Method for manufacturing a liquid dispensing head and liquid dispensing head

Abstract

A liquid ejection head that combines high pattern accuracy and high adhesion, resulting in excellent printing precision. [Solution] A method for manufacturing a liquid discharge head comprising a discharge port forming member on a substrate that forms a liquid discharge port and a liquid flow path communicating with the discharge port, the manufacturing method comprising the steps of: forming a mold for the liquid flow path on the substrate; applying a photosensitive resin composition for forming the discharge port forming member onto the substrate on which the mold is formed to form a cationic polymerizable resin layer; and exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, wherein the photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator having a specific structure and molar extinction coefficient. The technology described herein can contribute to the realization of a sustainable society such as a decarbonized / circular economy.

Description

【Technical Field】 【0001】 The present disclosure relates to a method for manufacturing a liquid ejection head and a liquid ejection head. 【Background Art】 【0002】 A liquid ejection head such as an inkjet recording head applied to an inkjet recording method (liquid injection recording method) usually includes a discharge port, a liquid flow path, and a plurality of energy generating elements that generate energy for discharging the liquid provided in a part of the flow path. In this liquid ejection head, not only the dimensions of the discharge port but also the distance between the energy generating element and the discharge surface (orifice) including the discharge port, etc. also have a great influence on the ink discharge performance. 【0003】 Patent Document 1 discloses a method of forming a discharge port using a photosensitive resin, that is, a method of forming a discharge port by photolithography, as a method of manufacturing a liquid ejection head with high dimensional accuracy and good reproducibility of these members. The photosensitive resin, that is, the discharge port forming member, is required to have high mechanical strength as a structural material, adhesion to a substrate including an energy generating element, ink resistance, and resolution for forming a fine pattern of the discharge port. Patent Document 1 discloses that a cationic polymerization cured product such as an epoxy resin is suitable as a photosensitive resin that satisfies these requirements. Further, in Patent Document 1, as the anion part of the cationic polymerization initiator (acid generator), SbF6 having good polymerization and crosslinking performance capable of expressing high adhesion - is used. 【Prior Art Documents】 【Patent Documents】 【0004】 【Patent Document 1】 Japanese Patent Laid-Open No. 06-286149 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0005】 However, SbF6 - Acid generators containing Sb, such as Sb, are highly toxic and designated as highly toxic substances, with their use restricted. The use of highly toxic substances threatens human health and the Earth's ecosystems, hindering the realization of sustainable societies such as decarbonization and circular economy. Therefore, the use of alternative initiators is required. SbF6 - As one of the alternatives to acid generators containing B(C6H5)6, the anionic part is B(C6H5)6 - There is a cationic polymerization initiator. However, the anionic part is B(C6H5)6 - While cationic polymerization initiators generate strong acids through their decomposition, which is effective in achieving high adhesion of resins, the resulting high amount of hydrogen fluoride (HF) can lead to deterioration of substrates and equipment. The inventors of this invention particularly focus on B(C6H5)6 - It has been found that when initiators containing [specific component] are used with alicyclic epoxy resins or glycidyl-type epoxy resins, film reduction due to resin decomposition reaction may occur during high-temperature curing, making it impossible to obtain the desired patterning dimensions. Furthermore, this film reduction may also reduce the adhesion of the components. This disclosure provides a method for manufacturing a liquid ejection head that combines high pattern accuracy and high adhesion, and a liquid ejection head that has good printing accuracy. [Means for solving the problem] 【0006】 This disclosure relates to a method for manufacturing a liquid discharge head, comprising a discharge port for discharging a liquid and a discharge port forming member on a substrate which forms a flow path for the liquid communicating with the discharge port, The aforementioned manufacturing method A step of forming a mold for the liquid flow path on the substrate, The photosensitive resin composition for forming the discharge port forming member is poured onto the substrate on which the mold is formed. A step of applying the resin to form a cationic polymerizable resin layer, The process includes a step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, The photosensitive resin composition contains at least one epoxy resin selected from the group consisting of an alicyclic epoxy resin and a glycidyl-type epoxy resin, and a photo cationic polymerization initiator (A). The photo cationic polymerization initiator (A) is a salt having an anion represented by the following formula (1). Relates to a method for manufacturing a liquid ejection head, wherein the molar absorption coefficient of the photo cationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. 【0007】 [Chemical formula] 【0008】 [In formula (1), R 1 ~R 4 are each independently an alkyl group having 1 to 18 carbon atoms or Ar, provided that at least one of the R 1 ~R 4 is Ar. Ar is an aryl group having 6 to 14 carbon atoms (the number of carbon atoms of the following substituents is not included). A part of the hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or aryloxy group represented by -OR 6 , an acyl group represented by R 7 CO-, an acyloxy group represented by R 8 COO-, an alkylthio group or arylthio group represented by -SR 9 , an amino group represented by -NR 10 R 11 R 6 ~R 9 are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms. The R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms.] 【0009】 Furthermore, the present disclosure provides a liquid discharge head comprising a discharge port for discharging a liquid and a discharge port forming member on a substrate which forms a flow path for the liquid communicating with the discharge port, The discharge port forming member is a cured product of a photosensitive resin composition, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having the anion represented by formula (1) described above, A liquid dispensing head characterized in that the molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. [Effects of the Invention] 【0010】 According to this disclosure, it is possible to provide a method for manufacturing a liquid ejection head that combines high pattern accuracy and high adhesion, and a liquid ejection head that has good printing accuracy. [Brief explanation of the drawing] 【0011】 [Figure 1] Figure 1 is a perspective view of an example of a liquid dispensing head. [Figure 2] Figures 2A to 2G are cross-sectional views showing a method for manufacturing a liquid dispensing head. [Figure 3] Figure 3 is a schematic diagram of a case where a cationic polymerizable resin layer is formed in a laminated configuration. [Modes for carrying out the invention] 【0012】 In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be any combination. In addition, in this disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of the following: XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. Note that if XX is a group, multiple values ​​may be selected from XX, and the same applies to YY and ZZ. 【0013】 Preferred embodiments of the present disclosure are described below. The method for manufacturing a liquid dispensing head of the present disclosure is not limited to the following embodiments. In the following description, components having the same function may be given the same number in the drawings and their descriptions may be omitted. 【0014】 This disclosure relates to a method for manufacturing a liquid discharge head, comprising a discharge port for discharging a liquid and a discharge port forming member on a substrate which forms a flow path for the liquid communicating with the discharge port, The aforementioned manufacturing method A step of forming a mold for the liquid flow path on the substrate, A step of forming a cationic polymerizable resin layer by applying the photosensitive resin composition for forming the discharge port forming member onto the substrate on which the mold is formed, The process includes a step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having an anion represented by the following formula (1), The present invention relates to a method for manufacturing a liquid dispensing head, wherein the molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. [ka] [In formula (1), R 1 ~R 4 Each of these is independently an alkyl group having 1 to 18 carbon atoms or Ar, however, R 1 ~R 4 At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents listed below), and some of the hydrogen atoms in the aryl group are replaced by alkyl groups having 1 to 18 carbon atoms, alkyl groups having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, cyano groups, -OR groups. 6 An alkoxy group or aryloxy group represented by R 7 The acyl group represented by CO-, R 8 Acyloxy groups represented by COO-, -SR 9 Alkylthio group or arylthio group represented by -NR 10 R 11 The R may be substituted with an amino group or halogen atom represented by . 6 ~R 9 Each of these is independently an alkyl group having 1 to 8 carbon atoms or an alkyl group having 6 to 14 carbon atoms. It is a R group, and the R 10 and R 11 Each of these is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. 【0015】 The following describes each component of the photosensitive resin composition. <Epoxy resin> The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl epoxy resins. This epoxy resin exhibits good reactivity and adhesion, resulting in good mask reproducibility and print evaluation. The epoxy resin may contain both alicyclic epoxy resins and glycidyl epoxy resins. 【0016】 Furthermore, the water-repellent material described later preferably contains a solvent with polar groups, such as alcohol, to provide compatibility with the photosensitive resin composition. Therefore, as the epoxy resin, it is preferable to use one containing an alicyclic epoxy resin and a glycidyl-type epoxy resin, or both, which have a higher affinity for polar groups. 【0017】 Furthermore, from a patterning standpoint, it is preferable that the epoxy resin is solid at room temperature. The epoxy equivalent (g / eq.) of the epoxy resin is, for example, 1000 or less, preferably 900 or less, more preferably 500 or less, and even more preferably 250 or less. By having an epoxy equivalent (g / eq.) of 900 or less, the crosslinking density does not decrease during the curing reaction, and a decrease in the glass transition temperature and adhesion of the cured product can be prevented. The epoxy equivalent (g / eq.) of the epoxy resin is, for example, 100 to 1000, preferably 120 to 900, more preferably 150 to 500, and even more preferably 150 to 250. Note that the epoxy equivalent is a value measured in accordance with JIS K-7236. 【0018】 Specifically, the epoxy resin may include at least one selected from the group consisting of, for example, methylenebis(3,4-epoxycyclohexane), propane-2,2-diylbis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, trimethylolpropane triglycidyl ether, and diglycidyl ether of polyethylene glycol. 【0019】 Specific commercially available epoxy resins include Denacol EX-612 (manufactured by Nagase ChemteX), Denacol EX-614 (manufactured by Nagase ChemteX), Denacol EX-622 (manufactured by Nagase ChemteX), Denacol EX-861 (manufactured by Nagase ChemteX), Denacol EX-252 (manufactured by Nagase ChemteX), EHPE-3150 (manufactured by Daicel Chemicals), and Celoxide 3000 (manufactured by Daicel Chemicals). 【0020】 <Photocation polymerization initiator> The photocationic polymerization initiator can be an ionic acid generator. The photosensitive resin composition contains a photocationic polymerization initiator (A), which is a salt having the anion shown in formula (1). The molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or higher. 【0021】 The photosensitive resin composition of this disclosure contains a specific photocationic polymerization initiator (A) in relation to the specific epoxy resin. The photocationic polymerization initiator (A) is thought to reduce the generation of HF during high-temperature curing of the photosensitive resin composition and suppress film loss due to resin decomposition reactions. As a result, it is thought that a liquid ejection head with good printing accuracy, combining high pattern accuracy and high adhesion can be provided. 【0022】 [ka] 【0023】 In formula (1), R 1 ~R 4 Each of these is independently an alkyl group having 1 to 18 carbon atoms or Ar, however, R 1 ~R 4 At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents listed below), and some of the hydrogen atoms in the aryl group are replaced by alkyl groups having 1 to 18 carbon atoms, alkyl groups having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, cyano groups, -OR groups. 6 An alkoxy group or aryloxy group represented by R 7 The acyl group represented by CO-, R 8 Acyloxy groups represented by COO-, -SR 9 Alkylthio group or arylthio group represented by -NR 10 R 11The R may be substituted with an amino group or halogen atom represented by . 6 ~R 9 Each of these is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the R 10 and R 11 Each of these is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. 【0024】 R 1 ~R 4 However, it is preferable that all of them be Ar. Ar is an aryl group having 6 to 14 carbon atoms (preferably 6 to 10, more preferably 6, excluding the carbon atoms of substituents below), and some of the hydrogen atoms in the aryl group are substituted with an alkyl group having 1 to 8 carbon atoms (preferably 1 to 3, more preferably 1) or a halogen atom. It is preferable that 50 to 100% of the hydrogen atoms in the aryl group are substituted with halogen atoms. The halogen atom is preferably fluorine (F). 【0025】 Specifically, in equation (1), R 1 ~R 4 In this context, aryl groups having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents listed below) include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl), and aromatic heterocyclic hydrocarbon groups (such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, and other monocyclic heterocyclic groups; and indolyl, beryl Examples include cinzofuranil, isobenzofuranil, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanil, isochromanil, coumarinyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranil, and other condensed polycyclic heterocycles. 【0026】 In addition to the above, aryl groups include groups in which some of the hydrogen atoms in the aryl group are replaced by C1-C18 alkyl groups, C1-C8 alkyl groups with halogen atoms, C2-C18 alkenyl groups, C2-C18 alkynyl groups, C6-C14 aryl groups, nitro groups, hydroxyl groups, cyano groups, and -OR groups. 6 An alkoxy group or aryloxy group represented by R 7 The acyl group represented by CO-, R 8 Acyloxy groups represented by COO-, -SR 9 Alkylthio group or arylthio group represented by -NR 10 R 11 It may be substituted with an amino group represented by or a halogen atom. 【0027】 These substituents are substituted with halogen atoms from the viewpoint of catalytic activity in cationic polymerization reactions. C1-C8 alkyl groups, halogen atoms, nitro groups, and cyano groups are preferred, and C1-C8 alkyl groups and fluorine atoms substituted with fluorine atoms are more preferred. In particular, tetrakis(pentafluorophenyl) gallate can be suitably used as the anion. 【0028】 The photocationic polymerization initiator (A) is, for example, a salt having a cation and an anion represented by formula (1). The cation can be an onium-based cation with high absorption. That is, it is preferable that the cation of the photocationic polymerization initiator (A) is onium-based. The onium-based cation is preferably at least one selected from the group consisting of onium ions such as oxonium-based, ammonium-based, phosphonium-based, sulfonium-based, and iodonium-based cations. Among these, the sulfonium-based cation is preferred. Sulfonium ions have excellent cationic polymerization performance and crosslinking reaction performance. 【0029】 Sulfonium-based cations include, for example, triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, and 4-(phenylthio)phenyldiphenylsulf 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)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thioxane] [4-(diphenylsulfonio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chloro) (4-fluorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 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)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthene-2-yl)thiophenyl-9-oxo-9H-thioxanthene-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthurenium, 5-phenylthiaanthurenium, 5-tolylthiaanthurenium Triarylsulfoniums such as 5-(4-ethoxyphenyl)thiaanthurenium, 5-(2,4,6-trimethylphenyl)thiaanthurenium, 2-[(phenyl)sulfinyl]-9,9-dimethylfluorene; diarylsulfoniums such as diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, Nium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium At least one selected from the group consisting of monoarylsulfoniums such as 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium; and trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium. 【0030】 At least one cation selected from the group consisting of 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, 4-hydroxyphenyl-methyl-benzylsulfonium, 4-hydroxyphenyl-methyl-4-nitrobenzylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-acetoxyphenyldimethylsulfonium, diphenyl[4-(phenylthio)phenyl]sulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, triphenylsulfonium, and 2-[(phenyl)sulfinyl]-9,9-dimethylfluorene can be preferably used. 【0031】 Furthermore, the cation moiety is more preferably at least one selected from the group consisting of 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, triphenylsulfonium, and 2-[(phenyl)sulfinyl]-9,9-dimethylfluorene. 【0032】 The molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or higher. A molar extinction coefficient of 0.1 L / mol·cm or higher prevents a decrease in crosslink density during the curing reaction, thus preventing a decrease in the glass transition temperature and adhesion of the cured product. 【0033】 The molar extinction coefficient of the photocationic polymerization initiator (A) is preferably 0.1 to 7.0 L / mol·cm, more preferably 0.3 to 5.0 L / mol·cm. The molar extinction coefficient of the gallate-based photoacid generator can be controlled, for example, by the structure of the cation. 【0034】 The method for measuring the molar extinction coefficient of compounds such as photocationic polymerization initiators (A) is as follows. The target compound is dissolved in a solvent that does not absorb at a wavelength of 365 nm, such as acetonitrile, to form a solution. This solution is then placed in a quartz cell, and the absorbance at a wavelength of 365 nm is measured using an ultraviolet-visible air pressure spectrophotometer (manufactured by JASCO). The molar extinction coefficient can be calculated from the obtained absorbance using the following formula. Molar extinction coefficient = absorbance ÷ molar concentration of compound ÷ optical path of cell 【0035】 Furthermore, the amount of photocationic polymerization initiator added can be any amount that achieves the target sensitivity, and is not particularly limited. Photocationic polymerization initiator in photosensitive resin composition (A The content of is, for example, 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, even more preferably 1 to 5 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of epoxy resin. 【0036】 The photosensitive resin composition may contain a solvent such as xylene. The amount of solvent may be, for example, 10 to 200 parts by mass or 20 to 100 parts by mass per 100 parts by mass of epoxy resin. 【0037】 Furthermore, it is preferable that the photosensitive resin composition contains a solvent that improves the distribution of the photocationic polymerization initiator (A) within the photosensitive resin composition. Ester solvents can be suitably used as solvents that readily dissolve the photocationic polymerization initiator (A). In other words, it is preferable that the photosensitive resin composition contains an ester solvent. 【0038】 Furthermore, in order to prevent material aggregation due to rapid evaporation of the solvent during the heating process when forming the coating film, ester solvents with high boiling points are preferably used. For example, ester solvents with boiling points of 75°C or higher and 100°C or higher are preferably used. The boiling point of the ester solvent is preferably between 75°C and 300°C and between 100°C and 250°C. Specific examples of such ester solvents include, for example, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene carbonate, ethyl acetate, and isobutyl acetate. More preferably, the ester solvent is at least one selected from the group consisting of propylene carbonate and ethyl acetate. 【0039】 Furthermore, two or more solvents can be used. Xylene and ester solvents may be used in combination. From the viewpoint of solubility, the photosensitive resin composition preferably contains, for example, 0.1 to 25 parts by mass, 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass of ester solvent per 100 parts by mass of epoxy resin. If the amount is 0.1 parts by mass or more, the solubility of the photoinitiator is improved, the coated film surface of the photosensitive resin solution becomes more uniform, and fine patterns are more easily formed. If the amount is 10 parts by mass or less, there is no residual solvent after baking, and fine patterns are more easily formed. 【0040】 Furthermore, it is preferable that the photosensitive resin composition contains, in addition to the above-mentioned photocationic polymerization initiator (A), a photocationic polymerization initiator (B) that has a quenching function, unlike the above-mentioned photocationic polymerization initiator (A). This makes it possible to capture the acid generated by leak light during exposure, and further improvement in pattern accuracy can be expected. 【0041】 The photocationic polymerization initiator (B) is preferably an anion with a weaker acid strength than the photocationic polymerization initiator (A). That is, it is preferable that the photosensitive resin composition further contains a photocationic polymerization initiator (B) that is different from the photocationic polymerization initiator (A) and has a lower acid strength than the photocationic polymerization initiator (A). Examples of photocationic polymerization initiator (B) include initiators having the structure of sulfonic acid or hexafluorophosphate. 【0042】 Furthermore, since the quenching effect is determined by the anionic structure, the structure of the cation is not particularly limited. A specific commercially available photoinitiator is TPS-1000 (manufactured by Midori Chemical Co., Ltd.). In addition, the content of the photocationic polymerization initiator (B) in the photosensitive resin composition is preferably 0.01 to 0.5 times the amount of the photocationic polymerization initiator (A) by mass, and more preferably 0.01 to 0.05 times the amount. 【0043】 Furthermore, to accelerate curing after nozzle formation, the photosensitive resin composition preferably also contains a thermal cationic polymerization initiator. While increasing the amount of photocatalytic polymerization initiator is one method for accelerating the curing of the nozzle forming member, this method may not yield the desired pattern accuracy from the viewpoint of photoresolution. This is possible. On the other hand, by using a thermal cationic polymerization initiator in combination with a photocationic polymerization initiator (A), the amount of photocationic polymerization initiator (A) can be reduced, thus achieving both high patternability and curability. 【0044】 As a thermal cationic polymerization initiator, a cationic polymerization initiator with high catalytic function that enables low-temperature curing can be suitably used. The thermal cationic polymerization initiator is preferably an ionic polymerization initiator. The anionic portion is preferably a gallate, phosphorus, antimony, borate, or methidic acid-based onium salt. The thermal cationic polymerization initiator is preferably a salt having a cation and an anion represented by formula (1). 【0045】 In thermal cationic polymerization initiators, the cation is preferably an onium-based cation that is decomposable by heat. More preferably, the cation in the thermal cationic polymerization initiator is an iodonium-based cation that exhibits excellent cationic polymerization performance and crosslinking reaction performance. Specifically, 4-isopropylphenyl(p-tolyl)iodonium is particularly preferred as the cation in the thermal cationic polymerization initiator. 【0046】 Furthermore, in order to suppress the impairment of the catalytic function of each initiator due to salt exchange between the photopolymerization initiator and the thermal polymerization initiator, it is preferable that the anion of the thermal cationic polymerization initiator has the same structure as the anion of the photocationic polymerization initiator (A). 【0047】 Furthermore, the amount of thermal cationic polymerization initiator in the photosensitive resin composition can be any amount added to achieve the desired curability, but in particular, to prevent material elution when in contact with ink, it is preferable that the amount of thermal cationic polymerization initiator in the photosensitive resin composition is less than the amount of photocatalytic polymerization initiator (A). Specifically, the amount of thermal cationic polymerization initiator in the photosensitive resin composition is preferably, for example, 0.00005 to 20 parts by mass, 0.0001 to 10 parts by mass, and more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of epoxy resin. 【0048】 Next, a method for manufacturing a liquid dispensing head using the photosensitive resin composition will be described. <Manufacturing method for liquid dispensing heads> The method for manufacturing a liquid dispensing head is not particularly limited, but the following methods are examples. 【0049】 Figure 1 is a schematic perspective view showing a liquid ejection head, such as an inkjet recording head. The liquid ejection head comprises a substrate 2 having multiple energy generating elements 1 for ejecting liquid such as ink, an ejection port forming member 4 with ejection ports 3 for ejecting liquid, and a liquid flow path 5 that communicates with the ejection ports 3 and holds the liquid. The liquid ejection head may further have grooves 6 formed to reduce internal stress in the ejection port forming member 4. The substrate 2 is also provided with a liquid supply port 7 for supplying liquid such as ink to the flow path 5. 【0050】 Figures 2A to 2G are schematic diagrams showing the manufacturing process when the liquid discharge head shown in Figure 1 is viewed from the A-A' cross-section. 【0051】 A method for manufacturing a liquid discharge head includes a step of forming a mold for a liquid channel on a substrate. First, a positive-type photosensitive resin layer containing a positive-type photosensitive resin, which can become the mold 10 for a liquid channel, is formed on the substrate 2 on which the energy generating element 1 is formed. The positive-type photosensitive resin is not particularly limited. In order to prevent the patternability from decreasing due to photosensitivity during exposure of the cationic polymerizable resin layer 9, which will be described later, the positive-type photosensitive resin is preferably a material with low absorbance to the light used for exposure of the cationic polymerizable resin layer 9. 【0052】 For example, if the light is ultraviolet light such as i-ray light, a positive-type photosensitive resin such as polymethylisopropenyl ketone that can be exposed to DeepUV light can be used. Furthermore, from the viewpoint of further improving pattern accuracy, if the photosensitive resin composition contains a solvent, it is preferable that the mold 10 is insoluble in the solvent contained in the photosensitive resin composition. 【0053】 One method for forming a positive-type photosensitive resin layer is to dissolve a positive-type photosensitive resin in a suitable solvent, apply the solution to a substrate 2 by spin coating, and then perform pre-baking to form the positive-type photosensitive resin layer. The thickness of the positive-type photosensitive resin layer corresponds to the height of the flow channel and is appropriately determined by the discharge design of the liquid discharge head, but is preferably 5 to 22 μm. 【0054】 Next, the positive-type photosensitive resin layer is patterned to form the flow channel mold 10 (Figure 2A). As a method for patterning the positive-type photosensitive resin layer, for example, the positive-type photosensitive resin layer is irradiated with an active energy ray that can expose the positive-type photosensitive resin through a mask to perform pattern exposure. After that, the exposed portion of the positive-type photosensitive resin layer is developed using a solvent that can dissolve it, and the mold 10 can be formed by rinsing. 【0055】 Next, a cationic polymerizable resin layer 9 is formed using a photosensitive resin composition (Figure 2B). For example, a photosensitive resin composition for forming the discharge port forming member is applied to a substrate 2 on which the mold 10 is formed to form a cationic polymerizable resin layer. In the step of forming the cationic polymerizable resin layer 9, for example, the photosensitive resin composition may be applied to form a coating film. After application, heating may be performed as needed. Examples of heating temperatures include 50-90°C and 55-70°C. Examples of heating times include 1-20 minutes and 5-15 minutes. 【0056】 There are no particular restrictions on the coating method, as long as it forms a uniform film. For example, spin coating or slit coating methods can be used. Furthermore, in order to improve accuracy in the nozzle depth direction, as shown in Figure 3, the lower layer 9-1 may be formed using the photosensitive resin composition by spin coating or slit coating, and the upper layer 9-2 may be formed using the same photosensitive resin composition by a dry film manufacturing method to form the cationic polymerizable resin layer 9 in a laminated configuration. 【0057】 Specifically, in the step of forming a cationic polymerizable resin layer by applying a photosensitive resin composition for forming an outlet-forming member onto a substrate on which a mold has been formed, it is preferable to perform the following method. That is, it is preferable to form a dry film of a photosensitive resin composition having the same composition as the applied photosensitive resin composition, and then attach the obtained dry film onto the applied photosensitive resin composition to form a cationic polymerizable resin layer. The thickness of the cationic polymerizable resin layer 9 is appropriately determined by the discharge design of the liquid discharge head, but is preferably 10 to 30 μm. 【0058】 Next, a water-repellent material may be applied to the cationic polymerizable resin layer as needed to provide a water-repellent layer. The water-repellent material is preferably applied after the formation of the cationic polymerizable resin layer and before exposure. For example, it is preferable to provide a water-repellent layer to prevent ink accumulation near the discharge port (not shown). Suitable water-repellent components of the water-repellent material include cationic polymerizable perfluoroalkyl compositions, cationic polymerizable perfluoropolyether compositions, silicone compositions having a dimethylsiloxane structure, and silane compounds having a perfluoroalkyl group. More preferably, the water-repellent component is a silane compound having a perfluoroalkyl group, even more preferably an alkoxysilane compound having a perfluoroalkyl group, and even more preferably an alkoxysilane compound having one perfluoroalkyl group and three alkoxy groups. Generally, these compositions can enhance water repellency by causing water-repellent groups to segregate at the air interface through baking after application. 【0059】 Furthermore, in the exposure and development processes described later, these layers are compatible and can be patterned simultaneously so that no steps are created in the nozzle shape, which consists of a cationic polymerizable resin layer and a water-repellent layer. It is preferable that the water-repellent material contains a solvent that dissolves the photosensitive resin composition, and more preferably a solvent having a polar group. Examples of solvents having a polar group include alcohols such as methanol and ethanol. Monohydric alcohols are preferred, and ethanol is more preferred. The thickness of the water-repellent layer is preferably 0.1 to 3.0 μm, and more preferably 0.2 to 2.0 μm. 【0060】 Next, the process of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member is carried out. First, the exposure process of the cationic polymerizable resin layer 9 is performed (Figure 2C). For exposure, a photomask 12 that matches the desired shape of the discharge port 3 can be used. The exposed portion 13 becomes the discharge port forming member 4, and the unexposed portion 11 becomes the discharge port 3. 【0061】 When using a cationic curing type photosensitive resin composition as described above, it is preferable to perform a heating step after exposure at a wavelength at which the photocuring reaction of the resin composition proceeds. At this time, it is preferable to perform the heating treatment immediately after exposure in order to suppress the diffusion of the catalyst into the unexposed areas due to retention after exposure and to improve patterning accuracy. Furthermore, the heating treatment temperature after exposure should be adjusted to 70°C or higher, so as to allow the reaction to proceed without removing the pattern in the exposed areas during the development process. Examples of temperatures include 70-120°C and 80-110°C. 【0062】 Next, the exposed cationic polymerizable resin layer 9 is developed to form a discharge port forming member having a discharge port 3 (Figure 2D). This allows the discharge port and the flow path to be formed from the same material. In other words, it is preferable that the photosensitive resin composition be a single layer. Therefore, compared to the case where the discharge port and flow path are formed from separate members, there is no concern about peeling at the interface between the members. 【0063】 For developing, a solvent capable of dissolving uncured epoxy resin is preferred. Specifically, ester solvents or ketone solvents such as propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl isobutyl ketone are suitable. 【0064】 Furthermore, heat treatment may be performed to accelerate the curing of the photosensitive resin composition (Figure 2E). For example, if the photosensitive resin composition contains a thermal cationic polymerization initiator, it is preferable to perform heat treatment at a temperature higher than the reaction initiation temperature of the thermal cationic polymerization initiator after development. Specifically, heating is preferably performed at temperatures of 100°C or higher, 130°C or higher, or 140°C or higher. Examples of heating temperatures include 100-170°C, 130-160°C, and 140-150°C. Examples of heating times include 1-10 minutes. 【0065】 Furthermore, it is preferable that the process following the step of exposing and developing the cationic polymerizable resin layer to form the nozzle forming member includes a firing step of 140°C or higher. This heat treatment may be a firing step of 140°C or higher, or the main firing described later may be a firing step of 140°C or higher, or both this heat treatment and the main firing described later may be firing steps of 140°C or higher. Firing at 140°C or higher can accelerate the curing of the photosensitive resin composition, making it easier to suppress peeling of the member. 【0066】 Next, as shown in Figure 2F, a liquid supply port, which is an ink supply port that penetrates the substrate 2, is formed. The method for forming the ink supply port is not particularly limited, but it can be done by anisotropic etching using a resin composition that has etching solution resistance as an etching mask. 【0067】 Next, as shown in Figure 2G, the flow channel 5 is formed by removing the mold 10. Since the mold 10 is a positive-type photosensitive resin layer, it can be removed by exposure and development. Furthermore, it is preferable to carry out the main firing. The main firing is carried out at a temperature higher than the reaction initiation temperature of the thermal cationic polymerization initiator. This is preferable. The heating temperature here can be, for example, 100-250°C, 140-230°C, or 180-220°C. The heating time is preferably 30 minutes or more, and more preferably 30-200 minutes. As mentioned above, the main firing may be a firing process at 140°C or higher. 【0068】 During the final firing, it is preferable that the film stress of the resulting cured product be 20 MPa or less in order to suppress cracks caused by increased film stress. Since the increase in film stress can occur due to thermal shrinkage and curing shrinkage, the heating temperature during the final firing and the amount of unreacted components added are the dominant influencing factors. Therefore, a plasticizer that does not react with light or heat may be added, and the greater the amount of such plasticizer added, the more the increase in film stress can be suppressed, allowing for final firing at higher temperatures. For example, if the amount of such plasticizer added is 10 to 40 parts by mass per 100 parts by mass of epoxy resin, heat treatment at 180 to 200°C can be performed during final firing. Examples of plasticizers include indene resins that do not have epoxy groups and organofluorine compounds. 【0069】 After the formation of the flow path 5, the liquid discharge head is completed by joining components (not shown) for liquid supply and making electrical connections (not shown) to drive the energy generating element 1. 【0070】 In other words, the liquid discharge head of the present disclosure is a liquid discharge head comprising on a substrate an outlet for discharging liquid and an outlet forming member that forms a flow path for the liquid communicating with the outlet, The discharge port forming member is a cured product of a photosensitive resin composition, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having an anion represented by the following formula (1), The molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or higher. 【0071】 By using the liquid ejection head manufacturing method described above, it becomes possible to manufacture a liquid ejection head in which the ink ejection port and ink flow path are formed with high precision. [Examples] 【0072】 The present disclosure will be described in detail below with reference to examples and comparative examples, but the present disclosure is not limited to the configurations embodied in these examples. In addition, the term "part" used in the examples and comparative examples means "parts by mass" unless otherwise specified. 【0073】 <Examples 1-6, 8-22, 24, Comparative Examples 1-3> (Manufacturing of inkjet recording heads) Referring to Figures 2A to 2G, we will explain the fabrication of an example liquid dispensing head. The liquid dispensing heads of Examples 1 to 6, 8 to 22, 24, and Comparative Examples 1 to 3 were fabricated using the materials listed in Tables 1 to 4. First, polymethyl isopropenyl ketone (trade name "ODUR-1010", manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the Si substrate 2 on which the energy generating element 1 was provided, using a spin-coating method, as a positive-type photosensitive resin to serve as the mold 10 for the ink channel. Then, a 14 μm thick positive-type photosensitive resin layer was formed by heat treatment at 120°C for 6 minutes. 【0074】 Next, the ink channel pattern was exposed using an exposure device UX3000 (product name, manufactured by Ushio Inc.), and after developing the exposed areas of the positive-type photosensitive resin layer using MIBK (methyl isobutyl ketone), mold 10 was formed by rinsing with IPA (isopropyl alcohol) (Figure 2A). 【0075】 Next, a photosensitive resin composition was applied to the mold 10 and substrate 2 by spin coating, and a 25 μm thick cationic polymerizable resin layer 9, which would serve as the discharge nozzle, was formed by heat treatment at 60°C for 9 minutes (Figure 2B). In this example and comparative example, the resin layer consisting of the photosensitive resin composition described in Tables 1 to 4 below was used as the cationic polymerizable resin layer 9. Furthermore, a water-repellent material was applied to the surface of the cationic polymerizable resin layer 9 to a thickness of 0.5 μm. The composition of the water-repellent material is as shown in Tables 1 to 4. 【0076】 Next, using a photomask 12, a 4000 J / m² i-line stepper was used to process the surface of the cationic polymerizable resin layer 9 so that the resulting openings on the surface of the resin layer 9 had a diameter of 8.3 μm. 2 Exposure was performed. This patterning was carried out on both the cationic polymerizable resin layer and the water-repellent material in a single process. Subsequently, the material was heat-treated at 90°C for 4 minutes (Figure 2C). 【0077】 Subsequently, the discharge port 3 was formed by developing the film. The developing process involved developing with a mixture of MIBK and xylene, followed by rinsing with xylene (Figure 2D). Furthermore, the film was heat-treated at 140°C for 4 minutes (Figure 2E). 【0078】 Next, an etching mask was formed on the back surface of substrate 2, and anisotropic etching of the silicon substrate was performed to form the ink supply port 7 (Figure 2F). At this time, a protective film (OBC manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied to the photosensitive resin layer to protect the discharge port formation surface from the etching solution. 【0079】 Next, after dissolving and removing the protective film with xylene, a UX-3000 Deep-UV exposure system manufactured by Ushio Inc. was used to expose the material through a negative resist at a rate of 250,000 mJ / cm². 2 The mold 10 was solubilized by full-surface exposure with the specified exposure dose. Then, it was immersed in methyl lactate while applying ultrasound to dissolve and remove the mold 10, forming the channel 5 (Figure 2G). After that, it was fired at 200°C for 60 minutes. 【0080】 Next, the inkjet recording head was completed by performing assembly processes such as joining components for ink supply (not shown), electrical joining for driving the energy generating element 1 (not shown), and sealing for protecting the electrical joining parts (not shown). 【0081】 <Example 7> (Manufacturing of inkjet recording heads) The heat treatment after development (Figure 2E) was performed at 100°C for 4 minutes, and the temperature for the final firing after the dissolution and removal of the mold material 10 was set to 100°C. For the other steps, the inkjet recording head of Example 7 was manufactured using the same method as in Example 1. 【0082】 <Example 23> (Manufacturing of inkjet recording heads) In the process of forming the cationic polymerizable resin layer 9, as shown in Figure 3, the cationic polymerizable resin layer 9 was formed on the mold 10 by spin coating to a thickness that covered the mold 10, and a dry film of the cationic polymerizable resin layer 9 was attached to the cationic polymerizable resin layer 9. For the other steps, the inkjet recording head of Example 23 was manufactured in the same manner as in Example 1. 【0083】 <Examples 1-24, Comparative Examples 1-3> The following evaluations were performed using each of the obtained inkjet recording heads. (Method for evaluating peeling / mask reproducibility) • Peeling A peel test was conducted to evaluate adhesion. An ink was prepared using a weight ratio of pure water / diethylene glycol / isopropyl alcohol lithium acetate / black dye hood black = 79.4 / 15 / 3 / 0.1. The completed inkjet recording head was immersed in this ink at 60°C for 3 months, and the bonding state between the ejection port forming member 4 and the substrate was evaluated. The evaluation criteria are as follows. A: No instances of the discharge port forming member detaching from the substrate were observed across the entire head surface. B: In less than 30% of the entire head surface, the discharge port forming member was observed to have peeled off from the substrate. C: In less than 50% of the entire head surface, the ejection port forming member was observed to have peeled off from the substrate. D: In more than 50% of the entire head surface, the discharge port forming member was observed to have peeled off from the substrate. 【0084】 • Mask reproducibility As an evaluation of pattern accuracy, mask reproducibility was confirmed. The mask reproducibility evaluation sample was prepared using the same method, but by changing the photomask 12 used for nozzle formation to a mask for mask reproducibility evaluation with a line / space pattern line width of 20 μm. The pattern width on the unexposed area of ​​the substrate was observed using a scanning electron microscope (product name: S-4300, manufactured by Hitachi High-Technologies Corporation). The appearance was evaluated according to the following criteria. A: The line width of the line / space pattern is 20 μm, and a linear pattern is obtained. Both the top surface shape and the cross-sectional shape reproduce the exposure photomask. B: The line / space pattern width is 18-19 μm or 21-22 μm, and a linear pattern is obtained. The top surface shape does not quite reproduce the photomask shape. Alternatively, a slight tapering of the pattern is observed in the cross-sectional shape. C: The line width of the line / space pattern is 16-17 μm or 23-24 μm, and a linear pattern is obtained. The top surface shape does not quite reproduce the photomask shape. Alternatively, a slight tapering of the pattern is observed in the cross-sectional shape. D: The line width of the line / space pattern is less than 16 μm or greater than 24 μm, or the pattern has an overhang (awning) shape. Either the top shape or the cross-sectional shape, or both, do not reproduce the exposure photomask. 【0085】 (Evaluation method for inkjet print heads) The evaluation ink was injected into a tank, and the printing characteristics were assessed. The printing was evaluated according to the following criteria. For impact accuracy, the amount of deviation between the actual impact position of the droplet on the recording medium and the impact position of the target was evaluated. A: Impact accuracy of 3μm or less B: Impact accuracy is between 3μm and 5μm C: Impact accuracy is between 5μm and 7μm D: Impact accuracy is over 7μm 【0086】 (Evaluation results) The results are shown in Tables 1-4. All examples showed excellent adhesion and pattern accuracy, and good printing performance was also obtained. Examples 20 and 22, in particular, showed excellent print quality. On the other hand, Comparative Examples 1-3 showed reduced print quality. The technologies described herein are SbF6 -It can serve as a substitute for acid generators containing [specific components]. In other words, the technology described herein can contribute to the realization of a sustainable society, such as a decarbonized / circular economy. 【0087】 [Table 1] [Table 2] [Table 3] [Table 4] 【0088】 The materials listed in the table are as follows: EHPE-3150: Manufactured by Daicel Chemical Industries, Ltd. EX-861: Denacol EX-861, manufactured by Nagase Chemtec Corporation. EX-171: Denacol EX-171, manufactured by Nagase Chemtec Corporation. EX-321L: Denacol EX-321L, manufactured by Nagase Chemtec Corporation. DE-102: Manufactured by ENEOS Corporation DE-103: Manufactured by ENEOS Corporation jER157S70: Manufactured by Mitsubishi Chemical Corporation SI-150: Manufactured by Sanshin Chemical Industry Co., Ltd. 【0089】 Note that a1-5, c1-6, and h1 in the table represent the following structures. a1: Tetrakis(pentafluorophenyl) gallate [ka] 【0090】 a2: Tetrakis(3,5-bis(trifluoromethyl)phenyl) gallate [ka] 【0091】 a4: Toshirato [ka] 【0092】 a5: Tetrakis(pentafluorophenyl) borate [ka] 【0093】 c1:[4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium [ka] c2:4-Hydroxyphenyl-methyl-1-naphthylmethylsulfonium c3:2-[(di-p-trill)sulfonio]thioxanthon c4:2-[(diphenyl)sulfonio]thioxanthone c5: 4-Isopropylphenyl(p-tolyl)iodonium 【0094】 c6: Triphenylsulfonium [ka] 【0095】 c7:2-[(phenyl)sulfinyl]-9,9-dimethylfluorene [ka] 【0096】 h1: Triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane [ka] 【0097】 This disclosure relates to the following methods and configurations. (Method 1) A method for manufacturing a liquid discharge head, comprising a discharge port for discharging liquid and a discharge port forming member on a substrate which forms a flow path for the liquid communicating with the discharge port, The aforementioned manufacturing method A step of forming a mold for the liquid flow path on the substrate, A step of forming a cationic polymerizable resin layer by applying the photosensitive resin composition for forming the discharge port forming member onto the substrate on which the mold is formed, The process includes a step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having an anion represented by the following formula (1), A method for manufacturing a liquid dispensing head, characterized in that the molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. TIFF2026096701000017.tif33170[In formula (1), R 1 ~R 4 Each of these is independently an alkyl group having 1 to 18 carbon atoms or Ar, however, R 1 ~R 4 At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents listed below), and some of the hydrogen atoms in the aryl group are replaced by alkyl groups having 1 to 18 carbon atoms, alkyl groups having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, cyano groups, -OR groups. 6 An alkoxy group or aryloxy group represented by R 7 The acyl group represented by CO-, R 8 Acyloxy groups represented by COO-, -SR 9Alkylthio group or arylthio group represented by -NR 10 R 11 The R may be substituted with an amino group or halogen atom represented by . 6 ~R 9 Each of these is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the R 10 and R 11 Each of these is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. (Method 2) The photocationic polymerization initiator (A) is a salt having a cation and an anion represented by formula (1), A method for manufacturing a liquid dispensing head according to Method 1, wherein the cation of the salt is onium-based. (Method 3) A method for manufacturing a liquid dispensing head according to Method 2, wherein the cation is sulfonium-based. (Method 4) The method for producing a liquid dispensing head according to Method 1, wherein the content of the photocationic polymerization initiator (A) in the photosensitive resin composition is 0.1 to 10 parts by mass per 100 parts by mass of the epoxy resin. (Method 5) In a step following the step of exposing and developing the cationic polymerizable resin layer to form the discharge nozzle forming member, the liquid according to any one of methods 1 to 4 includes a firing step of 140°C or higher. A method for manufacturing a discharge head. (Method 6) A method for manufacturing a liquid dispensing head according to any one of methods 1 to 4, wherein the epoxy resin is solid at room temperature. (Method 7) A method for manufacturing a liquid dispensing head according to any one of methods 1 to 4, wherein the epoxy equivalent of the epoxy resin is 900 or less. (Method 8) A method for manufacturing a liquid dispensing head according to any one of methods 1 to 4, wherein the epoxy equivalent of the epoxy resin is 500 or less. (Method 9) The photosensitive resin composition comprises a solvent, A method for manufacturing a liquid dispensing head according to any one of methods 1 to 4, wherein the mold is insoluble in the solvent contained in the photosensitive resin composition. (Method 10) The method for manufacturing the liquid dispensing head includes the step of forming the cationic polymerizable resin layer and then applying a water-repellent material to the cationic polymerizable resin layer. A method for manufacturing a liquid dispensing head according to any one of methods 1 to 4, wherein the water-repellent material contains a solvent having polar groups. (Method 11) In the step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, A method for manufacturing a liquid dispensing head according to method 10, wherein the cationic polymerizable resin layer and the water-repellent material are patterned together. (Method 12) A method for producing a liquid dispensing head according to any one of methods 1 to 4, wherein the photosensitive resin composition further comprises a thermal cationic polymerization initiator. (Method 13) The method for producing a liquid dispensing head according to method 12, wherein the thermal cationic polymerization initiator is a salt having the anion represented by formula (1). (Method 14) A method for manufacturing a liquid dispensing head according to method 13, wherein the anion of the thermal cationic polymerization initiator has the same structure as the anion of the photocatalytic cationic polymerization initiator (A). (Method 15) A method for producing a liquid dispensing head according to method 13, wherein the cation of the thermal cationic polymerization initiator is iodonium-based. (Method 16) A method for producing a liquid dispensing head according to Method 13, wherein the content of the thermal cationic polymerization initiator in the photosensitive resin composition is less than the content of the photo-cationic polymerization initiator (A). (Method 17) A method for producing a liquid dispensing head according to method 13, characterized in that the content of the thermal cationic polymerization initiator in the photosensitive resin composition is 0.0001 to 10 parts by mass per 100 parts by mass of the epoxy resin. (Method 18) A method for producing a liquid dispensing head according to any one of methods 1 to 4, wherein the photosensitive resin composition further comprises a photocationic polymerization initiator (B) that is different from the photocationic polymerization initiator (A) and has a lower acid strength than the photocationic polymerization initiator (A). (Method 19) The amount of the photocationic polymerization initiator (B) in the photosensitive resin composition is 0.01 to 0.5 times the amount of the photocationic polymerization initiator (A) by mass. A method for manufacturing a liquid dispensing head as described in Article 18 of the Act. (Method 20) A method for producing a liquid dispensing head according to any one of Methods 1 to 4, wherein the photosensitive resin composition contains 0.1 to 10 parts by mass of an ester solvent per 100 parts by mass of the epoxy resin. (Method 21) A method for manufacturing a liquid discharge head according to method 20, wherein the boiling point of the ester solvent is 75°C or higher. (Method 22) In the process of forming the cation polymerizable resin layer, A method for manufacturing a liquid dispensing head according to any one of methods 1 to 4, comprising forming a dry film of a photosensitive resin composition having the same composition as the coated photosensitive resin composition, and attaching the obtained dry film to the coated photosensitive resin composition to form a cationic polymerizable resin layer. (Composition 23) A liquid dispensing head comprising a dispensing port for dispensing liquid and a dispensing port forming member on a substrate that forms a flow path for the liquid communicating with the dispensing port, The discharge port forming member is a cured product of a photosensitive resin composition, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having an anion represented by the following formula (1), A liquid dispensing head characterized in that the molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. TIFF2026096701000018.tif33170[In formula (1), R 1 ~R 4 Each of these is independently an alkyl group having 1 to 18 carbon atoms or Ar, however, R 1 ~R 4 At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents listed below), and some of the hydrogen atoms in the aryl group are replaced by alkyl groups having 1 to 18 carbon atoms, alkyl groups having 1 to 8 carbon atoms substituted with halogen atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, aryl groups having 6 to 14 carbon atoms, nitro groups, hydroxyl groups, cyano groups, -OR groups. 6 An alkoxy group or aryloxy group represented by R 7 The acyl group represented by CO-, R 8 Acyloxy groups represented by COO-, -SR 9 Alkylthio group or arylthio group represented by -NR 10 R 11 The R may be substituted with an amino group or halogen atom represented by . 6 ~R 9 Each of these is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the R 10 and R 11 Each of these is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. (Composition 24) The liquid dispensing head according to configuration 23, wherein the photosensitive resin composition is a single layer. [Explanation of symbols] 【0098】 1. Energy generating element, 2. Substrate, 3. Discharge port, 4. Discharge port forming member, 5. Flow channel, 6. Groove, 7. Supply port, 9. Cationic polymerizable resin layer, 10. Mold, 11. Non-exposed portion, 12. Photomask, 13. Exposed portion

Claims

[Claim 1] A method for manufacturing a liquid discharge head, comprising a discharge port for discharging liquid and a discharge port forming member on a substrate which forms a flow path for the liquid communicating with the discharge port, The aforementioned manufacturing method A step of forming a mold for the liquid flow path on the substrate, A step of forming a cationic polymerizable resin layer by applying the photosensitive resin composition for forming the discharge port forming member onto the substrate on which the mold is formed, The process includes a step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having an anion represented by the following formula (1), A method for manufacturing a liquid dispensing head, characterized in that the molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. [In formula (1), R １ ~R ４ Each of these is independently an alkyl group having 1 to 18 carbon atoms or Ar, however, R １ ~R ４ At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (the number of carbon atoms of the following substituents is not included), and a part of the hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, -OR ６ an alkoxy group or an aryloxy group represented by, R ７ an acyl group represented by CO-, R ８ an acyloxy group represented by COO-, -SR ９ an alkylthio group or an arylthio group represented by, -NR １０ R １１ an amino group represented by, or may be substituted with a halogen atom. The R ６ to R ９ are each independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the R １０ and R １１ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms. ] [Claim 2] The photocationic polymerization initiator (A) is a salt having a cation and an anion represented by formula (1), The method for manufacturing a liquid discharge head according to claim 1, wherein the cation of the salt is onium-based. [Claim 3] The method for manufacturing a liquid dispensing head according to claim 2, wherein the cation is sulfonium-based. [Claim 4] The method for manufacturing a liquid dispensing head according to claim 1, wherein the amount of the photocationic polymerization initiator (A) in the photosensitive resin composition is 0.1 to 10 parts by mass per 100 parts by mass of the epoxy resin. [Claim 5] The process after the step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member. A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, comprising a firing step of 140°C or higher in the process. [Claim 6] A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the epoxy resin is solid at room temperature. [Claim 7] A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the epoxy equivalent g / eq. of the epoxy resin is 900 or less. [Claim 8] A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the epoxy equivalent g / eq. of the epoxy resin is 500 or less. [Claim 9] The photosensitive resin composition comprises a solvent, A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the mold is insoluble in the solvent contained in the photosensitive resin composition. [Claim 10] The method for manufacturing the liquid dispensing head includes the step of forming the cationic polymerizable resin layer and then applying a water-repellent material to the cationic polymerizable resin layer. A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the water-repellent material contains a solvent having polar groups. [Claim 11] In the step of exposing and developing the cationic polymerizable resin layer to form the discharge port forming member, A method for manufacturing a liquid dispensing head according to claim 10, wherein the cationic polymerizable resin layer and the water-repellent material are patterned together. [Claim 12] A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the photosensitive resin composition further comprises a thermal cationic polymerization initiator. [Claim 13] The method for manufacturing a liquid dispensing head according to claim 12, wherein the thermal cationic polymerization initiator is a salt having the anion represented by formula (1). [Claim 14] The method for manufacturing a liquid dispensing head according to claim 13, wherein the anion of the thermal cationic polymerization initiator has the same structure as the anion of the photocatalytic cationic polymerization initiator (A). [Claim 15] The method for manufacturing a liquid discharge head according to claim 13, wherein the cation of the thermal cationic polymerization initiator is iodonium-based. [Claim 16] The method for manufacturing a liquid dispensing head according to claim 13, wherein the content of the thermal cationic polymerization initiator in the photosensitive resin composition is less than the content of the photocatalytic cationic polymerization initiator (A). [Claim 17] The method for manufacturing a liquid dispensing head according to claim 13, characterized in that the amount of the thermal cationic polymerization initiator in the photosensitive resin composition is 0.0001 to 10 parts by mass per 100 parts by mass of the epoxy resin. [Claim 18] A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the photosensitive resin composition further comprises a photocationic polymerization initiator (B) that is different from the photocationic polymerization initiator (A) and has a lower acid strength than the photocationic polymerization initiator (A). [Claim 19] The method for manufacturing a liquid dispensing head according to claim 18, wherein the amount of the photocationic polymerization initiator (B) in the photosensitive resin composition is 0.01 to 0.5 times the amount of the photocationic polymerization initiator (A) by mass. [Claim 20] A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, wherein the photosensitive resin composition contains 0.1 to 10 parts by mass of an ester solvent per 100 parts by mass of the epoxy resin. [Claim 21] The method for manufacturing a liquid discharge head according to claim 20, wherein the boiling point of the ester solvent is 75°C or higher. [Claim 22] In the process of forming the cation polymerizable resin layer, A method for manufacturing a liquid dispensing head according to any one of claims 1 to 4, comprising forming a dry film of a photosensitive resin composition having the same composition as the coated photosensitive resin composition, and attaching the obtained dry film to the coated photosensitive resin composition to form a cationic polymerizable resin layer. [Claim 23] A liquid dispensing head comprising a dispensing port for dispensing liquid and a dispensing port forming member on a substrate that forms a flow path for the liquid communicating with the dispensing port, The discharge port forming member is a cured product of a photosensitive resin composition, The photosensitive resin composition comprises at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and glycidyl-type epoxy resins, and a photocationic polymerization initiator (A). The photocationic polymerization initiator (A) is a salt having an anion represented by the following formula (1), A liquid dispensing head characterized in that the molar extinction coefficient of the photocationic polymerization initiator (A) at a wavelength of 365 nm is 0.1 L / mol·cm or more. [In formula (1), R １ ~R ４ Each of these is independently an alkyl group having 1 to 18 carbon atoms or Ar, however, R １ ~R ４ At least one of them is Ar. The Ar is an aryl group having 6 to 14 carbon atoms (excluding the carbon atoms of the substituents listed below), and some of the hydrogen atoms in the aryl group are an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted with a halogen atom, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, or -OR ６ An alkoxy group or aryloxy group represented by R ７ Acyl group represented by CO-, R ８ Acyloxy group represented by COO-, -SR ９ Alkylthio group or arylthio group represented by -NR １０ R １１ The R may be substituted with an amino group or halogen atom represented by . ６ ~R ９ Each of these is independently an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and the R １０ and R １１ Each of these is independently a hydrogen atom, a C1-C8 alkyl group, or a C6-C14 aryl group. [Claim 24] The liquid dispensing head according to claim 23, wherein the photosensitive resin composition is a single layer.

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