JP2018161810A - Manufacturing method for liquid ejection head - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid ejection head that has high water-repellent performance such that an etching protective layer used for protecting a water repellent member during an etching process is prevented from sticking to the surface of the water repellent member as minute foreign matter after removed.SOLUTION: An organic layer formed from a composition expressed by the formula (1) given below is formed for a water-repellent member provided on the surface of an ejection port of a nozzle forming member. Subsequently, an etching protective layer is stuck on the organic layer, the etching protective layer is removed after etching and, subsequently, the organic layer is removed. (In the formula, n2, n3, n5, n6 are integers of 1 to 5, n4 is an integer of 2 to 200, Rto Rare H or C1 to 3 alkyl groups, R, R, R, Rare H, C1 to 3 alkyl groups or nitrile groups)SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a liquid discharge head that discharges liquid.

  In the case of a side shooter type ink jet recording head that ejects ink droplets in a direction substantially perpendicular to a substrate provided with an ink ejection energy generating element, a through-hole is formed in the substrate and an ink supply port is provided. In this type of ink jet recording head, a method of supplying ink from the back side of the substrate through an ink supply port is employed. As a method for manufacturing such an ink jet recording head, for example, the one described in Patent Document 1 is known.

  Here, when Si is used as the material of the substrate, a method has been proposed in which a through hole is formed by chemical etching and an ink supply port is provided. Chemical etching for Si is generally performed by anisotropic etching using an alkaline etching solution, which is advantageous in terms of increasing the density of circuit patterns to be formed. This method has an advantage in productivity in that a large amount of batch processing can be performed by wet etching in addition to performing high-precision processing. However, in such chemical etching, the surface of the substrate is exposed to an etching solution, which may affect the surface characteristics. The ink jet recording head reduces the wettability with respect to the ink around the discharge port, thereby stabilizing the size of the ink droplet, the discharge direction, the discharge speed, and the like, and performing high-quality printing. One means for realizing the object is to perform a water repellent treatment on the surface of the nozzle member on which the discharge port is formed. However, when the above-described chemical etching is performed, depending on the material and state of the water-repellent member, the water-repellent performance may be lowered.

  Therefore, a method for forming an etching protective layer has been proposed in order to protect the water repellent member from the etchant as described in Patent Document 1. Here, the water repellent member is covered with a cyclized rubber-based resin, and in this state, it is immersed in an alkaline etching solution to perform anisotropic etching. At this time, the etching protection layer covers the water-repellent member provided on the surface of the nozzle member and prevents the water-repellent member from touching the etching solution, and thus has a role of preventing the water-repellent performance from being lowered. As a result, the ink supply port can be formed without the etching liquid affecting the water repellent member.

Hereinafter, the conventional form is demonstrated based on drawing.
FIG. 2 is a schematic cross-sectional view showing the manufacturing process of a conventional ink jet recording head in the order of steps.
As shown in FIG. 2A, a heating resistor element 2 and a drive circuit (not shown) for driving the element are formed on the silicon substrate 1 by a method similar to the semiconductor manufacturing technique. Next, in a step shown in FIG. 2B, an etching mask 6 on the etching start surface for forming an ink supply port 10 to be described later is formed by photolithography. Next, as shown in FIG. 2C, an ink flow path pattern forming member 3 that can be removed later is formed by photolithography. The ink flow path pattern forming member 3 is formed by removing the ink flow path pattern forming member 3. Next, as shown in FIG. 2D, the nozzle forming member 4 provided with the water repellent member 5 is covered on the ink flow path pattern forming member 3, and the discharge port 7 is formed by photolithography. Next, as shown in FIG. 2E, an etching protective layer 9 is formed on the water-repellent member 5 including the discharge ports 7 by spin coating or the like. The etching protective layer 9 has a role of preventing the water-repellent performance from being lowered by the contact of the etching solution with the water-repellent member 5 when the ink supply port 10 is formed by anisotropic etching. Next, as shown in FIG. 2F, the substrate is etched by anisotropic etching to form a through hole, and an ink supply port 10 is provided. An etching stop film layer (not shown) is provided on the surface of the silicon substrate 1 to stop etching in the depth direction during anisotropic etching. Further, the etching stop film layer (not shown) is removed by dry etching or the like. Next, as shown in FIG. 2G, the etching protection layer 9 is removed. Finally, as shown in FIG. 2H, the ink flow path pattern forming member 3 is removed to form the nozzle member of the ink jet recording head.

JP 2000-351214 A

  Generally, a silicone compound or a fluorine compound is used as a material for forming a water repellent surface on the surface of the discharge port of an ink jet recording head. In addition, in order to maintain the state of the surface of the discharge port of the ink jet recording head, the ink remaining on the surface may be periodically wiped with a rubber blade or the like. Therefore, high durability against rubbing is required for the water-repellent treatment on the discharge port surface.

  Under such circumstances, a water repellent member using a fluorine group-containing silane compound having high water repellency and durability against rubbing is formed on the surface of the discharge port of the nozzle forming member. It has been found that when the cyclized rubber is applied as an etching protective layer on the water repellent member and the etching protective layer is removed after the etching process, there is a problem in its removability. That is, it was found that when the cyclized rubber used as the etching protective layer was removed after the etching step, minute foreign matters derived from the cyclized rubber adhered to the surface of the water repellent member. This deposit is a very fine deposit that cannot be visually confirmed and can be observed with an SEM or the like because it has a size of several nanometers to several hundred nanometers. Then, it was found that the water repellency is lowered due to the adhered matter, which affects the ejection performance. Conventionally, the amount of ejected ink was large and the size of the droplets to be ejected was large. Therefore, the decrease in water repellency due to the above phenomenon was not a problem. However, it has been found that the influence of this problem becomes more significant as the diameter of the discharge port decreases with the need for high image quality and the discharge amount decreases.

  The object of the present invention is to solve the above-mentioned problems. Provided is a method for manufacturing a liquid ejection head that prevents fine foreign matters from adhering to the surface of a water repellent member after an etching step, maintains sufficient water repellency, and exhibits good ejection characteristics.

  The present invention provides a substrate having an energy generating element for generating energy for discharging a liquid on a first surface, a liquid channel on the first surface of the substrate, and a nozzle having a discharge port communicating with the liquid channel. A liquid comprising: a member; a water repellent member on the nozzle forming member; and a liquid supply port penetrating from the first surface of the substrate to the second surface facing the first surface and communicating with the liquid channel. In the method for manufacturing a discharge head, a step of forming an organic layer containing a resin having an alkylsiloxane moiety represented by the following formula (1) on the inside of the discharge port and on the water repellent member, and etching protection on the organic layer A step of laminating layers, a step of forming the liquid supply port from the second surface of the substrate using an etchant, a step of removing the etching protection layer, and a step of removing the organic layer. With features That is a method for manufacturing a liquid discharge head.

(In Formula (1), n2, n3, n5 and n6 are each independently an integer of 1 to 5, and n4 is an integer of 2 to 200. Also, R _{4 to} R ₇ are each independently And R ₂ , R ₃ , R ₈ and R ₉ are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a nitrile group. Either)

  According to the above configuration, it is possible to effectively suppress adhesion of fine foreign substances to the surface of the water-repellent member after the etching protective layer provided on the surface of the discharge port is removed during the etching process. Therefore, a liquid discharge head having sufficient water repellency can be provided.

FIG. 3 is a schematic cross-sectional view showing an example of a basic manufacturing process of an ink jet recording head according to an embodiment of the present invention. FIG. 10 is a schematic cross-sectional view showing an example of a basic manufacturing process of a conventional inkjet recording head.

  A liquid discharge head to which the present invention is applied includes an energy generating element that generates energy for discharging a liquid onto a first surface of a substrate, a liquid channel, and a nozzle forming member having a discharge port communicating with the liquid channel And a water repellent member on the nozzle forming member. In addition, a liquid supply port that penetrates from the first surface of the substrate to a second surface facing the first surface and communicates with the liquid flow path is provided. In the method for manufacturing a liquid discharge head according to the present invention, the specific organic layer is provided so that the etching protective layer when forming the liquid supply port does not come into contact with the water repellent member. In addition, when the etching protective layer is removed, the organic layer can be selectively removed to prevent impurities derived from the etching protective layer from adhering to the surface of the water-repellent member and maintain sufficient water repellency. it can.

  In the method for manufacturing a liquid discharge head according to the present invention, first, an organic layer containing a resin having an alkylsiloxane moiety is formed on the inside of the discharge port and on the water repellent member. Then, by forming an etching protective layer on the organic layer, it is possible to prevent the water repellent member and the etching protective layer from coming into direct contact. After the substrate is etched from the second surface to form the liquid supply port, the etching protective layer and the organic layer are sequentially removed. At this time, the etching protection layer and the organic layer are removed using different solvents (removal solutions). Here, if the removal liquid for removing the etching protective layer is sufficiently removed, foreign substances derived from the etching protective layer are less likely to be mixed into the removal liquid for removing the next organic layer. In addition, since the resin having an alkylsiloxane moiety shown in the present invention is a resin to which minute foreign matters derived from the etching protective layer are difficult to adhere, no foreign matter is observed on the surface of the organic layer after the etching protective layer is removed. Therefore, even if the organic layer is removed after the etching protective layer removing step, foreign substances derived from the etching protective layer are hardly mixed in the organic layer removing liquid. As a result, the water-repellent member can effectively suppress the adhesion of minute foreign matters derived from the etching protective layer on the surface and maintain sufficient water repellency.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Hereinafter, among the liquid discharge heads, an ink jet recording head that discharges ink as a liquid will be described, but the present invention is not limited only to these embodiments. A detailed description of each member will be described later.

  1A to 1K are views showing a method of manufacturing an ink jet recording head according to an embodiment of the present invention in the order of steps. The recording head according to the present embodiment is of a so-called film boiling type in which a generating resistance element 2 that generates thermal energy is used as an ejection energy generating element and bubbles are generated by the thermal energy to eject ink. Although FIG. 1 shows a cross-sectional view of the recording head with respect to one unit (a pair) of heating resistance elements 2 and discharge ports 7, in this embodiment, the heating resistance elements are formed on the substrate in the same manner as in general semiconductor manufacturing technology. A plurality of recording head chips formed by arranging a plurality of 2 are simultaneously manufactured.

  In the manufacture of the recording head of the present embodiment, first, as shown in FIG. 1A, the heating resistor element 2 and this element are driven on the first surface of the silicon substrate 1 by the same method as the semiconductor manufacturing technique. A drive element circuit (not shown) for performing is formed. In the figure, only the heating resistor element 2 is shown.

  Next, in the step shown in FIG. 1B, the etching mask 6 on the etching start surface (second surface facing the first surface) for forming a liquid supply port (ink supply port) 10 to be described later is formed by photolithography. Form by technology.

  Next, as shown in FIG. 1C, an ink flow path pattern that can be removed later is formed by the photolithography technique using the ink flow path pattern forming member 3. A positive photosensitive material can be used as the ink flow path pattern forming member 3. As will be described later, an ink flow path is formed by removing the ink flow path forming pattern forming member 3.

  Next, in the step shown in FIG. 1D, first, the nozzle forming member 4 is formed so as to cover the ink flow path pattern forming member 3 formed in FIG. As the nozzle forming member 4, a photocationically polymerizable resin material can be used. A water repellent member 5 is formed on the uncured nozzle forming member 4.

  Next, as shown in FIG. 1 (e), pattern exposure is performed on the nozzle forming member 4 and the water repellent member 5, and heat treatment is performed to collectively cure the exposed portion. Thereafter, unexposed portions are removed by development, and discharge ports 7 are formed. The nozzle forming member 4 is a member that forms a wall portion of the liquid flow path together with the substrate.

  Next, in the step shown in FIG. 1 (f), the organic layer 8 is formed so as to cover the nozzle forming member 4 having the discharge port 7 and having the water repellent member 5 formed in FIG. 1 (e). Form. In the step of removing the etching protective layer 9 described later, the organic layer 8 has a good removability without attaching fine foreign matters derived from the etching protective layer 9, has water repellency, and is represented by the following formula (1). A composition comprising a resin having an alkylsiloxane moiety.

(In Formula (1), n2, n3, n5 and n6 are each independently an integer of 1 to 5, and n4 is an integer of 2 to 200. Also, R _{4 to} R ₇ are each independently And R ₂ , R ₃ , R ₈ and R ₉ are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a nitrile group. Either)

  The organic layer 8 can be dried by heat treatment. Further, in order to perform the selective removal in a later step more prominently, it can be cured to such an extent that it can be removed by a specific organic solvent, and either a thermosetting resin or a photocuring resin may be used.

  Next, in the step shown in FIG. 1G, an etching protective layer 9 is formed so as to cover the organic layer 8 formed in FIG. 1F, and is dried by heat treatment. The etching protection layer 9 is provided by being laminated on the organic layer 8 in order to prevent the water repellent member 5 formed in the step of FIG. As will be described later, since the etching protection layer 9 and the organic layer 8 are sequentially removed in the subsequent steps, it is possible to prevent minute foreign matters derived from the etching protection layer 9 from adhering to the surface of the water repellent member 5.

  Next, in the step shown in FIG. 1 (h), anisotropic etching is performed using an etching solution with the etching mask 6 formed on the second surface of the silicon substrate 1 as a mask to form through holes in the substrate 1. Thus, the ink supply port 10 is formed. The etching solution is not particularly limited as long as anisotropic etching is possible, but an alkaline etching solution is used. Examples of the alkaline etching solution include a KOH solution and a TMAH (tetramethylammonium hydroxide) solution. Etching of a substrate in which the silicon substrate 1 is (100) Si proceeds so that the {111} plane becomes a wall surface by crystal anisotropic etching.

  Next, in the step shown in FIG. 1I, the etching protective layer 9 is removed with a solvent. The solvent used for removing the etching protection layer 9 is preferably a solvent that can selectively remove the etching protection layer 9 so that the water-repellent member 5 is not exposed at the time of removal. However, when the etching protective layer 9 is removed, a part of the organic layer 8 may be dissolved as long as the water-repellent member 5 is not exposed and does not affect the water-repellent performance. When the organic layer 8 is formed of a thermosetting resin or a photo-curing resin, it becomes easier to selectively remove the etching protection layer 9.

  Next, in the step shown in FIG. 1J, the organic layer 8 is removed with a solvent. As the solvent for removing the organic layer 8, a solvent that can selectively remove the organic layer 8 with respect to the water repellent member 5 and the nozzle forming member 4 is used. The organic layer 8 is preferably completely removed. However, when the organic layer contains a fluorine-containing group, a part of the organic layer 8 may remain because it has water repellency.

  Finally, as shown in FIG. 1 (k), the ink flow path pattern forming member 3 is dissolved and removed to form the ink flow path (liquid flow path) 11, and the main manufacturing process of the ink jet recording head is completed.

  That is, the surface of the water-repellent member 5 that has undergone the steps of FIGS. 1A to 1K has less adhesion of minute foreign matters and can maintain sufficient water repellency. Further, even if a minute foreign matter derived from the organic layer 8 unintentionally adheres to the water repellent member 5, when the organic layer 8 has water repellency, the water repellency of the ink jet recording head can be maintained well. .

Next, each member of the present invention will be described in detail.
(substrate)
As the substrate 1, a silicon substrate, a glass substrate, a resin substrate, or the like can be used. In the present embodiment, a silicon substrate having a crystal orientation of <100> plane is preferable. Next, an electrical extraction electrode (not shown) is formed on the first surface of the substrate 1 in order to supply current to the heating resistor element 2. Further, on the first surface of the silicon substrate 1, various functional layers such as an adhesion improving layer (not shown) for the purpose of improving adhesion between the silicon substrate 1 and various resin layers formed on the silicon substrate 1. May be further provided. Detailed descriptions of these steps are omitted. Further, the manufacturing method is not particularly limited.

(Ink channel pattern forming member)
As a material for forming the ink flow path pattern, a positive photosensitive resin material can be used, and is not particularly limited, but has resistance to the patterning process of the nozzle forming member 4 composed of a photocationically polymerizable resin described later. Materials can be used. That is, it is preferable to have a resistance that does not break the pattern by the solvent used when applying the photocationically polymerizable resin material constituting the nozzle forming member 4. Therefore, as the positive photosensitive resin material, a polymer photodegradable positive resist is preferable. Examples of the polymer photodegradable positive resist include polymethyl isopropenyl ketone, polymethyl methacrylate, and polymethyl glutarimide. Further, as the positive photosensitive resin material, a material having a low absorbance with respect to the exposure wavelength of the cationic photopolymerizable resin material is preferable. Examples of the material include polymethyl isopropenyl ketone. These positive photosensitive resin materials may be used alone or in combination of two or more. Further, a plurality of layers can be stacked depending on the required film thickness and shape.

  As a method for forming the ink flow path pattern forming member 3 using the positive photosensitive resin, for example, the positive photosensitive resin material is appropriately dissolved in a solvent and applied by a spin coating method. Then, the layer which consists of positive photosensitive resin can be formed by evaporating and drying a solvent by heat processing. Since the thickness of the ink flow path pattern forming member 3 made of the positive photosensitive resin is the height of the ink flow path, it is appropriately determined depending on the design of the ink jet recording head. The thickness of the layer made of the positive photosensitive resin can be set to, for example, 5 to 30 μm. As a patterning method of the ink flow path pattern forming member 3 with the positive photosensitive resin, for example, an active energy ray capable of sensitizing the positive photosensitive resin material to the layer made of the positive photosensitive resin is used. If necessary, pattern exposure is performed by irradiating through a mask. Thereafter, the ink flow path pattern can be formed by developing the exposed portion of the ink flow path pattern forming member 3 using a solvent that can be dissolved.

(Nozzle forming member)
As a material constituting the nozzle forming member 4, a photocationically polymerizable resin material can be used, and is not particularly limited, and examples thereof include a photocationically polymerizable resin material containing an epoxy resin compound, a vinyl ether compound, an oxetane compound, and the like. It is done. However, as the photocationically polymerizable resin material, a photocationically polymerizable resin material containing an epoxy resin is preferable from the viewpoint of obtaining high mechanical strength and high adhesion to the base. Examples of the photocationically polymerizable resin material containing an epoxy resin include a bisphenol A type epoxy resin and a novolac type epoxy resin. Commercially available epoxy resins include Daicel Chemical Industries' trade names “Celoxide 2021”, “GT-300 series”, “GT-400 series”, “EHPE3150”, Japan Epoxy Resin trade names “157S70”, Dainippon Ink and Chemicals, Inc. Examples include trade name “Epicron N-865” manufactured by Kogyo Co., Ltd. and trade name “SU8” manufactured by Nippon Kayaku Co., Ltd. These materials may be used alone or in combination of two or more. The epoxy equivalent of the epoxy resin is preferably 2000 or less, and more preferably 1000 or less. When the epoxy equivalent is 2000 or less, a sufficient crosslinking density is obtained during the curing reaction, and the glass transition temperature of the cured product is not lowered, and high adhesion is obtained. The epoxy equivalent of the epoxy resin is preferably 50 or more. The epoxy equivalent is a value measured according to JISK-7236. Moreover, since the developability may deteriorate if the fluidity of the coating film is high, a material that is solid at 35 ° C. or lower is preferable as the photocationically polymerizable resin material.

  The cationic photopolymerizable resin material can contain a cationic photopolymerization initiator. As the cationic photopolymerization initiator, generally known ionic sulfonium salts, onium salts such as iodonium salts, sulfonic acid compounds, and the like can be used. Commercially available products include ADEKA trade names “Adekaoptomer SP-170”, “Adekaoptomer SP-172”, “SP-150”, Midori Chemical product names “BBI-103”, “BBI-102”, ( Trade names “IBPF”, “IBCF”, “TS-01”, “TS-91” manufactured by Sanwa Chemical Co., Ltd. and the like can be mentioned. These cationic photopolymerization initiators may be used alone or in combination of two or more. Further, the epoxy resin composition may contain a basic substance such as amines, a photosensitizer such as an anthracene derivative, a silane coupling agent, and the like for the purpose of improving photolithography performance and adhesion performance.

In addition, trade names “SU-8 series”, “KMPR-1000”, “TMMR S2000”, “TMMF S2000” manufactured by Kayaku Microchem Co., Ltd., which are commercially available as negative resists, are used as the photocationically polymerizable resin material. be able to.
As a method for forming a nozzle forming member using a photocationic polymerizable resin, for example, a solution obtained by appropriately dissolving the photocationic polymerizable resin material in a solvent is spin coated onto the ink flow path pattern forming member 3 and the substrate 1. It can form by apply | coating to. In the case of using a solvent, the ink flow path pattern forming member 3 that is difficult to dissolve can be selected and used.
The thickness of the nozzle forming member 4 on the ink flow path pattern forming member 3 is not particularly limited, but the thickness on the ink flow path pattern forming member may be, for example, 5 to 100 μm.

(Water repellent material)
As the water repellent member 5 used in the present invention, one having high water repellency or ink repellency and high durability against rubbing is used. The water repellent member 5 used in the present invention is a cured product of a condensate obtained by condensing a hydrolyzable silane compound containing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a fluorine-containing group. The thing containing is preferable. When the material of the water repellent member has an epoxy group, the adhesiveness with the photocationically polymerizable resin used as the nozzle forming member 4 is increased. Further, since the material of the water repellent member has a fluorine-containing group, it exhibits high water repellency or ink repellency. Furthermore, having a silicone skeleton has high durability against rubbing. The water repellent member 5 is applied on the nozzle forming member 4 and patterned to form the discharge port 7 at the same time, thereby having high water repellency and high durability against rubbing, and has a highly accurate discharge port 7. An ink jet recording head can be obtained.

A condensate obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a fluorine-containing group will be described. Although it does not specifically limit as a hydrolysable silane compound which has an epoxy group, It is preferable that it is a compound shown by following formula (A).
Formula (A)
R _c Si (R) _b X _(3-b)

In formula (A), R _c represents a non-hydrolyzable substituent having an epoxy group, R represents another non-hydrolyzable substituent, and X represents a hydrolyzable substituent. b is an integer of 0-2. b is preferably 0 or 1, and more preferably 0. In formula (A), R _c is an organic group having one or more epoxy groups. Specific examples of R _c include a glycidoxypropyl group and an epoxycyclohexylethyl group. Examples of the non-hydrolyzable substituent R include alkyl groups such as a methyl group and an ethyl group, and aryl groups such as a phenyl group. Examples of the hydrolyzable substituent X include a halogen atom, an alkoxy group, an amino group, and a hydrogen atom. Among them, an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group is preferable from the viewpoint that the group eliminated by the hydrolysis reaction does not inhibit the cationic polymerization reaction and the reactivity is easily controlled. Moreover, you may use what a part of hydrolysable substituent becomes a hydroxyl group by hydrolysis or forms a siloxane bond. Specific examples of the hydrolyzable silane compound having an epoxy group represented by the formula (A), wherein X is an alkoxy group, include glycidoxypropyltrimethoxysilane and glycidoxypropyltriethoxysilane. , Epoxycyclohexylethyltrimethoxysilane, epoxycyclohexylethyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxypropyldimethylmethoxysilane, glycidoxypropyldimethylethoxysilane, etc. It is done. These hydrolyzable silane compounds having an epoxy group may be used alone or in combination of two or more.

  Although it does not specifically limit as a hydrolysable silane compound which has a fluorine-containing group, The hydrolysable silane compound which has the alkyl group or aryl group substituted by the fluorine atom shown by the following formula (B) is preferable. Alternatively, a hydrolyzable silane compound having a perfluoropolyether group represented by the following formula (C) or (D) is preferable. At least one or more hydrolyzable silane compounds represented by the following formulas (B) to (D) are used. In particular, it is preferable to use a combination of the hydrolyzable silane compound represented by the formula (B) and the formula (C).

In the formula (B), R _f is an alkyl group or aryl group substituted with a fluorine atom, R is a non-hydrolyzable substituent, X is a hydrolyzable substituent, a is an integer of 1 or 2, and b is 0 to 0 An integer of 2, a + b is an integer of 1 to 3. Here, the alkyl group or aryl group substituted with a fluorine atom preferably has 3 to 30 fluorine atoms. Those having 3 to 25 fluorine atoms are particularly preferred. By containing a fluorine atom, when the hydrolyzable silane of the formula (C) is used, separation of the perfluoropolyether group and other components is prevented, and aggregation of the perfluoropolyether group is prevented. On the other hand, a compound having a large number of fluorine atoms and exhibiting water / oil repellency may aggregate itself, and the effect of preventing aggregation of perfluoropolyether groups is reduced. Specific examples of the alkyl group or aryl group substituted with a fluorine atom include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl And a group in which some or all of the hydrogen atoms such as a naphthyl group are substituted with fluorine atoms. Among commercially available reagents, hydrolyzable silane compounds having a 3,3,3-trifluoropropyl group, a pentafluorophenyl group, and a perfluorobutyl group are readily available. Examples of the hydrolyzable substituent X and the non-hydrolyzable substituent R include the same substituents as the hydrolyzable substituent X and the non-hydrolyzable substituent R in the formula (A). Specific examples of the hydrolyzable silane compound represented by the formula (B) include 3,3,3-trifluoropropyltrimethoxysilane, pentafluorophenyltrimethoxysilane, perfluorobutyltrimethoxysilane, 3,3, 3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropylmethyldiethoxysilane, 3,3,3-trifluoropropylphenyldimethoxysilane, 3 , 3,3-trifluoropropyldimethylmethoxysilane, 3,3,3-trifluoropropyldimethylethoxysilane, and the like. These hydrolyzable silane compounds represented by the formula (B) may be used alone or in combination of two or more.

In formulas (C) and (D), R _p is a perfluoropolyether group, A is an organic group having 1 to 12 carbon atoms, X is a hydrolyzable substituent, Y is a non-hydrolyzable substituent, and Z is hydrogen. An atom or an alkyl group, Q is a divalent or trivalent linking group. a is an integer of 1-3, m is an integer of 1-2, n is an integer of 1-4. The R _p, it is preferable that the number of repeating units of the perfluoropolyether group contained in R _p is an integer from 1 to 30. The perfluoroalkyl group contained in the perfluoropolyether group may be linear or branched. Examples of the hydrolyzable substituent X include a halogen atom, an alkoxy group, an amino group, and a hydrogen atom. Of these, alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group are preferable from the viewpoint that the group eliminated by the hydrolysis reaction does not inhibit the cationic polymerization reaction and the reactivity is easily controlled. Examples of the non-hydrolyzable substituent Y include a methyl group, an ethyl group, a propyl group, and a phenyl group. Examples of Q include a divalent or trivalent linking group having a bonding portion such as a carbon atom or a nitrogen atom, and examples thereof include a perfluoroalkylene group, an amide group, and combinations thereof. Q is a divalent or trivalent group in the formula (C) and a divalent group in the formula (D). Examples of the organic group having 1 to 12 carbon atoms of A include a linear alkylene group such as a methylene group, an ethylene group and a propylene group, and a branched alkylene group such as a methylmethylene group and a methylethylene group. An alkylene group having a substituent such as a phenyl group is also used. Examples of the alkyl group for Z include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isobutyl group, and a t-butyl group.

  Preferable specific examples of the hydrolyzable silane compound having a perfluoropolyether group represented by the formula (C) include a compound represented by the following formula (C) -1.

(In formula (C) -1, g is an integer of 1 to 30.)
In formula (C) -1, the number of repeating units g is preferably 3-20. If it is 3 or more, sufficient water repellency can be obtained, and if it is 20 or less, solubility in a solvent can be secured. In particular, when the condensation reaction is carried out in a non-fluorine general-purpose solvent such as alcohol, g is preferably 3 to 10. As a commercially available perfluoropolyether group-containing silane compound, trade name “KY-108” manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned. These hydrolyzable silane compounds having a perfluoropolyether group may be used alone or in combination of two or more.
Preferable specific examples of the hydrolyzable silane compound having a perfluoropolyether group represented by the formula (D) include compounds represented by the following formula (D) -1.

(In formula (D) -1, s is an integer of 1 to 30, and n is an integer of 1 to 4.)
The condensate is obtained by condensing a hydrolyzable silane compound represented by the following formula (E) in addition to a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a fluorine-containing group. A condensate is preferred.
Formula (E)
(R _d ) _a -SiX _(4-a)
In the formula (E), R _d is an alkyl group or an aryl group, and X is a hydrolyzable substituent similar to the formula (B). a is an integer of 1 to 3. _Examples of R _d include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a phenyl group. Specific examples of the hydrolyzable silane compound represented by the formula (E) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane. Propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and the like. These hydrolyzable silane compounds represented by the formula (E) may be used alone or in combination of two or more.

Due to the presence of the hydrolyzable silane compound represented by the formula (E), the polarity of the condensate and the crosslinking density can be controlled. Moreover, the degree of freedom of substituents in the condensate is improved by introducing non-reactive R _d . For this reason, the orientation of the perfluoropolyether group toward the air interface and the orientation of the epoxy group toward the nozzle forming member 4 are promoted. In addition, the presence of non-reactive R _d suppresses the cleavage of the siloxane bond and improves water repellency and durability.

The hydrolyzable silane compound used in the present invention is not particularly limited, but silane compounds described in JP-T-2007-518587 and Japanese Patent No. 5591361 can be preferably used.
The thickness of the water repellent member 5 is not particularly limited, but is preferably 0.2 μm or more from the viewpoint of durability against rubbing. The water repellent member 5 may be formed at least around the discharge port, and may not be formed on the entire upper surface of the nozzle forming member 4.
The water repellency of the water repellent member 5 is 90 ° or more as a pure water contact angle. Conventionally, a large amount of fine foreign matters derived from the etching protective layer adhere to make it difficult to maintain a pure water contact angle of 90 ° or more, and the function as a water repellent member may be impaired. The water repellency is preferably maintained at 93 ° or more as a pure water contact angle, and more preferably maintained at 96 ° or more.

(Organic layer)
The organic layer 8 used in the present invention preferably has a shape that is maintained when the etching protective layer 9 is removed, and can be easily removed with a solvent when it is removed.

  Since the composition used for the organic layer 8 contains a resin having an alkylsiloxane moiety represented by the formula (1) in its structure, minute foreign matters derived from the etching protective layer are difficult to adhere. The resin having an alkylsiloxane moiety further has an acrylic unit having a perfluoroalkyl group in the side chain in the molecule, so that it can be uniformly coated on the water-repellent member 5 containing a fluorine group and having high water repellency. Is possible. In addition, since the resin having an alkylsiloxane moiety further has an acrylic unit having an epoxy group in the side chain in the molecule, it can be cured to the extent that it can be removed with a solvent by adding a cationic polymerization initiator. . As a result, it is possible to prevent solvent from being dissolved simultaneously with removal of the etching protective layer 9, and it becomes easy to selectively remove it sequentially. When the organic layer 8 is removed, fine foreign matters derived from the etching protective layer 9 are unlikely to adhere to the surface thereof, so foreign matters derived from the etching protective layer 9 are difficult to be mixed into the removal liquid of the organic layer 8. Therefore, even if the removal liquid of the organic layer 8 touches the water repellent member 5, minute foreign matters derived from the etching protective layer 9 are not easily attached to the surface of the water repellent member 5. Furthermore, even if a small amount of the organic layer 8 remains on the surface of the water repellent member 5 unintentionally, the water repellent performance of the ink jet recording head is not significantly lowered because the organic layer 8 has water repellency.

  The composition used for the organic layer 8 contains at least a resin having an alkylsiloxane moiety represented by the above formula (1).

  The resin having an alkylsiloxane moiety represented by the formula (1) is obtained using, for example, a compound having an alkylsiloxane moiety represented by the following formula (1) -1.

(In the formula _{(1) -1, R 2 ~R} 9, n2~n6 is _R 2 _{to R} 9 in the formula (1), have the same meaning as _{n2~n6, R} 11 _{~R 14} are each independently And any one selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a nitrile group, and n8 and n9 represent 0 or an integer of 1 to 6. X represents a halogen atom.)

  The compound represented by the formula (1) -1 can be synthesized, for example, by the method described in JP-B-2-33053. That is, it can be obtained by reacting a diamine represented by the following formula (1) -2 with a dihalide represented by the following formulas (1) -3 and (1) -4.

(Each substituent in Formula (1) -2, (1) -3, and (1) -4 is as described in Formula (1) -1).)

  The resin having an alkylsiloxane moiety represented by the formula (1) is obtained, for example, by reacting the compound represented by the formula (1) -1 with a vinyl monomer. For example, the resin having an alkylsiloxane moiety represented by the formula (1) further has an acrylic unit having a perfluoroalkyl group represented by the following formula (2) in the side chain, or an epoxy group represented by the following formula (3). It is preferable to have an acrylic unit in the side chain. It is preferable to have one or more of these units in the molecule.

(In Formula (2), n1 is an integer of 1 to 5. R ₁ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Rf is a linear or branched group having 4 to 12 carbon atoms. A chain perfluoroalkyl group.)

(In the formula (3), n7 is an integer of 1 to 5. _{Also, R 10} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms. Further, Rp is an organic group having an epoxy group. )

  The structures of the above formulas (2) and (3) can be introduced using a vinyl monomer represented by the following formula (2) -1 or formula (3) -1.

(In the formula (2) -1 and the formula (3) -1, R ₁ , R ₁₀ , R _f , R _p , n1 and n7 are R ₁ , R ₁₀ , and R 7 in the formulas (2) and (3), respectively. R _f, the same meaning as _R p, n1 and n7.)

  Examples of the resin having an alkylsiloxane moiety used in the present invention include an alkylsiloxane resin represented by the following general formula (4).

In formula (4), R _{1 to} R ₁₀ , Rf, Rp and n1 to n7 are as described in the above formulas (1), (2) and (3). a, b, and c represent mol% of each unit, a is 0 to 99 mol%, b is 1 to 100 mol%, c is 0 to 99 mol%, and a + b + c is 100 mol%. a is preferably 20 to 50 mol%, b is preferably 5 to 40 mol%, and c is preferably 20 to 70 mol%.

In the alkyl-containing siloxane resin represented by the formula (4), for example, the compound represented by the formula (1) -1 is mixed with the vinyl monomers represented by the formulas (2) -1 and (3) -1. Obtained by radical polymerization. The radical polymerization can be performed by heating, light irradiation, or heating and light irradiation to generate radical species.
Specific examples of the alkyl-containing siloxane resin represented by the formula (4) include an alkyl-containing siloxane resin represented by the following formula (4) -1.

In formula (4) -1, n4 and ac are as described in formula (4). n4 is preferably 100. The alkylsiloxane resin represented by the formula (4) -1 preferably has a number average molecular weight of 8,000 to 22,000.
As such an alkyl-containing siloxane resin, an alkyl-containing siloxane resin described in Japanese Patent No. 4175620 can be preferably used.

  The composition containing a resin having an alkylsiloxane moiety used for the organic layer 8 of the present invention may contain a cationic polymerization initiator for curing by heat treatment or active energy irradiation. The resin having an alkylsiloxane moiety used in the present invention is highly reactive to an onium salt of a Lewis acid activated by heat or active energy rays, which can be cured at low temperature, particularly when having an epoxy group. Designed to. Accordingly, it is preferable to use an onium salt of Lewis acid as the cationic polymerization initiator.

  When the resin composition used for the organic layer 8 of the present invention is in a form containing a cationic polymerization initiator, its action is manifested by irradiation with heat treatment or active energy rays. Therefore, a cured state that can be removed after etching can be selected by adjusting the temperature or irradiation energy of the active energy ray or adjusting the addition amount of the cationic polymerization initiator. As a result, the organic layer 8 is hardly dissolved in the removal process of the etching protective layer 9 and can be easily removed in the removal process of the organic layer 8. If the cured state is too high, removal after etching becomes difficult, which may be undesirable.

  As the cationic thermal polymerization initiator that can be used in the present invention, a Lewis acid such as a boron trifluoride amine catalyst can be added and used. Examples of commercially available products include “TA-100” manufactured by San Apro Co., Ltd. As the cationic photopolymerization initiator, generally known ionic salts such as ionic sulfonium salts and iodonium salts, sulfonic acid compounds, and the like can be used. In a commercial item, ADEKA Co., Ltd. brand name "Adeka optomer SP-170", "Adeka optomer SP-172", "SP-150", Midori Chemical Co., Ltd. brand name "BBI-103", “BBI-102”, trade names “IBPF”, “IBCF”, “TS-01”, “TS-91” manufactured by Sanwa Chemical Co., Ltd., and the like. These cationic polymerization initiators may be used alone or in combination of two or more.

  It is preferable that the resin composition used for the organic layer 8 of the present invention further contains a compatibilizer as necessary. Examples of such a compatibilizer include 2,2-bis (4-glycidyloxyphenyl) hexafluoropropane and m-bis- [1- (2,3-epoxypropoxy) -2,2,2-trifluoro- 1- (trifluoromethyl) ethyl] benzene.

(Etching protective layer)
The etching protective layer 9 used in the present invention is excellent in alkali resistance in alkaline etching, and is provided on the organic layer 8 in order to prevent the water repellent member 5 from touching the etching solution, and can be removed after etching. is there. For example, a cyclized rubber-based resin or wax can be used. The cyclized rubber resin is particularly preferable because it can be coated at room temperature and has excellent resistance to an alkaline etching solution.

  As the cyclized rubber-based resin, there can be used a negative type photoresist conventionally used in photolithography, or one obtained by removing a photosensitive group therefrom. For example, trade names “OMR-83” and “OBC” manufactured by Tokyo Ohka Kogyo Co., Ltd. can be mentioned.

  In order to prevent the water-repellent member 5 and the etching protective layer 9 from coming into contact with each other, the film thickness uniformity of the organic layer 8 on the water-repellent member 5 may be required. In particular, the organic layer 8 is preferably formed uniformly, and is preferably formed to a certain thickness or more. If the thickness of the organic layer on the water repellent member is 0.5 μm or more, the etching protective layer can be laminated in a non-contact manner with the water repellent member. If the thickness of the organic layer on the water-repellent member is 1.0 μm or more, the organic layer can be formed uniformly, and the water-repellent member may be exposed when removing the etching protective layer. Absent. The upper limit of the thickness of the organic layer is not particularly limited, but since the removal time increases as the thickness increases, the thickness is preferably 2.0 μm or less.

  The removal of the etching protective layer can be performed using a solvent (removal solution) suitable for the material to be used. For example, in the case of a cyclized rubber-based resin, a hydrocarbon-based solvent such as toluene, xylene, or hexane can be used.

Next, the present invention will be described in more detail with reference to examples and comparative examples. In the text, “%” is based on mass unless otherwise specified. A configuration example of the present invention will be illustrated below. The following ratio shows the mass ratio of solid content.
(Preparation example of resin composition for water repellent member)
First, a resin composition 1 used as the water repellent member 5 was prepared with the composition shown in Table 1 below.

  Although the detailed description regarding the preparation method of the resin composition 1 is abbreviate | omitted, patent 5591361 can be referred, for example.

(Preparation example of organic layer composition)
Next, the alkyl-containing siloxane resin (A) used for the organic layer 8 uses the alkyl-containing siloxane resin represented by the formula (4) -1 and has a compounding ratio of a to c as shown in Table 2 below. It was prepared by changing.

The compounding ratio in the resins (1) to (4) is a ratio when a + b + c is 100 mol%.
Resin (1) shown in Table 2 as alkylsiloxane-containing resin (resin (A)), 2,2-bis (4-glycidyloxyphenyl) hexafluoropropane as compatibilizer (B), cationic polymerization initiator (C ) ADEKA Co., Ltd. trade name “ADEKA OPTMER SP-172” was blended at 95: 25: 0.014 (solid content mass ratio) to prepare a composition (a) for an organic layer.
Similarly, each of the alkylsiloxane resins shown in Table 2 is used as the resin (A), the compositions shown in Table 3 are used, and the compositions (b) to (j) used as the organic layer 8 in Examples and Comparative Examples. Was prepared.

  In Table 3, SP-172 of the cationic polymerization initiator (C) is a trade name “Adekaoptomer SP-172” manufactured by ADEKA Corporation, and TA-100 is a trade name “TA-100” manufactured by San Apro Corporation. Respectively.

Example 1
By using the obtained composition, an ink jet recording head was produced by the steps of FIGS.
First, a silicon substrate 1 having a heating resistor element 2 that generates thermal energy as a discharge energy generating element on the first surface is prepared, and a driving element circuit (not shown) and an electrical extraction electrode (not shown) for driving this element are prepared. Display) was formed (FIG. 1A). Next, the etching mask 6 on the etching start surface (second surface) for forming the ink supply port 10 was formed by photolithography using a silicon oxide film (FIG. 1B).
Next, “ODUR-1010” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the first surface of the silicon substrate 1 by spin coating. Next, the positive photosensitive resin layer 3 was formed by prebaking at 120 ° C. for 6 minutes. The thickness was 14 μm.
Next, UV light that can sensitize the positive photosensitive resin layer 3 is irradiated through a mask by a mask exposure apparatus “UX3000” (trade name, manufactured by USHIO INC.), And pattern exposure of the ink flow path is performed. did. The exposure time was 3 minutes. Thereafter, the exposed portion was dissolved with a mixed solution of methyl isobutyl ketone / xylene = 3/2 and developed to form an ink flow path pattern forming member 3 (FIG. 1C).

As a cationic photopolymerizable resin material, 100 parts by mass of Daicel Corporation trade name (EHPE-3150) and a cationic photopolymerization initiator (“ADEKA OPTMER SP-172” (trade name, manufactured by ADEKA Corporation) 6 mass A solution in which 80 parts by mass of xylene was dissolved was applied onto the ink flow path pattern forming member 3 and the silicon substrate 1 by a spin coating method to form the nozzle forming member 4. The thickness was determined based on the ink flow path pattern forming member. 3 was 10 μm.
Next, the resin composition 1 as the water repellent member 5 was diluted with 2-butanol / ethanol so that the active ingredient concentration was 7% by mass. This diluted solution was applied on the uncured nozzle forming member 4 with a slit coater to form a water repellent member 5 containing a condensate. The thickness was 0.5 μm.
Next, the i-line stepper “FPA-3000i5 +” (trade name, manufactured by Canon Inc.) is used to irradiate the nozzle forming member 4 and the water repellent member 5 including the condensate through the mask. (FIG. 1 (d)). The irradiation energy was 5000 J / m ² . Thereafter, heating was performed at 90 ° C. for 4 minutes, and development processing was performed with a mixed solution of methyl isobutyl ketone / xylene = 1/1. Then, the discharge port 7 was formed (FIG. 1E). The diameter of the discharge port was φ10 μm.

Next, as the organic layer 8, the composition (a) was prepared into a solution having a concentration of 30% using diethylene glycol dimethyl ether. This solution was applied by spin coating to form an organic layer 8 (FIG. 1 (f)). The thickness from the surface of the water repellent member 5 was 0.5 μm.
Next, the organic layer 8 was exposed using an i-line stepper “FPA-3000i5 +” (trade name, manufactured by Canon Inc.). The exposure amount was 700 J / m ² . Then, in order to dry the organic layer 8, it heated at 70 degreeC for 3 minute (s).
Next, “OBC” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied as a protective layer 9 on the organic layer 8 by a spin coating method, and then heated at 120 ° C. for 24 minutes (FIG. 1 ( g)). The thickness was 40 μm.

Next, TMAH 22 mass% solution was used for anisotropic etching at 80 ° C. for 12 hours to form through holes in the substrate to form ink supply ports 10 (FIG. 1 (h)). An etching stop layer (not shown) for stopping etching in the depth direction at the time of anisotropic etching is provided at a portion of the substrate surface where the ink supply port 10 is opened. The anisotropic etching stops in the state where the etching is completed.
Subsequently, the etching stop layer (not shown) separating the ink supply port 10 and the ink flow path pattern forming member 3 is removed by dry etching, and the ink supply port 10 and the ink flow path pattern forming member 3 are penetrated. It was.
Next, the etching protection layer 9 and the organic layer 8 were removed stepwise. As a first step, the etching protective layer 9 was removed by dipping in xylene for 15 minutes (FIG. 1 (i)). Thereafter, as a second step, the organic layer 8 was removed by immersing in diethylene glycol dimethyl ether for 5 minutes (FIG. 1 (j)).
Finally, the ink flow path pattern forming member 3 was dissolved and removed with methyl lactate to manufacture an ink jet recording head (FIG. 1 (k)).

Example 2
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (a) was used for the organic layer 8 and the exposure amount to the organic layer was 1000 J / m ² .

Example 3
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (b) was used for the organic layer 8.

Example 4
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (c) was used for the organic layer 8.

Example 5
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (d) was used for the organic layer 8 and the exposure amount to the organic layer was 500 J / m ² .

Example 6
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (d) was used for the organic layer 8.

Example 7
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (e) was used for the organic layer 8 and the exposure amount to the organic layer was 1000 J / m ² .

Example 8
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (f) was used for the organic layer 8 and the organic layer was not exposed.

Example 9
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (f) was used for the organic layer 8 and the thickness of the organic layer was 1.0 μm, and the organic layer was not exposed.

Example 10
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (f) was used for the organic layer 8 and the thickness of the organic layer was set to 0.3 μm and the organic layer was not exposed.

Example 11
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (g) was used for the organic layer 8.

Example 12
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (g) was used for the organic layer 8 and the thickness of the organic layer was 1.0 μm.

Example 13
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (g) was used for the organic layer 8 and the thickness of the organic layer was 0.3 μm.

Example 14
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (h) was used for the organic layer 8 and the organic layer was not exposed.

Example 15
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (h) was used for the organic layer 8 and the thickness of the organic layer was 1.0 μm, and the organic layer was not exposed.

Example 16
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and was thermally cured by heating at 110 ° C. for 7 minutes in an oven instead of i-line exposure. did.

Example 17
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and was thermally cured by heating at 110 ° C. for 5 minutes in an oven instead of i-line exposure. did.

Example 18
An ink jet recording head was produced in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and was thermally cured by heating at 110 ° C. for 10 minutes in an oven instead of i-line exposure. did.

Example 19
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and was thermally cured by heating at 100 ° C. for 15 minutes in an oven instead of i-line exposure. did.

Example 20
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and heat-cured by heating at 120 ° C. for 3 minutes in an oven instead of i-line exposure. did.

Example 21
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and heat-cured by heating at 130 ° C. for 7 minutes in an oven instead of i-line exposure. did.

Example 22
An ink jet recording head was prepared in the same manner as in Example 1 except that the composition (i) was used for the organic layer 8 and was thermally cured by heating at 110 ° C. for 20 minutes in an oven instead of i-line exposure. did.

Example 23
An ink jet recording head was produced in the same manner as in Example 16 except that the composition (i) was used for the organic layer 8.

Example 24
An ink jet recording head was produced in the same manner as in Example 16 except that the composition (i) was used for the organic layer 8 and the thickness of the organic layer was 1.0 μm.

Example 25
An ink jet recording head was produced in the same manner as in Example 16 except that the composition (i) was used for the organic layer 8 and the thickness of the organic layer was 0.3 μm.

Comparative Example 1
An ink jet recording head was manufactured by the steps shown in FIGS. 2A to 2I using the same materials and apparatus as in Example 1.

<Evaluation>
(Coating properties)
The coating properties of the organic layer 8 were evaluated with an optical microscope for the appearance after coating.

(Removability)
The removability of the organic layer 8 was evaluated by cross-sectional observation with an optical microscope after removal with a solvent. When the organic layer 8 was not visually confirmed, it was evaluated as ◯, and when it was visually confirmed as a layer, it was evaluated as △.

(Foreign matter adhesion)
After the etching process, the surface appearance of the water-repellent member 5 after the main manufacturing process of the ink jet recording head after the etching protective layer 9, the organic layer 8 and the ink flow path pattern forming member 3 were removed was evaluated by SEM. . ◎ if no foreign matter is observed, ○ if the number of foreign matters is scattered sparsely, ○ if the foreign matter adheres to the entire surface in a granular state, and foreign matter partially remains in a film state The thing was set as x.

(Pure water contact angle)
As an evaluation of the manufactured ink jet recording head, a dynamic contact angle θr with respect to pure water was measured using a micro contact angle meter (product name: DropMeasure, manufactured by Microjet Co., Ltd.) to evaluate water repellency. It was. As for the contact angle, A is 96 ° or more, B is 93 ° or more and less than 96 °, C is 90 ° or more and less than 93 °, and D is 90 ° or less.
The evaluation results are shown in Table 4.

In each of Examples 1 to 25, the surface of the water-repellent member 5 was less likely to adhere to the surface of the water-repellent member 5, and the water-repellent performance of the water-repellent member 5 was maintained. Especially in Examples 1, 3-5, 7, 9, 12, 15-20 and 24, the appearance was good, the contact angle was high, and the water repellency was also excellent.
In Example 2, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, the surface of the water-repellent member 5 was slightly adhered to the surface, and the contact angle was also reduced. did. However, it was better than the comparative example. About this, the exposure amount to the organic layer 8 is too high, and curing by photopolymerization becomes excessive. As a result, the removability of the organic layer is lowered, and the organic layer is attached to the water repellent member as a foreign matter. It is.

  In Example 6, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, a slight amount of foreign matter was adhered to the surface of the water-repellent member 5, and the contact angle was also lowered. did. However, it was better than the comparative example. About this, there are too many photocationic polymerization initiator addition amounts to the organic layer 8, and hardening by photopolymerization becomes excess, As a result, the removability of an organic layer falls and an organic layer becomes a foreign material in a water-repellent member. It seems to have remained.

  In Example 8, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, the surface of the water-repellent member 5 was slightly adhered to the surface, and the contact angle was also reduced. It was observed. However, it was better than the comparative example. About this, since it is an alkylsiloxane resin which does not contain a cycloaliphatic epoxy group as the organic layer 8, and the resin composition (f) which does not contain a photocationic polymerization initiator was used, hardening by photopolymerization was not performed. As a result, when the etching protective layer is removed, the organic layer is partially dissolved, the water repellent member is exposed, and the foreign matter derived from the etching protective layer 9 is attached.

  In Example 10, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, adhesion of foreign matters was observed on the surface of the water-repellent member 5, the appearance was deteriorated, and the contact angle was reduced. It led to a decline. However, it was better than the comparative example. This is an alkylsiloxane resin not containing a cycloaliphatic epoxy group as the organic layer 8 and was not cured by photopolymerization because the resin composition (f) containing no photocationic polymerization initiator was used. In addition, the thickness of the organic film was thin. As a result, when the etching protective layer is removed, the organic layer is partially dissolved, the water repellent member is exposed, and the foreign matter derived from the etching protective layer 9 is attached.

  In Example 11, as compared with Examples 1, 3-5, 7, 9, 12, 15-20 and 24, a slight amount of foreign matter was adhered to the surface of the water-repellent member 5, and the contact angle was also lowered. It was observed. However, it was better than the comparative example. About this, since the alkyl-containing siloxane resin used as the organic layer 8 does not have a perfluoroalkyl group in a molecule | numerator, the coating property to the water-repellent member 5 fell a little. As a result, the thinned portion with a non-uniform film thickness is dissolved during the removal of the etching protective layer, so that the water repellent member is exposed, and foreign substances derived from the etching protective layer 9 are attached.

  In Example 13, compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, adhesion of foreign matters was observed on the surface of the water-repellent member 5, and the appearance was deteriorated and the contact angle was reduced. It led to a decline. However, it was better than the comparative example. Regarding this, the alkyl-containing siloxane resin used as the organic layer 8 does not have a perfluoroalkyl group in the molecule, so that the coating property on the water repellent member 5 is slightly lowered, and the thickness of the organic film is The coating properties were thin. As a result, the thinned portion with a non-uniform film thickness is dissolved when the etching protective layer is removed, the water-repellent member is exposed, and foreign substances derived from the etching protective layer 9 are attached.

  In Example 14, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, a slight amount of foreign matter adhered to the surface of the water repellent member 5 and the contact angle was lowered. It was observed. However, it was better than the comparative example. In this regard, the alkylsiloxane resin used as the organic layer 8 did not have a cycloaliphatic epoxy group and was not cured by photopolymerization. Furthermore, since the molecule does not have a perfluoroalkyl group, the coating property on the water repellent member 5 is lowered, the water repellent member 5 is partially exposed, and foreign matter derived from the etching protective layer 9 is attached. It seems to be.

  In Example 21, compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, adhesion of minute foreign matters is often observed on the surface of the water repellent member 5, and the appearance is inferior. The contact angle was low and the water repellency was poor. However, it was better than the comparative example. About this, the heating temperature to the organic layer 8 is too high, and curing due to thermal polymerization becomes excessive. As a result, the removability of the organic layer is lowered, and the organic layer is attached to the water repellent member as a foreign matter. It is.

  In Example 22, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, adhesion of minute foreign matters was observed on the surface of the water-repellent member 5, resulting in deterioration in appearance and contact. This led to a decrease in corners. However, it was better than the comparative example. About this, the heating time to the organic layer 8 is too long, and curing due to thermal polymerization becomes excessive. As a result, the removability of the organic layer is lowered, and the organic layer is attached to the water-repellent member as a foreign matter. It is.

  In Example 23, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, a slight amount of foreign matter was adhered to the surface of the water-repellent member 5, and the contact angle was lowered. did. However, it was better than the comparative example. About this, the alkylsiloxane resin used as the organic layer 8 did not have a cycloaliphatic epoxy group in the molecule, and was not sufficiently cured by thermal polymerization. As a result, it is considered that the water-repellent member 5 is partially exposed by being dissolved in the etching solution, and foreign matter derived from the etching protective layer 9 is attached.

  In Example 25, as compared with Examples 1, 3 to 5, 7, 9, 12, 15 to 20 and 24, adhesion of foreign matters was observed on the surface of the water-repellent member 5, the appearance was inferior, and the contact angle. The water repellency was also low. However, it was better than the comparative example. In this regard, the alkylsiloxane resin used as the organic layer 8 does not have a cycloaliphatic epoxy group in the molecule and is not sufficiently cured by thermal polymerization. Had fallen. As a result, it is considered that the water-repellent member 5 is partially exposed in the etching solution, and the foreign matter derived from the etching protective layer 9 is adhered.

  Since the comparative example 1 did not use the organic layer 8 of the present invention, a large amount of foreign matters from the etching protective layer 9 adhered. As a result, the appearance decreased and the contact angle also decreased to a level where it could not be put to practical use.

  From the above, according to the present invention, by providing the organic layer 8, it is possible to suppress a large amount of minute foreign matters derived from the etching protective layer from adhering to the surface of the water repellent member 5. In addition, since the used organic layer can be selectively removed after the removal of the etching protective layer, the water-repellent performance of the water-repellent member can be maintained at a level at which there is no practical problem.

  The liquid discharge head according to the present invention can be mounted on an apparatus such as a printer, a copying machine, a facsimile having a communication system, a word processor having a printer unit, or an industrial recording apparatus combined with various processing apparatuses. By using an apparatus equipped with this liquid discharge head, it is possible to perform recording on various recording media such as paper, thread, fiber, leather, metal, plastic, glass, wood, and ceramic. Further, it can be applied as a head for ejecting a liquid for biochip manufacturing or electronic circuit printing. Among these, the liquid discharge head according to the present invention is suitable as an ink jet head using water-based ink or the like.

1. Substrate 2. 2. Heating resistance element 3. Ink flow path pattern forming member 4. Nozzle forming member 5. Water repellent member Etching mask 7. Discharge port 8. Organic layer9. Etch protection layer 10. Liquid supply port (ink supply port)
11. Liquid channel (ink channel)

Claims (11)

A substrate having an energy generating element for generating energy for discharging liquid on the first surface; a liquid channel on the first surface of the substrate; a nozzle forming member having a discharge port communicating with the liquid channel; Manufacture of a liquid discharge head comprising a water repellent member on a nozzle forming member, and a liquid supply port penetrating from the first surface of the substrate to the second surface facing the first surface and communicating with the liquid channel In the method
Forming an organic layer containing a resin having an alkylsiloxane moiety represented by the following formula (1) on the inside of the discharge port and on the water repellent member;
Laminating an etching protective layer on the organic layer;
Forming the liquid supply port from the second surface of the substrate using an etchant;
Removing the etching protection layer;
And a step of removing the organic layer.

(In Formula (1), n2, n3, n5 and n6 are each independently an integer of 1 to 5, and n4 is an integer of 2 to 200. Also, R _{4 to} R ₇ are each independently And R ₂ , R ₃ , R ₈ and R ₉ are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms and a nitrile group. Either.) The water repellent member is formed by curing a condensate of a hydrolyzable silane compound containing a hydrolyzable silane compound having a fluorine-containing group and a hydrolyzable silane compound having an epoxy group, and having the alkylsiloxane moiety The method for producing a liquid discharge head according to claim 1, further comprising an acrylic unit having a perfluoroalkyl group represented by the following formula (2) in a side chain in a molecule.

(In Formula (2), n1 is an integer of 1 to 5. R ₁ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Rf is a linear or branched group having 4 to 12 carbon atoms. A chain perfluoroalkyl group.) The method for producing a liquid discharge head according to claim 1, wherein the resin having an alkylsiloxane moiety further has an acrylic unit having an epoxy group represented by the following formula (3) in the side chain in the molecule.

(In the formula (3), n7 is an integer of 1 to 5. _{Also, R 10} is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms. Further, Rp is an organic group having an epoxy group. )   The method for manufacturing a liquid discharge head according to claim 3, wherein the material of the organic layer further contains a cationic polymerization initiator.   The method for producing liquid discharge according to claim 4, wherein the cationic polymerization initiator is an onium salt of a Lewis acid.   The method of manufacturing a liquid ejection head according to claim 4, wherein the step of forming the organic layer includes a step of applying a material of the organic layer and a step of irradiating the applied layer with light to cure. .   6. The method of manufacturing a liquid discharge head according to claim 4, wherein the step of forming the organic layer includes a step of applying a material of the organic layer and a step of heating and hardening the applied layer.   The method of manufacturing a liquid ejection head according to claim 1, wherein the step of removing the etching protective layer is performed without exposing the water repellent member.   The method of manufacturing a liquid ejection head according to claim 1, wherein the thickness of the organic layer on the water-repellent member is 0.5 μm or more.   The method for manufacturing a liquid ejection head according to claim 1, wherein the etching protection layer includes a cyclized rubber-based resin.   The method of manufacturing a liquid ejection head according to claim 1, wherein the etching protection layer and the organic layer are removed using different solvents.

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