Manufacturing method for patterned substrates

Abstract

A method for producing a patterned substrate, the method comprising a step (a) in which a film is formed on a substrate from a photosensitive polyimide resin composition, a step (b) in which the film is exposed to light, and a step (c) in which the exposed film is developed using a developing liquid to form, on the substrate, a pattern made of the film, wherein the relative energy difference (RED) between the developing liquid and the unexposed film is 0.50-1.4.

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 properties are used in surface protective films for semiconductor elements in electronic devices, interlayer insulating films, and wiring protective insulating films for circuit boards. Examples of techniques for pattern formation using photosensitive polyimide resin compositions include those described in Patent Documents 1 to 5. Patent documents 1 to 4 describe a developer for photosensitive polyimide containing water in an organic solvent. Patent document 5 describes using a developer containing an organic solvent with a ClogP of -1 to 5 as a developer for a photosensitive polyimide resin composition. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2008-292799 [Patent Document 2] Japanese Patent Publication No. 2002-214801 [Patent Document 3] Japanese Patent Application Publication No. 10-123725 [Patent Document 4] Japanese Patent Publication No. 2002-014476 [Patent Document 5] International Publication No. 2018 / 221457 [Overview of the project] [Problems that the invention aims to solve]

[0004] In pattern formation using a negative-type photosensitive polyimide resin composition, using an organic solvent with high dissolving power in unexposed areas as a developer to improve developability sometimes resulted in erosion of the exposed areas, causing cracks in the exposed areas.

[0005] The present invention has been made in view of the above circumstances, and provides a method for manufacturing a patterned substrate that can suppress the generation of residue in unexposed areas while also suppressing the occurrence of cracks in exposed areas after development. [Means for solving the problem]

[0006] The inventors diligently conducted research to solve the above problems. As a result, they discovered that by using a developer with a relative energy difference (RED) within a specific range with respect to a film made of a photosensitive polyimide resin composition, the generation of residue in unexposed areas and the occurrence of cracks in exposed areas after development can be suppressed, thereby improving developability, and thus completed the present invention.

[0007] In other words, the present invention provides a method for manufacturing a patterned substrate as shown below.

[0008] [1] (a) A step of forming a film made of a photosensitive polyimide resin composition on a substrate, (b) A step of exposing the above film, The process includes (c) developing the exposed film using a developer to form a pattern on the substrate, A method for manufacturing a patterned substrate, wherein the relative energy difference (RED) between the developer and the film before exposure is 0.50 or more and 1.4 or less. [2] The method for manufacturing a patterned substrate as described in [1], wherein step (c) includes a step (c1) of measuring the Hansen solubility parameter of the film before exposure, and a step (c2) of selecting a developer such that the relative energy difference (RED) with the film before exposure is 0.50 or more and 1.4 or less, using the obtained Hansen solubility parameter. [3] The manufacturing method of the patterned substrate according to [1] or [2] above, wherein the step (a) includes a step (a1) of applying a varnish-like photosensitive polyimide resin composition onto the substrate, and a step (a2) of removing an organic solvent from the applied photosensitive polyimide resin composition. [4] The manufacturing method of the patterned substrate according to any one of [1] to [3] above, further including a step (d) of heat-treating the pattern after the step (c). [5] The manufacturing method of the patterned substrate according to [4] above, wherein the thickness of the pattern after heat treatment is 5 μm or more and 85 μm or less. [6] The manufacturing method of the patterned substrate according to any one of [1] to [5] above, wherein 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).

Chemical formula

Chemical formula

[10] A method for producing 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.

[11] A method for producing a patterned substrate according to

[10] above, wherein the above-mentioned photopolymerizable compound contains a polyfunctional radical polymerizable monomer.

[12] A method for producing a patterned substrate according to

[10] or

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

[13] A method for manufacturing a patterned substrate according to any one of the above [1] to

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

[0009] According to the present invention, it is possible to provide a patterned substrate in which residue in unexposed areas and cracks in exposed areas are suppressed. [Modes for carrying out the invention]

[0010] A description in detail will be given of an embodiment for carrying out the present invention (hereinafter simply referred to as "this embodiment"). The following embodiment is illustrative for explaining the present invention and does not limit the content of the present invention. The present invention can be carried out by modifying it as appropriate within the scope of its gist. In this embodiment, the provisions that are considered preferred can be adopted arbitrarily, and combinations of preferred provisions are considered more preferred. In this embodiment, the description "XX~YY" means "XX or more and YY or less".

[0011] In this embodiment, "(meth)acrylate" means both "acrylate" and "methacrylate." The same applies to other similar terms ("(meth)acrylic acid," "(meth)acryloyl group," etc.).

[0012] The method for manufacturing a patterned substrate according to this embodiment includes the following steps (a), (b), and (c). Step (a): A step of forming a film made of a photosensitive polyimide resin composition on a substrate. Step (b): Step of exposing the above film to light. Step (c): A step of developing the exposed film using a developer to form a pattern consisting of the film on the substrate. Furthermore, the relative energy difference (RED) between the developer and the film before exposure is 0.50 or higher, preferably 0.52 or higher, more preferably 0.55 or higher, and even more preferably 0.60 or higher, from the viewpoint of suppressing the occurrence of cracks in the exposed areas after development, and 1.4 or lower, preferably 1.3 or lower, more preferably 1.2 or lower, and even more preferably 1.1 or lower, from the viewpoint of suppressing the generation of residue in the unexposed areas after development.

[0013] Here, the relative energy difference (RED) can be calculated using the following equation (1). RED = R a / R0(1) In the above formula (1), R a is the distance between the Hansen solubility parameter of the solute (i.e., the above film before exposure in this embodiment) (hereinafter also referred to as "HSP") and the HSP of the solvent (i.e., the developer in this embodiment), that is, the HSP distance, and R0 is the interaction radius of the solute. R a (HSP distance) can be calculated by the following formula (2). R a ={4(δdS - δdL) 2 +(δpS - δpL) 2 +(δhS - δhL) 2} 0.5 (2) In the above formula (2), δdS is the energy due to the London dispersion force of the solute, δpS is the energy due to the dipole interaction of the solute, δhS is the energy due to the hydrogen bond of the solute, δdL is the energy due to the London dispersion force of the solvent, δpL is the energy due to the dipole interaction of the solvent, and δhL is the energy due to the hydrogen bond of the solvent.

[0014] R0 (the interaction radius of the solute) is determined, for example, by the Hansen sphere method. First, prepare the solute for which R0 is to be determined and several solvents with known HSPs, and conduct a solubility test of the target solute with respect to each solvent. In the above solubility test, plot the HSPs of the solvents showing solubility and the HSPs of the solvents not showing solubility on the Hansen space, respectively. Based on the HSPs of each plotted solvent, create a virtual sphere (Hansen sphere) on the Hansen space that includes the HSPs of the solvents showing solubility and does not include the HSPs of the solvents not showing solubility. The radius of the above Hansen sphere is R0.

[0015] HSP is an index that represents the solubility of one substance in another, indicating how well one substance dissolves in that substance. HSP is composed of three parameters: energy due to London dispersion forces (δd), energy due to dipole interactions (δp), and energy due to hydrogen bonding (δh). It is expressed as a vector quantity (δd, δp, δh) and is plotted on a three-dimensional space (Hansen space) with the three parameters of HSP as the coordinate axes. Substances with similar vectors are considered to have high solubility. The unit of each parameter is usually MPa. 1 / 2 It is represented as follows: HSP is, for example, the internet<URL:http: / / hansen-solubility.com / > See reference. A known method for measuring the HSP of a target polymer material 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 target material in several solvents with known HSPs is confirmed by dissolution experiments. In this embodiment, version 5.3.02 of the software was used.

[0016] The following describes each step in the manufacturing method of the patterned substrate according to this embodiment.

[0017] [Process (a)] First, a film made of a photosensitive polyimide resin composition is formed on the substrate. Step (a) preferably includes, for example, a step (a1) of applying a varnish-like photosensitive polyimide resin composition (hereinafter also simply referred to as "polyimide varnish") onto a substrate, and a step (a2) of removing an organic solvent from the applied photosensitive polyimide resin composition.

[0018] The method for applying polyimide varnish to a substrate is not particularly limited and can include, for example, inkjet method, spin coating method, casting method, microgravure method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, die coating method, etc.

[0019] When applying polyimide varnish to a substrate, it is preferable to adjust the solid content concentration of the polyimide varnish according to this embodiment to be in the range of 5 to 50% by mass.

[0020] The organic solvent is removed from the polyimide varnish by drying the polyimide varnish applied to the substrate. The polyimide varnish is dried by heat treatment, for example, using a hot plate, hot air, or oven. The heating temperature is, for example, 80 to 140°C, preferably 90 to 120°C. The heating time is, for example, 30 to 600 seconds, preferably about 30 to 300 seconds.

[0021] The thickness of the film made of the photosensitive polyimide resin composition is not particularly limited and can be adjusted as appropriate depending on the pattern to be ultimately obtained. For example, the film thickness is 5 μm to 85 μm. The film thickness can be adjusted by changing the content of organic solvents in the polyimide varnish, the coating method, or the coating conditions.

[0022] Examples of the substrates mentioned above include glass, silicon wafers, metal foil, and plastic film. Among these substrates, silicon wafers and copper foil are particularly preferred.

[0023] <Photosensitive polyimide resin composition> The photosensitive polyimide resin composition according to 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. Furthermore, the photosensitive polyimide resin composition according to this embodiment may further comprise at least one selected from the group consisting of, for example, a sensitizer, a leveling agent, and an adhesion improver. The polyimide resin content in the photosensitive polyimide resin composition according to 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, and even more preferably 70% by mass or less, when the total solid content of the photosensitive polyimide resin composition is taken as 100% by mass. In this embodiment, the total solid content of the photosensitive polyimide resin composition refers to the components that remain as solids when the photosensitive polyimide resin composition is cured, and components that volatilize upon heating, such as organic solvents, are excluded. On the other hand, liquid components that are incorporated into the resin film when heated and cured are included in the total solid content.

[0024] (Polyimide resin) Examples of polyimide resins according to this embodiment include polyimide resins comprising structural unit A derived from tetracarboxylic dianhydride and structural unit B derived from a diamine compound.

[0025] Any tetracarboxylic acid can be used as the constituent unit A described above. Examples 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 bicyclopentanetetracarboxylic acid dianhydride. Among these, cyclohexanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, and cyclopentanetetracarboxylic dianhydride are more preferred, with cyclohexanetetracarboxylic dianhydride being even more preferred. The above-mentioned tetracarboxylic acid components include positional isomers.

[0026] More preferred specific examples of the above tetracarboxylic acid components include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid methyl ester, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid methyl ester, 1,2,4,5-cyclopentanetetracarboxylic acid, Examples include 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid methyl ester, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid methyl ester, dicyclohexyltetracarboxylic acid, dicyclohexyltetracarboxylic acid dianhydride, and dicyclohexyltetracarboxylic acid methyl ester. Among these, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester are particularly preferred because they are easy to increase in molecular weight when producing polyimide resins, and they are advantageous in that they easily produce flexible films.

[0027] The constituent unit B is derived from a diamine compound, and for example, at least one can be selected from the group consisting of compounds represented by the following formula.

[0028] [ka]

[0029] [ka]

[0030] Among those described above, it is more preferable that the constituent unit B1 is derived from at least one compound selected from the group consisting of compounds represented by the following formula.

[0031] [ka]

[0032] It is even more preferable that the constituent unit B includes a constituent unit B2 derived from at least one compound selected from the group consisting of compounds represented by the following formula.

[0033] [ka]

[0034] In particular, it is preferable when the above-mentioned structural unit B2 includes a structural unit derived from the compound represented by the following formula (4), because the resulting polyimide resin exhibits superior solubility in organic solvents.

[0035] [ka]

[0036] In this embodiment, the polyimide resin preferably contains the above-mentioned constituent unit B1 or constituent unit B2 in a ratio of 60 mol% or more as constituent unit B derived from diamine. If the ratio of constituent unit B1 or constituent unit B2 in constituent unit B is 60 mol% or more, a polyimide resin with excellent solubility in organic solvents can be obtained.

[0037] The ratio of the above-mentioned constituent unit B1 or constituent unit B2 in constituent unit B is more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%. In particular, it is preferable that constituent unit B includes constituent unit B2, and that constituent unit B2 contains constituent units derived from the diamine represented by formula (4) in the above ratio.

[0038] 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 better solubility in organic solvents, making it suitable for cured film formation. The weight-average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, even more preferably 45,000 or less, and even more preferably 40,000 or less. A weight-average molecular weight of 5,000 or more is preferable because a cured film with desired mechanical properties can be obtained. The weight-average molecular weight of the polyimide resin is more preferably 10,000 or more, even more preferably 13,000 or more, and even more preferably 15,000 or more. By having the weight-average molecular weight of the polyimide resin within the above range, along with solubility in organic solvents, a resin composition with excellent developability can be obtained, for example, when used as a photosensitive polyimide resin composition, with a low residual film rate in unexposed areas. Here, the weight-average molecular weight is the weight-average molecular weight on a polystyrene basis.

[0039] (Method for manufacturing polyimide resin) The polyimide resin according to this embodiment comprises a constituent unit A derived from tetracarboxylic dianhydride and a constituent unit B derived from a diamine compound, wherein the raw materials, tetracarboxylic dianhydride and diamine compound, are as described above. The polyimide resin according to this embodiment can be obtained by reacting the above tetracarboxylic acid with the diamine component. The polyimide resin according to this embodiment has an amino group at its terminal end.

[0040] The organic solvent used when reacting the tetracarboxylic acid component with the diamine component is not particularly limited, but an organic solvent containing at least one selected from the group consisting of cyclic ethers, cyclic ketones, cyclic esters, amides, and ureas is preferred. Specific examples of preferred solvents are not particularly limited, but 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-dioxolane, 1,4-dioxane, tetramethylurea, and tetrahydrofuran is preferred. Among these, it is more preferable that one or more are selected from the group consisting of γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone.

[0041] An imidation catalyst can be used when reacting the tetracarboxylic acid component with the diamine component. A tertiary amine compound is preferred as the imidation catalyst, 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.

[0042] The reaction temperature is, for example, in the range of 160 to 200°C, preferably in the range of 170 to 190°C, and more preferably in the range of 180 to 190°C. If the temperature is above the lower limit, imidization and molecular weight increase will proceed sufficiently. If the temperature is below the upper limit, the solution viscosity can be appropriately maintained, and problems such as the resin sticking to the walls of the reaction vessel can be avoided. In some cases, an azeotropic dehydrating agent such as toluene or xylene may be used. The reaction pressure is usually atmospheric pressure, but the reaction can be carried out under pressure if necessary. The holding time at the reaction temperature is preferably at least 1 hour, and more preferably 3 hours or more. If it is 1 hour or more, imidization and molecular weight increase can proceed sufficiently. There is no particular upper limit to the reaction time, but it is carried out in the range of 3 to 10 hours, for example.

[0043] In the production of the polyimide resin according to this embodiment, it is preferable to react the tetracarboxylic acid component "A moles" and the diamine component "B moles" in the range of 0.80 ≤ A / B ≤ 0.99, and more preferably in the range of 0.85 ≤ A / B ≤ 0.95. By setting A / B ≤ 0.99, it is possible to have an excess of diamine at the ends of the polyimide, thereby obtaining a polyimide resin having amino groups at the ends and a molecular weight that has sufficient solubility in organic solvents. If A / B is 0.80 ≤, a polyimide resin with a molecular weight that exhibits sufficient flexibility can be obtained. As the A / B ratio approaches 1.0, a higher molecular weight polyimide resin can be obtained. Therefore, by appropriately adjusting the A / B ratio, a polyimide resin with the desired molecular weight can be obtained.

[0044] (Modified polyimide resin (A)) It is preferable that the polyimide resin according to this embodiment includes a modified polyimide resin having a repeating structure represented by the following general formula (1).

[0045] [ka] [In general formula (1), R is a tetravalent group having 4 to 25 carbon atoms, preferably 4 to 10 carbon atoms, having a cyclic structure, an acyclic structure, or a combination of a cyclic and an acyclic structure. A is a divalent group having 2 to 39 carbon atoms, having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups. The main chain of A may contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-. n indicates the number of repeating units. The terminals of general formula (1) are either a group represented by general formula (2) or general formula (3) below, or a hydrogen atom, with at least one of the terminals being a group represented by general formula (2) or general formula (3).]

[0046] [ka] [In general formulas (2) and (3), X and X 2 Each of these groups is independently a group having 2 to 15 carbon atoms and may have at least one group selected from the group consisting of ester bonds and double bonds. 2 Each of these is independently either a hydrogen atom or a methyl group.

[0047] Preferably, R in the above general formula (1) has at least a cyclic structure, and examples of such cyclic structures include tetravalent groups formed by removing four hydrogen atoms from cyclohexane, cyclopentane, cyclobutane, bicyclopentane, and their stereoisomers. Furthermore, as mentioned above with respect to polyimide resins, R in the above general formula (1) can include a constituent unit derived from any tetracarboxylic acid. Preferred examples are as described above, and for example, the following structure can be given as a constituent unit.

[0048] [ka] [In the formula, * indicates a bond.]

[0049] Among the above, the tetravalent group formed by removing four hydrogen atoms from cyclohexane is more preferred.

[0050] In general formula (1), A is a divalent group having 2 to 39 carbon atoms, having at least one group selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and organosiloxane groups. The main chain of A may contain at least one group selected from the group consisting of -O-, -SO2-, -CO-, -CH2-, -C(CH3)2-, -C2H4O-, and -S-.

[0051] More specifically, A includes cyclohexane, dicyclohexylmethane, dimethylcyclohexane, isophorone, norbornane and their alkyl-substituted and halogen-substituted compounds; benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenyl sulfone, benzophenone and their alkyl-substituted and halogen-substituted compounds; and divalent groups formed by removing two hydrogen atoms from compounds such as organo(poly)siloxanes. A preferably has a cyclic structure and preferably has at least one selected from the group consisting of alicyclic hydrocarbon groups and aromatic hydrocarbon groups. A preferably has an aromatic ring as an aromatic hydrocarbon group. More specifically, divalent groups having 6 to 27 carbon atoms represented by the following structural formula are preferred.

[0052] [ka] [In the formula, * indicates a bond.]

[0053] More specifically, as the divalent group having 2 to 39 carbon atoms represented by A, at least one group (Ia) selected from the group consisting of the structures shown below is preferred.

[0054] [ka] [In the formula, * indicates a bond.]

[0055] It is more preferable that the group corresponding to example A includes at least one group (Ib) selected from the group consisting of the structures shown below.

[0056] [ka] [In the formula, * indicates a bond.]

[0057] In general formula (1), it is particularly preferable that A has a group represented by the following formula (Ic).

[0058] [ka] [In the formula, * indicates a bond.]

[0059] In this embodiment, the modified polyimide resin (A) preferably has a ratio of 60 mol% or more of at least one constituent unit selected from (Ia), (Ib), or (Ic) as A in general formula (1), from the viewpoint of solubility in organic solvents.

[0060] In general formula (1), the ratio of at least one constituent unit selected from (Ia), (Ib), or (Ic) in A is more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 95 mol% or more, and particularly preferably 100 mol%. In particular, it is preferable to include constituent units derived from the diamine represented by formula (Ic) in the above ratio.

[0061] n, which represents the number of repeating units of the structural unit represented by 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 desired mechanical properties can be obtained. If n is 250 or less, sufficient solubility in organic solvents can be ensured.

[0062] The modified polyimide resin (A) according to this embodiment has either a group represented by general formula (2) or general formula (3) or a hydrogen atom at one of its ends, and at least one of the ends is a group represented by general formula (2) or general formula (3). The modified polyimide resin (A) may have one end with a structure represented by general formula (2) or general formula (3), or both ends may have a structure represented by general formula (2) or general formula (3). X or X in general formula (2) or general formula (3) 2 The group represented by is a group having 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 group indicated by is either a hydrogen atom or a methyl group.

[0063] The structure represented by the above general formula (2) or general formula (3) more specifically corresponds to a structure obtained by reacting the terminal amine of a polyimide resin with a functional group-containing compound. Examples of such functional group-containing compounds include compounds having an isocyanate group or epoxy group and a (meth)acrylic group. Examples of such compounds include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, etc. The structure represented by general formula (2) or general formula (3) may have a structure obtained by reacting the compound with the amine terminal.

[0064] The weight-average molecular weight of the modified polyimide resin (A) is preferably 70,000 or less. A weight-average molecular weight of 70,000 or less provides better solubility in organic solvents, making it suitable for cured film formation. The weight-average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, even more preferably 45,000 or less, and even more preferably 40,000 or less. A weight-average molecular weight of 5,000 or more is preferable because a cured film with desired mechanical properties can be obtained. The weight-average molecular weight of the modified polyimide resin (A) is more preferably 10,000 or more, even more preferably 13,000 or more, and even more preferably 15,000 or more. By having the weight-average molecular weight of the modified polyimide resin (A) within the above range, a resin composition with a low residual film rate in the unexposed areas and excellent developability can be obtained. Here, the weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight.

[0065] Modified polyimide resin (A) can be obtained by reacting the diamine component described in detail below with the tetracarboxylic acid component.

[0066] 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 may be 100 mol%.

[0067] The above diamine may 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 which may include an aliphatic group, an alicyclic group, or other substituents in part of its structure. "Aliphatic diamine" refers to a diamine in which the amino group is directly bonded to an aliphatic group or an alicyclic group, and which may include an aromatic group or other substituents in part of its structure.

[0068] Generally, when aliphatic diamines are used as raw materials for polyimide resins, the intermediate product, polyamic acid, and the aliphatic diamine form a strong complex, making it difficult to obtain high molecular weight polyimides. Therefore, it is necessary to use organic solvents with relatively high complex solubility, such as cresol. When cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, or their derivatives are used as the tetracarboxylic acid component, a complex is formed in which the bond between the polyamic acid and the aliphatic diamine is relatively weak, making it easy to increase the molecular weight of the polyimide. Selecting a diamine with a fluorine substituent as a raw material is preferable because it results in a polyimide resin with excellent transparency.

[0069] Any aliphatic diamine can be used as described above. 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-xylylenediamine, p-xylylenediamine, isophoronediamine, norbornanediamine, and siloxanediamines.

[0070] Examples of the above aromatic diamines include 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)benzeneamine], and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine.

[0071] Preferably, the above diamine comprises at least 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-oxybis[3-(trifluoromethyl)benzeneamine], or 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine. By including at least one of these as a diamine component, the resulting photosensitive resin composition containing the modified polyimide resin (A) has high light transmittance at specific wavelengths and high solubility in organic solvents. Therefore, it exhibits excellent curability in exposed areas, low residual film rate in unexposed areas, and excellent developability. It is sufficient to include any of the above as a diamine component, and the excellent effect is maintained even when used in combination with other diamines. The modified polyimide resin (A) according to 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-inden-5-amine, or 4,4'-oxybis[3-(trifluoromethyl)benzeneamine].

[0072] 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 bicyclopentanetetracarboxylic acid dianhydride. Among these, cyclohexanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, and cyclopentanetetracarboxylic acid dianhydride are more preferred. Of the above, cyclohexanetetracarboxylic acid dianhydride is even more preferred. The various tetracarboxylic acid components described above include positional isomers.

[0073] More preferred specific examples of the above tetracarboxylic acid components include 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid methyl ester, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid methyl ester, 1,2,4,5-cyclopentanetetracarboxylic acid, Examples include 1,2,4,5-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclopentanetetracarboxylic acid methyl ester, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo[2.2.2]octa-7-ene-2,3,5,6-tetracarboxylic acid methyl ester, dicyclohexyltetracarboxylic acid, dicyclohexyltetracarboxylic acid dianhydride, and dicyclohexyltetracarboxylic acid methyl ester. Among these, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic acid methyl ester are particularly preferred because they are easy to increase in molecular weight when producing polyimide resins, and they are advantageous in that they easily produce flexible films.

[0074] The tetracarboxylic acid component may include other tetracarboxylic acids or their derivatives, to the extent that they do not impair the flexibility and thermocompression properties of the final cured film. Examples of these other tetracarboxylic acids or their derivatives include 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-dicarboxyphenyl)sulfone, and bi Examples include at least one selected from s(3,4-dicarboxyphenyl) ether, bis(2,3-dicarboxyphenyl) ether, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 4,4-(p-phenylenedioxy)diphthalic acid, 4,4-(m-phenylenedioxy)diphthalic acid, ethylenetetracarboxylic acid, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, and derivatives thereof.

[0075] (Method for producing modified polyimide resin (A)) The modified polyimide resin (A) according to this embodiment can be obtained by the following steps (1) and (2): Step (1): A tetracarboxylic acid component and a diamine component are reacted to obtain a polyimide resin having an amino group at the end. Step (2): The polyimide resin having an amino group at its end obtained in step (1) is reacted with the functional group-containing compound (a compound having an isocyanate group or epoxy group and a (meth)acrylic group). In step (1), the tetracarboxylic acid described above is reacted with a diamine component to obtain a polyimide resin having an amino group at its terminus. Step (1) described above is the same as the method for producing polyimide resin described above. The raw materials used, preferred materials, and reaction conditions are also the same.

[0076] Step (2) is a step to modify the ends of the polyimide resin obtained in step (1). Specifically, as described above, the polyimide is reacted with the functional group-containing compound (a compound having an isocyanate group or epoxy group and a (meth)acrylic group) to obtain a modified polyimide resin (A) having (meth)acrylic groups at its ends.

[0077] Functional group-containing compounds that modify the ends of polyimide resins are compounds having an isocyanate group or epoxy group and a (meth)acrylic group. Specifically, examples include 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, glycidyl methacrylate, and allyl glycidyl ether. These functional group-containing compounds may be used individually or in combination of two or more. It is preferable to use the functional group-containing compound in a ratio of 0.1 to 30 molar times with respect to the polyimide resin having amino groups at its ends.

[0078] 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. When reacting the amino group terminus of a polyimide resin with the isocyanate or epoxy group of a functional group-containing compound, the reaction may be carried out 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, which may be used individually or in combination of two or more. Polymerization inhibitors may be used to suppress side reactions during the reaction. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone, which may be used individually or in combination of two or more.

[0079] The polyimide resin according to this embodiment has a light transmittance of preferably 50% or more, more preferably 55% or more, even more preferably 60% or more, and even more preferably 70% or more at wavelengths of 200 to 400 nm.

[0080] The modified polyimide resin (A) according to this embodiment has high light transmittance at the above wavelength and excellent solubility in organic solvents. Therefore, the photopolymerization initiator that may be contained in the composition acts effectively, and a cured film can be obtained efficiently. In addition, by using the modified polyimide resin (A), when a cured film is formed from the composition, the residual film rate in unexposed areas is low, it has excellent developability, and the occurrence of cracks and the like can be effectively suppressed.

[0081] (organic solvent) As organic solvents, aprotic polar solvents are preferable from the viewpoint of solubility. Specifically, examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and γ-butyrolactone. These organic solvents may be used individually or in combination of two or more. To further improve coatability, solvents such as toluene, xylene, diethyl ketone, methoxybenzene, and cyclopentanone may be mixed in a range that does not adversely affect the solubility of the polymer. By using an appropriate organic solvent, the photosensitive polyimide resin composition according to this embodiment can be used in solution (varnish) form, which is convenient for film formation.

[0082] (Photopolymerizable compound) As the photopolymerizable compound, polyfunctional radical polymerizable monomers, such as bifunctional or (meth)acrylic monomers, can be used. Examples of (meth)acrylic monomers include tricyclodecanedimethanol 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)acryloxyethyl) isocyanurate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol (meth)acrylate, mono and dipentaerythritol (meth)acrylate, polypentaerythritol (meth)acrylate, polyglycerin-based (meth)acrylate, dendrimer (meth)acrylate, and the like. These photopolymerizable compounds may be used individually or in combination of two or more. Here, polyglycerin-based (meth)acrylate refers to a compound having a polyglycerin skeleton and a (meth)acryloyl group. Examples of polyglycerin-based (meth)acrylates include SA-TE6 and SA-TE60 manufactured by Sakamoto Pharmaceutical Co., Ltd. Examples of ethoxylated trimethylolpropane tri(meth)acrylates that can be used include ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate, and ethoxylated (15) trimethylolpropane triacrylate manufactured by Arkema Corporation. Furthermore, dendrimer (meth)acrylate refers to a polyfunctional (meth)acrylate having a dendrimer structure (including a hyperbranched structure). Examples of dendrimer (meth)acrylates include Viscoat 1000, Viscoat 1020, and STAR-501, manufactured by Osaka Organic Chemical Industry Co., Ltd. Viscoat 1000 and Viscoat 1020 mainly consist of dendrimer-type polyester acrylates having acrylate groups at their terminals. The molecular weight of Viscoat 1000 is approximately 1000 to 2000, and the molecular weight of Viscoat 1020 is approximately 1000 to 3000. STAR-501 mainly consists of a dipentaerythritol hexaacrylate-linked polybranched polyacrylate containing a core derived from dipentaerythritol and having acrylate groups at its terminals. The molecular weight of STAR-501 is approximately 16000 to 24000. Among these, as photopolymerizable compounds, polyfunctional (meth)acrylates having four or more (meth)acryloyl groups in the molecule are preferred from the viewpoint of suppressing the occurrence of cracks in the exposed areas after development, and polyfunctional (meth)acrylates having four to ten (meth)acryloyl groups in the molecule are more preferred. The flexibility and other properties of the photosensitive polyimide resin composition can be controlled by the structure of the photopolymerizable compound that is mixed. It is preferable to mix these photopolymerizable compounds in a ratio of 5 to 500 parts by mass per 100 parts by mass of the polyimide resin contained in the photosensitive polyimide resin composition.

[0083] (Photopolymerization initiator) The photopolymerization initiator is not particularly limited and known ones can be used. For example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1- Examples of photopolymerization initiators include (4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-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 may be used individually or in combination of two or more. The photopolymerization initiator is preferably mixed in a ratio of 0.1 to 10 parts by mass per 100 parts by mass of the polyimide resin contained in the photosensitive polyimide resin composition.

[0084] (Sensitizer) The sensitizer is not particularly limited, and known sensitizers can be used. For example, amino group-containing sensitizers can be cited, and compounds having an amino group and a phenyl group in the same molecule are preferably exemplified. More specifically, benzophenone compounds such as 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, and 2,5-bis(p-diethylaminophenyl)-1,3,4-oxadiazole Examples of p-dialkylaminophenyl group-containing compounds include 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. These sensitizers may be used alone or in combination of two or more. The sensitizer is preferably mixed in a ratio of 0.001 to 10 parts by mass per 100 parts by mass of the polyimide resin contained in the photosensitive polyimide resin composition.

[0085] (Leveling agent) The leveling agent is not particularly limited and any known type can be used. For example, various surface modifiers such as silicon-based surface modifiers, acrylic-based surface modifiers, fluorine-based surface modifiers, nonionic surface modifiers, cationic surface modifiers, and anionic surface modifiers can be used. These may be used individually or in combination of two or more types. The leveling agent is preferably mixed in a ratio of 0.001 to 20 parts by mass per 100 parts by mass of the polyimide resin contained in the photosensitive polyimide resin composition.

[0086] (Adhesion enhancer) The adhesion enhancer is not particularly limited and known ones can be used, including silane coupling agents such as amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, mercapto group-containing silane coupling agents, and (meth)acrylic group-containing silane coupling agents, as well as known coupling agents such as titanate coupling agents and aluminate 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.). These can be used individually or in combination of two or more types. The adhesion enhancer is preferably mixed in a ratio of 0.0005 to 20 parts by mass per 100 parts by mass of the polyimide resin contained in the photosensitive polyimide resin composition.

[0087] (Method for producing a photosensitive polyimide resin composition) The photosensitive polyimide resin composition according to this embodiment is not particularly limited, but can be prepared as follows. A photosensitive polyimide composition can be obtained by mixing a polyimide resin with at least one selected from the group consisting of organic solvents, photopolymerization initiators, and photopolymerizable compounds. If necessary, at least one selected from the group consisting of sensitizers, leveling agents, and adhesion improvers may be further mixed in, as described above.

[0088] (Polyimide varnish) The polyimide varnish according to this embodiment comprises a polyimide resin and an organic solvent, and may further contain at least one selected from the group consisting of a photopolymerization initiator and a photopolymerizable compound. Furthermore, as necessary, at least one selected from the group consisting of a sensitizer, a leveling agent and an adhesion improver may be further mixed in. Specific examples of each component are as described above. The polyimide varnish according to this embodiment may be the polyimide solution itself, in which the polyimide resin obtained by polymerization is dissolved in a reaction solvent, or it may be a polyimide solution that has been further diluted by adding an organic solvent.

[0089] The polyimide resin and modified polyimide resin (A) having amino groups at the ends according to this embodiment have excellent solvent solubility, making it possible to obtain a highly concentrated varnish that is stable at room temperature. The polyimide varnish according to this embodiment preferably contains 5 to 40% by mass of the polyimide resin described in detail, and more preferably contains 10 to 30% by mass.

[0090] The viscosity of the polyimide varnish is preferably 1 to 200 Pa·s, and more preferably 1 to 100 Pa·s. The viscosity of the polyimide varnish is the value measured at 25°C using an E-type viscometer.

[0091] The method for producing polyimide varnish is not particularly limited, and known methods can be applied.

[0092] [Step (b)] Next, the film obtained in step (a) is exposed to light. Film exposure can be performed, for example, by irradiating a film made of a photosensitive polyimide resin composition formed on a substrate with light (usually ultraviolet light) through a photomask with a predetermined pattern. The exposed film has a portion where light is blocked by the photomask and a portion where light is irradiated, that is, an exposed portion and an unexposed portion. In the exposed areas of the above film, the polyimide resin in the photosensitive polyimide resin composition crosslinks, forming a crosslinked polyimide film, which then forms a pattern in the next developing step (step (c)). On the other hand, in the unexposed areas, the polyimide resin is not crosslinked, and therefore becomes an uncrosslinked polyimide film that is dissolved and removed by developing. The UV irradiation dose is preferably 100 to 8,000 mJ / cm² as an integrated irradiation dose. 2 , more preferably 200~6,000 mJ / cm² 2 That is the case.

[0093] [Process (c)] Next, the exposed film is developed using a developing solution to form a pattern consisting of the film on the substrate. For example, a film made of a photosensitive polyimide resin composition formed on a substrate can be irradiated with light, and then the unexposed areas can be dissolved and removed with a developing solution to obtain a desired relief pattern.

[0094] The step (c) preferably includes the steps of measuring the Hansen solubility parameter of the film before exposure (c1) and selecting a developer (c2) in which the relative energy difference (RED) with the film before exposure is 0.50 or more and 1.4 or less, using the obtained Hansen solubility parameter. The RED value is 0.50 or higher, preferably 0.52 or higher, more preferably 0.55 or higher, and even more preferably 0.60 or higher, from the viewpoint of suppressing the occurrence of cracks in the exposed areas after development, and 1.4 or lower, preferably 1.3 or lower, more preferably 1.2 or lower, and even more preferably 1.1 or lower, from the viewpoint of suppressing the generation of residue in the unexposed areas after development.

[0095] In the method for manufacturing a patterned substrate according to this embodiment, it is preferable to use an organic solvent as the developer. The developer dissolves the photosensitive polyimide resin composition according to this embodiment and is not particularly limited as long as the relative energy difference (RED) with the film before exposure is within the above 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, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, 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, and 1,4-dioxane. These developers may be used individually or in combination of two or more types.

[0096] The relief pattern formed by development is then washed with a rinsing solution to remove the developing solvent. Suitable rinsing solutions include methanol, ethanol, isopropyl alcohol, and water, which have good miscibility with the developing solution.

[0097] [Step (d)] In the method for manufacturing a patterned substrate according to this embodiment, step (d) of heat-treating the pattern may be further included after step (c). This makes it possible to obtain a cured film (pattern) obtained by curing the photosensitive polyimide resin composition of this embodiment. For example, the relief pattern obtained by the above-described process can be heat-treated at a temperature selected from the range of 80 to 400°C to remove the organic solvent and cure the photosensitive polyimide resin composition of this embodiment to obtain a cured film (pattern). According to this embodiment, a resin composition is used that exhibits excellent developability, meaning that the exposed areas harden sufficiently, while the unexposed areas are thoroughly removed due to the high solubility of the modified polyimide resin contained in the photosensitive polyimide resin composition in organic solvents. As a result, a high-resolution relief pattern can be obtained.

[0098] In the method for manufacturing a patterned substrate according to this embodiment, the thickness of the pattern after heat treatment, that is, the thickness of the cured film obtained by curing the photosensitive polyimide resin composition of this embodiment, is preferably 5 μm or more and 85 μm or less. When the film thickness is within the above range, it can be used as an excellent insulating film. As the film thickness increases (i.e., as the amount of photosensitive polyimide resin composition applied to the substrate increases), problems often arise, particularly with the solubility of the polyimide resin in organic solvents. However, according to this embodiment, by using modified polyimide resin (A), it is possible to achieve both excellent solubility in organic solvents and transparency even in such situations. Therefore, the cured film of this embodiment can be suitably used, for example, in insulating film applications where high voltages are expected to be applied. The cured film obtained from the photosensitive polyimide resin composition of this embodiment, which includes the modified polyimide resin (A), can effectively suppress the occurrence of cracks and other defects and has excellent physical properties.

[0099] [Application] The patterned substrate according to this embodiment can be used for a variety of applications. For example, it can be suitably used as a surface protective film for semiconductor elements in electronic devices, an interlayer insulating film, and a wiring protective insulating film for circuit boards, particularly in high-density and highly integrated applications. In this case, the pattern on the patterned substrate becomes the surface protective film for semiconductor elements in electronic devices, the interlayer insulating film, or the wiring protective insulating film for circuit boards. [Examples]

[0100] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way by these examples.

[0101] (Synthesis Example 1) In a 1 L five-necked flask equipped with a nitrogen inlet tube, stirrer, thermometer, and condenser, 196.1581 g (0.583 mol) of 4,4'-oxybis[3-(trifluoromethyl)benzeneamine] (hereinafter, 6FODA), 124.1578 g (0.554 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter, HPMDA), and 391.50 g of γ-butyrolactone (hereinafter, GBL) were added under nitrogen introduction, and the mixture was heated to 90°C while stirring. Then, 2.802 g (0.028 mol) of triethylamine (hereinafter, TEA) was added, and the mixture was reacted at 190°C for 5 hours. After that, it was diluted with 308.10 g of GBL to obtain 999 g of polyimide varnish with a solid content of 30% by mass (total of 23.7 g of distillate water and distillate TEA). GPC measurements revealed that the weight-average molecular weight (Mw) of the polyimide obtained in this synthesis was 33,876. 200.03 g of this polyimide varnish was mixed with 100.01 g of GBL and 6.0264 g of 2-isocyanatoethyl acrylate (manufactured by Showa Denko K.K., Karenz AOI) and reacted at 50°C for 5 hours. The reaction solution was then added dropwise to water to precipitate the polyimide, and dried overnight at 70°C to obtain modified polyimide resin (A1).

[0102] The evaluation methods used in this embodiment and comparative example are as follows.

[0103] (1) Weight average molecular weight (Mw) Mw was determined by GPC analysis. The equipment and analytical conditions used are as follows. Equipment: HLC-8420GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperAWM-H x 2 (manufactured by Tosoh Corporation) Eluent: Dimethylformamide with (30 mM lithium bromide and 100 mM phosphoric acid) Standard polystyrene: PStQuick Kit-H (manufactured by Tosoh Corporation) Flow rate: 0.6ml / min Column temperature: 40℃ Detector: RI (Refractive Index Detector)

[0104] (2) Calculation of Hansen solubility parameter (HSP) of photosensitive polyimide resin composition 1 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) was added as a photopolymerizable compound, 0.0431 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, Omnirad 184) and 0.1005 g of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF, Omnirad 819) were added as photopolymerization initiators, 0.2876 g of LE-304 (manufactured by Kyoeisha Chemical Co., Ltd.) diluted 100-fold with GBL was added as a leveling agent, and 0.1496 g of KP-390 (manufactured by Shin-Etsu Chemical Co., Ltd.) diluted 100-fold with GBL was added as an adhesion improver. The mixture was stirred until these were sufficiently dissolved to obtain a photosensitive polyimide resin composition (polyimide varnish). This polyimide varnish was deposited onto a PET film by casting using a glass rod and a spacer with a film thickness of 300 μm, and dried at 100°C for 60 minutes to obtain a photosensitive polyimide resin composition film.

[0105] Cut this film to an appropriate size and use it with solvents for which HSPs are known (HSPs are registered in the HSPiP database): 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), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl Each film was completely immersed in one of the following solvents: 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, and left to stand at room temperature for 4 days. After that, the solubility or insolubility of the film in each solvent was visually determined, and the HSP (δd: dispersion term, δp: polarity term, δh: hydrogen bonding term) and R0: interaction radius were calculated using the Hansen sphere method described above. The result was δd: 15.54 MPa 1 / 2 δp: 11.73MPa 1 / 2 δh: 8.20MPa 1 / 2 R0 = 9.7 MPa 1 / 2 The Fit value, which represents the proportion of good solvent entering the Hansen bulb, was 0.882.

[0106] (2) Calculation of Hansen solubility parameter (HSP) of photosensitive polyimide resin composition 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.) was added as a photopolymerizable compound, 0.0346 g of 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, Omnirad 184) and 0.0820 g of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by BASF, Omnirad 819) were added as photopolymerization initiators, 0.2550 g of LE-304 (manufactured by Kyoeisha Chemical Co., Ltd.) diluted 100-fold with GBL was added as a leveling agent, and 0.1211 g of KP-390 (manufactured by Shin-Etsu Chemical Co., Ltd.) diluted 100-fold with GBL was added as an adhesion improver. The mixture was stirred until these were sufficiently dissolved to obtain a photosensitive polyimide resin composition (polyimide varnish). This polyimide varnish was deposited onto a PET film by casting using a glass rod and a spacer with a film thickness of 300 μm, and dried at 100°C for 60 minutes to obtain a photosensitive polyimide resin composition film.

[0107] Cut this film to an appropriate size and use it with solvents for which HSPs are known (HSPs are registered in the HSPiP database): 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), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl Each film was completely immersed in one of the following solvents: 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, and left to stand at room temperature for 4 days. After that, the solubility or insolubility of the film in each solvent was visually determined, and the HSP (δd: dispersion term, δp: polarity term, δh: hydrogen bonding term) and R0: interaction radius were calculated using the Hansen sphere method described above. The result was δd: 15.54 MPa 1 / 2 δp: 11.73MPa 1 / 2 δh: 8.20MPa 1 / 2 R0 = 9.7 MPa 1 / 2 The Fit value, which represents the proportion of good solvent that enters the Hansen bulb, was 0.879.

[0108] (Example 1) Polyimide varnish was prepared using the same mixing ratio as described in HSP calculation 1 above, as shown in Table 1. This polyimide varnish was applied to a silicon wafer using a spin coater (MS-B150) manufactured by Mikasa Corporation under conditions that resulted in a polyimide film thickness of 25-30 μm after drying, 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 Corporation was used, with a high-pressure mercury lamp as the light source, and an exposure dose of 5,000 mJ / cm² at an exposure wavelength of 365 nm was applied. 2 Under these conditions, a photomask with a 30 μm / 50 μm L / S (line and space) pattern was exposed to light and left to stand at room temperature for 15 minutes. Then, the wafer was immersed and developed for 90 seconds using ethyl lactate (EL) as the developer, rinsed with methanol, and the remaining solvent was removed under air circulation to form a 30 μm / 50 μm resin pattern on the silicon wafer. Next, a digital microscope was used to observe and evaluate the developability of the pattern and the presence or absence of cracks in the exposed areas.

[0109] [Table 1]

[0110] (Example 2) Polyimide varnish was prepared in the same manner as in Example 1, except that propylene glycol monomethyl ether acetate (PGMEA) was used as the developer, and was evaluated in the same manner as in Example 1.

[0111] (Example 3) Polyimide varnish was prepared in the same manner as in Example 1, except that propylene glycol monomethyl ether (PGME) was used as the developer, and evaluated in the same manner as in Example 1.

[0112] (Example 4) Polyimide varnish was prepared in the same manner as in Example 1, except that cyclohexanone was used as the developer, and evaluated in the same manner as in Example 1.

[0113] (Example 5) Polyimide varnish was prepared in the same manner as in Example 1, except that acetonitrile was used as the developer, and evaluated in the same manner as in Example 1.

[0114] (Example 6) Polyimide varnish was prepared in the same manner as in Example 1, except that methyl isobutyl ketone (MIBK) was used as the developer, and evaluated in the same manner as in Example 1.

[0115] (Example 7) Polyimide varnish was prepared in the same manner as in Example 1, except that a mixed solvent of 1,4-dioxane:ε-caprolactone = 53:47 (volume ratio) was used as the developer, and was evaluated in the same manner as in Example 1.

[0116] (Example 8) Polyimide varnish was prepared in the same manner as in Example 1, except that a mixed solvent of ε-caprolactone:toluene:benzyl alcohol = 35:35:30 (volume ratio) was used as the developer, and was evaluated in the same manner as in Example 1.

[0117] (Example 9) Polyimide varnish was prepared in the same manner as in Example 1, except that butyl acetate was used as the developer, and evaluated in the same manner as in Example 1.

[0118] (Example 10) Polyimide varnish was prepared in the same manner as in Example 1, except that 1,4-dioxane was used as the developer, and was evaluated in the same manner as in Example 1.

[0119] (Comparative Example 1) Polyimide varnish was prepared in the same manner as in Example 1, except that acetone was used as the developer, and evaluated in the same manner as in Example 1.

[0120] (Comparative Example 2) Polyimide varnish was prepared in the same manner as in Example 1, except that N,N-dimethylacetamide (DMAc) was used as the developer, and was evaluated in the same manner as in Example 1.

[0121] (Comparative Example 3) Polyimide varnish was prepared in the same manner as in Example 1, except that methyl ethyl ketone (MEK) was used as the developer, and evaluated in the same manner as in Example 1.

[0122] (Comparative Example 4) Polyimide varnish was prepared in the same manner as in Example 1, except that cyclohexane was used as the developer, and evaluated in the same manner as in Example 1.

[0123] The results obtained in Examples 1-10 and Comparative Examples 1-4 are shown in Table 2.

[0124] [Table 2]

[0125] (Example 11) Polyimide varnish was prepared using the same mixing ratio as described in HSP calculation 2 above, as shown in Table 3. This polyimide varnish was applied to a silicon wafer using a spin coater (MS-B150) manufactured by Mikasa Corporation under conditions that resulted in a polyimide film thickness of 25-30 μm after drying, 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 Corporation was used, with a high-pressure mercury lamp as the light source, and an exposure dose of 5,000 mJ / cm² at an exposure wavelength of 365 nm was applied. 2 Under these conditions, a photomask with a 30 μm / 50 μm L / S (line and space) pattern was exposed to light and left to stand at room temperature for 15 minutes. Then, a 30 μm / 50 μm resin pattern was formed on the silicon wafer by immersion development using N-methyl-2-pyrrolidone (NMP) as the developer for 90 seconds, rinsing with methanol, and removing the remaining solvent under air circulation. Next, a digital microscope was used to observe and evaluate the developability of the pattern and the presence or absence of cracks in the exposed areas.

[0126] [Table 3]

[0127] (Example 12) Polyimide varnish was prepared in the same manner as in Example 11, except that cyclopentanone was used as the developer, and evaluated in the same manner as in Example 11.

[0128] (Example 13) Polyimide varnish was prepared in the same manner as in Example 11, except that EL was used as the developer, and evaluated in the same manner as in Example 11.

[0129] (Example 14) Polyimide varnish was prepared in the same manner as in Example 11, except that PGMEA was used as the developer, and evaluated in the same manner as in Example 11.

[0130] (Example 15) Polyimide varnish was prepared in the same manner as in Example 11, except that cyclohexanone was used as the developer, and evaluated in the same manner as in Example 11.

[0131] (Example 16) Polyimide varnish was prepared in the same manner as in Example 11, except that a mixed solvent of 1,4-dioxane:ε-caprolactone = 53:47 (volume ratio) was used as the developer, and was evaluated in the same manner as in Example 11.

[0132] (Example 17) Polyimide varnish was prepared in the same manner as in Example 11, except that a mixed solvent of ε-caprolactone:toluene:benzyl alcohol = 35:35:30 (volume ratio) was used as the developer, and was evaluated in the same manner as in Example 11.

[0133] (Example 18) Polyimide varnish was prepared in the same manner as in Example 11, except that butyl acetate was used as the developer, and evaluated in the same manner as in Example 11.

[0134] (Example 19) Polyimide varnish was prepared in the same manner as in Example 11, except that 1,4-dioxane was used as the developer, and was evaluated in the same manner as in Example 11.

[0135] (Comparative Example 5) Polyimide varnish was prepared in the same manner as in Example 11, except that acetone was used as the developer, and evaluated in the same manner as in Example 11.

[0136] (Comparative Example 6) Polyimide varnish was prepared in the same manner as in Example 11, except that DMAc was used as the developer, and evaluated in the same manner as in Example 11.

[0137] (Comparative Example 7) Polyimide varnish was prepared in the same manner as in Example 11, except that cyclohexane was used as the developer, and evaluated in the same manner as in Example 11.

[0138] The results obtained in Examples 11-19 and Comparative Examples 5-7 are shown in Table 4.

[0139] [Table 4]

Claims

1. (a) A step of forming a film made of a photosensitive polyimide resin composition on a substrate, (b) a step of exposing the aforementioned film, The process includes (c) developing the exposed film using a developer to form a pattern consisting of the film on the substrate, The relative energy difference (RED) between the developer and the film before exposure is 0.50 or more and 1.4 or less. 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), A method for manufacturing a patterned substrate, comprising the photosensitive polyimide resin composition containing 5 to 40% by mass of the modified polyimide resin (A). 【Chemistry 1】 [In the above general formula (1), R is a tetravalent group formed by removing four hydrogen atoms from cyclohexane, cyclopentane, cyclobutane, bicyclopentane, and their stereoisomers. A has a divalent group represented by the following formula (I-c). n indicates the number of repeating units and is between 5 and 250. The terminals of the above general formula (1) are either the group represented by the following general formula (2) or general formula (3), or a hydrogen atom, and at least one of the terminals is the group represented by the following general formula (2) or general formula (3).] 【Chemistry 2】 [In the formula, * indicates a bond.] 【Transformation 3】 [In the above general formulas (2) and (3), X and X ２ Each of these groups is independently a group having 2 to 15 carbon atoms and may have at least one group selected from the group consisting of ester bonds and double bonds. Y and Y ２ Each of these is independently either a hydrogen atom or a methyl group.

2. The method for manufacturing a patterned substrate according to claim 1, wherein step (c) includes a step (c1) of measuring the Hansen solubility parameter of the film before exposure, and a step (c2) of selecting a developer such that the relative energy difference (RED) with the film before exposure is 0.50 or more and 1.4 or less, using the obtained Hansen solubility parameter.

3. The method for manufacturing a patterned substrate according to claim 1 or 2, wherein step (a) comprises a step (a1) of applying a varnish-like photosensitive polyimide resin composition onto the substrate, and a step (a2) of removing an organic solvent from the applied photosensitive polyimide resin composition.

4. A method for manufacturing a patterned substrate according to any one of claims 1 to 3, further comprising a step (d) of heat-treating the pattern after step (c).

5. The method for manufacturing a patterned substrate according to claim 4, wherein the thickness of the pattern after heat treatment is 5 μm or more and 85 μm or less.

6. A method for manufacturing a patterned substrate according to any one of claims 1 to 5, wherein the weight-average molecular weight of the polyimide resin contained in the photosensitive polyimide resin composition is 5,000 or more and 70,000 or less.

7. A method for manufacturing a patterned substrate according to any one of claims 1 to 6, 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 more.

8. The method for producing a patterned substrate according to any one of claims 1 to 7, 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.

9. The method for producing a patterned substrate according to claim 8, wherein the photopolymerizable compound comprises a polyfunctional radical polymerizable monomer.

10. The method for producing a patterned substrate according to claim 8 or 9, wherein the photopolymerizable compound comprises a polyfunctional (meth)acrylate having four or more (meth)acryloyl groups in the molecule.

11. The method for manufacturing a patterned substrate according to any one of claims 1 to 10, 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.

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