showing the XPS-based depth distribution of Example 3.

[0054] Figure 12A This is a graph representing the spectrum obtained by XPS-based analysis of the bonding state of nitrogen atoms in Example 1.

[0055] Figure 12B This is a graph representing the spectrum obtained by XPS-based analysis of the bonding state of nitrogen atoms in Example 2.

[0056] Figure 12C This is a graph representing the spectrum obtained by XPS-based analysis of the bonding state of nitrogen atoms in Example 3. Detailed Implementation

[0057] The inkjet apparatus of the present invention comprises a substrate, a resin layer laminated in such a way that at least one main surface is in contact with the substrate, and an ink flow path disposed in such a way that ink flows in contact with a portion of the resin layer, wherein the resin layer comprises carbon, oxygen, nitrogen and silicon, and at least one surface of the main surface satisfies the requirements of (1) and (2) below.

[0058] (1) The main surface is in contact with the substrate.

[0059] (2) When the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the main surface of the resin layer as determined by X-ray photoelectron spectroscopy are expressed by main surface N, main surface O and main surface Si respectively, and the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the interior of the resin layer are expressed by interior N, interior O and interior Si respectively, the main surface O > interior O and the main surface N > 0, and the ratio of main surface Si to interior Si expressed by main surface Si / interior Si is 5 or more.

[0060] This feature is a common or corresponding technical feature in the following embodiments.

[0061] As an embodiment of the present invention, from the viewpoint of further demonstrating the effects of the present invention, among the main surfaces that satisfy the requirements of (1) and (2), as a requirement of (3), it is preferable to further satisfy that "the ratio of the main surface N, expressed as the main surface N / internal N, to the internal N is 1.5 or more". This further improves the effect of capturing ink components at the interface between the main surface of the resin layer and the substrate.

[0062] As an embodiment of the present invention, from the viewpoint of further demonstrating the effects of the present invention, for the main surface satisfying the requirements of (1) and (2), the spectrum obtained by analyzing the bonding state of nitrogen atoms based on X-ray photoelectron spectroscopy preferably has -NH2 or -NH3. + The peak. This spectrum can have a peak with -NH2 but not with -NH3. + The spectrum of the peak can also have a peak with -NH3 but without -NH2. + The spectrum of the peaks can also include peaks with -NH2 and -NH3. + The spectra of these two peaks. In the principal plane, peaks with -NH2 and -NH3 are typically obtained. + The peaks of these two spectra.

[0063] -NH3 is considered to exist on the principal surface that satisfies the requirements of (1) and (2).+ As described above, this represents a state where the OH groups on the substrate surface are hydrogen-bonded. If the OH groups on the substrate surface are consumed by hydrogen bonding with -NH2, then hydrolytic silane bonding with the substrate surface cannot occur in this region. Furthermore, in the -NH2 state, it is possible to capture water and acids that have invaded from the outside, while in the -NH3 state… + In this case, water and acid cannot be captured unless the hydrogen bonds with the substrate surface are eliminated. Specifically, -NH3 + It can easily become -NH2, therefore the nitrogen atom present on the principal face satisfying requirements (1) and (2) is preferably -NH2 or -NH3. + And it exists.

[0064] As an embodiment of the present invention, from the viewpoint of further demonstrating the effects of the present invention, the resin layer preferably comprises an epoxy compound and H at 25°C. + Cured products of resin compositions of curing agents and amino silane coupling agents with a pKa of 3 or higher for the adduct.

[0065] As an embodiment of the present invention, from the viewpoint of further demonstrating the effects of the present invention, the curing agent is preferably a nitrogen-containing catalyst type curing agent.

[0066] As an embodiment of the present invention, from the viewpoint of being able to further demonstrate the effects of the present invention, the content of the curing agent is preferably in the range of 3 to 15% by mass relative to the total amount of the resin composition.

[0067] As an embodiment of the present invention, from the viewpoint of further demonstrating the effects of the present invention, the molecular weight of the unit nitrogen atom in the amino-based silane coupling agent is preferably 250 or less.

[0068] As an embodiment of the present invention, from the viewpoint of further demonstrating the effects of the present invention, the amino-based silane coupling agent preferably has two or more alkoxy groups bonded to silicon atoms.

[0069] As an embodiment of the present invention, when the material of the substrate in contact with the main surface that constitutes the requirements of (1) and (2) includes metal, metal oxide or glass, more significant effects can be obtained.

[0070] As an embodiment of the present invention, the ink comprises a compound having at least one group selected from carboxylic acid group, sulfonic acid group and phosphonic acid group, or a compound selected from SO4. 2- PO4 3- B(C6F5)4 - SbF6 - PF6 - BF4 - CF3SO3- and C4F9SO3 - More significant effects can be obtained when at least one anion is present.

[0071] The present invention, its constituent elements, and the forms and methods for implementing the invention will be described in detail below. It should be noted that in this application, "~" is used to encompass the numerical values ​​described before and after it as lower and upper limits.

[0072] [Inkjet Printing Device]

[0073] The inkjet apparatus of the present invention comprises a substrate, a resin layer laminated in such a way that at least one main surface is in contact with the substrate, and an ink flow path disposed in such a way that ink flows in contact with a portion of the resin layer, wherein the resin layer comprises carbon, oxygen, nitrogen and silicon, and at least one surface of the main surface satisfies the requirements of (1) and (2) below.

[0074] (1) The main surface is in contact with the substrate.

[0075] (2) When the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the main surface of the resin layer as determined by X-ray photoelectron spectroscopy are expressed by main surface N, main surface O and main surface Si respectively, and the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the interior of the resin layer are expressed by interior N, interior O and interior Si respectively, the main surface O > interior O and the main surface N > 0, and the ratio of main surface Si to interior Si expressed by main surface Si / interior Si is 5 or more.

[0076] Hereinafter, the main surface that satisfies the requirements of (1) and (2) will also be referred to as the "adhesive main surface (X)". In this invention, the main surfaces N, O and Si of the resin layer in the adhesive main surface (X), as well as the internal N, internal O and internal Si, are measured using X-ray photoelectron spectroscopy (XPS).

[0077] use Figure 1 and Figure 2 The positional relationship between the substrate, resin layer, and ink flow path, as well as the surface and internal structure of the resin layer, of the inkjet apparatus of the present invention will be described. Figure 1 This is a schematic cross-sectional view of the peripheral portion of the resin layer when only one main surface of the resin layer is in contact with the substrate, or more specifically, when the resin layer is disposed on the substrate and an ink flow path is provided on the resin layer. Figure 2 This is a schematic cross-sectional view of the peripheral portion of the resin layer when the two main surfaces of the resin layer are in contact with the substrate, or more specifically, when the resin layer is disposed between the substrates and an ink flow path is provided in such a way that it is in contact with the sides of the substrate and the resin layer.

[0078] exist Figure 1In this process, a resin layer P is formed on the surface BS of a substrate B. The resin layer P has a first main surface PSa and a second main surface PSb, with the surface BS in contact with the first main surface PSa. The second main surface PSb faces the ink flow path I through which the ink flows. Examples of resin layers with this configuration include protective layers. The resin layer P is composed of a first surface portion Pa, forming a region extending from the first main surface PSa to a depth of t1 [nm]; a second surface portion Pb, forming a region extending from the second main surface PSb to a depth of t2 [nm]; and an inner portion Pc, forming a region other than the first surface portion Pa and the second surface portion Pb. Figure 1 In the resin layer P shown, the requirement (2) is met in the relationship between the first main surface PSa and the inner Pc. That is, only the first main surface PSa is the bonding main surface (X).

[0079] It should be noted that, regarding the relationship with Figure 1 The same resin layer with an adhesive main surface (X) formed on a substrate, as shown, serves as an example of a specific component in an inkjet device, such as those described later. Figure 7 and Figure 8 The protective film 4 is shown in the figure.

[0080] exist Figure 2 In this structure, a resin layer P is formed between substrate B1 and substrate B2. Resin layer P has a first main surface PSa and a second main surface PSb. Surface B1S of substrate B1 contacts the first main surface PSa, and surface B2S of substrate B2 contacts the second main surface PSb. The side surface of resin layer P faces the ink flow path I through which the ink flows. Examples of resin layers include adhesive layers.

[0081] The resin layer P is composed of a first surface layer Pa, which extends from the first main surface PSa to a depth of t1 [nm]; a second surface layer Pb, which extends from the second main surface PSb to a depth of t2 [nm]; and an inner layer Pc, which is composed of the region other than the surface layers Pa and Pb. Figure 2 In the resin layer P shown, the requirement (2) is met in the relationship between the first main surface PSa and the inner Pc or the relationship between the second main surface PSb and the inner Pc. The relationship between the first main surface PSa and the inner Pc, and the relationship between the second main surface PSb and the inner Pc, can satisfy the requirement (2). That is, either the first main surface PSa or the second main surface PSb can be the bonding main surface (X), or both of them can be the bonding main surface (X).

[0082] It should be noted that, regarding the relationship with Figure 2The same resin layer with an adhesive main surface (X) formed between substrates, as shown, serves as an example of a specific component in an inkjet device, for example, as described later. Figure 7 and Figure 8 The image shows adhesive layer 2, and... Figure 9 and Figure 10 The adhesive layer 2A is shown in the figure.

[0083] Here, the determination of the main surface N, main surface O and main surface Si of the resin layer in the bonding main surface (X) of XPS, as well as the internal N, internal O and internal Si, can be performed, for example, as follows.

[0084] The determination of the atomic concentration (atm%) of various elements in a layered sample based on XPS is performed sequentially by etching from the main surface of the sample toward the thickness direction using ion sputtering, while measuring the energy of photoelectrons generated by irradiating the exposed surface with X-rays at given etching intervals. This yields a distribution curve of the atomic concentration (atm%) of various elements from the main surface of the sample toward the thickness direction (hereinafter referred to as "depth distribution"). It should be noted that H and He cannot be detected in XPS-based analysis; therefore, the atomic concentration (atm%) of this invention represents the atomic concentration (atm%) of each element except H and He.

[0085] exist Figure 1 In the resin layer P shown, the requirement (2) can be confirmed to be satisfied by preparing a depth distribution based on XPS measurement of the atomic composition from the first principal surface PSa toward the interior Pc. Here, the first principal surface PSa is the principal surface in contact with the substrate B. Therefore, in order to measure the principal surfaces N, O, and Si using XPS, the resin layer P is separated from the substrate B, and XPS-based measurements are performed in the separated first principal surface PSa to prepare a depth distribution in the thickness direction.

[0086] The depth distribution of the resin layer P thus obtained typically has the following pattern: in the first surface layer Pa, i.e., the region from the first principal surface PSa to a depth t1 [nm], the atomic composition varies in the thickness direction; and in the interior Pc, at a depth above the first principal surface PSa to a depth t1 [nm], the atomic composition is constant in the thickness direction. In this invention, in the XPS-based depth distribution of the resin layer, the region with a constant atomic composition in the thickness direction is defined as the interior of the resin layer.

[0087] It should be noted that, in Figure 1In the resin layer P shown, for example, the atomic composition of the internal Pc and the atomic composition of the first main surface PSa can be measured from the main surface that is not in contact with the substrate, i.e., the second main surface PSb side. That is, by measuring the atomic composition from the second main surface PSb toward the internal Pc using XPS, a depth distribution is created, and a region with a constant atomic composition in the thickness direction can be defined as the internal Pc, and the atomic composition in that region can be defined as the atomic composition of the internal Pc. Furthermore, in the depth distribution, the interface between the first main surface PSa of the resin layer P and the surface BS of the substrate B is clearly defined, so the atomic composition of this interface can be set as the atomic composition of the first main surface PSa of the resin layer P.

[0088] Figure 2 The bonding master surface (X) in the resin layer P shown is the first master surface PSa and / or the second master surface PSb, which can bond with... Figure 1 Similarly, the atomic composition of the bonding main surface (X) and the atomic composition of the internal Pc in the first main surface PSa of the resin layer P shown were determined.

[0089] The distribution curve obtained by XPS depth distribution measurement can be prepared, for example, by setting the vertical axis to the concentration of each element (unit: atm%) and the horizontal axis to the etching time (sputtering time). It should be noted that in such an atomic concentration distribution curve with etching time as the horizontal axis, the etching time is approximately related to the distance (depth) in the thickness direction from the main surface of the resin layer. The distance (depth) in the thickness direction from the main surface of the resin layer to the measurement location can be calculated based on the relationship between the etching rate and etching time used in XPS depth distribution measurement.

[0090] Furthermore, as a sputtering method used for measuring such XPS depth distribution, rare gas ion sputtering using argon (Ar) as the etching ion species can be employed. The etching rate can be determined using a SiO2 thermal oxide film with a known thickness, and in most cases, the etching depth is expressed as a conversion value of the SiO2 thermal oxide film.

[0091] In this invention, the atomic concentrations (atm%) of various elements in the bonding substrate (X) of the resin layer, as well as the N, O, and Si of the substrate, are measured using XPS depth distribution measurements from the bonding substrate (X) side, and are the values ​​from the first measurement (depth 0 nm) before etching begins. It should be noted that the bonding substrate (X) of the resin layer can, for example, be obtained as the separation surface on the resin layer side when separating the substrate with the resin layer at the interface between the substrate and the resin layer using a cutting tool or similar device.

[0092] Furthermore, for example, when performing XPS depth distribution measurement from the side of the resin layer opposite to the bonding master surface (X), the measured values ​​of the atomic concentration (atm%) of various elements at the interface with the substrate are the master surface N, master surface O, and master surface Si in the bonding master surface (X). It should be noted that when performing XPS depth distribution measurement from the side of the resin layer opposite to the bonding master surface (X), depending on the thickness of the resin layer, the resin layer is pre-removed from the side opposite to the bonding master surface (X) until the remaining resin layer reaches an appropriate thickness, preferably about 0.1 to 1 μm, before performing the XPS depth distribution measurement, which allows for effective measurement. In this case, internal N, internal O, and internal Si can be measured in the initial part of the measurement.

[0093] Regarding the interface between the resin layer and the substrate, in cases where the substrate contains inorganic materials such as metals, metal oxides, or glass, the interface can be determined based on the carbon atomic concentration (atm%). For example, the interface between the resin layer and the substrate (the bonding surface (X) of the resin layer and the surface of the substrate) can be defined as the range from a position where the carbon atomic concentration (atm%) relative to the internal carbon atomic concentration (atm%) of the resin layer is 0.82 (starting point) to a position that becomes the detection limit (end point). It should be noted that the starting point can be appropriately selected within the range of a position where the carbon atomic concentration (atm%) relative to the internal carbon atomic concentration (atm%) of the resin layer is 0.82 to a position where it is 0.5.

[0094] That is, when using the measurement method described above, the bonding main surface (X) in this invention can be set as a region with a given thickness. The given thickness is a range from a position where the atomic concentration (atm%) of carbon relative to the interior of the resin layer is 0.82 to 0.5 to a position below the detection limit; for example, a thickness of about 5 nm can be cited. It should be noted that the region of the bonding main surface (X) is specifically a region located on the substrate side as part of the surface portion of the resin layer. When using the measurement method described above, the relationship between the atomic concentrations (atm%) of various elements in this region measured by XPS in any plane orthogonal to the thickness direction of the resin layer should satisfy (2).

[0095] It should be noted that when the substrate and the resin layer are firmly bonded, a high level of skill is required to separate the resin layer from the resin-bearing substrate while maintaining the bonding surface (X). In such cases, it is preferable to perform XPS depth distribution measurement from the side of the resin layer opposite to the bonding surface (X). Furthermore, whether the resin layer can be separated from the resin-bearing substrate while maintaining the bonding surface (X) can be confirmed, for example, by performing XPS depth distribution measurement starting from the surface of the resin layer side of the separated substrate. In addition, in this method, the results of XPS depth distribution measurement starting from the bonding surface (X) of the separated resin layer can be combined with the results of XPS depth distribution measurement starting from the surface of the resin layer side of the substrate, and the bonding surface (X) can be used as a region with a given thickness to determine whether the requirement (2) is met.

[0096] Regarding internal N, internal O, and internal Si, when measuring the XPS depth distribution from the bonding master surface (X), for example, starting from the point where the atomic composition no longer changes in the thickness direction after sequentially measuring from the self-bonding master surface (X), the values ​​or average values ​​of N concentration (atm%), O concentration (atm%), and Si concentration (atm%) obtained by measuring at least 1 point, preferably at least 2 points, in the thickness direction can be set.

[0097] For example, similar to the method described below, whenever 10 nm is etched along the thickness direction from the bonding substrate (X), the atomic concentrations (atm%) of N, O, and Si are measured on the surface exposed by the etching. If the atomic composition remains constant at measurement points with a thickness (depth) of 10 nm or more from the bonding substrate (X), the value can be set as the average of six measurements taken at thicknesses (depths) from 10 nm to 60 nm from the bonding substrate (X). It should be noted that the etching thickness can be appropriately adjusted, for example, within the range of 2 to 30 nm.

[0098] Furthermore, when XPS depth distribution measurement is performed from the side of the resin layer opposite to the bonding main surface (X), the values ​​or average values ​​of the respective N concentration (atm%), O concentration (atm%), and Si concentration (atm%) obtained from the first measurement point to the point where the atomic composition begins to change in the thickness direction, with at least one measurement point in the thickness direction and preferably at least two measurement points, can be used as internal N, internal O, and internal Si.

[0099] It should be noted that, for the main surface N, main surface O and main surface Si, as well as the inner surface N, inner surface O and inner surface Si, it is preferable to randomly select at least two locations in the bonding main surface (X) of the resin layer in the surface direction to measure the atomic concentration of various elements in the surface and inner parts based on the method, and set them as their average values.

[0100] Here, in this invention, the internal N, internal O, and internal Si in the resin layer measured by the method described above are actually atomic concentrations (atm%) measured in a portion of the interior of a main surface side, but the interior of the entire interior other than the surface portion of the resin layer is considered to have the same composition, so the measurement method described above can be applied.

[0101] The following describes an example of specific conditions for XPS depth distribution measurement of the main surfaces N, O, and Si of the resin layer, as well as the internal N, internal O, and internal Si, applicable to the compositional analysis of the resin layer of the present invention. As a specific example of XPS depth distribution measurement performed under these conditions, examples from the embodiments are provided. Figure 11A (Example 1)

[0102] • Analytical apparatus: QUANTERA SXM manufactured by ULVAC-PHI

[0103] • X-ray source: Monochromatic Al-Kα 15kV 25W

[0104] Sputtered ions: Ar (1keV)

[0105] • Depth distribution: The sputtering thickness was converted to SiO2, and measurements were repeatedly taken at given thickness intervals to determine the depth distribution along the depth direction. This thickness interval was 10.8 nm (data was obtained every 10.8 nm along the depth direction).

[0106] • Quantitative analysis: Background was determined using the Shirley method, and quantification was performed using the relative sensitivity coefficient method based on the obtained peak area. Data processing was performed using a MultiPak system manufactured by ULVAC-PHI.

[0107] Here, the requirement (2) in the bonding main surface (X) is composed of three requirements: (2-1) main surface O > interior O, (2-2) main surface N > 0, and (2-3) main surface Si / interior Si ≥ 5.

[0108] In requirement (2-1), the main surface O > the interior O. The relationship between the main surface O and the interior O is preferably expressed as a ratio of 2 or more for the main surface O to the interior O, expressed as the ratio of the main surface O to the interior O. More preferably, the ratio of the main surface O to the interior O is 7.5 or more. There is no particular upper limit to the ratio of the main surface O to the interior O; for example, it can be 100 or less. A higher oxygen atom concentration in the adhesive main surface (X) than in the interior of the resin layer means that sufficient chemical bonds via oxygen exist at the interface between the resin layer and the substrate, thereby achieving high adhesion.

[0109] In requirement (2-2), the nitrogen atom concentration on the bonding surface (X) is greater than 0. A nitrogen atom concentration exceeding 0 on the bonding surface (X) means that nitrogen atoms are present on the surface of the resin layer on the bonding surface (X), thereby achieving adhesion. The nitrogen atoms are present, for example, in the form of amino groups, preferably as -NH2 or -NH3. + It exists in the form of ink and functions as described above, possessing the ability to capture ink components such as water and acid, thereby improving adhesion and ink resistance.

[0110] In the requirements of (2-3), the ratio of Si on the main surface to Si inside is 5 or more. Preferably, the ratio is 6 or more, more preferably 8 or more. There is no particular upper limit to the ratio of Si on the main surface to Si inside; it can also be infinitely large as internal Si may be undetectable. In the adhesive main surface (X), a silicon atom concentration that is 5 times higher than that inside the resin layer means that chemical bonds via siloxane bonds are sufficiently present at the interface between the resin layer and the substrate, thereby achieving high adhesion.

[0111] It should be noted that the specific value of Si on the main surface is preferably 1.0 to 10.0 atm%, more preferably 1.1 to 9.8 atm%, and even more preferably 1.3 to 9.5 atm%. If the Si on the main surface is 1.0 atm% or more, the amount of siloxane bonds at the interface is sufficient, making it easy to obtain high adhesion. When the Si on the main surface exceeds 10.0 atm%, the balance of the atomic concentrations in the bonding main surface (X) is disrupted, and there is a tendency for reduced adhesion and ink durability.

[0112] Regarding the requirement in (2-2), it is preferable that the ratio of main surface N to interior N is 1.5 or more, that is, it satisfies the requirement in (3) of the present invention. It is more preferable that the ratio of main surface N to interior N is 2 or more. There is no particular upper limit to the ratio of main surface N to interior N, for example, it can be 100 or less. In the adhesive main surface (X), a nitrogen atom concentration that is more than twice as high as that in the interior of the resin layer means that there is a sufficient amount of nitrogen atoms on the surface of the adhesive main surface (X) side of the resin layer, thereby obtaining high adhesion.

[0113] Regarding the requirement (2-2), the bonding master surface (X) preferably has a spectrum of -NH2 or -NH3 obtained by XPS-based nitrogen atom bonding state analysis. + The peak value. XPS-based bond state analysis can be performed, for example, by the following methods.

[0114] XPS allows for the analysis of the bonding states of various elements. In this invention, the bonding states of nitrogen atoms in the bonding master surface (X) are determined using XPS bonding state analysis, confirming -NH2 and -NH3 bonds. +The presence quantity. The following represents an example of specific conditions applicable to the XPS-based bonding state analysis of the present invention. As a specific example of the spectrum obtained by determining the bonding state of nitrogen atoms under these conditions, examples are provided. Figure 12A (Example 2)

[0115] • Analytical apparatus: QUANTERA SXM manufactured by ULVAC-PHI

[0116] • X-ray source: Monochromatic Al-Kα 15kV 25W

[0117] • Pass energy: 55eV

[0118] • Data processing: Using MultiPak manufactured by ULVAC-PHI

[0119] • Elemental composition analysis: The Shirley method was used for background processing, and the elemental composition was quantified using the relative sensitivity coefficient based on the obtained peak area.

[0120] -NH2 and -NH3 + The peaks and peak areas can be determined using the following method. First, the peak shift caused by charge is corrected based on the bond energy of the carbon 1s peak. Then, the nitrogen atom peak (represented by solid lines in the figure) is separated into peaks for each state. Figure 12A In the sample, the nitrogen atom peak can be separated into two states (a peak showing a maximum at 399.5 eV and a peak showing a maximum at 401.8 eV). The state of the nitrogen atom in each peak is determined based on bond energy. Figure 12A In the figure, the peak showing the maximum value at 399.5 eV is the peak of -NH2, and the peak showing the maximum value at 401.8 eV is the peak of -NH3. + The peak.

[0121] It should be noted that -NH2 and -NH3 + The bond energy is based on the literature value "Comprehensively Revised Edition of the Effects and Usage of Silane Coupling Agents (First Edition, November 15, 2012)" (-NH2; 399.0 eV, -NH3). + The value was confirmed to be 400.6 eV. This value was taken as the peak value, and the peak FWHM (full width at half maximum) was within the range of 1.0 to 2.5, and the peaks of -NH2 and -NH3 were considered. + Under the condition that the peaks have equal FWHM (full width at half maximum), the area of ​​each peak is calculated by fitting the data. Based on -NH2 and -NH3... + Calculate the peak areas to determine the nitrogen atoms originating from -NH2 and those originating from -NH3. + The ratio of nitrogen atoms to the total amount of nitrogen atoms.

[0122] Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the scope of the present invention is not limited to the examples shown in the drawings. The components shown in these drawings can be appropriately modified without departing from the spirit of the present invention. It should be noted that, in this specification, for ease of explanation, the direction in which ink is ejected from the inkjet device is designated as downward, and the direction opposite to the downward direction is designated as upward. Furthermore, the arrows in the ink flow paths of the accompanying drawings indicate the direction of ink flow.

[0123] Figure 3 This is a perspective view illustrating an example of an embodiment of the inkjet device of the present invention. Figure 4 yes Figure 3 The image shows a bottom view of the inkjet apparatus. During recording on a recording medium, the bottom surface of the inkjet apparatus is positioned opposite the recording surface of the recording medium. Specifically, the recording medium is positioned such that its recording surface is below the inkjet apparatus and orthogonal to the direction of ink ejection, and inkjet recording is performed while it is being transported. In the following description, for convenience, the direction of transporting the recording medium will be described as the front-back direction, and the direction orthogonal to the direction of transporting the recording medium on the recording surface will be described as the left-right direction.

[0124] Figure 5 It is Figure 3 The image shows a cross-sectional view of the lower part of the inkjet device cut along the left-right direction. Figure 6 yes Figure 3 An exploded perspective view of the magnetic head chip of the inkjet device shown. Figure 7 It is along Figure 6 Cross-sectional view of line VII-VII, Figure 8 yes Figure 7 An enlarged view of the portion surrounded by dashed lines.

[0125] like Figure 3 , Figure 4 as well as Figure 5 As shown, the inkjet apparatus 100 of this embodiment includes a magnetic head chip 10A and a manifold 5 for storing ink supplied to the magnetic head chip 10A. The magnetic head chip 10A includes a shear-mode actuator Ac and a nozzle plate 20 having nozzles 21 for ejecting ink from the actuator Ac to the outside of the inkjet apparatus 100. The actuator Ac includes a stacked substrate in which a flow path substrate 3A, an adhesive layer 2X, and a pressure chamber substrate 1A are sequentially stacked from the manifold 5 side. The pressure chamber substrate 1A of the actuator Ac is bonded to the nozzle plate 20 via the adhesive layer 2X.

[0126] Both adhesive layer 2X and adhesive layer 2 are resin layers with two main surfaces in contact with the substrate surface. It should be noted that, as described later, the side surfaces of adhesive layer 2X are covered by a protective film 4 (see reference). Figure 7Therefore, it will not come into contact with the ink flow path. On the other hand, the side of the adhesive layer 2 comes into contact with the ink flow path. The adhesive layer 2 is, for example, an adhesive layer that satisfies the requirements of the present invention, with at least one main surface satisfying the requirements described in (2). Furthermore, the protective film 4 covering the side of the adhesive layer 2X is typically a resin layer. Hereinafter, unless otherwise specified, both the "adhesive layer" and the "protective film" shall be composed of resin layers in this specification.

[0127] As described below, the pressure chamber substrate 1A is preferably made of a piezoelectric material, such as PZT, and the nozzle plate 20 is made of metal. When considering the materials of the pressure chamber substrate 1A and the nozzle plate 20, the adhesive layer 2 preferably has at least one main surface in contact with the nozzle plate 20 as the adhesive main surface (X), and more preferably two main surfaces as the adhesive main surfaces (X).

[0128] As described above, adhesive layer 2 is a resin layer. In this specification, "resin layer" refers to a layer primarily composed of resin. The resin contained in the resin layer can be a thermoplastic resin or a curing resin. It should be noted that curing resin refers to a resin obtained by polymerizing a curing compound through a reaction with light or heat, thereby curing it. The resin layer may also contain inorganic or organic components other than resin. Examples of components other than resin include additives and fillers added to the resin layer for various purposes. The content of resin contained in the resin layer can be set to approximately 50% by mass or more relative to the total amount of the resin layer. It should be noted that in this specification, plasticizers in thermoplastic resins and curing agents, polymerization initiators, catalysts, chain transfer inhibitors, polymerization inhibitors, and other components related to the polymerization (curing) of curing compounds in curing resins are included within the scope of resin.

[0129] The resin layer of the present invention comprises carbon, oxygen, nitrogen, and silicon. These elements may be included in any component of the resin and other components contained in the resin layer. It should be noted that the resin layer of the present invention typically contains hydrogen.

[0130] Examples of thermoplastic resins that can be used as the resin contained in the resin layer include: polyolefin resins, polystyrene resins, polyamide resins, polyimide resins, polyester resins, acrylic resins, polyurethane resins, polyvinyl chloride resins, vinyl acetate resins, ethylene vinyl acetate resins, epoxy resins, phenolic resins, melamine resins, polycarbonate resins, polyacetal resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, styrene-acrylonitrile copolymers (AS resins), styrene-(meth)acrylic acid copolymers, styrene-methyl methacrylate copolymers, acrylonitrile-butadiene-styrene copolymers (ABS resins), methyl methacrylate-butadiene-styrene copolymers (MBS resins), etc.

[0131] Examples of curing resins that can be used as the resin contained in the resin layer include: phenolic resins, epoxy resins, acrylic resins, polyurethane resins, melamine resins, alkyd resins, unsaturated polyester resins, urea-formaldehyde resins, and parylene resins.

[0132] These resins all contain carbon and hydrogen, and depending on the type, they may also contain oxygen or nitrogen. Furthermore, even resins with a typical structure that do not contain oxygen, nitrogen, or silicon can be modified to contain oxygen, nitrogen, and silicon through the introduction of substituents and other methods.

[0133] Here, when a resin layer containing a thermoplastic resin is formed on or between substrates, typically, the thermoplastic resin itself is coated onto the substrate as a liquid composition dissolved in a solvent, and then dried to form the resin layer. When a resin layer is formed between substrates, a liquid composition is coated onto one substrate, another substrate is laminated onto the coating of the liquid composition, and the coating is dried, thereby forming the resin layer. When the resin layer contains components other than resin, the components other than resin are incorporated into the liquid composition.

[0134] Furthermore, when a resin layer containing a curable resin is formed on or between substrates, typically, a liquid composition is applied to the substrate and cured by heat or light to form the resin layer. The liquid composition contains a curable compound and, as needed, components related to the polymerization (curing) of the curable compound, selected from curing agents, polymerization initiators, catalysts, chain transfer inhibitors, and polymerization inhibitors, and further, as needed, solvents, etc. In the case of forming a resin layer between substrates, a liquid composition is applied to one substrate, and another substrate is laminated on top of the coating of the liquid composition. The coating is then cured by heat or light to form the resin layer. In cases where the resin layer contains components other than resin, these components are incorporated into the liquid composition. Hereinafter, the curable compound and components related to the polymerization (curing) of the curable compound will be referred to together as "resin components."

[0135] In the above text, the solvent used in the preparation of the liquid composition for forming the resin layer, the coating method of the liquid composition, and the drying and curing conditions of the coating film can be appropriately selected according to the type of resin. The thickness of the resin layer is appropriately selected according to the type of resin, its application, and the location of application.

[0136] When using thermoplastic resins or curing resins to form resin layers on or between substrates, in order to ensure that the resin layer has a main surface that satisfies (1) and (2), it is preferable to include, as a component other than the resin incorporated in the liquid composition, a component that is located near the interface between the resin layer and the substrate during the formation of the resin layer and has at least nitrogen and silicon. Examples of components located near the interface between the resin layer and the substrate during the formation of the resin layer include coupling agents, and examples of coupling agents containing nitrogen and silicon include aminosilane coupling agents.

[0137] [Aminosilane coupling agents]

[0138] As an amino-based silane coupling agent, a compound with a structure represented by the following formula (I) is preferred.

[0139] Formula (I)R 1 4-n SiX n

[0140] R 1 This indicates a monovalent organic group, at least one of which is a monovalent organic group comprising at least one of a primary amino group, a secondary amino group, a tertiary amino group, an amino acid neutralizing group, or a quaternary ammonium base. X represents a monovalent hydrolyzable group. n represents an integer from 1 to 3. R 1 When there are more than two, more than two R 1 They can be the same or different.

[0141] Examples of monovalent hydrolyzable groups for X include: alkoxy, acyloxy, ketoxime, alkenyloxy, amino, aminooxy, amide, isocyanate, and halogen atoms. When n is 2 or more, multiple X groups can be the same or different.

[0142] Preferred hydrolyzable groups include alkoxy groups and halogen atoms, with alkoxy groups having 1 to 4 carbon atoms being particularly preferred. As amino-based silane coupling agents represented by formula (I), amino-based silane coupling agents with structures represented by formula (II) are more preferably examples. The amino-based silane coupling agent represented by formula (II) is a compound in which the hydrolyzable group X in formula (I) is an alkoxy group (1 to 4 carbon atoms).

[0143] [Chemical Formula 1]

[0144] Equation (II)

[0145]

[0146] In equation (II), R 2 and R 3 This refers to an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, and butyl. n represents an integer from 1 to 3, preferably 2 or 3.

[0147] In equation (II), R 4 This refers to any one of alkylene and aryl groups having 1 to 20 carbon atoms. Examples of alkylene groups having 1 to 20 carbon atoms include: methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl, 2-methyl-hexane-1,6-diyl, decane-1,10-diyl, etc. Examples of aryl groups include phenylene and naphthylene. These groups may optionally be substituted with halogens, hydroxyl groups, etc.

[0148] In equation (II), R 5 This refers to any one of the following: a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group. Examples of alkyl groups having 1 to 20 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, isohexyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, etc. Examples of aryl groups include: phenyl, naphthyl, etc. These groups may be further substituted with aryl, heterocyclic, amino, amide, imino, halogen atoms, hydroxyl, etc.

[0149] Specifically, examples of amino-based silane coupling agents include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, and N-butyl-3-aminopropyltrimethoxysilane. N,N-Dimethyl-3-aminopropyltrimethoxysilane, N,N-Diethyl-3-aminopropyltrimethoxysilane, N,N-Dibutyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-3-aminopropyltrimethoxysilane hydrochloride, octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, N-trimethoxysilylpropyl-N,N,N-tri-n-butylammonium bromide, N-trimethoxysilylpropyl-N,N,N-tri-n-butylammonium chloride, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, etc.

[0150] Among these, the preferred amino-based silane coupling agent is one with a molecular weight of 250 or less per nitrogen atom. Furthermore, amino-based silane coupling agents having two or more alkoxy groups bonded to silicon atoms are preferred, such as compounds with n being 2 or more in the compounds shown in formula (II).

[0151] Examples of amino-based silane coupling agents that meet these conditions include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, N,N-dimethyl-3-aminopropyltrimethoxysilane, and N,N-diethyl-3-aminopropyltrimethoxysilane.

[0152] Furthermore, amino silane coupling agents with a -NH2 group at the end are preferred, and 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane are particularly preferred.

[0153] By including an amino-based silane coupling agent in the resin composition described below, the hydrolyzable groups of the amino-based silane coupling agent are hydrolyzed during resin layer formation to generate silanol groups. These silanol groups can, for example, undergo dehydration co-condensation with OH groups on the substrate surface to form a "substrate-O-Si" bond. On the other hand, it is considered preferable that the terminal amino group is -NH2 or -NH3. + The state exists near the interface, performing the aforementioned function.

[0154] When forming a resin layer with a main surface satisfying the requirements of (1) and (2), the content of the aminosilane coupling agent is preferably in the range of 0.01 to 10% by mass, more preferably in the range of 0.1 to 5% by mass, relative to the total amount of the resin composition. If the content of the aminosilane coupling agent is within the range described above, the requirement of (2) is easily satisfied in the resin layer in contact with the substrate, and preferably the requirement of (3) is further satisfied, without affecting the film-forming properties, crosslinking structure, etc. of the resin layer.

[0155] When the resin layer is an adhesive layer, epoxy resin is preferred. When the resin layer is a protective layer, examples include polyimide resin and parylene resin. Hereinafter, embodiments in which the resin layer comprises epoxy resin will be described.

[0156] In cases where the resin layer of the present invention comprises epoxy resin, the resin layer is formed, for example, using a resin composition comprising a resin component and an amino-based silane coupling agent as a component other than the resin component, wherein the resin component comprises an epoxy compound as a raw material component of the epoxy resin and a curing agent. In the present invention, a "resin composition" is a composition composed of raw materials constituting the solid component of the resin layer, without solvent. When the resin composition is a liquid composition with a viscosity sufficient to form a coating on a substrate, solvent may not be specifically added. In cases where the resin composition is a solid or has a high viscosity that makes it difficult to form a coating on a substrate, a solvent is added to form a liquid composition of moderate viscosity for the formation of the resin layer.

[0157] Epoxy resin is a resin obtained by using an epoxy compound having multiple epoxy groups as a curing compound and curing the epoxy compound by a curing agent. When forming a resin layer using epoxy resin, a resin composition is used that includes a resin component for forming the epoxy resin and components other than the resin component, such as an amino-based silane coupling agent. Hereinafter, the components included in the resin composition (hereinafter also simply referred to as "resin composition" or "epoxy resin composition") used to form a resin layer using epoxy resin will be described.

[0158] (Epoxy compounds)

[0159] As for epoxy compounds, there are no particular limitations as long as they have at least two epoxy groups within the molecule, and they can be appropriately selected according to the purpose. For example, in order to obtain an epoxy resin with a cross-linked structure, the number of epoxy groups in the epoxy compound is preferably three or more, more preferably four or more. Furthermore, by using epoxy compounds with an epoxy equivalent preferably of 300 or less, more preferably 220 or less, it is easy to obtain an epoxy resin with a dense structure and short inter-crosslinking point distances.

[0160] Examples of epoxy compounds include: polyglycidyl ether compounds of mononuclear polyphenols, polyglycidyl ether compounds of polynuclear polyphenols, and polyglycidyl ethers of polyols; polyglycidyl ether compounds of polyols obtained by adding polyepoxides to mononuclear polyphenols, polynuclear polyphenols, or polyols; homopolymers or copolymers of glycidyl esters of aliphatic, aromatic, or alicyclic polyacids and glycidyl methacrylates; compounds obtained by internal crosslinking of epoxy compounds having glycidyl amino groups, epoxy compounds of cyclic olefins, heterocyclic compounds, or prepolymers of terminal isocyanates of these epoxy resins; and compounds obtained by polymerizing multi-component active hydrogen compounds (e.g., polyphenols, polyamines, carbonyl compounds, polyphosphates, etc.). They can be used individually or in combination of two or more.

[0161] Examples of mononuclear polyphenolic compounds include hydroquinone, resorcinol, catechol, phloroglucinol, etc.

[0162] Examples of such polynuclear polyphenolic compounds include: dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis(o-cresol), ethyl bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis(o-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxyisopropylphenylbenzene), 1,4-bis(4-hydroxyisopropylphenylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfonylbisphenol, oxybisphenol, phenolic varnish, o-cresol varnish, ethylphenol varnish, butylphenol varnish, octylphenol varnish, resorcinol varnish, terpene phenol, etc.

[0163] Examples of such polyols include: ethylene glycol, propylene glycol, butanediol, hexanediol, polyethylene glycol, dithioethylene glycol, dicyclopentadienedimethylethanol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-ethylene oxide adducts.

[0164] Examples of homopolymers or copolymers of glycidyl esters and (meth)acrylates of aliphatic, aromatic, or alicyclic polybasic acids include: maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, octanoic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and inner methylenetetrahydrophthalic acid, etc.

[0165] Examples of epoxy compounds having a glycidyl amino group include: N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl o-toluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, and N,N,N',N'-tetra(2,3-epoxypropyl)-4,4'-diaminodiphenylmethane.

[0166] Examples of epoxides that are cyclic olefin compounds include, for example, vinylcyclohexene diepoxide, dicyclopentane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexane carboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate. Examples of epoxidized conjugated diene polymers include, for example, epoxidized polybutadiene and epoxidized styrene-butadiene copolymers.

[0167] Examples of such heterocyclic compounds include triglycidyl isocyanurate.

[0168] From the perspective of the properties of the cured product, such as workability, adhesion, and solvent resistance during resin layer formation, polyglycidyl ether of polynuclear polyphenols, polyglycidyl ether of polyols, epoxy alkyl-modified epoxy resin of polynuclear polyphenols, and epoxy compounds with glycidyl amino groups are preferred.

[0169] As an epoxy compound, commercially available products can be used. Specific examples of commercially available products include the jER (registered trademark) series (manufactured by Mitsubishi Chemical Corporation), the EPPN series, and the EOCN series (manufactured by Nippon Kayaku Co., Ltd.).

[0170] The content of epoxy compound relative to the total amount of the epoxy resin composition can be set, for example, in the range of 25% to 99% by mass, more preferably in the range of 40% to 95% by mass. By setting the content of epoxy compound within the range described above, a cross-linked structure can be constructed within the resin composition, thereby improving resistance to ink penetration.

[0171] (Curing agent)

[0172] Curing agents are classified into addition polymerization curing agents and catalyst curing agents. Addition polymerization curing agents are compounds with multiple groups that react with epoxy groups. These reactive groups include carboxyl groups, hydroxyl groups, amino groups with active hydrogen, mercapto groups (-SH), and acid anhydride groups. Catalyst curing agents are compounds that promote the reaction between epoxy compounds; examples include tertiary amines, imidazole compounds, and phosphorus compounds.

[0173] In this invention, the curing agent is preferably H at 25°C. + Curing agents with a pKa of 3 or higher for the adduct. It should be noted that, unless otherwise specified, "pKa" in this specification refers to the pKa in water at 25°C. Furthermore, the pKa value in water at 25°C can be determined based on conductivity, etc.

[0174] Here, H is used. + Curing agents with a pKa of 3 or higher for the adduct are preferred as they can promote the reaction of epoxy compounds and amino silane coupling agents. The H in the curing agent...+ There is no particular upper limit to the pKa of the adduct; it can be set to approximately 50. As for H... + Curing agents with a pKa of 3 or higher for adducts are preferred, especially those containing nitrogen.

[0175] As H + Curing agents with a pKa of 3 or higher for the adduct; specifically, examples of addition-polymer curing agents include polyamine compounds having multiple amino groups with active hydrogen atoms. Examples of catalyst-type curing agents include tertiary amines and imidazole compounds. As H... + Curing agents with a pKa of 3 or higher for adducts are preferred, especially nitrogen-containing catalyst-type curing agents, and particularly imidazole compounds.

[0176] Imidazole compounds are a general term for compounds including imidazole and its derivatives. Preferred imidazole compounds are those in which at least one of the 1, 2, and 4 positions of the imidazole group is substituted with a substituent. Examples of substituents include alkyl, aryl, and aralkyl groups.

[0177] As alkyl, it refers to branched and straight-chain alkyl groups such as methyl, ethyl, isopropyl, tert-butyl, hexyl, dodecyl, undecyl, pentadecyl, and heptadecanyl, as well as cyclic alkyl groups such as cyclopentyl and cyclohexyl, which may have substituents.

[0178] Examples of substituents include: alkyl, alkenyl, aryl, heterocyclic, halogen atom, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, sulfonamide, aminosulfonyl, urea, acyl, acyloxy, carbamoyl, alkylsulfonyl, arylsulfonyl, cyano, nitro, sulfonyl, hydroxyl, etc.

[0179] Examples of aryl groups include phenyl and naphthyl groups, which may be optionally substituted with substituents listed among the alkyl groups.

[0180] As aryl alkyl groups, examples of alkyl groups that replace aryl groups include benzyl, phenethyl, and naphthylmethyl, which are optionally replaced by substituents listed among the alkyl groups.

[0181] Examples of imidazole compounds include: imidazole, 2-methylimidazolium, 4-methylimidazolium, 2-heptadecylimidazolium, 4-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 4-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazolium-(1')] -Ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, etc., but not limited to these.

[0182] Among them, 2-ethyl-4-methylimidazole, 4-methylimidazole, 4-heptadecylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, and other imidazole compounds having an alkyl or aryl group at the 4 position are preferred. Imidazole compounds can be used alone or in combination of two or more.

[0183] As imidazole compounds, commercially available products can be used. Specific commercially available products include, but are not limited to, the CUREZOL series manufactured by Shikoku Chemical Industry Co., Ltd., such as SIZ, 2MZ-H, C11Z, C17Z, 1.2DMZ, 2E4MZ, 2PZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN, 2PZ-CN, C11Z-CNS, 2PZCNS-PW, 2MZ-A, 2MZA-PW, C11Z-A, 2E4MZ-A, 2MA-OK, 2MAOK-PW, 2PZ-OK, 2PHZ-PW, and 2P4MHZ-PW.

[0184] The curing agent content is preferably in the range of 3 to 15% by mass relative to the total amount of the epoxy resin composition, and more preferably in the range of 5 to 11% by mass. By keeping the curing agent content within this range, ink resistance can be improved without hindering the formation of the crosslinked structure, which is therefore preferable.

[0185] As described above, H is preferably used in epoxy resin compositions. + Curing agents with a pKa of 3 or higher for adducts are used as curing agents. When using H... + In the case of a curing agent with a pKa of 3 or higher for the adduct, H can be further used as needed. + A curing agent with a pKa less than 3 for the adduct. Preferably, the curing agent contained in the epoxy resin composition is entirely H... + Curing agents with a pKa of 3 or higher. That is, the epoxy resin composition preferably contains H in the range of 3 to 15% by mass. + Curing agents with a pKa of 3 or higher for the adduct.

[0186] As mentioned above, as H + Curing agents with a pKa of 3 or higher for the adduct are preferred, especially nitrogen-containing catalyst-type curing agents, and particularly preferably imidazole compounds. In epoxy resin compositions, as H... + For curing agents with an adduct pKa of 3 or higher, when using nitrogen-containing catalyst-type curing agents, such as imidazole compounds, in addition to the nitrogen-containing catalyst-type curing agent, H can also be used. + Addition curing agents with a pKa of 3 or higher, such as polyamine compounds.

[0187] (Other resin components)

[0188] In addition to epoxy compounds and curing agents, epoxy resin compositions may also contain polymerization inhibitors, chain transfer inhibitors, etc., as resin components without impairing the effects of the present invention.

[0189] (Aminosilane coupling agents)

[0190] The epoxy resin composition used to form the epoxy resin layer preferably contains the amino-based silane coupling agent described above. This allows the resulting resin layer to satisfy (2) on any main surface in contact with the substrate.

[0191] (Other ingredients)

[0192] The epoxy resin composition may further include various additives or fillers and other solid components without impairing the effects of the present invention. Examples of additives include surfactants, ultraviolet absorbers, antioxidants, rheology control agents, antistatic agents, and photopolymerization initiators. Examples of fillers include carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and magnesium sulfate; silicates such as aluminum silicate and zirconium silicate; oxides such as silicon oxide, iron oxide, titanium oxide, aluminum oxide, and zinc oxide; and kaolin, talc, asbestos powder, quartz powder, mica, and glass fiber. Furthermore, conductive particles may be used as fillers as needed.

[0193] It should be noted that the other solid components sometimes contain oxygen atoms, silicon atoms, and nitrogen atoms, and these other solid components are typically dispersed in small amounts uniformly throughout the resin layer. In such cases, for example, as a result of combining the amino-based silane coupling agent with other solid components, it is sufficient to satisfy the requirement described in (2).

[0194] The method for forming the epoxy resin layer using the epoxy resin composition is not particularly limited. It can be used directly if the epoxy resin composition is a liquid composition, or, if the epoxy resin composition is not liquid, it can be prepared into a liquid composition using a solvent and coated onto a substrate to form a coating film. Other substrates can be further laminated onto the coating film as needed, and then cured using heat or light. The curing conditions using heat or light can be appropriately adjusted depending on the type of epoxy compound and curing agent used.

[0195] The epoxy resin composition has been described above. However, in resin compositions containing other resins besides epoxy resin, for example, in order to obtain the adhesive main surface (X) in the obtained resin layer, an amino silane coupling agent or the like is incorporated into the resin composition. This is usually done in the same way as forming a resin layer on or between substrates using the resin, thereby enabling the formation of the resin layer of the present invention.

[0196] In the inkjet device 100, the actuator Ac includes a flow path substrate 3A and a pressure chamber substrate 1A, and has a stacked substrate formed by bonding them together by an adhesive layer 2X. The structure of the actuator Ac is not limited to this; it may have multiple flow path substrates and pressure chamber substrates, or it may further have substrates other than flow path substrates and pressure chamber substrates.

[0197] In the case where the adhesive layer provided for bonding the substrates has a portion that contacts the ink flowing in the ink flow path, the adhesive layer preferably satisfies the requirements of the present invention, but is not required to do so. That is, in the inkjet apparatus of the present invention, as long as any one resin layer satisfies the requirements of the present invention, it is sufficient; as long as the adhesive layer 2 is a resin layer that satisfies the requirements of the present invention, other resin layers having portions that contact the ink are not required to satisfy the requirements of the present invention. However, it is preferable that all resin layers having a main surface that contacts the substrate and having portions that contact the ink satisfy the requirements of the present invention.

[0198] It should be noted that, although it also depends on the type of resin layer, especially when the material of the substrate that makes up the main surface of the resin layer in contact with the resin layer contains metal, metal oxide or glass, the main surface of the resin layer is preferably the bonding main surface (X) that satisfies the requirements of (2).

[0199] In a substrate composed of metal, metal oxide, and glass, the surface has OH groups, which react with an amino silane coupling agent preferably included in the resin composition used to form a resin layer on the substrate, thereby improving the adhesion at the interface between the substrate and the resin layer.

[0200] It should be noted that, as described below, the nozzle plate 20 is preferably made of metal. From this point of view, in the inkjet device of the present invention, the main surface of the nozzle plate 20 side of the adhesive layer 2 that bonds the actuator Ac to the nozzle plate 20 is preferably the adhesive main surface (X).

[0201] The flow path substrate 3A of the actuator Ac has wiring electrodes 33A and 33B (see reference). Figure 6 The inkjet device 100 has a flexible substrate 8 (see reference) above the actuator Ac, which is connected to the wiring electrodes of the flow path substrate 3A. Figure 6 The inkjet device 100 includes a housing 6 that houses the lower components (nozzle plate 20, actuator Ac, and manifold 5, etc.) and a cover component 7 that is mounted on the housing 6 to cover the upper components (flexible substrate 8 and drive circuit board, etc.).

[0202] The housing 6 is a component formed by die casting, for example, from aluminum, and is elongated in the left-right direction. The bottom surface of the housing 6 has an opening such that the nozzle plate 20 is exposed to the outside. Mounting holes 68 are formed at both ends of the housing 6 in the left-right direction for mounting the housing 6 to the side of the printer body.

[0203] The lower end of the manifold 5 is mounted and fixed to the outer edge of the upper surface 3Sb of the flow path substrate 3A by adhesive bonding. This bonding can be performed, for example, by forming an adhesive layer. In this case, if the adhesive layer has a portion that directly contacts the ink flow path, such as a side surface that directly contacts the ink flow path, one or both of the main surfaces of the adhesive layer can be used as the main adhesive surface (X).

[0204] Manifold 5, for example, is a component molded from resin, disposed on the upper side of the flow path substrate 3A of actuator Ac, and has the function of storing ink supplied to actuator Ac. Specifically, as... Figure 3 As shown, the manifold 5 is formed into a long strip in the left-right direction from a resin material, and has a hollow main body 52 constituting the ink storage section 51 and first to third ink ports 53 to 55 constituting the ink flow path. Furthermore, the ink storage section 51 is divided into an upper first liquid chamber 51a and a lower second liquid chamber 51b by a filter F for removing dust from the ink.

[0205] The first ink port 53 is connected to the upper right end of the first liquid chamber 51a and is used to introduce ink into the ink storage section 51. Furthermore, a first connector 81a is inserted externally at the front end of the first ink port 53. The second ink port 54 is connected to the upper left end of the first liquid chamber 51a and is used to remove air bubbles from the first liquid chamber 51a.

[0206] Furthermore, a second connector 81b is inserted externally at the front end of the second ink port 54. The third ink port 55 communicates with the upper left end of the second liquid chamber 51b and is used to remove air bubbles from the second liquid chamber 51b. Additionally, a third connector 82a is inserted externally at the front end of the third ink port 55. The manifold 5 may also have a fourth ink port (not shown) as an ink outlet for discharging unused residual ink discharged from the actuator Ac to the outside of the inkjet apparatus 100.

[0207] The nozzle plate 20 is disposed on the underside of the pressure chamber substrate 1A of the actuator Ac. The material constituting the nozzle plate 20 can be selected from materials with high mechanical strength, ink resistance, and excellent dimensional stability, such as inorganic materials, resin films, and various other materials. The material constituting the nozzle plate 20 is preferably an inorganic material such as a metal oxide or a metal, more preferably a metal such as iron (e.g., stainless steel (SUS)), aluminum, nickel, or stainless steel, and particularly preferably stainless steel (SUS). The nozzle plate 20 has nozzles 21A and 21B that become ink ejection orifices when ink is ejected from the pressure chamber substrate 1A toward the recording medium.

[0208] like Figure 6 As shown, the pressure chamber base plate 1A of the actuator Ac is a roughly quadrangular prism-shaped component that is elongated in the left-right direction, and has two rows of channels, A and B. Here, [the text abruptly ends here]. Figure 6 The rear channel column shown is designated as column A, and the front channel column is designated as column B. Each channel column is constructed by alternately configuring drive channels 11A and 11B and dummy channels 12A and 12B. The partition wall between adjacent drive channels 11A or 11B and dummy channels 12A or 12B is a drive wall 13 made of piezoelectric material.

[0209] As a piezoelectric material, it is preferred to contain perovskite-type compounds, such as barium titanate (BaTiO3) and lead zirconate titanate ([Pb(Zr·Ti)O3], also referred to as "PZT" in this specification), and preferably mainly PZT. It should be noted that the molar ratio of Zr to Ti in PZT is preferably Zr / Ti = 30 / 70 to 70 / 30. Furthermore, "mainly PZT" means that PZT accounts for 85% by mass or more relative to the total amount of the piezoelectric material.

[0210] To improve the performance of piezoelectric materials, donor ions can be added to PZT. Examples of donor ions include lanthanum (La), niobium (Nb), tantalum (Ta), tungsten (W), aluminum (Al), and strontium (Sr), with one or more ions selected from La, Nb, Ta, and W being preferred. Acceptor ions are preferably one or more metal ions selected from iron (Fe), cobalt (Co), and manganese (Mn).

[0211] In this specification, a drive channel is a channel that serves as the ink flow path for inkjet propagation based on image data during image recording. A dummy channel is a channel that is never propagated by ink and is independent of image data. Dummy channels do not require inkjet propagation and are therefore not filled with ink. Dummy channels are typically filled with gases such as air.

[0212] like Figure 6 and as its VII-VII line cross-section diagram Figure 7 As shown, each driving channel 11A, 11B and each dummy channel 12A, 12B opens on the lower surface 1Sa and upper surface 1Sb of the pressure chamber substrate 1A, respectively. The openings are linear across the lower surface 1Sa and upper surface 1Sb, and the cross-sections orthogonal to the thickness direction form rectangles, i.e., quadrangular prisms. It should be noted that... Figure 7 The cross-sectional view shows the cross-section of the channel columns in column B, but the cross-section of the channel columns in column A is also shown below. Figure 7 Explanation of the channel columns in columns A and B. Figure 8 The same applies to China.

[0213] A driving electrode 14 is formed on the surface of each of the four walls facing each driving channel 11A, 11B and each dummy channel 12A, 12B, and a protective film 4 is formed on the entire surface of the driving electrode 14 facing the driving channel 11A, 11B.

[0214] A protective film 4 is formed on the entire surface of the wall facing the through holes 32A and 32B in the flow path substrate 3A and on the entire surface of the wall facing the through holes in the adhesive layer 2. The through holes 32A and 32B (first ink flow path) in the flow path substrate 3A, the through holes in the adhesive layer 2, and the drive channels 11A and 11B (second ink flow path) are connected to form the ink flow path of the actuator Ac.

[0215] On the upper surface 1Sb of the pressure chamber substrate 1A, connection electrodes (not shown) are formed in a manner corresponding one-to-one with the drive channels 11A, 11B and the dummy channels 12A, 12B. One end of each connection electrode is connected to the drive electrode 14 in the corresponding drive channel 11A, 11B or dummy channel 12A, 12B.

[0216] The actuator Ac is an independently driven actuator in which drive channels 11A, 11B and dummy channels 12A, 12B are alternately arranged in each channel row of the pressure chamber substrate 1A. By applying a drive signal with a given voltage to the drive electrode 14, the drive wall 13 is sheared and deformed. As a result, a pressure change for ejection is applied to the ink supplied to the drive channels 11A, 11B, and the ink is ejected as droplets from the nozzles 21A, 21B of the nozzle plate 20, which is joined to the lower surface of the actuator Ac, i.e., the lower surface 1Sa of the pressure chamber substrate 1A, via the adhesive layer 2.

[0217] like Figure 7 and Figure 8 As shown, the adhesive layer 2 is a resin layer that bonds the nozzle plate 20 and the pressure chamber substrate 1A, and is disposed with its side facing the drive channel 11B, which serves as the ink flow path. The adhesive layer 2 has a first main surface 2Sa on the nozzle plate 20 side and a second main surface 2Sb on the pressure chamber substrate 1A side. Preferably, at least the first main surface 2Sa, and more preferably the first main surface 2Sa and the second main surface 2Sb, correspond to the adhesive main surface (X) that satisfies the requirements of (2) of the present invention in relation to the interior 2c.

[0218] The adhesive layer 2 is preferably a layer formed using a curable resin, and more preferably a layer formed using the epoxy resin composition. By setting the thickness of the adhesive layer 2 to, for example, a range of 0.1 to 5 μm, it can function as an adhesive layer. The adhesive layer 2 is, for example, a layer formed using an epoxy resin composition. Figure 2 The resin layer shown corresponds to the following structure.

[0219] On the nozzle plate 20, nozzles 21A and 21B are provided at positions corresponding to the drive channels 11A and 11B of the pressure chamber substrate 1A. Since ink is not sprayed from the dummy channels 12A and 12B, the nozzle plate 20 does not have nozzles at positions corresponding to the dummy channels 12A and 12B. Therefore, the openings on the lower side of the dummy channels 12A and 12B are closed by the nozzle plate 20.

[0220] The other end of each connecting electrode corresponding to the drive channel 11A and dummy channel 12A in column A extends from within each channel 11A, 12A toward one side of the upper surface 1Sb of the pressure chamber substrate 1A, and stops at an interval of approximately 200 μm from this edge. Furthermore, the other end of each connecting electrode corresponding to the drive channel 11B and dummy channel 12B in column B extends from within each channel 11B, 12B toward the column A side, and stops at an interval of approximately 200 μm from the column of channels in column A. Therefore, all connecting electrodes extend in the same direction from each channel 11A, 11B, 12A, and 12B.

[0221] The driving electrode 14 and the connecting electrode are made of a conductive material. Specifically, examples of conductive materials include one or more metals selected from platinum (Pt), gold (Au), copper (Cu), palladium (Pd), ruthenium (Ru), titanium (Ti), nickel (Ni), aluminum (Al), chromium (Cr), tungsten (W), and iridium (Ir). The conductive material can be a material containing one or more of these metals. The conductive material can be a mixture of metals or an alloy. In this case, it can also be a mixture or alloy of at least one of the metals with other metals.

[0222] The flow path substrate 3A is a flat substrate having a lower surface 3Sa and an upper surface 3Sb, both having an area larger than the upper surface 1Sb of the pressure chamber substrate 1A. The bonding region 31 of the lower surface 3Sa of the flow path substrate 3A (in...) Figure 6 (Indicated by a single-dot dash) It is bonded to the upper surface 1Sb of the pressure chamber substrate 1A via the adhesive layer 2X. At least one end of the bonded flow path substrate 3A extends outward from the bonding area 31 to which the pressure chamber substrate 1A is bonded, and extends laterally to a greater extent along the arrangement direction of the channel array of the pressure chamber substrate 1A.

[0223] It should be noted that the bonding area 31 is the area where the lower surface 3Sa of the flow path substrate 3A is covered by the pressure chamber substrate 1A to which it is bonded, and is defined by a line that descends from the outer periphery of the upper surface 1Sb of the pressure chamber substrate 1A to the flow path substrate 3A.

[0224] The flow path substrate 3A can be made of suitable materials such as glass, ceramic, silicon, or plastic. Among these, glass is preferred due to its moderate rigidity, low cost, and ease of processing.

[0225] In the bonding region 31, the flow path substrate 3A is bonded via the adhesive layer 2X in such a way that it covers all the openings of the channels located on the upper surface 1Sb of the pressure chamber substrate 1A. In the bonding region 31 of the pressure chamber substrate 1A in the flow path substrate 3A, through holes 32A and 32B are individually provided only at positions corresponding to the drive channels 11A and 11B of the pressure chamber substrate 1A, for supplying ink from the upper surface 3Sb side of the flow path substrate 3A to each drive channel 11A and 11B.

[0226] Each through hole 32A and 32B is formed such that the opening on the pressure chamber substrate 1A side, i.e., the opening on the lower surface 3Sa of the flow path substrate 3A, and the opening on the flow path substrate 3A side of each drive channel 11A and 11B, i.e., the opening on the upper surface 1Sb of the pressure chamber substrate 1A, have the same size and shape. In the actuator Ac, each through hole 32A and 32B of the flow path substrate 3A has a shape in which the cross-section expands from the lower surface 3Sa of the flow path substrate 3A toward the upper surface 3Sb.

[0227] On the other hand, in the flow path substrate 3A, no through holes are formed at the locations corresponding to the dummy channels 12A and 12B of the pressure chamber substrate 1A. Therefore, the openings on the upper side (flow path substrate 3A side) of the dummy channels 12A and 12B are closed by the flow path substrate 3A.

[0228] Wiring electrodes 33A and 33B are formed on the lower surface 3Sa of the flow path substrate 3A, which serves as the interface with the pressure chamber substrate 1A, in a manner corresponding one-to-one with each connection electrode arranged on the upper surface 1Sb of the pressure chamber substrate 1A. Wiring electrodes 33A correspond to each connection electrode in the channel column A, and wiring electrodes 33B correspond to each connection electrode 15B in the channel column B. Wiring electrodes 33A and 33B are made of a conductive material. Examples of conductive materials are the same as those described above.

[0229] like Figure 6As shown, one end of the wiring electrode 33A reaches the vicinity of the corresponding drive channel 11A and the dummy channel 12A, coinciding with the corresponding connection electrode in the top view viewed from above, and the other end extends toward the rear end of the flow path substrate 3A that extends laterally toward the pressure chamber substrate 1A. Similarly, one end of the wiring electrode 33B reaches the vicinity of the corresponding drive channel 11B and the dummy channel 12B, coinciding with the corresponding connection electrode in the top view viewed from above, and the other end passes through the adjacent drive channels 11A, 11A of column A, traversing the column A, and extends toward the rear end of the flow path substrate 3A in the same manner as the wiring electrode 33A. Therefore, on the lower surface 3Sa of the flow path substrate 3A extending laterally toward the pressure chamber substrate 1A, wiring electrodes 33A and 33B are arranged side-by-side in an alternating manner from the inside of the bonding region 31 to the rear end.

[0230] At the rear end of the flow path substrate 3A, a flexible substrate 8, serving as an example of an external wiring component, is connected via, for example, an ACF (anisotropic conductive film), and is electrically connected to a drive circuit (not shown). Thus, a drive signal with a given voltage from the drive circuit is applied to the drive electrodes 14 within each of the channels 11A, 11B, 12A, and 12B via the flexible substrate 8, the respective wiring electrodes 33A and 33B of the flow path substrate 3A, and the connection electrodes of the pressure chamber substrate 1A.

[0231] Wiring electrodes 33A and 33B extending from the bonding region 31 of the flow path substrate 3A to their rear ends are covered by an insulating film 34 of a given width on the outside of the bonding region 31. For example... Figure 6 As shown, the edge 34a of the bonding region 31 side of the insulating film 34 is formed in a straight line along the edge, contacting the rear edge of the bonding region 31. The width of the insulating film 34 preferably extends from the outer side of the bonding region 31 to the connection position with the flexible substrate 8. Thus, by covering the vicinity of the bonding region 31 with the insulating film 34, short circuits between the wiring electrodes 33A and 33B caused by the overflow of conductive adhesive, contamination of the wiring electrodes 33A and 33B, and short circuits caused by the adhesion of ink, etc., can be prevented. Examples of materials constituting the insulating film 34 include TiO2, SiO2, and Al2O3.

[0232] The adhesive layer 2X, which bonds the pressure chamber substrate 1A to the flow path substrate 3A, has through holes for communicating with each drive channel 11A, 11B of the pressure chamber substrate 1A and each through hole 32A, 32B of the flow path substrate 3A. The through holes have openings of the same size and shape on the pressure chamber substrate 1A side as the openings on the upper surface 1Sb of the drive channels 11A, 11B, and openings of the same size and shape on the flow path substrate 3A side as the openings on the lower surface 3Sa of the through holes 32A, 32B.

[0233] In the driver Ac, the adhesive layer 2X is a conductive adhesive layer containing a conductive adhesive. Because the adhesive layer 2X is conductive, electrical connection can be achieved between the connection electrode of the pressure chamber substrate 1A, which is bonded via the adhesive layer 2X, and the wiring electrodes 33A and 33B of the flow path substrate 3A. The thickness of the adhesive layer 2X is preferably in the range of 0.1 to 5 μm. It should be noted that the side surface of the adhesive layer 2X is covered by a protective film 4 and does not contact the drive channel 11B, which forms the ink flow path. Therefore, the adhesive layer 2X may not necessarily be an adhesive layer having the adhesive main surface (X) of the present invention. However, the adhesive layer 2X may also be an adhesive layer having the adhesive main surface (X) of the present invention.

[0234] As a conductive adhesive, for example, an adhesive in which conductive particles are dispersed can be used. As an adhesive, room temperature curing adhesives that cure at room temperature, thermosetting adhesives that cure by heating to promote polymerization, and active energy radiation curing adhesives that cure by irradiation with active energy rays such as ultraviolet light to promote polymerization can be used.

[0235] Among these, thermosetting adhesives are preferred. When thermosetting adhesives are heated to a given temperature for curing after bonding, the viscosity of the adhesive temporarily decreases, making it easier to flow, which is preferable from the perspective of the uniformity of the resulting adhesive layer thickness. Epoxy adhesives are preferred as thermosetting adhesives, but there are no particular limitations.

[0236] In addition to metal particles such as Au and Ni, conductive particles can also be particles on the surface of synthetic resin particles that have been coated with metal films such as Au and Ni. Any of these can be used in this invention.

[0237] In the actuator Ac, drive electrodes are formed on the wall surfaces of the partition walls of the pressure chamber substrate facing each channel. To electrically connect these drive electrodes to the wiring electrodes of the flow path substrate, as described above, the adhesive constituting the adhesive layer is a conductive adhesive. However, in the actuator of the present invention, the drive electrodes only need to be arranged in a manner that drives the partition walls, and may not necessarily be formed on the wall surfaces of the partition walls facing each channel. That is, the adhesive layer may not always need to be conductive. In this case, the adhesive layer may, for example, be an adhesive layer formed from an adhesive that does not contain conductive particles in the conductive adhesive.

[0238] like Figure 7 As shown, the actuator Ac has a protective film 4 formed on the entire surface of the wall of the laminated substrate facing the ink flow path, which connects the flow path substrate 3A and the pressure chamber substrate 1A, which are bonded together by the adhesive layer 2X. The wall of the laminated substrate facing the ink flow path is composed of the flow path substrate 3A, the adhesive layer 2X, and the respective walls of the pressure chamber substrate 1A facing the ink flow path.

[0239] The protective film 4 is a resin layer. The resin contained in the protective film 4 is preferably a polyimide resin or a parylene resin, with parylene resin being more preferred. Specifically, the parylene resin is composed of parylene or its derivatives. Examples of derivatives include compounds in which one or more hydrogen atoms bonded to the benzene ring of parylene are replaced by halogen atoms such as fluorine, chlorine, or bromine, or by alkyl groups.

[0240] A film composed of parylene or its derivatives is called a Parylene film, which can be formed by a vapor-phase synthesis method using a dimer (solid) of parylene or its derivatives as the evaporation source, a method known as Chemical Vapor Deposition (CVD). The protective film 4 can be a resin layer having the adhesive main surface (X) of this invention. In this case, the substrate is the drive electrode 14 or the pressure chamber substrate 1A, and the structure is such that the adhesive main surface (X) is in contact with the drive electrode 14 or the pressure chamber substrate 1A.

[0241] When the protective film 4 is a resin layer having the adhesive main surface (X) of the present invention, the resin composition used to form the protective film 4 preferably contains an amino-based silane coupling agent. In the parylene film, since p-xylene is composed only of carbon and hydrogen, components containing oxygen, nitrogen, and silicon can be used as derivatives. In order to obtain the protective film 4 as a resin layer having an adhesive main surface (X) having the requirement of contact with the substrate ((1)) and satisfying the requirement of (2), an amino-based silane coupling agent containing at least oxygen, nitrogen, and silicon is preferably used.

[0242] By setting the thickness of the protective film 4 to, for example, a range of 0.1 to 15 μm, it can function as a protective film. The protective film 4, for example, is... Figure 1 The structure corresponding to the resin layer shown.

[0243] Figure 8 Is Figure 7 The enlarged view of the portion enclosed by the dashed line in the cross-sectional view. Specifically, it is an enlarged view of the area around the nozzle 21B where the pressure chamber substrate 1A and the nozzle plate 20 are joined by the adhesive layer 2.

[0244] exist Figure 8 As indicated by the arrow, ink is ejected from the drive channel 11B via the nozzle 21B toward the recording medium located outside the inkjet device 100. That is, in Figure 8 In the middle, the drive channel 11B and the nozzle 21B are ink flow paths, and the two sides of the ink flow path are symmetrically arranged with the same components.

[0245] exist Figure 8 In the middle, the relationship between the pressure chamber substrate 1A, the adhesive layer 2, and the nozzle plate 20 is as follows: Figure 2 The substrate B1, resin layer P, and substrate B2 have the same relationship. The adhesive layer 2 has a first main surface 2Sa that contacts the upper surface of the nozzle plate 20 and a second main surface 2Sb that contacts the lower surface of the pressure chamber substrate 1A. The adhesive layer 2 is composed of a first surface portion 2a formed by a region extending from the first main surface 2Sa to a given depth, a second surface portion 2b formed by a region extending from the second main surface 2Sb to a given depth, and an interior portion 2c formed by the region other than the surface portions 2a and 2b.

[0246] As described above, the adhesive layer 2 preferably has at least a first main surface 2Sa, and more preferably a first main surface 2Sa and a second main surface 2Sb, which correspond to the adhesive main surface (X) that satisfies the requirements of (2) of the present invention in relation to the interior 2c.

[0247] exist Figure 8 In the middle, the relationship between the pressure chamber substrate 1A with driving electrode 14 and the protective film 4 and Figure 1 The substrate B and resin layer P have the same relationship. However, in Figure 8The difference lies in that the pressure chamber substrate 1A has a driving electrode 14, and a protective film 4 is formed on the ink flow path side surface of the driving electrode 14. The protective film 4 has a first main surface 4Sa that contacts the ink flow path side surface of the driving electrode 14 and a second main surface 4Sb that contacts the ink flow path. The protective film 4 is composed of a first surface portion 4a formed by a region extending from the first main surface 4Sa to a given depth, a second surface portion 4b formed by a region extending from the second main surface 4Sb to a given depth, and an interior portion 4c formed by the region other than the surface portions 4a and 4b. As described above, the first main surface 4Sa of the protective film 4 preferably corresponds to the bonding main surface (X) that satisfies the requirement (2) of the present invention in relation to the interior portion 4c.

[0248] The above description uses the magnetic head chip 10A as an example to illustrate the shear-mode type actuator Ac and the inkjet apparatus of the present invention having the actuator Ac. Hereinafter, referring to... Figure 9 and Figure 10 The inkjet device of the present invention having a bending mode actuator Ab will be described.

[0249] Figure 9 This is a partial cross-sectional view of another embodiment of the inkjet device of the present invention. Figure 9 A cross-sectional view of a head chip 10B in an inkjet device is shown. The head chip 10B has an actuator Ab and a nozzle plate 20 that is bonded to the actuator Ab via an adhesive layer 2A. The actuator Ab is a bending-mode actuator. Figure 10 for Figure 9 An enlarged view of the portion of the inkjet device shown, including the pressure chamber substrate 1B constituting the lower part of the actuator Ab, the adhesive layer 2A, the nozzle plate 20, and the pressure chamber 11, surrounded by dashed lines.

[0250] The actuator Ab includes: a flow path substrate 3B in which a wiring substrate 3a, an adhesive layer 3d, a spacer substrate 3b, and a vibrating plate 3v are stacked sequentially from top to bottom; an adhesive layer 2B located below the flow path substrate 3B; and a pressure chamber substrate 1B bonded to the flow path substrate 3B via the adhesive layer 2B. The spacer substrate 3b has a hollow portion, and a piezoelectric element has an upper electrode (driving electrode) 3e, a piezoelectric element 3P, and a lower electrode (driving electrode) 3f stacked sequentially from top to bottom inside the hollow portion. The portion of the hollow portion other than the piezoelectric element forms a space 3S.

[0251] The upper electrode 3e of the piezoelectric element is connected to an external power source via multiple wiring conductors E electrically connected from the spacer substrate 3b to the wiring substrate 3a. The lower electrode 3f is connected to the external power source via another path. The piezoelectric element 3P is driven by voltage applied to the upper electrode 3e and the lower electrode 3f. As a result, the vibrating plate 3v bends downward.

[0252] The vibrating plate 3v is bonded to the pressure chamber substrate 1B disposed on the lower side of the piezoelectric element via an adhesive layer 2B. On the lower side of the pressure chamber substrate 1B, a nozzle plate 20 having a nozzle 21 is bonded via an adhesive layer 2A. The nozzle plate 20 may be made of the same material as the nozzle plate bonded to the actuator Ac.

[0253] The pressure chamber substrate 1B has a pressure chamber (drive channel) 11 for containing ink, and the nozzle 21 is connected to the pressure chamber 11. When the piezoelectric element is driven, the volume of the pressure chamber 11 is reduced by the bending vibrating plate 3v, thereby the ink contained in the pressure chamber 11 is ejected from the nozzle 21.

[0254] The flow path substrate 3B and the adhesive layer 2B have through holes 32 that form an ink flow path communicating with the pressure chamber 11 of the pressure chamber substrate 1B. Ink is supplied from the upper side of the actuator Ab through the through holes 32 to the pressure chamber 11. The ink flow path in the magnetic head chip 10B consists of the through holes 32, the pressure chamber 11, and the nozzle 21.

[0255] The wiring substrate 3a, spacer substrate 3b, and pressure chamber substrate 1B in the flow path substrate 3B of actuator Ab can be made of materials such as SUS, nickel, alloy 42, silicon (Si), etc. The piezoelectric material constituting piezoelectric material 3P, as well as the conductor materials constituting upper electrode (drive electrode) 3e, lower electrode (drive electrode) 3f, wiring conductor, etc., can be the same materials described in actuator Ac.

[0256] As a 3V diaphragm, a general diaphragm for bending mode actuators can be used without particular restrictions.

[0257] Adhesive layer 3d, adhesive layer 2B, and adhesive layer 2A are all adhesive layers formed between substrates, and are configured to contact the ink flowing in the ink flow path from the side. Adhesive layer 3d, adhesive layer 2B, and adhesive layer 2A can all be configured with the same structure as adhesive layer 2 described in the magnetic head chip 10A. In particular, adhesive layer 2A, which bonds the pressure chamber substrate 1B and the nozzle plate 20, preferably has the same structure as adhesive layer 2.

[0258] Figure 10 The enlarged cross-section shown is the same as Figure 2 Corresponding. In Figure 10 In the middle, the relationship between the pressure chamber substrate 1B, the adhesive layer 2A, and the nozzle plate 20 is as follows: Figure 2The substrate B1, resin layer P, and substrate B2 have the same relationship. The adhesive layer 2A has a first main surface 2Sa that contacts the upper surface of the nozzle plate 20 and a second main surface 2Sb that contacts the lower surface of the pressure chamber substrate 1B. The adhesive layer 2A is composed of a first surface portion 2a formed by a region extending from the first main surface 2Sa to a given depth, a second surface portion 2b formed by a region extending from the second main surface 2Sb to a given depth, and an interior portion 2c formed by the region other than the surface portions 2a and 2b.

[0259] As described above, the adhesive layer 2A preferably has at least a first main surface 2Sa, and more preferably a first main surface 2Sa and a second main surface 2Sb, which correspond to the adhesive main surface (X) that satisfies the requirements of (2) of the present invention in relation to the interior 2c.

[0260] [Ink]

[0261] As the ink used in the inkjet apparatus of the present invention, inkjet recording inks can be used without particular limitation. In the inkjet apparatus of the present invention, the interface between the resin layer formed on or between the substrate and the substrate has excellent ink resistance, and it works well regardless of the type of ink.

[0262] Specifically, the effect is greater when using water-based inks containing components such as water, colorants, dispersants, surfactants, preservatives, humectants, and glycol solvents. Furthermore, it is also effective in reactive ray-curing inks, such as inks containing at least a reactive ray-polymerizing compound, a polymerization initiator, and a colorant. Reactive ray-polymerizing compounds include photocationic polymers and photoradical polymers, and correspondingly, photocationic polymerization initiators and photoradical polymerization initiators can be cited.

[0263] In this invention, in particular, compounds comprising at least one group selected from carboxylic acid groups, sulfonic acid groups, and phosphonic acid groups are used, as well as compounds selected from SO4. 2- PO4 3- B(C6F5)4 - SbF6 - PF6 - BF4 - CF3SO3 - and C4F9SO3 - The effect is significant when using inks containing at least one anion, etc. These compounds and anions include, for example, substances derived from colorants. Furthermore, B(C6F5)4 - SbF6 - PF6 - BF4 - CF3SO3 - and C4F9SO3- Substances containing photocationic polymerization initiators, etc.

[0264] The inkjet device of the present invention can be used even when using compounds containing at least one group selected from carboxylic acid group, sulfonic acid group and phosphonic acid group, or compounds selected from SO4. 2- PO4 3- B(C6F5)4 - SbF6 - PF6 - BF4 - CF3SO3 - and C4F9SO3 - In the case of inks containing at least one type of anionic ink, the resin layer formed on or between substrates exhibits excellent ink resistance at the interface with the substrate.

[0265] Example

[0266] The present invention will be specifically described below with reference to specific embodiments, but the present invention is not limited to these embodiments.

[0267] [Experimental Example]

[0268] The following method was used to form a resin layer between two SUS substrates, and the atomic composition of the bonding surface and interior was determined based on XPS.

[0269] (Preparation of the resin composition)

[0270] Specifically, the resin compositions of Examples 1 to 3 and Comparative Example 1, which are shown in Table I, were prepared. It should be noted that jER 828 (bisphenol A type epoxy compound, epoxy equivalent 184-194, weight-average molecular weight 370) and jER 152 (phenolic varnish type epoxy compound, epoxy equivalent 176-178, weight-average molecular weight 370) are both epoxy compounds manufactured by Mitsubishi Chemical Corporation. Furthermore, in 2-ethyl-4-methylimidazole, H... + The adduct has a pKa of 8.3 at 25 °C.

[0271] [Table 1]

[0272] Table I

[0273]

[0274] (Preparation of laminated samples)

[0275] As two SUS substrates, an SUS 304 nozzle plate substrate (with 1000 nozzles) and an SUS 304 flow path plate substrate (with ink flow paths) were used. First, the resin composition used in Example 1 was coated onto the nozzle plate substrate, and the flow path plate substrate was then attached thereon. A certain load was applied, and the substrate was heat-cured at 100°C for 1 hour to form a resin layer (thickness: 1.5 μm) between the two SUS substrates, thus creating a laminated sample. Using resin compositions other than those used in Example 1, resin layers were formed between the two SUS substrates in the same manner to prepare samples.

[0276] (1) XPS depth distribution measurement

[0277] A cutting blade was placed between the SUS substrate and the resin layer of each obtained laminated sample to prepare a gripping area for peeling, and peeling was performed using tweezers. XPS depth distribution was measured from the main surface of the peeled resin layer under the following conditions.

[0278] <Measurement Conditions>

[0279] • Analytical apparatus: QUANTERA SXM manufactured by ULVAC-PHI

[0280] • X-ray source: Monochromatic Al-Kα 15kV 25W

[0281] Sputtered ions: Ar (1keV)

[0282] • Depth distribution: The sputtering thickness was converted to SiO2, and the depth distribution in the depth direction was determined by repeatedly measuring at a given thickness interval. The thickness interval was set to 10.8 nm in Example 1 and Comparative Example 1, and to 11.4 nm in Examples 2 and 3 (data was obtained every 10.8 nm or every 11.4 nm in the depth direction).

[0283] • Quantitative analysis: Background was determined using the Shirley method, and quantification was performed using the relative sensitivity coefficient method based on the obtained peak area. Data processing was performed using a MultiPak system manufactured by ULVAC-PHI.

[0284] It should be noted that the atomic concentrations of each element within the resin layer are set as the average of six measurements taken at depths of 10.8 nm to 64.8 nm or 11.4 nm to 68.4 nm from the main surface. Measurements were taken at two randomly selected locations along the surface direction, and the atomic concentrations of each element on the main surface and within the layer were set as their average values.

[0285] The XPS measurements confirmed that each resin layer contains carbon, nitrogen, oxygen, and silicon. Table II shows the atomic concentration (atm%) of all elements measured, namely carbon, nitrogen, oxygen, silicon, chromium, and iron. It should be noted that chromium and iron are derived from the substrate. Furthermore, the detection limit in the measurements was 0.1 atm%. In Table II, "ND" indicates that the element was not detected. Additionally, the depth distributions of nitrogen, oxygen, and silicon in the XPS depth distribution measurements of Examples 1 to 3 are shown in Table II. Figures 11A to 11C .

[0286] In addition, for nitrogen, oxygen and silicon, the principal face / interior ratio (the ratio of the atomic concentration of the principal face to the atomic concentration of the interior) is also shown in Table II.

[0287] [Table 2]

[0288] Table II

[0289]

[0290] (2) Bonding state analysis of nitrogen atoms in the main surface of the resin layer based on XPS

[0291] For the main surface of the resin layer peeled off from the laminated samples of Examples 2 and 3 in the same manner, the bonding state of nitrogen atoms was analyzed based on XPS under the following conditions.

[0292] <Measurement Conditions>

[0293] • Analytical apparatus: QUANTERA SXM manufactured by ULVAC-PHI

[0294] • X-ray source: Monochromatic Al-Kα 15kV 25W

[0295] • Pass energy: 55eV

[0296] • Data processing: Using MultiPak manufactured by ULVAC-PHI

[0297] • Elemental composition analysis: The Shirley method was used for background processing, and the elemental composition was quantified using the relative sensitivity coefficient based on the obtained peak area.

[0298] For Examples 1 to 3, the spectra of the nitrogen atom peaks (represented by solid lines in the figures) separated by each peak in each state are shown below. Figure 12A , Figure 12B and Figure 12C . Figure 12A , Figure 12B and Figure 12CBoth indicate that the nitrogen atom peaks were separated into -NH2 and -NH3. + These two peaks.

[0299] Table III shows the results for Examples 1 through 3, consisting of -NH2 and -NH3. + The position of the peak maximum value is related to the bond energy (eV), and the values ​​of -NH2 and -NH3. + The peak areas were used to determine the nitrogen atoms originating from -NH2 and those originating from -NH3. + The ratio of nitrogen atoms to the total amount of nitrogen atoms. It should be noted that the literature values ​​mentioned above are also shown in Table III.

[0300] [Table 3]

[0301] Table III

[0302]

[0303] [evaluate]

[0304] Two laminated samples of each of the embodiments and comparative examples were prepared in the same manner as described above, and their ink resistance was evaluated using two test solutions in the following manner. The results are shown in Table IV.

[0305] (Preparation of actual ink for evaluation: Disperse dye ink (test solution 1))

[0306] <Preparation of Dispersion>

[0307] Disperse dye: CI Disperse Yellow 160

[0308] 24.0% by mass

[0309] Diethylene glycol 30.6% by mass

[0310] Styrene-maleic anhydride copolymer (dispersant) 12.0% by mass

[0311] Water 33.4% by mass

[0312] The mixture was dispersed for 5 hours using ceramic beads with a diameter of 0.5 mm in an IMEX sand mill at a speed of 2500 rpm. The dispersion was then diluted with water / diethylene glycol at a ratio of 1:4 to obtain dispersion 1, with the dye concentration being 5%.

[0313] <Preparation of Actual Ink>

[0314] Each composition was added to the dispersion 1 and stirred to prepare an actual ink (disperse dye ink) for evaluation.

[0315] Dispersion 1: 20.0% by mass

[0316] 10.0% by mass of ethylene glycol

[0317] 8.0% by weight of glycerin

[0318] EMULGEN 911 (manufactured by Kao Co., Ltd.) 0.05% by mass

[0319] Ion-exchanged water was added to the above components to a final concentration of 100% by mass, yielding disperse dye ink (test solution 1). Furthermore, the liquid properties of the prepared ink were investigated, confirming it to be alkaline (pH 8.0 or higher).

[0320] (Preparation of actual ink for evaluation: reactive dye ink (test solution 2))

[0321] CI Active Yellow 220 portions

[0322] Sodium dihydrogen phosphate 0.034 parts

[0323] 0.166 parts of disodium hydrogen phosphate

[0324] 79.8 parts water

[0325] The pH of the dye solution of the above composition was adjusted to 8.5 using a 10% aqueous solution of sodium carbonate to prepare a reactive dye ink (test solution 2).

[0326] (Evaluation of laminated samples)

[0327] For each of the obtained laminated samples, one sample was immersed in test solution 1 and test solution 2 at 60°C and left for 50 days.

[0328] After 50 days of immersion treatment, each laminated sample was washed and dried with pure water. For each laminated sample, the presence or absence of delamination at the interface between the nozzle plate substrate and the resin layer inside 1000 nozzles was confirmed. The adhesion resistance between the nozzle plate substrate and the resin layer of test solution 1 and test solution 2 was evaluated according to the following criteria.

[0329] <Evaluation Criteria>

[0330] ◎: No peeling was observed in any of the 1000 nozzles.

[0331] ○: Very weak peeling was observed in more than one but less than 5% of the nozzles, but there are no practical problems.

[0332] △: Weak isolation was observed in 5% to 10% of nozzles, which is a practically acceptable quality.

[0333] ×: The presence of nozzles with obvious peeling is a quality issue that becomes problematic in practical use.

[0334] [Table 4]

[0335] Table IV

[0336] Test solution 1 Test solution 2 Example 1 ◎ ◎ Example 2 〇 〇 Example 3 ◎ ◎ Comparative Example 1 △ ×

[0337] Industrial applicability

[0338] According to the present invention, an inkjet device is provided that provides long-term reliability due to the excellent ink resistance of the interface between the resin layer disposed between or on the substrate and the substrate.

[0339] Symbol Explanation

[0340] 100: Inkjet unit

[0341] 10A, 10B: Magnetic head chip

[0342] 1A, 1B: Pressure chamber substrate

[0343] 11, 11A, 11B: Drive channels (second ink flow path)

[0344] 12A, 12B: Virtual channels

[0345] 13: Drive Wall

[0346] 14: Driving electrode

[0347] 2, 2A, 2B: Adhesive layer

[0348] 3A, 3B: Flow path substrate

[0349] 31: Joint area

[0350] 32, 32A, 32B: Through holes (first ink flow path)

[0351] 33A, 33B: Wiring electrodes

[0352] 34: Insulating film

[0353] 3a: Wiring substrate

[0354] 3b: Spacer substrate

[0355] 3d: Adhesive layer

[0356] 3V: Vibrating plate

[0357] 3e: Upper electrode (driving electrode)

[0358] 3f: Lower electrode (driving electrode)

[0359] 3P: Piezoelectric element

[0360] 3S: Space

[0361] E: Wiring conductor

[0362] 4: Protective film

[0363] 5: Manifold

[0364] 6: Casing

[0365] 7: Cover components

[0366] 8: Flexible substrate

[0367] 20: Nozzle plate

[0368] 21, 21A, 21B: Nozzles

Claims

1. An inkjet apparatus comprising: a substrate, resin layers laminated thereon with at least one main surface in contact with the substrate, and an ink flow path disposed such that ink flows through and contacts a portion of the resin layer, wherein, The resin layer contains carbon, oxygen, nitrogen, and silicon, and At least one face of the main face satisfies the following requirements (1) and (2). (1) The main surface is in contact with the substrate. (2) When the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the main surface of the resin layer as determined by X-ray photoelectron spectroscopy are expressed by main surface N, main surface O and main surface Si respectively, and the atomic concentrations (atm%) of nitrogen, oxygen and silicon in the interior of the resin layer are expressed by interior N, interior O and interior Si respectively, the main surface O > interior O and the main surface N ≥ 3.62, and the ratio of main surface Si to interior Si expressed by main surface Si / interior Si is 8 or more.

2. The inkjet device according to claim 1, wherein, In the main facet that satisfies requirements (1) and (2), requirement (3) is also satisfied. (3) The ratio of the main face N to the interior N, represented by the ratio of the main face N to the interior N, is 2 or more.

3. The inkjet apparatus according to claim 1 or 2, wherein, For the principal facets that satisfy the requirements of (1) and (2), the spectrum obtained by analyzing the bonding state of nitrogen atoms based on X-ray photoelectron spectroscopy has -NH2 or -NH3. + The peak.

4. The inkjet apparatus according to any one of claims 1 to 3, wherein, The resin layer comprises an epoxy compound and H at 25°C. + Cured products of resin compositions of curing agents and amino silane coupling agents with a pKa of 3 or higher for the adduct.

5. The inkjet apparatus according to claim 4, wherein, The curing agent is a nitrogen-containing catalyst type curing agent.

6. The inkjet apparatus according to claim 4 or 5, wherein, The content of the curing agent is in the range of 5 to 11% by mass relative to the total amount of the resin composition.

7. The inkjet apparatus according to any one of claims 4 to 6, wherein, The molecular weight of each nitrogen atom in the amino-based silane coupling agent is below 250.

8. The inkjet apparatus according to any one of claims 4 to 7, wherein, The amino-based silane coupling agent has two or more alkoxy groups bonded to silicon atoms.

9. The inkjet apparatus according to any one of claims 1 to 8, wherein, The material of the substrate that is in contact with the main surface that constitutes the requirements of (1) and (2) includes metal, metal oxide or glass.

10. The inkjet apparatus according to any one of claims 1 to 9, wherein, The ink contains a compound having at least one group selected from carboxylic acid group, sulfonic acid group and phosphonic acid group, or a compound selected from SO4. 2- PO4 3- B(C6F5)4 - SbF6 - PF6 - BF4 - CF3SO3 - and C4F9SO3 - At least one anion.

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