Method for manufacturing a patterned substrate

Abstract

A method for manufacturing a substrate with a pattern, comprising: a step (a) of forming a film formed of a photosensitive polyimide resin composition on a substrate; a step (b) of exposing the film; and a step (c) of developing the exposed film by using a developer, thereby forming a pattern formed of the film on the substrate, wherein a relative energy difference (RED) of the developer to the film before exposure is 0.50 or more and 1.4 or less.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a patterned substrate. Background Technology

[0002] Photosensitive polyimide resin compositions with excellent heat resistance and insulation are used in surface protective films, interlayer insulating films, and wiring protective insulating films of semiconductor components in electronic devices.

[0003] As a related technology for forming patterns using photosensitive polyimide resin compositions, the technologies described in Patent Documents 1 to 5 can be cited as examples.

[0004] Patent documents 1-4 describe developing solutions for photosensitive polyimides in which water is mixed in an organic solvent. Patent document 5 describes a developing solution containing an organic solvent with a ClogP of -1 to 5 as the developing solution for a photosensitive polyimide resin composition.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2008-292799

[0008] Patent Document 2: Japanese Patent Application Publication No. 2002-214801

[0009] Patent Document 3: Japanese Patent Application Publication No. 10-123725

[0010] Patent Document 4: Japanese Patent Application Publication No. 2002-014476

[0011] Patent Document 5: International Publication No. 2018 / 221457 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] In pattern formation using a negative-type photosensitive polyimide resin composition, if an organic solvent with high dissolving power for the unexposed area is used as the developer in order to improve developability, it may sometimes corrode the exposed area, causing cracks to form in the exposed area.

[0014] The present invention was made in view of the above circumstances, and provides a method for manufacturing a patterned substrate that can suppress the generation of residue in the unexposed areas and also suppress the generation of cracks in the exposed areas after development.

[0015] Solution for solving the problem

[0016] The inventors conducted repeated and in-depth research to solve the above-mentioned problems. As a result, they discovered that if a developer solution with a relative energy difference (RED) of the film formed from the photosensitive polyimide resin composition is within a specific range, it is possible to suppress the formation of residue in the unexposed areas and the generation of cracks in the exposed areas after development, thereby improving developability, thus completing the present invention.

[0017] That is, according to the present invention, a method for manufacturing a patterned substrate is provided as shown below.

[0018] [1] A method for manufacturing a patterned substrate, comprising:

[0019] Step (a) of forming a film made of a photosensitive polyimide resin composition on a substrate;

[0020] The process of exposing the above-mentioned film (b); and

[0021] Step (c) involves developing the exposed film using a developing solution to form a pattern formed by the film on the substrate.

[0022] The relative energy difference (RED) between the developer and the film before exposure is 0.50 or more and 1.4 or less.

[0023] [2] The method for manufacturing a patterned substrate according to [1] above, wherein step (c) includes:

[0024] The process (c1) of measuring the Hansen solubility parameters of the above-mentioned film before exposure; and

[0025] The step (c2) of selecting the developer using the obtained Hansen solubility parameters described above, wherein the relative energy difference (RED) between the developer and the above-mentioned film before exposure is 0.50 or more and 1.4 or less.

[0026] [3] The method for manufacturing a patterned substrate according to [1] or [2] above, wherein step (a) includes:

[0027] The process of coating the varnish-like photosensitive polyimide resin composition onto the above-mentioned substrate (a1); and

[0028] Step (a2) to remove organic solvents from the coated photosensitive polyimide resin composition.

[0029] [4] The method for manufacturing a patterned substrate according to any one of [1] to [3] above further includes:

[0030] Step (d) involves heat treating the pattern following step (c).

[0031] [5] In the method for manufacturing a patterned substrate according to [4] above, the thickness of the pattern after heat treatment is 5 μm or more and 85 μm or less.

[0032] [6] The method for manufacturing a patterned substrate according to any one of [1] to [5] above, wherein the polyimide resin included in the photosensitive polyimide resin composition comprises a modified polyimide resin (A) having a repeating structure as shown in the following general formula (1).

[0033]

[0034] [In the above general formula (1), R is a tetravalent group having a cyclic structure, an acyclic structure, or a cyclic and acyclic structure with 4 to 25 carbon atoms. A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 to 39 carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-. n represents the number of repeating units. The end of the above general formula (1) is any of the groups or hydrogen atoms shown in the following general formula (2) or general formula (3), and at least one end is a group shown in the following general formula (2) or general formula (3).]

[0035]

[0036] In the above general formulas (2) and (3), X and X 2 Each is an independent group having 2 to 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds. Y and Y 2 Each can be independently a hydrogen atom or a methyl group.

[0037] [7] The method for manufacturing a patterned substrate according to [6] above, wherein A in the above general formula (1) includes at least one selected from the group consisting of alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0038] [8] The method for manufacturing a patterned substrate according to any one of [1] to [7] above, wherein the polyimide resin contained in the photosensitive polyimide resin composition has a weight-average molecular weight of 5,000 or more and 70,000 or less.

[0039] [9] The method for manufacturing a patterned substrate according to any one of [1] to [8] above, wherein the polyimide resin contained in the photosensitive polyimide resin composition has a light transmittance of 50% or more at a wavelength of 200 to 400 nm.

[0040]

[10] The method for manufacturing a patterned substrate according to any one of [1] to [9] above, wherein the photosensitive polyimide resin composition further comprises at least one selected from the group consisting of a photopolymerization initiator, an organic solvent and a photopolymerizable compound.

[0041]

[11] The method for manufacturing a patterned substrate according to

[10] above, wherein the photopolymerizable compound comprises a multifunctional free radical polymerizable monomer.

[0042]

[12] The method for manufacturing a patterned substrate according to

[10] or

[11] above, wherein the photopolymerizable compound comprises a polyfunctional (meth)acrylate having four or more (meth)acryloyl groups in the molecule.

[0043]

[13] The method for manufacturing a patterned substrate according to any one of [1] to

[12] above, wherein the photosensitive polyimide resin composition further comprises at least one selected from the group consisting of a sensitizer, a leveling agent and an adhesion improver.

[0044] The effects of the invention

[0045] According to the present invention, a patterned substrate can be provided in which residue in the unexposed portion and cracks in the exposed portion are suppressed. Detailed Implementation

[0046] The present invention will be described in detail with respect to a method for carrying out the present invention (hereinafter referred to as "this embodiment"). The following embodiments are illustrative examples of the present invention and do not limit the scope of the present invention. The present invention can be implemented with appropriate modifications within its scope. In this embodiment, preferred provisions can be arbitrarily adopted, and it can be said that a combination of preferred provisions is more preferred. In this embodiment, the description "XX~YY" refers to "XX or more and YY or less".

[0047] In this embodiment, "(meth)acrylate" refers to both "acrylate" and "methacrylate". The same applies to other similar terms ("(meth)acrylic acid", "(meth)acryloyl", etc.).

[0048] The method for manufacturing a patterned substrate described in this embodiment includes the following steps (a), (b), and (c).

[0049] Process (a): The process of forming a film made of a photosensitive polyimide resin composition on a substrate;

[0050] Process (b): The process of exposing the above-mentioned film;

[0051] Step (c): A step of developing the exposed film by using a developing solution to form a pattern formed by the film on the substrate.

[0052] Furthermore, regarding the relative energy difference (RED) between the developer and the film before exposure, from the viewpoint of suppressing cracks in the exposed portion after development, it is 0.50 or more, preferably 0.52 or more, more preferably 0.55 or more, and even more preferably 0.60 or more. Moreover, from the viewpoint of suppressing residue formation in the unexposed portion after development, it is 1.4 or less, preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.

[0053] Here, the relative energy difference (RED) can be calculated using the following equation (1).

[0054] RED=R a / R0 (1)

[0055] In equation (1) above, R a R0 is the distance between the Hansen solubility parameter (hereinafter also referred to as "HSP") of the solute (i.e., the film before exposure in this embodiment) and the HSP of the solvent (i.e., the developer in this embodiment), i.e., the HSP distance, and the interaction radius of the solute.

[0056] R a The HSP distance can be calculated using the following formula (2).

[0057] R a ={4(δdS-δdL)} 2 +(δpS-δpL) 2 +(δhS-δhL) 2} 0.5 (2)

[0058] In the above equation (2), δdS is the energy of the London dispersion force based on the solute, δpS is the energy of the dipole interaction based on the solute, δhS is the energy of the hydrogen bond based on the solute, δdL is the energy of the London dispersion force based on the solvent, δpL is the energy of the dipole interaction based on the solvent, and δhL is the energy of the hydrogen bond based on the solvent.

[0059] R0 (the interaction radius of the solute) is determined using, for example, the Hansen sphere method. First, prepare a solute for which R0 is to be determined and several known solvents with known HSPs, and conduct solubility tests on the target solute relative to each solvent. In these solubility tests, the HSPs of solvents that show solubility and those that do not are plotted in Hansen space. Based on the plotted HSPs of each solvent, an imaginary sphere (Hansen sphere) is constructed in Hansen space containing the HSPs of solvents that show solubility but not those that do not. The radius of this Hansen sphere is called R0.

[0060] HSP (Hansen space) is an index of solubility, indicating the degree to which one substance dissolves in another. HSP is composed of three parameters: the energy based on the London dispersion force (δd), the energy based on dipole interactions (δp), and the energy based on hydrogen bonds (δh). These are vector values ​​expressed as (δd, δp, δh), plotted in three-dimensional space (Hansen space) with the three HSP parameters as coordinate axes. Substances with similar vectors are more likely to dissolve in each other. The units for each parameter are typically expressed in MPa. 1 / 2 This indicates that, regarding HSP, refer to, for example, the Internet.<URL:http: / / hansen-solubility.com / > Regarding the method for determining the HSP of the polymeric material in question, the known method is the Hansen sphere method, which is included in the commercially available software HSPiP (Hansen Solubility Parameters in Practice). In this method, the solubility of the material in question relative to various solvents known for their HSP is confirmed by a dissolution experiment. It should be noted that in this embodiment, version 5.3.02 of the software is used.

[0061] Hereinafter, each step of the method for manufacturing a patterned substrate as described in this embodiment will be explained.

[0062] [Process(a)]

[0063] First, a film made of a photosensitive polyimide resin composition is formed on a substrate.

[0064] Step (a) preferably includes: for example, a step (a1) of coating a varnish-like photosensitive polyimide resin composition (hereinafter also referred to as "polyimide varnish") onto a substrate; and a step (a2) of removing organic solvents from the coated photosensitive polyimide resin composition.

[0065] There are no particular limitations on the method of coating polyimide varnish on the substrate. Examples include inkjet printing, spin coating, casting, micro-gravure printing, gravure coating, bar coating, roller coating, wire rod coating, dip coating, spraying, screen printing, flexographic printing, and die coating.

[0066] When coating a polyimide varnish onto a substrate, it is preferable to adjust the concentration of the solid components of the polyimide varnish described in this embodiment to be in the range of 5 to 50% by mass.

[0067] Organic solvents are removed from the polyimide varnish applied to the substrate by drying it.

[0068] The drying of polyimide varnish is carried out by heating, for example, using a heating plate, hot air, or an oven. The heating temperature is, for example, 80–140°C, preferably 90–120°C. The heating time is, for example, 30–600 seconds, preferably approximately 30–300 seconds.

[0069] The thickness of the film formed from the photosensitive polyimide resin composition is not particularly limited and can be adjusted appropriately according to the desired final pattern. For example, the film thickness can be 5 μm or more and 85 μm or less. It should be noted that the film thickness can be adjusted by changing the content of organic solvents in the polyimide varnish, the coating method / conditions, etc.

[0070] Examples of substrates include glass, silicon wafers, metal foils, and plastic films. Among these, silicon wafers and copper foils are particularly suitable.

[0071] <Photosensitive polyimide resin composition>

[0072] The photosensitive polyimide resin composition described in this embodiment preferably comprises a polyimide resin, and further comprises at least one selected from the group consisting of a photopolymerization initiator, an organic solvent, and a photopolymerizable compound. Additionally, the photosensitive polyimide resin composition described in this embodiment may further comprise, for example, at least one selected from the group consisting of a sensitizer, a leveling agent, and a adhesion improver.

[0073] When the total solid content of the photosensitive polyimide resin composition is set to 100% by mass, the content of polyimide resin in the photosensitive polyimide resin composition of this embodiment is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less.

[0074] In this embodiment, the term "all solid components" in the photosensitive polyimide resin composition refers to the components that remain as solid components when the photosensitive polyimide resin composition is cured, excluding components that evaporate, for example, through heating with organic solvents. On the other hand, even liquid components include those that enter the resin film during heat curing, which are also included in the total solid components.

[0075] (Polyimide resin)

[0076] Examples of polyimide resins described in this embodiment include, for instance, polyimide resins containing structural unit A derived from tetracarboxylic dianhydride and structural unit B derived from diamine compounds.

[0077] As the tetracarboxylic acid contained in the above structural unit A, any tetracarboxylic acid can be used, such as cyclohexanetetracarboxylic acid, cyclohexanetetracarboxylic acid esters, cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid, cyclobutanetetracarboxylic acid esters, cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid, cyclopentanetetracarboxylic acid esters, cyclopentanetetracarboxylic acid dianhydride, dicyclopentanetetracarboxylic acid dianhydride, etc.

[0078] Among these, cyclohexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, and cyclopentanetetracarboxylic dianhydride are more preferred, and cyclohexanetetracarboxylic dianhydride is even more preferred. The various tetracarboxylic acid components mentioned above include positional isomers.

[0079] More preferred specific examples of the aforementioned tetracarboxylic acid components include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, methyl 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic dianhydride, methyl 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, methyl 1,2,3,4-cyclobutanetetracarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid. Pentanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, methyl 1,2,4,5-cyclopentanetetracarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic methyl ester, dicyclohexyltetracarboxylic acid, dicyclohexyltetracarboxylic dianhydride, and dicyclohexyltetracarboxylic methyl ester, etc.

[0080] Among these, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride, and methyl 1,2,4,5-cyclohexanetetracarboxylic acid are particularly preferred because they are advantageous in that they can be easily increased in molecular weight and are easy to obtain flexible films when manufacturing polyimide resins.

[0081] Structural unit B is derived from diamine compounds and can be listed as at least one of the groups consisting of compounds represented by the following formula.

[0082]

[0083]

[0084] More preferably, it includes structural unit B1 derived from at least one of the groups consisting of compounds selected from the following formula.

[0085]

[0086] Structural unit B is further preferably composed of structural unit B2 derived from at least one of the groups consisting of compounds selected from the following formula.

[0087]

[0088] When the above-mentioned structural unit B2 contains a structural unit derived from the compound shown in formula (4), the resulting polyimide resin has better solubility in organic solvents, and is therefore preferred.

[0089]

[0090] In the polyimide resin described in this embodiment, the structural unit B derived from diamine preferably contains the aforementioned structural unit B1 or structural unit B2 at a ratio of 60 mol% or more. If the ratio of structural unit B1 or structural unit B2 in structural unit B is 60 mol% or more, a polyimide resin exhibiting excellent solubility in organic solvents can be obtained.

[0091] The ratio of the above-mentioned structural unit B1 or structural unit B2 in structural unit B is more preferably 70 mol% or more, further preferably 80 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%. Preferably, structural unit B2 is included as structural unit B, and structural unit B2 includes structural units derived from the diamine shown in formula (4) in the above-mentioned ratio.

[0092] The weight-average molecular weight of the polyimide resin is preferably 70,000 or less. A weight-average molecular weight of 70,000 or less provides superior solubility in organic solvents, making it suitable for forming cured films. The weight-average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, further preferably 45,000 or less, and even more preferably 40,000 or less. From the perspective of obtaining a cured film with desired mechanical properties, the weight-average molecular weight of the polyimide resin is preferably 5,000 or more. The weight-average molecular weight of the polyimide resin is more preferably 10,000 or more, further preferably 13,000 or more, and even more preferably 15,000 or more. By placing the weight-average molecular weight of the polyimide resin within the above range, it is possible to obtain a resin composition that has solubility in organic solvents and, for example, a low residual film rate in unexposed areas when forming a photosensitive polyimide resin composition, exhibits excellent developability. Here, the above-mentioned weight-average molecular weight is the weight-average molecular weight converted from polystyrene.

[0093] (Manufacturing method of polyimide resin)

[0094] The polyimide resin described in this embodiment comprises structural unit A derived from tetracarboxylic dianhydride and structural unit B derived from a diamine compound, the tetracarboxylic dianhydride and diamine compound being used as raw materials as described above. The polyimide resin described in this embodiment can be obtained by reacting the aforementioned tetracarboxylic acid with the diamine component. The polyimide resin described in this embodiment has amino groups at its terminals.

[0095] The organic solvent used to react the tetracarboxylic acid component with the diamine component is not particularly limited, but is preferably an organic solvent comprising, for example, at least one selected from the group consisting of cyclic ethers, cyclic ketones, cyclic esters, amides, and ureas. Specific examples of suitable solvents are not particularly limited, but include at least one selected from the group consisting of aprotic polar organic solvents such as γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, cyclopentanone, cyclohexanone, 1,3-dioxane, 1,4-dioxane, tetramethylurea, and tetrahydrofuran. More preferably, it is one or more selected from the group consisting of γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

[0096] When reacting the tetracarboxylic acid component with the diamine component, an imidization catalyst can be used. The imidization catalyst is preferably a tertiary amine compound, and specifically, at least one selected from the group consisting of trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, and isoquinoline can be used.

[0097] The reaction temperature is, for example, in the range of 160–200°C, preferably in the range of 170–190°C, and more preferably in the range of 180–190°C. If the temperature is above the lower limit of the above values, imidization and molecular weight increase will be sufficient. If the temperature is below the upper limit of the above values, the solution viscosity can be appropriately maintained, preventing adverse conditions such as resin scorching on the walls of the reaction vessel. Depending on the situation, azeotropic dehydrating agents such as toluene or xylene can be used. The reaction pressure is usually atmospheric pressure, but the reaction can also be carried out under pressure if necessary. The holding time of the reaction temperature is preferably at least 1 hour, more preferably at least 3 hours. If it is 1 hour or more, imidization and molecular weight increase will be sufficient. Regarding the reaction time, no upper limit is specifically stated, and it is carried out in the range of, for example, 3–10 hours.

[0098] In the manufacture of the polyimide resin described in this embodiment, it is preferable that the reaction occurs within a range of 0.80 ≤ A / B ≤ 0.99 for the tetracarboxylic acid component "A mole" and the diamine component "B mole", and more preferably within a range of 0.85 ≤ A / B ≤ 0.95. By setting A / B ≤ 0.99, the polyimide terminal can be made to have an excess of diamine, resulting in a polyimide resin with amino groups at the terminal, and a polyimide resin with a molecular weight that is sufficiently soluble in organic solvents. If the ratio is 0.80 ≤ A / B, a polyimide resin with a molecular weight exhibiting sufficient flexibility can be obtained.

[0099] The closer the A / B ratio is to 1.0, the higher the molecular weight of the polyimide resin can be obtained. Therefore, by appropriately adjusting the A / B ratio, the polyimide resin with the target molecular weight can be obtained.

[0100] (Modified polyimide resin (A))

[0101] The polyimide resin described in this embodiment preferably comprises a modified polyimide resin having a repeating structure as shown in the following general formula (1).

[0102]

[0103] [In general formula (1), R is a tetravalent group having a cyclic structure, an acyclic structure, or a cyclic and acyclic structure with 4 to 25 carbon atoms, preferably 4 to 10. A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 to 39 carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-. n represents the number of repeating units. The end of general formula (1) is any of the groups or hydrogen atoms shown in general formula (2) or general formula (3) below, and at least one end is a group shown in general formula (2) or general formula (3).]

[0104]

[0105] In general formulas (2) and (3), X and X 2 Each is an independent group having 2 to 15 carbon atoms, and may be selected from at least one group consisting of ester bonds and double bonds. Y and Y 2 Each can be independently a hydrogen atom or a methyl group.

[0106] R in the above general formula (1) preferably has at least a cyclic structure. Examples of such cyclic structures include tetravalent groups formed by removing four hydrogen atoms from cyclohexane, cyclopentane, cyclobutane, dicyclopentane and their stereoisomers.

[0107] Furthermore, R in the above general formula (1) may include structural units derived from any tetracarboxylic acid, as described above for polyimide resins. Preferred examples are as described above, and for example, the following structures can be listed as structural units.

[0108]

[0109] [In the formula, * represents a connector.]

[0110] Of the above, a more preferred option is a tetravalent group formed by removing four hydrogen atoms from cyclohexane.

[0111] In general formula (1), A is a divalent group having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups, and having 2 to 39 carbon atoms. The main chain of A may optionally contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-.

[0112] More specifically, A may include divalent groups formed by removing two hydrogen atoms from compounds such as cyclohexane, dicyclohexylmethane, dimethylcyclohexane, isophorone, norbornene and their alkyl-substituted and halogen-substituted derivatives; benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenyl sulfone, benzophenone and their alkyl-substituted and halogen-substituted derivatives; and organo(poly)siloxanes. A preferably has a cyclic structure, and more preferably has at least one group selected from alicyclic hydrocarbon groups and aromatic hydrocarbon groups. A preferably has an aromatic ring as an aromatic hydrocarbon group. More specifically, divalent groups with 6 to 27 carbon atoms as shown in the following structural formulas may be preferred.

[0113]

[0114] [In the formula, * represents a connector.]

[0115] More specifically, as a divalent group with 2 to 39 carbon atoms as shown in A, at least one group (Ia) selected from the group consisting of the structures shown below can be preferably listed.

[0116]

[0117] [In the formula, * represents a connector.]

[0118] As a group equivalent to A as illustrated, it is more preferable to include at least one group (Ib) selected from the group consisting of the structures shown below.

[0119]

[0120] [In the formula, * represents a connector.]

[0121] As A in general formula (1), it is particularly preferred to have a group shown in formula (Ic).

[0122]

[0123] [In the formula, * represents a connector.]

[0124] From the perspective of solubility in organic solvents, in the modified polyimide resin (A) of this embodiment, the ratio of at least one structural unit selected from (Ia), (Ib) or (Ic) as A in general formula (1) is preferably 60 mol% or more.

[0125] The ratio of at least one structural unit selected from (Ia), (Ib) or (Ic) in A of general formula (1) is more preferably 70 mol% or more, further preferably 80 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%. Preferably, the structural unit is derived from the diamine shown in formula (Ic) at the above ratio.

[0126] The number of repeating units, n, representing the structural unit shown in general formula (1), is preferably 5 to 250, more preferably 10 to 200, and even more preferably 15 to 150. If n is 5 or more, a cured film with the desired mechanical properties can be formed. If n is 250 or less, sufficient solubility in organic solvents can be ensured.

[0127] The modified polyimide resin (A) described in this embodiment has any of the groups or hydrogen atoms represented by the general formula (2) or general formula (3) at its ends, and at least one end is a group represented by the general formula (2) or general formula (3). The modified polyimide resin (A) may have the structure represented by the general formula (2) or general formula (3) at one end, or it may have the structure represented by the general formula (2) or general formula (3) at both ends.

[0128] X or X in general formula (2) or general formula (3) 2 The shown group is a group with 2 to 15 carbon atoms and may have at least one group selected from the group consisting of ester bonds and double bonds. Y or Y 2 The groups shown are hydrogen atoms or methyl groups.

[0129] More specifically, the structure shown in general formula (2) or general formula (3) above is equivalent to the structure obtained by reacting the terminal amine of a polyimide resin with a compound containing a functional group. Examples of such compounds containing a functional group include compounds having an isocyanate group or an epoxy group and having a (meth)acryloyl group. Examples of such compounds include ethyl 2-isocyanate methacrylate, ethyl 2-isocyanate acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, etc. The structure shown in general formula (2) or general formula (3) can have the structure obtained by reacting the compound with an amine terminal.

[0130] The weight-average molecular weight of the modified polyimide resin (A) is preferably 70,000 or less. If the weight-average molecular weight is 70,000 or less, it exhibits superior solubility in organic solvents, thus making it suitable for forming a cured film. The weight-average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, further preferably 45,000 or less, and even more preferably 40,000 or less. From the perspective of obtaining a cured film with desired mechanical properties, the weight-average molecular weight of the modified polyimide resin (A) is preferably 5,000 or more. The weight-average molecular weight of the modified polyimide resin (A) is more preferably 10,000 or more, further preferably 13,000 or more, and even more preferably 15,000 or more. By keeping the weight-average molecular weight of the modified polyimide resin (A) within the above range, a resin composition with low residual film rate in the unexposed portion and excellent developability can be obtained. Here, the above-mentioned weight-average molecular weight is the weight-average molecular weight converted from polystyrene.

[0131] Modified polyimide resin (A) can be obtained by reacting the diamine component, as detailed below, with the tetracarboxylic acid component.

[0132] Examples of diamine components include diamines, diisocyanates, and diaminodisilanes, with diamines being preferred. The diamine content in the diamine component used as a raw material is preferably 50 mol% or more, and can be 100 mol%.

[0133] The aforementioned diamine can be either an aliphatic diamine or an aromatic diamine, or a mixture thereof. In this embodiment, "aromatic diamine" refers to a diamine in which the amino group is directly bonded to an aromatic ring, and a portion of its structure may include an aliphatic group, an alicyclic group, or other substituents. "Aliphatic diamine" refers to a diamine in which the amino group is directly bonded to an aliphatic group or an alicyclic group, and a portion of its structure may include an aromatic group or other substituents.

[0134] Generally, if aliphatic diamines are used as raw materials for polyimide resins, the polyamic acid, as an intermediate product, forms a strong complex with the aliphatic diamine, making it difficult to obtain high molecular weight polyimides. Therefore, efforts must be made to use organic solvents with high solubility for the complex, such as cresol. If cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, or their derivatives are used as the tetracarboxylic acid component, a weaker complex is formed between the polyamic acid and the aliphatic diamine, thus making it easier to increase the molecular weight of the polyimide. As for the diamine, if a diamine with fluorine substituents is selected as the raw material, the resulting polyimide resin has excellent transparency and is therefore preferred.

[0135] Any aliphatic diamine can be used as the aforementioned aliphatic diamine. Examples of aliphatic diamines include 4,4'-diaminodicyclohexylmethane, ethylenediamine, hexamethylenediamine, polyethylene glycol bis(3-aminopropyl) ether, polypropylene glycol bis(3-aminopropyl) ether, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, m-phenylenediamine, p-phenylenediamine, isophorone diamine, norbornene diamine, and siloxane diamines.

[0136] Examples of the aforementioned aromatic diamines include, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, p-phenylenediamine, diaminobenzophenone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-oxybis[3-(trifluoromethyl)aniline], and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine.

[0137] The aforementioned diamine preferably contains at least 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-oxybis[3-(trifluoromethyl)aniline], or 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine. By including at least any of these as a diamine component, the photosensitive resin composition containing the resulting modified polyimide resin (A) exhibits high transmittance at a specific wavelength and high solubility in organic solvents. Therefore, the exposed portion has excellent curability and the unexposed portion has low residual film rate, resulting in excellent developability. As long as any of the above-mentioned components are included as a diamine component, excellent effects can be maintained even when used in combination with other diamines. The modified polyimide resin (A) described in this embodiment preferably contains at least one unit composed of 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine or 4,4'-oxybis[3-(trifluoromethyl)aniline].

[0138] Any tetracarboxylic acid component can be used. Examples of tetracarboxylic acid components include cyclohexanetetracarboxylic acid, cyclohexanetetracarboxylic acid esters, cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid, cyclobutanetetracarboxylic acid esters, cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid, cyclopentanetetracarboxylic acid esters, cyclopentanetetracarboxylic acid dianhydride, and dicyclopentanetetracarboxylic acid dianhydride. More preferably, cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, and cyclopentanetetracarboxylic acid dianhydride are also included. Among these, cyclohexanetetracarboxylic acid dianhydride is even more preferred. The various tetracarboxylic acid components described above include positional isomers.

[0139] More preferred specific examples of the aforementioned tetracarboxylic acid components include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, methyl 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic dianhydride, methyl 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, methyl 1,2,3,4-cyclobutanetetracarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid. Pentanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, methyl 1,2,4,5-cyclopentanetetracarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic methyl ester, dicyclohexyltetracarboxylic acid, dicyclohexyltetracarboxylic dianhydride, and dicyclohexyltetracarboxylic methyl ester, etc.

[0140] Among these, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride, and methyl 1,2,4,5-cyclohexanetetracarboxylic acid are particularly preferred because they are advantageous in that they can be easily increased in molecular weight and are easy to obtain flexible films when manufacturing polyimide resins.

[0141] The tetracarboxylic acid component may include other tetracarboxylic acids or their derivatives without impairing the final cured film's properties, such as flexibility and heat-pressurization. Examples of such other tetracarboxylic acids or their derivatives include, for example, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(3,4 ... At least one of the following: sulfone, bis(3,4-dicarboxyphenyl) ether, bis(2,3-dicarboxyphenyl) ether, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 4,4-(p-phenylenedioxy)bisphthalic acid, 4,4-(m-phenylenedioxy)bisphthalic acid, ethylenetetracarboxylic acid, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, and their derivatives.

[0142] (Method for manufacturing modified polyimide resin (A))

[0143] The modified polyimide resin (A) described in this embodiment can be obtained through the following steps (1) and (2).

[0144] Process (1): The tetracarboxylic acid component reacts with the diamine component to obtain a polyimide resin with amino groups at the ends.

[0145] Step (2): The polyimide resin with an amino group at the end obtained in step (1) above reacts with the above-mentioned compound containing a functional group (a compound having an isocyanate group or an epoxy group and a (meth)acryloyl group).

[0146] In step (1), the above tetracarboxylic acid is reacted with the diamine component to obtain a polyimide resin with an amino group at the end.

[0147] The above process (1) is the same as the above method for manufacturing polyimide resin. The raw materials, preferred materials, and reaction conditions are also the same.

[0148] Step (2) is a step of modifying the ends of the polyimide resin obtained in step (1) above. Specifically, as described above, the polyimide is reacted with the above-mentioned compound containing a functional group (a compound having an isocyanate group or an epoxy group and having a (meth)acryloyl group) to obtain a modified polyimide resin (A) having a (meth)acryloyl group at the end.

[0149] Compounds containing functional groups that modify the ends of polyimide resins are compounds having isocyanate or epoxy groups and (meth)acryloyl groups. Specifically, examples include ethyl 2-isocyanate methacrylate, ethyl 2-isocyanate acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, and allyl glycidyl ether. These functional group-containing compounds can be used alone or in combination of two or more. Preferably, the functional group-containing compound is used in a ratio of 0.1 to 30 molar times relative to the polyimide resin having an amino group at the end.

[0150] The reaction temperature in step (2) is preferably in the range of 30 to 100°C, and the reaction time is preferably 1 to 10 hours.

[0151] When the amino terminus of a polyimide resin reacts with the isocyanate group or epoxy group of a compound containing a functional group, the reaction can occur directly or, if necessary, in the presence of a catalyst. Examples of catalysts include amine compounds such as triethylamine and organophosphorus compounds such as triphenylphosphine; these can be used alone or in combination of two or more. To suppress side reactions during the reaction, polymerization inhibitors can be used. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone; these can be used alone or in combination of two or more.

[0152] The transmittance of the polyimide resin with a wavelength of 200-400 nm described in this embodiment is preferably 50% or more, more preferably 55% or more, further preferably 60% or more, and even more preferably 70% or more.

[0153] The modified polyimide resin (A) described in this embodiment has high transmittance at the aforementioned wavelength and excellent solubility in organic solvents. Therefore, the photopolymerization initiator that can be included in this composition will function effectively, thus enabling efficient acquisition of a cured film. Furthermore, by using the modified polyimide resin (A), when a cured film is formed from the composition, the residual film rate of the unexposed areas is low, exhibiting excellent developability, and the generation of cracks, etc., can be effectively suppressed.

[0154] (Organic solvents)

[0155] From a solubility perspective, aprotic polar solvents are ideal as organic solvents. Specifically, examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamine, N-acetyl-ε-caprolactam, dimethylimidazolium ketone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and γ-butyrolactone. These organic solvents can be used alone or in combination of two or more. To further improve coatability, solvents such as toluene, xylene, diethyl ketone, methoxybenzene, and cyclopentanone can be mixed within a range that does not adversely affect the solubility of the polymer.

[0156] By using a suitable organic solvent, the photosensitive polyimide resin composition described in this embodiment can be used in a solution (varnish) state, which is convenient for film formation.

[0157] (Photopolymerizable compounds)

[0158] As photopolymerizable compounds, polyfunctional radical polymerizable monomers, such as (meth)acrylic acid monomers with more than two functionalities, can be used.

[0159] Examples of (meth)acrylic acid monomers include tricyclodecanediethanol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, bis(trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol (meth)acrylate, monopentaerythritol (meth)acrylate and dipentaerythritol (meth)acrylate, polypentaerythritol (meth)acrylate, polyglycerol-based (meth)acrylates, and dendritic polymer (meth)acrylates. These photopolymerizable compounds can be used alone or in combination of two or more.

[0160] Here, polyglycerol-based (meth)acrylates refer to compounds having a polyglycerol backbone and (meth)acryloyl groups. Examples of polyglycerol-based (meth)acrylates include SA-TE6 and SA-TE60 manufactured by Sakamoto Pharmaceutical Chemicals Co., Ltd.

[0161] As ethoxylated trimethylolpropane tri(meth)acrylate, for example, ethoxylated (3)trimethylolpropane triacrylate, ethoxylated (6)trimethylolpropane triacrylate, ethoxylated (15)trimethylolpropane triacrylate manufactured by Arkema can be used.

[0162] In addition, dendritic polymeric (meth)acrylates refer to multifunctional (meth)acrylates with a dendritic polymeric structure (including hyperbranched structures). Examples of dendritic polymeric (meth)acrylates include Viscoat 1000, Viscoat 1020, and STAR-501 manufactured by Osaka Organic Chemicals Co., Ltd. Viscoat 1000 and Viscoat 1020 use dendritic polymeric polyester acrylates with acrylate groups at the ends as their main components. Furthermore, the molecular weight of Viscoat 1000 is approximately 1000–2000, and the molecular weight of Viscoat 1020 is approximately 1000–3000. STAR-501 uses a dipentaerythritol hexaacrylate-linked multibranched polyacrylate containing a core derived from dipentaerythritol and acrylate groups at the ends as its main component. The molecular weight of STAR-501 is approximately 16000–24000.

[0163] Among these, from the viewpoint of suppressing the generation of cracks in the exposed portion after development, polyfunctional (meth)acrylates having 4 or more (meth)acryloyl groups in the molecule are preferred as photopolymerizable compounds, and polyfunctional (meth)acrylates having 4 or more and 10 or fewer (meth)acryloyl groups in the molecule are more preferred.

[0164] Depending on the structure of the mixed photopolymerizable compounds, the softness and other properties of the photosensitive polyimide resin composition can be controlled. These photopolymerizable compounds are preferably mixed in a ratio of 5 to 500 parts by weight relative to 100 parts by weight of the polyimide resin contained in the photosensitive polyimide resin composition.

[0165] (Photopolymerization initiator)

[0166] There are no particular limitations on the photopolymerization initiator; any known photopolymerization initiator can be used. Examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one, Examples of photopolymerization initiators include 2-methyl-1-(4-methylthienyl)-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. These photopolymerization initiators can be used alone or in combination of two or more.

[0167] The photopolymerization initiator is preferably mixed in a ratio of 0.1 to 10 parts by weight relative to 100 parts by weight of polyimide resin contained in the photosensitive polyimide resin composition.

[0168] (Sensitizer)

[0169] The sensitizer is not particularly limited, and known sensitizers can be used. Examples include sensitizers containing an amino group, and compounds having both an amino and a phenyl group within the same molecule are preferred examples. More specifically, examples include benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; benzophenone-based compounds such as 2-(p-dimethylaminophenyl)benzo[4,5]benzo[5]benzo[6,7 ... Compounds containing p-dialkylaminophenyl groups, such as 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine, are used. These sensitizers can be used alone or in combination of two or more.

[0170] The sensitizer is preferably mixed in a ratio of 0.001 to 10 parts by weight relative to 100 parts by weight of polyimide resin contained in the photosensitive polyimide resin composition.

[0171] (Leveling agent)

[0172] There are no particular limitations on leveling agents; any known leveling agent can be used, such as silicone-based surface modifiers, acrylic-based surface modifiers, fluorinated surface modifiers, nonionic surface modifiers, cationic surface modifiers, anionic surface modifiers, and various other surface modifiers. They can be used individually or in combination of two or more.

[0173] The leveling agent is preferably mixed in a ratio of 0.001 to 20 parts by weight relative to 100 parts by weight of polyimide resin contained in the photosensitive polyimide resin composition.

[0174] (Adhesion improver)

[0175] There are no particular limitations on the adhesion modifier. Known adhesion modifiers can be used, such as silane coupling agents containing amino groups, silane coupling agents containing epoxy groups, silane coupling agents containing mercapto groups, silane coupling agents containing (meth)acryloyl groups, and other known coupling agents; titanate coupling agents, aluminate coupling agents, and other known coupling agents. Examples of coupling agents include KP-390, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, and KBE-9007 (all trade names; manufactured by Shin-Etsu Chemical Co., Ltd.). They can be used individually or in combination of two or more.

[0176] The adhesion improver is preferably mixed in a ratio of 0.0005 to 20 parts by weight relative to 100 parts by weight of polyimide resin contained in the photosensitive polyimide resin composition.

[0177] (Method for manufacturing photosensitive polyimide resin composition)

[0178] The photosensitive polyimide resin composition described in this embodiment is not particularly limited and can be prepared as follows.

[0179] A photosensitive polyimide composition can be obtained by mixing at least one selected from the group consisting of an organic solvent, a photopolymerization initiator, and a photopolymerizable compound into a polyimide resin. If necessary, at least one selected from the group consisting of a sensitizer, a leveling agent, and a adhesion improver can be further mixed in as described above.

[0180] (Polyimide varnish)

[0181] The polyimide varnish described in this embodiment may comprise a polyimide resin and an organic solvent, and further comprise at least one selected from the group consisting of photopolymerization initiators and photopolymerizable compounds. Furthermore, as needed, at least one selected from the group consisting of sensitizers, leveling agents, and adhesion improvers may be further mixed in as described above. Specific examples of each component are as described above.

[0182] The polyimide varnish described in this embodiment can be a polyimide solution obtained by dissolving a polyimide resin obtained by polymerization in a reaction solvent, or it can be a varnish obtained by further diluting the polyimide solution with an organic solvent.

[0183] The polyimide resin with amino groups at the ends and the modified polyimide resin (A) described in this embodiment have excellent solvent solubility, thus enabling the production of high-concentration varnishes that are stable at room temperature.

[0184] The polyimide varnish described in this embodiment preferably contains 5 to 40% by weight of the polyimide resin as detailed above, and more preferably 10 to 30% by weight.

[0185] The viscosity of the polyimide varnish is preferably 1–200 Pa·s, more preferably 1–100 Pa·s. The viscosity of the polyimide varnish is a value measured using an E-type viscometer at 25°C.

[0186] There are no particular limitations on the manufacturing method of polyimide varnish; well-known methods can be used.

[0187] [Process (b)]

[0188] Next, the film obtained in step (a) is exposed.

[0189] Exposure of the film can be performed by irradiating the film formed on a substrate by a photosensitive polyimide resin composition with light (usually ultraviolet light) through a light mask with a prescribed pattern, for example.

[0190] The exposed film has a portion that is blocked by a photomask and a portion that is exposed to light; in other words, it has an exposed portion and an unexposed portion.

[0191] Regarding the exposed portion of the aforementioned film, the polyimide resin in the photosensitive polyimide resin composition undergoes cross-linking to form a cross-linked polyimide film, and a pattern is formed through the following development process (step (c)). On the other hand, regarding the unexposed portion, the polyimide resin does not undergo cross-linking, and therefore, an uncross-linked polyimide film is formed that is dissolved and removed by development.

[0192] The preferred cumulative ultraviolet radiation dose is 100–8,000 mJ / cm². 2 More preferably, 200–6,000 mJ / cm² 2 .

[0193] [Process (c)]

[0194] Next, the exposed film is developed using a developing solution to form a pattern formed by the film on the substrate.

[0195] For example, after irradiating a film formed on a substrate by a photosensitive polyimide resin composition with light, the unexposed areas can be dissolved and removed using a developing solution, thereby obtaining the desired embossed pattern.

[0196] Step (c) preferably includes: a step (c1) of measuring the Hansen solubility parameter of the film before exposure, and a step (c2) of selecting a developer using the obtained Hansen solubility parameter, wherein the relative energy difference (RED) between the developer and the film before exposure is 0.50 or more and 1.4 or less.

[0197] Regarding RED, from the viewpoint of suppressing cracks in the exposed portion after development, it is 0.50 or more, preferably 0.52 or more, more preferably 0.55 or more, and even more preferably 0.60 or more. Furthermore, from the viewpoint of suppressing residue formation in the unexposed portion after development, it is 1.4 or less, preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less.

[0198] In the method for manufacturing a patterned substrate described in this embodiment, an organic solvent is preferably used as the developing solution. The developing solution is not particularly limited as long as it dissolves the photosensitive polyimide resin composition described in this embodiment and the relative energy difference (RED) between it and the film before exposure is within the aforementioned range. Specifically, suitable examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamine, N-acetyl-ε-caprolactam, dimethylimidazolium ketone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, acetone, methyl ethyl ketone, cyclopentanone, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl acetate, tetrahydrofuran, acetonitrile, methyl isobutyl ketone, butyl acetate, 1,4-dioxane, etc. These developers can be used alone or in combination of two or more.

[0199] Next, the embossed pattern formed by development is cleaned using a rinsing solution to remove the developing solvent. Suitable rinsing solutions include methanol, ethanol, isopropanol, and water, which are well miscible with the developing solution.

[0200] [Process (d)]

[0201] In the method for manufacturing a patterned substrate described in this embodiment, after step (c), a step (d) for heat treatment of the pattern may be further included.

[0202] Thus, a cured film (pattern) formed by curing the photosensitive polyimide resin composition of this embodiment can be obtained.

[0203] For example, the embossed pattern obtained by the above treatment is heated at a temperature selected from 80 to 400°C to remove the organic solvent, thereby obtaining a cured film (pattern) formed by curing the photosensitive polyimide resin composition of this embodiment.

[0204] According to this embodiment, a resin composition with excellent developability, i.e., the exposed portion is fully cured and the unexposed portion can be fully removed due to the high solubility of the modified polyimide resin contained in the photosensitive polyimide resin composition in organic solvents, is used. Therefore, the resulting embossed pattern can be obtained at high resolution.

[0205] In the method for manufacturing a patterned substrate according to this embodiment, the thickness of the pattern after heat treatment, i.e., the thickness of the cured film formed by curing the photosensitive polyimide resin composition of this embodiment, is preferably 5 μm or more and 85 μm or less.

[0206] If the film thickness is within the above range, it can be used as an excellent insulating film. The thicker the film (i.e., the greater the amount of photosensitive polyimide resin composition coated on the substrate), the more problems arise, especially with the solubility of the polyimide resin in organic solvents. However, according to this embodiment, by using a modified polyimide resin (A), even in this case, excellent solubility in organic solvents and excellent transparency can be achieved.

[0207] Therefore, the cured film of this embodiment can be suitably used, for example, in applications where high voltage is to be applied to an insulating film. The cured film obtained from the photosensitive polyimide resin composition of this embodiment, which includes modified polyimide resin (A), can effectively suppress the generation of cracks and the like, and has excellent physical properties.

[0208] [use]

[0209] The patterned substrate described in this embodiment can be used for various applications. It is suitable for applications such as surface protective films for semiconductor elements in electronic devices, interlayer insulating films, wiring protective insulating films for circuit boards, and especially for applications involving high density and high integration. In this case, the pattern of the patterned substrate forms the surface protective film, interlayer insulating film, and wiring protective insulating film for semiconductor elements in electronic devices.

[0210] Example

[0211] The present invention will now be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples at all.

[0212] (Synthesis example 1)

[0213] Under nitrogen atmosphere, 196.1581 g (0.583 mol) of 4,4'-oxybis[3-(trifluoromethyl)aniline] (hereinafter referred to as 6FODA), 124.1578 g (0.554 mol) of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (hereinafter referred to as HPMDA), and 391.50 g of γ-butyrolactone (hereinafter referred to as GBL) were added to a 1L five-necked flask equipped with a nitrogen inlet tube, a stirrer, a thermometer, and a cooler. The mixture was stirred and heated to 90°C. 2.802 g (0.028 mol) of triethylamine (hereinafter referred to as TEA) was added, and the mixture was allowed to react at 190°C for 5 hours. The mixture was then diluted with 308.10 g of GBL to obtain 999 g of polyimide varnish with a solid content of 30% by mass (23.7 g of distilled water and distilled TEA combined). According to the results determined by GPC, the weight-average molecular weight (Mw) of the polyimide obtained in this synthesis example is 33,876.

[0214] 100.01 g of GBL and 6.0264 g of ethyl 2-isocyanate acrylate (manufactured by Showa Denko Co., Ltd., Karenz AOI) were added to 200.03 g of the polyimide varnish, and the mixture was reacted at 50°C for 5 hours. Subsequently, the reaction solution was added dropwise to water to precipitate the polyimide, and the mixture was dried overnight at 70°C to obtain the modified polyimide resin (A1).

[0215] The evaluation methods used in this embodiment and the comparative example are as follows.

[0216] (1) Weight-average molecular weight (Mw)

[0217] Mw was determined using GPC analysis. The apparatus and analysis conditions used in the analysis are shown below.

[0218] Device: HLC-8420GPC (manufactured by Tosoh Corporation)

[0219] Pillar: TSKgel SuperAWM-H×2 (manufactured by Tosoh Corporation)

[0220] Eluent: Contains dimethylformamide (30 mM lithium bromide and 100 mM phosphoric acid).

[0221] Standard polystyrene: PStQuick Kit-H (manufactured by Tosoh Corporation)

[0222] Flow rate: 0.6 ml / min

[0223] Column temperature: 40℃

[0224] Detector: RI (Refractive Index Detector)

[0225] (2) Calculation of Hansen solubility parameter (HSP) of photosensitive polyimide resin composition 1

[0226] 2.8586 g of the modified polyimide resin (A1) obtained in Synthesis Example 1 was dissolved in 3.5269 g of GBL. 1.4596 g of Viscoat 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd., TriPEA) as a photopolymerizable compound, 0.0431 g of 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, Omnirad 184) and 0.1005 g of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF, Omnirad 819) as photopolymerization initiators, 0.2876 g of LE-304 (manufactured by Kyoeisha Chemical Co., Ltd.) diluted 100 times with GBL as a leveling agent, and 0.1496 g of KP-390 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) diluted 100 times with GBL as an adhesion improver were added. The mixture was stirred until fully dissolved to obtain a photosensitive polyimide resin composition (polyimide varnish). Using a glass rod and spacers with a film thickness of 300 μm, the polyimide varnish was cast onto a PET film using a casting method, and then dried at 100°C for 60 minutes to obtain a film of the photosensitive polyimide resin composition.

[0227] The film was cut into appropriate sizes and tested in solvents known to the HSP (HSP is registered in the HSP database), namely acetone, N,N-dimethylacetamide (DMAc), methyl ethyl ketone (MEK), diacetone alcohol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dichloromethane, cyclopentanone, ε-caprolactone, ethyl lactate (EL), and propylene glycol monomethyl ether acetate (PPD). One film was completely impregnated with each of the following solvents: PGMEA, propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl acetate, tetrahydrofuran, acetonitrile, GBL, methyl isobutyl ketone (MIBK), dimethyl sulfoxide, butyl acetate, butyl benzoate, benzyl alcohol, 2-phenoxyethanol, 1-butanol, 1,1,2,2-tetrachloroethane, dipropylene glycol, cyclohexanol, chloroform, ethanol, toluene, methanol, hexane, cyclohexane, water, 1,4-dioxane, and diethylene glycol. The films were then left to stand at room temperature for 4 days. Subsequently, the soluble and insoluble properties of the films in various solvents were visually determined. The HSP (δd: dispersion term, δp: polar term, δh: hydrogen bonding term) and R0 (interaction radius) were calculated using the aforementioned Hansen sphere method. δd: 15.54 MPa. 1 / 2 δp: 11.73 MPa 1 / 2 δh: 8.20MPa 1 / 2 R0 = 9.7 MPa 1 / 2 It should be noted that the proportion of good solvent falling into the Hansen sphere, i.e., the Fit value, is 0.882.

[0228] (2) Calculation of Hansen solubility parameter (HSP) of photosensitive polyimide resin composition 2

[0229] 2.3883 g of the modified polyimide resin (A1) obtained in Synthesis Example 1 was dissolved in 2.9267 g of GBL. 1.2033 g of diPE-penta / hexa-A (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) as a photopolymerizable compound, 0.0346 g of 1-hydroxycyclohexylphenyl ketone (manufactured by BASF, Omnirad 184) and 0.0820 g of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF, Omnirad 819) as photopolymerization initiators, 0.2550 g of LE-304 (manufactured by Kyoeisha Chemical Co., Ltd.) diluted 100 times with GBL as a leveling agent, and 0.1211 g of KP-390 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) diluted 100 times with GBL as an adhesion improver were added. The mixture was stirred until fully dissolved to obtain a photosensitive polyimide resin composition (polyimide varnish). Using a glass rod and spacers with a film thickness of 300 μm, the polyimide varnish was cast onto a PET film using a casting method, and then dried at 100°C for 60 minutes to obtain a film of the photosensitive polyimide resin composition.

[0230] The film was cut into appropriate sizes and tested in solvents known to the HSP (HSP is registered in the HSP database), namely acetone, N,N-dimethylacetamide (DMAc), methyl ethyl ketone (MEK), diacetone alcohol, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dichloromethane, cyclopentanone, ε-caprolactone, ethyl lactate (EL), and propylene glycol monomethyl ether acetate (PPD). One film was completely impregnated with each of the following solvents: PGMEA, propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl acetate, tetrahydrofuran, acetonitrile, GBL, methyl isobutyl ketone (MIBK), dimethyl sulfoxide, butyl acetate, butyl benzoate, benzyl alcohol, 2-phenoxyethanol, 1-butanol, 1,1,2,2-tetrachloroethane, dipropylene glycol, cyclohexanol, chloroform, ethanol, toluene, methanol, hexane, cyclohexane, water, 1,4-dioxane, and diethylene glycol. The films were then left to stand at room temperature for 4 days. Subsequently, the soluble and insoluble properties of the films in various solvents were visually determined. The HSP (δd: dispersion term, δp: polar term, δh: hydrogen bonding term) and R0 (interaction radius) were calculated using the aforementioned Hansen sphere method. δd: 15.54 MPa. 1 / 2 δp: 11.73 MPa 1 / 2 δh: 8.20MPa 1 / 2 R0 = 9.7 MPa 1 / 2It should be noted that the proportion of good solvent falling into the Hansen sphere, i.e., the Fit value, is 0.879.

[0231] (Example 1)

[0232] Polyimide varnish was prepared according to the same mixing ratio as shown in Table 1, the same as in calculation 1 of the aforementioned HSP. Using a spin coater (MS-B150) manufactured by MIKASA, the polyimide varnish was applied to a silicon wafer with a dried polyimide film thickness of 25–30 μm, and dried on a hot plate at 100°C for 5 minutes. After cooling to room temperature, a mask aligner (MA-10) manufactured by MIKASA was used, with a high-pressure mercury lamp as the light source, and an exposure dose of 5,000 mJ / cm at an exposure wavelength of 365 nm. 2 Under these conditions, the photomask, with a 30μm / 50μm L / S (line and space) pattern, is exposed from above and left to stand at room temperature for 15 minutes. Next, immersion development is performed for 90 seconds using ethyl lactate (EL) as the developer, followed by rinsing with methanol and removal of residual solvent under air circulation, thereby forming a 30μm / 50μm resin pattern on the silicon wafer.

[0233] Next, a digital microscope was used to observe / evaluate the developability of the pattern and the presence of cracks in the exposed areas.

[0234] [Table 1]

[0235] Table 1

[0236]

[0237] (Example 2)

[0238] Propylene glycol monomethyl ether acetate (PGMEA) was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0239] (Example 3)

[0240] Propylene glycol monomethyl ether (PGME) was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0241] (Example 4)

[0242] Cyclohexanone was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0243] (Example 5)

[0244] Acetonitrile was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0245] (Example 6)

[0246] Methyl isobutyl ketone (MIBK) was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0247] (Example 7)

[0248] As the developer, a mixed solvent of 1,4-dioxane:ε-caprolactone = 53:47 (volume ratio) was used. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0249] (Example 8)

[0250] As the developer, a mixed solvent of ε-caprolactone:toluene:benzyl alcohol = 35:35:30 (volume ratio) was used. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0251] (Example 9)

[0252] Butyl acetate was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0253] (Example 10)

[0254] 1,4-Dioxane was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0255] (Comparative Example 1)

[0256] Acetone was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0257] (Comparative Example 2)

[0258] N,N-dimethylacetamide (DMAc) was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0259] (Comparative Example 3)

[0260] Methyl ethyl ketone (MEK) was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0261] (Comparative Example 4)

[0262] Cyclohexane was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0263] The results obtained in Examples 1-10 and Comparative Examples 1-4 are shown in Table 2.

[0264] [Table 2]

[0265] Table 2

[0266]

[0267] ○: No residue from unexposed areas

[0268] ×: Residue exists in the unexposed area.

[0269] (Example 11)

[0270] Following the same mixing ratio as shown in Table 3 for calculation 2 of the aforementioned HSP, a polyimide varnish was prepared. Using a MIKASA spin coater (MS-B150), the polyimide varnish was applied to a silicon wafer with a dried polyimide film thickness of 25–30 μm, and dried on a heated plate at 100°C for 5 minutes. After cooling to room temperature, a MIKASA mask aligner (MA-10) was used, with a high-pressure mercury lamp as the light source, and an exposure dose of 5,000 mJ / cm at an exposure wavelength of 365 nm. 2 Under these conditions, the image was exposed from above a photomask with a 30μm / 50μm L / S (line and space) pattern and left to stand at room temperature for 15 minutes. Next, it was immersed and developed for 90 seconds using N-methyl-2-pyrrolidone (NMP) as the developer, rinsed with methanol, and residual solvent was removed under air circulation, thereby forming a 30μm / 50μm resin pattern on the silicon wafer.

[0271] Next, a digital microscope was used to observe / evaluate the developability of the pattern and the presence of cracks in the exposed areas.

[0272] [Table 3]

[0273] Table 3

[0274]

[0275] (Example 12)

[0276] Cyclopentanone was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0277] (Example 13)

[0278] EL was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0279] (Example 14)

[0280] PGMEA was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0281] (Example 15)

[0282] Cyclohexanone was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0283] (Example 16)

[0284] As the developer, a mixed solvent of 1,4-dioxane:ε-caprolactone = 53:47 (volume ratio) was used. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0285] (Example 17)

[0286] As the developer, a mixed solvent of ε-caprolactone:toluene:benzyl alcohol = 35:35:30 (volume ratio) was used. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0287] (Example 18)

[0288] Butyl acetate was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0289] (Example 19)

[0290] 1,4-Dioxane was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0291] (Comparative Example 5)

[0292] Acetone was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0293] (Comparative Example 6)

[0294] DMAc was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0295] (Comparative Example 7)

[0296] Cyclohexane was used as the developer. Otherwise, the polyimide varnish was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11.

[0297] The results obtained in Examples 11-19 and Comparative Examples 5-7 are shown in Table 4.

[0298] [Table 4]

[0299] Table 4

[0300]

[0301] ○: No residue from unexposed areas

[0302] ×: Residue exists in the unexposed area.

Claims

1. A method for manufacturing a patterned substrate, comprising: a step (a) of forming a film formed of a photosensitive polyimide resin composition on a substrate; a step (b) of exposing the film; and a step (c) of forming a pattern formed of the film on the substrate by developing the exposed film using a developing solution, the developing solution having a relative energy difference (RED) with the film before exposure of 0.50 or greater and 1.4 or less; wherein the developing solution is an organic solvent; and the polyimide resin contained in the photosensitive polyimide resin composition includes a modified polyimide resin (A) having a repeating structure represented by the following general formula (1), in the general formula (1), R is a tetravalent group having a cyclic structure, an acyclic structure, or a cyclic structure and an acyclic structure, having 4 to 25 carbon atoms; A is a divalent group having at least one group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an organosiloxane group, and having 2 to 39 carbon atoms, and at least one group selected from the group consisting of -0-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S- is optionally interposed in the main chain of A; n represents the number of repeating units; and the terminal of the general formula (1) is any of a group represented by the following general formula (2) or general formula (3) or a hydrogen atom, at least one terminal being a group represented by the following general formula (2) or the following general formula (3), the step (c) includes: In the general formula (2) and (3), X and X 2 each independently is a group having 2 to 15 carbon atoms, optionally having at least one group selected from the group consisting of an ester bond and a double bond; Y and Y 2 each independently is a hydrogen atom or a methyl group.

2. The method of manufacturing a patterned substrate according to claim 1, wherein, a step (cl) of measuring the Hansen solubility parameter of the film before exposure; and a step (c2) of selecting a developing solution using the obtained Hansen solubility parameter, the developing solution having a relative energy difference (RED) with the film before exposure of 0.50 or greater and 1.4 or less. the step (a) includes:

3. The method of manufacturing a patterned substrate according to claim 1 or 2, wherein, a step (al) of applying a varnish-like photosensitive polyimide resin composition on the substrate; and a step (a2) of removing an organic solvent from the applied photosensitive polyimide resin composition. a step (d) of heat-treating the pattern after the step (c).

4. The method of manufacturing a patterned substrate according to claim 1 or 2, further comprising: the thickness of the pattern after heat-treatment is 5 μm or greater and 85 μm or less.

5. The method of manufacturing a patterned substrate according to claim 4, wherein, A in the general formula (1) includes at least one group selected from the group consisting of an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

6. The method of manufacturing a patterned substrate according to claim 1 or 2, wherein, the weight average molecular weight of the polyimide resin contained in the photosensitive polyimide resin composition is 5,000 or greater and 70,000 or less.

7. The method of manufacturing a patterned substrate according to claim 1 or 2, wherein, the light transmittance of the polyimide resin contained in the photosensitive polyimide resin composition at a wavelength of 200 to 400 nm is 50% or greater.

8. The method of manufacturing a patterned substrate according to claim 1 or 2, wherein, the photosensitive polyimide resin composition further includes at least one selected from the group consisting of a photopolymerization initiator, an organic solvent, and a photopolymerizable compound.

9. The method of manufacturing a patterned substrate according to claim 1 or 2, wherein, the photopolymerizable compound includes a multifunctional radical polymerizable monomer.

10. The method of manufacturing a patterned substrate according to claim 9, wherein, the photopolymerizable compound includes a multifunctional (meth)acrylate having four or more (meth)acryl groups in a molecule.

11. The method of manufacturing a patterned substrate according to claim 9, wherein, ​ 12. The method of manufacturing a patterned substrate according to claim 1 or 2, wherein, The photosensitive polyimide resin composition further comprises at least one selected from the group consisting of a sensitizer, a leveling agent, and an adhesion improver. The photosensitive polyimide resin composition further comprises at least one selected from the group consisting of a sensitizer, a leveling agent, and an adhesion improver.

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