Photosensitive epoxy resin composition, liquid discharge head, liquid discharge device, and surface treatment method

Abstract

To provide: a photosensitive epoxy resin composition having an excellent patterning property and water repellency; a surface treatment method using the photosensitive epoxy resin composition; and a liquid discharge head and a liquid discharge device that have been surface-treated with the photosensitive epoxy resin composition and that can maintain printing quality at a high level over a long period.SOLUTION: A photosensitive epoxy resin composition comprises at least: (A) an epoxy resin comprising two or more epoxy groups in one molecule; (B) a cationic polymerization catalyst; (C) a silicone compound comprising one or more alkylsiloxane groups in one molecule; and (D) an alcohol or phenol compound comprising a long chain alkyl group having 9 to 18 carbon atoms.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition that enables surface treatment to impart water- and ink-repellent properties, particularly a photosensitive epoxy resin composition that can form a patterned coating film by ultraviolet irradiation. That is, the present disclosure relates to a photosensitive epoxy resin composition, a surface treatment method using the photosensitive epoxy resin composition, and a liquid ejection head and a liquid ejection device that have been surface-treated with the photosensitive epoxy resin composition. [Background technology]

[0002] In various fields, a method of applying a water-repellent coating to the surface of a substrate of a component that requires water resistance or ink repellency is generally known, and resin materials and coatings for use therein have been developed. For example, fluorine-based coatings containing fluoroolefin or perfluoro groups are extremely stable both thermally and chemically, and have excellent weather resistance, water resistance, chemical resistance, and solvent resistance, as well as excellent release properties, abrasion resistance, and water repellency, and are therefore widely used in a variety of applications.

[0003] An example of a component that requires water resistance and ink repellency is an inkjet recording head. A liquid ejection head is used in a liquid ejection device such as an inkjet recording device, and includes a photosensitive resin layer that forms ejection ports and flow paths, and a substrate. The photosensitive resin layer that forms the ejection ports and flow paths is provided on the substrate. A supply port that supplies liquid to the flow path is formed in the substrate. The surface of the substrate on the side where the flow path and ejection ports are provided has energy generating elements. The liquid is supplied from the supply port to the flow path, energy is imparted by the energy generating elements, and the liquid is ejected from the liquid ejection port and lands on a recording medium such as paper.

[0004] In this liquid ejection head, the surface condition of the ejection port forming member has a significant impact on the liquid ejection performance. Therefore, by forming a liquid-repellent layer on the surface of the ejection port forming member, adhesion of liquid is suppressed and the surface condition is maintained uniform. As such a liquid-repellent layer, a liquid-repellent layer made of a photosensitive epoxy resin composition containing an alkylsiloxane-containing epoxy resin, as described in Patent Document 1, is disclosed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-020323 Summary of the Invention [Problem to be solved by the invention]

[0006] Meanwhile, the demands for the performance of the liquid-repellent layer as described above have become extremely high in recent years, along with the rapid improvement in the performance of inkjet printers. That is, as inkjet heads become smaller and more numerous in nozzle size, the liquid-repellent layer is also required to have high patterning properties (e.g., excellent photoprocessability). In addition, basic properties that such a water-repellent film should have include adhesion to the substrate and ink resistance (e.g., the water repellency and adhesion should not be significantly affected by contact with ink).

[0007] Furthermore, various attempts have been made to improve the performance of the ink itself, such as using polar solvents or adjusting the pH value to a high level. Liquid-repellent layers are now required to have good ink resistance (e.g., alkali resistance and hydrolysis resistance) so that they do not lose their water repellency or lose their adhesion to the substrate even when in contact with such ink. However, there are many cases where these requirements are met while also achieving the above-mentioned high level of microfabrication. Developing such materials is not an easy task.

[0008] In the case of a liquid-repellent layer using a photosensitive epoxy resin composition containing an alkylsiloxane-containing epoxy resin as in Patent Document 1, the patterning ability is insufficient to form the above-mentioned fine nozzles due to the low compatibility between the siloxane component and the epoxy component, and the desired shape may not be formed. Furthermore, when an ink with the above-mentioned improved performance is used, the film-forming ability of the liquid-repellent layer and its adhesion to the application member may be impaired, resulting in peeling and a loss of water repellency.

[0009] According to at least one aspect of the present disclosure, there is provided a photosensitive epoxy resin composition suitable as a water repellent or water repellent coating to be applied to a location where there is a chance of contact with a solution or substance, such as ink, that contains a component that impairs the film-forming property or adhesion of the water repellent. Specifically, there is provided a photosensitive epoxy resin composition that has excellent patterning properties and water repellency and is capable of undergoing a surface modification treatment that can maintain the same surface condition at all times. Furthermore, by treating the surface of the substrate with this photosensitive epoxy resin composition, the nozzle surface can be maintained in a constant surface condition, and adhesion of ink to the print head surface can be suppressed even when the print head is in contact with the recording liquid for a long period of time. As a result, a liquid ejection head and a liquid ejection device can be provided that have good dot landing accuracy and can maintain high print quality for a long period of time. [Means for solving the problem]

[0010] According to at least one aspect of the present disclosure, (A) an epoxy resin having two or more epoxy groups in one molecule; (B) a cationic polymerization catalyst, (C) a silicone compound having one or more alkylsiloxane groups in one molecule, and (D) an alcohol or phenol compound having a long-chain alkyl group having a carbon number of C9 to C18; A photosensitive epoxy resin composition is provided, which is characterized by containing at least

[0011] According to yet another aspect of the present disclosure, a first step of applying the photosensitive epoxy resin composition to a substrate and drying it to form a coating film; a second step of irradiating the surface of the substrate on which the coating film has been formed with active energy rays in a pattern through a mask; and a third step of dissolving and removing the uncured photosensitive epoxy resin composition present in the area not irradiated with the active energy rays; The present invention provides a surface treatment method comprising the steps of:

[0012] According to yet another aspect of the present disclosure, there is provided a liquid ejection head having an ejection port for ejecting a recording liquid, wherein at least an opening of the ejection port is covered with a cured product made of the photosensitive epoxy resin composition. According to yet another aspect of the present disclosure, there is provided a liquid ejection device having the above-described liquid ejection head. [Effects of the Invention]

[0013] According to at least one aspect of the present disclosure, there are provided a photosensitive epoxy resin composition having excellent patterning properties and water repellency, a surface treatment method using the photosensitive epoxy resin composition, and a liquid ejection head and a liquid ejection device that are surface-treated with the photosensitive epoxy resin composition and can maintain print quality at a high level for a long period of time. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a cross-sectional view of a main portion of a configuration example of a liquid ejection head according to an embodiment of the present invention. [Figure 2] FIG. 2 is a perspective view of the main part of the liquid ejection head. [Figure 3] FIG. 1 is a diagram showing an example of a liquid ejection apparatus incorporating a liquid ejection head. [Figure 4] 3A to 3C are diagrams illustrating a manufacturing process of a liquid ejection head in an example. DETAILED DESCRIPTION OF THE INVENTION

[0015] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way. Furthermore, in the present disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of 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.

[0016] In an inkjet recording head that discharges ink as small droplets from a discharge port and deposits the ink on paper or the like to form a recording or image, it is desirable that the discharge port have the following performance. (1) The remaining ink in the ink column that has turned into droplets is quickly re-stored in the nozzle. (2) Ink droplets adhering to the surface can be easily wiped off by cleaning. (3) Ink droplets adhering to the surface have excellent scratch resistance during cleaning operations and paper transport. (4) The formation of a meniscus at the nozzle surface during repeated droplet formation and ink refilling. (5) The normal direction of the meniscus is the ejection direction. (6) The ink has sufficient interfacial tension, i.e., contact angle, to form a meniscus even when the ink has low surface tension or is under low negative pressure.

[0017] The reason why these various performance characteristics are required of the ejection ports is that in a liquid ejection head, if recording liquid such as ink adheres to the periphery of the ejection ports, the ejection (flight) direction of the droplets ejected from the ejection ports will be shifted, making it impossible to print with high precision, which is directly related to printing performance.In order to address this, a method is known in which a water-repellent treatment is applied to the surface on which the ejection ports are formed in order to prevent the adhesion of liquid to the vicinity of the ejection ports, which causes such a shift in the ejection direction.

[0018] One example of a liquid-repellent treatment method is the formation of a liquid-repellent layer made of a photosensitive epoxy resin composition containing an alkylsiloxane-containing epoxy resin, as described in Patent Document 1. However, in the case of a liquid-repellent layer made of a conventional photosensitive epoxy resin composition containing an alkylsiloxane-containing epoxy resin, the patterning ability is insufficient to form the above-mentioned fine nozzles due to the low compatibility between the siloxane component and the epoxy component, and the desired shape may not be formed. Furthermore, when a polar solvent is used to improve performance or an ink adjusted to a high pH value is used, the film-forming properties of the liquid-repellent layer and its adhesion to the application member may be impaired, resulting in peeling and loss of water repellency.

[0019] In response to the above-mentioned problems, the present inventors have discovered that a photosensitive epoxy resin composition containing specific components can achieve both high patterning properties and water repellency. Furthermore, they have discovered that by treating the surface of the ejection orifices with the photosensitive epoxy resin composition, it is possible to provide a liquid ejection head that can maintain good print quality even during long-term use.

[0020] The photosensitive epoxy resin composition of the present disclosure is an epoxy resin-based composition, and therefore has excellent adhesion to various members. The photosensitive epoxy resin composition has excellent thermal conductivity and can be cured at relatively low temperatures, providing a cured product with excellent physical properties. Furthermore, by including a silicone compound having an alkylsiloxane group in the photosensitive epoxy resin composition, a cured product with excellent water repellency can be provided. Furthermore, by including an alcohol or phenol compound having a C9 to C18 long-chain alkyl group as a compatibilizer, the compatibility between the epoxy resin and the silicone compound can be significantly improved, providing a photosensitive epoxy resin composition that can achieve both patternability and water repellency.

[0021] The photosensitive epoxy resin composition of the present disclosure is useful as a water repellent or water repellent coating to be applied to locations where there is a chance of contact with solutions or substances, such as ink, that contain components that impair the adhesion of the water repellent, and is particularly suitable for water-repellent and ink-repellent treatment of the ejection port surface of an inkjet recording head.

[0022] The present disclosure will be described in detail below. In the following description, the photosensitive epoxy resin composition may be simply referred to as a photosensitive resin composition or a resin composition. The photosensitive epoxy resin composition contains at least (A) an epoxy resin having two or more epoxy groups in one molecule, (B) a cationic polymerization catalyst, (C) a silicone compound having one or more alkylsiloxane groups in one molecule, and (D) an alcohol or phenol compound having a long-chain alkyl group with a carbon number of C9 to C18.

[0023] (A) Epoxy resin Epoxy resins have two or more epoxy groups in one molecule. Bifunctional or higher epoxy resins promote a curing reaction. By including an epoxy resin in a photosensitive resin composition, three-dimensional crosslinking occurs during curing, resulting in a cured product with desired properties.

[0024] Examples of epoxy resins having two or more epoxy groups in one molecule include the following: Examples of the epoxy resin include cationically polymerizable epoxy resins such as epoxy resins having a bisphenol skeleton, such as bisphenol A or F epoxy resins, epoxy resins having a phenol novolac skeleton, such as phenol novolac epoxy resins, epoxy resins having a cresol novolac skeleton, such as cresol novolac epoxy resins, epoxy resins having a norbornene skeleton, epoxy resins having a terpene skeleton, epoxy resins having a dicyclopentadiene skeleton, and polyfunctional epoxy resins such as epoxy resins having an oxycyclohexane skeleton. These may be used alone or in combination of two or more.

[0025] The photosensitive epoxy resin composition preferably contains a cationic polymerization type epoxy resin in consideration of reactivity, resolution, adhesion to various members, and physical properties of the cured product. By further adding a cationic polymerization catalyst, a photo-cationic type photosensitive epoxy resin composition can be prepared.

[0026] The epoxy resin having two or more epoxy groups in one molecule is not particularly limited, and known epoxy resins can be used. Examples of commercially available bifunctional epoxy resins include "jER1004," "jER1007," "jER1009," "jER1010," and "jER1256" (trade names) manufactured by Mitsubishi Chemical Corporation, and "EPICLON 4050" and "EPICLON 7050" (trade names) manufactured by Dainippon Ink and Chemicals, Inc.

[0027] The epoxy resin preferably contains an epoxy resin having three or more functional epoxy groups in one molecule. The epoxy resin having three or more epoxy groups in one molecule is not particularly limited, and known epoxy resins can be used. Commercially available epoxy resins having three or more epoxy groups include "Celloxide 2021," "GT-300 series," and "GT-400 series" manufactured by Daicel Chemical Industries, Ltd. "," "EHPE-3150" (trade name), Mitsubishi Chemical Corporation's "jER1031S" and "157S70" (trade name), and Dainippon Ink and Chemicals Co., Ltd.'s "EPICLON N-695", "EPICLON N-865", "EPICLON HP-6000", "EPICLON HP-4710", "EPICLON HP-7200 series", and "EPICLON EXA-4816" (trade name).

[0028] The content of the epoxy resin in the photosensitive epoxy resin composition is not particularly limited, but is preferably 50 to 90 parts by mass, more preferably 55 to 85 parts by mass, and even more preferably 60 to 80 parts by mass, relative to the total mass of the photosensitive epoxy resin composition.

[0029] From the viewpoint of further improving the patterning property of the resin composition, it is more preferable to use an epoxy resin having tri- or higher functional epoxy groups that has high compatibility with the silicone compound described below. When an epoxy resin having low compatibility with the silicone compound is used, the patterning property of the resin composition can be improved by increasing the amount of component (D) added as a compatibilizer described below.

[0030] (B) Cationic polymerization catalyst The photosensitive epoxy resin composition contains a cationic polymerization catalyst, which is a catalyst for curing the epoxy resin.

[0031] The cationic polymerization catalyst can be appropriately selected from substances known as curing agents for epoxy resins. The epoxy resin composition can be polymerized by adding aromatic and aliphatic amines and acid anhydrides and curing them by heating.

[0032] In particular, from the viewpoint of more suitably modifying the surface of the substrate, it is preferable to use, for example, the following substances as the cationic polymerization catalyst. Preferred examples of such compounds include sulfonic acid compounds, diazomethane compounds, sulfonium salt compounds, iodonium salt compounds, disulfone compounds, etc. Commercially available products include "OPTOMER SP-170," "OPTOMER SP-172," and "SP-150" (trade names) manufactured by ADEKA CORPORATION, "BBI-103" and "BBI-102" (trade names) manufactured by Midori Chemical Co., Ltd., "IBPF," "IBCF," "TS-01," and "TS-91" (trade names) manufactured by Sanwa Chemical Co., Ltd., "CPI-210," "CPI-300," and "CPI-410" (trade names) manufactured by San-Apro Co., Ltd., and "Irgacure 290" (trade name) manufactured by BASF Japan Ltd.

[0033] The content of the cationic polymerization catalyst in the photosensitive epoxy resin composition is not particularly limited, but is preferably 1 to 20 parts by mass, and more preferably 5 to 10 parts by mass, relative to the total mass of the photosensitive epoxy resin composition.

[0034] The use of the cationic polymerization catalyst exhibits high reactivity with onium salts of Lewis acids activated by active energy rays, which allows low-temperature curing, and enables selective surface treatment by photolithography. Furthermore, the surface modification can be suitably performed on substrates that are difficult to maintain at high temperatures.

[0035] (C) Silicone Compound The photosensitive epoxy resin composition contains a silicone compound having one or more alkylsiloxane groups in one molecule, and the silicone compound having an alkylsiloxane group acts as a water-repellent component.

[0036] Silicone compounds having alkylsiloxane groups include various organically modified silicone compounds. The photosensitive epoxy resin composition can be appropriately selected from among various compounds. Since the photosensitive epoxy resin composition is an epoxy system, it is preferable to use an epoxy-modified silicone in which an epoxy group is introduced into a silicone compound. By introducing an epoxy group into the silicone compound, the silicone compound also reacts as the curing of the epoxy resin progresses, and strong water repellency durability can be obtained.

[0037] The epoxy-modified silicone is not particularly limited, and known epoxy-modified silicones can be used. For example, both-end, one-end, or side-chain epoxy-modified silicones can be used. Commercially available epoxy-modified silicones include "BY 16-839," "SF 8411," "SF-8413," and "SF-8421" (trade names) manufactured by Toray Dow Co., Ltd., and "X-22-163," "KF-105," "X-22-163A," "X-22-163B," "X-22-163C," "X-22-169AS," "X-22-169B," "X-22-173BX," "X-22-173DX," and "X-22-9002" (trade names) manufactured by Shin-Etsu Silicones Co., Ltd.

[0038] More preferably, a photosensitive resin composition that exhibits both patterning ability and water repellency can be provided by using a dual-end epoxy-modified silicone. That is, the silicone compound is preferably a dual-end epoxy-modified silicone compound in which both ends of a molecule are modified with epoxy groups.

[0039] By introducing epoxy groups into both ends of a molecule, it is possible to orient water-repellent groups (methyl groups) on the surface more efficiently than with side-chain modification. Also, since it is thought that the water-repellent groups on the outermost surface of the cured product are less likely to invert than with single-end modification, it is preferable to use a double-end epoxy-modified silicone compound.

[0040] The dual-end epoxy-modified silicone compound is not particularly limited and any known compound can be used, for example, commercially available products such as "X-22-163," "KF-105," "X-22-163A," "X-22-163B," and "X-22-163C" manufactured by Shin-Etsu Silicones Co., Ltd.

[0041] Among the dual-end epoxy-modified silicone compounds, it is more preferable to use a compound having an epoxy functional group equivalent of 150 or more and 3000 or less. Furthermore, a compound having an epoxy functional group equivalent of 490 or more and 1800 or less is even more preferable. It is believed that an epoxy functional group equivalent of 150 or more means that the reactivity of the terminal epoxy groups is not too high, making it easier for the water-repellent groups to orient on the surface during curing. On the other hand, an epoxy functional group equivalent of 3000 or less means that the main chain silicone structure is not too long, making it less likely to aggregate in the epoxy resin, which is thought to make it easier to improve patterning properties.

[0042] The content of the silicone compound relative to 100 parts by mass of the epoxy resin is preferably 0.5 parts by mass or more and 10 parts by mass or less. When the content is 0.5 parts by mass or more, sufficient water-repellent groups are present in the resin, making it easier to improve water repellency. Furthermore, when the content is 10 parts by mass or less, it is easier to further improve patterning properties. The content of the silicone compound in the photosensitive epoxy resin composition is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, relative to the total mass of the photosensitive epoxy resin composition.

[0043] (D) Alcohol or phenolic compounds The photosensitive epoxy resin composition contains an alcohol or phenol compound having a long-chain alkyl group with carbon atoms of 9 to 18 as a compatibilizer. The alcohol or phenol compound acts as a compatibilizer between the alcohol group or phenyl group, which has hydrophilic properties, and the long-chain alkyl group, which has hydrophobic (lipophilic) properties. By including the alcohol or phenol compound in the photosensitive epoxy resin composition, it is possible to improve the compatibility between the epoxy resin and the silicone compound. Furthermore, by using an alcohol or phenol compound in which the carbon number of the long-chain alkyl group is C9 to C18, it is possible to provide a resin composition that has patterning properties and water repellency.

[0044] The use of an alcohol or phenol compound having a long-chain alkyl group with 9 or more carbon atoms increases the boiling point and makes it less likely to volatilize during curing, thereby further improving the patterning properties of the photosensitive epoxy resin composition. Furthermore, the use of an alcohol or phenol compound having 18 or fewer carbon atoms allows the chain length to be kept from becoming too long, thereby enabling the composition to function satisfactorily as a compatibilizer.

[0045] Examples of alcohol or phenol compounds having a long-chain alkyl group with carbon atoms of C9 to C18 include lauryl alcohol (C12), myristyl alcohol (C14), cetanol (C16), stearyl alcohol (C18), and p-nonylphenol (the alkyl group in the side chain has a carbon number of C9). In order to further improve patterning properties and water repellency, it is more preferable to use lauryl alcohol, myristyl alcohol, or stearyl alcohol as a compatibilizer, i.e., the alcohol or phenol compound is preferably at least one selected from the group consisting of lauryl alcohol, myristyl alcohol, and stearyl alcohol.

[0046] The total content of the alcohol or phenol compound relative to 100 parts by mass of the epoxy resin is preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 20 parts by mass or more and 40 parts by mass or less, and even more preferably 25 parts by mass or more and 35 parts by mass or less.

[0047] When the total content of the alcohol or phenol compound is 10 parts by mass or more, the alcohol or phenol compound functions appropriately as a compatibilizer, making it difficult for segregation to occur in the epoxy resin or silicone compound, and further improving water repellency. Also, when the total content of the alcohol or phenol compound is 50 parts by mass or less, it is possible to suppress the residue of the alcohol or phenol compound after curing and further improve patterning properties.

[0048] If the total content of the alcohol or phenol compound exceeds 50 parts by mass, the patterning property tends to be reduced when an epoxy resin having low compatibility with silicone compounds is used as the component (A). That is, by setting the total content of the alcohol or phenol compound within the above range, a resin composition having excellent patterning property can be obtained even when an epoxy resin having low compatibility with silicone compounds is used.

[0049] The content of the alcohol or phenol compound in the photosensitive epoxy resin composition is not particularly limited, but is preferably 3 to 40 parts by mass, and more preferably 5 to 30 parts by mass, relative to the total mass of the photosensitive epoxy resin composition.

[0050] The photosensitive epoxy resin composition may contain components other than the above (A) to (D). For example, a silane coupling agent may be added to further improve adhesion. An example of a commercially available silane coupling agent is "A-187" (trade name) manufactured by Momentive Performance Materials, Inc.

[0051] The photosensitive resin composition can be used as a water repellent or a water repellent coating material to be applied to a location where there is a chance of contact with a solution or substance containing a component that impairs the adhesion of the water repellent, such as ink. In addition, the photosensitive resin composition can be used to make the surface of the ejection port of a liquid ejection head water repellent or water repellent. This allows for favorable ink treatment.

[0052] <Surface treatment method> A method for performing a surface treatment using a photosensitive epoxy resin composition will be described below. The photosensitive epoxy resin composition can be used, for example, for surface treatment of the ejection ports of a liquid ejection head having ejection ports for ejecting a recording liquid.

[0053] The first surface treatment method comprises, in this order: a first step of applying a photosensitive epoxy resin composition to a substrate and drying the composition to form a coating film; a second step of irradiating the surface of the substrate on which the coating film has been formed with active energy rays in a pattern through a mask; and a third step of dissolving and removing uncured photosensitive epoxy resin composition present in areas not irradiated with active energy rays in the second step. In order to complete the reaction of the photosensitive epoxy resin composition, it is desirable to further include a fourth step of carrying out a heat treatment or irradiation with active energy rays after the third step. Each step will be described in detail below.

[0054] <First step> In the first step, the substrate is not particularly limited. For example, a silicon wafer substrate can be used as the substrate. The substrate may be a substrate provided with ejection energy generating elements of a liquid ejection head.

[0055] The photosensitive epoxy resin composition is used in a state of being dissolved in an organic solvent, which may be any known organic solvent such as an aromatic solvent, an aliphatic hydrocarbon solvent, an ester solvent, an ether solvent, or a fluorine solvent. For example, propylene glycol monomethyl ether acetate (PGMEA) can be used as the organic solvent. The content of the photosensitive epoxy resin composition in the solution is not particularly limited, but is preferably 10 to 50 mass % and more preferably 30 to 40 mass % relative to the total mass of the solution.

[0056] The method for applying the photosensitive epoxy resin composition to the substrate is not particularly limited, and any known method can be used. For example, when the thickness of the applied photosensitive epoxy resin composition is small, such as a few μm, it can be applied using a conventional precision coating device such as a roll coater, a spin coater, or a spray coater.

[0057] The thickness of the photosensitive epoxy resin composition solution applied to the substrate is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and even more preferably 1 to 3 μm. The temperature and time for drying the photosensitive epoxy resin composition solution applied to the substrate can be adjusted appropriately depending on the substrate and the composition of the photosensitive epoxy resin composition. For example, drying at 100 to 200° C. for 5 to 30 minutes is preferred. The applied photosensitive epoxy resin composition solution is dried to remove the solvent from the solution, and a coating film containing the photosensitive epoxy resin composition is formed.

[0058] <Second process> The second step is a step of irradiating the surface of the coating film formed in the first step with active energy rays in a pattern through a mask. By irradiating through a mask, only the photosensitive resin composition in the area irradiated with the active energy rays can be selectively cured to form a desired shape.

[0059] In the second step, a mask having a flow path pattern (described later) formed thereon is used. The material of the mask is not particularly limited, and any material generally used as a photomask can be used. As the active energy rays, for example, ultraviolet rays containing a large amount of light with a wavelength of 250 to 480 nm can be used.

[0060] <Third process> The third step is a step of dissolving and removing the uncured photosensitive resin composition present in the area not irradiated with active energy rays in the second step by a development treatment using a developer. It is necessary to select a solvent suitable for the resin composition as the developer. Aromatic hydrocarbons, ketones, esters, glycol ethers, and mixtures thereof can be used as the developer. For example, a solution of methyl isobutyl ketone (MIBK) or NaOH can be used as the developer.

[0061] In the third step, the method of the development treatment is not particularly limited, and a known method can be used. For example, by immersing the substrate on which the pattern has been formed after the second step in a developer, the uncured resin composition present in the portion not irradiated with the active energy rays can be dissolved and removed.

[0062] If necessary, a fourth step may be carried out after the third step. In the fourth step, for example, the substrate after the third step is subjected to a heat treatment at a heating temperature of 100 to 200° C. Alternatively, the substrate may be further irradiated with active energy rays such as ultraviolet rays.

[0063] The second surface treatment method includes a method in which the photosensitive epoxy resin composition is molded into a pattern by a method different from the first surface treatment method. The second surface treatment method includes, in this order: a first step of applying a resin composition to a substrate and drying the composition to form a coating film; a second step of subjecting the entire surface of the substrate on which the coating film has been formed to a heat treatment or irradiating with active energy rays to polymerize and cure the entire surface of the photosensitive epoxy resin composition to obtain a cured product; and a third step of selectively irradiating the cured product with disintegrative active energy rays to mold the cured product into a pattern.

[0064] In order to complete the curing reaction, the second surface treatment method also preferably further comprises a fourth step of performing a heat treatment or irradiating with polymerizable active energy rays after the second step or the third step.

[0065] In the second method, the first and fourth steps can be carried out in the same manner as in the first surface treatment method described above. In the second step, the entire surface of the coating film formed in the first step is irradiated with heat or active energy rays to promote polymerization and harden it. The active energy rays that promote polymerization are ultraviolet light sources that are rich in light with wavelengths of 250 to 480 nm. Alternatively, polymerization may be promoted by heat treatment. For example, heat treatment at a heating temperature of 100 to 200°C is preferred.

[0066] In the third step, the cured product obtained in the second step is irradiated with decaying active energy rays so as to selectively remove desired portions of the product. As the decaying active energy source, light having a wavelength of 210 nm or less, such as an excimer laser, is used. By selectively removing desired portions of the cured product, the photosensitive epoxy resin composition can be molded into a desired pattern shape.

[0067] <Liquid ejection head> For application to liquid ejection heads, by treating the ejection port surface with the above-mentioned photosensitive epoxy resin composition by the above-mentioned method, a surface with excellent release properties is formed, which prevents strong ink adhesion and allows ink to be easily wiped off by cleaning treatment. As described above, the surface of a liquid ejection head can be treated by applying a photosensitive epoxy resin composition to the surface of the liquid ejection head and curing the composition. The photosensitive epoxy resin composition can also be cured in a pattern and used as the ejection opening of the liquid ejection head.

[0068] Many of the cleaning mechanisms installed in liquid ejection heads involve wiping with a rubber blade, suction with a pump, or blank ejection at a position outside the recording paper. However, with any of these methods, when the ink column drawn out by the ejection pressure turns into droplets, not all of the ink forms droplets, making it difficult to completely eliminate the adhesion of extra tiny ink droplets around the ejection orifice. However, if the tiny ink droplets can be easily removed by falling under their own weight or being sucked back into the ejection orifice, it can be assumed that there will be no impact on ink ejection.

[0069] By treating the surface of the ejection orifice with the photosensitive epoxy resin composition, the nozzle surface can be maintained in a constant surface condition, and adhesion of ink to the print head surface can be suppressed even when the print head is in contact with the recording liquid for a long period of time. As a result, it is possible to provide a liquid ejection head and a liquid ejection device that can maintain print quality at a high level for a long period of time.

[0070] 1 and 2 show the main parts of an example of the configuration of a liquid ejection head to which a photosensitive epoxy resin composition can be applied. Fig. 1 is a cross-sectional view taken along the flow path of the liquid ejection head, and Fig. 2 is a perspective view.

[0071] The liquid ejection head 13 has a configuration in which a member 14, which is formed by molding a cured product of a resin composition into a desired pattern and forming at least a flow path, is laminated and bonded onto a substrate 15 on which ejection energy generating elements and the like are arranged. The resin composition can be the above-mentioned photosensitive epoxy resin composition. Alternatively, a thermosetting resin composition and / or an active energy ray-curable resin composition can be used as the resin composition, and the surface of the cured product can be coated with the above-mentioned photosensitive epoxy resin composition to perform surface treatment.

[0072] The base 15 has a structure in which a heat storage layer 19, a heat generating resistor layer 18 made of a metal, electrodes 17a and 17b made of aluminum or the like, and a protective layer 16 are laminated in this order on the surface of a substrate 20 made of a material with good heat dissipation properties such as alumina. By passing current through the electrodes 17a and 17b, the ejection energy generating elements formed in the portions of the heat generating resistor layer 18 where no electrodes are laminated (portions within the region indicated by n) generate heat, and the thermal energy acts on the recording liquid 21 located above them.

[0073] During recording, the recording liquid 21 is filled up to the discharge port (orifice) 22, which is a minute opening at the end of the flow path of the member 14. In this state, when the electrodes 17a and 17b are energized in response to a recording signal, the region indicated by n suddenly heats up, causing film boiling to generate bubbles in the recording liquid 21 in contact with this region, and the resulting pressure causes the recording liquid 21 to be discharged from the discharge port 22 as small droplets 24, which then fly toward the recording medium 25.

[0074] In the liquid ejection head, the cured product of the photosensitive epoxy resin composition is applied as a water-repellent and ink-repellent agent to at least the openings of the ejection ports of the ejection surface 29 (the surface having the openings of the ejection ports), and this prevents the droplets from adhering to this surface and causing deviation in the ejection direction of the droplets. In other words, at least the openings of the ejection ports of the liquid ejection head are covered with the cured product of the photosensitive epoxy resin composition.

[0075] As described above, the discharge port may be formed using a cured product of the photosensitive epoxy resin composition. Alternatively, the discharge port may be formed using a different resin composition by applying the photosensitive epoxy resin composition to the surface of the discharge port. Surface treatment may also be carried out by applying and curing a material. That is, the method for manufacturing a liquid ejection head may include the steps of applying the above-mentioned photosensitive epoxy resin composition to the surface on which the ejection ports are formed, and curing the photosensitive epoxy composition by exposure to light and heat treatment.

[0076] The method for manufacturing a liquid ejection head may also include a step of performing a surface treatment on a substrate provided with ejection energy generating elements of the liquid ejection head by the surface treatment method including the above-mentioned first, second, and third steps. The surface treatment method may also include the above-mentioned fourth step, if necessary. The cured product of the photosensitive epoxy resin composition not only has excellent adhesion, but also does not lose its water repellency or adhesion even if the recording liquid (ink) contains an organic solvent, particularly a polar organic solvent.

[0077] Figure 3 shows an example of an inkjet recording apparatus, which is a liquid ejection apparatus incorporating a liquid ejection head such as that shown in Figure 2. As the liquid ejection head of the liquid ejection apparatus, a liquid ejection head that has been surface-treated with the above-mentioned photosensitive epoxy resin composition can be used.

[0078] In FIG. 3, 61 denotes a blade serving as a wiping member, one end of which is held by a blade holding member as a fixed end, forming a cantilever. Blade 61 is disposed at a position adjacent to the recording area of ​​the recording head, and in this example, is held in a form protruding into the recording head movement path. 62 denotes a cap, disposed at a home position adjacent to blade 61, which moves in a direction perpendicular to the recording head movement direction to abut against the ejection orifices for capping. Furthermore, 63 denotes an ink absorber disposed adjacent to blade 61, which, like blade 61, is held in a form protruding into the recording head movement path. Blade 61, cap 62, and ink absorber 63 constitute an ejection recovery unit 64, and blade 61 and ink absorber 63 remove moisture, dust, and the like from the ink ejection orifice surface.

[0079] Reference numeral 65 denotes a recording head that performs recording by an inkjet method, and has a configuration that ejects recording liquid such as ink using thermal energy, for example, as shown in Figures 1 and 2. Reference numeral 66 denotes a carriage that carries the recording head 65 and moves the recording head 65. The carriage 66 is slidably engaged with a guide shaft 67, and a portion of the carriage 66 is connected to a belt 69 (not shown) that is driven by a motor 68. This allows the carriage 66 to move along the guide shaft 67, i.e., to move to the recording area by the recording head 65 and its adjacent areas.

[0080] Reference numeral 51 denotes a paper feed section for inserting a recording medium, and 52 denotes a paper feed roller driven by a motor (not shown). With this configuration, the recording medium is fed to a position opposite the ejection port face of the recording head, and as recording progresses, the paper is ejected via paper ejection roller 53. In the above configuration, when the recording head 65 returns to the home position after recording is completed, the cap 62 of the ejection recovery section 64 is retracted from the movement path of the recording head, but the blade 61 protrudes into the movement path. As a result, the ejection port face of the recording head 65 is wiped.

[0081] Furthermore, when the cap 62 comes into contact with the ejection port surface of the recording head 65 to cap it, the cap 62 moves so as to protrude into the moving path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same positions as those during the wiping described above. As a result, the ejection port surface of the recording head 65 is wiped even during this movement.

[0082] The above-mentioned movement of the print head to the home position occurs not only at the end of printing or when ejection recovery is performed, but also at predetermined intervals while the print head is moving through the printing area for printing, and the above-mentioned wiping is performed in conjunction with this movement. In the case of an inkjet recording device, color recording can be performed using a recording head in which cyan, magenta, yellow, and black ink ejection ports are arranged in parallel within one head. Alternatively, recording heads for each color may be independently arranged in parallel. In these cases, each color may be ejected from a single ejection port, or each color may be ejected simultaneously from multiple ejection ports so that two or more droplets of the same color simultaneously adhere to the recording medium.

[0083] The liquid ejection head is surface-treated with a photosensitive epoxy resin, which is an ink-repellent material with the composition described above, so the nozzle surface can always be maintained in the same condition. As a result, even if the head is in contact with the recording liquid for a long period of time, inkjet ink does not adhere to the head, and any ink that does adhere is very easily removed with a cleaning wiper blade. This dramatically increases the durability of the print, and the print quality can be maintained for a long period of time. [Example]

[0084] The present invention will be described in more detail below by showing examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the number of parts is based on parts by mass.

[0085] The components used in the following Examples and Comparative Examples are shown in Tables 1 to 3. Note that CPS-410S (trade name, manufactured by San-Apro Co., Ltd.) was used as the (B) cationic polymerization catalyst in all Examples and Comparative Examples. [Table 1] In Table 1, the number of functional groups indicates the number of epoxy groups in one molecule of the epoxy resin.

[0086] [Table 2] In Table 2, "modified" indicates the type of modification of the epoxy-modified silicone. Functional group equivalent indicates the epoxy group functional group equivalent.

[0087] [Table 3] In Table 3, the carbon number indicates the number of carbon atoms in the alkyl group of the alcohol or phenol compound.

[0088] [Examples 1 to 49] Photosensitive epoxy resin compositions 1 to 49 shown in Table 4 were dissolved in a PGMEA solvent to prepare 30% by mass solutions. The resulting photosensitive epoxy resin solution was applied wet to a thickness of 1 μm on a silicon wafer substrate with a 5 μm-thick thermal oxide film using a spinner, and then the substrate was dried on a hot plate at 110°C for 5 minutes to remove the solvent. After removing the solvent, the surface of the substrate was exposed to 2 J / cm UV irradiation using a high-pressure mercury lamp through a mask. 2 The substrate was irradiated with ultraviolet light at an integrated dose of 10 ...

[0089] The substrates prepared by the above method were subjected to the following evaluations. <Patterning ability> The pattern of the cured product on the substrate was observed under a microscope (metallurgical microscope). All 100 cylindrical shapes formed were observed, and if the number of cylindrical shapes that were patterned without problems was 90 or more, it was evaluated as ◎, if it was 80 to less than 90, it was evaluated as 〇, if it was 70 to less than 80, it was evaluated as △, and if it was less than 70, it was evaluated as ×. Note that if the shape was cylindrical and not distorted, it was determined that the patterning was without problems. The evaluation results of patterning ability are shown in Tables 4 and 5.

[0090] <Initial water repellency> The static contact angle of pure water on the substrate on which the cylindrical pattern was formed was measured in a room temperature environment. The static contact angle was measured when pure water was dropped onto the substrate on which the cylindrical pattern was formed. The initial water repellency was evaluated based on the measured static contact angle using the following criteria: A static contact angle of 100 degrees or more was rated as ⊚, a static contact angle of 90 degrees or more but less than 100 degrees was rated as ◯, a static contact angle of 80 degrees or more but less than 90 degrees was rated as △, a static contact angle of 75 degrees or more but less than 80 degrees was rated as △', and a static contact angle of less than 75 degrees was rated as ×.

[0091] The evaluation results of the initial water repellency are shown in Tables 4 and 5. [Table 4]

[0092] [Table 5]

[0093] Examples 1 to 4, 6 to 10, 12 to 17, 19 to 21, 23 to 25, 34 to 37, 43, Particularly excellent patterning properties were observed in the compositions of Examples 44, 47, and 48. Particularly good initial water repellency was observed in the compositions of Examples 1, 3 to 5, 16 to 18, 27 to 32, 33 to 35, 39 to 41, and 43 to 45, and the compositions that were excellent in both patterning properties and initial water repellency were Examples 1, 3, 4, 16, 17, 34, 35, 43, and 44. The following is a discussion of each result.

[0094] Examples 1 to 10 show the results of compositions in which various silicone compounds (both-end epoxy-modified, one-end epoxy-modified, side-chain epoxy-modified) were used as component (C) as shown in Table 1, and added in an amount of 0.8 parts by mass per 100 parts by mass of the epoxy resin, component (A). Examples 1 to 5, which used a double-end epoxy-modified silicone, had better initial water repellency. This is because the introduction of epoxy groups into both ends of the silicone compound molecule allows the water-repellent groups (methyl groups) to be oriented on the surface more efficiently than with side-chain modification, and the water-repellent groups on the outermost surface of the cured product are less likely to invert than with a single-end type.

[0095] Furthermore, among the dual-end epoxy-modified silicone compounds, Examples 1, 3, and 4, which used a silicone compound with an epoxy functional group equivalent of 490 or more and 1800 or less, showed the best results. Examples 1, 3, and 4 had better initial water repellency than Example 2, which had a functional group equivalent of 200. This is presumably because the silicone compound used in Example 2 had highly reactive terminal epoxy groups, which made it difficult for the water-repellent groups to orient on the surface during curing.

[0096] Furthermore, Examples 1 to 4 had better patterning properties than Example 5, which had a functional group equivalent of 2,700. This is thought to be because the silicone compound used in Example 5 had a relatively long main chain silicone structure and was prone to agglomeration in the epoxy resin.

[0097] Examples 11 to 26 show the results of compositions in which the type of silicone compound of component (C) and the amount added relative to 100 parts by mass of epoxy resin were changed as shown in Table 1. For each silicone compound, when the amount added relative to 100 parts by mass of epoxy resin was 0.5 parts by mass or more and 10 parts by mass or less, the patterning properties and initial water repellency were particularly good.

[0098] Examples 12, 16, 20, and 24, in which the silicone compound was added in an amount of 0.5 parts by mass, had even better initial water repellency than Examples 11, 15, 19, and 23. This is thought to be due to the sufficient amount of water repellent groups contained in the photosensitive epoxy resin composition. On the other hand, Examples 13, 17, 21, and 25, in which the silicone compound was added in an amount of 10 parts by mass, had even better patterning properties than Examples 14, 18, 22, and 26.

[0099] Examples 27 to 32 show the results for compositions using trifunctional or difunctional epoxy resins as component (A) as shown in Table 1. Compared with Example 32, which used a difunctional epoxy resin, Examples 1 and 27 to 31, which used a trifunctional epoxy resin, showed better patterning properties. Furthermore, among the examples using a trifunctional epoxy resin, Example 27 tended to have slightly lower patterning properties, which is presumably due to its low compatibility with component (C). However, as in Examples 28 to 31, excellent patterning properties were obtained by adding a large amount of compatibilizer as component (D).

[0100] Examples 33 to 37 show the results for compositions using component (D), an alcohol or phenol compound having a long-chain alkyl group with C9 to C18, as shown in Table 1. Examples 1, 34, 35, and 36, which used lauryl alcohol, myristyl alcohol, and cetanol, each having 12 to 16 carbon atoms, showed the best results in terms of patterning ability and initial water repellency.

[0101] Examples 34 to 36, in which the alkyl group has 12 or more carbon atoms, are similar to Example 3, in which the alkyl group has 9 carbon atoms. The patterning properties were even better than those of Example 3. It is believed that the greater the number of carbon atoms in the alkyl group, the higher the boiling point and the less likely it is to volatilize during baking, resulting in better patterning properties.

[0102] On the other hand, Examples 33 to 35, in which the alkyl group had 16 or less carbon atoms, had even better initial water repellency than Example 36, in which the alkyl group had 18 carbon atoms. This is thought to be because the alkyl group chain length of component (D) used in Examples 33 to 35 was not too long, and the effect as a compatibilizer was fully exerted. Example 37 used a phenol compound, but Examples 33 to 35, in which an alcohol compound was used, had better initial water repellency.

[0103] In Examples 38 to 49, compositions were used in which the type of component (D) and the amount added relative to 100 parts by mass of epoxy resin were changed as shown in Table 1. Regardless of which compound was used, the best results were obtained when the amount added was 10 parts by mass or more and 40 parts by mass or less.

[0104] In Examples 39, 43, and 47, in which the amount of component (D) added was 10 parts by mass, the patterning properties and initial water repellency were even better than in Examples 38, 42, and 46, in which the amount added was less than 10 parts by mass. This is because the compatibilizer worked properly and no segregation occurred in the epoxy resin or silicone compound.

[0105] Furthermore, Examples 40, 44, and 48, in which the amount of component (D) added was 40 parts by mass, exhibited better patterning properties than Examples 41, 45, and 49, in which the amount added was greater than 40 parts by mass. When a large amount of component (D) was added, compatibility improved, but the proportion of component (D) remaining in the cured product after baking also increased. Therefore, it is believed that setting the amount of component (D) added to 40 parts by mass or less makes it easier to improve patterning properties.

[0106] Subsequently, an ink jet recording head was fabricated in the following manner. <Fabrication of Inkjet Recording Head> 4A, a positive photoresist 42 ("PMER AR-900" manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated to a thickness of 30 μm onto a substrate 41 previously provided with discharge energy generating elements, etc. Then, the substrate was pre-baked in an oven at 90° C. for 40 minutes to form a resist layer. The formed resist layer was patterned using a mask 43 as shown in Figures 4B and 4C to obtain a resist pattern 44. The symbol hv in Figure 4B indicates active energy rays. As shown in Figure 4D, a flow path forming material was prepared by mixing "EPICLON N-695" manufactured by Dainippon Ink and Chemicals Inc. with a curing agent (modified aliphatic amine, "Fujicure FXK 830" manufactured by Fuji Chemical Industry Co., Ltd.) at a base / curing agent ratio of 100 / 50 (weight ratio), and the mixture was laminated on the resist pattern 44 to a thickness of 100 µm to form a flow path forming material layer 45. After laminating the flow path forming material layer 45, the laminate was left at 25°C for 24 hours, and then subjected to a thermal curing treatment at 100°C for 2 hours to obtain a laminate. Next, the obtained laminate was immersed in a 3 wt% aqueous solution of sodium hydroxide to dissolve and remove the resist pattern 44. After dissolution and removal, the laminate was washed and dried to form liquid flow paths 46 (Figure 4E), and an inkjet recording head, which is a liquid ejection head, was obtained.

[0107] <Surface treatment of the liquid ejection surface> The photosensitive epoxy resin composition of Example 1 was applied to the ejection surface (the surface on which the ejection ports were formed) of the obtained ink jet recording head, and this was applied at 8 J / cm 2 The surface was treated by curing the inkjet recording head through UV exposure and heating at 200°C for 1 hour. After the surface treatment, the inkjet recording head was electrically wired as required and installed in a printer. The inkjet recording head was then subjected to the following long-term printing durability test using an inkjet ink consisting of pure water, glycerin, Food Black 2 (a water-soluble black dye), and N-methylpyrrolidone in a ratio of 70 / 15 / 3 / 12 (by weight). The photosensitive epoxy resin compositions of Examples 2 to 49 were also subjected to the same method as in Example 1. and a long-term printing durability test was carried out.

[0108] <Print durability test> In the printing durability test, a document and a pattern for evaluating ink droplet landing accuracy were printed on 100 sheets, and the final printed sample was evaluated for dot irregularities. Dot irregularity was measured using the following method. The 100th print sample was observed under a microscope, and the ratio of the number of off-center dots (dot position irregularity) to the total number of dots was calculated. The calculated value was evaluated according to the following criteria. Evaluation A: The dot position is distorted by less than 3%, and the characters are clear. Rating B: The dot position is distorted by 3% or more and less than 10%, and the effect on the quality of the characters is slight. C: Disorder of dot position is 10% or more but less than 50%, and the clarity of characters is reduced. Rating D: Dot position is out of alignment by 50% or more, and the quality of characters is significantly reduced.

[0109] The evaluation results are shown in Table 6. In the examples in which good results were obtained in both patterning ability and initial water repellency, the printing durability test also showed high evaluation results. [Table 6]

[0110] [Comparative Examples 1 and 2] Table 7 shows the formulations of the resin compositions of the comparative examples and the results of evaluation of the patterning properties and initial water repellency in the same manner as in the examples. In Comparative Example 1, 1-octanol, which has 8 carbon atoms, was added as component (D), but the patterning properties were inferior to those of the Examples. This is thought to be because the evaporation rate of component (D) was faster than the curing rate of the resin, resulting in a decrease in the compatibility of the cured product. In Comparative Example 2, arachidyl alcohol having 20 carbon atoms was added as component (D), but the initial water repellency was inferior to that of the Examples. This is thought to be because the hydrophobic alkyl group has a long chain, which disrupts the balance with the hydrophilic hydroxyl group, preventing it from being effective as a compatibilizer.

[0111] Furthermore, the ejection surface of an inkjet recording head was subjected to surface treatment in the same manner as in Examples using the resin compositions of Comparative Examples 1 and 2. The inkjet recording heads thus obtained were subjected to a print durability test in the same manner as in Examples, and the results are shown in Table 8. The evaluation results for both were D. [Table 7] [Table 8]

[0112] The present disclosure relates to the following configurations and methods. (Configuration 1) (A) an epoxy resin having two or more epoxy groups in one molecule; (B) a cationic polymerization catalyst, (C) a silicone compound having one or more alkylsiloxane groups in one molecule, and (D) an alcohol or phenol compound having a long-chain alkyl group having a carbon number of C9 to C18; A photosensitive epoxy resin composition comprising at least (Configuration 2) 2. The photosensitive epoxy resin composition according to claim 1, wherein the silicone compound is a double-end epoxy-modified silicone compound in which both ends of a molecule are modified with epoxy groups. (Configuration 3) 3. The photosensitive epoxy resin composition according to claim 1, wherein the epoxy functional group equivalent of the dual-end epoxy-modified silicone compound is 150 or more and 3,000 or less. (Configuration 4) 4. The photosensitive epoxy resin composition according to any one of configurations 1 to 3, wherein the content of the silicone compound is 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the epoxy resin. (Configuration 5) 5. The photosensitive epoxy resin composition according to any one of Aspects 1 to 4, wherein the epoxy resin comprises an epoxy resin having three or more functional epoxy groups in one molecule. (Configuration 6) 6. The photosensitive epoxy resin composition according to any one of configurations 1 to 5, wherein the alcohol or phenol compound is at least one selected from the group consisting of lauryl alcohol, myristyl alcohol, and cetanol. (Configuration 7) 7. The photosensitive epoxy resin composition according to any one of Configurations 1 to 6, wherein the total content of the alcohol or phenol compound is 10 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the epoxy resin. (Method 8) a first step of applying the photosensitive epoxy resin composition according to any one of Configurations 1 to 7 to a substrate and drying it to form a coating film; a second step of irradiating the surface of the substrate on which the coating film has been formed with active energy rays in a pattern through a mask; and a third step of dissolving and removing the uncured photosensitive epoxy resin composition present in the area not irradiated with the active energy rays; A surface treatment method comprising the steps of: (Method 9) The surface treatment method according to Method 8, further comprising a fourth step of performing a heat treatment or irradiation with active energy rays after the third step. (Method 10) a first step of applying the photosensitive epoxy resin composition according to any one of Configurations 1 to 7 to a substrate and drying it to form a coating film; a second step of subjecting the entire surface of the substrate on which the coating film has been formed to heat treatment or active energy ray irradiation to polymerize and cure the photosensitive epoxy resin composition to obtain a cured product; and a third step of selectively irradiating the cured product with disintegrating active energy rays to form the cured product into a pattern; A surface treatment method comprising the steps of: (Method 11) The surface treatment method according to Method 10, further comprising a fourth step of performing a heat treatment or irradiation with active energy rays after the second step or the third step. (Method 12) a step of applying the photosensitive epoxy resin composition according to any one of Configurations 1 to 7 to a surface of a liquid ejection head having ejection ports, the surface having the ejection ports formed thereon; curing the photosensitive epoxy resin composition by exposure to light and heat treatment; A method for manufacturing a liquid ejection head, comprising: (Method 13) A method for manufacturing a liquid ejection head, comprising: A step of carrying out the surface treatment method according to any one of Methods 8 to 11, A method for manufacturing a liquid ejection head, wherein the substrate is a substrate on which ejection energy generating elements of the liquid ejection head are provided. (Configuration 14) A liquid ejection head having an ejection port for ejecting a recording liquid, wherein at least the opening of the ejection port is covered with a cured product made of the photosensitive epoxy resin composition according to any one of Configurations 1 to 7. (Configuration 15) A liquid ejection device comprising the liquid ejection head according to Configuration 14. [Explanation of symbols]

[0113] 13 liquid ejection head, 14 member having liquid flow path formed thereon, 15 base body, 16 protective layer, 17a and 17b electrodes, 18 heating resistor, 19 heat storage layer, 20 substrate, 21 recording liquid, 22 ejection port, 24 droplet, 25 recording medium, 29 ejection surface, 41 base material, 42 positive photoresist, 43 mask, 44 resist pattern, 45 material for forming liquid flow path, 46 liquid flow path

Claims

1. (A) an epoxy resin having two or more epoxy groups in one molecule; (B) a cationic polymerization catalyst, (C) a silicone compound having one or more alkylsiloxane groups in one molecule, and (D) an alcohol or phenol compound having a long-chain alkyl group having a carbon number of C9 to C18; A photosensitive epoxy resin composition comprising at least

2. 2. The photosensitive epoxy resin composition according to claim 1, wherein the silicone compound is a double-end epoxy-modified silicone compound in which both ends of a molecule are modified with epoxy groups.

3. 3. The photosensitive epoxy resin composition according to claim 2, wherein the epoxy functional group equivalent of the dual-end epoxy-modified silicone compound is 150 or more and 3,000 or less.

4. 2. The photosensitive epoxy resin composition according to claim 1, wherein the content of the silicone compound is 0.5 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the epoxy resin.

5. 2. The photosensitive epoxy resin composition according to claim 1, wherein the epoxy resin comprises an epoxy resin having three or more functional epoxy groups in one molecule.

6. 2. The photosensitive epoxy resin composition according to claim 1, wherein the alcohol or phenol compound is at least one selected from the group consisting of lauryl alcohol, myristyl alcohol, and cetanol.

7. 2. The photosensitive epoxy resin composition according to claim 1, wherein the total content of the alcohol or phenol compound is 10 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the epoxy resin.

8. A first step of applying the photosensitive epoxy resin composition according to any one of claims 1 to 7 to a substrate and drying it to form a coating film; a second step of irradiating the surface of the substrate on which the coating film has been formed with active energy rays in a pattern through a mask; and a third step of dissolving and removing the uncured photosensitive epoxy resin composition present in the area not irradiated with the active energy rays; A surface treatment method comprising the steps of:

9. The surface treatment method according to claim 8 , further comprising a fourth step of performing a heat treatment or irradiation with active energy rays after the third step.

10. A first step of applying the photosensitive epoxy resin composition according to any one of claims 1 to 7 to a substrate and drying it to form a coating film; a second step of subjecting the entire surface of the substrate on which the coating film has been formed to heat treatment or active energy ray irradiation to polymerize and cure the photosensitive epoxy resin composition to obtain a cured product; and a third step of selectively irradiating the cured product with disintegrating active energy rays to form the cured product into a pattern; A surface treatment method comprising the steps of:

11. The surface treatment method according to claim 10 , further comprising a fourth step of performing a heat treatment or irradiating with active energy rays after the second step or the third step.

12. A step of applying the photosensitive epoxy resin composition according to any one of claims 1 to 7 to a surface of a liquid ejection head having ejection ports, the surface having the ejection ports formed thereon; curing the photosensitive epoxy resin composition by exposure to light and heat treatment; A method for manufacturing a liquid ejection head, comprising:

13. A method for manufacturing a liquid ejection head, comprising: The method of claim 8, A method for manufacturing a liquid ejection head, wherein the substrate is a substrate on which ejection energy generating elements of the liquid ejection head are provided.

14. A liquid ejection head having an ejection port for ejecting a recording liquid, characterized in that at least the opening of the ejection port is covered with a cured product made of the photosensitive epoxy resin composition according to any one of claims 1 to 7.

15. A liquid ejection apparatus comprising the liquid ejection head according to claim 14.

Images