JP2018051883A - Liquid discharge head and manufacturing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid discharge head that has high printing quality, has high discharge stability at the time of resuming liquid discharge, and suppresses deterioration in rigidity of a discharge port forming member.SOLUTION: The liquid discharge head comprises a substrate, and a discharge port forming member having a discharge port for discharging liquid and a flow path for liquid communicated with the discharge port, formed on the substrate. The discharge port forming member has a discharge port forming layer A, an intermediate water repellent layer and a discharge port forming member layer B in this order, when viewed from the substrate side. The discharge port forming member has a protrusion protruding toward inside of the discharge port, and the discharge port forming member has a water repellent protruding part, at least part of the intermediate water repellent layer, which protrudes toward inside of the discharge port more than the discharge port forming member layer A and the discharge port forming member layer B.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a liquid discharge head and a method for manufacturing the same.

  As an application example of a liquid discharge head capable of discharging liquid, there is an ink jet recording head that performs recording by discharging ink onto a recording medium. Inkjet recording heads generally include a plurality of fine ejection ports and flow paths, and a plurality of energy generating elements for ejecting ink. In recent years, ink jet recording heads have a large number of ejection openings, and the ejection ink droplets have become smaller, so the influence of ejection ink droplets that do not originally contribute to printing cannot be ignored. Specifically, the ink droplets that land on the recording medium are divided into multiple (main droplets and satellites) images, and the ink droplets (hereinafter referred to as mist) that lose their speed and float before reaching the recording medium. ) And the like to transfer the dirt of the recording apparatus to the recording medium. Patent Document 1 discloses that a protrusion is provided in an ejection port and ink is held between the protrusions. Thereby, the tail of the droplet at the time of ink droplet ejection can be shortened, and satellites and mist can be reduced.

JP 2011-207235 A

  The protrusion in the discharge port disclosed in Patent Document 1 can reduce satellites and mist, but on the other hand, by providing the protrusion in the discharge port, the peripheral length of the discharge port becomes longer, and the front resistance in the discharge port is increased. Increase.

  On the other hand, when ink droplets are ejected using an ink jet recording head, if printing is paused for a predetermined time and printing is resumed, ink droplets do not eject or the ink droplets do not advance straight, and the print medium is not intended There are times when it ’s landed. It is considered that the ejection failure at the time of resuming the ejection occurs because the ink in the ejection port evaporates while the printing is stopped and the ink viscosity increases.

  Further, another factor that causes a discharge failure when resuming discharge is the forward resistance in the discharge port mentioned above. That is, if the front resistance in the ejection port becomes too high, it becomes difficult to eject ink, and ejection failure is likely to occur. In order to express the effect of reducing satellites and mist at the discharge port provided with the protrusion, it is required to hold the liquid by the protrusion at the time of discharge. Therefore, the protrusion is required to have a certain size. That is, if the resistance at the protrusions that hold the ink is high, the effect of reducing satellites and mist increases. However, along with this, the forward resistance is increased by the protrusion, so that ejection failure at the time of resuming ejection tends to occur.

  On the other hand, as a method of reducing the front resistance in the discharge port, it is effective to make the discharge port forming member on which the discharge port is formed thin. However, when the discharge port forming member is thinned, the rigidity of the discharge port forming member is reduced, and the discharge port and the discharge port forming member are deformed, or the discharge port forming member is cracked due to an external force such as wiping. Sometimes. In this case, variations in the ejection direction of the ejected ink droplets and changes in the ejection amount of the ink droplets may occur, and the output image may be uneven.

  As described above, in order to achieve both high printing quality and high durability, the discharge port having protrusions improves the discharge stability when resuming discharge while reducing satellites and mist, and the discharge port forming member. It is required to maintain rigidity. An object of the present invention is to provide a liquid ejection head that has high print quality, high ejection stability when resuming liquid ejection, and suppresses a decrease in rigidity of an ejection port forming member.

  A liquid discharge head according to the present invention includes a substrate, and a discharge port forming member that is formed on the substrate and has a discharge port that discharges the liquid and a liquid channel that communicates with the discharge port. The discharge port forming member has a discharge port forming member layer A, an intermediate water-repellent layer, and a discharge port forming member layer B in order from the substrate side, and the discharge port forming member is formed of the discharge port. The discharge port forming member has at least a portion of the intermediate water-repellent layer more than the discharge port forming member layer A and the discharge port forming member layer B; It has the water-repellent protrusion part which protrudes inside.

  The method of manufacturing a liquid discharge head according to the present invention includes a step of forming a liquid flow path mold made of a flow path forming resin composition on a substrate, and a discharge port forming member by curing on the mold and the substrate. A step of forming a layer made of the photosensitive resin composition A to be the layer A, and a photosensitive resin composition C that becomes an intermediate water-repellent layer by curing on the layer made of the photosensitive resin composition A A step of forming a layer, a step of forming a layer made of the photosensitive resin composition B which becomes the discharge port forming member layer B by curing on the layer made of the photosensitive resin composition C, and the photosensitive resin A layer made of the composition A, a layer made of the photosensitive resin composition C, and a layer made of the photosensitive resin composition B are exposed, and a discharge port for discharging a liquid, and convex toward the inside of the discharge port Forming a pattern of protrusions and water repellent protrusions, The step of removing the unexposed portion of the layer comprising the photosensitive resin composition A, the layer comprising the photosensitive resin composition C and the layer comprising the photosensitive resin composition B, and the step of removing the mold material, A method of manufacturing a liquid discharge head comprising: the water-repellent protrusion, wherein at least a part of the intermediate water-repellent layer is more than the discharge port forming member layer A and the discharge port forming member layer B. It is the part which protrudes inside.

  The method of manufacturing a liquid discharge head according to the present invention includes a step of forming a liquid flow path mold made of a flow path forming resin composition on a substrate, and a discharge port forming member by curing on the mold and the substrate. A step of forming a layer made of the photosensitive resin composition A to be the layer A, a step of exposing the layer made of the photosensitive resin composition A to form a pattern of discharge ports for discharging a liquid, A step of forming a layer made of photosensitive resin composition C, which becomes an intermediate water-repellent layer by curing, on the layer made of photosensitive resin composition A, and exposing the layer made of photosensitive resin composition C A step of forming a pattern of the discharge port, a protrusion that protrudes toward the inside of the discharge port, and a water-repellent protrusion, a layer formed of the photosensitive resin composition A, and the photosensitive resin composition C Removing the unexposed portion of the layer, and the intermediate water repellent A step of forming a layer made of the photosensitive resin composition B, which becomes the discharge port forming member layer B by curing, and a layer made of the photosensitive resin composition B are exposed to form the discharge port and the protrusion A method of manufacturing a liquid discharge head, comprising: a step of forming a pattern; a step of removing an unexposed portion of a layer made of the photosensitive resin composition B; and a step of removing the mold material. The water protruding portion is a portion in which at least a part of the intermediate water-repellent layer protrudes more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B. .

  The method for producing a liquid ejection head according to the present invention includes a step of forming a layer made of a photosensitive resin composition E, which becomes a flow path forming member by curing on a substrate, and a layer made of the photosensitive resin composition E A step of forming a layer made of the photosensitive resin composition A, which becomes the discharge port forming member layer A by curing, and a layer of the photosensitive resin composition E are exposed to form a pattern of a liquid flow path Forming a pattern of a discharge port for discharging a liquid, exposing the layer made of the photosensitive resin composition A, and forming the layer made of the photosensitive resin composition E and the photosensitive resin A step of removing an unexposed portion of the layer made of the composition A, a layer made of the photosensitive resin composition C which becomes an intermediate water-repellent layer by curing on the discharge port forming member layer A, and a discharge port by curing It consists of the photosensitive resin composition B used as the formation member layer B And exposing the layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B to project toward the inside of the ejection port and the ejection port. And a step of forming a pattern of protrusions and water repellent protrusions, and a step of removing unexposed portions of the layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B. In the method for manufacturing a liquid discharge head, the water-repellent protrusion, and at least a part of the intermediate water-repellent layer is more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B. It is the part which protrudes in.

  According to the present invention, it is possible to provide a liquid discharge head that has high print quality, high discharge stability when resuming liquid discharge, and suppresses a decrease in rigidity of the discharge port forming member.

1A and 1B are a perspective view and a cross-sectional view illustrating an example of an ink jet recording head according to an embodiment of the invention. FIG. 2 is a top view and a cross-sectional view of the vicinity of an ejection port of an example of an ink jet recording head according to an embodiment of the present invention. FIG. 6 is a top view and a cross-sectional view of the vicinity of an ejection port of an example of an inkjet recording head according to the background art. FIG. 2 is a top view illustrating an example of a discharge port shape of an ink jet recording head according to an embodiment of the present invention. It is sectional drawing which shows an example of the manufacturing method of the inkjet recording head which concerns on embodiment of this invention. It is sectional drawing which shows an example of the manufacturing method of the inkjet recording head which concerns on embodiment of this invention. It is sectional drawing which shows an example of the manufacturing method of the inkjet recording head which concerns on embodiment of this invention. It is sectional drawing which shows an example of the manufacturing method of the inkjet recording head which concerns on embodiment of this invention. It is sectional drawing which shows an example of the manufacturing method of the inkjet recording head of background art.

[Liquid discharge head]
A liquid discharge head according to the present invention includes a substrate, and a discharge port forming member that is formed on the substrate and has a discharge port that discharges the liquid and a liquid channel that communicates with the discharge port. The discharge port forming member has a discharge port forming member layer A, an intermediate water repellent layer, and a discharge port forming member layer B in order from the substrate side. Further, the discharge port forming member has a protrusion that is convex toward the inside of the discharge port. Further, in the discharge port forming member, at least a part of the intermediate water-repellent layer has a water-repellent protrusion that protrudes more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B Have

  Since the liquid ejection head according to the present invention has a projection in the ejection port that protrudes toward the inside of the ejection port, the liquid is held by the projection, and the tail of the droplet can be shortened when the droplet is ejected. . Thereby, satellites and mist can be reduced, and printing quality can be improved. In addition, since the liquid discharge head according to the present invention has a water-repellent protrusion formed by protruding at least a part of the intermediate water-repellent layer in the discharge port, the liquid meniscus position of the liquid is set in the water-repellent protrusion in the discharge port. It can be the position of the part. As a result, even if the protrusion is present, the forward resistance in the discharge port can be reduced, so that it is possible to improve the discharge stability when resuming the liquid discharge after the suspension of printing. Furthermore, since the front resistance in the discharge port can be reduced without reducing the thickness of the discharge port forming member, the rigidity of the discharge port forming member can be maintained.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. As an application example of the present invention, an ink jet recording head which is an example of a liquid discharge head will be described as an example. However, the application range of the liquid discharge head according to the present invention is not limited to this.

  FIG. 1A is a schematic diagram showing an example of an ink jet recording head according to an embodiment of the present invention. FIG. 1B is a schematic cross-sectional view taken along line A-A ′ in FIG. The ink jet recording head shown in FIG. 1 has a substrate 2 on which energy generating elements 1 that generate energy used to eject ink are formed at a predetermined pitch. A supply path 3 for supplying ink passes through the substrate 2. On the substrate 2, an ejection port forming member 5 that forms an ink flow path 4 and an ink ejection port 9 is formed. The discharge port forming member 5 includes a discharge port forming member layer A6, an intermediate water repellent layer 7, and a discharge port forming member layer B8. A projection 11 is formed in the discharge port 9 so as to protrude toward the inside of the discharge port 9. Note that “toward the inside of the ejection port 9” indicates a direction toward the center line of the ejection direction of the ink (liquid) at the ejection port 9. Further, at least a part of the intermediate water-repellent layer 7 is formed with a water-repellent protrusion 12 other than the protrusion 11 that protrudes more inside the discharge port 9 than the discharge port forming member layer A6 and the discharge port forming member layer B8. ing. Note that “projecting toward the inside of the ejection port 9” means projecting in a direction toward the center line of the ejection direction of the ink (liquid) at the ejection port 9. A surface water-repellent layer 10 is formed on the first surface of the discharge port forming member 5 where the discharge port 9 opens. In the ink jet recording head shown in FIG. 1, by applying energy generated by the energy generating element 1 to the ink supplied from the supply path 3 through the flow path 4, the ink is discharged from the discharge port 9 as ink droplets. Discharged.

  FIG. 2A shows a top view of the vicinity of the discharge port 9 of an example of the ink jet recording head according to the embodiment of the present invention as viewed from the direction of discharging the liquid. 2B and 2C are cross-sectional views taken along line B-B 'in FIG. 2D and 2E are cross-sectional views taken along line C-C ′ in FIG. As shown in FIGS. 2A to 2E, in the ink jet recording head according to the embodiment of the present invention, at least a part of the intermediate water-repellent layer 7 includes the discharge port forming member layer A6 and the discharge port forming member layer. A water-repellent protrusion 12 protruding by a length d is provided inside the discharge port 9 from B8. Here, the major axis of the discharge port 9 is Φ1, and the minor axis is Φ2. The protrusion 11 has a width x, a length y, and an interval a. Satellite and mist can be reduced as a is smaller, but the forward resistance in the discharge port 9 is increased. On the other hand, although the forward resistance can be reduced by reducing x, the strength of the protrusion 11 is lowered and the durability is lowered.

  For comparison, FIG. 3A shows a top view of the vicinity of the ejection port 9 of an example of the background art ink jet recording head. FIG. 3B is a cross-sectional view taken along line D-D ′ in FIG. FIG. 3C is a cross-sectional view taken along line E-E ′. In the inkjet recording head of the background art shown in FIGS. 3A to 3C, the liquid meniscus position is the first surface of the discharge port forming member where the discharge port 9 opens. In order to reduce the forward resistance, it was necessary to reduce the thickness H of the discharge port forming member on the flow path 4. However, when the thickness H of the discharge port forming member on the flow path 4 is reduced, the strength of the discharge port forming member is reduced, the discharge port 9 and the discharge port forming member are deformed, or external force is applied to the discharge port 9 such as wiping. A crack may occur near the discharge port 9 due to the applied operation.

  On the other hand, in the ink jet recording head according to the embodiment of the present invention, since the water repellent protrusion 12 is provided in the discharge port 9 as shown in FIG. 2, the meniscus position is the position of the water repellent protrusion 12 in the discharge port 9. It is. For this reason, in the present invention, it is possible to reduce the front resistance in the discharge port 9 without reducing the thickness H of the discharge port forming member on the flow path 4, that is, without reducing the strength of the discharge port forming member. it can. As shown in FIG. 2, in the present invention, the front resistance in the discharge port 9 is not the thickness H of the discharge port forming member on the flow channel 4 but the thickness h of the discharge port forming member layer A6 on the flow channel 4. Dependent. Therefore, even if the intermediate water-repellent layer 7 is laminated on the entire surface of the discharge port forming member layer A6 as shown in FIGS. 2B and 2D, the intermediate water-repellent layer 7 is not shown in FIGS. As shown, even if patterned and laminated partially, the meniscus position is not affected. The shape of the discharge port 9 according to the present invention is not limited to the shape shown in FIG. 2 (A), and is appropriately selected including the shapes shown in FIGS. 4 (a) to 4 (c). . Further, the horizontal cross-sectional shape of the discharge port 9 other than the protrusion 11 is not limited to an arc shape.

  In the present invention, the protrusion 11 and the water-repellent protrusion 12 are both formed in the discharge port, but the protrusion 11 and the water-repellent protrusion 12 are not the same, but indicate different protrusions. For example, the water repellent protrusion 12 may be formed on a portion other than the protrusion 11 on the inner wall of the discharge port 9, may be formed on the surface of the protrusion 11, or may be formed on both. For example, in FIG. 2, the water-repellent protrusion 12 is formed on a portion other than the protrusion 11 on the inner wall of the discharge port 9.

  The protrusion 11 can be composed of the intermediate water repellent layer 7 and the discharge port forming member layer B8. Further, the protrusion 11 can be composed of the discharge port forming member layer A 6 and the intermediate water repellent layer 7. Further, the protrusion 11 can be composed of a discharge port forming member layer A6, an intermediate water repellent layer 7, and a discharge port forming member layer B8. The length of the discharge port 9 in the depth direction of the protrusion 11 is not particularly limited, but can be 4 to 30 μm.

When the static contact angle with respect to pure water of the water repellent protrusion 12 is θ _s and the static contact angles with respect to pure water of the discharge port forming member layer A6 and the discharge port forming member layer B8 are θ _A and θ _B , respectively, It is preferable that _s > θ _A and θ _s > θ _B are satisfied. This is because satisfying θ _s > θ _A and θ _s > θ _B makes it easier to maintain the liquid meniscus at the position of the water-repellent protrusion 12. θ _s is preferably larger than θ _A and θ _B by 10 ° or more, and more preferably 20 ° or more.

Further, from the viewpoint of easily maintaining a liquid meniscus at the position of the water-repellent protrusion 12, it is preferable that θ _s > 70 °, more preferably θ _s > 80 °, and θ _s > 90 °. More preferably it is. The upper limit of θ _s is not particularly limited, but can be set to θ _s ≦ 120 °, for example. Further, the ranges of θ _A and θ _B are not particularly limited, but can be set to 5 ° ≦ θ _A ≦ 70 °, 10 ° ≦ θ _B ≦ 70 °, for example. In addition, the measurement of (theta) _s , (theta) _A, and (theta) _B is performed by measuring the contact angle of a 10 microliter pure water droplet using contact angle meter CA-X150 (brand name, Kyowa Interface Science Co., Ltd. product).

  The discharge port forming member layer A6 and the discharge port forming member layer B8 are required to have mechanical strength, resistance to a liquid such as ink, and adhesion to a base, and further, resolution as a photolithography material is considered. The From the viewpoint of satisfying these characteristics, at least one of the discharge port forming member layer A6 and the discharge port forming member layer B8 generates a acid by absorbing light and a cationically polymerizable resin having two or more epoxy groups. It is preferable to consist of the hardened | cured material of the composition containing the photo-acid generator to do. By using a cationically polymerizable resin having two or more epoxy groups, the resulting cured product has three-dimensional cross-linking, and the above characteristics are easily obtained. Examples of the cationic polymerizable resin having two or more epoxy groups include epoxy resins such as bisphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and polyfunctional epoxy resins having an oxycyclohexane skeleton. It is done. Examples of commercially available products include “Celoxide 2021”, “EHPE3150” (trade name, manufactured by Daicel Corporation), “157S70”, “jER1031S” (trade name, manufactured by Mitsubishi Chemical Corporation), “Epiclon N-695”. ”,“ Epicron N-865 ”,“ Epicron HP-7200 ”(trade name, manufactured by DIC Corporation) and the like. These may use 1 type and may use 2 or more types together.

  Examples of the photoacid generator include sulfonic acid compounds, diazomethane compounds, sulfonium salt compounds, iodonium salt compounds, disulfone compounds, and the like. Commercially available products include, for example, “Adekaoptomer SP-170”, “Adekaoptomer SP-172”, “Adekaoptomer SP-150” (trade name, manufactured by ADEKA Corporation), “BBI-103”, “ “BBI-102” (trade name, manufactured by Midori Chemical Co., Ltd.), “IBPF”, “IBCF”, “TS-01”, “TS-91” (trade name, manufactured by Sanwa Chemical Co., Ltd.), "CPI-210", "CPI-300", "CPI-410", "CPI-410S" (trade name, manufactured by San Apro Co., Ltd.), "Irgacure 290" (trade name, manufactured by BASF), etc. . These may use 1 type and may use 2 or more types together.

  Further, for the purpose of improving photolithography performance, adhesion performance, and the like, the composition is a photosensitizer such as a silane coupling agent or anthracene derivative, a basic substance such as amines, a weak acid (pKa = −1. The acid generator etc. which generate | occur | produce toluenesulfonic acid of 5-3.0) can also be included. Examples of the acid generator that generates commercially available toluenesulfonic acid include “TPS-1000” (trade name, manufactured by Midori Chemical Co., Ltd.) and “WPAG-367” (trade name, manufactured by Wako Pure Chemical Industries, Ltd.). Etc. These may use 1 type and may use 2 or more types together. Moreover, as the composition, “SU-8 series” (trade name, manufactured by Nippon Kayaku Co., Ltd.), “TMMR S2000”, “TMMF S2000” (trade name, Tokyo Ohka) are commercially available as negative resists. Kogyo Co., Ltd.) can also be used. The cured product of the composition generally has a static contact angle with pure water of around 60 °.

The intermediate water-repellent layer 7 includes a hydrolyzable silane compound having an epoxy group and a condensate of a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group, and a cationic polymerizable resin having two or more epoxy groups. And a cured product of a composition comprising a photoacid generator that absorbs light and generates an acid. In a composition containing a condensate of a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group, the fluorine-containing group is segregated at the interface between the composition and air by baking. For this reason, the static contact angle with respect to the pure water of hardened | cured material tends to become 70 degrees or more, and can satisfy | fill (theta) _s > (theta) _A and (theta) _s > (theta) _B easily. Examples of the hydrolyzable silane compound having an epoxy group include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. It is done. These may use 1 type and may use 2 or more types together. Examples of the hydrolyzable silane compound having a perfluoropolyether group include compounds represented by the following formulas (1) to (4).

  In said Formula (1), g is 1-30. In said Formula (2), Rm is a methyl group or a hydrogen atom, h is 1-30. In said Formula (3), i is 1-30 and j is 1-4. In said Formula (4), k is 1-30. These may use 1 type and may use 2 or more types together. Moreover, about the cationically polymerizable resin which has 2 or more of epoxy groups, and a photo-acid generator, the thing similar to the compound in discharge port formation member layer A6 and discharge port formation member layer B8 can be used.

  In the ink jet recording head according to the embodiment of the present invention, as shown in FIG. 1B, a surface water-repellent layer 10 is formed on the first surface of the discharge port forming member 5 where the discharge port 9 opens. It is preferable from the viewpoint of prevention of adhesion of dust such as paper dust and ease of removal of attached dust. As a material for the surface water-repellent layer 10, a perfluoroalkyl composition or a perfluoropolyether composition having cationic polymerizability is preferably used. For example, a condensate containing a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having a cationic polymerizable group, as disclosed in JP-A-2007-518587, is preferably used.

  Although the height of the flow path 4 is not specifically limited, It can be 3-20 micrometers. The thickness h of the discharge port forming member layer A6 on the flow path 4 is preferably 2/3 or less, more preferably 1/3 or less, of the thickness H of the discharge port forming member 5 on the flow path 4. The thickness of the intermediate water repellent layer 7 is preferably 0.3 μm or more, and more preferably 1 to 3 μm. The thickness of the discharge port forming member layer B8 on the intermediate water repellent layer 7 is not particularly limited, but can be 2 μm or more. The thickness H of the discharge port forming member 5 on the flow path 4 is not particularly limited, but can be 4 to 30 μm. When the discharge port 9 is circular, the major axis Φ1 is not particularly limited, but can be 10 to 30 μm. The minor axis Φ2 is not particularly limited, but can be 10 to 30 μm. The width x of the protrusion 11 is not particularly limited, but can be 1.5 to 5 μm. The length y of the protrusion 11 is not particularly limited, but can be 1/6 or more of the short diameter Φ2. When there are a plurality of protrusions 11, the interval a between the protrusions 11 is not particularly limited, but can be 1 to 15 μm. The protrusion length d of the water-repellent protrusion 12 is preferably 0.1 to 3 μm, and more preferably 0.5 to 1.5 μm.

[Liquid discharge head manufacturing method]
A method for manufacturing a liquid ejection head according to the present invention will be described based on each embodiment. Note that, as an application example of the present invention, an ink jet recording head which is an example of a liquid discharge head will be described below as an example. However, the scope of application of the method for manufacturing a liquid discharge head according to the present invention is not limited thereto. Absent.

(First embodiment)
The method for manufacturing a liquid ejection head according to this embodiment includes the following steps. A step of forming a liquid flow path mold comprising a flow path forming resin composition on a substrate. Forming a layer made of the photosensitive resin composition A, which becomes the discharge port forming member layer A by curing, on the mold material and the substrate; Forming a layer made of the photosensitive resin composition C, which becomes an intermediate water-repellent layer by curing on the layer made of the photosensitive resin composition A; A step of forming a layer made of the photosensitive resin composition B on the layer made of the photosensitive resin composition C, which becomes the discharge port forming member layer B by curing. A layer made of the photosensitive resin composition A, a layer made of the photosensitive resin composition C, and a layer made of the photosensitive resin composition B are exposed to discharge liquid to the inside of the discharge port. Forming a pattern of protrusions that are convex toward the surface and a pattern of water-repellent protrusions Removing the unexposed portions of the layer made of the photosensitive resin composition A, the layer made of the photosensitive resin composition C, and the layer made of the photosensitive resin composition B; Removing the mold material; Here, the water repellent protrusion is a portion in which at least a part of the intermediate water repellent layer protrudes more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B. . According to this method, the liquid discharge head according to the present invention can be manufactured efficiently and accurately.

  FIG. 5 is a schematic cross-sectional view showing each step of the manufacturing method of the ink jet recording head which is an example of the present embodiment. The schematic cross-sectional view is a cross-sectional view taken along line B-B ′ in FIG. 2A, and the same applies to FIGS. 6 to 9.

  First, as shown in FIG. 5A, a liquid flow path mold 13 made of a flow path forming resin composition is formed on a substrate 2 on which an energy generating element 1 is disposed. For example, after forming a layer made of a flow path forming resin composition on the substrate 2 on which the energy generating element 1 is disposed, the layer is formed by exposing through a flow path pattern mask and dissolving and removing the exposed portion. Can be formed. The flow path forming resin composition is not particularly limited as long as it is a material that can be removed after the discharge port forming member 5 is formed. For example, a polymethacrylic ester positive resist or a polyacrylic ester positive resist that has positive photolithography performance and is decomposed by Deep UV and becomes soluble in an organic solvent can be used. In particular, polymethyl isopropenyl ketone can be preferably used. As polymethyl isopropenyl ketone, ODUR-1010 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be used as a commercially available product.

  Next, as shown in FIG. 5B, a layer 14 made of a photosensitive resin composition A and a layer 15 made of a photosensitive resin composition C are formed in this order on the mold material 13 and the substrate 2. To do. The layer 14 made of the photosensitive resin composition A is a layer that becomes the discharge port forming member layer A6 by curing. The layer 15 made of the photosensitive resin composition C is a layer that becomes the intermediate water-repellent layer 7 by curing. As described above, the photosensitive resin composition A preferably includes a cationic polymerizable resin having two or more epoxy groups and a photoacid generator that absorbs light to generate an acid. Further, as described above, the photosensitive resin composition C is a hydrolyzable silane compound containing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group. It is preferable to include a condensate, a cationic polymerizable resin having two or more epoxy groups, and a photoacid generator that absorbs light and generates an acid. As a method for forming the layer 14 made of the photosensitive resin composition A and the layer 15 made of the photosensitive resin composition C, for example, after each photosensitive resin composition containing a solvent is applied by spin coating or slit coating. And a method of volatilizing the solvent in the baking step. Alternatively, a laminate method may be used in which each layer is once formed on a film substrate made of PET (polyethylene terephthalate), polyimide, or the like and then transferred. These forming methods can be properly used depending on the type of resin material and the type of solvent.

  Next, as shown in FIG. 5C, a layer 16 made of the photosensitive resin composition B and a layer 17 made of the photosensitive resin composition D are formed on the layer 15 made of the photosensitive resin composition C. They are formed in this order. The layer 16 made of the photosensitive resin composition B is a layer that becomes the discharge port forming member layer B8 by curing. The layer 17 made of the photosensitive resin composition D is a layer that becomes the surface water-repellent layer 10 by curing. As described above, the photosensitive resin composition B preferably includes a cationic polymerizable resin having two or more epoxy groups and a photoacid generator that absorbs light to generate an acid. It is preferable that the photosensitive resin composition D includes the material for the surface water-repellent layer 10 described above. In the step shown in FIG. 5, the surface water-repellent layer 10 is formed, but the formation of the surface water-repellent layer 10 is optional.

Next, as shown in FIG. 5D, the layer 14 made of the photosensitive resin composition A, the layer 15 made of the photosensitive resin composition C, and the photosensitive resin through the discharge port pattern mask 18. The layer 16 made of the resin composition B and the layer 17 made of the photosensitive resin composition D are exposed. Thereby, the pattern of the protrusion 11 which becomes convex toward the inner side of the discharge port 9 and the discharge port 9 is formed. As the discharge port pattern mask 18, a substrate made of a material such as glass or quartz that transmits light having an exposure wavelength and a light shielding film such as a chromium film formed in accordance with the pattern can be used. The same applies to other masks described later. As the exposure apparatus, use a projection exposure apparatus having a light source of a single wavelength such as an i-line exposure stepper or a KrF stepper or a mercury lamp such as a mask aligner MPA-600 Super (trade name, manufactured by Canon Inc.) as a light source. Can do. Further, a broad wavelength exposure machine may be used in combination with a filter that transmits a specific wavelength. The same applies to other exposures described later. Although the exposure amount in this step depends on the material of each photosensitive resin composition, it can be set to, for example, 500 to 20000 J / m ² .

Next, as shown in FIG. 5E, the layer 15 made of the photosensitive resin composition C is exposed through the water repellent protrusion pattern mask 19 to form a pattern of the water repellent protrusion 12. . The photosensitive resin composition A, the photosensitive resin composition B, and the photosensitive resin composition C are provided with a sensitivity difference, and when exposed through the water-repellent protrusion pattern mask 19, the photosensitive resin composition A, the photosensitive resin composition B, and the photosensitive resin composition C have a sensitivity difference. The water-repellent protrusion 12 can be formed by selecting an exposure amount at which only the conductive resin composition C is cured. Specifically, the curing exposure amounts of the photosensitive resin composition A, the photosensitive resin composition B, and the photosensitive resin composition C are Eth1, Eth2, and Eth3, respectively. At this time, when the exposure amount E satisfies Eth1>E> Eth3 and Eth2>E> Eth3, only the photosensitive resin composition C can be cured. That is, it is preferable to satisfy Eth1> Eth3 and Eth2> Eth3. Here, the cured exposure amount is the minimum exposure at which the photosensitive resin composition becomes insoluble in the solvent for removal and removal used in the negative photosensitive resin composition, that is, the photosensitive resin composition remains as a residue during development and cannot be removed. The quantity E = Eth. The curing exposure amount of each photosensitive resin composition can be adjusted by the type and addition amount of the photoacid generator, basic substance, acid generator, and photosensitizer described above. The sensitivity difference of the photosensitive resin composition can also be changed by changing the wavelength at which the photosensitive resin composition reacts depending on the type of photoacid generator or photosensitizer and changing the wavelength of exposure according to the photosensitive resin composition. The same effect as that provided can be expected. Although the exposure amount in this step depends on the material of each photosensitive resin composition, it can be set to, for example, 500 to 20000 J / m ² .

  Next, as shown in FIG. 5 (F), the layer 14 made of the photosensitive resin composition A, the layer 15 made of the photosensitive resin composition C, the layer 16 made of the photosensitive resin composition B, and The unexposed portion of the layer 17 made of the photosensitive resin composition D is removed. For example, first, the exposed portion is cured by heat treatment (Post Exposure Bake). Thereafter, a layer 14 made of the photosensitive resin composition A, a layer 15 made of the photosensitive resin composition C, a layer 16 made of the photosensitive resin composition B, and a layer 17 made of the photosensitive resin composition D. Uncured parts can be removed using a solvent. As the solvent, for example, propylene glycol monomethyl ether acetate (PGMEA), methyl isobutyl ketone (MIBK) or the like can be used although it depends on the material of each photosensitive resin composition. Thereby, the discharge port forming member layer A6, the intermediate water repellent layer 7, the discharge port forming member layer B8, the discharge port 9, the surface water repellent layer 10, the protrusions 11, and the water repellent protrusions 12 are formed.

  Next, as shown in FIG. 5G, a liquid supply path 3 is formed in the substrate 2, and the mold member 13 is removed. For example, after the discharge port forming member on the substrate 2 is protected with a rubber film, the supply path 3 can be formed in the substrate 2 using an alkaline etching solution. Further, after removing the rubber film, the flow path 4 can be formed by dissolving and removing the mold material 13 with a solvent. As the solvent, for example, methyl lactate or the like can be used although it depends on the material of the mold 13. When the mold member 13 is made of a positive resist, the solubility may be improved by irradiating with ultraviolet rays. Further, in the step shown in FIG. 5A, the substrate 2 on which the supply path 3 has already been formed is used at the time of the step shown in FIG. You can also

  The method according to this embodiment includes a layer 14 composed of the photosensitive resin composition A, a layer 15 composed of the photosensitive resin composition C, a layer 16 composed of the photosensitive resin composition B, and, if necessary, the above-described method. It is preferable to further include a step of heating to 90 ° C. or higher and 250 ° C. or lower after the step of removing the unexposed portion of the layer 17 made of the photosensitive resin composition D. The heating temperature is more preferably 120 ° C. or higher and 240 ° C. or lower, and further preferably 150 ° C. or higher and 220 ° C. or lower. When the heating temperature is 90 ° C. or higher, the fluorine-containing group of the water-repellent protrusion 12 can be sufficiently segregated at the interface with the air, compared to the discharge port forming member layer A6 and the discharge port forming member layer B8. The surface energy can be made sufficiently low. As a result, the liquid meniscus can be easily held at the position of the water-repellent protrusion 12. Moreover, when the heating temperature is 250 ° C. or lower, it is possible to sufficiently prevent a decrease in durability of the discharge port forming member due to decomposition of the resin. The heating step may be performed after the step of removing the mold material 13.

  Thereafter, electrical connection is performed, and an ink supply unit is appropriately disposed to obtain an ink jet recording head.

(Second embodiment)
The method for manufacturing a liquid ejection head according to this embodiment includes the following steps. A step of forming a liquid flow path mold comprising a flow path forming resin composition on a substrate. Forming a layer made of the photosensitive resin composition A, which becomes the discharge port forming member layer A by curing, on the mold material and the substrate; A step of exposing a layer made of the photosensitive resin composition A to form a pattern of ejection openings for ejecting liquid. Forming a layer made of the photosensitive resin composition C, which becomes an intermediate water-repellent layer by curing on the layer made of the photosensitive resin composition A; A step of exposing the layer made of the photosensitive resin composition C to form a pattern of the discharge port, a protrusion that protrudes toward the inside of the discharge port, and a water-repellent protrusion. Removing the unexposed portions of the layer made of the photosensitive resin composition A and the layer made of the photosensitive resin composition C; A step of forming a layer made of the photosensitive resin composition B, which becomes the discharge port forming member layer B by curing, on the intermediate water-repellent layer. Exposing the layer made of the photosensitive resin composition B to form a pattern of the ejection openings and the protrusions; A step of removing an unexposed portion of the layer made of the photosensitive resin composition B; Removing the mold material; Here, the water repellent protrusion is a portion in which at least a part of the intermediate water repellent layer protrudes more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B. . According to this method, the liquid discharge head according to the present invention can be manufactured efficiently and accurately.

  FIG. 6 is a schematic cross-sectional view showing each step of the manufacturing method of the ink jet recording head which is an example of the present embodiment. In addition, although formation of the surface water repellent layer 10 is abbreviate | omitted in each process shown by FIG. 6, the surface water repellent layer 10 can also be provided similarly to the manufacturing method shown by FIG. 5 mentioned above.

  First, as shown in FIG. 6A, a liquid flow path mold 13 made of a flow path forming resin composition is formed on a substrate 2 on which an energy generating element 1 is arranged. The mold member 13 can be formed by the same method as in the first embodiment.

  Next, as shown in FIG. 6B, a layer 14 made of a photosensitive resin composition A is formed on the mold material 13 and the substrate 2, and exposed through a discharge port pattern mask 20. A pattern of the discharge ports 9 is formed. Formation of the layer 14 made of the photosensitive resin composition A and exposure through the discharge port pattern mask 20 can be performed by the same method as in the first embodiment. After the exposure, the exposed portion may be cured by heat treatment.

  Next, as shown in FIG. 6C, the layer 15 made of the photosensitive resin composition C is formed on the layer 14 made of the photosensitive resin composition A, and the water-repellent protrusion pattern mask 19 is formed. Through the exposure. Thereby, the pattern of the protrusion 11 which protrudes toward the inner side of the discharge port 9, the discharge port 9, and the water-repellent protrusion part 12 is formed in the layer 15 which consists of the photosensitive resin composition C. Here, a difference in sensitivity is provided between the photosensitive resin composition A and the photosensitive resin composition C, and when the photosensitive resin composition C and the photosensitive resin composition C are exposed through the water-repellent protrusion pattern mask 19, the photosensitive resin composition C. The water-repellent protrusion 12 can be formed by selecting an exposure amount that only cures. Specifically, when the curing exposure amounts of the photosensitive resin composition A and the photosensitive resin composition C are Eth1 and Eth3, respectively, and the exposure amount E satisfies Eth1> E> Eth3, the photosensitive resin Only composition C can be cured. That is, it is preferable to satisfy Eth1> Eth3. Formation of the layer 15 made of the photosensitive resin composition C and exposure through the water-repellent protrusion pattern mask 19 can be performed by the same method as in the first embodiment. After the exposure, the exposed portion may be cured by heat treatment.

  Next, as shown in FIG. 6D, unexposed portions of the layer 14 made of the photosensitive resin composition A and the layer 15 made of the photosensitive resin composition C are removed. The removal of the unexposed portion can be performed using a solvent. As a solvent, although depending on the material of each photosensitive resin composition, for example, PGMEA, MIBK or the like can be used. Thereby, the discharge port forming member layer A6, the intermediate water repellent layer 7, a part of the protrusion 11 and the water repellent protrusion 12 are formed.

  Next, as shown in FIG. 6E, a layer 16 made of a photosensitive resin composition B is formed on the intermediate water repellent layer 7 and the discharge port forming member layer A6, and a discharge port pattern mask 18 is formed. Then, the pattern of the discharge ports 9 and the projections 11 is formed. The formation of the layer 16 made of the photosensitive resin composition B is preferably performed using a laminating method. The exposure through the discharge port pattern mask 18 can be performed by the same method as in the first embodiment. After the exposure, the exposed portion may be cured by heat treatment.

  Next, as shown in FIG. 6F, the unexposed portion of the layer 16 made of the photosensitive resin composition B is removed. The removal of the unexposed portion can be performed using a solvent. As a solvent, although depending on the material of the photosensitive resin composition B, for example, PGMEA, MIBK, or the like can be used. Thereby, the discharge port forming member layer B8, the discharge port 9, and the protrusion 11 are formed.

  Next, as shown in FIG. 6G, a liquid supply path 3 is formed in the substrate 2, and the mold material 13 is removed to form a liquid flow path 4. The formation of the supply path 3 and the removal of the mold material 13 can be performed in the same manner as in the first embodiment. In the step shown in FIG. 6A, the substrate 2 on which the supply path 3 is already formed is used at the time of the step shown in FIG. 6A by using a laminating method for forming the mold material 13. You can also

  As in the first embodiment, the method according to this embodiment is further heated to 90 ° C. or more and 250 ° C. or less after the step of removing the unexposed portion of the layer 16 made of the photosensitive resin composition B. It is preferable to have the process to do. The heating step may be performed after the step of removing the mold material 13.

  Thereafter, electrical connection is performed, and an ink supply unit is appropriately disposed to obtain an ink jet recording head.

(Third embodiment)
The method for manufacturing a liquid ejection head according to this embodiment includes the following steps. The process of forming the layer which consists of the photosensitive resin composition E used as a flow-path formation member by hardening on a board | substrate. A step of forming a layer made of the photosensitive resin composition A on the layer made of the photosensitive resin composition E, which becomes the discharge port forming member layer A by curing. A step of exposing a layer made of the photosensitive resin composition E to form a liquid flow path pattern. A step of exposing a layer made of the photosensitive resin composition A to form a pattern of ejection openings for ejecting liquid. Removing the unexposed portions of the layer made of the photosensitive resin composition E and the layer made of the photosensitive resin composition A; On the discharge port forming member layer A, a layer made of a photosensitive resin composition C that becomes an intermediate water-repellent layer by curing, and a layer made of a photosensitive resin composition B that becomes a discharge port forming member layer B by curing. And forming in this order. The layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B are exposed to form a pattern of the discharge port, a protrusion protruding toward the inside of the discharge port, and a water-repellent protrusion. Forming. Removing the unexposed portions of the layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B; Here, the water repellent protrusion is a portion in which at least a part of the intermediate water repellent layer protrudes more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B. . According to this method, the liquid discharge head according to the present invention can be manufactured efficiently and accurately.

  FIG. 7 is a schematic cross-sectional view showing each step of the manufacturing method of the ink jet recording head which is an example of the present embodiment. In addition, although formation of the surface water repellent layer 10 is abbreviate | omitted in each process shown by FIG. 7, the surface water repellent layer 10 can also be provided similarly to the manufacturing method shown by FIG. 5 mentioned above.

  First, as shown in FIG. 7A, a layer 22 made of a photosensitive resin composition E and a layer 14 made of a photosensitive resin composition A are formed on a substrate 2 on which an energy generating element 1 is arranged. They are formed in this order. The layer 22 made of the photosensitive resin composition E is a layer that becomes the flow path forming member 21 by curing. As the photosensitive resin composition E, the same material as the photosensitive resin compositions A and B described above can be used, and a cationic polymerization type epoxy resin composition can be preferably used. Formation of the layer 22 made of the photosensitive resin composition E and the layer 14 made of the photosensitive resin composition A can be performed by the same method as in the first embodiment.

  Next, as shown in FIG. 7B, the layer 22 made of the photosensitive resin composition E is exposed through the flow path pattern mask 23, and the layer 22 made of the photosensitive resin composition E. The pattern of the flow path 4 is formed in The exposure through the flow path pattern mask 23 can be performed by the same method as in the first embodiment.

  Next, as shown in FIG. 7C, the layer 14 made of the photosensitive resin composition A is exposed through the discharge port pattern mask 20, and the layer 14 made of the photosensitive resin composition A. The pattern of the discharge ports 9 is formed on the substrate. The photosensitive resin composition A and the photosensitive resin composition E are provided with a difference in sensitivity, and when the exposure is performed through the discharge port pattern mask 20, only the photosensitive resin composition A is cured. By selecting the amount, the discharge port 9 can be formed. Specifically, when the exposure amounts of the photosensitive resin composition A and the photosensitive resin composition E are Eth1 and Eth4, respectively, and the exposure amount E satisfies Eth1 <E <Eth4, the photosensitive resin Only composition A can be cured. That is, it is preferable to satisfy Eth1 <Eth4. The exposure through the discharge port pattern mask 20 can be performed by the same method as in the first embodiment. After the exposure, the exposed portion may be cured by heat treatment.

  Next, as shown in FIG. 7D, unexposed portions of the layer 22 made of the photosensitive resin composition E and the layer 14 made of the photosensitive resin composition A are removed. The removal of the unexposed portion can be performed using a solvent. As a solvent, although depending on the material of each photosensitive resin composition, for example, PGMEA, MIBK or the like can be used. Thereby, the flow path forming member 21, the discharge port forming member layer A6, the flow path 4, and a part of the discharge port 9 are formed.

  Next, as shown in FIG. 7E, the layer 16 made of the photosensitive resin composition B and the layer 15 made of the photosensitive resin composition C are formed in this order on the film substrate 24. . As the film base 24, a film base made of PET, polyimide, or the like can be used. Formation of the layer 16 composed of the photosensitive resin composition B and the layer 15 composed of the photosensitive resin composition C can be performed by the same method as in the first embodiment.

  Next, as shown in FIG. 7 (F), the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B on the film substrate 24 are laminated by a laminating method. Transfer onto the discharge port forming member layer A6. Thereby, the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B are formed in this order on the discharge port forming member layer A6.

  Next, as shown in FIG. 7G, the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B are exposed through an ejection port pattern mask 18. Thereby, the pattern of the protrusion 11 which becomes convex toward the inside of the discharge port 9 and the discharge port is formed. The exposure through the discharge port pattern mask 18 can be performed by the same method as in the first embodiment.

  Next, as shown in FIG. 7H, the layer 15 made of the photosensitive resin composition C is exposed through a water-repellent protrusion pattern mask 19 to be made of the photosensitive resin composition C. A pattern of the water repellent protrusion 12 is formed on the layer 15. The photosensitive resin composition B and the photosensitive resin composition C have a sensitivity difference, and only the photosensitive resin composition C is cured when exposed through the water repellent protrusion pattern mask 19. The water-repellent protrusion 12 can be formed by selecting the amount of exposure to be performed. Specifically, when the curing exposure amounts of the photosensitive resin composition B and the photosensitive resin composition C are Eth2 and Eth3, respectively, and the exposure amount E satisfies Eth2> E> Eth3, the photosensitive resin Only composition C can be cured. That is, it is preferable to satisfy Eth2> Eth3. The exposure through the water repellent protrusion pattern mask 19 can be performed by the same method as in the first embodiment. After the exposure, the exposed portion may be cured by heat treatment.

  Next, as shown in FIG. 7I, unexposed portions of the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B are removed. The removal of the unexposed portion can be performed using a solvent. As a solvent, although depending on the material of each photosensitive resin composition, for example, PGMEA, MIBK or the like can be used. Thereby, the intermediate water repellent layer 7, the discharge port forming member layer B8, the discharge port 9, the protrusion 11 and the water repellent protrusion 12 are formed.

  Next, as shown in FIG. 7J, a liquid supply path 3 is formed in the substrate 2. The formation of the supply path 3 can be performed similarly to the first embodiment. In addition, in the process shown by FIG. 7 (A), by using the laminating method for formation of the layer 22 which consists of the photosensitive resin composition E, the supply path 3 has already been carried out at the time of the process shown by FIG. It is also possible to use the substrate 2 on which is formed.

  As in the first embodiment, the method according to this embodiment is further performed after the step of removing the unexposed portion of the layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B. It is preferable to have a step of heating to 90 ° C. or higher and 250 ° C. or lower.

  Thereafter, electrical connection is performed, and an ink supply unit is appropriately disposed to obtain an ink jet recording head.

[Example 1]
In this example, an ink jet recording head was manufactured by the steps shown in FIGS.

  First, as shown in FIG. 8A, a liquid flow path mold 13 made of a flow path forming resin composition was formed on a substrate 2. Specifically, polymethylisopropenyl ketone (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name: ODUR-1010) is placed on a silicon substrate 2 on which an energy generating element 1 for generating energy for discharging liquid is disposed. ) Was applied. Thereafter, a heat treatment was performed at 120 ° C. for 5 minutes to form a layer made of a flow path forming resin composition having a thickness of 15 μm. After exposing the layer made of the flow path forming resin composition with an exposure apparatus UX3000 (trade name, manufactured by Ushio Electric Co., Ltd.) through a flow path pattern mask, the exposed portion is dissolved and removed with MIBK. A mold material 13 was formed.

  Next, as shown in FIG. 8B, the layer 14 made of the photosensitive resin composition A and the layer 15 made of the photosensitive resin composition C are formed in this order on the mold material 13 and the substrate 2. did. Specifically, a photosensitive resin composition having a composition shown in Table 1 that becomes a discharge port forming member layer A6 by curing was applied onto the mold material 13 and the substrate 2 by spin coating. Then, the heat processing was performed at 90 degreeC for 5 minute (s), and the layer 14 which consists of the photosensitive resin composition A with a thickness of 18 micrometers was formed. Further, a photosensitive resin composition having the composition shown in Table 2 and which becomes the intermediate water-repellent layer 7 by curing was applied onto the layer 14 made of the photosensitive resin composition A by a slit coating method. Thereafter, a heat treatment was performed at 50 ° C. for 3 minutes to form a layer 15 made of a photosensitive resin composition C having a thickness of 2 μm.

  In Table 2, the silane condensate was prepared by the following method. γ-glycidoxypropyltriethoxysilane 12.53 g (0.045 mol), methyltriethoxysilane 8.02 g (0.0225 mol), phenyltrimethoxysilane 4.46 g (0.0225 mol), in the formula (1) In a flask equipped with a condenser tube, 0.96 g (0.726 mmol) of the compound represented, 5.93 g of water, 15.15 g of ethanol and 3.83 g of hydrofluoroether (trade name: HFE7200, manufactured by Sumitomo 3M Limited) Put in. These were stirred at room temperature for 5 minutes and then heated to reflux for 24 hours to prepare silane condensates.

Further, the photosensitive resin composition shown in Table 1 was formed on a silicon substrate, exposed at 10000 J / m ² , and then subjected to a heat treatment at 90 ° C. for 5 minutes. The angles (θ _A , θ _B ) were 59 °. In addition, the photosensitive resin composition shown in Table 2 was formed on a silicon substrate, exposed at 1000 J / m ² , and then subjected to heat treatment at 90 ° C. for 5 minutes. The angle (θ _s ) was 98 °. In addition, the contact angle meter CA-X150 (trade name, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the static contact angle, and the contact angle of 10 μl of pure water droplets was measured.

  Next, as shown in FIG. 8C, a layer 16 made of the photosensitive resin composition B was formed on the layer 15 made of the photosensitive resin composition C. Specifically, a dry film of the photosensitive resin composition shown in Table 1 that becomes the discharge port forming member layer B8 by curing is prepared, and this is laminated on the layer 15 made of the photosensitive resin composition C. Was laminated. Thereby, the layer 16 made of the photosensitive resin composition B having a thickness of 6 μm was formed. The dry film was prepared by applying the photosensitive resin composition shown in Table 1 on a PET film having a thickness of 100 μm by spin coating, and heating the solution at 90 ° C. for 5 minutes to volatilize the solvent.

Next, as shown in FIG. 8D, a layer 14 made of the photosensitive resin composition A, a layer 15 made of the photosensitive resin composition C, and a layer 16 made of the photosensitive resin composition B are formed. It exposed and formed the pattern of the processus | protrusion 11 which becomes convex toward the inner side of the discharge port 9 and the discharge port 9. As shown in FIG. Specifically, the layer 14 composed of the photosensitive resin composition A, the layer 15 composed of the photosensitive resin composition C, and the photosensitive resin are arranged through an ejection port pattern mask 18 having a pattern of ejection ports 9 and protrusions 11. The layer 16 made of the conductive resin composition B was subjected to pattern exposure. An i-line exposure stepper was used for exposure. The exposure amount was 10,000 J / m ² .

Next, as shown in FIG. 8E, the layer 15 made of the photosensitive resin composition C was exposed to form a pattern of the water-repellent protrusions 12. Specifically, the layer 15 made of the photosensitive resin composition C is formed at 1000 J / m ² using an i-line exposure stepper through the water-repellent protrusion pattern mask 19 having the pattern of the water-repellent protrusion 12. Pattern exposure was performed with an exposure amount. The cured exposure amount Eth1 of the photosensitive resin composition A, the cured exposure amount Eth2 of the photosensitive resin composition B, and the cured exposure amount Eth3 of the photosensitive resin composition C satisfied Eth1> Eth3 and Eth2> Eth3. . For this reason, in this exposure, only the layer 15 made of the photosensitive resin composition C was partially cured by pattern exposure.

  Next, as shown in FIG. 8F, the layer 14 made of the photosensitive resin composition A, the layer 15 made of the photosensitive resin composition C, and the layer 16 made of the photosensitive resin composition B. Unexposed areas were removed. Specifically, after heating at 90 ° C. for 4 minutes to cure the exposed portion, the layer 14 made of the photosensitive resin composition A, the layer 15 made of the photosensitive resin composition C, and the photosensitive resin composition The unexposed portion of the layer 16 made of the product B was dissolved and removed with PGMEA. Thereby, the discharge port forming member layer A6, the intermediate water repellent layer 7, the discharge port forming member layer B8, the discharge port 9, the protrusion 11, and the water repellent protrusion 12 were formed.

  Next, as shown in FIG. 8G, a liquid supply path 3 was formed in the substrate 2 and the mold material 13 was removed. Specifically, after the discharge port forming member on the substrate 2 was protected with a rubber film, the supply path 3 was formed on the substrate 2 using an alkaline etching solution. Thereafter, the rubber film was removed, and the mold material 13 was dissolved and removed with methyl lactate to form a liquid flow path 4. Furthermore, after heating at 200 ° C. for 1 hour and thermosetting, electrical connection was performed, and an ink supply unit was appropriately disposed to obtain an ink jet recording head. Table 5 shows the size of each part of the obtained ink jet recording head. Each symbol in Table 5 corresponds to each symbol in FIG.

[Example 2]
In this example, an ink jet recording head was manufactured by the steps shown in FIGS.

  First, as shown in FIG. 6A, a liquid flow path mold 13 made of a flow path forming resin composition was formed on the substrate 2 by the same method as in Example 1.

Next, as shown in FIG. 6B, a layer 14 made of a photosensitive resin composition A is formed on the mold material 13 and the substrate 2, and this is exposed to form a pattern of the discharge ports 9. did. Specifically, the layer 14 made of the photosensitive resin composition A was formed by the same method as in Example 1. Thereafter, the layer 14 made of the photosensitive resin composition A was subjected to pattern exposure at an exposure amount of 10,000 J / m ² using an i-line exposure stepper through the discharge port pattern mask 20 having the pattern of the discharge ports 9.

Next, as shown in FIG. 6C, a layer 15 made of the photosensitive resin composition C is formed on the layer 14 made of the photosensitive resin composition A, and this is exposed to a discharge port. 9, the pattern of the protrusion 11 which becomes convex toward the inner side of the discharge port 9 and the pattern of the water-repellent protrusion 12 were formed. Specifically, the layer 15 made of the photosensitive resin composition C was formed by the same method as in Example 1. Thereafter, the layer 15 made of the photosensitive resin composition C is formed by using an i-line exposure stepper through a water repellent protrusion pattern mask 19 having a pattern of the discharge port 9, the protrusion 11, and the water repellent protrusion 12. Pattern exposure was performed at an exposure amount of / m ² . In addition, the curing exposure amount Eth1 of the photosensitive resin composition A and the curing exposure amount Eth3 of the photosensitive resin composition C satisfied Eth1> Eth3. For this reason, in this exposure, only the layer 15 made of the photosensitive resin composition C was partially cured by pattern exposure.

  Next, as shown in FIG. 6D, unexposed portions of the layer 14 made of the photosensitive resin composition A and the layer 15 made of the photosensitive resin composition C were removed. Specifically, after heating the exposed part by heating at 90 ° C. for 4 minutes, the unexposed part of the layer 14 made of the photosensitive resin composition A and the layer 15 made of the photosensitive resin composition C is made of PGMEA. Dissolved and removed. Thus, the discharge port forming member layer A6, the intermediate water repellent layer 7, a part of the protrusion 11 and the water repellent protrusion 12 were formed.

Next, as shown in FIG. 6E, a layer 16 made of a photosensitive resin composition B is formed on the intermediate water repellent layer 7 and the discharge port forming member layer A6, and this is exposed. A pattern of the discharge ports 9 and the protrusions 11 was formed. Specifically, a dry film of the photosensitive resin composition shown in Table 3 was prepared and laminated on the intermediate water-repellent layer 7 and the discharge port forming member layer A6 by a laminating method. Thereby, the layer 16 made of the photosensitive resin composition B having a thickness of 6 μm was formed. The dry film was produced by applying the photosensitive resin composition shown in Table 3 on a PET film having a thickness of 100 μm by a spin coating method and heating the solution at 90 ° C. for 5 minutes to volatilize the solvent. Thereafter, the layer 16 made of the photosensitive resin composition B is patterned at an exposure amount of 4000 J / m ² using an i-line exposure stepper through an ejection port pattern mask 18 having a pattern of ejection ports 9 and protrusions 11. Exposed.

In addition, the photosensitive resin composition shown in Table 3 was formed on a silicon substrate, exposed at 4000 J / m ² , and then subjected to a heat treatment at 90 ° C. for 5 minutes. The angle (θ _B ) was 60 °.

  Next, as shown in FIG. 6F, the unexposed portion of the layer 16 made of the photosensitive resin composition B was removed. Specifically, the exposed portion was cured by heating at 90 ° C. for 4 minutes, and then the unexposed portion of the layer 16 made of the photosensitive resin composition B was dissolved and removed with MIBK. Thereby, the discharge port forming member layer B8, the discharge port 9, and the protrusion 11 were formed.

  Next, as shown in FIG. 6G, the liquid supply path 3 was formed on the substrate 2 as in Example 1, and the mold material 13 was removed to form the liquid flow path 4. Furthermore, after heating at 200 ° C. for 1 hour and thermosetting, electrical connection was performed, and an ink supply unit was appropriately disposed to obtain an ink jet recording head. Table 5 shows the size of each part of the obtained ink jet recording head.

[Example 3]
In this example, an ink jet recording head was manufactured by the steps shown in FIGS.

  First, as shown in FIG. 7A, the layer 22 made of the photosensitive resin composition E and the layer 14 made of the photosensitive resin composition A were formed on the substrate 2 in this order. Specifically, a photosensitive resin composition having the composition shown in Table 1 is applied on a substrate 2 made of silicon on which the energy generating element 1 is disposed by spin coating, and heat-treated at 90 ° C. for 5 minutes. A layer 22 made of a photosensitive resin composition E having a thickness of 15 μm was formed. Furthermore, a dry film of a photosensitive resin composition having the composition shown in Table 4 was prepared, and this was laminated on the layer 22 made of the photosensitive resin composition E by a laminating method, and a photosensitive film having a thickness of 3 μm. A layer 14 made of the resin composition A was formed.

Next, as shown in FIG. 7B, the layer 22 made of the photosensitive resin composition E was exposed to form a pattern of the flow path 4. Specifically, using the i-line exposure stepper through the flow path pattern mask 23 having the pattern of the flow path 4, the layer 22 made of the photosensitive resin composition E and the photosensitive resin composition A are used. Layer 14 was pattern exposed with an exposure dose of 10,000 J / m ² .

Next, as shown in FIG. 7C, the layer 14 made of the photosensitive resin composition A was exposed to form a pattern of the discharge ports 9. Specifically, the layer 14 made of the photosensitive resin composition A is patterned with an exposure amount of 1000 J / m ² using an i-line exposure stepper through the discharge port pattern mask 20 having the pattern of the discharge ports 9. Exposed. In addition, the curing exposure amount Eth1 of the photosensitive resin composition A and the curing exposure amount Eth4 of the photosensitive resin composition E satisfied Eth1 <Eth4. Therefore, in this exposure, only the layer 14 made of the photosensitive resin composition A was partially cured by pattern exposure.

  Next, as shown in FIG. 7D, unexposed portions of the layer 22 made of the photosensitive resin composition E and the layer 14 made of the photosensitive resin composition A were removed. Specifically, after the exposed portion was cured by heating at 90 ° C. for 4 minutes, the unexposed portion of the layer 22 made of the photosensitive resin composition E and the layer 14 made of the photosensitive resin composition A was changed to PGMEA. And removed by dissolution. Thereby, the flow path forming member 21, the discharge port forming member layer A6, the flow path 4, and a part of the discharge port 9 were formed.

  Next, as shown in FIG. 7E, the layer 16 made of the photosensitive resin composition B and the layer 15 made of the photosensitive resin composition C were formed in this order on the film substrate 24. . Specifically, a photosensitive resin composition having the composition shown in Table 1 is applied on a film substrate 24 made of PET having a thickness of 100 μm by spin coating, and heat-treated at 90 ° C. for 5 minutes. A layer 16 made of a photosensitive resin composition B having a thickness of 6 μm was formed. Further, a photosensitive resin composition having the composition shown in Table 2 was applied on the layer 16 made of the photosensitive resin composition B by a slit coating method, and was heat-treated at 50 ° C. for 3 minutes. A layer 15 composed of the composition C was formed.

  Next, as shown in FIG. 7 (F), the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B on the film substrate 24 are laminated by a laminating method. Transferred onto the discharge port forming member layer A6. Thereby, the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B were formed in this order on the discharge port forming member layer A6.

Next, as shown in FIG. 7G, the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B are exposed to expose the discharge port 9 and the inside of the discharge port. The pattern of the protrusion 11 which becomes convex toward is formed. Specifically, the layer 15 made of the photosensitive resin composition C and the photosensitive resin composition using an i-line exposure stepper through the discharge port pattern mask 18 having the pattern of the discharge ports 9 and the protrusions 11. The layer 16 made of B was subjected to pattern exposure with an exposure amount of 10,000 J / m ² .

Next, as shown in FIG. 7H, the layer 15 made of the photosensitive resin composition C was exposed to form a pattern of the water-repellent protrusions 12. Specifically, the layer 15 made of the photosensitive resin composition C is exposed at 1000 J / m ² using an i-line exposure stepper through the water repellent protrusion pattern mask 19 having the pattern of the water repellent protrusion 12. Exposed in quantity. In addition, the curing exposure amount Eth2 of the photosensitive resin composition B and the curing exposure amount Eth3 of the photosensitive resin composition C satisfy Eth2> Eth3. For this reason, in this exposure, only the layer 15 made of the photosensitive resin composition C was partially cured by pattern exposure.

  Next, as shown in FIG. 7I, unexposed portions of the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B were removed. Specifically, after the exposed portion was cured by heating at 90 ° C. for 4 minutes, the unexposed portions of the layer 15 made of the photosensitive resin composition C and the layer 16 made of the photosensitive resin composition B were changed to PGMEA. And removed by dissolution. Thereby, the intermediate water repellent layer 7, the discharge port forming member layer B8, the discharge port 9, the protrusion 11 and the water repellent protrusion 12 were formed.

  Next, as shown in FIG. 7J, a liquid supply path 3 was formed on the substrate 2 in the same manner as in Example 1. Furthermore, after heating at 200 ° C. for 1 hour and thermosetting, electrical connection was performed, and an ink supply unit was appropriately disposed to obtain an ink jet recording head. Table 5 shows the size of each part of the obtained ink jet recording head.

[Example 4]
An ink jet recording head was prepared in the same manner as in Example 1 except that the pattern shape of the water repellent protrusion pattern mask 19 was changed and the protrusion length d of the water repellent protrusion 12 was changed to 0.5 μm. Table 5 shows the size of each part of the obtained ink jet recording head.

[Example 5]
The thickness of the layer 14 made of the photosensitive resin composition A is changed to 20 μm, the thickness of the layer 16 made of the photosensitive resin composition B is changed to 4 μm, and the thickness h of the discharge port forming member layer A6 on the flow path 4 is changed. An ink jet recording head was produced in the same manner as in Example 1 except that the thickness was changed to 5 μm. Table 5 shows the size of each part of the obtained ink jet recording head.

[Comparative Example 1]
In this comparative example, an ink jet recording head was manufactured by the steps shown in FIGS.

  First, as shown in FIG. 9A, a liquid flow path mold 13 made of a flow path forming resin composition was formed on the substrate 2 by the same method as in Example 1.

  Next, as shown in FIG. 9B, a layer 14 made of a photosensitive resin composition A was formed on the mold material 13 and the substrate 2. Specifically, a photosensitive resin composition having the composition shown in Table 3 is applied onto the mold material 13 and the substrate 2 by a spin coating method, and heat-treated at 90 ° C. for 5 minutes to obtain a thickness of 25 μm. A layer 14 made of the photosensitive resin composition A was formed.

Next, as shown in FIG. 9C, the layer 14 made of the photosensitive resin composition A is exposed to form a discharge port 9 and a pattern of protrusions 11 protruding toward the inside of the discharge port 9. Formed. Specifically, the layer 14 made of the photosensitive resin composition A is exposed to 4000 J / m ² using an i-line exposure stepper through the discharge port pattern mask 18 having the pattern of the discharge ports 9 and the protrusions 11. Pattern exposure.

  Next, as shown in FIG. 9D, the unexposed portion of the layer 14 made of the photosensitive resin composition A was removed. Specifically, after heating at 90 ° C. for 4 minutes to cure the exposed portion, the unexposed portion of the layer 14 made of the photosensitive resin composition A was dissolved and removed with PGMEA. Thereby, the discharge port forming member layer A6, the discharge port 9, and the protrusion 11 were formed.

  Next, as shown in FIG. 9E, as in Example 1, the liquid supply path 3 was formed on the substrate 2, and the mold material 13 was removed to form the liquid flow path 4. Furthermore, after heating at 200 ° C. for 1 hour and thermosetting, electrical connection was performed, and an ink supply unit was appropriately disposed to obtain an ink jet recording head. Table 5 shows the size of each part of the obtained ink jet recording head.

[Comparative Example 2]
An ink jet recording head was produced in the same manner as in Comparative Example 1 except that the thickness of the layer 14 made of the photosensitive resin composition A was changed to 18 μm. Table 5 shows the size of each part of the obtained ink jet recording head.

[Comparative Example 3]
9C, in the same manner as in Comparative Example 1 except that the exposure is performed through the discharge port pattern mask 18 that has the pattern of the discharge ports 9 and does not have the pattern of the protrusions 11. An ink jet recording head was produced. Table 5 shows the size of each part of the obtained ink jet recording head.

[Evaluation]
The ink jet recording heads produced in Examples 1 to 5 and Comparative Examples 1 to 3 were filled with ink having a viscosity of 2.4 cps and a surface tension of 33 dyn / cm, and the following evaluation was performed.

(Print pause evaluation)
Printing was performed again after 0.9 seconds and 2.7 seconds, and whether or not ink can be normally ejected was evaluated according to the following criteria. The results are shown in Table 6.
○: Ink can be normally discharged even after the printing pause time.
X: Ink cannot be ejected normally after the printing pause time.

(1000 sheet printing evaluation)
The print quality after printing 1000 sheets was evaluated according to the following criteria. The results are shown in Table 6.
○: The occurrence of satellites and slight deviation of ink droplets do not affect the image quality.
Δ: Satellites are generated separately from the main ink droplets, and the image quality is disturbed.
X: Ink droplets that have not been ejected or deviation of ink droplets are generated, and the image quality is greatly disturbed.

  As shown in Table 6, the ink jet recording heads of Examples 1 to 5 were able to eject ink normally even after the printing pause time in the printing pause evaluation. Also, the printing quality after printing 1000 sheets was good. On the other hand, in the inkjet recording head of Comparative Example 1, when printing was stopped for 2.7 seconds, the ink was not ejected after that, or the landing position was shifted without ejecting ink normally. In the ink jet recording head of Comparative Example 2, the initial print quality was good in 1000 sheet print evaluation, but the print quality gradually decreased. After printing 1000 sheets, the discharge port forming member of the ink jet recording head of Comparative Example 2 was observed, and cracks were confirmed in several places. Since the discharge port forming member is thin and has low rigidity, it is presumed that cracking occurred due to the force applied by wiping. Further, in the ink jet recording head of Comparative Example 3, there was a deviation between the landing positions of the main droplet and the satellite after printing 1000 sheets.

2 Substrate 4 Channel 5 Discharge port forming member 6 Discharge port forming member layer A
7 Intermediate water repellent layer 8 Discharge port forming member layer B
9 Discharge port 10 Surface water-repellent layer 11 Projection 12 Water-repellent protrusion 13 Mold material 14 Layer 15 made of photosensitive resin composition A Layer 16 made of photosensitive resin composition C Layer 22 made of photosensitive resin composition B Photosensitivity Layer made of resin composition E

Claims (22)

A liquid discharge head comprising: a substrate; and a discharge port forming member formed on the substrate and having a discharge channel for discharging a liquid and a liquid channel communicating with the discharge port,
The discharge port forming member has, in order from the substrate side, a discharge port forming member layer A, an intermediate water repellent layer, and a discharge port forming member layer B.
The discharge port forming member has a protrusion that is convex toward the inside of the discharge port,
The discharge port forming member has a water-repellent protruding portion in which at least a part of the intermediate water-repellent layer protrudes more inside the discharge port than the discharge port forming member layer A and the discharge port forming member layer B. A liquid discharge head. When the static contact angle with respect to pure water of the water repellent protrusion is θ _s , and the static contact angles with respect to pure water of the discharge port forming member layer A and the discharge port forming member layer B are θ _A and θ _B , respectively. , Θ _s > θ _A and θ _s > θ _B are satisfied. When the static contact angle theta _s to pure water of the water repellent protruding portions, theta _s> liquid discharge head according to claim 1 or 2 satisfy 70 °.   Cationic polymerizable resin in which the intermediate water-repellent layer has a hydrolyzable silane compound having an epoxy group and a condensate of a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group, and two or more epoxy groups. 4. The liquid discharge head according to claim 1, comprising a cured product of a composition comprising: a photoacid generator that absorbs light and generates an acid. 5.   A composition in which at least one of the discharge port forming member layer A and the discharge port forming member layer B includes a cationic polymerizable resin having two or more epoxy groups and a photoacid generator that absorbs light and generates an acid. The liquid discharge head according to claim 1, comprising a cured product.   6. The liquid discharge head according to claim 1, wherein a surface water-repellent layer is formed on a first surface of the discharge port forming member where the discharge port opens. Forming a liquid flow path mold material comprising a flow path forming resin composition on a substrate;
Forming a layer made of the photosensitive resin composition A to be a discharge port forming member layer A by curing on the mold material and the substrate;
Forming a layer made of the photosensitive resin composition C, which becomes an intermediate water-repellent layer by curing on the layer made of the photosensitive resin composition A;
Forming a layer made of the photosensitive resin composition B, which becomes the discharge port forming member layer B by curing, on the layer made of the photosensitive resin composition C;
A layer made of the photosensitive resin composition A, a layer made of the photosensitive resin composition C, and a layer made of the photosensitive resin composition B are exposed to discharge liquid to the inside of the discharge port. Forming a projection that is convex toward the surface, and a pattern of the water-repellent protrusion,
Removing the unexposed portion of the layer made of the photosensitive resin composition A, the layer made of the photosensitive resin composition C, and the layer made of the photosensitive resin composition B;
Removing the mold material;
A method of manufacturing a liquid discharge head having
The water repellent protrusion is a portion in which at least a part of the intermediate water repellent layer protrudes to the inside of the discharge port from the discharge port forming member layer A and the discharge port forming member layer B. A method for manufacturing a liquid discharge head.   The photosensitive resin composition C comprises a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound condensate containing a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group, and an epoxy group. The method for producing a liquid discharge head according to claim 7, comprising: a cationically polymerizable resin having two or more of a photoacid generator and a photoacid generator that absorbs light to generate an acid.   At least one of the photosensitive resin composition A and the photosensitive resin composition B includes a cationic polymerizable resin having two or more epoxy groups, and a photoacid generator that absorbs light and generates an acid. Item 9. A method for producing a liquid discharge head according to Item 7 or 8.   When the curing exposure amount of the photosensitive resin composition A is Eth1, the curing exposure amount of the photosensitive resin composition B is Eth2, and the curing exposure amount of the photosensitive resin composition C is Eth3, Eth1> Eth3 and Eth2 The method for manufacturing a liquid ejection head according to claim 7, wherein> Eth3 is satisfied.   After the step of removing unexposed portions of the layer made of the photosensitive resin composition A, the layer made of the photosensitive resin composition C, and the layer made of the photosensitive resin composition B, 90 ° C. or more, 250 The method for manufacturing a liquid discharge head according to claim 7, further comprising a step of heating to a temperature of less than or equal to degrees Celsius. Forming a liquid flow path mold material comprising a flow path forming resin composition on a substrate;
Forming a layer made of the photosensitive resin composition A to be a discharge port forming member layer A by curing on the mold material and the substrate;
Exposing a layer made of the photosensitive resin composition A to form a pattern of discharge ports for discharging a liquid;
Forming a layer made of the photosensitive resin composition C, which becomes an intermediate water-repellent layer by curing on the layer made of the photosensitive resin composition A;
Exposing the layer made of the photosensitive resin composition C to form a pattern of the discharge port, a protrusion protruding toward the inside of the discharge port, and a water-repellent protrusion;
Removing the unexposed portions of the layer made of the photosensitive resin composition A and the layer made of the photosensitive resin composition C;
On the intermediate water repellent layer, a step of forming a layer made of the photosensitive resin composition B, which becomes the discharge port forming member layer B by curing,
Exposing a layer comprising the photosensitive resin composition B to form a pattern of the ejection openings and the protrusions;
Removing the unexposed portion of the layer made of the photosensitive resin composition B;
Removing the mold material;
A method of manufacturing a liquid discharge head having
The water repellent protrusion is a portion in which at least a part of the intermediate water repellent layer protrudes to the inside of the discharge port from the discharge port forming member layer A and the discharge port forming member layer B. A method for manufacturing a liquid discharge head.   The photosensitive resin composition C comprises a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound condensate containing a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group, and an epoxy group. The method for producing a liquid discharge head according to claim 12, comprising a cationically polymerizable resin having two or more of the above and a photoacid generator that absorbs light to generate an acid.   At least one of the photosensitive resin composition A and the photosensitive resin composition B includes a cationic polymerizable resin having two or more epoxy groups, and a photoacid generator that absorbs light and generates an acid. Item 14. A method for manufacturing a liquid discharge head according to Item 12 or 13.   The liquid according to any one of claims 12 to 14, wherein Eth1> Eth3 is satisfied, where Eth1 is a curing exposure amount of the photosensitive resin composition A and Eth3 is a curing exposure amount of the photosensitive resin composition C. Manufacturing method of the discharge head.   The liquid according to any one of claims 12 to 15, further comprising a step of heating to 90 ° C or higher and 250 ° C or lower after the step of removing the unexposed portion of the layer made of the photosensitive resin composition B. Manufacturing method of the discharge head. Forming a layer made of the photosensitive resin composition E, which becomes a flow path forming member by curing on the substrate;
On the layer made of the photosensitive resin composition E, a step of forming a layer made of the photosensitive resin composition A, which becomes the discharge port forming member layer A by curing,
Exposing a layer made of the photosensitive resin composition E to form a liquid flow path pattern; and
Exposing a layer made of the photosensitive resin composition A to form a pattern of discharge ports for discharging a liquid;
Removing the unexposed portions of the layer made of the photosensitive resin composition E and the layer made of the photosensitive resin composition A;
On the discharge port forming member layer A, a layer made of a photosensitive resin composition C that becomes an intermediate water-repellent layer by curing, and a layer made of a photosensitive resin composition B that becomes a discharge port forming member layer B by curing. And in this order,
The layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B are exposed to form a pattern of the discharge port, a protrusion protruding toward the inside of the discharge port, and a water-repellent protrusion. Forming a step;
Removing the unexposed portions of the layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B;
A method of manufacturing a liquid discharge head having
The water repellent protrusion is a portion in which at least a part of the intermediate water repellent layer protrudes to the inside of the discharge port from the discharge port forming member layer A and the discharge port forming member layer B. A method for manufacturing a liquid discharge head.   The photosensitive resin composition C comprises a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound condensate containing a hydrolyzable silane compound having a perfluoropolyether group or a perfluoroalkyl group, and an epoxy group. 18. The method of manufacturing a liquid discharge head according to claim 17, comprising a cationically polymerizable resin having two or more and a photoacid generator that absorbs light to generate an acid.   A cationic polymerizable resin in which at least one composition selected from the group consisting of the photosensitive resin composition A, the photosensitive resin composition B, and the photosensitive resin composition E has two or more epoxy groups; The method of manufacturing a liquid discharge head according to claim 17, comprising a photoacid generator that absorbs light and generates an acid.   20. The liquid according to claim 17, wherein Eth1 <Eth4 is satisfied, where Eth1 is a curing exposure amount of the photosensitive resin composition A and Eth4 is a curing exposure amount of the photosensitive resin composition E. Manufacturing method of the discharge head.   21. The liquid according to any one of claims 17 to 20, wherein Eth2> Eth3 is satisfied, where Eth2 is a curing exposure amount of the photosensitive resin composition B and Eth3 is a curing exposure amount of the photosensitive resin composition C. Manufacturing method of the discharge head.   18. The method further comprises a step of heating to 90 ° C. or more and 250 ° C. or less after the step of removing the unexposed portion of the layer made of the photosensitive resin composition C and the layer made of the photosensitive resin composition B. 22. A method for manufacturing a liquid discharge head according to any one of items 1 to 21.

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