Liquid ejecting head and method for manufacturing liquid ejecting head

Abstract

The present application provides a liquid ejection head and a method for manufacturing a liquid ejection head. The liquid ejection head includes: an ejection port for ejecting a liquid; and an energy generating element for generating energy for ejecting the liquid from the ejection port, wherein a film containing silicone is formed on a surface of the liquid ejection head in which the ejection port is provided, and the film containing silicone contains a cured product of a resin composition containing a two-terminal epoxy silicone resin and a photocationic polymerization initiator.

Description

Technical Field

[0001] This disclosure relates to a liquid jet head and a method for preparing the liquid jet head. Background Technology

[0002] Fluorinated water-repellent materials are generally known for forming liquid-repellent and antifouling membranes, and compounds with perfluoroalkyl or perfluoropolyether groups, in particular, exhibit excellent liquid repellency and durability and are widely used in various applications. However, due to the high chemical stability and resistance to decomposition of fluorinated compounds when continuously released into the environment, they remain in the environment for extended periods and may impact human health, animal and plant habitats, and growth through the environment and food chain. Therefore, recently, in order to achieve a sustainable society, such as a circular society, there is a need to convert fluorinated water-repellent materials into non-fluorinated water-repellent materials.

[0003] Organosilicon compounds are fluorine-free water-repellent materials that also exhibit excellent liquid repellency and can be used as substitutes for fluorine-based water-repellent materials. Organosilicon compounds can address environmental impact and fluorine source issues.

[0004] For example, Japanese Patent Publication No. 2001-158818 discloses a method in which an organosilicon compound, especially an epoxy resin composition containing siloxane, is used as a non-fluorinated water-repellent material. Summary of the Invention

[0005] For liquid ejector heads, such as inkjet recorders, liquid repellency, such as ink resistance, is required, and water-repellent materials are sometimes applied to the surface of components near the ejector nozzle, etc.

[0006] Fluorine-based, silicone-based, and other water-repellent materials exhibit water repellency by segregating water-repellent groups on the surface of the water-repellent and antifouling membrane. The inventors have recognized that when water-repellent materials with a comb-like water-repellent structure, as described in Japanese Patent Publication No. 2001-158818, come into contact with inks used for commercial and industrial printing, structural degradation occurs, and the liquid repellency deteriorates.

[0007] This disclosure provides a liquid jet head with excellent liquid repellency capable of handling inks used in commercial and industrial printing, and a method for preparing the liquid jet head.

[0008] This disclosure relates to a liquid jet head, comprising: a jet nozzle for jetting a liquid; and an energy generating element for generating energy for jetting the liquid from the jet nozzle, wherein a silicone-containing film is formed on a surface of the liquid jet head having the jet nozzle, and the silicone-containing film comprises a cured resin composition comprising a two-terminated epoxy silicone resin and a photocationic polymerization initiator.

[0009] This disclosure also relates to a method for preparing a liquid jet head having a jet nozzle for jetting liquid and an energy generating element for generating energy for jetting the liquid from the jet nozzle, wherein a silicone-containing film is formed on the surface of the liquid jet head having the jet nozzle, and the surface having the jet nozzle is the surface of a jet nozzle forming member forming a flow path for the liquid communicating with the jet nozzle. The preparation method includes: a step of forming a photosensitive resin layer, the photosensitive resin layer forming the jet nozzle forming member; a step of forming a layer of a resin composition forming the silicone-containing film on the photosensitive resin layer; and a step of exposing and developing the photosensitive resin layer and the layer of the resin composition to form the jet nozzle forming member and the silicone-containing film, wherein the resin composition contains a two-terminated epoxy silicone resin and a photocationic polymerization initiator.

[0010] According to this disclosure, a liquid ejector head with excellent liquid repellency capable of handling inks used in commercial and industrial printing, and a method for preparing the liquid ejector head are provided. The liquid ejector head according to this disclosure exhibits advantageous water repellency even without any fluorine-based water-repellent material. Therefore, the technology described in this specification can contribute to the realization of a sustainable society, such as a decarbonized / circular society.

[0011] The features of this disclosure will become apparent from the following description of embodiments with reference to the accompanying drawings. The following description of embodiments is by way of illustration. Attached Figure Description

[0012] Figure 1A and 1B This is a schematic diagram of an inkjet recording head using a membrane containing silicone.

[0013] Figure 2A-2H This is a figure illustrating an example of a method for preparing an inkjet recording head using a film containing organosilicon.

[0014] Figures 3A-3H This is a figure illustrating an example of a method for preparing an inkjet recording head using a film containing organosilicon.

[0015] Figure 4A and 4B This is a diagram illustrating the process of forming a film containing organosilicon.

[0016] Figure 5A and 5B This is a schematic diagram of an inkjet recording head using a membrane containing silicone.

[0017] Figures 6A-6D This is a schematic diagram illustrating a method for forming a liquid-repellent and antifouling film on the nozzle. Detailed Implementation

[0018] In this disclosure, unless otherwise stated, the symbols "from XX to YY" and "XX to YY" indicating a numerical range refer to a numerical range including a lower limit and an upper limit as endpoints. When describing numerical ranges in stages, the upper and lower limits of the various numerical ranges can be combined arbitrarily. For example, in this disclosure, phrases such as "at least one selected from the group consisting of XX, YY, and ZZ" include combinations of XX, YY, ZZ, XX and YY, combinations of XX and ZZ, combinations of YY and ZZ, and combinations of XX, YY, and ZZ.

[0019] Embodiments of this disclosure will be described below, but this disclosure is not limited to these embodiments, and not all combinations of features described in these embodiments are necessary for the solutions of this disclosure. The constituent elements described in the embodiments are merely examples and are not intended to limit the scope of this disclosure.

[0020] As described above, the water-repellent properties of a water-repellent material with a comb-like water-repellent structure may become insufficient when it comes into contact with inks used in commercial and industrial printing. It is believed that structural deterioration occurs due to the adhesion of pigment components in pigment inks used in commercial and industrial printing or due to excessive solvents, resulting in a deterioration in water repellency. On the other hand, in the liquid ejector head of this disclosure, a silicone-containing film with excellent water repellency can be formed using a silicone-containing film with two-terminal epoxy silicone resin. The silicone-containing film can be used as a water- and oil-repellent film. The two-terminal epoxy silicone resin in the liquid ejector head will be described below.

[0021] Two-terminal epoxy silicone resin

[0022] Organosilicones possess low surface free energy and exhibit liquid repellency. The degrees of freedom of the organosilicon backbone vary depending on the structure of the compound and the length of the backbone, thus affecting liquid repellency. When the organosilicon compound has an epoxy group at one end, the degrees of freedom of the backbone are high, and the liquid repellency tends to deteriorate in liquid repellency tests. Specifically, it is believed that when the organosilicon does not have a reactive group at one end, the degrees of freedom are high, but the bond between the organosilicon chain and the resin is weak, and structural degradation occurs when the organosilicon comes into contact with inks used in commercial and industrial printing due to pigments or solvents.

[0023] On the other hand, in the case of organosilicon compounds with epoxy groups at both ends, as in two-terminated epoxy organosilicon resins, it is believed that the organosilicon compounds undergo linear polymerization and the degree of freedom of the organosilicon backbone is reduced. Therefore, it is believed that by fixing the organosilicon backbone, the liquid repellency is not easily deteriorated in liquid repellency tests, even when using inks used in commercial and industrial printing.

[0024] In the case of organosilicon compounds that have epoxy-containing groups on the side chains instead of two ends, the organosilicon backbone has degrees of freedom at the ends, similar to a single-end type, and therefore the liquid repellency tends to deteriorate easily in the liquid repellency test.

[0025] On the other hand, in two-terminated epoxy silicone resins with epoxy-containing groups in at least some side chains besides the two ends, the degree of freedom of the silicone backbone is reduced, so it is considered that the liquid repellency is less likely to deteriorate in the liquid repellency test. Therefore, the two-terminated epoxy silicone resin is preferably at least one selected from the group consisting of two-terminated linear epoxy silicone resins and two-terminated side-chain epoxy silicone resins, and more preferably a two-terminated linear epoxy silicone resin.

[0026] This disclosure relates to a liquid ejector head having an ejection port for ejecting a liquid; and an energy generating element for generating energy for ejecting the liquid from the ejection port. Furthermore, a silicone-containing film is formed on the surface of the liquid ejector head with the ejection port, and the silicone-containing film may contain a cured resin composition comprising a two-terminated epoxy silicone resin and a photocationic polymerization initiator. The liquid ejector head of this disclosure exhibits excellent liquid repellency even for inks used in commercial and industrial printing.

[0027] Resin compositions containing a two-terminated epoxy silicone resin and a photocationic polymerization initiator are, for example, photosensitive resin compositions. There are no particular limitations on the two-terminated epoxy silicone resin, and known epoxy silicone resins can be used. The two-terminated epoxy silicone resin is, for example, a silicone oil having epoxy-containing groups at both ends, and preferably an alkyl polysiloxane having epoxy-containing groups at both ends. The alkyl group in the alkyl polysiloxane preferably has 1-12 carbon atoms, more preferably 1-4. The two-terminated epoxy silicone resin may have epoxy-containing groups at at least two ends and may further have epoxy-containing groups at positions other than the two ends, for example, on the side chain.

[0028] The two-terminal epoxy silicone resin is preferably an alkylsiloxane resin having a structure represented by the following formula (1), and more preferably an alkylsiloxane resin having a structure represented by the following formula (1-2).

[0029]

[0030] In formula (1), R5 and R6 are each independently an alkyl group having 1-12 carbon atoms or an aryl group having 6-12 carbon atoms.

[0031] X3 and X4 are each independently an epoxy group, R8 is an epoxy group, an alkyl group with 1-12 carbon atoms or an aryl group with 6-12 carbon atoms, R7 is an alkyl group with 1-12 carbon atoms or an aryl group with 6-12 carbon atoms, and the arrangement of structures in parentheses with m and structures in parentheses with n can be random or block, where m is an integer from 0 to 3 and n+m is an integer from 1 to 60.

[0032] Preferably, R5 and R6 are each independently an alkyl group having 1-4 carbon atoms, R8 is an alkyl group containing an epoxy group or having 1-4 carbon atoms, R7 is an alkyl group having 1-4 carbon atoms, and m is 0 or 1.

[0033]

[0034] In formula (1-2), R5 and R6 are each independently an alkyl group having 1-12 carbon atoms or an aryl group having 6-12 carbon atoms.

[0035] X3 and X4 are each independently an epoxy group, and n is an integer from 1 to 60.

[0036] Examples of epoxy-containing groups include groups having a glycidyl ether group or a group having an alicyclic epoxy group. Preferably, the epoxy-containing group has a glycidyl ether group or a cyclohexyl epoxide group.

[0037] The epoxy-containing group is more preferably a glycidoxyalkyl group having 1-4 (preferably 2-4) carbon atoms in the alkyl chain or an epoxycyclohexylalkyl group having 1-8 (preferably 2-6) carbon atoms in the alkyl chain. The epoxy-containing group is more preferably a 3-glycidoxyalkyl group having 1-4 (preferably 2-4) carbon atoms in the alkyl chain or a 2-(3,4-epoxycyclohexyl)alkyl group having 1-8 (preferably 2-6) carbon atoms in the alkyl chain.

[0038] Further preferred examples of epoxy-containing groups include 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, and 2-(3,4-epoxycyclohexyl)pentyl. The epoxy-containing group is further preferably 2-(3,4-epoxycyclohexyl)ethyl. In particular, epoxycyclohexylalkyl groups exhibit excellent reactivity and can achieve high liquid repellency.

[0039] As alkyl groups having 1-12 carbon atoms in formulas (1) and (1-2), alkyl groups having 1-4 carbon atoms, such as methyl, ethyl, propyl, or butyl, are particularly preferred, and methyl is more preferred. From the viewpoint of compatibility with resins or film strength, phenyl or the like can exist as aryl groups having 6-12 carbon atoms in formula (1).

[0040] In formula (1), m+n is 1-60, and from the viewpoint of compatibility with resin and solubility in solvent, it is preferably 10-60. From the viewpoint of liquid repellency, m+n is more preferably 30-60. m+n can be 20-60, and can also be 25-45.

[0041] In equation (1), m is preferably 0 or 1. Furthermore, the arrangement of structures within parentheses containing m and structures within parentheses containing n can be random or segmented. The arrangement of structures within parentheses containing m and structures within parentheses containing n is preferably random.

[0042] In formulas (1-2), from the viewpoint of compatibility with the resin and solubility in the solvent, n is 1-60, preferably 10-60. From the viewpoint of liquid repellency, n is more preferably 30-60. n can be 20-60 or 25-45.

[0043] In this disclosure, the above-described two-terminal epoxy silicone resin is used, thereby making the binding of the silicone compound stronger and exhibiting higher liquid repellency.

[0044] There are no particular limitations on the thickness of the silicone-containing film. The thickness of the silicone-containing film is, for example, 0.1-100 μm, preferably 0.1-10 μm, and more preferably 0.2-2.0 μm.

[0045] Furthermore, to improve adhesion to the underlying membrane, such as an inorganic membrane, a silane coupling agent can be added to the organosilicon compound. The organosilicon-containing membrane can be, for example, a laminate having an organosilicon-containing membrane (an organosilicon-containing layer) on a substrate.

[0046] Epoxy resin

[0047] Furthermore, using epoxy resins in resin compositions for forming silicone-containing films is also effective. For example, in the polymerization of bi-terminated epoxy silicone resins, a linear structure is mainly formed, but it is also considered that when bi-terminated epoxy silicone resins and epoxy resins are used together, the silicone is incorporated into the network structure of the epoxy resin, and the liquid repellency is further improved. From the viewpoint of forming strong bonds, alicyclic epoxy resins are preferred as epoxy resins.

[0048] The resin composition preferably contains an epoxy resin different from a two-terminated epoxy silicone resin. The silicone-containing membrane can be a cured product of a resin composition containing a two-terminated epoxy silicone resin, a photocationic polymerization initiator, and an epoxy resin. The silicone-containing membrane contains, for example, an epoxy resin as a binder.

[0049] The epoxy resin is preferably a cationic polymeric epoxy resin, and can be selected considering the adhesive properties, mechanical strength, and swelling resistance of the cured resin composition. For example, the epoxy resin may be a resin other than an alkylsiloxane resin having a structure represented by the above formulas (1) and (1-2).

[0050] The epoxy resin is preferably selected from at least one group consisting of epoxy resins having an alicyclic skeleton, epoxy resins having a bisphenol skeleton, epoxy resins having a phenolic varnish skeleton, epoxy resins having a cresol varnish skeleton, epoxy resins having a norbornene skeleton, epoxy resins having a terpene skeleton, epoxy resins having a dicyclopentadiene skeleton, and epoxy resins having an oxycyclohexane skeleton.

[0051] More specific examples may include cationic polymeric epoxy resins, such as multifunctional epoxy resins, such as epoxy resins having an alicyclic backbone, such as a cyclohexane backbone; epoxy resins having a bisphenol backbone, such as bisphenol A and F type epoxy resins; epoxy resins having a phenolic varnish backbone, such as phenolic varnish type epoxy resins; epoxy resins having a cresolic varnish backbone, such as cresolic varnish type epoxy resins; epoxy resins having a norbornene backbone; epoxy resins having a terpene backbone; epoxy resins having a dicyclopentadiene backbone; and epoxy resins having an epoxycyclohexane backbone. These can be used alone or in combination of two or more of them.

[0052] The epoxy resin is more preferably an alicyclic epoxy resin. Alicyclic epoxy resins have advantageous reactivity with cationic catalysts and can produce a higher crosslinking density in cured products than other epoxy resins. Furthermore, the epoxy resin preferably does not contain benzene rings.

[0053] Furthermore, the epoxy equivalent of the epoxy resin is preferably 300 g / eq. or less. The epoxy equivalent is preferably 100-300 g / eq., more preferably 100-230 g / eq., even more preferably 100-200 g / eq., and still more preferably 150-200 g / eq. When the epoxy equivalent is 300 g / eq. or less, the epoxy resin exhibits excellent reactivity with organosilicon compounds, thus resulting in excellent ink durability.

[0054] The epoxy equivalent is defined as (the molecular weight of the epoxy resin / the number of epoxy groups in one molecule of the epoxy resin).

[0055] When epoxy resins having two or more epoxy groups are used as epoxy resins, the cured product undergoes three-dimensional cross-linking, achieving the desired curing properties. Epoxy resins having three or more epoxy groups are more suitable. Furthermore, trifunctional or higher epoxy resins can be used after adding at least one difunctional epoxy resin.

[0056] Examples of commercially available trifunctional or higher epoxy resins include "jER157S70" and "jER1031S" (trade names) manufactured by Mitsubishi Chemical Corporation; "EPICLON N-695" and "EPICLON N-865" (trade names) manufactured by DIC Corporation; "CELLOXIDE 2021", "GT-300 series", "GT-400 series" and "EHPE3150" (trade names) manufactured by Celelum Corporation; "SU8" (trade name) manufactured by Nippon Kayaku Co., Ltd.; "VG3101" (trade name) and "EPOX-MKR1710" (trade name) manufactured by Printec Corporation; and "DENACOL series" manufactured by Nagase ChemteX Corporation.

[0057] Examples of commercially available difunctional epoxy resins include “jER1004”, “jER1007”, “jER1009”, “jER1010” and “jER1256” (trade names) manufactured by Mitsubishi Chemical Corporation, and “EPICLON4050” and “EPICLON 7050” (trade names) manufactured by DIC Corporation.

[0058] The content of the two-terminal epoxy silicone compound in the resin composition containing an epoxy resin capable of forming a silicone-containing film, a photocationic polymerization initiator, and a two-terminal epoxy silicone resin (preferably an alkylsiloxane resin having a structure represented by formula (1)) is, for example, 0.1-10.0 parts by weight, preferably 0.2-5.0 parts by weight, more preferably 0.4-2.0 parts by weight, and even more preferably 0.5-1.5 parts by weight, relative to 100 parts by weight of an epoxy resin different from the two-terminal epoxy silicone resin.

[0059] When the content is within the above range, high liquid repellency can be obtained.

[0060] Coating solvent

[0061] When applying a resin composition as a solution, from the viewpoint of solubility, a polar organic solvent is preferred as the coating solvent. Specific examples include polar solvents such as alcohols, ketones, esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate (PGMEA), ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, and PGME, and glycols such as diethylene glycol. Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, etc., and examples of ketones include methyl ethyl ketone and methyl isobutyl ketone.

[0062] The resin composition preferably contains an organic solvent. The amount of organic solvent may be varied depending on the method of applying the resin composition, such as ease of application. The content of organic solvent in the resin composition is, for example, 100-1500 parts by weight and 600-1200 parts by weight, relative to the amount of resin contained in 100 parts by weight of the resin composition.

[0063] Photocationic polymerization initiator

[0064] The resin composition contains a photocationic polymerization initiator. Therefore, the resin composition can be a photosensitive resin composition. When the resin composition is applied to a substrate and cured, the resin composition is cured by light irradiation in the presence of the photocationic polymerization initiator, thereby forming a silicone-containing film as a liquid-repellent and antifouling film. In this case, compared with the case of heat curing, the liquid repellency or mechanical strength is significantly improved, and fine processing through patterning is also possible.

[0065] As photopolymerization initiators, photocationic polymerization initiators that can cure at low temperatures and have high catalytic activity are suitable. Specifically, ionic acid-producing agents can be selected as photocationic polymerization initiators. For the cationic portion, ononium systems with high absorption can be selected, and ononium ions such as oxonium, ammonium, phosphonium, sulfonium, and iodonium can be selected. Among these, sulfonium, which has high i-line (wavelength 365 nm) absorption and excellent cationic polymerization and crosslinking reaction properties, is more preferred.

[0066] Specific examples of sulfonium cations include triarylsulfonium such as triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tris(1-naphthyl)sulfonium, tris(2-naphthyl)sulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyl Di-p-tolylsulfonium, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, [4-(2-thioxanonethio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonium)phenyl]sulfide, bis[4-{bis(4-(2-hydroxyethoxy)phenyl]sulfonium}phenyl]sulfonium, bis{4-[bis(4-fluorophenyl)sulfonium]phenyl}sulfonium, bis{4-[bis(4-methylphenyl)sulfonium]phenyl}sulfonium, bis{4-[bis(4-methoxyphenyl)sulfonium]phenyl}sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonyl]thioxanthone, 2-[(diphenyl)sulfonyl]thioxanthone, 4-(9-oxo-9H-thioxanth-2-yl)phenylthio-9-oxo-9H-thioxanth-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenylthio [4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl diphenyl sulfonium, 4-[4-(benzoylphenylthio)]phenyl diphenyl sulfonium, 4-[4-(benzoylphenylthio)]phenyl diphenyl sulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaanthrenium, 5-tolylthiaanthrenium, 5-(4-ethoxyphenyl)thiaanthrenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenium; diaryl sulfonium, such as diphenylbenzoylmethyl sulfonium, diphenyl-4-nitrobenzylmethyl sulfonium, diphenylbenzyl sulfonium, and diphenylmethyl sulfonium;Arylsulfonates, such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-(acetylcarbonyloxy)phenylmethylbenzylsulfonium, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylbenzoylmethylsulfonium, 4-hydroxyphenylmethyl Benzoylmethylsulfonium, 4-methoxyphenylmethylbenzoylmethylsulfonium, 4-(acetylcarbonyloxy)phenylmethylbenzoylmethylsulfonium, 2-naphthylmethylbenzoylmethylsulfonium, 2-naphthyloctadecylbenzoylmethylsulfonium, and 9-anthraylmethylbenzoylmethylsulfonium; and trialkylsulfonium such as dimethylbenzoylmethylsulfonium, benzoylmethyltetrahydrothiophenonium, dimethylbenzylsulfonium, benzyltetrahydrothiophenonium, and octadecylmethylbenzoylmethylsulfonium.

[0067] The preferred molar extinction coefficient of the photopolymerization initiator at a wavelength of 365 nm is 400 M. -1 cm -1 That's all. When the molar extinction coefficient is 400M... -1 cm -1 At the above levels, the crosslinking density does not decrease during the curing reaction, and it can develop water repellency and impart photopatterning properties.

[0068] The method for determining the molar extinction coefficient of compounds, such as photopolymerization initiators, is as follows. The target compound is dissolved in a solvent that does not absorb at 365 nm, such as acetonitrile, to form a solution, which is then injected into a quartz cell. The absorbance at 365 nm is measured using a UV-Vis-NIR spectrophotometer (manufactured by JASCO). The molar extinction coefficient can be calculated from the obtained absorbance using the following formula.

[0069] Molar extinction coefficient = absorbance / molar concentration of compound / optical path of cell

[0070] For the anionic portion, borate anions, phosphate anions, antimony anions, and gallate anions with high acid strength can be selected, and at least one from the group consisting of gallate anions and borate anions is preferred. Among these, tetra(pentafluorophenyl)borate ions, trifluorotri(pentafluoroethyl) phosphate ions, hexafluoroantimonate ions, and tetra(pentafluorophenyl)gallate ions, which have excellent cationic polymerization and crosslinking properties, are more preferred. For the same reasons as for cation selection, this allows for the development of water repellency and the imparting of photopatterning properties.

[0071] Examples of suitable photocationic polymerization initiators include “ADEKA ARKLS SP-170,” “ADEKA ARKLS SP-172,” and “ADEKA ARKLS SP-150” (all trade names) manufactured by Adico Corporation, and “BBI-103” and “BBI-102” (both trade names) manufactured by Green Chemicals Co., Ltd. Other examples include “IBPF,” “IBCF,” “TS-01,” and “TS-91” (all trade names) manufactured by Sanwa Chemical Co., Ltd., and “CPI-410S,” “CR-C1,” “CPI-410B,” “CPI-310B,” “CPI-310FG,” “ES-1B,” “VC-1FG,” and “CPI-101A” (all trade names) manufactured by San-Apro Ltd. Furthermore, in order to improve photolithography performance, adhesion performance, etc., the composition may contain alkaline substances such as amines, photosensitizers such as anthracene derivatives, silane coupling agents, etc.

[0072] Depending on the resin used, the content of the photopolymerization initiator can be appropriately varied, and there are no particular limitations. The amount of photopolymerization initiator added is, for example, 0.09-7.0 parts by weight, preferably 1.4-6.0 parts by weight, more preferably 1.9-5.5 parts by weight, and even more preferably 2.5-5.2 parts by weight, relative to the amount of resin (preferably epoxy resin) contained in 100 parts by weight of the photosensitive resin composition.

[0073] substrate

[0074] Silicone-containing films can be used as liquid-repellent and anti-fouling membranes in liquid jet nozzles. The substrate for forming the silicone-containing film is, for example, a surface with a nozzle. The silicone-containing film can be further disposed in a location other than the surface of the liquid jet nozzle with the nozzle. There are no particular limitations on the materials used as the substrate (the surface with the nozzle) and other components of the liquid jet nozzle, and they can be primarily selected from inorganic substrates and resin compositions.

[0075] Examples of inorganic substrates include Si, SiO2, SiOC, SiC, SiCN, Ta, TaO, Al2O3, etc.

[0076] As a resin composition, a negative epoxy resin composition containing a multifunctional epoxy resin as the main agent is used. Specific examples include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, alicyclic epoxy resin, etc.

[0077] The surface with the nozzle is preferably a cured product of a negative epoxy resin composition containing a multifunctional epoxy resin. When the surface with the nozzle is made of the above-mentioned material, adhesion to the silicone-containing film becomes more advantageous, and liquid repellency is more advantageously exhibited. The above-mentioned epoxy resin, which is the epoxy resin in the resin composition, can also be used as the epoxy resin that can be used on the surface with the nozzle.

[0078] Examples of commercially available epoxy resins include "157S70" and "jER1031S" (both trade names) manufactured by Mitsubishi Chemical Corporation, and "EPICLON N-695" and "EPICLON N-865" (both trade names) manufactured by DIC Corporation. Other examples include "CELLOXIDE 2021," "GT-300 series," "GT-400 series," and "EHPE3150" (all trade names) manufactured by Celelum Corporation, "SU8" (trade name) manufactured by Nippon Kayaku Co., Ltd., "VG3101" and "EPOX-MKR1710" (both trade names) manufactured by Printec Corporation, and "DENACOL series" (trade name) manufactured by Nagase ChemteX Corporation.

[0079] The epoxy ring-opening rate of the cured resin composition is preferably 40% or more. The epoxy ring-opening rate is preferably 40%-100%, more preferably 55%-99%, further preferably 60%-99%, and even more preferably 65%-99%. When the epoxy ring-opening rate is within the above range, it is considered that the organosilicon compound is more fully fixed and the liquid repellency becomes more advantageous.

[0080] The ring-opening rate of epoxy resin can be controlled by the type of epoxy resin used and the type and amount of photocationic polymerization initiator.

[0081] As an example of coating a silicone-containing film, the following describes a method for preparing a liquid jet head, such as an inkjet recorder head in which a silicone-containing film is used as a liquid-repellent and anti-fouling film, with reference to the accompanying drawings. The applications of the silicone-containing film according to this disclosure are not limited thereto.

[0082] Preparation method of liquid injection head

[0083] The recording head 1 uses a resin composition as a substrate.

[0084] Figure 1A This is a schematic diagram illustrating an example of a liquid ejector head, such as an inkjet recording head. Figure 1B for Figure 1A A cross-sectional view of the recording head as seen in a cross section perpendicular to substrate 1 passing through A and B.

[0085] Figure 1A and1B The recording head shown has a substrate 1 on which two rows of energy generating elements 2 for generating energy to spray liquid are formed side by side at a predetermined interval. A liquid feed port 3 is opened between the two rows of energy generating elements 2 on the substrate 1. Spray nozzles 5 are formed on the substrate 1, respectively, at positions facing the energy generating elements 2, using spray nozzle forming members 4.

[0086] The nozzle 5 can be a so-called conical shape, wherein the area of ​​the cross-section parallel to the substrate 1 decreases from the substrate 1 side toward the nozzle 5. The nozzle forming component 4 consists of a sidewall 8 forming a flow path 6 communicating from the feed port 3 to each nozzle 5 and a top plate 9 opening the nozzle 5. In the nozzle forming component 4, the sidewall 8 and the top plate 9 can be integrated with each other.

[0087] A liquid-repellent and anti-fouling film (liquid-repellent layer) 7 is provided on the nozzle forming component. For example, the inkjet recorder head has a silicone-containing film (liquid-repellent and anti-fouling film 7) on the surface where the nozzle is provided. The liquid-repellent and anti-fouling film 7 prevents ink ejected from the nozzle 5 from adhering to the surface of the recorder head. There are no particular limitations on the shape, material, etc. of the substrate 1, as long as the substrate 1 can function as a component constituting part of the flow path 6 and as a support for the nozzle forming component 4. In this embodiment, a silicon substrate is used as the substrate 1 because it is easy to process.

[0088] The liquid-repellent and antifouling film 7 contains the same resin as the nozzle-forming component, thereby improving coatability and film flatness. As a result, the liquid repellency is considered further improved. Therefore, it is preferable that the resin composition contains an epoxy resin different from the two-terminated epoxy silicone resin, and that the surface where the nozzle is provided (e.g., the nozzle-forming component) contains a cured epoxy resin. Furthermore, the epoxy resin forming the surface where the nozzle is provided (e.g., the nozzle-forming component) preferably contains an epoxy resin having the same structure as the epoxy resin in the resin composition.

[0089] The epoxy resin in the resin composition and the epoxy resin forming the surface with the nozzle (e.g., the nozzle forming component) are preferably selected from at least one of the following groups: epoxy resin having an alicyclic skeleton, epoxy resin having a bisphenol skeleton, epoxy resin having a phenolic varnish skeleton, epoxy resin having a cresol varnish skeleton, epoxy resin having a norbornene skeleton, epoxy resin having a terpene skeleton, epoxy resin having a dicyclopentadiene skeleton, and epoxy resin having an epoxide cyclohexane skeleton.

[0090] The epoxy resin forming the surface with the nozzle (e.g., the nozzle forming component) and the epoxy resin composition preferably include an alicyclic epoxy resin. Preferably, the resin composition is a negative epoxy resin composition containing a multifunctional epoxy resin and the surface with the nozzle is a cured product of a negative epoxy resin composition containing a multifunctional epoxy resin.

[0091] In this recording head, the surface with the ejection port 5 is configured as the recording surface facing the recording medium. Furthermore, energy generated by the energy generating element 2 is applied to the ink loaded into the flow path 6 via the feed port 3, causing ink droplets to be ejected from the ejection port 5 and adhered to the recording medium for recording. The energy generating element 2 can be an electrothermal conversion element (a so-called heater) or similar element that generates energy through heat, or a piezoelectric element or similar element that generates energy mechanically.

[0092] The liquid-repellent and antifouling film 7 is a cured product of the resin composition. Specifically, as the liquid-repellent and antifouling film 7, a liquid-repellent and antifouling film can be formed as a cured product by applying a solution containing the resin composition and curing the coating of the solution.

[0093] Next, refer to Figure 2A-2H An example of a method for manufacturing an inkjet recording head will be described. In the inkjet recording head, components known in the art can be used as components other than the liquid-repellent and anti-fouling membrane 7.

[0094] This disclosure relates to a method for preparing a liquid jet head having a jet nozzle for jetting liquid and an energy generating element for generating energy for jetting the liquid from the jet nozzle, wherein a silicone-containing film is formed on the surface of the liquid jet head having the jet nozzle, and the surface having the jet nozzle is the surface of a jet nozzle forming member forming a flow path for the liquid communicating with the jet nozzle. The preparation method includes: a step of forming a photosensitive resin layer, the photosensitive resin layer forming the jet nozzle forming member; a step of forming a layer of a resin composition forming the silicone-containing film on the photosensitive resin layer; and a step of exposing and developing the photosensitive resin layer and the layer of the resin composition to form the jet nozzle forming member and the silicone-containing film, wherein the resin composition contains a two-terminated epoxy silicone resin and a photocationic polymerization initiator.

[0095] Regarding the resin composition, as described above.

[0096] Figure 2A-2H This is a cross-sectional schematic diagram illustrating an example of a method for preparing an inkjet recording head according to the steps described above, and the position of the cross-section is relative to... Figure 1B Same as above.

[0097] First, such as Figure 2AAs shown, a substrate 1 is prepared having an energy generating element 2 disposed on its surface. For the energy generating element 2, a control signal input electrode (not shown) for operating the element is connected. Furthermore, various functional layers may be provided, such as a protective layer (not shown) to improve the durability of the energy generating element 2 and an adhesion-improving layer (not shown) to improve the adhesion between the nozzle forming member 4 and the substrate 1.

[0098] Next, as Figure 2B As shown, an ink feed port 3 is formed through the substrate 1. The feed port 3 can be formed by wet etching or dry etching, such as reactive ion etching, using an alkaline etchant such as tetramethylammonium hydroxide (TMAH).

[0099] Next, as Figure 2C As shown, a first photosensitive resin layer 10 containing a photosensitive resin and a photopolymerization initiator is formed on a substrate 1 including an energy generating element 2. The first photosensitive resin layer 10 is a so-called negative photosensitive resin layer. The first photosensitive resin layer 10 is preferably formed by applying the photosensitive resin to a film substrate made of PET or polyimide and transferring the photosensitive resin onto the substrate 1 using a lamination method. Since the photosensitive resin contained in the first photosensitive resin layer 10 must meet various properties such as high mechanical strength, adhesion to the substrate, ink resistance, and resolution of the fine pattern of the patterned nozzle 5, epoxy resin can be appropriately used.

[0100] The same epoxy resin and photopolymerization initiator as described above can be used as the epoxy resin and photopolymerization initiator.

[0101] The amount of photopolymerization initiator added can be set to any amount to obtain the desired sensitivity. The amount of photopolymerization initiator added is preferably in the range of 0.5-5% by mass relative to the epoxy resin. Furthermore, wavelength sensitizers can be added as needed, and examples of wavelength sensitizers include “SP-100” (trade name) manufactured by Adico Corporation and “UVS-1101,” “UVS-1331,” and “UVS-2171” (all trade names) manufactured by Air Water Performance Chemical Inc.

[0102] In addition, additives can be added to the photosensitive resin as needed. For example, to reduce the elastic modulus of the epoxy resin, a flexibility enhancer can be added, or a silane coupling agent can be added to improve adhesion to the substrate.

[0103] Next, as Figure 2DAs shown, pattern exposure is performed via a mask (not shown), followed by heat treatment to form sidewalls 8. The mask is formed by forming a light-shielding film, such as a chromium film, on a substrate made of a material that transmits light with an exposure wavelength, such as glass or quartz, according to the pattern of the flow path 6. As the exposure equipment, a projection exposure device that can use a single-wavelength light source, such as an i-ray stepper or a KrF stepper, or a wide-wavelength light source with a mercury lamp, such as the "MASK ALIGNER MPA-600Super" (trade name) manufactured by Canon Corporation, is possible.

[0104] like Figure 2E As shown, a second photosensitive resin layer 11 is formed on the substrate 1, on which the sidewall 8 has been formed as described above (the step of forming a photosensitive resin layer for forming a nozzle forming member). The second photosensitive resin layer 11 is the same negative photosensitive resin layer as the first photosensitive resin layer 10. As the photosensitive resin contained in the second photosensitive resin layer 11, bisphenol type epoxy resin or phenolic varnish type epoxy resin is preferably used. The second photosensitive resin layer 11 can be formed using the same method as the first photosensitive resin layer 10.

[0105] The second photosensitive resin layer 11 can form a surface with a spray nozzle. That is, the surface with the spray nozzle is the surface (outer surface) of the spray nozzle forming member that forms a liquid flow path communicating with the spray nozzle and the surface (outer surface) of the top plate 9. Therefore, the second photosensitive resin layer 11 is preferably a negative epoxy resin composition containing a multifunctional epoxy resin.

[0106] Next, as Figure 2F As shown, a coating film 12 is formed on the second photosensitive resin layer 11, which is a solution of a photosensitive resin composition for forming a liquid-repellent and antifouling film 7 (the step of forming a layer of a resin composition for forming an organosilicon film on the photosensitive resin layer). The coating film 12 can be formed by applying the resin composition using methods such as spin coating, roll coating, or slot coating.

[0107] Next, the photosensitive resin layer and the resin composition are exposed and developed to form the nozzle forming component and the silicone-containing film.

[0108] like Figure 2GAs shown, pattern exposure is performed via a mask (not shown) and then cured to form a top plate 9 and a liquid-repellent and anti-fouling film 7. The mask is formed by forming a light-shielding film, such as a chromium film, on a substrate made of a material that transmits light with an exposure wavelength, such as glass or quartz, according to the pattern of the nozzle 5. As the exposure equipment, a projection exposure device that can use a single-wavelength light source, such as an i-ray stepper or a KrF stepper, or a wide-wavelength light source with a mercury lamp, such as the "MASK ALIGNER MPA-600Super" (trade name) manufactured by Canon Corporation, is possible.

[0109] Next, as Figure 2H As shown, the unexposed portions of the second photosensitive resin layer 11 and the coating film 12 are removed by a developing process to form the jet nozzle 5. When the second photosensitive resin layer 11 and the coating film 12 are exposed and developed together, the cationic polymeric groups in the second photosensitive resin layer 11 and the coating film 12 react with each other, and a liquid-repellent and antifouling film 7 with high durability and high antistatic properties can be obtained. At this time, the unexposed portions of the first photosensitive resin layer 10 are also dissolved and removed simultaneously, and a flow path 6 is formed.

[0110] Furthermore, the inkjet recorder is completed by performing heat treatment as needed, and by engaging the ink supply components (not shown) and electrically engaging the drive energy generating element 2 (not shown).

[0111] Recording head 2 using a resin composition as a substrate

[0112] Can be adopted Figures 3A-3H The steps shown are used to prepare the inkjet recording head. The inkjet recording head is an example in which the top plate 9 and the sidewall 8 in the nozzle forming member 4 are integrated with each other. Therefore, the surface where the nozzle is provided serves as the surface (outer surface) of the nozzle forming member.

[0113] For passing Figures 3A-3H The method for preparing the inkjet recording head shown in the steps will be described below. First, a positive photosensitive resin, which serves as a mold for the ink flow path 6, is applied onto a substrate 1 on which the energy generating element 2 is provided to form a positive photosensitive resin layer. For example, polymethyl isopropyl ketone (trade name "ODUR-1010", manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied by spin coating and heat-treated thereon at 120°C for six minutes, thereby forming a positive photosensitive resin layer with a thickness of 14 μm.

[0114] Next, the pattern of the ink flow path is exposed to form mold material 13 ( Figure 3AFor example, the pattern of the ink flow path is exposed using an exposure device UX3000 (trade name, manufactured by Ushio Inc.), the exposed portion of the positive photosensitive resin layer is developed using MIBK (methyl isobutyl ketone), and then the exposed portion is rinsed with IPA (isopropyl alcohol), thereby forming mold material 13. Figure 3A As described above, the method for preparing a liquid jet head may include the step of forming a mold for liquid flow paths on a substrate.

[0115] Next, a step is performed to form a photosensitive resin layer for forming the nozzle forming component. A photocationic polymeric resin layer 14 is formed for forming the nozzle forming component, which is used to form the nozzle 5. Figure 3B The photocationic polymerizable resin contained in the photocationic polymerizable resin layer preferably contains an epoxy resin. The same epoxy resin and photopolymerization initiator as described above can be used. The photocationic polymerizable resin layer 14 is, for example, negative.

[0116] For example, as a nozzle forming component for forming a nozzle 5, consisting of a photocationic polymeric resin layer 14, a photocationic polymeric resin having the composition shown in Table 1 is applied by spin coating and heat-treated thereon at 60°C for nine minutes, thereby forming a mold material 13 and a photocationic polymeric resin layer 14 on the substrate 1, wherein the thickness of the mold material 13 on the mold material 13 reaches 25 μm. Figure 3B ).

[0117] As described above, the method for preparing a liquid jet head may include the step of applying a photosensitive resin composition for forming a jet nozzle forming component onto a substrate on which a mold has been formed to form a cationic polymeric resin layer.

[0118] Table 1

[0119]

[0120] Next, a step is performed to form a layer of resin composition for forming a silicone-containing film on the photosensitive resin layer. A silicone-containing film (liquid-repellent layer 7) is formed on the photocationic polymerizable resin layer 14. Figure 3C For example, a liquid-repellent layer 7 is applied to an uncured photocationic polymeric resin layer 14 using a slot coating method, and then heat-treated at 70°C for three minutes to evaporate the diluent and form the liquid-repellent layer 7, wherein the thickness of the photocationic polymeric resin layer 14 reaches 0.5 μm. Figure 3C Regarding the photosensitive resin layer, when the same resin is used for films containing silicone, the coatability is further improved, and the flatness of the film is also improved.

[0121] Next, the photosensitive resin layer and the resin composition are exposed and developed to form the nozzle forming component and the silicone-containing film. The photocationic polymeric resin layer 14 and the liquid-repellent layer 7 are exposed and developed to form the nozzle forming component and the liquid-repellent layer 7. Figure 3D-3G ).

[0122] For example, firstly, a first exposure step is performed. An i-ray stepper (manufactured by Canon Corporation) is used at 4000 J / m². 2 Exposure is performed through the first mask 15 for 16 such that the portion forming the jet nozzle 5 becomes the unexposed portion. Figure 3D ).

[0123] Next, a second exposure step can be performed. If necessary, a second exposure step can be used to form the non-liquid-repellent region 19. For example, using an MA200 compact (trade name, manufactured by SUSS MicroTec KK) and a wavelength below 270 nm at 150 J / m 2 The area corresponding to the non-repellent region 19 (excluding the area corresponding to the nozzle 5) is exposed through the second mask 17. Figure 3E ).

[0124] Next, heat treatment was performed at 95°C for four minutes. Figure 3F Then, the non-repellent areas were developed with a xylene / MIBK (methyl isobutyl ketone) mixture (6 / 4 mass ratio) and rinsed with xylene, thereby forming jet nozzle 5. Figure 3G ).

[0125] Moreover, an ink feed port 3 can be formed. Figure 3H For example, anisotropic etching is performed on substrate 1 using TMAH (tetramethylammonium hydroxide) as an alkaline solution to form feed port 3. Then, substrate 1 is immersed in methyl lactate, thereby dissolving and removing mold material 13 and forming flow path 6. Figure 3H ).

[0126] Then, electrical connections are made for the drive energy generating element 2. Furthermore, ink feed components for supplying ink are connected to fabricate an inkjet recording head. The inkjet recording head is evaluated using the evaluation method described below.

[0127] Recording method

[0128] In the recording method according to embodiments of the present disclosure, an image is recorded on a recording medium by using an inkjet recording head to eject liquid, particularly ink containing pigment.

[0129] In an inkjet recorder head loaded with ink, the side surface of the liquid-repellent and anti-fouling membrane is always in contact with the ink. When using an inkjet recorder head, the liquid-repellent and anti-fouling membrane 7 is liquid-repellent, thus preventing ejection failure even with prolonged use of the inkjet recorder head.

[0130] In the liquid jet head, an inorganic substrate is used as the base material.

[0131] Steps for forming a bonding substrate

[0132] In liquid ejection heads, such as inkjet recording heads, inorganic substrates can be used as the substrate. Figure 5A An example of an inkjet recording head using an inorganic substrate is shown.

[0133] The liquid injection head 28 includes a flow path substrate 22, an actuator substrate 23, and a nozzle substrate 24, and the substrates are bonded together by an adhesive 25. The actuator substrate 23 has a piezoelectric element 2 disposed on its surface. As the piezoelectric element 2, for example, a lead zirconate titanate (PZT) film formed by a sol-gel method or sputtering method can be used. Such a piezoelectric element 2 is made of a sintered body of metal oxide crystals.

[0134] A silicon-containing flow path substrate 22 is provided to cover the piezoelectric element 2 and is bonded to the front surface of the actuator substrate 23 via adhesive 25. Furthermore, a nozzle substrate 24 is bonded to the rear surface of the actuator substrate 23 via adhesive 25. An ink can (not shown) is provided on the flow path substrate 22, and a liquid flow path 26 is formed to pass through the flow path substrate 22. The liquid flow path 26 communicates with the interior of the actuator substrate and is connected to the liquid injection port 5 in the nozzle substrate.

[0135] When a driving voltage is applied to the piezoelectric element 2 from the driving IC (not shown), the piezoelectric element 2 deforms due to the inverse piezoelectric effect. When a pull-push-pull waveform driving voltage is applied, the interior of the cavity expands and contracts to cause a volume change, and when the liquid in the liquid flow path is pressurized, the meniscus expands on the surface of the liquid injection port 5. Then, the liquid pressurized by contraction is ejected from the liquid injection port 5 as a droplet.

[0136] The inkjet printhead has a liquid-repellent and anti-fouling film 27 on its surface where the liquid ejection nozzle 5 is provided. As the liquid-repellent and anti-fouling film 27, a silicone-containing film as described above can be used. However, when the interior of the nozzle of the liquid ejection nozzle 5 repels water, it expands at the meniscus behind the nozzle, and the ejection volume or direction may become unstable. Therefore, it is preferable to form the liquid-repellent and anti-fouling film 27 in the following manner. Figure 5A and 5B In this context, the area surrounding the liquid injection port 5 is defined as region A. Figures 6A-6D In the image, region A is shown in a magnified manner.

[0137] Methods for forming liquid-repellent and antifouling films

[0138] The method for forming a liquid-repellent and antifouling film in a liquid jet nozzle is described.

[0139] The liquid-repellent and antifouling film is formed by performing the following steps on a substrate bonded by an adhesive:

[0140] (1) The liquid-repellent and antifouling film forming step, which forms a liquid-repellent and antifouling film on the surface of the nozzle substrate and inside the nozzle.

[0141] (2) A surface protection step of forming a protective component on a liquid-repellent and anti-fouling film on the surface of the nozzle substrate.

[0142] (3) A plasma treatment step that makes the liquid-repellent and anti-fouling membrane inside the nozzle hydrophilic, and

[0143] (4) Protective component stripping step.

[0144] The following provides a detailed explanation of each step.

[0145] (1) Steps for forming a liquid-repellent and antifouling membrane

[0146] A liquid-repellent and antifouling film is formed on a nozzle substrate with multiple nozzles, which is made of a cured resin composition containing a two-terminal epoxy silicone resin and a photocationic polymerization initiator. Figure 6A This is an enlarged view of the portion in region A where the nozzle 5 has been formed. It is preferable to use the nozzle substrate 24 with the flow path substrate 22 and actuator substrate 23 already bonded together. The surface of the nozzle substrate can be cleaned before the formation of the liquid-repellent and anti-fouling film. For example, plasma treatment, ion beam cleaning, UV ozone cleaning, etc., can be used.

[0147] A liquid-repellent and antifouling film 27 can be formed through the above-mentioned application and curing of the coating.

[0148] like Figure 6A As shown, a liquid-repellent and anti-fouling film 27 is formed on the surface where the nozzle 5 is provided. Here, since the nozzle 5 has already been formed in the nozzle substrate 24, a liquid-repellent and anti-fouling film 29 has also been formed inside the nozzle 5. Therefore, the liquid-repellent and anti-fouling film 27 remains on the surface of the nozzle substrate, and the liquid-repellent and anti-fouling film 29 on the sidewall portion of the nozzle is made hydrophilic.

[0149] (2) Surface protection steps

[0150] Next, as Figure 6B As shown, a protective component 30 is formed where the liquid-repellent and antifouling membrane 27 needs to remain.

[0151] There are no particular limitations on the protective component 30, and resin materials, tapes, etc., can be appropriately selected. When the protective component around the nozzle floats up, the liquid-repellent and anti-fouling film on the surface is made hydrophilic through subsequent plasma treatment. In this case, the spraying does not proceed correctly in the nozzle due to the unstable meniscus. Therefore, it is also possible to attach the protective tape under depressurization to prevent the protective tape from floating up.

[0152] (3) Plasma treatment steps

[0153] Next, as Figure 6C As shown, plasma treatment is performed from the flow path substrate side, thereby making the liquid-repellent and antifouling membrane 29 on the sidewall portion of the jet nozzle hydrophilic and forming a hydrophilic liquid-repellent and antifouling membrane 31.

[0154] As an example of a plasma processing method, a nozzle substrate is placed in a vacuum pressure chamber, and oxygen plasma is generated. For example... Figure 6C As shown, plasma travels from the actuator substrate 23, which forms the flow path, to the ejector port. Depending on the purpose, devices using microwave or remote plasma can be employed. Since the plasma travels through a tortuous flow path, it is preferable to remove the substrate bias and avoid ion-assisted conditions. Therefore, by primarily utilizing the reaction of free radicals, isotropic movement of free radicals is possible. Regarding the processing temperature, the lower limit temperature relates to the processing rate and thus needs to be determined considering the throughput, while the upper limit temperature needs to be determined from the viewpoint of the heat resistance of the protective band.

[0155] (4) Protective component peeling step

[0156] Finally, as Figure 6D As shown, a liquid jet head is fabricated by peeling the protective member 30 from the nozzle substrate. In the liquid jet head thus obtained, the jet volume or jet direction is stabilized because the interior of the nozzle is hydrophilic.

[0157] Example

[0158] The present disclosure will be further described in detail below with reference to the embodiments, but the present disclosure is not limited to the following embodiments.

[0159] Example 1

[0160] Preparation of liquid-repellent and antifouling film on substrate

[0161] according to Figure 4A and 4BThe procedure shown forms a liquid-repellent and anti-fouling film. A photosensitive resin composition, consisting of an organosilicon compound, epoxy resin, initiator, and solvent, was applied to a silicon substrate 21 according to the formulation of Example 1 shown in Table 3 to form a coating 12, and the coating was heat-treated at 70°C for three minutes. Subsequently, an i-ray stepper ("FPA-3000i5+" manufactured by Canon Corporation) was used at 5000 Jm. -2 The coating 12 is then exposed to the air and heat-treated at 90°C for five minutes. After cleaning with PGMEA, the coating is further heat-treated at 200°C for one hour, thereby forming a liquid-repellent and antifouling film 7.

[0162] PGMEA is used as a solvent.

[0163] Preparation of inkjet recording heads

[0164] Furthermore, independently of the liquid-repellent and antifouling membrane... Figure 2A-2H The steps shown in the diagram prepare the inkjet recording head.

[0165] First, such as Figure 2A As shown, a substrate 1 on which the energy generating element 2 is disposed is prepared, and an etching process using TMAH is employed to form... Figure 2B The ink feed port 3 passing through the substrate 1 is shown in the figure.

[0166] Next, as Figure 2C As shown, the cationic polymeric resin composition shown in Table 2 is transferred onto a substrate 1 including the energy generating element 2 by a lamination method to form a first photosensitive resin layer 10. Furthermore, as... Figure 2D As shown, the pattern is exposed through a quartz mask (not shown) and heat-treated at 90°C for five minutes, thereby forming the sidewall 8. An i-ray stepper (FPA-3000i5+ manufactured by Canon Corporation) was used as the exposure equipment, and the exposure dose was set to 10000 Jm. -2 .

[0167] like Figure 2E As shown, a second photosensitive resin layer 11 is formed on a substrate 1 on which sidewalls 8 have been formed as described above. The second photosensitive resin layer 11 is transferred using a lamination method using the cationic polymeric resin composition shown in Table 2.

[0168] Next, as Figure 2FAs shown, the photosensitive resin composition having the formulation of Example 1 shown in Table 4 was applied to the second photosensitive resin layer 11 and heat-treated at 70°C for three minutes. Furthermore, the second photosensitive resin layer 11 and the coating 12 were jointly pattern-exposed via a mask (not shown) with a pattern having nozzles 5, and heat-treated at 90°C for five minutes. As the exposure equipment, an i-ray stepper ("FPA-3000i5+" manufactured by Canon Corporation) was used, and the exposure dose was set to 5000 Jm. -2 ( Figure 2G ).

[0169] Finally, PGMEA is used to dissolve and remove the unexposed portions of the photosensitive resin layer and coating, and the mixture is heat-treated at 200°C for one hour, thereby forming the jet nozzle 5, flow path 6, and liquid-repellent and antifouling film 7. Figure 2H ).

[0170] Table 2

[0171]

[0172] [Table 3]

[0173]

[0174] Examples 2-36

[0175] Except that the resin compositions having the formulations shown in Examples 2-36 in Table 4 were used in the formation of the liquid-repellent and antifouling film 7, the liquid-repellent and antifouling film on the substrate and the inkjet recording head were prepared in the same manner as in Example 1.

[0176] Comparison of Examples 1 and 2

[0177] Except that the resin compositions having the formulations of Comparative Examples 1 and 2 shown in Table 4 were used in the formation of the liquid-repellent and antifouling film 7, the liquid-repellent and antifouling film on the substrate and the inkjet recording head were prepared in the same manner as in Example 1.

[0178] The organosilicon compounds, epoxy resins, and initiators used in each of the examples and comparative examples in Table 4 are described below.

[0179] Examples of alkylsiloxane resins having a structure represented by formula (1) are Examples 1-36 and Comparative Example 2.

[0180] In Examples 1-36 and Comparative Examples 1 and 2, the photopolymerization initiator was cationic.

[0181] Evaluation of liquid-repellent and antifouling membranes

[0182] The liquid-repellent and antifouling films prepared in Examples 1 to 36 and Comparative Examples 1 and 2 were evaluated as follows.

[0183] Liquid repellency

[0184] The liquid-repellent and antifouling membrane was immersed in ink containing pigment and solvent and kept at 70°C for one week. Then, the dynamic receding contact angle θr of the liquid-repellent and antifouling membrane relative to pure water was measured using a micro contact angle meter (DropMeasure, manufactured by MicroJet Inc.) to evaluate the liquid repellency.

[0185] Epoxy ring opening rate

[0186] To evaluate the ring-opening rate of epoxy groups in the water-repellent and antifouling membrane, FT-IR was used to calculate the reduction rate of the peak area of ​​epoxy groups after exposure and thermal curing, based on the peak area of ​​the epoxy groups in the uncured state. The epoxy ring-opening rate was calculated using the following formula.

[0187] Epoxy ring opening rate (%) = [1 - (peak area of ​​epoxy groups after exposure and heat curing) / (peak area of ​​epoxy groups in the uncured state)] × 100

[0188] FT-IR measurement conditions

[0189] Device Name: Cary 620 FT-IR, manufactured by Agilent Technologies.

[0190] Measurement resolution: 8cm -1

[0191] Number of scans: 60

[0192] Wavenumber range for measurement: 4000-900 cm⁻¹ -1

[0193] Evaluation of inkjet recorders

[0194] The inkjet recording heads prepared in Examples 1-36 and Comparative Examples 1 and 2 were evaluated as follows.

[0195] A continuous printing test was conducted using an MB5330 printer manufactured by Canon Corporation at 30°C and 80% RH, and the presence of dot gain was visually confirmed. In the continuous printing test, 100 A4-sized solid fill sheets were printed consecutively. Even if dot gain occurred in one location on an A4-sized sheet, the print quality was determined to be NG (Not Good).

[0196] Table 4

[0197]

[0198]

[0199] In the table, "parts" refers to "parts by mass". These are organosilicon compounds manufactured by Shin-Etsu Chemical Co., Ltd., with product names beginning with X-22. The DOWSIL series is manufactured by Dow Toray Co., Ltd. Epoxy equivalents are measured in g / eq.

[0200] Epoxy silicone is described below.

[0201] The two-terminal alicyclic type is an organosilicon compound with alicyclic epoxy groups at both ends of the organosilicon backbone, and the organosilicon compound does not have epoxy groups in the side chain.

[0202] The terminology refers to organosilicon compounds with epoxy groups (not alicyclic epoxides) at both ends of the organosilicon backbone, and which do not have epoxy groups in their side chains. The terminology also refers to organosilicon compounds with epoxy groups at both ends of the organosilicon backbone and in their side chains.

[0203] An organosilicon compound having an epoxy group at one end of the organosilicon backbone.

[0204] EHPE 3150 is manufactured by Celeron Corporation. 157S70 is manufactured by Mitsubishi Chemical Corporation. N-695 is EPICRON N-695; N865 is EPICRON N-695; HP7200 is EPICRON HP-7200, and they are all manufactured by DIC Corporation. 2021P is CELLOXIDE 2021P manufactured by Celeron Corporation.

[0205] Regarding the initiator, the photopolymerization initiator is as described above in the specification. Benzoyl peroxide, manufactured by Tokyo Chemical Industry Co., Ltd., is used as the BPO.

[0206] As shown in Table 4, in Examples 1-36, the strong bonding resulting from the polymerization reaction between the epoxides exhibits high liquid repellency.

[0207] This is believed to be because the siloxane backbone is fully fixed in the membrane by an epoxy silicone resin with epoxy groups at both ends.

[0208] It was found that epoxy resins with a small epoxy equivalent have excellent reactivity with organosilicon compounds, and therefore exhibit excellent liquid repellency.

[0209] Furthermore, it was found that EHPE3150, as an alicyclic epoxy resin, has excellent compatibility with organosilicon compounds, resulting in high liquid repellency, and that EHPE3150 is suitable as an epoxy resin.

[0210] Furthermore, when initiators with borate anions are used, high liquid repellency is achieved. This is believed to be because even when the anionic moiety is borate, phosphorus, antimony, or gallate anions with high acid strength, the cationic polymerization or crosslinking reaction performance is excellent.

[0211] On the other hand, in Comparative Examples 1 and 2, the liquid repellency was insufficient. It was believed that the organosilicon compounds were not adequately immobilized in the film. In organosilicon compounds containing one epoxy group, the degree of freedom of the siloxane backbone is too high, therefore the structure is considered prone to degradation and exhibits poor liquid repellency. Furthermore, when the resin composition does not contain a photocationic polymerization initiator, polymerization does not occur, therefore the immobilization of the organosilicon compounds is considered insufficient.

[0212] In the evaluation of the use of the inkjet recording head, in Examples 1-36, there was no increase even during continuous printing and high print quality was observed. On the other hand, in Comparative Examples 1 and 2, an increase was observed after continuous printing.

[0213] Although this disclosure has been described with reference to embodiments, it should be understood that this disclosure is not limited to the disclosed embodiments. The scope of the following claims should be interpreted in the broadest possible sense to include all such variations and equivalent structures and functions.

Claims

1. A liquid injection head, comprising: A nozzle, used to spray liquid; and An energy-generating element for generating energy for ejecting the liquid from the nozzle. A film containing organosilicon is formed on the surface of the liquid injection head, which is provided with the injection port. The silicone-containing membrane comprises a cured resin composition comprising a two-terminated epoxy silicone resin and a photocationic polymerization initiator.

2. The liquid injection head according to claim 1, wherein the epoxy silicone resin at both ends is an alkylsiloxane resin having the structure shown in formula (1): In formula (1), R5 and R6 are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms. X3 and X4 are each independently epoxy-containing groups. R8 is a group containing an epoxy group, an alkyl group with 1 to 12 carbon atoms, or an aryl group with 6 to 12 carbon atoms. R7 is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and The permutations of bracketed structures with m and bracketed structures with n can be random permutations or segmented permutations, where m is an integer from 0 to 3, and n + m is an integer from 1 to 60.

3. The liquid injection head according to claim 2, wherein R5 and R6 are each independently an alkyl group having 1 to 4 carbon atoms, R8 is an epoxy group or an alkyl group having 1 to 4 carbon atoms, R7 is an alkyl group having 1 to 4 carbon atoms, and m is 0 or 1.

4. The liquid injection head according to claim 2, wherein the epoxy-containing group is a group having a glycidyl ether group or a group having an epoxy cyclohexyl group.

5. The liquid injection head according to claim 2, wherein the epoxy-containing group is 2-(3,4-epoxycyclohexyl)ethyl.

6. The liquid injection head according to any one of claims 1-5, wherein the cured resin composition has an epoxy ring-opening ratio of 40% or more.

7. The liquid injection head according to any one of claims 1-5, wherein the resin composition contains an epoxy resin different from the two-terminal epoxy silicone resin.

8. The liquid injection head according to claim 7, wherein the surface on which the injection port is provided contains a cured epoxy resin, and the epoxy resin forming the surface on which the injection port is provided contains an epoxy resin having the same structure as the epoxy resin in the resin composition.

9. The liquid injection head according to claim 7, wherein the epoxy resin in the resin composition is at least one selected from the group consisting of epoxy resins having an alicyclic skeleton, epoxy resins having a bisphenol skeleton, epoxy resins having a phenolic varnish skeleton, epoxy resins having a cresol varnish skeleton, epoxy resins having a norbornene skeleton, epoxy resins having a terpene skeleton, epoxy resins having a dicyclopentadiene skeleton, and epoxy resins having an epoxide cyclohexane skeleton.

10. The liquid injection head according to claim 7, wherein the epoxy resin in the resin composition has an epoxy equivalent of less than 300 g / eq.

11. The liquid injection head according to claim 7, wherein the epoxy resin in the resin composition is an alicyclic epoxy resin.

12. The liquid injection head according to claim 7, wherein the content of the two-terminal epoxy silicone resin in the resin composition is 0.2-5.0 parts by weight relative to 100 parts by weight of the epoxy resin.

13. The liquid injection head according to any one of claims 1-5, wherein the surface on which the injection port is provided is a cured product of a negative epoxy resin composition containing a multifunctional epoxy resin.

14. The liquid jet head according to any one of claims 1-5, wherein the photocationic polymerization initiator contains an initiator having borate anions.

15. A method for manufacturing a liquid jet head, the liquid jet head having a jet nozzle for jetting liquid and an energy generating element for generating energy for jetting the liquid from the jet nozzle, wherein a film containing organosilicon is formed on the surface of the liquid jet head having the jet nozzle. The surface of the injection port is the surface of the injection port forming component that forms a flow path for the liquid communicating with the injection port. The preparation method includes: The step of forming a photosensitive resin layer, wherein the photosensitive resin layer forms the nozzle forming component; The step of forming a layer of the resin composition that forms the silicone-containing film on the photosensitive resin layer; and The steps of exposing and developing the photosensitive resin layer and the resin composition to form the nozzle forming component and the silicone-containing film, and The resin composition contains a two-terminated epoxy silicone resin and a photocationic polymerization initiator.

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