Liquid dispensing head and method for manufacturing a liquid dispensing head

Abstract

A liquid dispensing head with excellent ink resistance and scratch resistance. [Solution] A liquid dispensing head having a cured product of a liquid-repellent coating material, wherein the coating material comprises a condensation product of a silane mixture containing a hydrolyzable silane compound (a) having a specific structure having a perfluoropolyether group and a cyclic polyorganosiloxane group, and a hydrolyzable silane compound (b) having an epoxy group.

Description

[Technical Field]

[0001] This disclosure relates to a liquid dispensing head and a method for manufacturing a liquid dispensing head. [Background technology]

[0002] In various fields, it is common practice to apply water-repellent coatings to the surfaces of components requiring water resistance and ink repellency to obtain these properties, and resin materials and coatings for this purpose have been developed. For example, fluoroolefins and fluorine-based coatings containing perfluoro groups are extremely stable both thermally and chemically, and in addition to weather resistance, water resistance, chemical resistance, and solvent resistance, they also exhibit excellent release properties, abrasion resistance, and water repellency, and are widely used in a variety of applications.

[0003] To give one specific example, in an inkjet liquid ejection head that ejects ink as small droplets from an ejection port and adheres them to paper or other materials to record or form images, the ejection port should ideally have the following characteristics. (1) The remaining ink in the droplet-formed ink column is quickly re-stored inside the nozzle. (2) Ink droplets adhering to the surface can be easily swept away by the cleaning operation. (3) The ink droplets adhering to the surface provide excellent scratch resistance during cleaning operations and paper transport. (4) During repeated droplet formation and ink refilling, a meniscus is formed at the nozzle surface. (5) The normal direction of the meniscus is the discharge direction. (6) Even with inks that have low surface tension, or under low negative pressure conditions, the nozzle has sufficient interfacial tension, i.e., a contact angle, to form a meniscus.

[0004] The reason these performance requirements are necessary for the nozzle is that they directly relate to printing performance. If ink or other recording liquid adheres to the area around the nozzle, it can cause a deviation in the direction of droplet ejection (flight), making high-precision printing impossible. To prevent liquid from adhering to the area around the nozzle, which causes such deviations in the ejection direction, a method of applying a water-repellent treatment to the surface on which the nozzle is formed is known. For example, Patent Document 1 discloses a liquid-repellent layer made of a fluorine-containing coating material containing a condensation product of a hydrolyzable silane compound. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2014-205739 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] Incidentally, the demand for liquid repellency in the liquid-repellent layer described above has become extremely high in recent years, due to the rapid improvement in the performance of inkjet printers. Specifically, the types and amounts of solvents contained in inkjet inks have increased, and there is a need for a liquid-repellent layer that can withstand such inks. Furthermore, inkjet heads need to have the ink on the head surface removed by wiping, and with the extension of the lifespan of inkjet heads, there is a demand for a liquid-repellent layer with better abrasion resistance than conventional layers. Achieving such ink resistance and abrasion resistance is not easy, and the liquid-repellent layer described in Patent Document 1 may be insufficient to meet the performance requirements of modern inkjet heads.

[0007] Therefore, this disclosure relates to a liquid ejection head with excellent ink resistance and scratch resistance, and liquid ejection. This is intended for use in manufacturing the head. [Means for solving the problem]

[0008] The present disclosure relates to a liquid ejection head having a cured product of a liquid-repellent coating material, where the coating material contains a hydrolyzable silane compound (a) represented by the following formula (1) having a perfluoropolyether group and a cyclic polyorganosiloxane group, a hydrolyzable silane compound (b) having an epoxy group, and relates to a liquid ejection head containing a condensation product of a silane mixture containing <00000-six6>

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] According to the present disclosure, it is possible to provide a liquid ejection head excellent in ink resistance and scratch resistance, and a method for manufacturing a liquid ejection head.

Brief Description of the Drawings

[0010] [Figure 1] FIG. 1 is a perspective view of a main part of a configuration example of a liquid ejection head. [Figure 2] [[ID=E]]FIG. 2 is a cross-sectional view of the liquid ejection head. [Figure 3] FIGS. 3A to 3E show an example of a method for manufacturing the liquid ejection head. [Figure 4] FIGS. 4A to 4F show an example of a method for manufacturing the liquid ejection head. MODE FOR CARRYING OUT THE INVENTION …In the present disclosure, descriptions such as "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise specified. When numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined. In the present disclosure, descriptions such as "at least one selected from the group consisting of XX, YY, and ZZ" mean any one 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. When XX is a group, a plurality may be selected from XX, and the same applies to YY and ZZ.

[0012] [Liquid-repellent coating material] The liquid ejection head according to the present disclosure has a cured product of a liquid-repellent coating material such as a water-repellent material. The liquid-repellent coating material includes a condensation product of a silane mixture containing a hydrolyzable silane compound. The hydrolyzable silane compound includes a hydrolyzable silane compound (a) represented by formula (1) having a perfluoropolyether group and a cyclic polyorganosiloxane group, and a hydrolyzable silane compound (b) having an epoxy group. [[ID=3F]]

[0013] ​​In a liquid-repellent coating material, the liquid-repellent and antifouling function is exhibited by a hydrolyzable silane compound (a) represented by formula (1), which has a perfluoropolyether group and a cyclic polyorganosiloxane group. The hydrolyzable silane compound (a) has a long-chain polyfluoropolyether group represented by formula (2), which improves its slipperiness and significantly enhances wipe durability. Furthermore, the cyclic polyorganosiloxane group suppresses the aggregation of fluorine components and has the effect of orienting fluorine groups on the surface. In addition, the durability of the coating film can be enhanced by using a hydrolyzable silane compound (b) having an epoxy group in combination with the hydrolyzable silane compound (a). The present disclosure will be described in detail below.

[0014] ((a) Component: A hydrolyzable silane compound represented by formula (1) having a perfluoropolyether group and a cyclic polyorganosiloxane group (a)) The coating material comprises a hydrolyzable silane compound (a) represented by the following formula (1), which has a perfluoropolyether group and a cyclic polyorganosiloxane group.

[0015] [ka]

[0016] In formula (1), p is an integer of 1 or more, for example, 1 to 5, preferably 1 to 3, more preferably 1 or 2. q is an integer of 1 or more, for example, 1 to 5, preferably 1 to 3, more preferably 2 or 3. p+q is 4 or more, for example, 4 to 10, preferably 4 to 8, more preferably 4 to 6. From the viewpoint of smoothing the surface when a coating film is formed on the coating material and suppressing development residue, it is particularly preferable that p+q is 4. Furthermore, from the viewpoint of further improving liquid repellency and abrasion resistance, it is even more preferable that p is 1 or 2 and q is 2 or 3, and it is particularly preferable that p is 1 and q is 3. The arrangement of the structure of the parentheses with p and the structure of the parentheses with q may be in blocks or random.

[0017] Xa represents an alkyl group, for example, an alkyl group having 1 to 3 carbon atoms (preferably 1 or 2 carbon atoms, more preferably 1 carbon atom). Xb represents an alkyl group, for example, having 1 to 3 carbon atoms (preferably 1 or 2, more preferably). It is the alkyl group in 1). Rp is a perfluoropolyether group represented by the following formula (2). Y is a hydrolyzable silyl group represented by the following formula (3).

[0018] A perfluoropolyether group is a group consisting of one or more structures containing a perfluoroalkyl group and an oxygen atom (ether bond). Specifically, a perfluoropolyether group is represented by the following formula (2). Perfluoropolyether groups can provide liquid repellency and slipperiness. [ka]

[0019] In formula (2), r is 20 to 30, preferably 23 to 30, more preferably 25 to 30, or may be 23 to 27. s is 20 to 30, preferably 23 to 30, more preferably 25 to 30, or may be 23 to 27. r and s are, for example, integers. The arrangement of the parentheses with r and the parentheses with s may be in blocks or random. It is particularly preferable that r = s = 25. A represents an organic group, preferably an alkylene group having 1 to 6 carbon atoms (more preferably 2 to 4 carbon atoms). It is more preferable that A is -C3H6-. That is, the group represented by formula (2) is preferably represented by the following formula (5).

[0020] [ka]

[0021] Furthermore, cyclic polyorganosiloxane groups are groups in which Si atoms and oxygen atoms are alternately bonded, forming a ring. Specifically, cyclic polyorganosiloxane groups are the cyclic structures included in formula (1). Cyclic polyorganosiloxane groups provide liquid-repellent properties and inhibit the aggregation of fluorine components.

[0022] As described above, in formula (1), Y is a hydrolyzable silyl group represented by the following formula (3). [ka]

[0023] In formula (3), c is an integer less than or equal to 3, preferably 2 or 3, and more preferably 3. B is an organic group having 1 to 12 carbon atoms, for example, an alkylene group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms). From the viewpoint of smoothing the surface when a coating film is formed on the coating material and suppressing development residue, it is more preferable that B is an alkylene group having 4 to 10 carbon atoms. From the viewpoint of further improving liquid repellency and abrasion resistance, it is even more preferable that B is an alkylene group having 6 to 9 carbon atoms, and even more preferable that B is an alkylene group having 8 carbon atoms. Q is a hydrolyzable substituent, and each is independently, for example, a halogen atom, an alkoxy group, a hydroxyl group, an amino group, or a hydrogen atom. The number of carbon atoms in the alkoxy group is, for example, 1 to 6, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. Q is preferably an alkoxy group. R is a non-hydrolyzable substituent, and examples include, independently, a methyl group, an ethyl group or other C1-C3 alkyl group, or a phenyl group.

[0024] Y preferably has the structure shown in formula (6) below. [ka]

[0025] Of the hydrolyzable silane compounds (a), compounds represented by the following formula (I) are particularly preferred from the viewpoint of liquid repellency, slipperiness, and inhibition of fluorine aggregation. [ka]

[0026] The structure of hydrolyzable silane compound (a) can be analyzed by nuclear magnetic resonance (NMR). Specifically, 1 H, 13 C, 19 F, 29 By combining this with Si-NMR, structural analysis becomes possible.

[0027] (Hydrolyzable silane compound having an epoxy group (b)) The hydrolyzable silane compound (b) having an epoxy group is not particularly limited, but compounds represented by the following formula (9) are preferred.

[0028] [ka]

[0029] In formula (9), Rc is a non-hydrolyzable substituent having an epoxy group, represented for example by -EZ. Z is an epoxy group, a glycidyl group, a glycidoxy group, or an epoxycycloalkyl group (preferably a glycidoxy group or an epoxycyclohexyl group), and E is an alkylene group having 1 to 8 carbon atoms (preferably 2 to 8). R is a non-hydrolyzable substituent, for example, independently of each other, an alkyl group having 1 to 3 carbon atoms such as a methyl group or an ethyl group, or a phenyl group. X is a hydrolyzable substituent. b is an integer from 0 to 2. b is preferably 0 or 1, and more preferably 0.

[0030] In formula (9), Rc is preferably a glycidoxypropyl group, an epoxycyclohexylethyl group, and the like, with the glycidoxypropyl group being more preferred. R can be an alkyl group such as a methyl group or an ethyl group, or a phenyl group. X can be a halogen atom, an alkoxy group, a hydroxyl group, an amino group, a hydrogen atom, etc. The number of carbon atoms in the alkoxy group is, for example, 1 to 6, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0031] Among these, X is preferably an alkoxy group such as a methoxy group, ethoxy group, or propoxy group, from the viewpoint that the group removed by hydrolysis does not inhibit the cationic polymerization reaction and the reactivity can be easily controlled. Alternatively, a compound in which some has been converted to a hydroxyl group by hydrolysis or which has formed a siloxane bond by dehydration condensation may also be used.

[0032] Specific examples of compounds represented by formula (9) in which X is an alkoxy group include at least one selected from the group consisting of glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, epoxycyclohexylethyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropyldimethylmethoxysilane, glycidoxypropyldimethylethoxysilane, etc. One of these compounds may be used, or two or more may be used in combination.

[0033] A more preferred specific example of the hydrolyzable silane compound (b) having an epoxy group is at least one selected from the group consisting of the compound represented by formula (7) and the compound represented by formula (8), from the viewpoint of reactivity with the photopolymerizable resin layer used as a substrate. [ka]

[0034] The structure of hydrolyzable silane compounds (b) containing epoxy groups can be analyzed by nuclear magnetic resonance (NMR). Specifically, 1 H, 13 C, 29 By combining this with Si-NMR, structural analysis becomes possible.

[0035] ((c) component: other hydrolyzable silane compounds) The silane mixture in the coating material may also contain a hydrolyzable silane compound (c), which is a different hydrolyzable silane compound from component (a) and component (b). The hydrolyzable silane compound (c) is not particularly limited, but from the viewpoint of fluorine surface orientation, it is preferably a hydrolyzable silane compound represented by the following formula (10) that has a fluorine-containing group other than a perfluoropolyether group.

[0036] [ka]

[0037] In formula (10), Rf has one or more fluorine atoms. That is, Rf is an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 3 to 8 carbon atoms) or an aryl group (preferably having 6 to 10 carbon atoms, more preferably 6 carbon atoms) in which one or more hydrogen atoms are substituted with fluorine atoms. R is a non-hydrolyzable biodegradable substituent, and X is a hydrolyzable substituent. a is an integer of 1 or 2, preferably 1. b is an integer from 0 to 2, preferably 0. a+b is an integer from 1 to 3.

[0038] In formula (10), Rf is preferably an alkyl or aryl group in which 1 to 15 hydrogen atoms are substituted with fluorine atoms, and more preferably an alkyl or aryl group in which 3 to 10 (more preferably 3 to 5) hydrogen atoms are substituted with fluorine atoms. When Rf is an alkyl group, it is preferable that 40 to 80% of the hydrogen atoms from the terminal end of the alkyl chain are substituted with fluorine atoms. When Rf is an aryl group (more preferably a phenyl group), it is preferable that all hydrogen atoms are substituted with fluorine atoms.

[0039] The presence of fluorine atoms in Rf prevents the separation of the perfluoropolyether group from other components and prevents the aggregation of the perfluoropolyether group. Specific examples of Rf include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, isobutyl groups, tert-butyl groups, phenyl groups, naphthyl groups, etc., in which some or all of the hydrogen atoms are substituted with fluorine atoms.

[0040] In formula (10) above, R can be an alkyl group such as a methyl group, ethyl group, or propyl group, or an aryl group such as a phenyl group. X can be a halogen atom, or an alkoxy group such as a methoxy group, ethoxy group, or propoxy group.

[0041] (c) Specific preferred examples of components include the following readily available compounds (C10) to (C17). 3,3,3-Trifluoropropyltrimethoxysilane (C10) Trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (C11) Trimethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (C12) Trimethoxy(pentafluorophenyl)silane (C13) 3,3,3-Trifluoropropyltriethoxysilane (C14) Triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (C15) Triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (C16) Triethoxy(pentafluorophenyl)silane (C17) These compounds may be used individually or in combination of two or more.

[0042] In the hydrolyzable silane compound contained in the silane mixture, the content of hydrolyzable silane compound (a) having a perfluoropolyether group and a cyclic polyorganosiloxane group is, for example, 0.005 to 1.0 mol%, preferably 0.01 to 0.80 mol%, more preferably 0.03 to 0.50 mol%, and even more preferably 0.04 to 0.20 mol%.

[0043] (a) If component is present in an amount of 0.01 mol% or more, more sufficient liquid repellency can be achieved. Furthermore, if component (a) is present in an amount of 0.80 mol% or less, aggregation of fluorine atoms can be prevented more effectively, and the occurrence of irregularities and developer residue on the surface of the liquid-repellent coating can be further suppressed.

[0044] In the hydrolyzable silane compound contained in the silane mixture, the content of hydrolyzable silane compound (b) having an epoxy group is, for example, 40.0 to 99.995 mol%, preferably 45.0 to 99.90 mol%. The hydrolyzable silane compound contained in the silane mixture may contain, for example, 0.00 to 50.00 mol% of hydrolyzable silane compound (c), preferably 20.00 to 60.00 mol%.

[0045] In the hydrolyzable silane compound contained in the silane mixture, the content of hydrolyzable silane compound (a) having a perfluoropolyether group and a cyclic polyorganosiloxane group is, for example, 0.2 to 10.0% by mass, preferably 0.5 to 9.0% by mass, and more preferably 0.7 to 3.0% by mass. In the hydrolyzable silane compound contained in the silane mixture, the content of hydrolyzable silane compound (b) having an epoxy group is, for example, 20.0 to 99.8% by mass, and preferably 25.0 to 99.5% by mass.

[0046] In the coating material of this disclosure, each hydrolyzable silane compound is used not individually, but as a condensation product of a silane mixture containing the hydrolyzable silane compound. This results in good film formation during application and a stable, smooth coating film. Furthermore, while the coating material can be applied on a photopolymerizable resin layer and cured together with the photopolymerizable resin layer to enhance durability, its nature as a condensation product allows for control over compatibility with the resin layer and patterning characteristics.

[0047] The condensation reaction of hydrolyzable silane compounds can be carried out by heating them in a solvent in the presence of water, thereby allowing the hydrolysis and condensation reactions to proceed. By appropriately controlling the temperature, time, concentration, pH, etc., of the hydrolysis and condensation reactions, the desired degree of condensation can be obtained. The conditions are not particularly limited as they vary depending on the hydrolyzable silane compound used, and suitable conditions should be selected for the hydrolyzable silane compound being used.

[0048] Furthermore, metal alkoxides, acids, alkalis, etc., can be used as catalysts during hydrolysis and condensation reactions. Examples of metal alkoxides include aluminum alkoxide, titanium alkoxide, zirconia alkoxide, and their media (such as acetylacetone complexes). These metal alkoxides may be used individually or in combination of two or more.

[0049] Furthermore, adjusting the pH with acids or alkalis is also useful. However, when using an alkaline catalyst, solids such as gels may precipitate in the solution, so an acid catalyst is preferred. In other words, it is preferable for the silane mixture to contain an acid catalyst. Specific examples include carboxylic acids such as acetic acid, glycolic acid, and formic acid. These may be used individually or in combination of two or more. These organic acids are added during the reaction, but since they are often present in trace amounts in the hydrolyzable silane compounds used as raw materials, the acid may be added separately.

[0050] In this disclosure, since multiple hydrolyzable silane compounds are used in combination, if the rates of hydrolysis and condensation reactions differ significantly depending on the type of hydrolyzable silane compound, the faster-reacting compound may undergo condensation while the slower-reacting compound remains unreacted. Therefore, from the viewpoint of reacting each hydrolyzable silane compound as uniformly as possible, it is preferable to use a catalyst such as an acid.

[0051] The condensation product can be synthesized in a solvent containing hydroxyl groups, carbonyl groups, ether bonds, etc. That is, the silane mixture may contain a solvent. Specific examples of solvents include alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; ethers such as propylene glycol monomethyl ether, diglyme, and tetrahydrofuran; and glycols such as diethylene glycol. These may be used individually or in combination of two or more. Furthermore, since water is used in the synthesis, alcohols with high water solubility are preferred. Therefore, when carrying out the reaction under reflux, it is preferable to use an organic solvent with a boiling point of 50 to 100°C.

[0052] The amount of water used in the reaction is preferably 0.5 to 3 equivalents, and more preferably 0.8 to 2 equivalents, relative to the hydrolyzable substituent of the hydrolyzable silane compound. A water amount of 0.5 equivalents or more allows for sufficient reaction rates in the hydrolysis and condensation reactions. A water amount of 3 equivalents or less suppresses the precipitation of the hydrolyzable silane compound having a perfluoropolyether group.

[0053] [Liquid-repellent coating] The liquid dispensing head includes a liquid-repellent coating. The liquid-repellent coating is a cured product of a liquid-repellent coating material. The liquid-repellent coating is, for example, a cured product of condensation products contained in the coating material. The liquid-repellent coating can be obtained, for example, by using a liquid-repellent coating material and curing the condensation products contained in the liquid-repellent coating material with a photopolymerization initiator. That is, the liquid-repellent coating may be a cured product of a coating material containing condensation products and a photopolymerization initiator.

[0054] To cure the condensation product having epoxy groups and silanol groups by light irradiation, it is preferable to use a photopolymerization initiator. As a photopolymerization initiator, onium salt compounds such as sulfonium salts and iodonium salts, sulfonic acid compounds, and photoacid generators such as diazomethane compounds can be used.

[0055] Commercially available products include "ADEKA Optomer SP-170," "ADEKA Optomer SP-172," and "SP-150" (product names) from ADEKA Corporation, "BBI-103" and "BBI-102" (product names) from Midori Chemical Co., Ltd., and "IBPF," "IBCF," "TS-01," and "TS-91" (product names) from Sanwa Chemical Co., Ltd. One of these photopolymerization initiators may be used, or two or more may be used in combination.

[0056] When a photoacid generator is used as a photopolymerization initiator, it is preferable because the acid promotes not only the dehydration condensation reaction of epoxy groups but also that of silanol groups. Furthermore, light absorbers, sensitizers, etc., can be used to improve patterning properties. By adding these photopolymerization initiators to a liquid-repellent coating material, a coating solution for liquid-repellent coatings can be prepared. Furthermore, if the substrate for the liquid-repellent coating (e.g., a photopolymerizable resin composition) contains a photoacid generator, the acid moves from the substrate to the coating material and diffuses, allowing the coating film to harden even without adding a photoacid generator to the liquid-repellent coating material.

[0057] A coating film for a liquid-repellent coating can be formed by applying a coating solution, for example, prepared by dissolving a liquid-repellent coating material and a photopolymerization initiator in an appropriate solvent, using a coating apparatus. General-purpose equipment such as spin coaters, die coaters, slit coaters, and spray coaters can be used as the coating apparatus. Furthermore, dip coating can also be applied by adjusting the concentration of the liquid-repellent coating material.

[0058] The concentration of condensation products in the coating solution is appropriately determined depending on the composition of the condensation products, the coating method, and the intended use. However, the concentration of condensation products in the coating solution is preferably 0.1 to 20% by mass, and more preferably 1 to 15% by mass. If the concentration of condensation products is within the above range, sufficient liquid repellency and durability can be obtained, and uniform liquid repellency can be obtained across the entire surface of the coating film.

[0059] The film thickness is preferably 50 to 10,000 nm, and more preferably 80 to 5,000 nm. A film thickness of 50 nm or more provides uniform liquid repellency and sufficient durability. A film thickness of 10,000 nm or less suppresses the deterioration of patterning characteristics such as pattern deformation and a decrease in resolution.

[0060] After creating a coating film on a substrate using any method, the film is cured by light irradiation and, if necessary, by light or heat. By using a combination of cationic polymerization of epoxy groups and thermal condensation polymerization of silanes (silanol groups) in the curing reaction of the coating film, high durability can be achieved even with thin films.

[0061] Furthermore, by performing pattern exposure during light irradiation, a liquid-repellent coating can be applied to fine areas. Surface treatment can be performed. When pattern exposure is performed, curing can be carried out by further strong light irradiation or heating after development. By performing appropriate curing treatment and completely hardening the unreacted substrate, durability can be increased.

[0062] Furthermore, the coating material may also contain epoxy compounds other than the hydrolyzable silane compound (b) having an epoxy group. That is, the liquid-repellent coating may be a cured product of the coating material containing the coating material, an epoxy compound other than the hydrolyzable silane compound (b), and a photopolymerization initiator. Including the epoxy compound can increase the viscosity of the coating solution and increase the film thickness.

[0063] Examples of epoxy compounds other than hydrolyzable silane compounds include bisphenol A type epoxy resins and novolac type epoxy resins. Commercially available products include Daicel Corporation's "Celoxide 2021," "GT-300 series," "GT-400 series," and "EHPE3150" (product names), Japan Epoxy Resin Co., Ltd.'s "157S70" (product name), Dainippon Ink and Chemicals, Inc.'s "Epiclon N-695" (product name), and Nippon Kayaku Co., Ltd.'s "SU-8" (product name). These may be used individually or in combination of two or more.

[0064] The epoxy equivalent of epoxy compounds other than hydrolyzable silane compound (b) is preferably 2000 or less, and more preferably 1000 or less. An epoxy equivalent of 2000 or less ensures sufficient crosslinking density during the curing reaction, preventing a decrease in the glass transition temperature of the cured product and resulting in high adhesion. The epoxy equivalent of the epoxy compound is preferably 50 or more. Note that the epoxy equivalent values ​​were measured according to JIS K-7236.

[0065] Furthermore, when forming patterns using coating materials, high fluidity of the material can reduce resolution; therefore, epoxy compounds other than hydrolyzable silane compounds (b) are preferred to be solid at 35°C or below. In addition to the materials mentioned above, commercially available negative resists such as "SU-8 series" and "KMPR-1000" (product names) from Kayaku Microchem, and "TMMR S2000" and "TMMF S2000" (product names) from Tokyo Ohka Kogyo Co., Ltd. can also be used as the epoxy compound.

[0066] The condensation product is a material with excellent compatibility with epoxy compounds. Therefore, similar to the photopolymerization initiators mentioned above, epoxy compounds other than hydrolyzable silane compound (b) may be added to the coating material or used as a substrate. Even when epoxy compounds other than hydrolyzable silane compound (b) are used as a substrate, the compatibility between the coating material and the substrate allows for the same effect as when the epoxy compound is directly added to a liquid-repellent coating material.

[0067] Liquid-repellent coatings can be used for applications such as coating fine patterns on liquid dispensing heads.

[0068] "Method for manufacturing a liquid-repellent coating" The method for manufacturing a liquid-repellent coating can be used for coating various known materials, but can be applied, for example, to a method for manufacturing a liquid dispensing head. The method for manufacturing a liquid-repellent coating can be applied, for example, to a method for manufacturing a liquid dispensing head in which the coating material contains, in addition to the condensation product of a silane mixture, a photopolymerizable resin and a photopolymerization initiator. The method for manufacturing a liquid dispensing head in this embodiment is, for example, as follows.

[0069] As an example of a method for manufacturing a liquid-repellent coating, a method for manufacturing a liquid dispensing head (A) is: (1) Condensation product of the above silane mixture, Photopolymerization initiator, and Epoxy compounds other than (b) hydrolyzable silane compounds that can form photopolymerizable resins, A step of applying a coating material containing the coating material to a substrate (and drying it if necessary) to form a coating film of the coating material, (2) A step of exposing and developing the coating film of the coating material, (3) The process includes a step of curing the coating film after exposure and development to form the cured product of the coating material.

[0070] In method (A), the liquid-repellent coating material includes a photopolymerization initiator and an epoxy compound other than the hydrolyzable silane compound (b). Therefore, the liquid-repellent coating obtained by curing the coating material exhibits high liquid-repellent and antifouling properties, durability, and smoothness.

[0071] Furthermore, this disclosure includes embodiments in which the liquid dispensing head contains a cured product of a photopolymerizable resin containing a photopolymerization initiator. In this case, it is preferable that a cured product of a liquid-repellent coating material is formed on the cured product of the photopolymerizable resin in the liquid dispensing head. A method for manufacturing the liquid dispensing head of this embodiment is as follows, for example.

[0072] In other words, as an example of a method for manufacturing a liquid-repellent coating, the method for manufacturing a liquid dispensing head (B) is: (1) A step of forming a photopolymerizable resin layer by applying a photopolymerizable resin mixture containing an epoxy compound other than a hydrolyzable silane compound (b) capable of forming a photopolymerizable resin and a photopolymerization initiator onto a substrate and drying it, (2) A step of applying a coating material onto the photopolymerizable resin layer to form a coating film of the coating material, (3) A step of simultaneously exposing and developing the photopolymerizable resin layer and the coating film, (4) The process includes a step of curing the photopolymerizable resin layer and the coating film together after exposure and development.

[0073] Step (4) allows for the formation of a cured coating material and a cured photopolymerizable resin. In this manufacturing method (B), the underlying photopolymerizable resin layer contains an epoxy compound other than a hydrolyzable silane compound and a photopolymerization initiator, and the coating film of the coating material formed thereon is partially compatible with the photopolymerizable resin layer. For this reason, the method may include a step to remove unexposed areas and form a fine pattern, similar to the method described above. Furthermore, when the coating film of the coating material and the photopolymerizable resin layer are partially compatible, a clear interface may not be observed between the photopolymerizable resin layer and the cured coating material.

[0074] This document describes a liquid dispensing head to which a photopolymerizable resin layer and a coating material can be applied. Liquid ejection heads are used in liquid ejection devices such as inkjet recording devices. An example of the configuration of a liquid ejection head is shown in Figure 1. A cross-sectional view of the liquid ejection head at point A and B in Figure 1 is shown in Figure 2.

[0075] The liquid discharge head comprises a photosensitive resin layer 4 that forms a discharge port 9 and a flow path 8, and a substrate 1. The photosensitive resin layer 4 that forms the discharge port 9 and the flow path 8 is provided on the substrate 1. A supply port 3 for supplying liquid to the flow path is formed on the substrate 1. The surface of the substrate on the side where the flow path 8 and discharge port 9 are provided has an energy generating element 2. The liquid is supplied from the supply port 3 to the flow path 8, given energy by the energy generating element 2, discharged from the discharge port 9, and lands on a recording medium such as paper.

[0076] For example, the discharge port 9 is formed by the discharge port forming layer 7. The flow channel 8 is formed by the flow channel forming layer 5. The photosensitive resin layer 4 includes the discharge port forming layer 7 and the flow channel forming layer 5. A layer for improving adhesion (not shown) may be placed between the discharge port forming layer 7 and the flow channel forming layer 5.

[0077] Regarding the manufacturing method (B) described above, the photosensitive resin layer 4 can be the photopolymerizable resin layer described above. The liquid dispensing head may have a cured coating material 10 on the surface where the dispensing port 9 is formed, for example, as shown in Figures 1 and 2. For example, the dispensing port forming layer 7 is a cured photopolymerizable resin, and the cured coating material 10 is formed on the surface of the dispensing port forming layer 7. When the photosensitive resin layer and the coating material are compatible, a clear interface may not be observed between the photosensitive resin layer 4 and the cured coating material 10.

[0078] Furthermore, with respect to the above-described manufacturing method (A), at least one of the photopolymerizable resin layers, the nozzle-forming layer 7 and the channel-forming layer 5, can be a cured product of the coating material. The nozzle-forming layer 7 and the channel-forming layer 5 may be cured products of the coating material, in which case the entire photosensitive resin layer 4 has good liquid repellency and abrasion resistance.

[0079] Figures 3A to 3E are schematic cross-sectional views showing an example of the liquid dispensing head manufacturing method (A) described above. First, a photosensitive resin layer 4-1 for forming a channel-forming layer 5 is formed on the substrate 1 having the energy generating element 2 and the supply port 3 (Figure 3A). The photosensitive resin layer 4-1 may be the coating material in the manufacturing method (A) described above. If an adhesion-improving layer (not shown) is to be formed between the discharge port-forming layer 7 and the channel-forming layer 5, the adhesion-improving layer material may be formed on the photosensitive resin layer 4-1. Next, the photosensitive resin layer 4-1 is pattern-exposed through a mask 14 having a channel pattern to form a channel-forming layer 5 for creating the channel 8 (Figure 3B).

[0080] Next, a photosensitive resin layer 4-2 is formed on the channel forming layer 5 (Figure 3C). The photosensitive resin layer 4-2 is pattern-exposed through a mask 16 having an outlet pattern to form an outlet forming layer 7 for creating the outlet 9 (Figure 3D). Then, the unexposed areas are removed with an organic solvent or the like, and the coating material is cured to obtain a liquid discharge head (Figure 3E). The photosensitive resin layer 4-2 may be the coating material in the manufacturing method (A) described above. For example, at least one or both of the photosensitive resin layer 4-1 and the photosensitive resin layer 4-2 may be the coating material in the manufacturing method (A) described above.

[0081] Figures 4A to 4F are schematic cross-sectional views showing an example of the manufacturing method (B) of the liquid dispensing head described above. First, a photosensitive resin layer 4-1 for forming a channel-forming layer 5 is formed on the substrate 1 having the energy generating element 2 and the supply port 3 (Figure 4A). The photosensitive resin layer 4-1 may be a photopolymerizable resin layer in manufacturing method (B), a coating material in manufacturing method (A) described above, or a known photosensitive resin layer. If an adhesion-improving layer (not shown) is to be formed between the discharge port-forming layer 7 and the channel-forming layer 5, the adhesion-improving layer material may be formed on the photosensitive resin layer 4-1. Next, the photosensitive resin layer 4-1 is pattern-exposed through a mask 14 having a channel pattern to form a channel-forming layer 5 for creating the channel 8 (Figure 4B).

[0082] Next, a photosensitive resin layer 4-2 is formed on the channel forming layer 5 (Figure 4C). The photosensitive resin layer 4-2 is the photopolymerizable resin layer in manufacturing method (B) (step (1) in manufacturing method (B)). Then, a coating material is applied on top of the photosensitive resin layer 4-2 to form the coating material. A coating film 10-1 of the material is formed (Figure 4D) (Step (2) in manufacturing method (B)).

[0083] Next, the photosensitive resin layer 4-2 and the coating film 10-1 are simultaneously pattern-exposed through a mask 16 having an outlet pattern to form an outlet-forming layer 7 for creating the outlet 9 (Figure 4E). Then, the unexposed areas are removed with an organic solvent or the like, and the photosensitive resin layer 4-1, the photosensitive resin layer 4-2, and the coating film 10-1 are cured to obtain a liquid discharge head (Figure 4F). By curing the photosensitive resin layer 4-2 and the coating film 10-1, a cured product 10 (liquid-repellent layer 10) of the coating material on top of the cured product 7 (outlet-forming layer 7) of the photopolymerizable resin can be obtained. [Examples]

[0084] Examples and comparative examples are shown below, but this disclosure is not limited to these. Various measurements and evaluations were performed by the methods described below.

[0085] (Appearance of the coating) The development residue and surface condition of the coating film were observed using a scanning electron microscope (product name: S-4300, manufactured by Hitachi High-Technologies Corporation). The appearance of the coating film was evaluated according to the following criteria. [Developing residue] A: No development residue was found. B: Tiny development residues smaller than 0.3 μm were observed. C: Development residue larger than 0.3 μm was observed. [Surface condition] A: The surface is smooth. B: Tiny irregularities of 0.3 μm or less are observed on the surface. C: Surface irregularities larger than 0.3 μm are observed.

[0086] (Pure water contact angle) To evaluate the fabricated coating film, the dynamic receding contact angle θr in relation to pure water was measured using a micro-contact angle meter (product name: DropMeasure, manufactured by Microjet Co., Ltd.) to assess its initial water repellency. Furthermore, to evaluate the durability of the coating film surface, the coating film was immersed in an alkaline aqueous solution with pH=10, held at 60°C for one week, rinsed with water, and then θr in relation to pure water was measured. Furthermore, to evaluate durability against abrasion (abrasion resistance evaluation), an aqueous solution containing carbon black was sprayed onto the coating film, and the wiping operation was performed 2000 times using an HNBR (hydrogenated nitrile rubber) blade. The θr value relative to pure water was then measured. The measured θr value was evaluated according to the following criteria.

[0087] S:θr is 90° or greater A: θr is between 85° and 90° B:θr is between 80° and 85° C:θr is less than 80°

[0088] [Example 1] The condensation product was prepared by the following method: (a) 0.1 g (0.05 mol%) of the compound represented by formula (C1) as component, and (b) 9.6 g (99.95 mol%) of the compound represented by formula (C2), 8.9 g of propylene glycol monomethyl ether (hereinafter PGME), 22.2 g of ethanol (hereinafter EtOH), and 0.21 g of aqueous acetate at a concentration of 4200 ppm were stirred in a flask equipped with a condenser at room temperature for 5 minutes. Subsequently, a condensation product was prepared by heating under reflux for 24 hours. The solution of the condensation product was diluted fourfold with an ethanol / butanol mixed solvent to prepare a water-repellent coating material.

[0089] Next, 100 parts by mass of epoxy compound (product name: EHPE-3150, manufactured by Daicel Corporation) and 6 parts by mass of photoacid generator (product name: SP-172, manufactured by ADEKA Corporation) were dissolved in 80 parts by mass of xylene, a solvent, to obtain a photopolymerizable resin composition. This photopolymerizable resin composition was applied to a substrate by spin coating to a thickness of 10 μm, and a photopolymerizable resin layer was formed by heat treatment at 90°C for 5 minutes. The aforementioned water-repellent coating material was applied to a photopolymerizable resin layer using a slit coater and then heat-treated at 90°C. The coating thickness of the water-repellent coating material after heat treatment was equivalent to 0.5 μm. However, due to compatibility with the underlying photopolymerizable resin layer, the interface was not visible, and therefore the thickness of the coating material film on the photopolymerizable resin layer could not be measured.

[0090] Next, the photopolymerizable resin composition layer and the water-repellent coating material were irradiated with i-rays through a mask having an evaluation pattern. Afterward, they were heat-treated at 90°C for 4 minutes. Development was performed with a mixture of MIBK (methyl isobutyl ketone) and xylene, followed by rinsing with isopropanol to form the desired pattern. The coating was further cured by heating at 200°C for 1 hour to obtain a water-repellent coating. The results are shown in Table 1. The photopolymerizable resin layer with the water-repellent coating had a smooth appearance, and the pure water contact angle was high both initially and after the durability test.

[0091] [Chemical formula]

[0092] [Example 2] A condensation product was synthesized in the same manner as in Example 1 except that the compound (C1) was changed to the compound of the following formula (C3), and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Further, a waterproof coating was obtained in the same procedure as in Example 1. The results are shown in Table 1. Similar to Example 1, the surface of the water-repellent coating material was smooth, and the initial contact angle showed a high value. However, since the hydrolyzable silyl group of the component (a) was less than that in Example 1, the reactivity with the underlying photopolymerizable resin layer was low , and it is considered that the pure water contact angle after the durability test decreased slightly. [Chemical formula] R p1 And Y1 are the same as (C1).

[0093] [Example 3] A condensation product was synthesized in the same manner as in Example 1 except that the compound (C1) was changed to the compound of the following formula (C4), and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Further, a waterproof coating was obtained in the same procedure as in Example 1. The results are shown in Table 1. The fluorine content of the component (a) was higher compared to (C1), and it is considered that the fluorine components aggregated and slight irregularities were observed on the coating film appearance. Also, although the initial contact angle showed a high value, since the hydrolyzable silyl group of the component (a) was less than that of (C1) and (C2), the reactivity with the underlying photopolymerizable resin layer was low, and it is considered that the pure water contact angle after the durability test decreased more than that in Example 2. [Chemical formula] R p1 And Y1 are the same as (C1).

[0094] [Example 4] Except for changing compound (C1) to the compound of formula (C5) below, the condensation product was synthesized in the same manner as in Example 1, and a water-repellent coating material was prepared by diluting it with an ethanol / butanol mixed solvent. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. The results are shown in Table 1. The number of Si in the cyclic polyorganosiloxane was higher than in Example 1, which is thought to have reduced the surface orientation and dispersibility of fluorine, resulting in a decrease in the appearance of the coating film and the contact angle after both the initial and durability tests compared to Example 1. [ka] R p1 And Y1 is the same as (C1).

[0095] [Example 5] Except for changing compound (C1) to the compound of formula (C6) below, the condensation process is the same as in Example 1. The compound was synthesized and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. The results are shown in Table 1. The coating film had a smooth appearance and showed a high initial contact angle. However, compared to Example 1, the alkyl group bonded to the hydrolyzable silyl group was shorter, which is thought to have reduced reactivity with the underlying photopolymerizable resin layer, resulting in a lower contact angle after the durability test. [ka] R p1 This is the same as (C1).

[0096] [Example 6] Except for changing compound (C1) to the compound of formula (C7) below, the condensation product was synthesized in the same manner as in Example 1, and a water-repellent coating material was prepared by diluting it with an ethanol / butanol mixed solvent. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. The results are shown in Table 1. The coating film had a smooth appearance, and both the initial contact angle and the contact angle after wipe durability were high. However, compared to Example 1, the alkyl group bonded to the hydrolyzable silyl group was longer and had higher molecular mobility, which is thought to have caused the contact angle to decrease after ink durability. [ka] R p1 This is the same as (C1).

[0097] [Examples 7 and 8] In Examples 7 and 8, the amount of component (a) added was changed to the values ​​shown in Table 1. Aside from these changes, the condensation product was synthesized in the same manner as in Example 1, and the water-repellent coating material was prepared by dilution with an ethanol / butanol mixed solvent. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. In Example 7, the amount of component (a) added was less than in Example 1, resulting in a smooth coating surface, but the contact angles were slightly lower both initially and after the durability test. Conversely, in Example 8, the amount of component (a) added was higher, resulting in high contact angles both initially and after the durability test, but the fluorine component aggregated, causing some unevenness in the coating surface.

[0098] [Examples 9 and 10] In Examples 9 and 10, component (b) was obtained from compound (C2) using the following formula (C8), ( Except for changing C9), the condensation product was synthesized in the same manner as in Example 1, and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. In Example 9, even when component (b) was changed, the coating film appearance remained smooth, and the contact angles were high both initially and after the durability test. In Example 10, the compound was changed to one with a cyclohexyl skeleton (C9). The reactivity with the underlying photosensitive resin layer was slightly lower, and the contact angle after the wipe durability test decreased slightly, but the coating film appearance remained smooth, and the contact angles were high both initially and after ink immersion. [ka]

[0099] [Examples 11, 12] In Example 11, 0.4 parts by mass of a photoacid generator (product name: SP-172, manufactured by ADEKA Corporation) was added to 100 parts by mass of the water-repellent coating material prepared in Example 1 to prepare a water-repellent coating material. The water-repellent coating material was applied to the substrate by spin coating and treated at 90°C to obtain a coating film with a thickness of 0.5 μm. The results are shown in Table 1. Similar to Example 1, the coating film had a smooth appearance, and the contact angles were high both initially and after the durability test.

[0100] In Example 12, 0.8 parts by mass of a photoacid generator (product name: SP-172, manufactured by ADEKA Corporation) and 7 parts by mass of an epoxy compound (product name: EHPE-3150, manufactured by Daicel Corporation) were added to 100 parts by mass of the water-repellent coating material prepared in Example 1 to prepare a water-repellent coating material. The water-repellent coating material was applied to the substrate by spin coating and treated at 90°C to obtain a coating film with a thickness of 0.5 μm. The results are shown in Table 1. Similar to Example 1, the coating film had a smooth appearance, and the contact angles were high both initially and after the durability test.

[0101] [Examples 13-20] In Examples 13-20, 0.1 g (0.05 mol%) of the compound represented by formula (C1) as component (a), 12.99 g (49.98 mol%) of the compound represented by formula (C2) as component (b), 49.97 mol% of component (C) listed in Table 1, 8.9 g of propylene glycol monomethyl ether (hereinafter PGME), 22.2 g of ethanol (hereinafter EtOH), and 0.21 g of aqueous acetic acid at a concentration of 4200 ppm were stirred in a flask equipped with a condenser at room temperature for 5 minutes. The condensation product was then prepared by heating under reflux for 24 hours. A solution of the condensation product was diluted fourfold with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. A waterproof coating was then obtained using the same procedure as in Example 1. The results are shown in Table 1.

[0102] Examples 13 to 20 were obtained by adding component (c) of the following formulas (C10) to (C17) compared to Example 1. However, similar to Example 1, the coating surface was smooth, and the contact angles were high both initially and after durability testing. 3,3,3-Trifluoropropyltrimethoxysilane (C10) Trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (C11) Trimethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (C12) Trimethoxy(pentafluorophenyl)silane (C13) 3,3,3-Trifluoropropyltriethoxysilane (C14) Triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane (C15) Triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane (C16) Triethoxy(pentafluorophenyl)silane (C17)

[0103] [Comparative Example 1] (a) Except for changing component (C1) to the formula (C18) below, the condensation product was synthesized in the same manner as in Example 1, and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. Note that in Comparative Example 1, Novec HFE7200 (hydrofluoroether, manufactured by 3M) was used instead of PGME. The results are shown in Table 1. Compound (C18) lacks a cyclic polyorganosiloxane and has a short polyfluoropolyether group, resulting in a significant decrease in the contact angle to below 30° (unmeasurable level) after durability testing.

[0104] [ka]

[0105] [Comparative Example 2] (a) Except for changing component (C1) to the following formula (C19), the condensation product was synthesized in the same manner as in Example 1, and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. The results are shown in Table 1. Although compound (C19) has long-chain polyfluoropolyether groups, it lacks cyclic polyorganosiloxanes, resulting in reduced fluorine orientation to the surface. Consequently, the contact angle, both initially and after durability testing, was significantly reduced to below 30° (unmeasurable level).

[0106] [ka] R p1 And Y1 is the same as (C1).

[0107] [Comparative Example 3] (a) Except for changing component (C1) to the following formula (C20), the condensation product was synthesized in the same manner as in Example 1, and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. The results are shown in Table 1. Although compound (C20) contains a cyclic polyorganosiloxane, its polyfluoropolyether group is short and has low slipperiness, resulting in a significant decrease in the contact angle to below 30° (unmeasurable level) after durability testing.

[0108] [ka] Y1 is the same as (C1).

[0109] [Comparative Example 4] (a) Except for changing component (C1) to the following formula (C21), the condensation product was synthesized in the same manner as in Example 1, and diluted with an ethanol / butanol mixed solvent to prepare a water-repellent coating material. Furthermore, a waterproof coating was obtained using the same procedure as in Example 1. The results are shown in Table 1. Compound (C21) contains a cyclic polyorganosiloxane, but because the perfluoropolyether group is longer-chained than in Example 1, it exhibits superior slipperiness, but fluorine is less likely to orient on the surface, and the dispersibility of the fluorine component is also reduced. As a result, irregularities were observed in the appearance of the coating film, and the contact angles both in the initial and after durability tests were low, below 30° (unmeasurable level).

[0110] [ka] Y1 is the same as (C1).

[0111] [Table 1]

[0112] In the table, component (a) represents a hydrolyzable silane compound (a) represented by formula (1), component (b) represents a hydrolyzable silane compound (b) having an epoxy group, and component (c) represents ( (a) shows component (b), and (c) shows another hydrolyzable silane compound different from component (b). In Examples 1-10 and 13-20, and Comparative Examples 1-4, the coating material was applied to a photopolymerizable resin layer on a substrate. In Examples 11 and 12, the coating material was applied directly to the substrate.

[0113] This disclosure relates to the following configuration and method. (Composition 1) A liquid dispensing head having a cured product of a liquid-repellent coating material, The coating material is A hydrolyzable silane compound (a) represented by the following formula (1), having a perfluoropolyether group and a cyclic polyorganosiloxane group, (b) A hydrolyzable silane compound having an epoxy group, A liquid dispensing head characterized by containing a condensation product of a silane mixture containing [a specific compound]. TIFF2026065462000026.tif34153(In expression (1), p is an integer greater than or equal to 1, q is an integer greater than or equal to 1, p+q is greater than or equal to 4, and the arrangement of the structure of parentheses with p and the structure of parentheses with q may be a block or random. Xa represents an alkyl group. Xb represents an alkyl group. Rp is a perfluoropolyether group represented by the following formula (2). Y has a structure containing a hydrolyzable silyl group represented by the following formula (3). TIFF2026065462000027.tif8153(In formula (2), r is between 20 and 30, and s is between 20 and 30. The arrangement of the structures in the brackets with r and the structures in the brackets with s may be in a block or random. A represents an organic group.) TIFF2026065462000028.tif8153 (In formula (3), c is an integer less than or equal to 3, B is an organic group having 1 to 12 carbon atoms, Q is a hydrolyzable substituent, and R is a non-hydrolyzable substituent.) (Configuration 2) The liquid dispensing head according to configuration 1, wherein the hydrolyzable silane compound (b) having an epoxy group is a compound represented by the following formula (9). TIFF2026065462000029.tif8153(In formula (9), Rc is a non-hydrolyzable substituent having an epoxy group and is represented as -EZ, where Z is an epoxy group, a glycidyl group, a glycidoxy group or an epoxycycloalkyl group, and E is an alkylene group having 1 to 8 carbon atoms. R is a non-hydrolyzable substituent, independently of any other alkyl group having 1 to 3 carbon atoms or a phenyl group. X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, or a hydrogen atom, and b is an integer from 0 to 2. (Composition 3) The aforementioned p is 1 to 5, the aforementioned q is 1 to 5, and the aforementioned p+q is 4 to 10. The above Xa is an alkyl group having 1 to 3 carbon atoms, and Xb is an alkyl group having 1 to 3 carbon atoms. , The above A is an alkylene group having 1 to 6 carbon atoms, The aforementioned c is 2 or 3, The above B is an alkylene group having 1 to 12 carbon atoms, Each of the aforementioned Qs is independently a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, or a hydrogen atom. The liquid dispensing head according to configuration 1 or 2, wherein R is an alkyl group having 1 to 3 carbon atoms, or a phenyl group. (Composition 4) A liquid dispensing head according to any of configurations 1 to 3, wherein in formula (1), p is 1 and q is 3. (Composition 5) A liquid dispensing head according to any of configurations 1 to 4, wherein A in formula (2) is -C3H6-. (Composition 6) A liquid dispensing head according to any of configurations 1 to 5, wherein in equation (2) above, r = s = 25. (Composition 7) A liquid dispensing head according to any of configurations 1 to 6, wherein Y has the structure shown in the following formula (6). TIFF2026065462000030.tif8153 (composition 8) A liquid dispensing head according to any one of configurations 1 to 7, wherein the hydrolyzable silane compound contained in the silane mixture has a content of 0.01 to 0.80 mol% of the hydrolyzable silane compound (a). (Composition 9) The liquid dispensing head according to any one of configurations 1 to 8, wherein the hydrolyzable silane compound (b) having the epoxy group is at least one selected from the group consisting of compounds represented by formula (7) and compounds represented by formula (8). TIFF2026065462000031.tif35153 (configuration 10) The liquid dispensing head contains a cured product of a photopolymerizable resin containing a photopolymerization initiator. A liquid dispensing head according to any one of configurations 1 to 9, wherein a cured product of the liquid-repellent coating material is formed on the cured product of the photopolymerizable resin. (Composition 11) A liquid dispensing head according to any one of configurations 1 to 9, wherein the coating material further contains a photopolymerizable resin and a photopolymerization initiator. (Method 12) A method for manufacturing a liquid dispensing head as described in configuration 10, The manufacturing method is (1) A step of applying the photopolymerizable resin mixture, which includes an epoxy compound other than the hydrolyzable silane compound (b) capable of forming the photopolymerizable resin, and the photopolymerization initiator, onto a substrate and drying it to form a photopolymerizable resin layer, (2) A step of applying the coating material onto the photopolymerizable resin layer to form a coating film of the coating material, (3) A step of simultaneously exposing and developing the photopolymerizable resin layer and the coating film, (4) After exposure and development, a step of curing the photopolymerizable resin layer and the coating film together, A method for manufacturing a liquid dispensing head, characterized by including the following: (Method 13) A method for manufacturing a liquid dispensing head as described in configuration 11, The manufacturing method is (1) Condensation product of the silane mixture, The aforementioned photopolymerization initiator, and Epoxy compounds other than the hydrolyzable silane compound (b) that can form the aforementioned photopolymerizable resin, A step of applying the coating material containing the coating material to a substrate to form a coating film of the coating material, (2) A step of exposing and developing the coating film of the coating material, (3) A step of curing the coating film after exposure and development to form the cured product of the coating material, A method for manufacturing a liquid dispensing head, characterized by including the following: [Explanation of Symbols]

[0114] 1. Substrate, 2. Energy generating element, 3. Supply port, 4. Photosensitive resin layer, 5. Channel forming layer, 7. Discharge port forming layer, 8. Channel, 9. Discharge port, 10. Liquid-repellent layer

Claims

1. A liquid dispensing head having a cured product of a liquid-repellent coating material, The coating material is A hydrolyzable silane compound (a) represented by the following formula (1), having a perfluoropolyether group and a cyclic polyorganosiloxane group, A hydrolyzable silane compound (b) having an epoxy group, A liquid dispensing head characterized by containing a condensation product of a silane mixture containing [a specific compound]. (In equation (1), p is an integer greater than or equal to 1, q is an integer greater than or equal to 1, p + q is greater than or equal to 4, and the arrangement of the structure of the parentheses with p and the structure of the parentheses with q may be a block or random.) Xa represents an alkyl group. Xb represents an alkyl group. Rp is a perfluoropolyether group represented by the following formula (2). Y has a structure containing a hydrolyzable silyl group represented by the following formula (3). (In formula (2), r is between 20 and 30, and s is between 20 and 30. The arrangement of the structures in the brackets with r and the structures in the brackets with s may be in a block or random. A represents an organic group.) (In formula (3), c is an integer less than or equal to 3, B is an organic group having 1 to 12 carbon atoms, Q is a hydrolyzable substituent, and R is a non-hydrolyzable substituent.)

2. The liquid dispensing head according to claim 1, wherein the hydrolyzable silane compound (b) having an epoxy group is a compound represented by the following formula (9). (In formula (9), Rc is a non-hydrolyzable substituent having an epoxy group, represented as -E-Z, where Z is an epoxy group, a glycidyl group, a glycidoxy group, or an epoxycycloalkyl group, and E is an alkylene group having 1 to 8 carbon atoms. R is a non-hydrolyzable substituent, independently of any other alkyl group having 1 to 3 carbon atoms or a phenyl group. X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, or a hydrogen atom, and b is an integer from 0 to 2.

3. The above p is 1 to 5, the above q is 1 to 5, and the above p + q is 4 to 10. The above Xa is an alkyl group having 1 to 3 carbon atoms, and Xb is an alkyl group having 1 to 3 carbon atoms. The above A is an alkylene group having 1 to 6 carbon atoms, The above c is 2 or 3, The above B is an alkylene group having 1 to 12 carbon atoms, Each of the aforementioned Qs independently comprises a halogen atom, a carbon-1 to carbon-6 alkoxy group, and a hydroxyl group. It is a group, an amino group, or a hydrogen atom, The liquid dispensing head according to claim 1 or 2, wherein R is an alkyl group having 1 to 3 carbon atoms, or a phenyl group.

4. The liquid discharge head according to claim 1 or 2, wherein in formula (1), p is 1 and q is 3.

5. In the above formula (2), A is -C ３ H ６ - The liquid dispensing head according to claim 1 or 2.

6. The liquid dispensing head according to claim 1 or 2, wherein in formula (2), r = s = 25.

7. The liquid dispensing head according to claim 1 or 2, wherein Y has the structure shown in formula (6) below.

8. The liquid dispensing head according to claim 1 or 2, wherein the hydrolyzable silane compound contained in the silane mixture has a content ratio of 0.01 to 0.80 mol% of the hydrolyzable silane compound (a).

9. The liquid discharge head according to claim 1 or 2, wherein the hydrolyzable silane compound (b) having an epoxy group is at least one selected from the group consisting of compounds represented by formula (7) and compounds represented by formula (8).

10. The liquid dispensing head contains a cured product of a photopolymerizable resin containing a photopolymerization initiator. The liquid dispensing head according to claim 1 or 2, wherein the cured product of the liquid-repellent coating material is formed on the cured product of the photopolymerizable resin.

11. The liquid dispensing head according to claim 1 or 2, wherein the coating material further contains a photopolymerizable resin and a photopolymerization initiator.

12. A method for manufacturing a liquid dispensing head according to claim 10, The manufacturing method is (1) A step of forming a photopolymerizable resin layer by applying the photopolymerizable resin mixture, which includes an epoxy compound other than the hydrolyzable silane compound (b) capable of forming the photopolymerizable resin and the photopolymerization initiator, onto a substrate and drying it, (2) A step of applying the coating material onto the photopolymerizable resin layer to form a coating film of the coating material, (3) A step of simultaneously exposing and developing the photopolymerizable resin layer and the coating film, (4) After exposure and development, a step of curing the photopolymerizable resin layer and the coating film together, A method for manufacturing a liquid dispensing head, characterized by including the following:

13. A method for manufacturing a liquid dispensing head according to claim 11, The manufacturing method is (1) Condensation product of the silane mixture, The aforementioned photopolymerization initiator, and Epoxy compounds other than the hydrolyzable silane compound (b) that can form the aforementioned photopolymerizable resin, A step of applying the coating material containing the coating material to a substrate to form a coating film of the coating material, (2) A step of exposing and developing the coating film of the coating material, (3) A step of curing the coating film after exposure and development to form the cured product of the coating material, A method for manufacturing a liquid dispensing head, characterized by including the following:

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