Method for manufacturing liquid ejecting head and liquid ejecting head

Abstract

A method of manufacturing a liquid ejecting head including an ejection port forming member and a flow path forming member on a substrate, the method including: forming a layer of a photosensitive resin composition (1) for forming the flow path forming member on the substrate and exposing the layer to light; a step in which a layer of a photosensitive resin composition (2) for forming the ejection port forming member is superimposed on the layer of the photosensitive resin composition (1) and exposed; and removing an unexposed portion to form the flow path forming member and the ejection port forming member. The photosensitive resin composition (1) contains a specific epoxy resin and a specific gallate-based photoacid generator.

Description

Technical Field

[0001] This disclosure relates to a method for manufacturing a liquid jet head and the liquid jet head itself. Background Technology

[0002] A liquid ejector head for discharging liquid is used in liquid ejection devices such as inkjet recording apparatuses, and includes, for example, an ejector nozzle forming member, a flow path forming member, and a substrate. The flow path forming member is disposed on the substrate and forms a liquid flow path, and in some cases forms a liquid ejector nozzle. A liquid supply port is formed on the substrate, and an energy generating element is provided. Liquid is supplied from the liquid supply port into the flow path, energized by the energy generating element, discharged from the liquid ejector nozzle, and falls onto a recording medium such as paper.

[0003] An insulating or protective layer covering the energy-generating element is provided on the substrate, or in many cases, an inorganic material layer for various other purposes. On the other hand, flow path forming components and other structures on the substrate are known to be formed from organic material layers. In particular, when the organic material layer is formed from a photosensitive resin, it can be precisely shaped using photolithography.

[0004] For example, according to the method for manufacturing a liquid jet head described in Japanese Patent Application Publication No. 2016-064641, a dry film of a photosensitive resin layer serving as a liquid flow path is formed on a substrate having an inorganic material layer by a lamination method, and the resulting object is exposed to light in the shape of the flow path. Next, a dry film of a photosensitive resin layer serving as a flow path is laminated on the photosensitive resin layer serving as a flow path, the dry film serving as a nozzle portion connecting the jet orifice to the flow path and serving as a jet orifice, the resulting object is exposed to light in the shape of the jet orifice, and the uncured portions of each photosensitive resin layer are removed together by development, thereby forming the flow path, the nozzle portion, and the jet orifice.

[0005] However, as the requirements for inkjet image recording become increasingly demanding, the performance requirements for inks also increase. Therefore, from the viewpoint of fixing properties relative to the recording material, solvents with high boiling points can be added to the ink. Ink obtained in this way can permeate between the photosensitive resin layer made of epoxy resin, etc., and other components such as the substrate, potentially stripping the flow path forming components or deforming them.

[0006] Therefore, in cases where highly penetrating inks are used, considering the structure described in Japanese Patent Application Publication No. 2016-064641, the peeling or deformation of the flow path forming component occurs at a higher rate than with ink types in the prior art, thus allowing for improvement in long-term reliability. For example, prolonged use of the inkjet recorder head may cause the flow path forming component to peel off from the substrate, or may result in unsatisfactory inkjet performance.

[0007] Furthermore, the adhesion between the photosensitive resin layer and the substrate depends on the curing properties of the photosensitive resin. Japanese Patent Application Publication No. 2016-064641 discloses a method that incorporates PF6 into the anion of the cationic photoinitiator (acid generator) in a photosensitive resin composition. - Or SbF6 - The obtained substance contains PF6. - The acid strength of the acid-producing agent is insufficient to achieve high curing properties, requiring the addition of a large amount of PF6-containing agents. - Acid-generating agents are used to achieve high curability. However, adding large amounts of PF6-containing agents... - In the case of acid-generating agents, the physical properties of the cured product may deteriorate due to the presence of a large amount of unreacted acid-generating agent and acid-generating agent residues after the reaction, and the adhesion reliability between the photosensitive resin layer and other components such as the substrate may deteriorate.

[0008] On the other hand, due to toxicity issues, SbF6-containing... - The acid-producing agent has been identified as a hazardous substance, and its use is restricted. The use of hazardous substances can threaten human health and the global ecosystem, and can also hinder the implementation of sustainable societies, such as decarbonized / circular societies. Depending on the method of use, it can produce hydrogen fluoride and there may be concerns about circuit corrosion; therefore, the process and amount added are restricted.

[0009] On the other hand, from the viewpoint of improving the manufacturing efficiency of liquid jet heads, the photosensitive resin forming the flow path forming component and the photosensitive resin forming the jet nozzle forming component on the substrate can be exposed to light of the same wavelength and can be developed together. As a result of research, the inventors have recognized that using an acid-generating agent (such as one containing PF6) from related technologies in this method... - In the case of an acid-producing agent, deformation of the nozzle forming component or peeling of the flow path forming component may occur. Summary of the Invention

[0010] This disclosure relates to a method for manufacturing a liquid ejector head, which can suppress deformation of the ejector nozzle forming component, further prevent ink penetration between the flow path forming component and other components, suppress peeling of the flow path forming component, and ensure high reliability, and relates to the liquid ejector head.

[0011] This disclosure relates to a method for manufacturing a liquid injection head, the liquid injection head including, on a substrate, an injection port forming component for forming an injection port for discharging liquid and a flow path forming component for forming a flow path communicating with the injection port.

[0012] The method includes:

[0013] 1) A layer of photosensitive resin composition (1) for forming flow path forming components is formed on a substrate;

[0014] 2) The layer of the photosensitive resin composition (1) is subjected to pattern exposure and heat treatment;

[0015] 3) A layer of photosensitive resin composition (2) for forming a jet nozzle forming component is laminated on a layer of photosensitive resin composition (1);

[0016] 4) The layer of the photosensitive resin composition (2) is subjected to pattern exposure and heat treatment;

[0017] 5) Remove the unexposed portions of the layers of the photosensitive resin composition (1) and the photosensitive resin composition (2) to form a flow path forming component and an injection nozzle forming component, wherein

[0018] The photosensitive resin composition (1) contains

[0019] At least one epoxy resin selected from epoxy resins having an aromatic ring and alicyclic epoxy resins, and

[0020] Gallate-based photoacid generators have a salt structure represented by formula (1) and a molar extinction coefficient of at least 0.10 L / mol∙cm at a wavelength of 365 nm:

[0021]

[0022] In equation (1), R 1 To R 4 Each is independently an alkyl group or Ar having 1 to 18 carbon atoms, and R 1 To R 4 At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atom numbers of the following substituents), wherein some hydrogen atoms in the aryl group may be substituted by the following groups: alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, denoted as -OR. 6 The alkoxy or aryloxy group is represented as R. 7 The acyl group of CO- is represented as R. 8 The acyl group of COO- is represented as -SR 9 The alkylthio or arylthio group is represented as -NR. 10 R 11 The amino group, or halogen atom. R 6 To R 9Each is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R 10 and R 11 Each element is an alkyl group with 1 to 8 carbon atoms, or an aryl group with 6 to 14 carbon atoms. E represents an element with a valence of n from groups 15 to 17 (IUPAC nomenclature), where n is an integer from 1 to 3. R 5 For organic groups bonded to E; R 5 The number is n+1, (n+1) R 5 They can be the same or different from each other, and there must be at least 2 Rs. 5 It can form a ring structure, which includes element E directly therein or via O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene, or phenylene.

[0023] Furthermore, this disclosure relates to a liquid injection head, the liquid injection head comprising, on a substrate:

[0024] An injection nozzle forming component that forms an injection port for spraying liquid; and

[0025] A flow path forming component that forms a flow path communicating with the injection port, wherein

[0026] The flow path forming component is a cured product of the photosensitive resin composition (1).

[0027] The nozzle forming component is a cured product of the photosensitive resin composition (2), and

[0028] The photosensitive resin composition (1) contains

[0029] At least one epoxy resin selected from epoxy resins having an aromatic ring and alicyclic epoxy resins, and

[0030] The photoacid generator is based on a gallate and has a salt structure represented by the following formula (1) and has a molar extinction coefficient of at least 0.10 L / mol ωcm at a wavelength of 365 nm.

[0031] The features of this disclosure will become apparent from the following description of the embodiments with reference to the accompanying drawings. The following description of the embodiments is illustrated by examples. Attached Figure Description

[0032] Figure 1A This is a schematic perspective view showing the structure of a liquid injection head. Figure 1B It is along Figure 1A A schematic cross-sectional view of line A-A' in the diagram.

[0033] Figure 2Aand Figure 2B This is a schematic cross-sectional view illustrating an example of a method for manufacturing a transfer component made of a photosensitive resin composition.

[0034] Figures 3A to 3H This is a schematic cross-sectional view illustrating an example of a method for manufacturing a liquid injection head.

[0035] Figures 4A to 4H This is a schematic cross-sectional view illustrating an example of a method for manufacturing a liquid injection head in the implementation scheme. Detailed Implementation

[0036] In this disclosure, the description of a numerical range, "from XX to YY" or "XX to YY," refers to a numerical range that includes a lower limit and an upper limit as endpoints, unless otherwise stated. When the numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, in this disclosure, for example, the description "selected from at least one of XX, YY, and ZZ" means any of the following: XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. When XX is a set, multiple constituent elements can be selected from XX, and the same applies to YY and ZZ.

[0037] In the following description, preferred embodiments of the present disclosure will be described with reference to the accompanying drawings. The method of manufacturing the liquid injection head of the present disclosure is not limited to the following aspects. Furthermore, in the following description, components having the same function will be identified by the same reference numerals in the drawings, and their description may be omitted.

[0038] Figure 1A This is a schematic perspective view showing a liquid injection head. Figure 1B Is when passing through Figure 1A A schematic cross-sectional view of the liquid jet head when viewed in a plane perpendicular to the substrate, A-A'.

[0039] Figure 1A and 1B The liquid jet head shown includes, on a substrate 1, a jet forming member 10 forming a jet nozzle 8 for jetting liquid, and a flow path forming member 6 forming a flow path 7 communicating with the jet nozzle 8. The liquid jet head has a substrate 1 on which energy generating elements 2 are formed at predetermined intervals, the energy generating elements being used to generate energy for jetting liquid. The substrate 1 is formed of, for example, silicon. Examples of energy generating elements 2 include electrothermal conversion elements and piezoelectric elements. The energy generating elements 2 can be configured to contact the surface of the substrate 1, or can be configured to be partially hollow relative to the surface of the substrate 1. A control signal input electrode (not shown) for operating the energy generating elements 2 is connected to the energy generating elements 2. Furthermore, a supply port 3 for supplying ink is opened in the substrate 1.

[0040] Inorganic material layer 4 and protective layer 5 are sequentially formed on the surface side of substrate 1, specifically on the surface of the nozzle 8 side. Examples of substrate 1 include silicon substrates formed of silicon. The silicon substrate is preferably a single crystal silicon, and the crystal orientation on the surface is (100).

[0041] Preferably, an inorganic material layer is present between the substrate and the flow path forming component. The flow path forming component is preferably in contact with the inorganic material layer. The inorganic material layer 4 preferably comprises at least one material selected from the group consisting of: metal films such as Ta, Ir, W, Ti, Pt, Au, Pd, Cu, Al or Si, silicon oxide (SiO2), silicon nitride (SiN), silicon carbide (SiC), silicon carbonitride (SiCN), and silicon carbon oxycarbonate (SiOC).

[0042] exist Figure 1B In this structure, the inorganic material layer 4 serves as a heat storage layer or an insulation layer. The protective layer 5 is suitable for protecting the energy generating element and is formed of, for example, Ta or Ir. The inorganic material layer 4 may cover the energy generating element.

[0043] exist Figure 1B In this process, an inorganic material layer 4 is formed over substantially the entire surface of the substrate 1. A flow path 7 sidewall is formed on the inorganic material layer 4 by a flow path forming member 6. Furthermore, an injection nozzle forming member 10, including an injection port 8 and a nozzle portion 9, is formed on the flow path forming member 6 and the flow path 7. Additionally, a liquid-repellent layer 11 is formed on the injection nozzle forming member 10 as needed.

[0044] The liquid jet head sprays ink supplied from the supply port 3 through the flow path 7 in the form of ink droplets from the jet port 8 via the nozzle section 9 by applying pressure generated by the energy generating element 2.

[0045] Next, we will refer to the following. Figure 2A , Figure 2B and Figures 3A to 3H Describe the method for manufacturing a liquid jet head. Figure 2A and Figure 2B This is a diagram illustrating an example of a method for manufacturing a transfer component made from a photosensitive resin composition (1).

[0046] Figures 3A to 3H This is a schematic cross-sectional view illustrating an example of a method for manufacturing a liquid injection head, and is shown in the completed state. Figure 1B The view taken from the same cross-section location.

[0047] First, such as Figure 2A As shown, a film substrate 12 made of PET, polyimide, etc., is prepared. Next, as... Figure 2BAs shown, a transfer component made of the photosensitive resin composition (1) 13 is applied to the film substrate 12 by spin coating or slot coating and pre-baked to produce a transfer component.

[0048] In the case of being transferred to a substrate pre-formed with a liquid supply port, the photosensitive resin composition (1) 13 may be a negative photosensitive epoxy resin composition. The photosensitive resin composition (1) contains, for example, an epoxy resin with a weight average molecular weight equal to or greater than 5000, a polyol having two or three hydroxyl groups at the end and free from perfluoroalkyl and perfluoroalkylene groups, a photoacid-generating agent, and a solvent. Their composition will be described in detail below.

[0049] Since the thickness of the layer of the photosensitive resin composition (1) 13 corresponds to the height of the flow path, the thickness is appropriately determined according to the spray design of the liquid spray head, for example, preferably set to 3 μm to 45 μm, more preferably set to 3 μm to 30 μm, and even more preferably set to 5 μm to 20 μm.

[0050] Next, as Figure 3A As shown, a substrate 1 is prepared with an energy generating element 2 on the front surface side.

[0051] Then, as Figure 3B As shown, an inorganic material layer 4 is formed on the front surface side of the substrate 1 to cover the energy generating element 2 as needed. Furthermore, a protective layer 5 is formed on the inorganic material layer 4 on the outer surface side of the energy generating element 2 as needed. The inorganic material layer 4 and the protective layer 5 can be patterned as required.

[0052] Next, as Figure 3C As shown, a supply port 3 is formed through the substrate to supply ink. The supply port 3 can be formed at the desired location using an alkaline etching solution (such as tetramethylammonium hydroxide (TMAH)) for wet etching or a dry etching method (such as reactive ion etching).

[0053] Next, as Figure 3D As shown, a film of a photosensitive resin composition (1) is formed on a substrate having a liquid jet energy generating element. For example, it can be formed by applying a liquid jet energy generating element to a substrate containing a liquid jet energy generating element. Figure 2B A film is manufactured by transferring a transfer component consisting of a photosensitive resin composition (1) 13 made in the substrate to a substrate. In the case where an inorganic material layer 4 is provided, it is only necessary to use a lamination method to transfer the transfer component to the inorganic material layer 4 on the substrate 1 where the energy generating element 2 and the supply port 3 are provided. It should be noted that in the case where the supply port 3 is not provided in the substrate, the photosensitive resin composition (1) may not be used as a transfer component, and may be applied by spin coating, slot coating, etc., thereby forming a film.

[0054] Considering the adhesion to the nozzle forming component 10 described later, the mechanical strength, stability to liquids such as ink, resolution, etc., the photosensitive resin composition (1) 13 is preferably formed from a cationic polymeric epoxy resin composition.

[0055] Next, as Figure 3E As shown, the photosensitive resin composition (1) 13 is patterned and exposed via a flow path forming mask 14 having a flow path pattern, and further, the exposed portion is cured by heat treatment (post-exposure baking) to form the flow path forming component 6. The mask 14 is formed by forming a light-shielding film, such as a chromium film, on a substrate made of a material such as glass or quartz, which transmits light with an exposure wavelength according to the flow path pattern. As an exposure device, a single-wavelength light source (e.g., an i-line exposure stepper or a KrF stepper) or a projection exposure device with a wide wavelength range including a mercury lamp in the light source, such as the mask aligner MPA-600 Super (trade name; manufactured by Canon Corporation), can be used.

[0056] Next, as Figure 3F As shown, a photosensitive resin composition (2) 15 is applied to a film substrate made of PET, polyimide, etc., and then transferred to a photosensitive resin composition (1) 13 and a flow path forming member 6 by a lamination method to form a film. In addition, a liquid repellent layer 11 is formed on the photosensitive resin composition (2) 15 as needed.

[0057] Considering the adhesion, mechanical strength, stability to liquids such as ink, and resolution of the flow path forming component 6, the photosensitive resin composition (2) 15, which serves as the nozzle forming component 10, is preferably formed from a cationic polymeric epoxy resin composition. Furthermore, although the thickness of the photosensitive resin composition (2) 15 is appropriately determined according to the spray design of the liquid nozzle and is not particularly limited, from the viewpoint of mechanical strength, for example, the thickness is preferably set to 3 μm to 25 μm, and more preferably to 3 μm to 15 μm.

[0058] The liquid-repellent layer 11 needs to be liquid-repellent to liquids such as inks, and preferably uses a perfluoroalkyl composition or a perfluoropolyether composition with cationic polymerization properties. Generally, it is known that in perfluoroalkyl compositions and perfluoropolyether compositions, fluorinated alkyl chains segregate at the interface between the composition and air through a post-coating baking treatment, and can enhance the liquid-repellent properties on the surface of the composition.

[0059] Next, as Figure 3G As shown, the photosensitive resin composition (2) 15 and the liquid-repellent layer 11 are patterned and exposed through a nozzle forming mask 16 with a nozzle pattern. In addition, heat treatment (post-exposure baking) is performed to cure the exposed portion, thereby forming the nozzle forming component 10.

[0060] This disclosure relates to a method for manufacturing a liquid injection head, the liquid injection head including a flow path forming component and an injection orifice forming component on a substrate. The manufacturing method includes:

[0061] 1) A process of forming a layer of photosensitive resin composition (1) to form a flow path forming component on a substrate;

[0062] 2) The process of patterning and heat-treating the layer of the photosensitive resin composition (1);

[0063] 3) The process of laminating layers of the photosensitive resin composition (2) to form the nozzle forming component on layers of the photosensitive resin composition (1);

[0064] 4) The process of patterning and heat-treating the layer of the photosensitive resin composition (2); and

[0065] 5) Remove the unexposed portions of the layers of the photosensitive resin composition (1) and the layers of the photosensitive resin composition (2) to form a flow path forming component and an injection nozzle forming component.

[0066] Furthermore, this disclosure also provides a liquid injection head, which includes an injection orifice forming component and a flow path forming component on a substrate. The injection orifice forming component forms an injection orifice for injection of liquid, and the flow path forming component forms a flow path communicating with the injection orifice. In the liquid injection head, the flow path forming component is a cured product of a photosensitive resin composition (1), and the injection orifice forming component is a cured product of a photosensitive resin composition (2).

[0067] As described above, the photosensitive resin composition (1) forming the flow path forming component and the photosensitive resin composition (2) forming the nozzle forming component on the substrate can be exposed to light of the same wavelength. In cases where an acid-generating agent in the prior art is used in this method, deformation of the nozzle forming component or peeling of the flow path forming component may occur.

[0068] As a result of the research, the inventors have recognized that the anti-reflective properties of the acid-generating agents in the prior art are insufficient, which may lead to deformation of the nozzle-forming component. In other words, the inventors have recognized that if the anti-reflective properties of the photosensitive resin composition (1) are low in cases where the photosensitive resin composition (1) is exposed and then the photosensitive resin composition (2) is subsequently exposed, a new problem arises where the photosensitive resin composition (2) deforms due to reflected light. If the photosensitive resin composition (2) deforms, deformation of the nozzle occurs.

[0069] Furthermore, as a method for enhancing antireflective properties by using an acid-generating agent in the prior art in the photosensitive resin composition (1), there are ways to increase, for example, the amount of the acid-generating agent and the antireflective agent. However, the inventors have recognized that if this method is used, there is a problem of reduced adhesion between the flow path forming component and other components such as the substrate and the inorganic material layer, and peeling of the flow path forming component.

[0070] As a result of in-depth research, the inventors have realized that this problem can be solved by using a gallate-based photoacid generator in the photosensitive resin composition (1) having a salt structure represented by formula (1) (described thereafter) and having a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm.

[0071] The inventors have considered the reasons why this problem can be solved by gallium-based photoacid generators, as described below.

[0072] Gallate-based photoacid generators having a salt structure represented by formula (1) and a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm exhibit satisfactory antireflective properties. Therefore, by using gallate-based photoacid generators in the photosensitive resin composition (1), deformation of the photosensitive resin composition (2) due to reflected light during exposure can be reduced.

[0073] Gallate-based photoacid generators possess high antireflective properties. Therefore, the antireflective properties of the photosensitive resin composition (1) can be improved without the need for large amounts of acid generators and antireflective agents. As a result, it is believed that the deterioration of the physical properties of the cured product of the photosensitive resin composition (1) is not caused by the residue of acid generators and antireflective agents, the adhesion of the flow path forming components is improved, and peeling can be reduced.

[0074] When the photosensitive resin composition (2) 15 is exposed to light of the same wavelength as that used in the photosensitive resin composition (1) 13, the amount of exposure required to cure the photosensitive resin composition (2) 15 is preferably less than the amount of exposure required to cure the photosensitive resin composition (1) 13. Therefore, when the photosensitive resin composition (2) 15 is exposed, the light that has already passed through the photosensitive resin composition (2) 15 is unlikely to cure the photosensitive resin composition (1) 13. As a result, the unexposed portions of the photosensitive resin composition (1) 13 are easily removed during the development process (described thereafter) and flow paths 7 are easily formed. Therefore, preferably, the photosensitive resin composition (2) 15 has a relatively higher sensitivity than the photosensitive resin composition (1) 13.

[0075] The amount of exposure required to cure the photosensitive resin composition (2) 15 is preferably equal to or less than 1 / 10 of the amount of exposure required to cure the photosensitive resin composition (1) 13.

[0076] For example, the amount of exposure required to cure the photosensitive resin composition (2) 15 is 1 / 40 to 1 / 10 or 1 / 35 to 1 / 10 of the amount of exposure required to cure the photosensitive resin composition (1) 13.

[0077] The exposure required to cure the photosensitive resin composition (1) 13 is preferably, for example, 5000 J / m. 2 Up to 25000 J / m 2 Or 10000 J / m 2 Up to 20000 J / m 2 .

[0078] The exposure required to cure the photosensitive resin composition (2) 15 is preferably, for example, 150 J / m. 2 Up to 2500 J / m 2 Or 300 J / m 2 Up to 1000 J / m 2 .

[0079] The amount of exposure required to cure the photosensitive resin composition can be controlled by the amount of photoacid generator and the amount of basic substances such as amines or acid generators that produce weak acids (pKa = -1.5 to 3.0) such as toluenesulfonic acid.

[0080] The nozzle forming mask 16 is obtained by forming a light-shielding film (such as a chromium film) on a substrate made of a material such as glass or quartz, which transmits light with an exposure wavelength according to the pattern of the nozzle. As an exposure device, a single-wavelength light source (such as an i-line exposure stepper or a KrF stepper) or a projection exposure device with a wide wavelength in which a mercury lamp is incorporated, such as the mask aligner MPA-600 Super (trade name; manufactured by Canon), can be used.

[0081] Next, as Figure 3H As shown, the uncured portions of the photosensitive resin composition (1) 13, the photosensitive resin composition (2) 15, and the liquid-repellent layer 11 are developed with a developer, thereby removing them together to form the flow path 7, the jet nozzle 8, and the nozzle portion 9, and then subjected to heat treatment as needed to complete the liquid jet head. Examples of developers include propylene glycol monomethyl ether acetate (PGMEA), methyl isobutyl ketone (MIBK), xylene, etc. Furthermore, isopropanol (IPA) can be used for rinsing as needed.

[0082] In the above manufacturing method, after the photosensitive resin composition (1) 13 is exposed, the photosensitive resin composition (2) 15 is laminated on the flow path forming member 6 and the photosensitive resin composition (1) 13. However, the photosensitive resin composition (2) 15 may also be laminated before the photosensitive resin composition (1) 13 is exposed.

[0083] Although the flow path forming component 6 and the nozzle forming component 10 are formed in two layers in the above-described liquid jet head manufacturing method, this disclosure is not limited thereto. More photosensitive resins can be used to form each component.

[0084] The photosensitive resin composition will be described below.

[0085] Considering the adhesive properties, mechanical strength, liquid (ink) resistance, swelling resistance, reactivity as a photolithography material, and resolution of the cured product, the photosensitive resin composition (1) and the photosensitive resin composition (2) are preferably formed from cationic polymeric epoxy resin compositions.

[0086] The photosensitive resin composition (1) contains an epoxy resin. Specifically, the photosensitive resin composition (1) contains at least one epoxy resin selected from epoxy resins having an aromatic ring and alicyclic epoxy resins. The photosensitive resin composition (2) may also contain an epoxy resin. The following description of "photosensitive resin composition" refers to both the photosensitive resin composition (1) and the photosensitive resin composition (2). The epoxy resin preferably has at least one skeleton selected from the group consisting of: bisphenol skeleton, phenol novolac skeleton, cresol novolac skeleton, norbornene skeleton, cyclic terpene skeleton, and dicyclopentadiene skeleton.

[0087] Examples of epoxy resins having aromatic rings include at least one selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin. Furthermore, examples of alicyclic epoxy resins include at least one selected from alicyclic epoxy resins having at least one backbone selected from norbornene, cyclic terpene, and dicyclopentadiene backbones.

[0088] The photosensitive resin composition preferably contains at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, and cresol phenolic epoxy resin.

[0089] The photosensitive resin composition may contain epoxy resins other than the epoxy resin having an aromatic ring.

[0090] In the epoxy resin included in the photosensitive resin composition, the percentage of the epoxy resin having an aromatic ring is preferably 50% to 100% by mass, more preferably 60% to 100% by mass.

[0091] The photosensitive resin composition is preferably a cationic photopolymerizable epoxy resin composition. The epoxy resin included in the photosensitive resin composition preferably contains a difunctional or higher epoxy resin having two or more epoxy groups per molecule. This epoxy resin may contain, for example, a difunctional epoxy resin and a trifunctional or higher epoxy resin, or it may contain a difunctional epoxy resin and a trifunctional epoxy resin. The use of difunctional or higher epoxy resins leads to three-dimensional crosslinking of the cured article, thus making it suitable for obtaining the desired properties. The percentage of difunctional or higher (e.g., difunctional) epoxy resin in the epoxy resin is preferably 50% to 100% by mass, more preferably 80% to 100% by mass. Based on the mass of the epoxy resin, the photosensitive resin composition preferably contains 10% to 45% by mass, or more preferably 20% to 45% by mass, of a trifunctional or higher (e.g., trifunctional) epoxy resin.

[0092] In the case of a liquid jet head obtained by transfer while applying heat to a substrate having openings and recesses, the photosensitive resin composition (1) 13 preferably has heat resistance to the thermal process in order to maintain the stability of the pattern shape. For example, the photosensitive resin composition (1) 13 preferably has film strength such that the layer does not deform even in the uncured state when heat is applied to the substrate having openings and recesses while the photosensitive resin composition (1) 13 is transferred as a dry film or in other thermal processes such as heat treatment after exposure.

[0093] Therefore, the epoxy resin contained in the photosensitive resin composition (1) 13 preferably has a high weight-average molecular weight. Specifically, the weight-average molecular weight (Mw) of the epoxy resin contained in the photosensitive resin composition (1) 13 is preferably 5,000 to 100,000. The softening point of the epoxy resin contained in the photosensitive resin composition (1) 13 is preferably equal to or greater than 90°C.

[0094] If the weight-average molecular weight (Mw) is equal to or greater than 5,000, the film strength is improved, the formability of the photosensitive resin composition (1) 13 is improved during transfer or other thermal processes, and the layer height becomes uniform. Furthermore, if the softening point is equal to or greater than 90°C, the film strength may be improved in a similar manner. On the other hand, if the weight-average molecular weight (Mw) is equal to or less than 100,000, the crosslinking density of the photosensitive resin composition is likely to be improved, and the stability of the pattern shape becomes satisfactory.

[0095] Furthermore, from a reactivity point of view, the epoxy resin in the photosensitive resin composition (1) 13 is preferably a difunctional or higher epoxy resin, and more preferably contains a difunctional epoxy resin and a trifunctional or higher epoxy resin. By including a trifunctional or higher epoxy resin, crosslinking occurs in a three-dimensional manner, and the sensitivity as a photosensitive material can be improved.

[0096] Trifunctional or higher epoxy resins preferably have an epoxy equivalent of less than 500. If the epoxy equivalent is less than 500, satisfactory sensitivity is achieved, pattern resolution is improved, and satisfactory mechanical strength and adhesion of the cured article are obtained. The weight-average molecular weight (Mw) of these resins can be calculated as polystyrene using gel permeation chromatography (e.g., manufactured by Shimadzu Corporation).

[0097] The photosensitive resin composition (2) preferably contains a multifunctional epoxy resin. The photosensitive resin composition (2) preferably contains a phenolic epoxy resin.

[0098] Commercially available epoxy resins that can be used as a flow path forming component (1) 13 and as a discharge port forming component (2) 15 include the following epoxy resins: "Celloxide 2021", "GT-300 series" and "GT-400 series" (trade names) manufactured by Daicel Chemical Industries, Ltd.; "jER1004", "jER1007", "jER1009", "jER1009F", "jER1009 SK", "jER1010", "jER1256" and "157S70" (trade names) manufactured by Mitsubishi Chemical Corporation; and "EPICLON N-695", "EPICLON N-865", "EPICLON 4050", "EPICLON 7050", "EPICLON HP-6000", "EPICLON HP-4710", "EPICLON HP-7200 series, EPICLON EXA-4816 (trade name), EPOX MKR-1710 (trade name) manufactured by DIC Corporation, Denacol series (trade name) manufactured by NagaseChemteX Corporation, and EP-4000 series (trade name) manufactured by ADEKA Corporation.

[0099] The photosensitive resin composition (1) contains a gallium-based photoacid generator having a salt structure represented by formula (1) and a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm. The photosensitive resin composition (2) may also contain a gallium-based photoacid generator having a salt structure represented by formula (1) and a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm.

[0100]

[0101] In equation (1), R 1 To R 4 Each is independently an alkyl group having 1 to 18 carbon atoms or Ar, and R 1 To R 4 At least one of them is Ar.

[0102] Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atom numbers of the following substituents), and some of the hydrogen atoms in the aryl group may be substituted by the following groups: alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, denoted as -OR 6 The alkoxy or aryloxy group is represented as R. 7 The acyl group of CO- is represented as R. 8 The acyl group of COO- is represented as -SR 9 The alkylthio or arylthio group is represented as -NR. 10 R 11 The amino group, or halogen atom. R 6 To R 9 Each is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R 10 and R 11 Each is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

[0103] Preferably, R 1 To R 4All are Ar. Ar is an aryl group having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms or more preferably 6 carbon atoms; excluding the number of carbon atoms in the substituents below), and some hydrogen atoms in the aryl group are substituted with alkyl or halogen atoms, wherein the alkyl group has 1 to 8 carbon atoms (preferably 1 to 3 carbon atoms or more preferably 1 carbon atom) and is substituted with halogen atoms. Preferably, 50% to 100% of the hydrogen atoms in the aryl group are substituted with halogen atoms. The halogen atom is preferably F.

[0104] E represents an element with a valence of n from groups 15 to 17 (IUPAC nomenclature). E is preferably S. n is an integer from 1 to 3, and preferably 2. R 5 R is an organic group that bonds with E. 5 The number is n+1, and there are (n+1) R... 5 They can be the same as or different from each other. Two or more R's 5 It can form a ring structure, which includes element E directly thereon or via O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene, or phenylene.

[0105] Preferably, (n+1) R 5 Each group is independently an alkyl group having 1 to 8 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms) (some hydrogen atoms in the aryl group may be replaced by hydroxyl or halogen atoms), or a group having an aromatic ring and a sulfur element. Examples of groups having an aromatic ring and a sulfur element include at least one selected from the group consisting of: groups having a sulfonyl structure, groups having a diphenyl sulfone structure, and groups having a thioxanthone structure.

[0106] As represented in equation (1), [R] 5 ] n+1 -E + The cationic structural portion can be selected from onium-based cationic structural portions with high absorbance, and onium ions such as oxonium, ammonium, phosphonium, sulfonium, or iodonium can be selected. Among these, sulfonium-based cationic structural portions with excellent cationic polymerization and crosslinking reaction properties are further preferred. In other words, the expression in formula (1) is [R 5 ] n+1 -E + The cationic structure portion is preferably based on sulfonium cationic structure portion.

[0107] In equation (1), [R] 5 ] n+1 -E +Examples of the represented cationic structural moiety include at least one selected from the group consisting of: triarylsulfonium, such as triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium. (4-Methoxyphenyl)sulfonium, 4-(phenylthio)phenyl di-p-tolylsulfonium, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, [4-(2-thioxanthonethio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonium)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonium}phenyl]sulfonium, bis{4-[bis(4-fluorophenyl)sulfonium]phenyl}sulfonium, bis{4-[bis(4-methylphenyl)sulfonium]phenyl}sulfonium, bis{4-[bis(4-methoxyphenyl)sulfonium]phenyl}sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyl bis(4-fluorophenyl) Sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyl diphenylsulfonium, 4-(4-benzoylphenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonyl]thioxanthone, 2-[(diphenyl)sulfonyl]thioxanthone, 4-(9-oxo-9H-thioxanth-2-yl)phenylthio-9-oxo-9H-thioxanth-2-ylphenylsulfonium, 4 -[4-(4-tert-butylbenzoyl)phenylthio]phenyl di-p-tolyl sulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl diphenyl sulfonium, 4-[4-(benzoylphenylthio)]phenyl di-p-tolyl sulfonium, 4-[4-(benzoylphenylthio)]phenyl diphenyl sulfonium, 5-(4-methoxyphenyl)thianthanene, 5-phenylthianthianthanene, 5-tolylthianthianthanene, 5-(4-ethoxyphenyl)thianthianthanene and 5-(2,4,6-trimethylphenyl)thianthianthanene; diaryl sulfonium, such as diphenylbenzoylmethyl sulfonium, diphenyl-4-nitrobenzylmethyl sulfonium, diphenylbenzyl sulfonium and diphenylmethyl sulfonium;Monoarylsulfones, such as phenylmethylbenzylsulfone, hydroxyphenylmethylsulfone, 4-methoxyphenylmethylbenzylsulfone, 4-acetylcarbonyloxyphenylmethylbenzylsulfone, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfone, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfone, 2-naphthylmethylbenzylsulfone, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfone, phenylmethylbenzoylmethylsulfone, 4-hydroxyphenylmethylbenzoylmethyl Sulfonium, 4-methoxyphenylmethylbenzoylmethylsulfonium, 4-acetylcarbonyloxyphenylmethylbenzoylmethylsulfonium, 2-naphthylmethylbenzoylmethylsulfonium, 2-naphthyloctadecylbenzoylmethylsulfonium, and 9-anthraylmethylbenzoylmethylsulfonium; and trialkylsulfonium, such as dimethylbenzoylmethylsulfonium, benzoylmethyltetrahydrothiophenonium, dimethylbenzylsulfonium, benzyltetrahydrothiophenonium, and octadecylmethylbenzoylmethylsulfonium.

[0108] In equation (1), it is represented as [R] 5 ] n+1 -E + The cationic structural portion is preferably selected from at least one of the following groups: 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, 2-[(di-p-tolyl)sulfonyl]thioxanthone, and 2-[(diphenyl)sulfonyl]thioxanthone.

[0109] From the viewpoint of cationic photopolymerization and antireflection, a gallate-based photoacid generator having a salt structure represented by formula (1) has a molar extinction coefficient at a wavelength of 365 nm that is equal to or greater than 0.10 L / mol∙cm. The molar extinction coefficient of the gallate-based photoacid generator is preferably from 0.10 L / mol∙cm to 7.00 L / mol∙cm, more preferably from 0.30 L / mol∙cm to 5.00 L / mol∙cm. The molar extinction coefficient of the gallate-based photoacid generator can be controlled, for example, by the structure of the cationic structural portion.

[0110] The content of the gallium-based photoacid generator having the salt structure shown in formula (1) is preferably from 0.5 to 10.0 parts by mass, more preferably from 1.0 to 5.0 parts by mass, relative to 100 parts by mass of epoxy resin. Satisfactory curability is achieved if the content is equal to or greater than 0.5 parts by mass. Furthermore, if the content is equal to or less than 10.0 parts by mass, the amount of unreacted residue is reduced, and more satisfactory adhesion is achieved.

[0111] Without impairing the effects of this disclosure, the photosensitive resin composition (1) may contain other photoacid generators besides the gallium-based photoacid generator described above, which has a salt structure represented by formula (1) and a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm. The content of other photoacid generators in the photosensitive resin composition (1) is preferably 0 to 3.0 parts by mass relative to 100 parts by mass of epoxy resin, more preferably 0 to 1.0 parts by mass. Within the above range, the amount of unreacted residue is reduced, and more satisfactory adhesion is achieved.

[0112] The photosensitive resin composition (1) may contain an additive with antireflective properties. The additive with antireflective properties is preferably a compound with a molar extinction coefficient at a wavelength of 365 nm equal to or greater than 0.1 L / mol∙cm. Examples of molar extinction coefficients for additives with antireflective properties include 0.1 L / mol∙cm to 40.0 L / mol∙cm and 3.0 L / mol∙cm to 30.0 L / mol∙cm.

[0113] The method for measuring the molar extinction coefficient of photoacid-producing agents and additives is as follows.

[0114] Each target compound was dissolved in a solvent (such as acetonitrile) that did not absorb at 365 nm to obtain a solution. This solution was then fed into a quartz tank, and the light absorption at 365 nm was measured using a UV-Vis-NIR spectrophotometer (manufactured by JASCO). The molar extinction coefficient could be calculated from the absorbance obtained by the following equation.

[0115] Molar absorptivity = Absorbance / Molar concentration of compound / Optical path length of cell

[0116] The absorbance of the layer of the photosensitive resin composition (1) at a wavelength of 365 nm per μm film thickness is preferably equal to or greater than 0.01 abs / μm. Preferred examples of absorbance include 0.01 abs / μm to 0.05 abs / μm or 0.01 abs / μm to 0.04 abs / μm.

[0117] The absorbance of the layer of the photosensitive resin composition (2) at a wavelength of 365 nm per μm film thickness is preferably equal to or greater than 0.01 abs / μm. Preferred examples of absorbance include 0.01 abs / μm to 0.05 abs / μm or 0.01 abs / μm to 0.04 abs / μm.

[0118] Satisfactory stability of the pattern shape is achieved when the absorbance per 1 μm film thickness is equal to or greater than 0.01 abs / μm. Furthermore, by using a compound with a molar extinction coefficient equal to or greater than 0.1 L / mol∙cm, the desired absorbance for antireflection is obtained without requiring large amounts of addition. As a result, the amount of uncured residue is reduced, and more satisfactory adhesion is achieved.

[0119] The method for measuring the absorbance of the photosensitive resin composition layer per 1 μm film thickness at a wavelength of 365 nm is as follows.

[0120] A film of the target photosensitive resin composition was formed on a quartz substrate, and the absorbance at 365 nm was measured using a UV-Vis-NIR spectrophotometer (manufactured by JASCO). The absorbance per 1 μm of film thickness at 365 nm could be calculated by dividing the obtained absorbance value by the film thickness after deposition.

[0121] Furthermore, additives with antireflective properties preferably provide a sensitizing effect on cationic photopolymerization initiators upon i-ray irradiation. Polycyclic aromatic or heterocyclic compounds, dyes, metal complexes, etc., undergo energy transfer upon i-ray irradiation and can enhance the reactivity of cationic photopolymerization initiators with weak i-ray absorption. Specific examples of additives with antireflective properties include compounds with anthracene structures, compounds with carbazole structures, and curcumin. In particular, compounds with anthracene structures are preferred because there is no concern about yellow discoloration, and even small amounts can provide the desired effect.

[0122] In particular, dialkoxyanthracene is highly soluble in the resin, making it more preferable. On the other hand, compounds that generate free radicals through hydrogen extraction or electron transfer induced by i-ray irradiation also effectively assist cationic photopolymerization initiators. Specific examples include compounds having anthraquinone structures and compounds having thioxanthone structures. The additive with antireflective properties is preferably at least one selected from compounds having an anthraquinone structure, compounds having an anthraquinone structure, and compounds having a thioxanthone structure.

[0123] Examples of compounds having an anthracene structure include compounds in which the hydrogen atoms in the anthracene are substituted with an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). Compounds having an anthracene structure are preferably, for example, diethoxyanthracene or dibutoxyanthracene.

[0124] Examples of compounds having an anthraquinone structure include compounds in which the hydrogen atom in the anthraquinone is substituted by an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). Compounds having an anthraquinone structure are preferably, for example, ethylanthraquinone.

[0125] Examples of compounds having a thioxanthone structure include compounds in which the hydrogen atom in the thioxanthone is substituted with an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms) or an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). Compounds having a thioxanthone structure are preferably, for example, diethylthioxanthone.

[0126] When using these additives, high efficiency can be achieved when combined with cationic polymerization initiators containing iodonium salts with high electron affinity from onium salts. One or more of these can be used in combination.

[0127] Examples of commercially available additives include: "Curcumin", "2-Ethylanthraquinone" and "2-Isopropylthioxanthone" (trade names) manufactured by Fujifilm Wako Pure Chemical Corporation; "Anthracure UVS-1331" and "Anthracure UVS-1101" (trade names) manufactured by Air Water Performance Chemical Inc.; "Omnicat250" and "OmnipolTX" (trade names) manufactured by IGMresins; and "CPI-410S" and "CPI-410B" (trade names) manufactured by San-Apro Ltd.

[0128] The content of the additive can be appropriately determined based on the exposure of the photosensitive resin composition (2), the film thickness of the photosensitive resin composition (1), and the reflectivity of the film present on the substrate surface, and there are no particular limitations thereto. From the viewpoint of adhesion, the content of the additive with anti-reflective function is preferably 0.05 to 5.0 parts by weight, more preferably 0.1 to 1.3 parts by weight, and even more preferably 0.1 to 0.4 parts by weight, relative to 100 parts by weight of epoxy resin. If this content is equal to or less than the upper limit, satisfactory curability is achieved, and more satisfactory adhesion is achieved. In addition, satisfactory patterning characteristics of the cured article are also achieved.

[0129] Furthermore, from the viewpoint of curability, the ratio of the gallium-based photoacid generator to the antireflective additive in the photosensitive resin composition (1) is preferably within the following range. In other words, the content of the gallium-based photoacid generator in the photosensitive resin composition (1) is preferably equal to or greater than three times the content of the antireflective additive, more preferably three to 15 times, and even more preferably three to 10 times.

[0130] In addition, silane coupling agents may be added for the purpose of improving adhesion properties. In other words, the photosensitive resin composition (1) preferably contains a silane coupling agent. Examples of commercially available silane coupling agents include "A-187" (trade name) manufactured by Momentive Performance Materials Inc. For the purpose of improving adhesion properties, polyols such as polyethylene glycol may also be added as polymerization promoters.

[0131] The content of silane coupling agent in the photosensitive resin composition (1) is preferably 1 to 10 parts by mass relative to 100 parts by mass of epoxy resin, more preferably 2 to 5 parts by mass.

[0132] In addition, photosensitizers such as anthracene compounds, basic substances such as amines, and acid-generating agents for producing weakly acidic (pKa = -1.5 to 3.0) toluenesulfonic acid can be added to improve pattern resolution and adjust sensitivity (exposure required for curing). In other words, the photosensitive resin composition (1) and the photosensitive resin composition (2) preferably contain basic substances or weakly acidic (pKa = -1.5 to 3.0) acid-generating agents. The photosensitive resin composition (1) and the photosensitive resin composition (2) preferably contain acid-generating agents for producing weakly acidic (pKa = -1.5 to 3.0) toluenesulfonic acid. The weakly acidic (pKa = -1.5 to 3.0) acid-generating agent can correspond to the other acid-generating agents mentioned above.

[0133] Examples of commercially available acid-generating agents for producing toluenesulfonic acid include “TPS-1000” (trade name) manufactured by Midori Kagaku Co., Ltd. and “WPAG-367” (trade name) manufactured by Wako Pure Chemical Corporation. Examples of acid-generating agent contents with pKa = -1.5 to 3.0 in the photosensitive resin composition (1) and the photosensitive resin composition (2) relative to 100 parts by weight of epoxy resin include 0.002 parts by weight to 1.0 parts by weight, 0.003 parts by weight to 0.50 parts by weight, and 0.003 parts by weight to 0.05 parts by weight.

[0134] Alternatively, you can use the “SU-8 series” and “KMPR-1000” (trade names) manufactured by Kayaku MicroChem Corporation, and the “TMMR S2000” and “TMMF S2000” (trade names) manufactured by Tokyo Ohka Kogyo Co., Ltd., which are available on the market as negative resists.

[0135] The photosensitive resin composition (1) preferably contains a polyol. The polyol is preferably a polyol that does not contain perfluoroalkyl or perfluoroalkylene groups.

[0136] Examples of polyols include at least one selected from the group consisting of: polyethylene glycols, such as PEG200, PEG600, and PEG1000; trimethylolalkanes, such as trimethylolethane and trimethylpropane; fatty alcohols having 1 to 10 carbon atoms (preferably 2 to 8 carbon atoms), such as 1,6-hexanediol; and polyether polyols. The polyol preferably has two or three hydroxyl groups at the end and preferably has a repeating structure in the molecule. For example, the polyol is preferably at least one selected from polyethylene glycols and polyether polyols.

[0137] The content of polyol in the photosensitive resin composition (1) is preferably from 0.5 parts by weight to 30.0 parts by weight, more preferably from 1.0 parts by weight to 10.0 parts by weight, and even more preferably from 1.5 parts by weight to 5.0 parts by weight, relative to 100 parts by weight of epoxy resin.

[0138] The photosensitive resin composition may contain known solvents, such as propylene glycol monomethyl ether acetate (PGMEA), as needed. For example, the amount of solvent may be appropriately varied depending on the film formation method of the photosensitive resin composition.

[0139] Example

[0140] Although the present disclosure will be described in further detail below by way of illustrated embodiments, the present disclosure is not limited to these embodiments.

[0141] Examples 1 to 30

[0142] For each embodiment, the photosensitive resin composition (1) and photosensitive resin composition (2) described in Tables 1 to 4 are used, by... Figure 2A and 2B as well as Figures 4A to 4H The liquid jet head is manufactured using the process shown. In each table, the composition is expressed in parts by mass. It should be noted that the sensitivity of each photosensitive resin composition (1) is adjusted using a-5 / c-6 material such that the exposure required to cure the photosensitive resin composition (2) is less than the exposure required to cure the photosensitive resin composition (1).

[0143]

[0144]

[0145]

[0146]

[0147] In each table, the molar extinction coefficient represents the molar extinction coefficient (L / mol∙cm) at a wavelength of 365 nm. The following materials are used as materials in each table.

[0148] e-1: 157S70 (manufactured by Mitsubishi Chemical Corporation; trade name)

[0149] e-2: EPICLON N-695 (manufactured by DIC Corporation; trade name)

[0150] e-3: EPICLON HP-7200H (manufactured by DIC Corporation; trade name)

[0151] e-4: jER1009F (manufactured by Mitsubishi Chemical Corporation; trade name)

[0152] e-5: jER1009SK (manufactured by Mitsubishi Chemical Corporation; trade name)

[0153] b-1: Anthracure UVS-1331 (manufactured by Air Water Performance Chemical Inc.; trade name)

[0154] b-2: Anthracure UVS-1101 (manufactured by Air Water Performance Chemical Inc.; trade name)

[0155] b-3: 2-Ethylanthraquinone (Fujifilm Wako Pure Chemical Corporation; trade name)

[0156] b-4: OmniradDETX (IGM Resins; trade name)

[0157] b-5: Anthracure UVS-2171 (manufactured by Air Water Performance Chemical Inc.; trade name)

[0158]

[0159]

[0160]

[0161] c-1: 4-Hydroxyphenyl-methyl-1-naphthylmethylsulfonium

[0162] c-2: [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium

[0163] c-3: 2-[(di-p-tolyl)sulfonyl]thioxanone

[0164] c-3: 2-[(diphenyl)sulfonyl]thioxanthone

[0165]

[0166]

[0167]

[0168] Example 1

[0169] First, such as Figure 2A As shown, a PET film 12 with a thickness of 100 μm was prepared.

[0170] Next, as Figure 2B As shown, the photosensitive resin composition (1) 1 with the composition described in Table 2 is applied to the PET film 12 by spin coating as... Figure 2B The figure is labeled 13 in the figure. The resulting object is then baked at 90°C for 10 minutes to allow the PGMEA solvent to evaporate, thereby forming a 7.0 μm film.

[0171] Next, as Figure 4A As shown, a substrate 1 is fabricated from silicon and has an energy generating element 2 made of TaSiN on the front surface side.

[0172] Next, as Figure 4B As shown, a 100 nm thick Ta layer is formed on the front surface of the substrate 1 as an inorganic material layer 4 and a protective layer 5 by sputtering, thereby covering the energy generating element 2. Furthermore, the inorganic material layer 4 and the protective layer 5 are patterned using photolithography and reactive ion etching.

[0173] Then, as Figure 4C The supply port 3 is shown. The supply port 3 is formed as follows: an etch mask with openings is formed using a positive photosensitive resin manufactured by OFPR (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and reactive ion etching is performed through the openings of the etch mask. Reactive ion etching is performed using an ICP etching apparatus (manufactured by Alcatel-Lucent Enterprise; model: 8E) via the Bosch process. After forming the supply port 3, the etch mask is removed using a release agent.

[0174] Next, as Figure 4D As shown, a photosensitive resin composition (1) is formed. Figure 4D(Ref. 13 in the attached figure). Specifically, by applying heat of 70°C and applying pressure thereto using a lamination method, a material with... Figure 2B The film of the photosensitive resin composition (1) generated in the process is transferred to the substrate 1 provided with the energy generating element 2 and the supply port 3. Thereafter, the PET film 12 is peeled off from the photosensitive resin composition (1) by a peeling tape (not shown).

[0175] Next, as Figure 4E As shown, an i-line exposure stepper (manufactured by Canon; trade name: i5) is used to form mask 14 via a flow path with a flow pattern at 16000 J / m. 2 The exposure amount is used to pattern the photosensitive resin composition (1), and the exposed portion is cured by further heat treatment at 50°C for 5 minutes to form the flow path forming component 6.

[0176] Next, as Figure 4F As shown, the photosensitive resin composition (2) 8 in Table 1 is formed as follows: Figure 4F Reference numeral 15 in the figure. First, the photosensitive resin composition (2) 8 from Table 1 is applied to a PET film with a thickness of 100 μm, and the resulting object is baked at 90°C for 5 minutes to allow the solvent to evaporate, thereby forming a 5.0 μm film. Next, the photosensitive resin composition (2) is transferred and stacked on the photosensitive resin composition (1) and the flow path forming component 6 by applying heat at 50°C using a lamination method.

[0177] Next, as Figure 4G As shown, a mask 16 is formed through a nozzle with a nozzle pattern, and an i-line exposure stepper (manufactured by Canon; trade name: i5) is used at 500 J / m 2 The photosensitive resin composition (2) is patterned by exposure to a certain amount of light. Furthermore, the exposed portion is cured by further heat treatment at 90°C for 5 minutes, thereby forming the nozzle forming part 10.

[0178] Next, as Figure 4H As shown, by developing with PGMEA for 1 hour, the uncured portions of the photosensitive resin composition (1) and the photosensitive resin composition (2) are removed together, thereby forming the flow path 7, the spray nozzle 8 and the nozzle part 9, and curing under heating at 200°C, thereby obtaining a liquid spray head.

[0179] Examples 2 to 30

[0180] Similar to Example 1, the liquid spray heads of Examples 2 to 30 were obtained, except that in Example 1, the photosensitive resin compositions (1) and (2) described in Tables 1 to 4 were modified to use the combinations in Table 7.

[0181] Comparative Examples 1 to 3

[0182] Similar to Example 1, the liquid spray heads of Comparative Examples 1 to 3 were obtained, except that the photosensitive resin compositions (1) and (2) described in Tables 1 to 4 were modified to use the combinations in Table 7 in Example 1.

[0183] evaluate

[0184] Pattern Shape

[0185] In each of the liquid jet heads manufactured in Examples 1 to 30 and Comparative Examples 1 to 3, the area of ​​the jet pattern was measured using a white interference microscope (manufactured by Hitachi High-Tech Science Corporation), and the ratio of the measured area of ​​the pattern to the mask area (230 μm) was used as the standard shown in Table 5. 2 Determine the pattern shape (pattern reproducibility).

[0186]

[0187] Table 7 shows the evaluation results of the pattern shape. Satisfactory pattern reproducibility was achieved in each liquid jet head manufactured in Examples 1 to 30. On the other hand, Comparative Example 1 does not contain a gallate-based photoacid generator having a salt structure represented by Formula (1) and a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm. Therefore, it is considered to have insufficient anti-reflection capability, and the jet nozzle is deformed due to reflected light when exposed to the photosensitive resin composition (2), resulting in reduced pattern reproducibility.

[0188] Peel test (ink resistance)

[0189] The flow path of each liquid jet head manufactured in Examples 1 to 30 and Comparative Examples 1 to 3 was filled with the ink shown in Table 6 below, and placed in an oven at 80°C for 90 days.

[0190]

[0191] The bonding state between the inorganic material layer 4 and the flow path forming component 6 was observed using a metal microscope and evaluated using the following criteria.

[0192] A: Even after being stored at 80°C for 90 days, no delamination occurs between the inorganic material layer 4 and the flow path forming component 6.

[0193] B: After being stored at 80°C for 90 days, slight peeling occurred between the inorganic material layer 4 and the flow path forming component 6. This slight peeling was not observed when the liquid jet head was completed and did not affect the jetting.

[0194] C: After being stored at 80°C for 90 days, delamination occurred between the inorganic material layer 4 and the flow path forming component 6. This delamination was not observed when the liquid jet head was completed.

[0195] Table 7 shows the evaluation results of the peeling test. In each liquid jet head manufactured in Examples 1 to 30, no peeling was observed between the inorganic material layer and the flow path forming component, or even in cases where peeling occurred, it was a slight peeling that did not affect the jetting, and satisfactory ink resistance was achieved. Comparative Examples 2 and 3 did not contain a gallate-based photoacid generator having a salt structure represented by Formula (1) and a molar extinction coefficient equal to or greater than 0.10 L / mol∙cm at a wavelength of 365 nm. It is believed that due to the residues of the photoacid generator and antireflective agent, the adhesion between the inorganic material layer and the flow path forming component is reduced, and peeling phenomena that were not observed when the liquid jet head was completed can be seen between the inorganic material layer and the flow path forming component.

[0196]

[0197] Print Evaluation

[0198] Each liquid jet head manufactured in the examples and comparative examples was filled with ink similar to that used in the peel test, and a print evaluation was performed after storage at 70°C for 90 days.

[0199] Satisfactory printing evaluations were achieved in each liquid jet head manufactured in Examples 1 to 30. On the other hand, in Comparative Examples 1 to 3, pattern reproducibility deteriorated, and localized peeling occurred between the inorganic material layer and the flow path forming components, resulting in a deterioration in printing quality.

[0200] According to this disclosure, a liquid ejector head can be provided that can reduce deformation of the ejector nozzle forming component, further prevent ink from penetrating between the flow path forming component and other components, thereby reducing peeling of the flow path forming component and ensuring high reliability.

[0201] Furthermore, the technology described in this specification can replace SbF6-containing... - The acid-producing agent. In other words, the technology described in this specification can contribute to the realization of sustainable societies, such as decarbonized / circular societies.

[0202] Although this disclosure has been described with reference to embodiments, it should be understood that this disclosure is not limited to the disclosed embodiments. The scope of the following claims should be given the broadest interpretation to cover all such modifications and equivalent structures and functions.

Claims

1. A method for manufacturing a liquid injection head, the liquid injection head comprising, on a substrate, an injection port forming component for forming an injection port for discharging liquid and a flow path forming component for forming a flow path communicating with the injection port. The method includes: 1) A layer of the photosensitive resin composition (1) for forming the flow path forming component is formed on the substrate; 2) The layer of the photosensitive resin composition (1) is subjected to pattern exposure and heat treatment; 3) A layer of photosensitive resin composition (2) for forming the nozzle forming component is laminated on the layer of the photosensitive resin composition (1); 4) The layer of the photosensitive resin composition (2) is subjected to pattern exposure and heat treatment; and 5) Remove the unexposed portions of the layers of the photosensitive resin composition (1) and the photosensitive resin composition (2) to form the flow path forming component and the nozzle forming component, wherein The photosensitive resin composition (1) contains At least one epoxy resin selected from epoxy resins having an aromatic ring and alicyclic epoxy resins, and A gallate-based photoacid generator having a salt structure represented by formula (1) and exhibiting a concentration of at least 0.10 L / mol at a wavelength of 365 nm. molar extinction coefficient in cm: In equation (1), R 1 To R 4 Each is independently an alkyl group or Ar having 1 to 18 carbon atoms, and R 1 To R 4 At least one of them is Ar; said Ar is an aryl group having 6 to 14 carbon atoms (excluding the number of carbon atoms of the following substituents), and some of the hydrogen atoms in said aryl group may be substituted by the following groups: alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, denoted as -OR 6 The alkoxy or aryloxy group is represented as R. 7 The acyl group of CO- is represented as R. 8 The acyl group of COO- is represented as -SR 9 The alkylthio or arylthio group is represented as -NR. 10 R 11 The amino or halogen atom; the R 6 To R 9 Each is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R 10 and R 11 Each element is an alkyl group with 1 to 8 carbon atoms, or an aryl group with 6 to 14 carbon atoms; E represents an element with a valence of n from groups 15 to 17 (IUPAC nomenclature), where n is an integer from 1 to 3; R 5 For organic groups bonded to E; R 5 The number is n+1, (n+1) R 5 They can be the same or different from each other, and there must be at least 2 Rs. 5 It can form a ring structure, which includes element E directly therein or via O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene or phenylene.

2. The method for manufacturing a liquid injection head according to claim 1, wherein, The absorbance of the layer of the photosensitive resin composition (1) at a wavelength of 365 nm per 1 μm film thickness is at least 0.01 abs / μm, and The absorbance of the layer of the photosensitive resin composition (2) at a wavelength of 365 nm per 1 μm film thickness is at least 0.01 abs / μm.

3. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The expression in the above formula (1) is [R] 5 ] n+1 -E + The cationic structure part is based on the cationic structure part of sulfonium.

4. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The amount of exposure required to cure the photosensitive resin composition (2) is less than the amount of exposure required to cure the photosensitive resin composition (1).

5. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The content of the gallate-based photoacid generator is from 0.5 parts by weight to 10.0 parts by weight relative to 100 parts by weight of the epoxy resin.

6. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The epoxy resin has at least one skeleton selected from the group consisting of: bisphenol skeleton, phenol-formaldehyde skeleton, cresol-formaldehyde skeleton, norbornene skeleton, cyclic terpene skeleton, and dicyclopentadiene skeleton.

7. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The epoxy resin in the photosensitive resin composition (1) comprises a difunctional or higher epoxy resin.

8. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The epoxy resin in the photosensitive resin composition (1) comprises a difunctional epoxy resin and a trifunctional or higher epoxy resin.

9. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The photosensitive resin composition (1) contains additives with anti-reflective properties, and The additive with antireflective function comprises at least one selected from the group consisting of: compounds having an anthracene structure, compounds having an anthraquinone structure, and compounds having a thioxanthone structure.

10. The method for manufacturing a liquid injection head according to claim 9, wherein, The content of the gallate-based photoacid generator in the photosensitive resin composition (1) is at least three times the content of the additive with antireflective function.

11. The method for manufacturing a liquid injection head according to claim 9, wherein, The content of the additive with anti-reflective function is from 0.05 parts by weight to 5.0 parts by weight relative to 100 parts by weight of the epoxy resin.

12. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The photosensitive resin composition (1) and the photosensitive resin composition (2) contain an alkaline substance or a weakly acidic (pKa = -1.5 to 3.0) acid generator.

13. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The photosensitive resin composition (1) contains a silane coupling agent.

14. The method for manufacturing a liquid injection head according to claim 1 or 2, wherein, The photosensitive resin composition (1) contains a polyol.

15. The method for manufacturing a liquid injection head according to claim 14, wherein, The polyol has two or three hydroxyl groups at the end and has repeating structures in the molecule.

16. The method for manufacturing a liquid injection head according to claim 14, wherein, The content of the polyol in the photosensitive resin composition (1) is from 0.5 parts by weight to 30.0 parts by weight relative to 100 parts by weight of the epoxy resin.

17. A liquid injection head, the liquid injection head comprising, on a substrate: A nozzle forming component that forms a nozzle for spraying liquid; and A flow path forming component that forms a flow path communicating with the injection port, wherein The flow path forming component is a cured product of the photosensitive resin composition (1). The nozzle forming component is a cured product of the photosensitive resin composition (2). The photosensitive resin composition (1) contains At least one epoxy resin selected from epoxy resins having an aromatic ring and alicyclic epoxy resins, and Gallate-based photoacid generators, having a salt structure represented by formula (1) and a molar extinction coefficient of at least 0.10 L / mol⁻¹ at a wavelength of 365 nm: In equation (1), R 1 To R 4 Each is independently an alkyl group or Ar having 1 to 18 carbon atoms, and R 1 To R 4 At least one of them is Ar; said Ar is an aryl group having 6 to 14 carbon atoms (excluding the number of carbon atoms of the following substituents), and some of the hydrogen atoms in said aryl group may be substituted by the following groups: alkyl group having 1 to 18 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, denoted as -OR 6 The alkoxy or aryloxy group is represented as R. 7 The acyl group of CO- is represented as R. 8 The acyl group of COO- is represented as -SR 9 The alkylthio or arylthio group is represented as -NR. 10 R 11 The amino or halogen atom; the R 6 To R 9 Each is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R 10 and R 11 Each element is an alkyl group with 1 to 8 carbon atoms, or an aryl group with 6 to 14 carbon atoms; E represents an element with a valence of n from groups 15 to 17 (IUPAC nomenclature), where n is an integer from 1 to 3; R 5 For organic groups bonded to E; R 5 The number is n+1, (n+1) R 5 They can be the same or different from each other, and there must be at least 2 Rs. 5 It can form a ring structure, which includes element E directly therein or via O-, -S-, -SO-, -SO2-, -NH-, -CO-, -COO-, -CONH-, alkylene or phenylene.

18. The liquid injection head according to claim 17, wherein, The absorbance of the layer of the photosensitive resin composition (1) at a wavelength of 365 nm per 1 μm film thickness is at least 0.01 abs / μm, and The absorbance of the layer of the photosensitive resin composition (2) at a wavelength of 365 nm per 1 μm film thickness is at least 0.01 abs / μm.

19. The liquid injection head according to claim 17 or 18, wherein, The expression in the above formula (1) is [R] 5 ] n+1 -E + The cationic structure part is based on the cationic structure part of sulfonium.

20. The liquid injection head according to claim 17 or 18, wherein, The content of the gallate-based photoacid generator is from 0.5 parts by weight to 10.0 parts by weight relative to 100 parts by weight of the epoxy resin.

21. The liquid injection head according to claim 17 or 18, wherein, The epoxy resin has at least one skeleton selected from the group consisting of: bisphenol skeleton, phenol-formaldehyde skeleton, cresol-formaldehyde skeleton, norbornene skeleton, cyclic terpene skeleton, and dicyclopentadiene skeleton.

22. The liquid injection head according to claim 17 or 18, wherein, The epoxy resin in the photosensitive resin composition (1) comprises a difunctional or higher epoxy resin.

23. The liquid injection head according to claim 17 or 18, wherein, The epoxy resin in the photosensitive resin composition (1) contains difunctional epoxy resin and trifunctional or higher epoxy resin.

24. The liquid injection head according to claim 17 or 18, wherein, The photosensitive resin composition (1) contains additives with anti-reflective properties, and The additive with antireflective function comprises at least one selected from the group consisting of: compounds having an anthracene structure, compounds having an anthraquinone structure, and compounds having a thioxanthone structure.

25. The liquid injection head according to claim 24, wherein, The content of the gallate-based photoacid generator in the photosensitive resin composition (1) is at least three times the content of the additive with antireflective function.

26. The liquid injection head according to claim 24, wherein, The content of the additive with anti-reflective function is from 0.05 parts by weight to 5.0 parts by weight relative to 100 parts by weight of the epoxy resin.

27. The liquid injection head according to claim 17 or 18, wherein, The photosensitive resin composition (1) and the photosensitive resin composition (2) contain an alkaline substance or a weakly acidic (pKa = -1.5 to 3.0) acid generator.

28. The liquid injection head according to claim 17 or 18, wherein, The photosensitive resin composition (1) contains a silane coupling agent.

29. The liquid injection head according to claim 17 or 18, wherein, The photosensitive resin composition (1) contains a polyol.

30. The liquid injection head according to claim 29, wherein, The polyol has two or three hydroxyl groups at the end and has repeating structures in the molecule.

31. The liquid injection head according to claim 17 or 18, wherein, An inorganic material layer is included between the substrate and the flow path forming component.

32. The liquid injection head according to claim 31, wherein, The inorganic material layer comprises at least one selected from the group consisting of: Ta, Ir, W, Ti, Pt, Au, Pd, Cu, Al, Si, silicon oxide (SiO2), silicon nitride (SiN), silicon carbide (SiC), silicon carbonitride (SiCN), and silicon carbon oxyoxide (SiOC).

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