Method for producing polyimide and photosensitive resin composition

Abstract

To provide a method for producing polyimide that enables reduction in development time, and the like.SOLUTION: There is provided a method for producing polyimide by chemically imidizing a polyimide precursor having an amino group at a terminal thereof in the presence of a specific acid anhydride and a basic catalyst, the polyimide precursor having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). (In formula (1), A1 represents a tetravalent organic group. In formula (2), A2 represents a divalent aromatic group having a photopolymerizable group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polyimide, a photosensitive resin composition, an insulating film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate having a cured relief pattern, and a semiconductor device having a cured relief pattern. [Background technology]

[0002] Polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used as insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors can easily form heat-resistant relief pattern coatings by applying the precursor, exposing it to light, developing it, and subjecting it to a thermal imidization treatment through curing. Such photosensitive polyimide precursors have the advantage of enabling significant process reduction compared to conventional non-photosensitive polyimide resins.

[0003] On the other hand, as a method of imidization in the production of polyimide, there is chemical imidization in addition to thermal imidization. In chemical imidization, a carboxylic acid anhydride such as acetic anhydride is used as the acid anhydride (see, for example, Patent Document 1).

[0004] A photosensitive resin composition for forming an insulating film has been proposed, which contains at least one polymer selected from polyimide, polyamic acid, and polyamic acid ester, and a solvent, the polymer having a photopolymerizable group, an aromatic group, and an alkyl group having 5 or more carbon atoms (see Patent Document 2). In a specific example of this proposed technology (e.g., Synthesis Example 1), acetic anhydride and triethylamine are used as chemical imidizing agents when obtaining a polyimide from a polyamic acid. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 61-181833 [Patent Document 2] International Publication No. 2023 / 176259 Brochure Summary of the Invention [Problem to be solved by the invention]

[0006] In photolithography processes using photosensitive resin compositions, there is a demand for shortening the process time.

[0007] In view of the above circumstances, an object of the present invention is to provide a method for producing a polyimide capable of producing a polyimide capable of shortening the development time, a photosensitive resin composition capable of shortening the development time, an insulating film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate having a cured relief pattern, and a semiconductor device having a cured relief pattern. [Means for solving the problem]

[0008] As a result of extensive research aimed at achieving the above object, the present inventors have discovered that the use of a specific acid anhydride for chemical imidization in the production of polyimide makes it possible to shorten the development time in a photolithography process using a photosensitive resin composition, and have thus completed the present invention.

[0009] [1] A method for producing a polyimide by chemically imidizing a polyimide precursor having an amino group at its terminal in the presence of an acid anhydride and a base catalyst, comprising: The polyimide precursor has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), The acid anhydride is a compound represented by the following formula (A): Polyimide manufacturing method. [ka] (In formula (1), A1 represents a tetravalent organic group. In formula (2), A2 represents a divalent aromatic group having a photopolymerizable group. [ka] (In formula (A), each R1 represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent.) [2] The method for producing a polyimide according to [1], wherein the polyimide precursor is a reaction product of at least one tetracarboxylic dianhydride and at least one diamine component, and 90 mol % to 99 mol % of the tetracarboxylic dianhydride is used relative to 100 mol % of the diamine component. [3] The method for producing a polyimide according to [1] or [2], wherein the structural unit represented by the formula (2) is a structural unit represented by the following formula (2a): [ka] (In formula (2a), V1 represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond; W1 represents an oxygen atom or an NH group; R2 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxy group; and R3 represents a hydrogen atom or a methyl group.) [4] The method for producing a polyimide according to [3], wherein in the formula (2a), V1 represents an ester bond and W1 represents an oxygen atom. [5] The method for producing a polyimide according to [3] or [4], wherein in the formula (2a), R2 represents a 1,2-ethylene group. [6] The method for producing a polyimide according to any one of [1] to [5], wherein the polyimide has a terminal structure represented by the following formula (A1): [ka] (In formula (A1), R1 has the same definition as in formula (A), and * represents a bond.) [7] The method for producing a polyimide according to any one of [1] to [6], wherein the base catalyst comprises at least one selected from the group consisting of triethylamine, 4-dimethylaminopyridine, diazabicycloundecene, 2,6-lutidine, diisopropylethylamine, diisopropylamine, diisobutylamine, 2-picoline, imidazole, 1,8-diaminonaphthalene, 1,4-diazabicyclo[2.2.2]octane, pyrimidine, pyridazine, pyrazine, and guanidine compounds. [8] A photosensitive resin composition comprising a polyimide having a structural unit represented by the following formula (11), a structural unit represented by the following formula (2), and a terminal structure represented by the following formula (A1), a crosslinkable compound, a photoradical polymerization initiator, and a solvent. [ka] (In formula (11), A1 represents a tetravalent organic group. In formula (2), A2 represents a divalent aromatic group having a photopolymerizable group. In formula (A1), R1 represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent, and * represents a bond. [9] The photosensitive resin composition according to [8], wherein the structural unit represented by the formula (2) is a structural unit represented by the following formula (2a): [ka] (In formula (2a), V1 represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond; W1 represents an oxygen atom or an NH group; R2 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxy group; and R3 represents a hydrogen atom or a methyl group.)

[10] The photosensitive resin composition according to [9], wherein in the formula (2a), V1 represents an ester bond and W1 represents an oxygen atom.

[11] The photosensitive resin composition according to [9] or

[10] , wherein in the formula (2a), R2 represents a 1,2-ethylene group.

[12] The photosensitive resin composition according to any one of [8] to

[11] , further comprising an adhesion promoter.

[13] The photosensitive resin composition according to any one of [8] to

[12] , further comprising an azole compound.

[14] An insulating film which is a fired product of a coating film of the photosensitive resin composition according to any one of [8] to

[13] .

[15] A photosensitive resist film comprising a substrate film, a photosensitive resin layer formed from the photosensitive resin composition according to any one of [8] to

[13] , and a cover film.

[16] (1) A step of applying the photosensitive resin composition according to any one of [8] to

[13] onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; A method for producing a substrate with a cured relief pattern, comprising:

[17] The method for producing a substrate having a cured relief pattern according to

[16] , wherein the developer used for the development is an organic solvent.

[18] A substrate having a cured relief pattern produced by the method according to

[16] or

[17] .

[19] A semiconductor device comprising a semiconductor element and a cured film provided on the upper or lower part of the semiconductor element, wherein the cured film is a cured relief pattern formed from the photosensitive resin composition according to any one of [8] to

[13] . [Effects of the Invention]

[0010] According to the present invention, there are provided a method for producing a polyimide capable of producing a polyimide capable of shortening the development time, a photosensitive resin composition capable of shortening the development time, an insulating film obtained from the composition, a photosensitive resist film using the composition, a method for producing a substrate having a cured relief pattern, and a semiconductor device having a cured relief pattern. DETAILED DESCRIPTION OF THE INVENTION

[0011] (Polyimide manufacturing method) The method for producing a polyimide of the present invention is a method for producing a polyimide by chemically imidizing a polyimide precursor having an amino group at its terminal in the presence of an acid anhydride and a base catalyst. The polyimide precursor has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). The acid anhydride is a compound represented by the following formula (A). [ka] (In formula (1), A1 represents a tetravalent organic group. In formula (2), A2 represents a divalent aromatic group having a photopolymerizable group. [ka] (In formula (A), each R1 represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent.)

[0012] When a polyimide is produced by chemically imidizing a polyimide precursor having an amino group at its terminal in the presence of an acid anhydride, by using a compound represented by formula (A) as the acid anhydride, the development time in a photolithography process using a photosensitive resin composition containing the resulting polyimide can be shortened compared to when acetic anhydride is used as the acid anhydride. The inventors believe that the reason why the development time can be shortened is as follows. When a polyimide precursor having an amino group at its terminal is chemically imidized in the presence of an acid anhydride to produce a polyimide, a terminal structure having an amide group derived from the acid anhydride is introduced into the resulting polyimide. When acetic anhydride is used as the acid anhydride, the terminal structure of the resulting polyimide becomes a CH3-CO-NH- structure (corresponding to the terminal structure represented by formula (A1) below, where R1 is a methyl group). This structure is an amide group with little steric hindrance and readily forms hydrogen bonds with the imide groups in the polyimide, reducing the solubility of the polyimide in a developer. On the other hand, when a compound represented by formula (A) is used as the acid anhydride, the terminal structure of the resulting polyimide becomes a terminal structure represented by formula (A1) below. This structure has greater steric hindrance than the CH3-CO-NH- structure, and hydrogen bonding between this structure and the imide groups in the polyimide is weaker. This increases the solubility of the polyimide in a developer. As a result, the development time in the photolithography process is shortened. [ka] (In formula (A1), R1 has the same definition as in formula (A), and * represents a bond.)

[0013] Furthermore, by shortening the development time, the amount of developer consumed can be reduced. Furthermore, the mechanical properties, thermal properties and electrical properties of the film obtained from the photosensitive resin composition are not inferior to those obtained when acetic anhydride is used. In addition, the improved developability allows the introduction of a rigid structure into the polyimide structure, which has poor developability but is expected to improve mechanical and thermal properties.

[0014] <Acid anhydride> The acid anhydride is a compound represented by the following formula (A). [ka] (In formula (A), each R1 represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent.)

[0015] The hydrocarbon group of R1 may or may not have a carbon-carbon multiple bond, such as a carbon-carbon double bond or a carbon-carbon triple bond. The hydrocarbon group of R1 may be an aliphatic group, an aromatic group, or a combination thereof. The aliphatic group may be a saturated aliphatic group (an alkyl group) or an unsaturated aliphatic group. The hydrocarbon group of R1 may be linear, branched, or cyclic, or may be a combination of two or more of these.

[0016] Examples of the substituent that R1 may have include a halogen atom and an alkoxy group. Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When R1 has a substituent, the number of the substituent may be one or two or more. The "2 to 22 carbon atoms" in the "hydrocarbon group having 2 to 22 carbon atoms which may have a substituent" refers to the number of carbon atoms in the hydrocarbon group, and does not include the number of carbon atoms in the substituent.

[0017] The two R1s in formula (A) may be the same or different, but are preferably the same.

[0018] The acid anhydride used in the chemical imidization may be one type or two or more types.

[0019] Examples of the compound represented by formula (A) include the following compounds. [ka] [ka] [ka]

[0020] <Base catalyst> The base catalyst may, for example, be a nitrogen-containing compound. When the base catalyst is a nitrogen-containing compound, the base catalyst may have one, two, three, or four or more nitrogen atoms, preferably one to three. When the base catalyst is a nitrogen-containing compound, the base catalyst may or may not have heteroatoms other than nitrogen atoms. For example, the base catalyst may be composed only of carbon atoms, nitrogen atoms, and hydrogen atoms. The number of carbon atoms in the base catalyst is not particularly limited, but may be, for example, 3 to 25. The molecular weight of the base catalyst is not particularly limited, but may be, for example, 59 to 200. The base catalyst used in the chemical imidization may be one type or two or more types.

[0021] Examples of the base catalyst include dialkylamines, trialkylamines, imidazole compounds, pyridine compounds, pyrimidine compounds, pyridazine compounds, pyrazine compounds, guanidine compounds, non-aromatic nitrogen-containing cyclic compounds, and nitrogen-containing compounds having an aromatic hydrocarbon ring. Examples of dialkylamines include diisopropylamine and diisobutylamine. Examples of trialkylamines include trimethylamine, triethylamine, diisopropylethylamine, tributylamine, and trioctylamine. The imidazole compound is a compound having an imidazole ring, and examples of the imidazole compound include imidazole. The pyridine compound is a compound having a pyridine ring, and examples of the pyridine compound include pyridine, 2-picoline, 2,6-lutidine, and 4-dimethylaminopyridine. The pyrimidine compound is a compound having a pyrimidine ring. Examples of the pyrimidine compound include pyrimidine. The pyridazine compound is a compound having a pyridazine ring, and examples of the pyridazine compound include pyridazine. The pyrazine compound is a compound having a pyrazine ring, and examples of the pyrazine compound include pyrazine. The guanidine compound is guanidine or a guanidine derivative. The guanidine derivative is a compound in which a hydrogen atom of guanidine is substituted. Examples of the guanidine derivative include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and toluylguanidine. Examples of non-aromatic nitrogen-containing cyclic compounds include diazabicycloundecene (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1,4-diazabicyclo[2.2.2]octane (DABCO). An example of the nitrogen-containing compound having an aromatic hydrocarbon ring is 1,8-diaminonaphthalene.

[0022] The chemical imidization can be carried out, for example, by adding the compound represented by formula (A) and a base catalyst to a solution of a polyimide precursor and stirring the mixture at -20°C to 250°C, preferably 0°C to 180°C. The amount of the compound represented by formula (A) is, for example, 1 to 50 times by mole, and preferably 1.5 to 30 times by mole the amount of the amic acid groups in the polyimide precursor. The amount of the base catalyst is 0.1 to 30 times by mole, preferably 0.2 to 20 times by mole, the amount of the amic acid groups in the polyimide precursor. The imidization rate (the ratio of ring-closed repeating units to all repeating units in the polyimide precursor, also called the ring-closure rate) in chemical imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0023] When recovering the imidized product produced from the imidization reaction solution, the reaction solution may be poured into a solvent to cause precipitation. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by pouring into the solvent can be recovered by filtration and then dried at room temperature or by heating under normal or reduced pressure.

[0024] <Polyimide precursor> The polyimide precursor has an amino group at the end. The polyimide precursor has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). [ka] (In formula (1), A1 represents a tetravalent organic group. In formula (2), A2 represents a divalent aromatic group having a photopolymerizable group.

[0025] The polyimide precursor may further have at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). [ka] (In formula (3), A 11 represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms. In formula (4), A 12 is A2 in formula (2) and A in formula (3) 11 represents a divalent organic group other than A in equation (3) 11 is a group different from A2 in formula (2).

[0026] <<A1 in formula (1)>> The tetravalent organic group of A1 is not particularly limited, but is preferably a tetravalent organic group having two or more aromatic rings, since this reduces the dielectric loss tangent of the insulating film.

[0027] The number of aromatic rings contained in the tetravalent organic group having two or more aromatic rings is not particularly limited as long as it is two or more, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, eight or less, or six or less.

[0028] Regarding the counting of aromatic rings in "two or more aromatic rings," polycyclic aromatic rings formed by the fusion of two or more aromatic rings, such as naphthalene rings and anthracene rings, are counted as one aromatic ring. Therefore, a naphthalene ring is counted as one aromatic ring. On the other hand, a biphenyl ring is counted as two aromatic rings because it is not a fused ring. And a perylene ring is considered to be a structure formed by the fusion of two naphthalene rings, and is counted as two aromatic rings. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.

[0029] A1 preferably represents a tetravalent organic group represented by the following formula (1-1). [ka] [In formula (1-1), X1 and X2 each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO2-). R a1 and R a2 each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms. Z1 represents a divalent organic group represented by the following formula (5-a), (5-b), (5-c), or (5-d). n1 and n2 each independently represent an integer of 0 to 3. R a1 If there are multiple, multiple R a1 may be the same or different. a2 If there are multiple, multiple R a2may be the same or different. * represents a bond.]

[0030] R in formula (1-1) a1 and R a2 In the above, examples of the optionally substituted alkyl group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. In this specification, unless otherwise specified, the alkyl group and alkylene group may be linear, branched, or cyclic, or may be a combination of two or more of these. Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and an alkoxy group having 1 to 6 carbon atoms. The "carbon atom number of 1 to 6" in the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding the substituent. The number of substituents is not particularly limited.

[0031] [ka] [In formula (5-a), R3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m1 represents an integer of 0 to 4. When m1 is 2 or greater, R3 may be the same or different. In formula (5-b), Z2 represents a direct bond or a divalent organic group represented by the following formula (6-a) or (6-b), R4 and R5 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m2 and m3 each independently represent an integer of 0 to 4. When m2 is 2 or greater, R4s may be the same or different. When m3 is 2 or greater, R5s may be the same or different. In formula (5-c), R6 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and m4 represents an integer of 0 to 6. When m4 is 2 or greater, R6 may be the same or different. In formula (5-d), Z3 represents a direct bond or a divalent organic group represented by the following formula (6-a) or (6-b). * represents a bond.]

[0032] [ka] [In formula (6-a), R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.] In formula (6-b), R9 and R 10 each independently represents an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylene group having 6 to 12 carbon atoms. * represents a bond.]

[0033] Z1 preferably represents a divalent organic group represented by formula (5-b). In formula (5-b), Z2 preferably represents a direct bond. In formula (5-b), R4 and R5 preferably represent a methyl group.

[0034] Examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom in R7 and R8 include an alkyl group having 1 to 6 carbon atoms and a halogenated alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenation in the halogenated alkyl group having 1 to 6 carbon atoms may be partial or complete.

[0035] R9 and R 10 Examples of the substituent in the optionally substituted alkylene group having 1 to 6 carbon atoms in the formula (I) include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the optionally substituted alkylene group having 1 to 6 carbon atoms include an alkylene group having 1 to 6 carbon atoms and a halogenated alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. The "carbon atom number of 1 to 6" in the "optionally substituted alkylene group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkylene group" excluding the substituents. The number of substituents is not particularly limited.

[0036] R9 and R 10 Examples of the substituent in the optionally substituted arylene group having 6 to 10 carbon atoms in the formula (I) include a halogen atom, an optionally halogenated alkyl group having 1 to 6 carbon atoms, and an optionally halogenated alkoxy group having 1 to 6 carbon atoms. The halogenation may be partial or complete. Examples of the arylene group include a phenylene group and a naphthylene group. The "6 to 10 carbon atoms" in the "optionally substituted arylene group having 6 to 10 carbon atoms" refers to the number of carbon atoms in the "arylene group" excluding the substituents. The number of substituents is not particularly limited.

[0037] Examples of the divalent organic group represented by formula (6-a) include divalent organic groups represented by the following formulas: [ka] In the formula, * represents a bond.

[0038] Examples of the divalent organic group represented by formula (6-b) include divalent organic groups represented by the following formulas: [ka] In the formula, R 31 ~R 33 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom. n31 represents an integer of 0 to 5. n32 and n33 each independently represent an integer of 0 to 4. R 31 If there are multiple, multiple R 31 may be the same or different. 32 If there are multiple, multiple R 32 may be the same or different. 33 If there are multiple, multiple R 33 may be the same or different. * represents a bond.

[0039] R 31 ~R 33 Specific examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom include alkyl groups having 1 to 6 carbon atoms and halogenated alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the halogen atom in the halogenated alkyl group having 1 to 6 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely halogenated. R 31 ~R 33 Specific examples of the alkoxy group having 1 to 6 carbon atoms which may be substituted with a halogen atom include an alkoxy group formed from an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom.

[0040] Examples of the tetravalent organic group having two or more aromatic rings include tetravalent organic groups represented by the following formula: [ka] [ka] In the formula, * represents a bond.

[0041] Examples of A1 in formula (1) other than the tetravalent organic group having two or more aromatic rings include the following tetravalent organic groups. [ka] [ka] In the formula, * represents a bond.

[0042] <<A2 in formula (2)>> A2 represents a divalent aromatic group having a photopolymerizable group. Examples of the photopolymerizable group include a radically polymerizable group, a cationically polymerizable group, and an anionically polymerizable group. Of these, the radically polymerizable group is preferred. Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a propenyl ether group, a vinyl ether group, and a vinyl group.

[0043] Examples of the aromatic ring in the divalent aromatic group having a photopolymerizable group include a benzene ring, a naphthalene ring, and an anthracene ring.

[0044] The divalent aromatic group having a photopolymerizable group is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having a photopolymerizable group.

[0045] The structural unit represented by formula (2) is preferably a structural unit represented by the following formula (2a). [ka] (In formula (2a), V1 represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), or a urea bond (-NHCONH-), W1 represents an oxygen atom or an NH group, R2 represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxy group, and R3 represents a hydrogen atom or a methyl group.)

[0046] In this specification, examples of the alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxy group include a 1,1-ethylene group, a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,4-butylene group, a 1,2-butylene group, a 2,3-butylene group, a 1,2-pentylene group, a 2,4-pentylene group, a 1,2-hexylene group, a 1,2-cyclopropylene group, a 1,2-cyclobutylene group, a 1,3-cyclobutylene group, a 1,2-cyclopentylene group, a 1,2-cyclohexylene group, and alkylene groups in which at least a portion of the hydrogen atoms have been substituted with a hydroxy group (for example, a 2-hydroxy-1,3-propylene group).

[0047] V1 preferably represents an ester bond (-COO-). Preferably, W1 represents an oxygen atom. Preferably, R2 represents a 1,2-ethylene group.

[0048] Examples of A2 in formula (2) include divalent organic groups represented by the following formulas. [ka] In the formula, * represents a bond, and the two bonds are, for example, located at meta positions relative to the substituent having the photopolymerizable group.

[0049] <<A in formula (3) 11 >> A 11 represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms. The alkyl group having 5 or more carbon atoms may be directly bonded to the aromatic ring of the divalent aromatic group, or may be bonded via another linking group. The number of carbon atoms in the alkyl group is not particularly limited as long as it is 5 or more, and may be, for example, 40 or less, 35 or less, or 30 or less. The alkyl group preferably has 8 or more and 40 or less carbon atoms, more preferably 10 or more and 35 or less carbon atoms, and particularly preferably 12 or more and 30 or less carbon atoms. The alkyl group may be linear, branched, or cyclic, or may be a combination of two or more of these.

[0050] A divalent aromatic group having an alkyl group with 5 or more carbon atoms is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having an alkyl group with 5 or more carbon atoms.

[0051] A 11 is preferably a divalent aromatic group represented by any one of formulas (V-1) to (V-6). [ka] (In formula (V-1), X v1 represents -O-, -CH2-O-, -CH2-OCO-, -COO-, or -OCO-. v1 represents an alkyl group having 5 to 20 carbon atoms. In formulas (V-2) to (V-5), X v2 ~Xv5 are each independently -(CH2) a R represents - (where a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2-O-, -CH2-OCO-, -COO-, or -OCO-. v2 ~R v5 each independently represents an alkyl group having 5 to 20 carbon atoms. In formula (V-6), X a represents a single bond, -O-, -NH-, -O-(CH2) m -O- (m represents an integer of 1 to 6), -C(CH3)2-, -CO-, -(CH2) m - (m represents an integer of 1 to 6), -SO2-, -OC(CH3)2-, -CO-(CH2) m - (m represents an integer of 1 to 6), -NH-(CH2) m - (m represents an integer of 1 to 6), -SO2-(CH2) m -(m represents an integer of 1 to 6), -CONH-(CH2) m -(m represents an integer of 1 to 6), -CONH-(CH2) m -NHCO- (m represents an integer of 1 to 6), -COO-(CH2) m -OCO- (m represents an integer of 1 to 6), -CONH-, -NH-(CH2) m -NH- (m represents an integer of 1 to 6), or -SO2-(CH2) m -SO2- (where m represents an integer of 1 to 6). X p1 and X p2 are each independently -(CH2) a R represents - (where a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2-O-, -CH2-OCO-, -COO-, or -OCO-. 1a and R 1b each independently represents an alkyl group having 5 to 20 carbon atoms. k1 and k2 each independently represents an integer of 0 to 2. In formulas (V-1) to (V-6), * represents a bond.

[0052] X v1~X v5 is preferably —O—. X p1 and X p2 is preferably —CH2—O—. X a It is preferable that represents a single bond.

[0053] A 11 Examples of the divalent aromatic group include the following: [ka] * represents a bond.

[0054] <<A in Equation (4) 12 >> A 12 As for A2 in formula (2) and A in formula (3), 11 represents a divalent organic group other than As such a divalent organic group, for example, a divalent organic group having three or more aromatic rings is preferable because it can provide a lower dielectric tangent in the resulting insulating film. The divalent organic group having three or more aromatic rings is, for example, a residue obtained by removing two amino groups from an aromatic diamine compound having three or more aromatic rings.

[0055] The number of aromatic rings in a divalent organic group having three or more aromatic rings is not particularly limited as long as it is three or more, and may be, for example, four or more. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, eight or less, or six or less.

[0056] The divalent organic group having three or more aromatic rings is not particularly limited, but is preferably a divalent organic group represented by the following formula (4-1). [ka] [In formula (4-1), X 21 and X 22each independently represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond (-NHCOO-), a urea bond (-NHCONH-), a thioether bond (-S-), or a sulfonyl bond (-SO2-). R 21 and R 22 each independently represents an optionally substituted alkyl group having 1 to 6 carbon atoms. Y 20 represents a divalent organic group represented by the above formula (5-a), (5-b) or (5-c). n21 and n22 each independently represent an integer of 0 to 4. R 21 If there are multiple, multiple R 21 may be the same or different. 22 If there are multiple, multiple R 22 may be the same or different. * represents a bond.]

[0057] R in formula (4-1) 21 and R 22 In the above, examples of the optionally substituted alkyl group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. In this specification, unless otherwise specified, the alkyl group and alkylene group may be linear, branched, or cyclic, or may be a combination of two or more of these. Examples of the substituent in the optionally substituted alkyl group having 1 to 6 carbon atoms include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and an alkoxy group having 1 to 6 carbon atoms. The "carbon atom number of 1 to 6" in the "optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms in the "alkyl group" excluding the substituent. The number of substituents is not particularly limited.

[0058] Examples of the divalent organic group having three or more aromatic rings include divalent organic groups represented by the following formulas: [ka] [ka] In the formula, * represents a bond.

[0059] A 12 Examples of other divalent organic groups include divalent organic groups represented by the following formulas: These divalent organic groups are, for example, residues obtained by removing two amino groups from a diamine. [ka] In the formula, * represents a bond.

[0060] The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to all the tetracarboxylic acid derivatives constituting the polyimide precursor is not particularly limited, but is preferably 20 mol % to 100 mol %, more preferably 40 mol % to 100 mol %.

[0061] The ratio of the aromatic diamine compound having a photopolymerizable group to all diamine components constituting the polyimide precursor is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 mol % to 90 mol %, more preferably 15 mol % to 85 mol %, and particularly preferably 20 mol % to 80 mol %.

[0062] The proportion of the aromatic diamine compound having an alkyl group having 5 or more carbon atoms relative to all diamine components constituting the polyimide precursor is not particularly limited, but is preferably 5 mol % to 80 mol %, more preferably 10 mol % to 70 mol %, and particularly preferably 15 mol % to 65 mol %.

[0063] In the polyimide precursor, the molar ratio (A:B) of the aromatic diamine compound (A) having a photopolymerizable group to the aromatic diamine compound (B) having an alkyl group having 5 or more carbon atoms is not particularly limited, but is preferably 3:1 to 0.3:1, more preferably 2:1 to 0.5:1, and particularly preferably 1.5:1 to 0.5:1.

[0064] The total molar ratio of the aromatic diamine compound having a photopolymerizable group and the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to all diamine components constituting the polyimide precursor is not particularly limited, but is preferably 30 mol% or more, more preferably 40 mol% or more, and particularly preferably 50 mol% or more. The upper limit of the total molar ratio is not particularly limited, but the total molar ratio may be 100 mol% or less, or may be 90 mol% or less.

[0065] The polyimide precursor is, for example, a reaction product of at least one tetracarboxylic dianhydride and at least one diamine component. During the reaction, it is preferable to use 90 to 99 mol% of the tetracarboxylic dianhydride relative to 100 mol% of the diamine component. By doing so, amino groups can be introduced into the terminals.

[0066] <<Method of manufacturing polyimide precursor>> The method for producing the polyimide precursor is not particularly limited, and the polyimide precursor can be synthesized by a known method such as that described in WO2013 / 157586.

[0067] The polyimide precursor is produced, for example, by reacting a diamine component with a tetracarboxylic acid derivative in a solvent (condensation polymerization). Here, examples of the tetracarboxylic acid derivative include tetracarboxylic acid, tetracarboxylic acid diester, tetracarboxylic acid dihalide, and tetracarboxylic acid dianhydride.

[0068] To produce a polyamide precursor having an amino group at its terminal, it is preferable that the diamine component is in excess of the tetracarboxylic acid derivative during the reaction. In this respect, the molar ratio of the tetracarboxylic acid derivative to the diamine component during the reaction is preferably 90 mol% to 99 mol%, more preferably 95 mol% to 99 mol%.

[0069] The structural unit represented by formula (1) in the polyimide precursor is derived from, for example, an acid dianhydride represented by the following formula (1A). The structural unit represented by formula (2) in the polyimide precursor is derived from, for example, a diamine represented by the following formula (2A). The structural unit represented by formula (3) in the polyimide precursor is derived from, for example, a diamine represented by the following formula (3A). The structural unit represented by formula (4) in the polyimide precursor is derived from, for example, a diamine represented by the following formula (4A). [ka] (In formula (1A), A1 has the same meaning as A1 in formula (1). In formula (2A), A2 has the same meaning as A2 in formula (2). In formula (3A), A 11 is A in equation (3) 11 is synonymous with. In formula (4A), A 12 is A in equation (4). 12 is equivalent to

[0070] Specific examples of the solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas [D-1] to [D-3] can be used. [ka] (In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms.

[0071] These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the polyimide precursor, it may be mixed with the above-mentioned solvent to the extent that the polyimide precursor does not precipitate.

[0072] When the diamine component and the tetracarboxylic acid derivative are reacted in a solvent, the reaction can be carried out at any concentration, preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The reaction can be carried out at a high concentration in the early stages, and then additional solvent can be added.

[0073] When the diamine component and the tetracarboxylic acid derivative are reacted, a thermal polymerization inhibitor may be added to the reaction system to prevent polymerization of the photopolymerizable group. Examples of the thermal polymerization inhibitor include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt. The amount of the thermal polymerization inhibitor used is not particularly limited.

[0074] <Polyimide> The polyimide obtained by the polyimide production method of the present invention preferably has a terminal structure represented by the following formula (A1). [ka] (In formula (A1), R1 has the same definition as in formula (A), and * represents a bond.)

[0075] The imidization rate of the polyimide does not need to be 100% and may be, for example, 90% or more, 95% or more, or 98% or more.

[0076] The weight-average molecular weight of the polyimide is not particularly limited, but the weight-average molecular weight measured in terms of polyethylene oxide by gel permeation chromatography (hereinafter abbreviated as GPC in this specification) is preferably 5,000 to 100,000, more preferably 7,000 to 50,000, still more preferably 10,000 to 50,000, and particularly preferably 10,000 to 40,000.

[0077] (Photosensitive resin composition) The photosensitive resin composition of the present invention contains at least a polyimide, a crosslinkable compound, a photoradical polymerization initiator, and a solvent, and may further contain other components as required.

[0078] The polyimide has a structural unit represented by the following formula (11), a structural unit represented by the following formula (2), and a terminal structure represented by the following formula (A1). Hereinafter, this polyimide may be referred to as a "specific polyimide." [ka] (In formula (11), A1 represents a tetravalent organic group. In formula (2), A2 represents a divalent aromatic group having a photopolymerizable group. In formula (A1), R1 represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent, and * represents a bond.

[0079] Specific and preferred examples of A1 in formula (11) include the specific and preferred examples of A1 in formula (1) in the description of the method for producing polyimide. Specific and preferred examples of A2 in formula (2) include the specific and preferred examples of A2 in formula (2) described in the description of the method for producing polyimide. Specific and preferred examples of R1 in formula (A1) include the specific and preferred examples of R1 in formula (A) in the explanation of the method for producing polyimide.

[0080] The specific polyimide may further have at least one of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). [ka] (In formula (3), A 11 represents a divalent aromatic group having an alkyl group having 5 or more carbon atoms. In formula (4), A 12 is A2 in formula (2) and A in formula (3) 11 represents a divalent organic group other than A in equation (3) 11is a group different from A2 in formula (2).

[0081] A in equation (3) 11 Specific and preferred examples of the compound are A in formula (3) in the description of the method for producing polyimide. 11 Specific and preferred examples include: A in equation (4) 12 Specific and preferred examples of the compound A in formula (4) in the description of the method for producing polyimide include: 12 Specific and preferred examples include:

[0082] The specific polyimide is preferably obtained by the polyimide production method of the present invention.

[0083] The ratio of the aromatic tetracarboxylic acid derivative having two or more aromatic rings to all the tetracarboxylic acid derivatives constituting the specific polyimide is not particularly limited, but is preferably 20 mol % to 100 mol %, more preferably 40 mol % to 100 mol %.

[0084] The ratio of the aromatic diamine compound having a photopolymerizable group to all diamine components constituting the specific polyimide is not particularly limited, but from the viewpoint of obtaining sufficient photosensitivity, it is preferably 10 mol % to 90 mol %, more preferably 15 mol % to 85 mol %, and particularly preferably 20 mol % to 80 mol %.

[0085] The proportion of the aromatic diamine compound having an alkyl group having 5 or more carbon atoms relative to all diamine components constituting the specific polyimide is not particularly limited, but is preferably 5 mol % to 80 mol %, more preferably 10 mol % to 70 mol %, and particularly preferably 15 mol % to 65 mol %.

[0086] In the specific polyimide, the molar ratio (A:B) of the aromatic diamine compound (A) having a photopolymerizable group to the aromatic diamine compound (B) having an alkyl group having 5 or more carbon atoms is not particularly limited, but is preferably 3:1 to 0.3:1, more preferably 2:1 to 0.5:1, and particularly preferably 1.5:1 to 0.5:1.

[0087] The total molar ratio of the aromatic diamine compound having a photopolymerizable group and the aromatic diamine compound having an alkyl group having 5 or more carbon atoms to all diamine components constituting the specific polyimide is not particularly limited, but is preferably 30 mol% or more, more preferably 40 mol% or more, and particularly preferably 50 mol% or more. The upper limit of the total molar ratio is not particularly limited, but the total molar ratio may be 100 mol% or less, or may be 90 mol% or less.

[0088] The imidization rate of a specific polyimide does not need to be 100%. The imidization rate of a polyimide may be, for example, 90% or more, 95% or more, or 98% or more.

[0089] The weight-average molecular weight of the specific polyimide is not particularly limited, but the weight-average molecular weight measured in terms of polyethylene oxide by gel permeation chromatography (hereinafter abbreviated as GPC in this specification) is preferably 5,000 to 100,000, more preferably 7,000 to 50,000, still more preferably 10,000 to 50,000, and particularly preferably 10,000 to 40,000.

[0090] The content of the specific polyimide in the photosensitive resin composition is not particularly limited, but is preferably 50 to 99 parts by mass, more preferably 55 to 95 parts by mass, and particularly preferably 60 to 90 parts by mass, per 100 parts by mass of the film-constituting components. The film-constituting components refer to components other than the solvent in the photosensitive resin composition.

[0091] <Crosslinkable compound> In order to improve the resolution of the relief pattern, a monomer having a photoradical polymerizable unsaturated bond (a crosslinkable compound (also called a "crosslinking agent")) is contained in the photosensitive resin composition. Such a crosslinkable compound is preferably a compound containing a polymerizable group that undergoes a radical polymerization reaction in the presence of a photoradical polymerization initiator, and examples thereof include (meth)acrylic compounds and maleimide compounds, but are not particularly limited to the following. Examples of the (meth)acrylic compound include diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene glycol or polyethylene glycol mono- or di(meth)acrylate, propylene glycol or polypropylene glycol mono- or di(meth)acrylate, glycerol mono-, di-, or tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, cyclohexane di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dioxane glycol di(meth)acrylate, bisphenol A mono- or di(meth)acrylate, bisphenol F di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, (meth)acrylate, benzene trimethacrylate, di(meth)acrylate of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, isobornyl (meth)acrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri(meth)acrylate, di- or tri(meth)acrylate of glycerol, di-, tri-, or tetra(meth)acrylate of pentaerythritol Examples of such compounds include (meth)acrylates, and ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (meth)acrylates, and compounds obtained by adding a blocking agent such as methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, or 1-methoxy-2-propanol to these compounds.Examples of maleimide compounds include 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, 1,6-bis(maleimido)hexane, N,N'-1,4-phenylenebismaleimide, N,N'-1,3-phenylenedimaleimide, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(2-maleimidoethyl)disulfide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 1,6'-bismaleimido-(2,2,4-trimethyl)hexane. Commercially available maleimide compounds include BMI-689, BMI-1500, BMI-1700, and BMI-3000 (all manufactured by Designer Molecules Inc.). These compounds may be used alone or in combination of two or more. In this specification, (meth)acrylate means acrylate and methacrylate.

[0092] The content of the crosslinkable compound is not particularly limited, but is preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, relative to 100 parts by mass of the specific polyimide.

[0093] <Photoradical polymerization initiator> The photoradical polymerization initiator (also referred to as "photoradical initiator") is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. Examples thereof include tert-butylperoxy-iso-butylate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert organic peroxides such as 3,3'-bis(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, and di-tert-butyldiperoxyisophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin;2,2-Dimethoxy-1,2-diphenylethan-1-one, 1-Hydroxycyclohexyl phenyl 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, Phenylglyoxylic acid methyl ester, 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl) Examples of suitable compounds include alkylphenone compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and oxime ester compounds such as 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone. Oxime ester compounds are particularly preferred from the viewpoint of i-ray curability.

[0094] The photoradical polymerization initiator is commercially available, and examples thereof include IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, OXE03, OXE04, 250, 1173, MBF, TPO, 4265, and TPO (all manufactured by BASF), KAYACURE [registered trademark] DETX-S, MBP, DMBI, EPA, and OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, and 55 (all manufactured by STAUFFER Co., Ltd.), and ESACURE Examples include KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, and Triazine B (all manufactured by Nippon SiberHegner Co., Ltd.), ADEKA OPTOMER N-1717, N-1414, and N-1606, ADEKA ARCLES (registered trademark) N-1919T, NCI-831E, NCI-930, and NCI-730 (all manufactured by ADEKA Corporation). These photoradical polymerization initiators may be used alone or in combination of two or more.

[0095] The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polyimide, and more preferably 0.5 to 15 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the photoradical polymerization initiator is 0.1 part by mass or more relative to 100 parts by mass of the specific polyimide, the photosensitivity of the photosensitive resin composition is likely to be improved, while when the content is 20 parts by mass or less, the thick-film curability of the photosensitive resin composition is likely to be improved.

[0096] <Solvent> As the solvent contained in the photosensitive resin composition, an organic solvent is preferably used from the viewpoint of the solubility of a specific polyimide. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylisobutyric acid amide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl 2-hydroxyisobutyrate, ethyl lactate, and solvents represented by the following formulas [D-1] to [D-3]. These may be used alone or in combination of two or more. [ka] (In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms.

[0097] The solvent can be used in an amount of, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass, per 100 parts by mass of the specific polyimide, depending on the desired coating film thickness and viscosity of the photosensitive resin composition.

[0098] <Other ingredients> In an embodiment, the photosensitive resin composition may further contain other components in addition to the specific polyimide, the photoradical initiator, the crosslinkable compound, and the solvent, such as a thermosetting agent, other resin components, a filler, a sensitizer, an adhesion promoter, a thermal polymerization inhibitor, an azole compound, and a hindered phenol compound.

[0099] <<Thermal hardener>> Examples of heat curing agents include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea. The content of the heat curing agent in the photosensitive resin composition is not particularly limited.

[0100] <<Filler>> Examples of the filler include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like. The content of the filler in the photosensitive resin composition is not particularly limited.

[0101] <<Other resin components>> In an embodiment, the photosensitive resin composition may further contain a resin component other than the specific polyimide. Examples of the resin component that can be contained in the photosensitive resin composition include polyimides other than the specific polyimide, polyoxazoles, polyoxazole precursors, phenolic resins, polyamides, epoxy resins, siloxane resins, and acrylic resins. The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the specific polyimide.

[0102] <<Sensitizer>> In embodiments, the photosensitive resin composition may optionally contain a sensitizer to improve photosensitivity. Examples of sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylideneindano. p-Dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone methyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These may be used alone or in combination.

[0103] The content of the sensitizer is not particularly limited, but is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the specific polyimide.

[0104] <<Adhesion aid>> In an embodiment, an adhesion promoter may be optionally incorporated into the photosensitive resin composition to improve adhesion between the film formed using the photosensitive resin composition and the substrate. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(meth)acryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]furan, Examples of suitable adhesives include silane coupling agents such as thalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane, and aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0105] Among these adhesion aids, it is more preferable to use a silane coupling agent in terms of adhesive strength.

[0106] The content of the adhesion aid is not particularly limited, but is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the specific polyimide.

[0107] <<Thermal polymerization inhibitor>> In an embodiment, a thermal polymerization inhibitor may be optionally blended to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition, particularly during storage in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor that can be used include hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

[0108] The content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 to 12 parts by mass relative to 100 parts by mass of the specific polyimide.

[0109] <<Azole compounds>> For example, when a substrate made of copper or a copper alloy is used, an azole compound can be optionally blended into the photosensitive resin composition to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, and 2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole. benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are 4-carboxy-1H-benzotriazole and 5-carboxy-1H-benzotriazole. These azole compounds may be used alone or in combination of two or more.

[0110] The content of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polyimide, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the azole compound relative to 100 parts by mass of the specific polyimide is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the photosensitive resin composition is formed on copper or a copper alloy, while when the content is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0111] <<Hindered phenol compounds>> In embodiments, a hindered phenol compound may optionally be incorporated into the photosensitive resin composition to inhibit discoloration on copper. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene Glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t -butylphenol), pentaerythrityl tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxybenzyl) 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3, 5-Tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxy-2 ,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc., but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione is particularly preferred.

[0112] The content of the hindered phenol compound is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the specific polyimide, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity. When the content of the hindered phenol compound relative to 100 parts by mass of the specific polyimide is 0.1 part by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the content is 20 parts by mass or less, excellent photosensitivity is achieved, which is preferable.

[0113] The photosensitive resin composition can be suitably used as a negative photosensitive resin composition for producing a cured relief pattern, which will be described later.

[0114] (insulating film) The insulating film of the present invention is a fired product of a coating film of the photosensitive resin composition of the present invention. As the application method, a method conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used. The firing method for obtaining the fired product can be selected from various methods, such as using a hot plate, an oven, or a temperature-programmable heating oven. Firing can be carried out, for example, at 130°C to 250°C for 30 minutes to 5 hours. The atmospheric gas used during heat curing may be air, or an inert gas such as nitrogen or argon. The thickness of the insulating film is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

[0115] (Photosensitive resist film) The photosensitive resin composition of the present invention can be used for a photosensitive resist film (so-called dry film resist). The photosensitive resist film comprises a base film, a photosensitive resin layer (photosensitive resin film) formed from the photosensitive resin composition of the present invention, and a cover film. Usually, a photosensitive resin layer and a cover film are laminated in this order on a substrate film.

[0116] The photosensitive resist film can be produced, for example, by applying a photosensitive resin composition onto a substrate film, drying it to form a photosensitive resin layer, and then laminating a cover film on the photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as a method of applying using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a method of spray application using a spray coater, can be used. The drying method may be, for example, at 20°C to 200°C for 1 minute to 1 hour. The thickness of the resulting photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

[0117] The substrate film may be a known film, such as a thermoplastic resin film. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 μm to 150 μm. The cover film may be a known film, such as a polyethylene film or a polypropylene film. The cover film is preferably a film having a lower adhesive strength with the photosensitive resin layer than the base film. The thickness of the cover film is preferably 2 μm to 150 μm, more preferably 2 μm to 100 μm, and particularly preferably 5 μm to 50 μm. The base film and the cover film may be made of the same film material, or different films may be used.

[0118] (Method for manufacturing a substrate having a cured relief pattern) The method for producing a substrate having a cured relief pattern of the present invention comprises the steps of: (1) a step of applying the photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer (photosensitive resin film) on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; Includes.

[0119] Each step will be described below. (1) A step of applying the photosensitive resin composition of the present invention onto a substrate to form a photosensitive resin layer on the substrate. In this step, the photosensitive resin composition according to the present invention is applied onto a substrate, and then dried as necessary to form a photosensitive resin layer. As the application method, a method conventionally used for applying a photosensitive resin composition, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or spray application using a spray coater, can be used.

[0120] If necessary, the coating film made of the photosensitive resin composition can be dried, and examples of the drying method include air drying, heat drying using an oven or a hot plate, vacuum drying, etc. Specifically, when air drying or heat drying is performed, drying can be carried out under conditions of 20°C to 200°C for 1 minute to 1 hour. In this way, a photosensitive resin layer can be formed on the substrate.

[0121] (2) A step of exposing the photosensitive resin layer to light In this process, the photosensitive resin layer formed in the above process (1) is exposed to an ultraviolet light source or the like using an exposure device such as a contact aligner, mirror projection, or stepper, either directly or through a photomask or reticle having a pattern. Examples of light sources used for exposure include g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure dose is 25 mJ / cm. 2~2000mJ / cm 2 is desirable.

[0122] Thereafter, post-exposure baking (PEB) and / or pre-development baking may be performed at any temperature and time combination as necessary for the purpose of improving photosensitivity, etc. The baking conditions are preferably in the range of a temperature of 50°C to 200°C and a time of 10 seconds to 600 seconds, but are not limited to these ranges as long as they do not impair the properties of the photosensitive resin composition.

[0123] (3) A step of developing the exposed photosensitive resin layer to form a relief pattern. In this step, the unexposed portions of the exposed photosensitive resin layer are developed and removed. The development method for developing the exposed (irradiated) photosensitive resin layer can be any method selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, and the immersion method accompanied by ultrasonic treatment. After development, rinsing may be performed to remove the developer. Furthermore, post-development baking may be performed at any temperature and time combination, as needed, for the purpose of adjusting the shape of the relief pattern, etc. The developer used for development is preferably an organic solvent. Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α-acetyl-γ-butyrolactone. Two or more types of each solvent can also be used, for example, in combination. The rinse solution used for rinsing is preferably an organic solvent that is miscible with the developer and has low solubility in the photosensitive resin composition. Examples of preferred rinse solutions include methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, toluene, and xylene. Two or more types of each solvent, for example, a combination of several types, can also be used.

[0124] (4) A step of heat-treating the relief pattern to form a hardened relief pattern. In this step, the relief pattern obtained by the development is heated to convert it into a cured relief pattern. Various methods can be selected for heat curing, such as using a hot plate, an oven, or a temperature-programmable heating oven. Heating can be performed, for example, at 130°C to 250°C for 30 minutes to 5 hours. The atmospheric gas used for heat curing may be air, or an inert gas such as nitrogen or argon.

[0125] The thickness of the cured relief pattern is not particularly limited, but is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.

[0126] (Semiconductor Devices) In an embodiment, a semiconductor device is provided that includes a semiconductor element and a cured film provided on or below the semiconductor element. The cured film is a cured relief pattern formed from the photosensitive resin composition of the present invention. The cured relief pattern can be obtained, for example, by steps (1) to (4) in the method for producing a substrate with a cured relief pattern described above. The present invention can also be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-mentioned method for manufacturing a substrate having a cured relief pattern as part of its steps. The semiconductor device of the present invention can be manufactured by forming a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for manufacturing a semiconductor device.

[0127] (Display device) In an embodiment, a display device is provided that includes a display element and a cured film provided on the display element, the cured film having the above-described cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer sandwiched therebetween. Examples of the cured film include surface protection films, insulating films, and planarizing films for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, protrusions for MVA (Multi-domain Vertical Alignment) liquid crystal display devices, and partition walls for cathodes of organic EL (Electro-Luminescence) elements.

[0128] The photosensitive resin composition of the present invention is useful not only for application to the semiconductor devices described above, but also for applications such as an interlayer insulating film for a multilayer circuit, a cover coat for a flexible copper-clad board, a solder resist film, and a liquid crystal alignment film. [Example]

[0129] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0130] The compounds shown in the following synthesis examples and comparative synthesis examples are as follows. TMPBP-TME: 2,2',3,3',5,5'-hexamethyl-[1,1'-biphenyl]-4,4'-diylbis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (Honshu Chemical Industry Co., Ltd.) [ka]

[0131] 6FDA: 4,4'-[perfluoro(propane-2,2-diyl)]diphthalic anhydride (manufactured by Daikin Industries, Ltd.) [ka]

[0132] BEM-S: 2-(methacryloyloxy)ethyl 3,5-diaminobenzoate [ka]

[0133] APC-18: 4-octadecyloxy-1,3-phenylenediamine [ka]

[0134] BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Wakayama Seika Kogyo Co., Ltd.) [ka]

[0135] mPDA: 1,3-phenylenediamine [ka]

[0136] The weight-average molecular weight (Mw) shown in the following synthesis examples in this specification is the result of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurement, a GPC device (HLC-8320GPC (manufactured by Tosoh Corporation)) was used, and the measurement conditions were as follows. Column: Shodex (registered trademark) KD-805 / Shodex (registered trademark) KD-803 (Resonac Co., Ltd.) Column temperature: 50℃ ·Flow rate: 1mL / min Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30 mM) / phosphoric acid (30 mM) / tetrahydrofuran (1%) Standard sample: Polyethylene oxide

[0137] The chemical imidization ratio shown in the synthesis examples below in this specification was calculated as follows. 100 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5 (Kusano Scientific Co., Ltd.)), and deuterated tetrahydrofuran (THF-d8, 0.05% TMS (tetramethylsilane) mixture) (0.53 ml) was added. Complete dissolution was achieved using ultrasound. This solution was measured by proton NMR at 500 MHz using an NMR spectrometer (JNM-ECA500) (JEOL Datum Co., Ltd.). The proton derived from the structure that remains unchanged before and after imidization was determined as the reference proton. The chemical imidization ratio was calculated using the integrated peak value of this proton and the integrated peak value of the proton derived from the NH group of the amic acid that appears around 9.5 ppm to 11.0 ppm according to the following formula: Chemical imidization rate (%) = (1 - α x / y) × 100 In the above formula, x is the integrated value of the proton peak derived from the NH group of the amide acid, y is the integrated value of the peak of the reference proton, and α is the ratio of the number of reference protons to one NH group proton of the amide acid in the case of polyamide acid (imidization rate 0%).

[0138] <Synthesis Example 1> Synthesis of polyamic acid (P-1) A four-neck flask was charged with 14.873 g (56.3 mmol) of BEM-S, 9.241 g (22.5 mmol) of BAPP, 12.717 g (33.8 mmol) of APC-18, 0.1397 g (1.13 mmol) of 4-methoxyphenol, and 334.8 g of N-ethyl-2-pyrrolidone. The mixture was stirred under air at room temperature to dissolve the mixture. Then, 46.648 g (75.4 mmol) of TMPBP-TME was added and stirred at room temperature until the mixture became clear. Then, 15 g (33.8 mmol) of 6FDA and 223.217 g of N-ethyl-2-pyrrolidone were added and stirred at 50 °C for 20 hours. The resulting polyamic acid solution (P-1) had a weight-average molecular weight (Mw) of 34,446 by GPC. The resulting polyamic acid had terminal amino groups.

[0139] <Comparative Synthesis Example 1> Synthesis of polyimide (P-2) To 87.5 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1, 43.8 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, and 4.59 g of acetic anhydride were added and stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. Subsequently, 56.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 482 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 193 g of methanol and then filtered off. The precipitate was washed again with 193 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-2). The weight-average molecular weight (Mw) of the resulting polyimide (P-2) measured by GPC was 31,814, and the chemical imidization rate calculated by NMR measurement was 99%.

[0140] <Synthesis Example 2> Synthesis of polyimide (P-3) To 87.5 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1, 43.8 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, and 5.86 g of propionic anhydride were added and stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. Subsequently, 56.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 486 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 194 g of methanol and then filtered off. The precipitate was washed again with 194 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-3). The weight-average molecular weight (Mw) of the resulting polyimide (P-3) measured by GPC was 31,565, and the chemical imidization rate calculated by NMR measurement was 99%.

[0141] <Synthesis Example 3> Synthesis of polyimide (P-4) To 87.5 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1, 43.8 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, and 7.12 g of butyric anhydride were added and stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 3 hours. Subsequently, 56.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 488 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 196 g of methanol and then filtered off. The precipitate was washed again with 196 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-4). The weight-average molecular weight (Mw) of the resulting polyimide (P-4) measured by GPC was 28,553, and the chemical imidization rate calculated by NMR measurement was 92%.

[0142] <Synthesis Example 4> Synthesis of polyimide (P-5) To 87.5 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1, 43.8 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, and 8.39 g of valeric anhydride were added and stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 2 hours. To accelerate the reaction, 18.3 mg of 4-dimethylaminopyridine (hereinafter abbreviated as DMAP) was added and stirred at 70°C for 1 hour. Subsequently, 56.3 g of N-ethyl-2-pyrrolidone was added for dilution. The resulting solution was slowly added to 492 g of stirring methanol, stirred for 10 minutes, and the resulting precipitate was filtered off. The precipitate was washed with 197 g of methanol and then filtered off. The precipitate was washed again with 197 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-5). The resulting polyimide (P-5) had a weight average molecular weight (Mw) of 27,296 as determined by GPC, and a chemical imidization rate of 96% as calculated by NMR measurement.

[0143] <Synthesis Example 5> Synthesis of polyimide (P-6) To 65.7 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1, 32.8 g of N-ethyl-2-pyrrolidone, 0.57 g of triethylamine, and 11.0 g of decanoic anhydride were added and stirred in air at room temperature for 30 minutes, followed by stirring at 60°C for 2 hours. To accelerate the reaction, 13.8 mg of DMAP was added and stirred at 70°C for 1 hour. Then, 42.2 g of N-ethyl-2-pyrrolidone was added for dilution. This solution was slowly added to 380.8 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 152 g of methanol and then filtered off. The precipitate was washed again with 152 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-6). The resulting polyimide (P-6) had a weight average molecular weight (Mw) of 27,470 as determined by GPC, and a chemical imidization rate of 99% as calculated by NMR measurement.

[0144] <Synthesis Example 6> Synthesis of polyimide (P-7) To 43.8 g of the polyamic acid solution (P-1) obtained in Synthesis Example 1, 21.9 g of N-ethyl-2-pyrrolidone, 0.38 g of triethylamine, 2.84 g of acrylic anhydride, and 13.8 mg of DMAP were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 28.2 g of N-ethyl-2-pyrrolidone was added for dilution. The resulting solution was slowly added to 243 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 97 g of methanol and then filtered off. The precipitate was washed again with 97 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-7). The weight-average molecular weight (Mw) of the resulting polyimide (P-7) measured by GPC was 27,211, and the chemical imidization rate calculated by NMR measurement was 99%.

[0145] Comparative Synthesis Example 2: Synthesis of polyamic acid (P-8) 8.114 g (75 mmol) of mPDA, 12.321 g (30 mmol) of BAPP, 16.956 g (45 mmol) of APC-18, and 406.6 g of N-ethyl-2-pyrrolidone were added and dissolved under air by stirring at room temperature. 62.197 g (100.5 mmol) of TMPBP-TME was then added and stirred at room temperature until the mixture became clear. 20 g (45 mmol) of 6FDA and 271.06 g of N-ethyl-2-pyrrolidone were then added and stirred at 50°C for 20 hours. The weight-average molecular weight (Mw) of the resulting polyamic acid solution (P-8) was 42,163 by GPC. The resulting polyamic acid had terminal amino groups.

[0146] <Comparative Synthesis Example 3> Polyimide (P-9) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, and 4.6 g of acetic anhydride were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 441 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 176 g of methanol and then filtered off. The precipitate was washed again with 176 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-9). The weight-average molecular weight (Mw) of the resulting polyimide (P-9) measured by GPC was 36,672, and the chemical imidization rate calculated by NMR measurement was 99%.

[0147] Comparative Synthesis Example 4: Polyimide (P-10) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, and 5.86 g of propionic anhydride were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 444 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 178 g of methanol and then filtered off. The precipitate was washed again with 178 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-10). The weight-average molecular weight (Mw) of the resulting polyimide (P-10) measured by GPC was 34,105, and the chemical imidization rate calculated by NMR measurement was 99%.

[0148] <Comparative Synthesis Example 5> Polyimide (P-11) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, 7.12 g of butyric anhydride, and 18 mg of DMAP were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 446.8 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 179 g of methanol and then filtered off. The precipitate was washed again with 179 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-11). The weight-average molecular weight (Mw) of the resulting polyimide (P-11) measured by GPC was 40,774, and the chemical imidization rate calculated by NMR was 99%.

[0149] Comparative Synthesis Example 6: Polyimide (P-12) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, 8.39 g of valeric anhydride, and 18 mg of DMAP were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 450 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 180 g of methanol and then filtered off. The precipitate was washed again with 180 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-12). The weight-average molecular weight (Mw) of the resulting polyimide (P-12) measured by GPC was 39,457, and the chemical imidization rate calculated by NMR measurement was 99%.

[0150] <Comparative Synthesis Example 7> Polyimide (P-13) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, 14.70 g of decanoic anhydride, and 18 mg of DMAP were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added for dilution. The resulting solution was slowly added to 466 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 186 g of methanol and then filtered off. The precipitate was washed again with 186 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-13). The weight-average molecular weight (Mw) of the resulting polyimide (P-13) measured by GPC was 39,905, and the chemical imidization rate calculated by NMR was 99%.

[0151] <Comparative Synthesis Example 8> Polyimide (P-14) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, 6.94 g of methacrylic anhydride, and 18 mg of DMAP were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added for dilution. The resulting solution was slowly added to 447 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 179 g of methanol and then filtered off. The precipitate was washed again with 179 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-14). The weight-average molecular weight (Mw) of the resulting polyimide (P-14) measured by GPC was 37,520, and the chemical imidization rate calculated by NMR measurement was 99%.

[0152] Comparative Synthesis Example 9: Polyimide (P-15) To 79.7 g of the polyamic acid solution (P-8) obtained in Comparative Synthesis Example 2, 39.9 g of N-ethyl-2-pyrrolidone, 0.76 g of triethylamine, 5.68 g of acrylic anhydride, and 18 mg of DMAP were added. The mixture was stirred in air at room temperature for 30 minutes and then at 60°C for 3 hours. Subsequently, 51.3 g of N-ethyl-2-pyrrolidone was added and diluted. The resulting solution was slowly added to 450 g of stirring methanol and stirred for 10 minutes. The resulting precipitate was filtered off. The precipitate was washed with 177 g of methanol and then filtered off. The precipitate was washed again with 177 g of methanol, filtered off, and dried under reduced pressure at 60°C to obtain a powder of polyimide (P-15). The weight-average molecular weight (Mw) of the resulting polyimide (P-15) measured by GPC was 40,695, and the chemical imidization rate calculated by NMR measurement was 99%.

[0153] The compounds shown in the examples and comparative examples are as follows. NK Ester A-DOD-N: 1,10-decanediol diacrylate (Shin-Nakamura Chemical Co., Ltd.) BMI-689: A maleimide compound represented by the following formula (manufactured by Designer Molecules, Inc.) [ka]

[0154] NCI-930 (O-acyloxime compound, manufactured by ADEKA Corporation) Omnirad (registered trademark) 819: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (manufactured by IGM Resins Co., Ltd.) KBM-5103: 3-acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) CBT-SG: A mixture of 4-carboxybenzotriazole and 5-carboxybenzotriazole (manufactured by Johoku Chemical Industry Co., Ltd.)

[0155] <Comparative Example 1> A negative photosensitive resin composition (solution) was prepared by mixing and dissolving 3.9146 g of the polyimide (P-2) powder obtained in Comparative Synthesis Example 1, 5.85 g of N-ethyl-2-pyrrolidone, 7.8 g of γ-butyrolactone, 5.85 g of cyclohexanone, 0.5872 g of NK-ester A-DOD-N, 0.5872 g of BMI-689, 0.0391 g of NCI-930, 0.2349 g of Omnirad819, 0.0783 g of KBM-5103, and 0.0587 g of CBT-SG, and then filtering the mixture using a polypropylene filter having a pore size of 5 μm.

[0156] Example 1 A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-3) obtained in Synthesis Example 2 was used as the polyimide.

[0157] <Example 2> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-4) obtained in Synthesis Example 3 was used as the polyimide.

[0158] Example 3 A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-5) obtained in Synthesis Example 4 was used as the polyimide.

[0159] Example 4 A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-6) obtained in Synthesis Example 5 was used as the polyimide.

[0160] <Example 5> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-7) obtained in Synthesis Example 6 was used as the polyimide.

[0161] <Comparative Example 2> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-9) obtained in Comparative Synthesis Example 3 was used as the polyimide.

[0162] <Comparative Example 3> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-10) obtained in Comparative Synthesis Example 4 was used as the polyimide.

[0163] <Comparative Example 4> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-11) obtained in Comparative Synthesis Example 5 was used as the polyimide.

[0164] <Comparative Example 5> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-12) obtained in Comparative Synthesis Example 6 was used as the polyimide.

[0165] <Comparative Example 6> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-13) obtained in Comparative Synthesis Example 7 was used as the polyimide.

[0166] <Comparative Example 7> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-14) obtained in Comparative Synthesis Example 8 was used as the polyimide.

[0167] <Comparative Example 8> A negative photosensitive resin composition (solution) was prepared in the same manner as in Comparative Example 1, except that the polyimide (P-15) obtained in Comparative Synthesis Example 9 was used as the polyimide.

[0168] [Photosensitivity and developability evaluation] The negative photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 8 were applied to an 8-inch silicon wafer using a spin coater (CLEAN TRACK ACT-8, manufactured by Tokyo Electron Ltd.), and then baked at 115°C for 270 seconds to form a photosensitive resin film with a thickness of approximately 25 µm on the silicon wafer. An exposure pattern of 7 x 7 mm square (exposure dose: 300 mJ / cm) was then formed on the resulting photosensitive resin film using an i-line stepper (NSR-2205i12D, manufactured by Nikon Corporation). 2 After exposure, an automatic developing apparatus (AD-1200, manufactured by Mikasa Co., Ltd.) was used to perform spray development using cyclopentanone as the developer, followed by spray rinsing using propylene glycol monomethyl ether acetate (PGMEA) as the rinse solution. The development time with cyclopentanone was 0 mJ / cm for the unexposed area (0 mJ / cm). 2 The time required for the film to be completely developed was 10 seconds, and the rinse time with PGMEA was 10 seconds. 2 The film thickness after development in the exposed area was measured using an interference film thickness meter (Lambda Ace VM-2110, manufactured by SCREEN Co., Ltd.), and the percentage of film thickness remaining without development in the exposed area (remaining film ratio (%)) was calculated using the following formula. Residual film rate (%) = [(film thickness of exposed area)] / (film thickness immediately after film formation) × 100 In other words, if the remaining film ratio is 70%, it means that 70% of the film thickness immediately after the film formation remains undeveloped after development. In the photosensitivity evaluation, if the film remaining rate was 70% or more, the composition was deemed suitable as a negative-type photosensitive resin composition for the relief pattern production process and marked with "Good", whereas if the film remaining rate was less than 70%, the composition was deemed to have insufficient photosensitivity and marked with "Poor".

[0169] Furthermore, for the evaluation of developability, a photosensitive resin film formed from a negative-type photosensitive resin composition containing a polyimide obtained by carrying out chemical imidization using acetic anhydride (acetic anhydride) was used as a standard. In the case of a photosensitive resin film formed from a negative-type photosensitive resin composition containing a polyimide obtained by carrying out chemical imidization using another acid anhydride instead of acetic anhydride, if the development time was shortened, the developability was deemed good and was marked with "◯", and if the development time was the same or longer, it was marked with "X". For Examples 1 to 5, Comparative Example 1 was used as the reference, and for Comparative Examples 3 to 8, Comparative Example 2 was used as the reference. The results of the photosensitivity evaluation and the developability evaluation are shown in Table 1.

[0170] [Table 1]

[0171] From the results in Table 1, the photosensitive resin films obtained from the negative photosensitive resin compositions of Examples 1 to 5 had shorter development times and higher film retention rates of 70% or more than the photosensitive resin film obtained from the negative photosensitive resin composition of Comparative Example 1. On the other hand, the photosensitive resin films obtained from the negative-type photosensitive resin compositions of Comparative Examples 3 to 8 required shorter development times than the photosensitive resin film obtained from the negative-type photosensitive resin composition of Comparative Example 2, but because the polyimide did not contain a photopolymerizable group, the remaining film rate was insufficient and the film was not suitable as a photosensitive resin film.

Claims

1. A method for producing a polyimide by chemically imidizing a polyimide precursor having an amino group at its terminal in the presence of an acid anhydride and a base catalyst, comprising: The polyimide precursor has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), The acid anhydride is a compound represented by the following formula (A): Polyimide manufacturing method. 【Chemistry 1】 (In formula (1), A １ represents a tetravalent organic group. In formula (2), A ２ represents a divalent aromatic group having a photopolymerizable group. 【Chemistry 2】 (In formula (A), R １ represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent.

2. 2. The method for producing a polyimide according to claim 1, wherein the polyimide precursor is a reaction product of at least one tetracarboxylic dianhydride and at least one diamine component, and the tetracarboxylic dianhydride is used in an amount of 90 mol % to 99 mol % relative to 100 mol % of the diamine component.

3. 3. The method for producing a polyimide according to claim 1, wherein the structural unit represented by formula (2) is a structural unit represented by the following formula (2a): 【Transformation 3】 (In formula (2a), V １ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond; W １ represents an oxygen atom or an NH group, R ２ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxy group, R ３ represents a hydrogen atom or a methyl group.

4. In the formula (2a), V １ represents an ester bond, W １ The method for producing a polyimide according to claim 3 , wherein represents an oxygen atom.

5. In the formula (2a), R ２ The method for producing a polyimide according to claim 3, wherein represents a 1,2-ethylene group.

6. The method for producing a polyimide according to claim 1 or 2, wherein the polyimide has a terminal structure represented by the following formula (A1): 【Chemistry 4】 (In formula (A1), R １ is defined as in formula (A), and * represents a bond.

7. 3. The method for producing a polyimide according to claim 1, wherein the base catalyst comprises at least one selected from the group consisting of triethylamine, 4-dimethylaminopyridine, diazabicycloundecene, 2,6-lutidine, diisopropylethylamine, diisopropylamine, diisobutylamine, 2-picoline, imidazole, 1,8-diaminonaphthalene, 1,4-diazabicyclo[2.2.2]octane, pyrimidine, pyridazine, pyrazine, and guanidine compounds.

8. A photosensitive resin composition comprising: a polyimide having a structural unit represented by the following formula (11), a structural unit represented by the following formula (2), and a terminal structure represented by the following formula (A1); a crosslinkable compound; a photoradical polymerization initiator; and a solvent. 【Transformation 5】 (In formula (11), A １ represents a tetravalent organic group. In formula (2), A ２ represents a divalent aromatic group having a photopolymerizable group. In formula (A1), R １ represents a hydrocarbon group having 2 to 22 carbon atoms which may have a substituent, and * represents a bond.

9. The photosensitive resin composition according to claim 8, wherein the structural unit represented by formula (2) is a structural unit represented by formula (2a): 【Transformation 6】 (In formula (2a), V １ represents a direct bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond; W １ represents an oxygen atom or an NH group, R ２ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted with a hydroxy group, R ３ represents a hydrogen atom or a methyl group.

10. In the formula (2a), V １ represents an ester bond, W １ The photosensitive resin composition according to claim 9 , wherein represents an oxygen atom.

11. In the formula (2a), R ２ The photosensitive resin composition according to claim 9, wherein represents a 1,2-ethylene group.

12. The photosensitive resin composition according to claim 8 or claim 9, further comprising an adhesion promoter.

13. The photosensitive resin composition according to claim 8 or claim 9, further comprising an azole compound.

14. An insulating film which is a fired product of a coating film of the photosensitive resin composition according to claim 8 or 9.

15. A photosensitive resist film comprising: a substrate film; a photosensitive resin layer formed from the photosensitive resin composition according to claim 8; and a cover film.

16. (1) applying the photosensitive resin composition according to claim 8 or 9 onto a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer to light; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) heat-treating the relief pattern to form a hardened relief pattern; A method for producing a substrate with a cured relief pattern, comprising:

17. The method for producing a substrate having a cured relief pattern according to claim 16, wherein the developer used for the development is an organic solvent.

18. 17. A substrate with a cured relief pattern produced by the method of claim 16.

19. A semiconductor device comprising a semiconductor element and a cured film provided on an upper or lower part of the semiconductor element, wherein the cured film has a cured relief pattern formed from the photosensitive resin composition according to claim 8 or 9.

Images