JP2016132111A - Membrane manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a uniform film having water repellency.SOLUTION: A method for producing a film includes the steps of: forming an intermediate layer containing a compound represented by the following formula (1) on a resin layer containing a resin having a benzene ring in the structure; and forming a film containing a condensation product of a hydrolyzable silane compound containing the hydrolyzable silane compound having a fluorine-containing group on the intermediate film. A water-repellent film is formed on the surface of a discharge port forming member by the method for producing the film. In the formula (1), n is an integer of 0-3; and R represents a hydrogen atom, a hydroxyl group or a methyl group.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a membrane.

  When recording on a recording medium by an ink jet recording apparatus, ink is ejected in a state where the ink jet recording head and the recording medium are close to each other, so that the ejected ink rebounds from the recording medium and adheres to the ejection surface of the ink jet recording head. There is a case. In addition, when the ink remains in the ejection port and becomes highly viscous, or when fiber or dust of the recording medium adheres to the ejection surface, the ejection port may be clogged. This clogging reduces the discharge pressure of the ink, so that the ink adheres to the discharge surface also in this case. When such attached ink is generated, the ink is transferred to the recording medium and the recording quality is deteriorated. For this reason, it is known to prevent adhesion of ink by forming a water-repellent layer on the ejection surface of the ink jet recording head. For example, Patent Document 1 discloses forming a water-repellent layer on a coated photosensitive resin layer that forms a discharge port.

JP 2009-255415 A

  In the technique disclosed in Patent Document 1, the coated photosensitive resin layer and the water repellent layer are collectively patterned by diffusing the acid generated from the photopolymerization initiator in the coated photosensitive resin layer into the water repellent material. To do. This method is premised on that when a water-repellent material is applied on the coated photosensitive resin layer, the water-repellent material dissolves the coated photosensitive resin layer to some extent, and the both are compatible. However, when a coated photosensitive resin layer that is incompatible with the water repellent material is used, the water repellent layer cannot be formed uniformly, resulting in poor printing. For example, when a water repellent material is applied by spin coating, the water repellent material is repelled to the outer periphery by centrifugal force before forming a uniform film on the coated photosensitive resin layer, and a uniform film may not be formed. is there. In addition, even in the case where a uniform film can be formed, in the case of a fluorine-based water repellent material, aggregation proceeds with the fluorine component as a nucleus after film formation, resulting in a decrease in resolution and non-uniformity in water repellency. There is.

  An object of this invention is to provide the method of manufacturing the uniform film | membrane which shows water repellency by hardening.

The method for producing a film according to the present invention includes a step of forming an intermediate layer containing a compound represented by the following formula (1) on a resin layer containing a resin having a benzene ring in the structure;
Forming a film containing a condensation product of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group on the intermediate layer;
It is characterized by including.

(In formula (1), n represents an integer of 0 to 3, and R represents a hydrogen atom, a hydroxyl group or a methyl group).

Moreover, the method for producing a film according to the present invention includes a step of forming a resin layer containing a resin having a benzene ring in the structure and a compound represented by the formula (1),
Heat-treating the resin layer;
Forming a film containing a condensation product of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group on the heat-treated resin layer;
It is characterized by including.

  According to the present invention, a uniform film exhibiting water repellency can be produced by curing.

It is (A) typical perspective view and (B) typical sectional view showing an example of the liquid discharge head obtained by applying the manufacturing method of the film concerning the present invention. It is typical sectional drawing which shows an example of the manufacturing method of the liquid discharge head to which the manufacturing method of the film | membrane which concerns on this invention is applied. It is a typical top view which shows the example of the discharge port shape of the liquid discharge head to which the manufacturing method of the film | membrane concerning this invention is applied. It is typical sectional drawing which shows an example of the manufacturing method of the liquid discharge head to which the manufacturing method of the film | membrane which concerns on this invention is applied.

  As an example to which the film manufacturing method according to the present invention can be applied, a liquid discharge head manufacturing method will be described below. The film manufacturing method according to the present invention can be applied to a water repellent treatment by forming a water repellent film on the surface of a member made of various resins having a benzene ring in the structure, and the applicable range thereof is the manufacture of a liquid discharge head. The method is not limited.

(First embodiment)
FIG. 1A is a schematic perspective view showing an example of a liquid discharge head obtained by applying the film manufacturing method according to the present embodiment. FIG. 1B is a schematic cross-sectional view showing a cross section of the liquid ejection head taken along the line AB of FIG.

  The liquid discharge head shown in FIG. 1 has a substrate 2 on which energy generating elements 1 that generate energy used for discharging liquid are arranged at a predetermined pitch. A supply unit 3 for supplying a liquid to the substrate 2 is opened between two rows of the energy generating elements 1. A liquid flow path 5 is formed on the substrate 2 by a flow path forming member 4. Further, the discharge port 7 is formed by the discharge port forming member 6 corresponding to the resin layer in the method according to the present invention. The flow path forming member 4 and the discharge port forming member 6 may be integrated. An intermediate layer 8 is formed on the discharge port forming member 6. On the intermediate layer, a water repellent material layer 9 corresponding to the film in the method according to the present invention is formed. In the liquid discharge head shown in FIG. 1, energy generated by the energy generating element 1 is given to the liquid supplied from the supply unit 3 through the flow path 5, thereby supplying the liquid via the discharge port 7. It is discharged as a droplet. The liquid discharge head can be preferably used as an ink jet recording head for recording on a recording medium by discharging ink.

  According to the method according to the present embodiment, even when the material constituting the discharge port forming member 6 and the material constituting the water repellent material layer 9 are not compatible, the affinity between the two due to the presence of the intermediate layer 8. The water repellent material layer 9 can be uniformly formed on the discharge port forming member 6.

  2A to 2D are schematic cross-sectional views illustrating an example of a manufacturing method of a liquid discharge head to which the film manufacturing method according to this embodiment is applied. 2A to 2D show the discharge unit 10 of FIG. 1B in an enlarged manner for each step.

  First, as shown in FIG. 2A, the intermediate layer 8 is formed on the resin layer 11. The resin layer 11 is a layer that becomes the discharge port forming member 6, and its cured product is required to have mechanical strength, resistance to liquids such as ink, adhesion to the ground, and resolution as a photolithography material. The From this point of view, in the present invention, the resin layer 11 contains a resin having a benzene ring in the structure. In particular, from the viewpoint of high mechanical strength and liquid resistance, the resin layer 11 preferably includes a bifunctional or higher functional epoxy resin having a benzene ring in the structure. By using an epoxy resin having two or more epoxy groups, the cured product can be three-dimensionally cross-linked, and desired characteristics can be obtained. Examples of the bifunctional or higher functional epoxy resin having a benzene ring in the structure include a bisphenol A type novolak type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and the like. Commercially available products include “157S70”, “jER1031S” (trade name, manufactured by Mitsubishi Chemical Corporation), “Epicron N-695”, “Epicron N-865” (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), and the like. . These may use 1 type and may use 2 or more types together. In addition, the composition containing such a resin is a negative epoxy resin composition.

  It is preferable that the resin layer 11 further contains a photopolymerization initiator. As the photopolymerization initiator, sulfonic acid compounds, diazomethane compounds, sulfonium salt compounds, iodonium salt compounds, disulfone compounds, and the like are preferable. Commercially available products include “Adekaoptomer SP-170”, “Adekaoptomer SP-172”, “Adekaoptomer SP-150” (trade name, manufactured by ADEKA), “BBI-103”, “BBI-102” ( (Trade name, manufactured by Midori Kagaku), “IBPF”, “IBCF”, “TS-01”, “TS-91” (trade name, manufactured by Sanwa Chemical), “CPI-410” (trade name, manufactured by San Apro), etc. Is mentioned. These may use 1 type and may use 2 or more types together. The resin layer 11 can further contain basic substances such as amines, photosensitizers such as anthracene derivatives, silane coupling agents, and the like for the purpose of improving photolithography performance and adhesion performance.

  The resin layer 11 can be formed, for example, by dissolving a resin having a benzene ring in the structure and a photopolymerization initiator in a solvent, applying this by a spin coating method, and drying by heat treatment. Although the thickness of the resin layer 11 is not specifically limited, For example, it can be 3-25 micrometers.

  The intermediate layer 8 has a function of increasing the affinity between the resin layer 11 and the film 13. In the present invention, the intermediate layer 8 contains a compound represented by the following formula (1).

(In formula (1), n represents an integer of 0 to 3, and R represents a hydrogen atom, a hydroxyl group or a methyl group)
Since the compound represented by the formula (1) has a benzene ring and a fluorine-containing group in the structure, the affinity between the resin layer 11 and the film 13 can be increased. When the material of the intermediate layer 8 is provided on the resin layer, the resin layer 11 and the intermediate layer 8 exhibit high affinity due to the π-π stacking interaction between the benzene structures included in both, and the intermediate layer 8 is a resin layer. 11 is uniformly formed. In the formula (1), R is a hydrogen atom, a hydroxyl group or a methyl group. A hydrogen atom, a hydroxyl group, or a methyl group hardly affects the π-π stacking interaction from the viewpoint of the three-dimensional structure. In addition, since the critical surface tension of fluorine-based functional groups, particularly —CF ₃ groups, is significantly lower than other functional groups, the presence of —CF ₃ groups in the resin minimizes the surface free energy at the air interface. The driving force to try works. For this reason, the —CF ₃ group is easily segregated on the air interface side. Therefore, when the resin layer 11 on which the intermediate layer 8 is formed is heat-treated, the fluorine component is segregated on the surface. In said Formula (1), n is an integer of 0-3. In particular, in the above formula (1), it is preferable that n is an integer of 0 to 2 because water repellency is improved without affecting the surface orientation of the fluorine component contained in the film 13 described later. The intermediate layer 8 may contain one type of compound represented by the formula (1), or may contain two or more types. Further, the intermediate layer 8 may be made of a compound represented by the formula (1).

  The intermediate layer 8 is obtained by, for example, dissolving the compound represented by the formula (1) in a solvent such as PGMEA (propylene glycol-1-methyl ether acetate), applying it by a spin coat method, and drying by heat treatment. Can be formed. The heat treatment can be performed at 40 to 100 ° C. for 2 to 20 minutes, for example. Although the thickness of the intermediate | middle layer 8 is not specifically limited, For example, it can be 0.1-2 micrometers.

  Next, as shown in FIG. 2B, a film 13 is formed on the intermediate layer 8. The film 13 exhibits water repellency by curing, and includes a condensation product of a hydrolyzable silane compound including a hydrolyzable silane compound having a fluorine-containing group as a water repellent material. Since the fluorine component is segregated on the surface of the intermediate layer 8, the intermediate layer 8 is excellent in affinity with the film 13. Therefore, even when the film 13 is formed by applying the material of the film 13, the material of the film 13 can be uniformly applied without being repelled. Furthermore, since the fluorine component is oriented in advance on the surface of the intermediate layer 8, the aggregation of the fluorine component contained in the film 13 does not easily proceed, and the resolution and the non-uniform water repellency can be prevented. That is, by forming the intermediate layer 8 containing the compound represented by the formula (1) having a benzene ring and a fluorine-containing group in the structure on the surface of the resin layer 11, the resin layer 11 and the film 13 are compatible. Even if not, the film 13 can be uniformly formed on the resin layer 11. Furthermore, by applying the material of the film 13 and then drying by heat treatment, the fluorine component contained in the film 13 is segregated on the surface of the film 13, and high water repellency can be expressed by curing.

  From the viewpoint of high water repellency, the film 13 is a condensation product of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having a cationic polymerizable group as a water repellent material. It is preferable that a thing is included. Examples of the fluorine-containing group of the hydrolyzable silane compound having a fluorine-containing group include fluoroalkyl groups such as 2-perfluorodecylethyl group and tridecafluoro-1,1,2,2-tetrahydrooctyl group, and the following formula (2 Perfluoropolyether group represented by ().

  In the formula (2), o, p, q and r are each 0 or an integer of 1 or more, and at least one of o, p, q and r is an integer of 1 or more. o, p, q or r is preferably an integer of 1 to 30.

  Specific examples of the hydrolyzable silane compound having a fluorine-containing group include 2-perfluorodecylethyltriethoxysilane and tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane. These may use 1 type and may use 2 or more types together. When the total number of moles of the hydrolyzable silane compound is calculated as 100 mol%, the hydrolyzable silane compound having a fluorine-containing group is preferably contained in an amount of 0.01 to 10 mol%. An epoxy group is mentioned as a cationically polymerizable group of the hydrolyzable silane compound which has a cationically polymerizable group. Specific examples of the hydrolyzable silane compound having a cationic polymerizable group include glycidylpropyltriethoxysilane and glycidylbutylethoxysilane. These may use 1 type and may use 2 or more types together. When the total number of moles of the hydrolyzable silane compound is calculated as 100 mol%, it is preferable that 20 to 80 mol% of the hydrolyzable silane compound having a cationic polymerizable group is contained. In addition to the hydrolyzable silane compound having a fluorine-containing group and the hydrolyzable silane compound having a cationic polymerizable group, the hydrolyzable silane compound is, for example, hydrolyzable such as methyltriethoxysilane and phenyltriethoxysilane. Silane compounds can be included.

  For the condensation reaction of the hydrolyzable silane compound, a solvent other than water can be used. As the solvent, alcohols such as ethanol, methanol, 1-propanol and 2-propanol are preferable. Therefore, when the film 13 is formed by applying the material of the film 13, it is preferable to use the alcohol as a dilution solvent for the condensation product.

  The film 13 is prepared by, for example, diluting a condensation product of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having a cationic polymerizable group with an alcohol and spin-coating it. After applying by the method, it can be formed by drying by heat treatment. The heat treatment can be performed, for example, at 40 to 200 ° C. for 2 to 60 minutes. Although the thickness of the film | membrane 13 is not specifically limited, For example, it can be 0.1-2 micrometers.

  Next, as shown in FIG. 2C, the resin layer 11 and the film 13 are subjected to pattern exposure in a lump through a mask 14 having a pattern of the discharge ports 7 and further subjected to heat treatment to cure the exposed portion. . As the mask 14, a substrate made of a material such as glass or quartz that transmits light having an exposure wavelength and having a light shielding film such as a chromium film formed in accordance with the pattern of the discharge ports 7 can be used. As the exposure apparatus, a projection exposure apparatus having a light source having a broad wavelength of a mercury lamp, such as a single wavelength light source such as an i-line exposure stepper or KrF stepper, or a mask aligner MPA-600 Super (trade name, manufactured by Canon) is used. Can do.

  The pattern of the discharge port 7 does not necessarily have a circular shape, and can take the shape shown in, for example, FIGS. 3A to 3C in consideration of discharge characteristics and the like. In particular, by forming the projections 16 in the discharge port as shown in FIG. 3C, the liquid can be held between the projections 16, and a plurality of droplets (main droplets and main droplets) are ejected during droplet ejection. (Satellite) can be greatly reduced, and high-quality printing can be realized.

  Next, as shown in FIG. 2D, the uncured portions of the resin layer 11 and the film 13 are removed with an organic solvent, thereby forming the discharge ports 7. Thereby, the resin layer 11 and the film | membrane 13 can be collectively patterned by photolithography. Further, the discharge port forming member 6, the intermediate layer 8, and the water repellent material layer 9 can be formed.

  In the above description, the production method of the discharge port forming member 6, the intermediate layer 8, and the water repellent material layer 9 has been described, but other members can be produced by a known production method. Thereby, a liquid discharge head can be manufactured.

(Second embodiment)
4A to 4E are schematic cross-sectional views illustrating an example of a manufacturing method of a liquid discharge head to which the film manufacturing method according to this embodiment is applied. 4A to 4E show the discharge unit 10 of FIG. 1B in an enlarged manner for each process.

  First, as shown in FIG. 4A, a resin layer (mixed) 15 is formed. The resin layer (mixed) 15 includes a resin having a benzene ring in the structure and a compound represented by the formula (1). As the resin having a benzene ring in the structure, the same resin as in the first embodiment can be used. The resin layer (mixed) 15 preferably further contains a photopolymerization initiator. As a photoinitiator, the thing similar to 1st embodiment can be used. The content of the compound represented by the formula (1) in the resin layer (mixture) 15 can be 2 to 30 parts by mass with respect to 100 parts by mass of the resin having a benzene ring in the structure. The method for forming the resin layer (mixed) 15 can be formed by coating, similar to the method for forming the resin layer 11 in the first embodiment. Although the thickness of the resin layer (mixing) 15 is not specifically limited, For example, it can be 3-25 micrometers.

Next, as shown in FIG. 4B, the resin layer (mixed) 15 is heated into a resin layer 11 and the intermediate layer 8 by heat treatment. In addition to the method of forming the intermediate layer 8 on the resin layer 11 by coating or the like as in the first embodiment, the resin layer is used by utilizing the above-described property that the —CF ₃ group is easily segregated to the air interface side. The resin layer 11 and the intermediate layer 8 can also be formed by a method in which a resin layer (mixed) 15 in which the material of 11 and the material of the intermediate layer 8 are mixed in advance is formed and heated. As conditions of heat processing, it can carry out for 2 to 60 minutes at 40-200 degreeC, for example. In FIG. 4 (B), the resin layer 11 and the intermediate layer 8 are clearly separated in form. However, the boundary between the resin layer 11 and the intermediate layer 8 does not need to be clear, and both are mixed. There may be a region that does.

  Next, similarly to the steps shown in FIGS. 2B to 2D in the first embodiment, the steps shown in FIGS. 4C to 4E are performed to manufacture the liquid discharge head. can do.

  Examples of the present invention will be shown below, and the present invention will be further described in detail. However, the present invention is not limited to these examples.

[Example 1]
The discharge port forming member of the liquid discharge head and the like were manufactured by the steps shown in FIGS. First, an epoxy resin composition having the composition shown in Table 1 was applied and dried to form a resin layer 11.

  On the resin layer 11, a solution obtained by dissolving 5% by mass of a compound represented by the following formula (3) in PGMEA (propylene glycol-1-methyl ether acetate) has a coating film thickness of 0.5 μm by spin coating. And then heat-treated at 50 ° C. for 5 minutes. As a result, the intermediate layer 8 was formed on the resin layer 11 as shown in FIG.

  Next, 5.31 mol% of glycidylpropyltriethoxysilane, 5.31 mol% of methyltriethoxysilane, 0.69 mol% of 2-perfluorodecylethyltriethoxysilane, 50.98 mol% of water, and 37.70 mol% of ethanol are mixed. To produce a condensation product. The condensation product was diluted with ethanol to adjust the nonvolatile content to 30% by mass. This solution was applied onto the intermediate layer 8 by spin coating so that the thickness of the coating film became 0.5 μm, and heat-treated at 50 ° C. for 5 minutes. Thus, a film 13 was formed on the intermediate layer 8 as shown in FIG.

Subsequently, as shown in FIG. 2C, the resin layer 11 and the film 13 were collectively subjected to pattern exposure through a mask 14 having a pattern of the discharge ports 7. An i-line exposure stepper (manufactured by Canon Inc.) was used as the exposure machine. The exposure amount was 1300 J / m ² . Thereafter, the exposed portion was cured by further heat treatment.

  Thereafter, as shown in FIG. 2D, the resin layer 11 and the uncured portion of the film 13 are dissolved and removed using PGMEA, and the discharge port forming member 6, the discharge port 7, the intermediate layer 8, and the water repellent material layer are removed. 9 was formed. About members other than these, it produced with the well-known manufacturing method, and obtained the liquid discharge head shown by FIG. 1 (B).

[Example 2]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (4) was used instead of the compound represented by the above formula (3).

[Example 3]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (5) was used instead of the compound represented by the above formula (3).

[Example 4]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (6) was used instead of the compound represented by the above formula (3).

[Example 5]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (7) was used instead of the compound represented by the above formula (3).

[Example 6]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (8) was used instead of the compound represented by the above formula (3).

[Example 7]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (9) was used instead of the compound represented by the above formula (3).

[Example 8]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (10) was used instead of the compound represented by the above formula (3).

[Example 9]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (11) was used instead of the compound represented by the formula (3).

[Example 10]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (12) was used instead of the compound represented by the above formula (3).

[Example 11]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (13) was used instead of the compound represented by the above formula (3).

[Example 12]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (14) was used instead of the compound represented by the above formula (3).

[Example 13]
The discharge port forming member of the liquid discharge head and the like were manufactured by the steps shown in FIGS. First, a mixture of an epoxy resin composition having the composition shown in Table 2 and a compound represented by the above formula (3) was applied to form a resin layer (mixed) 15 (FIG. 4A).

  Thereafter, heat treatment was performed at 50 ° C. for 5 minutes, and the resin layer (mixed) 15 was used as the resin layer 11 and the intermediate layer 8 (FIG. 4B). The subsequent steps shown in FIGS. 4C to 4E were performed in the same manner as the steps shown in FIGS. 2B to 2D of Example 1, and a liquid discharge head was manufactured.

[Example 14]
A liquid discharge head was produced in the same manner as in Example 13 except that the compound represented by the formula (4) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15.

[Example 15]
A liquid discharge head was produced in the same manner as in Example 13 except that in the formation of the resin layer (mixed) 15, the compound represented by the formula (5) was used instead of the compound represented by the formula (3).

[Example 16]
A liquid discharge head was produced in the same manner as in Example 13 except that in the formation of the resin layer (mixed) 15, the compound represented by the formula (6) was used instead of the compound represented by the formula (3).

[Example 17]
A liquid discharge head was produced in the same manner as in Example 13 except that in the formation of the resin layer (mixed) 15, the compound represented by the formula (7) was used instead of the compound represented by the formula (3).

[Example 18]
A liquid ejection head was produced in the same manner as in Example 13 except that the compound represented by the formula (8) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15.

[Example 19]
A liquid discharge head was produced in the same manner as in Example 13 except that in the formation of the resin layer (mixed) 15, the compound represented by the formula (9) was used instead of the compound represented by the formula (3).

[Example 20]
A liquid discharge head was produced in the same manner as in Example 13 except that the compound represented by the formula (10) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15.

[Example 21]
A liquid discharge head was produced in the same manner as in Example 13 except that the compound represented by the formula (11) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15.

[Example 22]
A liquid ejection head was produced in the same manner as in Example 13 except that the compound represented by the formula (12) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15.

[Example 23]
A liquid discharge head was produced in the same manner as in Example 13 except that in the formation of the resin layer (mixed) 15, the compound represented by the formula (13) was used instead of the compound represented by the formula (3).

[Example 24]
A liquid discharge head was produced in the same manner as in Example 13 except that the compound represented by the formula (14) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15.

[Example 25]
A liquid discharge head was produced in the same manner as in Example 1 except that a dry film having the composition shown in Table 1 above except the solvent was used as the resin layer 11.

[Example 26]
A liquid discharge head was produced in the same manner as in Example 1 except that the epoxy resin composition shown in Table 3 was used instead of the epoxy resin composition having the composition shown in Table 1 in forming the resin layer 11.

[Example 27]
A liquid discharge head was produced in the same manner as in Example 1 except that the following steps were used in forming the film 13. Glycidylpropyltriethoxysilane (5.37 mol%), methyltriethoxysilane (5.37 mol%), compound represented by the following formula (15) (0.087 mol%), water (39.29 mol%), and ethanol (49.88 mol%) were mixed. A condensation product was produced. The condensation product was diluted with ethanol to adjust the nonvolatile content to 30% by mass. This solution was applied onto the intermediate layer 8 by spin coating so that the thickness of the coating film became 0.5 μm, and heat-treated at 50 ° C. for 5 minutes. Thus, a film 13 was formed on the intermediate layer 8 as shown in FIG.

(In Formula (15), a is an integer of 1-30.).

[Example 28]
A liquid discharge head was produced in the same manner as in Example 1 except that the following steps were used in forming the film 13. Glycidylhexyltriethoxysilane 5.33 mol%, methyltriethoxysilane 5.33 mol%, 2-perfluorodecylethyltriethoxysilane 0.69 mol%, water 50.94 mol%, and ethanol 37.71 mol% are mixed and condensed. A product was produced. The condensation product was diluted with ethanol to adjust the nonvolatile content to 30% by mass. This solution was applied onto the intermediate layer 8 by spin coating so that the thickness of the coating film became 0.5 μm, and heat-treated at 50 ° C. for 5 minutes. Thus, a film 13 was formed on the intermediate layer 8 as shown in FIG.

[Comparative Example 1]
A liquid discharge head was produced in the same manner as in Example 1 except that the intermediate layer 8 was not formed on the resin layer 11. At this time, when the film 13 was formed, the solution containing the condensation product was applied by spin coating so that the thickness of the coating film became 0.5 μm. 13 could not be formed.

[Comparative Example 2]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (16) was used instead of the compound represented by the above formula (3).

  At this time, when the film 13 was formed, the solution containing the condensation product was applied by spin coating so that the thickness of the coating film became 0.5 μm. 13 could not be formed.

[Comparative Example 3]
A liquid discharge head was produced in the same manner as in Example 1 except that in the formation of the intermediate layer 8, a compound represented by the following formula (17) was used instead of the compound represented by the above formula (3).

  At this time, when the intermediate layer 8 was formed, a solution in which 5% by mass of the compound represented by the formula (17) was dissolved in PGMEA was applied by spin coating so that the thickness of the coating film became 0.5 μm. . However, the solution was repelled by centrifugal force during spinning, and the intermediate layer 8 could not be formed. Further, since the intermediate layer 8 could not be formed, the film 13 could not be formed as in the comparative example 1.

[Comparative Example 4]
A liquid discharge head was produced in the same manner as in Example 13 except that the compound represented by the formula (16) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15. At this time, since the compound represented by the formula (16) does not have a fluorine-containing group, the resin layer (mixed) 15 includes the resin layer 11 and the intermediate layer 8 as illustrated in FIG. It did not take form. Thereafter, a solution containing the condensation product was applied onto the resin layer (mixed) 15 by spin coating so that the thickness of the coating film became 0.5 μm. Could not be formed.

[Comparative Example 5]
A liquid discharge head was produced in the same manner as in Example 13 except that the compound represented by the formula (17) was used instead of the compound represented by the formula (3) in the formation of the resin layer (mixed) 15. At this time, in the formation of the resin layer (mixed) 15, the epoxy resin composition having the composition shown in Table 2 and the compound represented by the formula (17) were mixed, and these were mixed uniformly. I couldn't. For this reason, the resin layer (mixed) 15 could not be formed, and the liquid discharge head could not be manufactured.

[Evaluation]
About the produced liquid discharge head, the printing quality for every wiping frequency was evaluated. As the printing pattern, a pattern capable of confirming ink ejection, non-ejection, misalignment, and the like at each ejection port was used. The criteria for evaluation are as follows. The evaluation results are shown in Table 3.
○: Print deviation could not be recognized.
Δ: Print deviation was slightly recognized, but was within an acceptable range.
X: Print deviation was recognized.

  In addition, regarding the formation of the intermediate layer in Table 3, the case where the intermediate layer could be formed is indicated as “◯”, and the case where the intermediate layer was not formed is indicated as “X”. The same applies to film formation.

  As shown in Table 3, the method according to this example was able to form a uniform film. In particular, in Examples 1 to 9, 13 to 21, and 25 to 28, no deterioration in print quality was observed in the evaluation. On the other hand, the method according to the comparative example cannot form a uniform film. In particular, in the liquid discharge heads of Comparative Examples 1 to 3, when the wiping was performed 10,000 times, it was confirmed that the print quality was lowered. This is considered to be because the discharge of ink droplets became unstable because the vicinity of the discharge port was worn and deteriorated with the increase in the number of wiping operations.

DESCRIPTION OF SYMBOLS 1 Energy generating element 2 Substrate 3 Supply part 4 Channel formation member 5 Channel 6 Discharge port formation member 7 Discharge port 8 Intermediate layer 9 Water repellent material layer 10 Discharge part 11 Resin layer 13 Film 14 Mask 15 Resin layer (mixing)
16 protrusion

Claims (7)

Forming an intermediate layer containing a compound represented by the following formula (1) on a resin layer containing a resin having a benzene ring in the structure;
Forming a film containing a condensation product of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group on the intermediate layer;
A method for producing a film, comprising:

(In formula (1), n represents an integer of 0 to 3, and R represents a hydrogen atom, a hydroxyl group or a methyl group.)   The manufacturing method of the film | membrane of Claim 1 in which the said resin layer contains the bifunctional or more epoxy resin which has a benzene ring in a structure, and a photoinitiator. Forming a resin layer containing a resin having a benzene ring in the structure and a compound represented by the following formula (1);
Heat-treating the resin layer;
Forming a film containing a condensation product of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group on the heat-treated resin layer;
A method for producing a film, comprising:

(In formula (1), n represents an integer of 0 to 3, and R represents a hydrogen atom, a hydroxyl group or a methyl group.)   The manufacturing method of the film | membrane of Claim 3 in which the said resin layer contains the bifunctional or more epoxy resin which has a benzene ring in a structure, a photoinitiator, and the compound shown by the said Formula (1).   5. The film according to claim 1, wherein the film includes a condensation product of a hydrolyzable silane compound including a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having a cationic polymerizable group. The manufacturing method of the film | membrane as described in a term.   In the said Formula (1), n is an integer of 0-2, The manufacturing method of the film | membrane of any one of Claim 1 to 5. Producing a membrane by the method according to any one of claims 1 to 6;
Patterning the resin layer and the film at once by photolithography;
A method for manufacturing a liquid discharge head, comprising:

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