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    • 专利摘要:
    inkjet recording head and its manufacturing method. an inkjet recording head is provided, including an element provided with an ejection hole for ejecting ink, in which the inkjet recording head further includes a water-repellent layer including a cured product of a condensed product obtained. by condensing a hydrolyzable silane compound having an epoxy group and a hydrolysable silane compound having a perfluoropolyether group on a surface of the element on one side at which the ejection hole opens.
    公开号:BR112014025014B1
    申请号:R112014025014-6
    申请日:2013-04-17
    公开日:2021-08-10
    发明作者:Etsuko Sawada；Hiroaki Mihara；Ken Ikegame；Satoshi Tsutsui；Yohei Hamade
    申请人:Canon Kabushiki Kaisha；
    IPC主号:
    专利说明:

    technical field
    [0001] The present invention relates to an inkjet recording head and a method of manufacturing the same. Fundamentals of technique
    [0002] Characteristics of an ejection hole surface of an inkjet recording head are important to provide satisfactory ejection performance. When a tub stays right in the vicinity of an ejection hole, an ink droplet flight direction is deflected and an ink droplet ejection rate decreases in some cases. Thus, as a method of ejecting ink with good accuracy, a method involving subjecting the vicinity of an ejection orifice portion to water repellent treatment is given. In general, a silicon-containing compound, a fluorine-containing compound, or the like is used as a material to form a water-repellent surface. The fluorine compound is suitable for ejecting inks containing various solvents and dyes like the inkjet recording head. As the fluorine compound exhibits satisfactory water repellency, for example, a compound containing perfluoroalkyl group and a compound containing perfluoropolyether group are known. Of these, a compound containing a perfluoropolyether group has drawn attention from the standpoint of adequately sustainable in recent years.
    [0003] Additionally, in order to maintain a condition of an ejection hole part surface in the inkjet recording head, ink remaining on the surface is regularly cleaned with a rubber blade or the like in some cases. However, the surface of part of the ejection hole after water repellent treatment is required to have high durability against abrasion. Patent Literature 1 discloses an example using a compound having a perfluoropolyether group and an alkoxysilyl group as a water repellency treatment method in which a water repellent film having high durability is provided. Citation ListPatent LiteraturePTL 1: Open Japanese Patent Application No. 2009-214338 Invention SummaryTechnical Problem
    [0004] An inkjet recording head according to the present invention is an inkjet recording head including an element provided with an eject hole for ejecting ink, in which the inkjet recording head further includes a water repellent layer including a cured product of a condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group on a surface of the element on a side in which the orifice eject button opens.
    [0005] A manufacturing method for an inkjet recording head according to the present invention is a manufacturing method for an inkjet recording head including a substrate, an element provided with an ejection hole for ejecting ink, and a water-repellent layer provided on a surface of the element on one side at which the ejection hole opens, the manufacturing method includes the steps of: (1) forming a photopolymerizable resin layer comprising a photopolymerizable resin material having an epoxy group on a substrate; (2) forming a layer comprising a condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group in the cationically photopolymerizable resin layer prior to curing; (3) pattern exposure of the cationically light-cured resin layer and the layer comprising the condensed product simultaneously; (4) subjecting exposed portions of the cationically light-curing resin layer and the layer comprising the condensed product to curing simultaneously; and (5) removing unexposed portions of the photopolymerizable resin layer and the layer comprising the condensed product to form an ejection orifice, thus providing an element and a water repellent layer.
    [0006] Additional features of the present invention will become apparent from the following description of the exemplary embodiments with reference to the accompanying drawings. Brief Description of Drawings
    [0007] FIG. 1 is a perspective view illustrating an ink jet recording head in accordance with an embodiment of the present invention.
    [0008] FIGS. 2A, 2B, 2C, 2D, 2E, 2F and 2G are cross-sectional views illustrating a manufacturing method for an inkjet recording head in accordance with the present invention. Description of Modalities
    [0009] Hereinafter, the present invention will be described in detail using suitable modalities.
    [0010] In recent years, a manufacturing method for an inkjet recording head involving using a photosensitive resin has been employed in order to form a high-definition, high-precision ejection hole part. However, the method disclosed in Patent Literature 1, which requires a SiO2 film as an inorganic film to increase adhesive strength between a water-repellent material and a surface to be subjected to water-repellent treatment, is not applicable to the method involving use a photosensitive resin. Additionally, the perfluoropolyethylether group-containing compound disclosed in Patent Literature 1 is soluble in a solvent containing fluorine only, and so it is difficult to introduce a photosensitive group having high polarity such as an acrylate or an epoxy compound. However, when an inkjet recording head is manufactured using a photosensitive resin, it is difficult to apply the method disclosed in Patent Literature 1. Additionally, there is a demand for further improvements in water repellency and abrasion durability.
    [0011] An object of the present invention is to provide an inkjet recording head having greater water repellency and greater durability against abrasion.
    [0012] An inkjet recording head according to the present invention is an inkjet recording head including an element provided with an eject hole for ejecting ink, in which the inkjet recording head further includes a water repellent layer including a cured product of a condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group on a surface of the element on a side in which the orifice eject button opens.
    [0013] According to the present invention, the hydrolyzable silane compound having an epoxy group which can be chemically bonded to the hydrolyzable silane compound having a perfluoropolyether group. Thus, a water-repellent material having high adhesion property with a cationically photopolymerizable resin layer as a prime layer is obtained. The water-repellent material is laminated to the cationically light-curing resin layer to be an element, and the material and layer are patterned concurrently to form an ejection hole. Then, an inkjet recording head having high water repellency and high abrasion durability and including a high precision ejection hole can be obtained.
    [0014] Embodiments of the present invention are described in detail herein with reference to the drawings. It should be noted that, in the following description, constituent elements having the same function are denoted by at least number in the drawings, and descriptions thereof are omitted in some cases.
    [0015] FIG. 1 is a schematic perspective view illustrating an ink jet recording head in accordance with an embodiment of the present invention. The inkjet recording head illustrated in FIG. 1 includes a substrate 1 provided with multiple power generating elements 2. Substrate 1 is provided with an element 4, which forms an ink flow path 11 for holding ink and is provided with ejection holes 9 for ejecting communicated ink with the ink flow path 11. A water-repellent layer (not shown) is provided on the surface of the element 4 on the side on which the ejection holes 9 are formed. In the present invention, the water repellent layer includes a cured product of a condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group. It is preferred that the water repellent layer further includes a cured product obtained by subjecting the condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group to a curing reaction with an epoxy resin . In this case, the epoxy resin is contained in the element 4 and is present on the surface where the element 4 comes into contact with the water-repellent layer, or the epoxy resin is mixed into the condensed product in forming the water-repellent layer.
    [0016] An ink supply port 10 for supplying ink to the ink flow path 11 is provided on the rear surface of substrate 1.
    [0017] A manufacturing method for an inkjet recording head according to the present invention is a manufacturing method for an inkjet recording head including a substrate, an element provided with an ejection hole for ejecting paint, and a water-repellent layer provided on a surface of the element on one side in which the ejection hole opens, the manufacturing method including the steps of: (1) forming a photopolymerizable resin layer comprising a photopolymerizable resin material having an epoxy group on a substrate; (2) forming a layer comprising a condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group in the cationically photopolymerizable resin layer prior to curing; (3) pattern exposure of the cationically light-curing resin layer and the layer comprising the condensed product simultaneously; (4) subject r exposed portions of the cationically light-curing resin layer and the layer comprising the condensed product to cure simultaneously; and (5) removing unexposed portions of the photopolymerizable resin layer and the layer comprising the condensed product to form an ejection orifice, thus providing an element and a water repellent layer.
    [0018] FIGS. 2A-2G are cross-sectional views illustrating sections taken along line 2G-2G of the inkjet recording head illustrated in FIG. 1 for the respective manufacturing steps. A manufacturing method for an inkjet recording head according to an embodiment of the present invention is described herein with reference to FIGS. 2A to 2G. However, the present invention is not limited thereto.
    [0019] First, a photosensitive resin layer is formed on the substrate 1 having the energy generating elements 2 formed thereon. The photosensitive resin layer is patterned to form an ink path pattern 3 (FIG. 2A).
    [0020] A silicon substrate, a glass substrate, a resin substrate, or the like can be used as the substrate 1. Power generating elements 2 are not particularly limited while the elements can transmit ejection energy to eject ink. for ink and eject ink from ejection holes. For example, a head generating resistor element, a piezoelectric element or the like can be used. It should be noted that the power generating elements 2 can be connected to a control signal input electrode (not shown) to drive the elements. Additionally, the substrate 1 can be further provided with various functional layers such as a protective layer (not shown) for the purposes of improving the durability of the power generating elements 2 or a tack-improving layer (not shown) for the purposes of improving adhesiveness between a cationically light-curing resin material to be described below and substrate 1.
    [0021] A positive photosensitive resin material contained in the positive photosensitive resin layer is not particularly limited, and a material having strength for the standardization step of a cationically photopolymerizable resin layer 4 to be described below can be used. That is, it is desired that the material have such strength that a pattern is not deformed by a solvent to be used in the application of a cationically photopolymerizable resin material constituting the cationically photopolymerizable resin layer 4. Thus, the positive photosensitive resin material is preferably a polymeric photodegradable positive repeller. Examples of the polymeric photodegradable positive repellent include polymethyl isopropenyl ketone, polymethyl methacrylate, and polymethyl glutarimide. Additionally, the positive photosensitive resin material causes a pattern failure through its photosensitization at the time of exposure of the cationically photopolymerizable resin layer 4 in some cases, and so is preferably a material having a low absorbance upon exposure to the material's wavelengths. of cationically light cured resin. Examples of the material include polymethyl isopropenyl ketone. One type of the positive photosensitive resin materials can be used alone, or two or more types of the same can be used in combination. It is also useful to add a light absorbing material in order to prevent pattern deformation caused by light reflected from the substrate.
    [0022] In addition, multiple layers can be laminated depending on a required thickness or shape.
    [0023] As a method of forming the positive photosensitive resin layer, for example, the following method is given. The positive photosensitive resin material is appropriately dissolved in a solvent, and the solution is applied by a spin coating method. After that, the solvent is evaporated by cooking. Thus, the positive photosensitive resin layer can be formed.
    [0024] The thickness of the positive photosensitive resin layer is equal to the height of the ink flow path, and then is appropriately determined depending on the inkjet recording head design. The thickness of the positive photosensitive resin layer can be adjusted to, for example, 5 to 30 µm.
    [0025] As a method of patterning the positive photosensitive resin layer, for example, the following method is given. The positive photosensitive resin layer is pattern exposed by irradiation with an active energy beam capable of photosensitizing the positive photosensitive resin material, as required, through a mask. After that, development is carried out through the use, for example, of a solvent capable of dissolving the exposed part of the positive photosensitive resin layer. Thus, the ink flow path pattern 3 can be formed.
    [0026] Next, the cationically light cured resin layer 4 including cationically polymerizable resin material is formed in the ink flow path pattern 3 and the substrate 1 (FIG. 2B).
    [0027] The cationically polymerizable resin material is not particularly limited and examples thereof include cationically photopolymerizable resin materials containing an epoxy compound, a vinyl ether compound, and an oxetane compound. However, the cationically light cured resin material is preferably a cationically light cured resin material containing an epoxy resin from the viewpoint of providing high mechanical strength and high tack with a prime layer. Examples of the cationically polymerizable resin material containing an epoxy resin include a bisphenol A type epoxy resin and a novolac type epoxy resin. As commercially available products of the epoxy resin, for example, "CELLOXIDE 2021", "GT-300 series", "GT-400 series", and "EHPE3150" (trademarks) manufactured by Daicel Corporation, "157S70" are given ( trademark) manufactured by Mitsubishi Chemical Corporation, “Epiclon N-865” (trademark) manufactured by DIC Corporation, and “SU8” manufactured by NIPPON KAYAKU Co., Ltd. One type of these materials can be used alone, or two or more types of it can be used in combination. The epoxy equivalent of the epoxy resin is preferably 2,000 or less, more preferably 1,000 or less. When the epoxy equivalent is 2000 or less, a sufficient crosslink density is obtained in a curing reaction, the glass transition temperature of a cured product does not decrease, and high tack is obtained. The epoxy equivalent of the epoxy resin is preferably 50 or more. It should be noted that the epoxy equivalent is a measured value in accordance with JIS K-7236. Additionally, when the fluidity of a coating film is high, resolution appropriately decreases in some cases. Then, the cationically light-curing resin material is preferably a material in a solid form at 35°C or less.
    [0028] Additionally, the cationically photopolymerizable resin material may contain a photopolymerization initiator. As the photopolymerization initiator, for example, generally known cationic salts such as a sulphonium salt and an iodonium salt, and sulphonic acid compounds can be used. As commercially available products of the light curing initiator, there are given, for example, "ADEKA OPTOMER SP-170," "ADEKA OPTOMER SP-172," and "SP-150" (trademarks) manufactured by ADEKA CORPORATION; "BBI-103" and "BBI-102" (trademarks) manufactured by Midori Kagaku Co., Ltd.; and "IBPF," "IBCF," "TS-01," and "TS-91" (trademarks) manufactured by SANWA CHEMICAL CO., LTD. One type of these light curing initiators can be used alone, or two or more types of the same can be used in combination.
    [0029] In addition, the aforementioned epoxy resin composition may contain, for example, a basic substance such as an amine, a photosensitizing substance such as an anthracene derivative, and a silane binding agent for improvement purposes, for example, photolithography performance and adhesion performance.
    [0030] Additionally, as commercially available, cationically light-curing resin material resists negatively such as "SU-8 Series" and "KMPR-1000" (trademarks) manufactured by Kayaku MicroChem CO., LTD. and “TMMR S2000” and “TMMF S2000” (trademarks) manufactured by TOKYO OHKA KOGYO CO., LTD can be used.
    [0031] As a method to form the cationically photopolymerizable resin layer 4, for example, the following method is given. The cationically light cured resin material is suitably dissolved in a solvent, and the solution is applied to the ink flow path pattern 3 and the substrate 1 by a spin coating method. Thus, the cationically photopolymerizable resin layer can be formed. In case of using a solvent, the solvent that hardly dissolves the ink flow path pattern 3 can be selected and used.
    [0032] The thickness of the cationically light-cured resin layer 4 in the ink flow path pattern 3 is not particularly limited and can be adjusted to, for example, 5 to 100 µm.
    [0033] Next, a layer 5 including a condensed product obtained by condensation of a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group is formed in the cationically photopolymerizable resin layer 4 before curing ( FIG. 2C). Layer 5 including the condensed product obtained by the condensation of a hydrolyzable silane compound having an epoxy group and a hydrolysable silane compound having a perfluoropolyether group is referred to herein as layer 5 including the condensed product.
    [0034] When the condensed product is applied as a solution in the cationically light-curing resin layer 3, 4 before curing, the perfluoropolyether group, which has low surface free energy, is oriented in a large amount in the outermost layer on the side of air interface. On the other hand, in a part other than the outermost layer, the amounts of an epoxy group and a siloxane component, which are components other than the perfluoropolyether group, increase depending on the amount of the perfluoropolyether group oriented in the outermost layer, and the crosslinking of the epoxy group and the dehydration condensation of a silane group proceeds due to acid generated from a photoinitiator and heat. This curing reaction between the epoxy group and the siloxane component allows layer 5 including the condensed product to exhibit high durability.
    [0035] In addition, when layer 5 including the condensed product is formed in the cationically light cured resin layer 4 prior to curing, an epoxy group present on the side of the cationically light cured resin layer 4 in layer 5 including the condensed product may react with an epoxy group on the cationically photopolymerizable resin layer 4 to form a bond between the cationically photopolymerizable resin layer 4 and the layer 5 including the condensed product. Additionally, in some cases of applied solvents and resins, the cationically photopolymerizable resin layer 4 and the layer 5 including the condensable product dissolve into each other at their interface, and thus a bond at the interface can be made stronger. With this, high water repellency and high durability against abrasion can be transmitted.
    [0036] Next, the condensed product obtained by condensation of a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group is described. The hydrolyzable silane compound having an epoxy group is not particularly limited but is preferably a compound represented by the following formula (1).Formula (1)

    [0037] In formula (1), Rc represents a non-hydrolyzable substituent having an epoxy group, R represents a non-hydrolyzable substituent, X represents a hydrolyzable substituent, and b represents an integer from 0 to 2. b represents preferably 0 or 1, more preferably 0.
    [0038] In formula (1), Rc represents an organic group having one or more epoxy groups. Specific examples of the organic group Rc include a glycidoxypropyl group and an epoxycyclohexylethyl group. Examples of the non-hydrolyzable substituent R include an alkyl group such as a methyl group or an ethyl group, and a phenyl group. Examples of the hydrolyzable X substituent include a halogen atom, an alkoxy group, an amino group, and a hydrogen atom. Of these, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group is preferred from the point of view of a leaving group, after a hydrolysis reaction it does not inhibit a cationic polymerization reaction and the reactivity is easily controlled. Furthermore, in a part of a hydrolyzable group a hydroxy group is hydrolyzed, or forms a siloxane linkage can be used. Specific examples of the hydrolyzable silane compound containing an epoxy group, represented by a formula (1) wherein the hydrolyzable substituent contains an alkoxy group, such as X include, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, epoxycyclohexylethytrimethoxysilane, epoxycyclohexylethyltriethoxysilane, glycidoxyglycoylmethyldimethoxypropyldimethyoxysilane, glycidoxyglycoylmethyldimethoxypropyldimethyoxysilane One type of such hydrolyzable silane compounds containing an epoxy group can be used alone, or two or more types can be used in combination.
    [0039] The hydrolyzable silane compound containing a perfluoropolyether group has no limited particularities, but is preferably at least one type selected from the group consisting of compounds represented by the following formula (2), (3), (4) and (5).Formula (2)
    Formula (3)
    Formula (4)
    Formula (5)

    [0040] In formulas (2), (3), (4) and (5) Rp represents a perfloropolyether group, 'A' represents an organic group containing 1 to 12 carbon atoms, X represents a hydrolyzable substituent, Y represents a non-hydrolyzable substituent, Z represents a hydrogen atom or an alkyl group, R represents a non-hydrolyzable substituent, Q represents a bivalent or trivalent bond group, where when Q represents a bivalent bond group, n=1 and when Q represents a trivalent linking group, n=2, 'a' represents an integer 1 to 3 and 'm' represents an integer from 1 to 4.
    [0041] Examples of a hydrolyzable X substituent in the formulas (2), (3), (4) and (5) include a halogen atom, an alkoxy group, an amino group and a hydrogen atom. Of these, an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group is preferred from the point of view of a leaving group, after a hydrolysis reaction it does not inhibit a cationic polymerization reaction and the reactivity is easily controlled. Examples of non-hydrolyzable Y substituents include a methyl group, an ethyl group, a propyl group and a phenyl group. Examples of an alkyl group Z include a methyl group, an ethyl group and a propyl group. Examples of a non-hydrolyzable R substituent include an alkyl group containing 1 to 20 carbon atoms and a phenyl group. Examples of a linking group Q include a carbon atom and a nitrogen atom. Examples of the organic group A containing 1 to 12 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group. Also, an alkyl group containing a substituent can be used.
    [0042] In formulas (2), (3), (4) and (5), it is preferable that the number of repeating units in the perfluoropolyether group Rp is an integer from 1 to 30. It should be noted the number of units repeated contained in the group of Rp. The perfluoropolyether group Rp is preferably a group represented by the following formula (6):Formula (6)

    [0043] In formula (6), o, p, q, and r represent an integer of 0 or 1 or more, and at least one o, p, q, or r represents an integer of 1 or more. The ,p,q, or preferably represents an integer from 1 to 30. The,p,q, or r in formula (6) corresponds to a number of repeating units described above.
    [0044] The average molecular weight of the perfluoropolyether group Rp in formulas (2), (3), (4) and (5) is preferably 500 to 5000, more preferably 500 to 2000. When the average molecular weight of the group Perfluoropolyether Rp is 500 or more, sufficient water repellency is obtained. Furthermore, when the average molecular weight of the perfluoropolyether group Rp is 5000 or less, sufficient solubility in the solvent is obtained. It should be noted that the perfluoropolyether group is a mixture of different numbers of repeating units (eg o, p, q or r in formula (6) by its nature). In context, the average molecular weight of the perfluoropolyether group refers to an average of the total molecular weights of the radicals represented by the repeating units of formula (6).
    Specific preferred examples of the silane compound containing a perfluoropolyether group include compounds represented by the following formulas (7), (8), (9), (10) and (11).Formula (7)
    (In formula (7) s represents an integer from 1 to 30 and m represents an integer from 1 to 4.)Formula (8)
    (1) (In formula (8), t represents an integer from 1 to 30) (2) Formula (9)
    (In formula (9), and f represent an integer from 1 to 30) Formula (10)
    (In formula (10), g represents an integer from 1 to 30.)Formula (11)

    [0046] (In formula (11), rm represents a methyl group or a hydrogen atom and r represents an integer from 1 to 30.)
    [0047] In formula (7) with formula (11) s, t, e, f, g, or h, the number of repeated units, preferably represents 3 to 20. When the number is less than 3, a water repellency tends to decrease. When the number is greater than 20, the solvent solubility decreases. It is particularly preferred that the number be from 3 to 10, in the case of carrying out a condensation reaction in a use not containing fluorine-solvent such as an alcohol.
    [0048] As commercially available products of the silane compound containing a perfluoropolyether group are indicated, for example: "OPTOOL DSX" and "OPTOOL AES" manufactured by Daikin Industries, Ltd.; "KY-108" and "KY-164", manufactured by Shin-Etsu Chemical Co., Ltd.; "Novec 1720", manufactured by Sumitomo 3M Limited; and "Fluorolink S10", manufactured by Solvay Special Polymers Japan K.K.
    [0049] The condensed product is preferably a condensation product obtained by condensation of the hydrolyzable silane compound containing an epoxy group, the hydrolyzable silane compound containing a perfluoropolyether group and a hydrolyzable silane compound represented by the following formula (12). (12)

    [0050] In formula (12), Rd represents an alkyl group or an aromatic group, X represents the same hydrolyzable substituent as in formula (1), a represents an integer from 1 to 3. Examples of the alkyl group or aromatic group Rd 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 compounds are represented by formula (12) which include methyltrimethoxy, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, dimethyldiphenylethoxysilane, dimethylphenylethoxysilanes. One of the types of hydrolyzable silane compounds represented by formula (12) can be used alone or two or more of them can be used in combination.
    [0051] By virtue of the presence of the hydrolyzable silane compound represented in formula (12), the polarity and crosslink density of the condensation product can be controlled. Furthermore, the degree of freedom of the condensed product substituent is improved by introducing a non-reactive group Rd. Therefore, the orientation of the perfluoropolyether group to the air interface side and the orientation of the epoxy group to the light-curing side 4 are cationically promoted. Furthermore, by virtue of the presence of the alkyl group, cleavage of a siloxane bond is suppressed, which results in improved water repellency and durability.
    [0052] In the condensed product, which is useful for further use, a hydrolyzable silane compound containing a fluorine group other than the perfluoropolyether group in combination with the above-mentioned components. When the perfluoropolyether group is present in the resin solution or in a resin coating film, aggregation of portions of the perfluoropolyether groups occurs and impairs the homogeneity of the material in some cases. However, by virtue of the presence of the hydrolyzable silane compound containing fluorine, aggregation of the perfluoropolyether group is prevented. Thus, a homogeneous film can be stably obtained. A general formula of these is represented by the following formula (13). Formula (13)

    [0053] In formula (13), Rf represents an alkyl group or aryl group having a fluorine atom, X represents a hydrolyzable substituent, R represents a non-hydrolyzable substituent, 'a' represents an integer of 1 or 2, b represents an integer from 0 to 2 and a+b represents an integer from 1 to 3.
    [0054] In that case, the alkyl group or the aryl group containing one fluorine atom is preferably with 1 to 10 fluorine atoms, in particular preferably one with 3 to 5 fluorine atoms. The incorporation of the fluorine atom prevents the separation of the perfluoropolyether group from the other components and prevents the aggregation of the perfluoropolyether group. On the other hand, a compound which has a large number of fluorine atoms and which exhibits water repellency and oil repellency may aggregate itself, with the result that the aggregation preventing effect of the perfluoropolyether group decreases.
    [0055] Specific examples of the alkyl group or aryl group having a fluorine atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a phenyl group and a naphthyl group and part or all of the hydrogen atoms thereof are replaced by a fluorine atom. For example, hydrolyzable silane compounds having a 3,3,3-trifluoropropyl group, a pentafluorophenyl group and a perefluorobutyl group are readily available as commercial reagents. One type of such hydrolyzable silane compounds represented by formula (13) can be used alone or two or more types thereof can be used in combination. The mixing ratio of the hydrolyzable silane compound in the preparation of condensation products according to the present invention is appropriately determined depending on usage patterns. However, the proportion of the mixture of the hydrolyzable silane compound having a perfluoropolyether group is 0.01 to 5 mol%, when calculated with respect to 100 mol% of the total number of moles of the hydrolysable silane compounds to be used. The proportion of the mixture is more preferably 0.005 to 3 mol%. When the mixing ratio is 0.01 mol% or less, sufficient water repellency is not obtained in some cases. Furthermore, when the mixing ratio is 5 mol% or more, aggregation and precipitation of the hydrolyzable silane compound having a perfluoropolyether group occurs, with the result that a homogeneous coating or film coating solution is not obtained in some cases.
    [0056] In addition, the amount of mixture of the hydrolyzable silane compound having an epoxy can be controlled from a viewpoint of providing the adhesion property with the cationically light-curing resin layer 4 with a lower layer and the durability of the chamber water repellent. The mixing amount of the hydrolyzable silane compound having an epoxy group is preferably 10 to 90 mol%, more preferably 30 to 70 mol%, when calculated with respect to 100 mol% of the total number of moles of the hydrolyzable silane compounds to be used. When the mixing ratio is 10 mol% or less, sufficient durability of the coating film is not obtained. When the mixing ratio is 90% molar or more, a reduction in water repellency due to the polarity of the epoxy group occurs in some cases.
    [0057] In the case of using a hydrolyzable silane compound represented by the formula (12), the amount of the mixture of the hydrolyzable silane compound represented by the formula (12) is preferably from 5 to 70 mol%, more preferably from 10 to 50 Mol%, when calculated with respect to 100% mole of the total number of moles of the hydrolyzable silane compound, to be used.
    [0058] Furthermore, in the case of using the hydrolyzable silane compound represented by the formula (13), the mixing amount of the hydrolyzable silane compound represented by the formula (13) is preferably from 5 to 70 mol%, more preferably from 10 to 50 mol% when calculated with respect to 100 mol% of the total number of mols of the hydrolyzable silane compound to be used.
    [0059] It should be noted that the hydrolyzable silane compound having a fluorine group other than the perfluoropolyether group prevents the aggregation of the perfluoropolyether group and hence the ratio of the compound to the hydrolyzable silane compound having a group of perfluoropolyether is important.
    [0060] The molar ratio of hydrolyzable silane compound having a different fluorine group than the perfluoropolyether group is preferably 2 times to 100 times, more preferably 5 times to 50 times, which also depends on the respective numbers of fluorine atoms with respect to the molar ratio of the hydrolyzable silane compound having a perfluoropolyether group. When the molar ratio of the hydrolyzable silane compound having a fluorine group other than the perfluoropolyether group is less than that described above, an effect of preventing aggregation of the perfluoropolyether group decreases, with the result that the surface coating film of unevenness, a development of residues and the like occurs in some cases.
    [0061] However, most hydrolyzable silane compounds that have a different fluorine group than the perfluropolyether group do not exhibit water repellency, oil repellency and ati-scalant functions by themselves. Therefore, when the addition amount of the hydrolyzable silane compound having a fluorine group different from the perfluoropolyether group is too great, the water repellency, oil repellency and anti-fouling functions tend to decrease.
    [0062] In the present invention, each of the hydrolyzable silane components are not used alone, but the hydrolyzable silane compounds are condensed to be used as a condensed product. With this, the compatibility between the cationically light-cured resin layer 4 and the condensed product and the film-forming property of the coating film at the time of application were satisfactory and the satisfactory characteristics can be obtained also when the modeling is performed by cationic light-curing.
    [0063] This condensation reaction is allowed by the hydrolysis reaction and/or a condensation reaction to proceed under heating in the presence of water. A desired degree of condensation can be appropriately obtained by controlling the hydrolysis/condensation reaction by means of temperature, time, concentration, pH and the like.
    [0064] In this case, the degree of progress of the condensation reaction (degree of condensation) can be defined by the ratio between the numbers of the condensable functional groups with respect to the numbers of the condensable functional groups. Condensable functional groups correspond to the hydrolyzable substituents mentioned above. The degree of condensation can be estimated by measuring 29Si-NMR. For example, in the case of the silane compound having three hydrolyzable substituents in a molecule, the degree of condensation is calculated according to the following equation from the following ratios.
    [0065] Formula T0: Si atom not bound to any other silane compound
    [0066] Formula T1: Si atom bonded to a silane compound through oxygen
    [0067] Formula T2: Si atom bonded to two silane compounds through oxygen
    [0068] Formula T3: Si atom bonded to three silane compounds through oxygen

    [0069] The degree of condensation, which also varies depending on the type of hydrolyzable silane compounds used and the preparation conditions, is preferably 20% or more, more preferably 30% or more, even more preferably 40% or more of the point view of resin compatibility and application property. Furthermore, the degree of condensation is preferably 90% or less from the standpoint of preventing precipitation, gelling and the like. In this regard, however, it is rare for the degree of condensation to be greater than 90% in the dissolution state in a solution.
    [0070] In addition, when the proportion of an unreacted silane is high, the homogeneity of the coating film decreases in some cases and consequently, the proportion of unreacted silane (formula T0) is preferably 20% or less. Furthermore, when the proportion of silane in which all hydrolyzable groups are condensed, water repellency and lower condensed antifouling is increased and a gel precipitates out of solution in some cases. For example, in a silane converted to a T3 formula in a solution, the degree of freedom of a substituent decreases and the surface orientation of the fluorine in a coating film to be obtained is changed in some cases, with the result that the water repellency and anti-fouling properties in some cases. Therefore, it is preferable that the amount of formula T3 be controlled to 50% or less.
    [0071] It should be noted that, likewise, in the case of the hydrolyzable silane compound having two substituents relative to one silane atom, the degree of condensation can be calculated according to the following equation.
    [0072] Formula D0: Si atom not bound to any other compound through silane
    [0073] Formula D1: Si atom bonded to a silane compound through oxygen
    [0074] Formula D2: Si atom bonded to two silane compounds through oxygen

    [0075] Similarly in the case of a silane compound having one or four hydrolyzable substituents with respect to one silane atom, the degree of condensation is calculated as a proportion of the number of condensed groups with respect to hydrolyzable substituents (condensed groups ).
    [0076] Furthermore, in the hydrolysis reaction and/or condensation reaction, a metal alkoxide, an acid, an alkali or the like can be used as a hydrolysis catalyst to control the degree of condensation. Examples of the metal alkoxide include an aluminum alkoxide, a titanium alkoxide, a zirconia alkoxide and complexes (eg an acetylacetone complex) thereof. One type of these metal alkoxides can be used alone or two or more types of them can be used in combination. It is also useful to adjust the pH with an acid or an alkali. When an alkali catalyst is used, solid matter such as a gel in solution precipitates in some cases. Thus, an acid catalyst is most preferred. In this regard, however, when a strong organic acid such as hydrochloric acid or sulfuric acid remains, the acid affects the remaining surrounding members, such as a base material, in some cases. In addition, when the pH is too low, the epoxy group on the condensation product may be subjected to ring opening, which decreases the characteristics of the coating film. Therefore, an acid that is weak, such as a carboxylic acid, and has a low molecular weight and volatility is preferred. Suitable specific examples include low molecular weight organic acids such as acetic acid, glycolic acid and formic acid. It should be noted that organic acids are added at the time of synthesis but are often contained in trace amounts in silane compounds which serve as raw materials. Thus, even when no acid is added, the synthesis is carried out without any problem in many cases.
    [0077] In the present invention, various silane compounds are used in combination. Therefore, care must be exercised when the hydrolysis reaction and/or condensation reaction rate varies significantly depending on the types of silane compounds. When the condensation reaction proceeds by only one silane compound that has a high reaction rate and a low reaction rate silane compound remains unreacted, the homogeneity and repellency to water containing a coating film is lower in some cases. It is preferable to use a catalyst, such as an acid, in order to subject the respective silane compounds to as homogeneous a reaction as possible.
    [0078] The condensed product is synthesized in a non-fluorine-containing organic solvent having a linking group or containing an oxygen atom, such as a hydroxy group, a carbonyl group or an ether linkage.
    [0079] Specific examples of these include polar solvents not containing fluorine: alcohols such as methanol, ethanol, propanol, isopropanol and butanol; ketones such as methyl, ethyl, ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; ethers such as diglyme and tetrahydrofuran; and glycols such as diethylene glycol. Of these, alcohols that have high water solubility are more suitable. Furthermore, heating is preferably carried out at 100°C or less from the viewpoint of controlling the water content. Therefore, when the reaction is carried out under heating and reflux, a polar solvent that has a boiling point of 50°C to 100°C is suitable. One type of these polar solvents can be used alone or two or more types of them can be used in combination. A polar solvent such as an alcohol is generally used for the hydrolysis/condensation reaction of a silane compound. Furthermore, in the present invention, water and a silane compound having a polar group such as an epoxy group are used for synthesis, and therefore the use of a polar solvent is required. On the other hand, however, the hydrolyzable silane compound that has a perfluoropolyether group tends to have a low solubility in a polar solvent. The inventors of the present invention have found that a homogeneous condensed product can be synthesized using a mixed solvent of a non-fluorine-containing polar solvent and a fluorine-containing solvent and controls the length of a perfluoropolyether group to a suitable length.
    [0080] Furthermore, when the number of repeating units in the aforementioned perfluoropolyether group is large, the solubility in a polar solvent not containing fluorine decreases, and therefore the condensed product is preferably obtained by heating a hydrolyzable silane compound which has an epoxy group and a hydrolyzable silane compound that has a perfluoropolyether group in a mixture of a non-fluorine-containing organic solvent and a fluorine-containing solvent. In the hydrolyzable silane compound that has a perfluoropolyether group, as a number of fluorine atoms becomes higher, the solubility in a polar solvent becomes lower. However, the water content is low in the fluorine-containing solvent, which is easy to dissolve a hydrolyzable silane compound having a perfluoropolyether group, and hence the reaction hardly proceeds. The inventors of the present invention have found that the homogeneous condensed product can be synthesized using a mixed solvent of a polar solvent which does not contain fluor and a solvent which contains fluor although in the case using a hydrolyzable silane compound having a perfluoropolyether group, which it has low solubility.
    [0081] In that case, examples of the fluorine-containing solvent that can be used in combination with a non-fluorine-containing polar solvent include a fluorinated hydrocarbon, a perfluorocarbon, a hydrofluorether, a hydrofluoropolyether and a perfluoropolyether. Of these, a hydrofluoroether, a hydrofluoropolyether, a perfluoropolyether or the like, which has an oxygen atom and has an affinity for water, is preferred because the addition of water is necessary for hydrolysis. One type of said fluorine-containing solvents can be used alone or two or more types thereof can be used in combination.
    [0082] It should be noted that, in each of the non-fluorine-containing organic solvents and the fluorine-containing solvent, a solvent is called a heteroatom such as a nitrogen atom or a sulfur atom is not preferred because the solvent may affect a process of curing a coating film.
    [0083] When the fluorine-containing solvent and the non-fluorine-containing organic solvent are used mixed, a combination thereof is not particularly limited, but is preferably the combination of an alcohol and a hydrofluorether.
    [0084] The mixing ratio (volume ratio) between the non-fluorine-containing organic solvent and the fluorine-containing solvent is preferably 2:8 to 9:1, more preferably 3:7 to 8:2. It should be noted that the hydrolyzable silane compound having an epoxy group is poorly soluble in the fluorine-containing solvent (the fluorine-containing solvent alone) and the hydrolyzable silane compound having a perfluorolyether group is poorly soluble in alcohol. In addition, the hydrolyzable silane compound having a perfluoropolyether group is often used to be dissolved in the fluorine-containing solvent from the standpoint of storage stability and the fluorine-containing solvent mixture can supply an unnecessary condensation reaction.
    [0085] The concentration of active compound of a reaction solution is preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 50% by mass or less. When the concentration of the active component is 5% by mass or more, a sufficient reaction rate is obtained. When the concentration of the active component is 60% by mass or less, the occurrence of gelling and precipitation can be suppressed. It should be noted that when the hydrolyzable group of the hydrolyzable silane compound is an alkoxy group, an alcohol and water are generated through the hydrolysis reaction and/or a condensation reaction. Therefore, it is difficult to calculate the actual concentration of the compound in a solution. In view of the above, a value calculated assuming a 100% degree of condensation state in which all alkoxy groups are hydrolyzed and all silane groups are condensed is defined herein as a concentration of active compound.
    [0086] The amount of water addition to be used in the reaction is preferably 0.5 to 3 equivalents, more preferably 0.8 to 2 equivalents, relative to the hydrolyzable substituents of the hydrolyzable silane compounds. When the amount of water addition is 0.5 equivalents or more, a sufficient reaction rate in the hydrolysis/condensation reaction is obtained. When the amount of water addition is 3 equivalents or less, precipitation on the hydrolyzable silane compound having a perfluoropolyether group can be suppressed.
    [0087] For layer 5, including the condensed product, a desired coating film can be produced by applying a solution including the resulting condensed product onto the cationically photopolymerizable resin layer 4 before curing by means of an application apparatus for general use, a groove coater or spin machine, a dead coater, a groove coater or a spray coating machine. Furthermore, when the material concentration is adjusted, the dip coating is also applicable.
    [0088] When the resulting condensed product is applied as a solution, the concentration of the solution including the condensed product is appropriately determined depending on the material of layer 5, including the condensed product, an application method and an intended use. When using the spin coater, the die coater, the groove coater or a spray coater and thus the concentration of the condensed product in the solution, including the condensed product is preferably 0.1 to 20% by mass. , but preferably 1 to 10% by mass. When the concentration of a condensed product falls within this range, sufficient water repellency and durability is obtained and homogeneous water repellency is obtained over the entire surface of the coating film.
    [0089] The thickness of layer 5 including the condensed product is preferably 50 to 10,000 nm, more preferably 80 to 5,000 nm. When the thickness is less than 50nm, homogeneous water repellency is hardly obtained and the durability is insufficient in some cases. In addition, when the thickness is too wide, there are reductions in patterning characteristics such as pattern deformation and a reduction in property resolution occurs in some cases. According to the embodiment of the present invention, a thin coating film can express high durability through the use of a cationic polymerization and heat-induced silane polycondensation in combination with the coating film curing reaction.
    [0090] Then, the cured regions of cationically light-cured resin 4 and layer 5 including the condensed product are exposed to the pattern of lights 8 through a mask 6 (FIG. 2D). UV light can be used as light 8. For example, exposure to a single wavelength with the i-line (365nm) can be employed. In regions of irradiation, an acid generated by cationically photopolymerization 4 diffuses into layer 5, including the condensed product.
    [0091] It is also suitable to add a light curing indicator, an absorbing light, a sensitizer, an epoxy resin or the like, to layer 5, including the condensed product for the purpose of improving the pattern characteristics of layer 5, including the product condensed.
    [0092] Then, the heating treatment is carried out in order to subject the exposed portions in the cationically light-cured resin layer 4 and the layer 5, including the condensed product for simultaneous curing (FIG. 2E). When the heat treatment is carried out, the reaction proceeds on exposed portions and resistance in the subsequent step in development can be transmitted. At that point, an ether bond is formed between the chaotically photopolymerizable resin layer 4 and the layer 5 include the condensed product through the reaction of the epoxy group. Furthermore, it is considered that a dehydration condensation reaction between a silane group and a hydroxy group also proceeds between the chaotically photopolymerizable resin layer 4 and the layer 5 including the condensed product. As a result, a stronger bond is formed between the cationically photopolymerizable resin layer 4 and the layer 5 including the condensed product and thus adhesiveness is ensured. In addition, the cationically photopolymerizable resin layer 4 and the layer 5 including the condensed product dissolve each other at its interface. When a layer in which the resin layer 4 and the layer 5 including the condensed product are mutually mixed is present, an even stronger bond is formed, and thus drastically improving the durability.
    [0093] Next, the cationically photopolymerizable resin layer 4 and layer 5 including the condensed product are developed to remove the unexposed portion. In this way, ejection holes 9 are formed (FIG. 2F). Furthermore, with this, the element 4 and the water-repellent layer 5 are formed. The developer solution to be used for the development is not particularly limited, as long as the solution is capable of developing the unexposed parts of the cationically photopolymerizable resin layer 4 and the layer 5, including the condensed product. For example, a mixture of methyl isobutyl ketone (MIBK) and xylene can be used for solution development. Rinse treatment with isopropanol or the like can be carried out after treatment, development has been carried out.
    [0094] Next, an ink supply hole 10 is formed in the rear surface of substrate 1. Furthermore, an ink flow passage 11 is formed by removing the pattern from the ink flow path (FIG. 2G) . A method of forming the ink supply port 10 is not particularly limited. For example, the ink supply port 10 can be formed by anisotropic etching with an alkaline solution by laser irradiation. As a method of removing the pattern from the ink flow path 3, for example, a method of removing the pattern from the ink flow path 3 is given which involves immersing the substrate 1 in a solvent capable of dissolving the pattern from the ink. ink flow path 3. Furthermore, it is necessary that the standard ink flow path 3 can be exposed to an active energy beam capable of degrading the pattern of the ink flow path 3 in order to improve its solubility.
    [0095] After that, the electrical union is immediately established in order to drive the energy generated elements are 2. In addition, an ink supply member for ink supply and the like are connected. In this way, an inkjet recording head can be completed. Examples
    [0096] Examples and comparative examples are shown below. However, the present invention is not limited to them. Various measurements and evaluations were carried out by the methods below. (Degree of condensation)
    [0097] The degree of condensation of the prepared condensed product was calculated based on the definition mentioned above, performing the measurement of 29Si-NMR through the use of a nuclear magnetic resonance apparatus (product name: AVANCE II 500 MHz, manufactured by Bruker BioSpin Co.). (Outward appearance)
    [0098] The external appearances of a solution that includes a condensed product and a coating film of the solution were evaluated by an optical microscope. (Contact angle of pure water)
    [0099] As an evaluation of a produced inkjet recording head, a dynamic relapse contact angle θr with pure water was measured using a microcontact angle meter (product name: measuring drop, manufactured by microjet Corporation), and initial water repellency was evaluated. In addition, as an assessment of the durability of the nozzle surface, the nozzle surface was immersed in paint, kept at 60°C for 1 week, and then washed with water and the dynamics of a contact angle decompression θr with pure water in the vicinity of the ejection hole was measured. In addition, as an assessment of durability against abrasion, a scraping operation with a hydrogenated nitrile rubber (HNBR) blade was performed 2000 times, while pigment ink was sprayed onto the surface of the nozzle, and then , a decompression dynamics of a contact angle θr with pure water was measured. With this, the durability against scraping was examined.Example 1
    [00100] A substrate 1 made of silicone on which the power generating elements have been prepared. The solution obtained by dissolving polymethyl isopropenyl ketone with a positive photosensitive resin material in ethyl acetate was applied onto substrate 1 by a spin coating method. After that, the result was cured to form a positive photosensitive resin layer. The positive resin layer had a thickness of 14 µm.
    [00101] Then, the positive photosensitive resin layer was exposed to the pattern by means of irradiation with UV light capable of photosensitizing the exposed layer by means of a mask. Thereafter, the exposed portion was dissolved and developed using a mixed solvent of propylene glycol ether acetate and methyl isobutyl ketone to form a standard ink flow path 3.
    [00102] 100 parts by mass of cationically photopolymerizable resin material (trade name: EHPE-3150, manufactured by Daicel Corporation) and 6 parts by mass of cationic photopolymerization inactivator (trade name: SP-172, manufactured by Adeka CORPORATION) were dissolved in 80 parts by mass of xylene as solvent. The solution was applied over the standard ink flow path 3 and the substrate 1 by a spin coating method to form the cationically photopolymerizable resin layer 4.
    [00103] A condensed product obtained by the condensation of a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group was prepared by a method shown below. 12.53g (0.045 mol) of y-glycidoxyporpyltrimethozysilane, 8.02 g (0.045 mol) of methyltriethoxysilane, 1.05 g (0.00091 mol) of a compound represented by the formula (10), 5.95 g of water, 13.4 g of ethanol, and 4.20 g of hydrofluorether (trade name: HFE 7200, manufactured by Sumitomo 3M limited) were stirred at room temperature for 5 minutes in a flask equipped with a cooling tube. Thereafter, the mixture was heated with reflux for 24 hours to prepare a condensation product.
    [00104] The resulting condensed product was diluted through the use of 2-butanol/ethanol, so as to have the concentration of the active ingredient of 7% by mass. The diluted solution was applied onto the cationically light cured resin layer 4 prior to curing using a agent coater to form layer 5 including the condensed product.
    [00105] Then, the chaotically photopolymerizable resin layer 4 and the layer 5, including the condensed product were irradiated with i-line through the mask 6, followed by a heating treatment at 90°C for 4 minutes, so that the irradiated area has been healed. The development of the treatment with the mixture MIBK and xylene was carried out and a washing treatment with isopropanol was carried out in order to form an ejection hole 9.
    [00106] Then, anisotropic conditioning with an alkaline solution was carried out from the back surface of substrate 1 to form an ink supply hole 10. Thereafter, the substrate was irradiated with a UV light to degrade the pattern path of ink peeling 3 and then immersed in methyl lactate to dissolve and remove the standard ink flow path 3, to thereby form an ink flow path 11.
    [00107] Thereafter, the electrical union was established in order to drive the power generating elements 2. In addition, an ink supply member for ink supply was connected. The resulting inkjet recording head was evaluated by the aforementioned methods. Table 1 shows the results.Example 2 to 24
    [00108] An inkjet recording head was produced and evaluated in the same way as in Example 1, except that the types and mixing ratios of silane compounds and solvent ratios shown in Table 1 were used. shows the results. Comparison between Examples 1 and 2
    [00109] An inkjet recording head was produced and evaluated in the same manner as in Example 1, except for the types and mixing ratios of hydrolyzable silane compounds, catalyst ratios and solvent ratios shown in Table 1. Table 1 shows the results. Comparison of Example 3
    [00110] An inkjet recording head was produced and evaluated in the same manner as in Example 1, except that the hydrolyzable silane compound having an epoxy group and the hydrolyzable silane compound having a perfluoropolyether group were not condensed , but were simply mixed. Table 1 shows the results.





    Abbreviations of Table 1 are described below: (i) The compound represented by the formula (10)(ii) The compound represented by the formula (11)(iii) The compound represented by the formula (7)(iv) The compound represented by the formula ( 8)(v) The compound represented by the formula (9)(vi) Tridecafluoro-1,1,2,20tetrahydrocootyltriethoxysilaneGPTES: y-glycidoxypropyltriethoxysilaneGPMDMS: y-glycidoxypropyltrimethoxysilaneMTEOS: methyltriethoxysilaneDMDES: dimethyldiethoxysilanePhtoxysilanePhtoxy-ETHS: triethoxysilanetriethytES: triethoxysilanemTEOS: methyltriethoxysilaneDMDES: dimethyldiethoxysilanePhsyl-ETSyl-ETS:trimethylphenyltriethEt: 3,3-trifluoropropyltrimethoxysilanePFPTES: pentafluorophenyltriethoxysilaneC4FTMS: nanofluorohexitrimethoxysilaneC6FTES: (Tridecafluoro-1,1,2,2-tetrahydrootyl)triethoxysilane
    [00111] Table 1 reveals that the inkjet recording head produced in the examples had satisfactory surface smoothness, had large initial θr, and thus exhibited satisfactory water repellency. Furthermore, it was found that the high water repellency was shown after the durability test. The above-mentioned results showed that, under one of the conditions of Examples 1 to 24, the adhesion strength between the water-repellent layer 5 and the member 4 was improved and the durability against cleaning was improved. Also, when the print was evaluated using the inkjet recording head, the point of misalignment or how was not observed and the high print quality was displayed.
    [00112] On the other hand, water repellency and durability was low in each of Comparative Examples 1, 2 and 3.
    [00113] According to the present invention, an inkjet recording head with high water repellency and high durability against abrasion can be provided.
    [00114] Although the present invention has been described with reference to the exemplary embodiments, it is to be understood that the invention is not limited to the described exemplary embodiments. The scope of the following claims is to be given the broadest interpretation to encompass all modifications and equivalent structures and functions.
    [00115] This application claims the benefit of Japanese Patent Application No. 2012-094782, filed April 18, 2001, and Japanese Patent Application No. 2013-041650, filed March 4, 2013, which are incorporated herein by reference in its entirety.
    权利要求:
    Claims (16)
    [0001]
    1. Inkjet recording head, characterized in that it comprises an element (4) provided with an ejection hole (9) for ejecting ink, wherein the inkjet recording head further comprises a water repellent layer (5 ) comprising a cured product of a condensed product obtained by condensation of a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group on a surface of element (4) on a side in which the ejection hole ( 9) opens.
    [0002]
    An inkjet recording head according to claim 1, characterized in that the water repellent layer (5) further comprises a cured product obtained by subjecting the condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group and an epoxy resin to a cure reaction.
    [0003]
    An inkjet recording head according to claim 1, characterized in that the hydrolyzable silane compound having an epoxy group is represented by the formula (1): Formula (1)
    [0004]
    An inkjet recording head according to claim 1, characterized in that the hydrolyzable silane compound having a perfluoropolyether group comprises at least one compound selected from the group consisting of compounds represented by the following formulas (2), (3) , (4), and (5): Formula (2)
    [0005]
    5. Inkjet recording head according to claim 4, characterized in that the perfluoropolyether group Rp in formulas (2), (3), (4) and (5) is represented by the following formula (6):Formula (6)
    [0006]
    An inkjet recording head according to claim 4, characterized by one of a number of repeating units in the perfluoropolyether group Rp in formulas (2), (3), (4) and (5) and the , p, q, or r in formula (6) is an integer from 1 to 30.
    [0007]
    The inkjet recording head of claim 3, characterized in that the condensed product comprises a condensed product obtained by condensing the hydrolyzable silane compound having an epoxy group, the hydrolysable silane compound having a perfluoropolyether group, and a hydrolyzable silane compound represented by the following formula (12): Formula (12)
    [0008]
    An inkjet recording head according to claim 3, characterized in that the condensed product comprises a condensed product obtained by condensing the hydrolyzable silane compound having an epoxy group, the hydrolysable silane compound having a perfluoropolyether group, and a hydrolyzable silane compound having a fluorine-containing group other than the perfluoropolyether group.
    [0009]
    An inkjet recording head according to claim 8, characterized in that the hydrolyzable silane compound having a fluorine-containing group other than the perfluoropolyether group comprises a hydrolyzable silane compound represented by formula (13):Formula (13) )
    [0010]
    A manufacturing method for the inkjet recording head as defined in claim 1, the manufacturing method comprising providing the condensed product obtained by condensing a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a perfluoropolyether group by heating the hydrolyzable silane compound having an epoxy group and the hydrolyzable silane compound having a perfluoropolyether group in a mixture of a non-fluorine-containing organic solvent and a fluorine-containing solvent.
    [0011]
    A manufacturing method for the inkjet recording head according to claim 10, characterized in that the mixture of a non-fluorine-containing organic solvent and a fluorine-containing solvent comprises a mixture of an alcohol and a hydrofluoroether.
    [0012]
    A manufacturing method for the inkjet recording head according to claim 10, characterized in that the condensation of the hydrolyzable silane compound having an epoxy group and the hydrolyzable silane compound having a perfluoropolyether group is carried out through use of an organic acid as a catalyst for a hydrolysis reaction and/or a condensation reaction.
    [0013]
    A manufacturing method for the inkjet recording head according to claim 12, characterized in that the organic acid comprises one of acetic acid and formic acid.
    [0014]
    14. Manufacturing method for the inkjet recording head, comprising a substrate (1), an element (4) provided with an ejection hole (9) for ejecting ink, and a water-repellent layer (5) provided on a surface of the element (4) on a side on which the ejection hole (9) opens, the manufacturing method characterized by comprising the steps of: (1) forming a cationically photopolymerizable resin layer (4) comprising a material of cationically photopolymerizable resin having an epoxy group on a substrate (1); (2) form a layer (5) comprising a condensed product obtained by condensation of a hydrolyzable silane compound having an epoxy group and a hydrolyzable silane compound having a group perfluoropolyether in the cationically light-cured resin layer (4) before curing; (3) pattern exposure of the cationically light-cured resin layer (4) and the layer (5) comprising the condensed product simultaneously; (4) subject to exposed surfaces of the cationically photopolymerizable resin layer (4) and the layer (5) comprising the condensed product to cure simultaneously; and (5) removing unexposed parts of the cationically photopolymerizable resin layer (4) and the layer (5) comprising the condensed product to form an ejection orifice (9), thus providing an element (4) and a water-repellent layer (5).
    [0015]
    15. Manufacturing method for the inkjet recording head according to claim 14, characterized in that in step (2) the layer (5) comprising the condensed product is formed by applying a solution comprising a condensed product obtained by condensation of a hydrolyzable silane compound having an epoxy group and a hydrolysable silane compound having a perfluoropolyether group in the cationically photopolymerizable resin layer (4) prior to curing.
    [0016]
    Inkjet recording head according to claim 1, characterized in that the condensed product has a degree of condensation of 40% or more and 90% or less.
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    同族专利:
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012094782|2012-04-18|
    JP2012-094782|2012-04-18|
    JP2013-041650|2013-03-04|
    JP2013041650A|JP5591361B2|2012-04-18|2013-03-04|Inkjet recording head|
    PCT/JP2013/061960|WO2013157659A1|2012-04-18|2013-04-17|Ink jet recording head and manufacturing method therefor|
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